CN109092349A - It is used to prepare the catalyst and its preparation method and application of glycol dimethyl ether - Google Patents
It is used to prepare the catalyst and its preparation method and application of glycol dimethyl ether Download PDFInfo
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- CN109092349A CN109092349A CN201710468616.5A CN201710468616A CN109092349A CN 109092349 A CN109092349 A CN 109092349A CN 201710468616 A CN201710468616 A CN 201710468616A CN 109092349 A CN109092349 A CN 109092349A
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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
- B01J29/65—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
- B01J29/66—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 containing iron group metals, noble metals or copper
- B01J29/68—Iron group metals or copper
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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
- 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
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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
- B01J29/65—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
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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
- B01J29/65—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
- B01J29/655—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
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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
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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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
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- 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
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The present invention provides a kind of catalyst for being used to prepare glycol dimethyl ether, and with the total weight of catalyst, the catalyst includes following components: a) SiO of 20-90 weight %2/Al2O3Molar ratio is the metal of 120-350 and/or the zeolite molecular sieve of its oxide modifying；Wherein total weight of the content of metal and/or its oxide based on catalyst is 0.01-5 weight %, and the metal is selected from least one of Fe, Co, Ni, Cu, Zn and Zr；And b) the carrier of 10-80 weight %, wherein the summation of each component adds up as 100 weight %.The present invention also provides a kind of method for preparing catalyst of the present invention, a kind of methods and catalyst of the present invention using catalyst preparation glycol dimethyl ether of the present invention in the application prepared in glycol dimethyl ether.
Description
Technical field
The present invention relates to catalyst for being used to prepare glycol dimethyl ether and its preparation method and application.
Background technique
Glycol dimethyl ether is a kind of very good aprotic polar solvent of performance, water-soluble, can also with alcohol,
The compounds such as ether, ketone, ester, hydrocarbon dissolve each other, and have preferable solvability to various celluloses and resin；It can be used as gas absorption
SO is dissolved in agent2, methane, the gases such as ethylene；In recent years, glycol dimethyl ether has opened up some new applications again, such as extracting
Drug is used as aligning agent for liquid crystal etc..
Oxygen content is 35.6% in glycol dimethyl ether, and the Cetane number of glycol dimethyl ether is up to 98, ignition properties
It can be good.Result of study shows that glycol dimethyl ether can be used as novel cleaning diesel component, without any changes in diesel engine
In the case of, 30% glycol dimethyl ether is added in diesel oil, can sufficiently be improved the combustion position of diesel oil within the engine, be mentioned
High thermal efficiency substantially reduces the smoke emission of diesel engine；Moreover, glycol dimethyl ether has lower freezing point, it is a kind of non-
Often ideal aviation fuel additive.
With the extension of glycol dimethyl ether use scope, the demand of glycol dimethyl ether constantly expands.From
Coal sets out as raw material, and the industry for carrying out glycol dimethyl ether is combined to and application study, has to the development of coal chemical industry important
Meaning.
There are many synthetic line of glycol dimethyl ether, and synthesizing glycol dimethyl ether is mainly the following method at present:
(1) methylation method.This method is raw material using ethylene glycol or glycol monoethyl ether, and chloromethanes is methylating reagent,
Crown ether or quaternary ammonium salt etc. are phase transfer catalyst, obtain glycol dimethyl ether.This method is high there are catalyst price and cannot return
The shortcomings that receipts.Zhu Xinbao etc. (" chemical industry in Jiangsu Province " 1996,24 (5) 18-20) makees catalyst using homemade polyglycol ether, in temperature
Purity 99.9%, the glycol dimethyl ether of yield 90% can be obtained under the conditions of.The product purity that this method obtains is high, yield
Height, catalyst is recyclable, has been carried out commercialization, but this method has used the chloromethanes of severe toxicity, and also uses highly basic
NaOH corrodes equipment big.
(2) insertion of ethylene oxide open loop and dimethyl ether.CN101263101 report Clariant Corporation dimethyl ether with
The direct synthesizing glycol dimethyl ether of ethylene oxide, has invented a kind of novel composite catalyst, which becomes HBF4With/
Or BF3With H2SO4、HNO3And/or H3PO4Combination, the preferred 1:(0.3-0.5 of mass ratio).Particularly preferred acid is H2SO4With
H3PO4.Using this catalyst, obtain higher glycol dimethyl ether selectivity, formed a certain amount of by-product such as dioxanes or
Triglyme.The shortcomings that technique is product complexity, and separating difficulty is bigger.
(3) the oxidative coupling method of dimethyl ether.Dimethyl ether carries out oxidative coupling reaction under the action of catalyst can be made second
Glycol dimethyl ether, catalyst are the IVA metal oxide being carried on MgO, at 200 DEG C, 1.6MPa, 5%SnO2/ MgO and two
Methyl ether/O2Molar ratio be 5.0 under conditions of, the selectivity of glycol dimethyl ether is 34.5%.The technological design is novel, but deposits
In the selectively low problem of glycol dimethyl ether.CN1836775A reports a kind of with compared with high reaction activity and high ethylene glycol two
The O composite metallic oxide catalyst of methyl ether selectivity, expression formula MOx-SnOy-MgO.It is solid that the composite catalyst is placed in flowing
In fixed bed reactor assembly, it is passed through a certain proportion of dimethyl ether, oxygen and inert gas, is carried out in certain temperature range anti-
It answers, the glycol dimethyl ether of high yield can be prepared, dimethyl ether conversion rate is higher, but the technique is easy to produce CO2By-product.
(4) evaporation between molecule.Ethylene glycol or glycol monoethyl ether carry out catalysis with methanol or dimethyl ether and react and can make
Glycol dimethyl ether is obtained, the method process flow is short, and raw material is easy to get, and is very suitable to industrialized developing.Japan Patent JP2004-
196783 report by catalyst of the composite oxides of Cs-P-Si when the proportion of ethylene glycol and methanol is 1:20, and pressure is
Under 8.2MPa, the conversion ratio of ethylene glycol is 35%, and the selectivity of glycol monoethyl ether is 67%, and the selectivity of diethylene glycol is
30%, the selectivity of glycol dimethyl ether is 0%；With γ-Al2O3As catalyst, ethylene glycol reforming rate is 96%, ethylene glycol
The selectivity of dimethyl ether is 18%, and the selectivity of dioxanes is 5%.The selectivity or ethylene glycol of glycol dimethyl ether in terms of result
Conversion ratio it is relatively low, industrialized requirement cannot be reached, need to develop high activity and highly selective catalyst.
The beta-zeolite molecular sieve that a kind of Ca modification is reported in patent PCT/CN2015/079691 is closed as glycol ether
At catalyst, the catalyst is at 210 DEG C, 5.0MPa, and the molar ratio of methanol and ethylene glycol is under 4:1, and the conversion ratio of ethylene glycol is
75.42%, the selectivity of glycol ether is 98.6%, and wherein the selectivity of glycol dimethyl ether is 41.44%, catalyst it is steady
It is qualitative more than 2000 hours, but have by-product dioxanes generation；The patent reports the modified alkali magnesium zeolite of Ca simultaneously
Ferrierite (abbreviation FER) molecular sieve catalyst, under the same conditions, Transformation efficiency is up to 90 .71% is disliked without by-product two
Alkane, the selectivity of glycol ether are 100%, and still, the selectivity of glycol dimethyl ether is low, only 24.53%, moreover, this is urged
Agent inactivation is fast, and stability is poor.The level of industrialization synthesizing glycol dimethyl ether all has not been reached yet in both catalyst.
(5) carbonylation method.Ge Xin etc. (chemical reagent, 1997,19 (3) 150-153) reports a kind of carbonylation method preparation
The method of glycol dimethyl ether, this method are raw material by synthesis gas and methanol, and synthesis gas is passed through methanol, in Re/ active carbon or
It is 200 DEG C in reaction temperature under the effect of Co base complex, reaction pressure is to obtain the second two that yield is 41.8% under 10.0MPa
Diethylene glycol dimethyl ether.
FER is that a kind of aperture is smaller, and acid stronger solid acid catalyst is mainly used in the different of small molecule hydro carbons
The reaction such as structureization and cracking, since aperture is small, the generation for the cyclic side products that some molecular dimensions can be inhibited bigger, separately
Outside, since acidity is strong, some reactions can be made to carry out at low temperature.The FER zeolite molecular sieve of small-bore is conducive in ethylene glycol
The generation of cyclic annular harmful by-products dioxanes is controlled in reaction with methanol-fueled CLC glycol dimethyl ether；In addition, glycol dinitrate
Ether synthetic reaction is easy to produce the polymers such as polyol ether at high temperature, and catalyst is made to be easy inactivation.Therefore, which is suitble to strong
Sour, low-temperature catalyzed reaction.
In conclusion methylation method is the most mature in existing glycol dimethyl ether preparation method, but the method use
Highly basic NaOH, it is larger to equipment corrosion, generate a large amount of NaCl or Na2SO4.Using ethylene oxide and ether as in the technique of raw material,
The dangerous property of the ethylene oxide used, in addition, this method is the disadvantage is that product is complicated, separating difficulty is bigger.Dimethyl ether
Coupling method, although raw material is simple and easy to get, reaction is not easily controlled, and is easy to produce CO2Equal by-products, have not been reached yet business
The standard of change；Carbonylation method, also raw material sources are extensive, somewhat expensive but there are catalyst, the low problem of performance.
With the successful commercialization of coal-ethylene glycol technique, ethylene glycol is protected as the raw material of production glycol dimethyl ether
Barrier, same methanol is also the base product of coal chemical industry, using ethylene glycol and methanol as synthesizing glycol two in terms of the source of raw material
The raw material of methyl ether, it should be the most extensively and inexpensive.But existing by ethylene glycol and methanol is that raw material prepares glycol dinitrate
The status that in the technology of ether, ethylene glycol reforming rate is relatively low, glycol dimethyl ether is selectively low, can't reach industrialized water
It is flat, therefore, need to find one kind with preferable ethylene glycol reforming rate, high glycol dimethyl ether is selective and well stable
Property, and without the generation of by-product dioxanes, the reproducible method of solid catalyst realize that ethylene glycol is reacted with methanol etherification
Produce the industrialization of glycol dimethyl ether.
Summary of the invention
It is an object of the present invention to provide one kind for methanol and/or dimethyl ether and ethylene glycol and/or ethylene glycol list
Methyl ether is the catalyst that raw material prepares glycol dimethyl ether, wherein the catalyst includes with the following group with the total weight of catalyst
Point:
A) SiO of 20-90 weight %2/Al2O3Molar ratio is the metal of 120-350 and/or the zeolite of its oxide modifying
Molecular sieve；Wherein total weight of the content of metal and/or its oxide based on catalyst is 0.01-5 weight %, the metal choosing
From at least one of Fe, Co, Ni, Cu, Zn and Zr；With
B) carrier of 10-80 weight %,
Wherein the summation of each component adds up as 100 weight %.
It is a further object of the present invention to provide a kind of methods for preparing catalyst of the present invention, method includes the following steps:
(1) SiO is provided2/Al2O3Molar ratio is the H-type zeolite molecular sieve of 120-350；
(2) after contacting the aqueous solution of water-soluble metal salt with the zeolite molecular sieve of step (1), be filtered, washed, dry and
Roasting, obtains modified zeolite molecular sieve, wherein the metal is selected from least one of Fe, Co, Ni, Cu, Zn and Zr；
(3) zeolite molecular sieve for the modification that step (2) obtains is pinched with carrier or precursor carrier, shaping assistant, water and acid
It closes, then forms, is dry, roasting, being crushed and sieve later, obtain solid particle；
The wherein total weight that the dosage of each component makes with catalyst, the catalyst include following components:
A) SiO of 20-90 weight %2/Al2O3Molar ratio is the metal of 120-350 and/or the zeolite of its oxide modifying
Molecular sieve；Wherein total weight of the content of metal and/or its oxide based on catalyst is 0.01-5 weight %, the metal choosing
From at least one of Fe, Co, Ni, Cu, Zn and Zr；With
B) carrier of 10-80 weight %,
Wherein the summation of each component adds up as 100 weight %.
Another object of the present invention is to provide a kind of method for preparing glycol dimethyl ether, this method comprises: in etherificate item
Under part, contact material a and material b with catalyst of the present invention, wherein the material a be ethylene glycol and/or glycol monoethyl ether,
The material b is methanol and/or dimethyl ether.
It is yet another object of the invention to provide the catalyst for being used to prepare glycol dimethyl ether to prepare glycol dimethyl ether
In application.
Specific embodiment
One aspect of the present invention provides a kind of for methanol and/or dimethyl ether and ethylene glycol and/or glycol monoethyl ether
The catalyst of glycol dimethyl ether is prepared for raw material, wherein the catalyst includes following components with the total weight of catalyst:
A) SiO of 20-90 weight %2/Al2O3Molar ratio is the metal of 120-350 and/or the zeolite of its oxide modifying
Molecular sieve；Wherein total weight of the content of metal and/or its oxide based on catalyst is 0.01-5 weight %, the metal choosing
From at least one of Fe, Co, Ni, Cu, Zn and Zr；With
B) carrier of 10-80 weight %,
Wherein the summation of each component adds up as 100 weight %.
Catalyst of the present invention includes preferred 30-85 weight %, the component a) of more preferable 40-80 weight %.
Catalyst of the present invention includes preferred 15-70 weight %, the component b) of more preferable 20-60 weight %.
The SiO of zeolite molecular sieve used in catalyst of the present invention2/Al2O3Molar ratio is preferably 140-320, more preferable 150-
300。
Total weight of the content of metal and/or its oxide based on catalyst is preferably 0.1-3 weight in catalyst of the present invention
Measure %.
Zeolite molecular sieve used is based on zeolite molecular sieve known in those skilled in the art in catalyst of the present invention, such as
Zeolite molecules are excellent screened from least one of USY, FER, ZSM-5, ZSM-11, ZSM-23, MCM-22 and beta-zeolite molecular sieve
Choosing is selected from least one of ZSM-5, FER and beta-zeolite molecular sieve, more preferably FER and/or beta-zeolite molecular sieve, particularly preferably
For FER zeolite molecular sieve.
The present invention does not specially require the source of zeolite molecular sieve, can be obtained by commercially available, can also be by existing
The method of technology synthesis zeolite obtains, and hydro-thermal method can be used for example and synthesize to obtain.
In a preferred embodiment of the present invention, the zeolite molecular sieve is FER zeolite molecular sieve, synthetic method
May include:
(i) silicon source, silicon source, template, acid and water are mixed, obtains reaction mixture；
(ii) the reaction mixture hydrothermal crystallizing for obtaining step (i), obtained solid is dry, roasting, obtains after filtering
To Na type FER zeolite molecular sieve；
(iii) it after exchanging the Na type FER zeolite molecular sieve that step (ii) obtains with ammonium salt aqueous solution, is roasted, is obtained
To H-type FER zeolite molecular sieve.
The silicon source can be silicon source known in those skilled in the art, be preferably selected from waterglass, silica solution, silica gel and
Silicon powder.Source of aluminium and acid are known to those skilled in the art, such as source of aluminium can be selected from aluminum sulfate, sodium aluminate and silicon
Aluminium glue；The acid can be selected from sulfuric acid, hydrochloric acid and nitric acid.
Template of the invention can be the template known in those skilled in the art for being used to prepare FER zeolite molecular sieve
Agent, for example, the template can be pyridine, piperidines, tetrahydrofuran etc..
It, can be in wider model to the silicon source, template, sour and water molar ratio without particular/special requirement in step (i)
Interior selection is enclosed, the molar ratio of silicon source, template, acid and water preferably in terms of silicon is 1:0.1-0.2:0.4-0.6:50-90, preferably
For 1:0.12-0.18:0.45-0.55:60-80.
The dosage of silicon source described in above-mentioned steps (i) and silicon source should make the SiO of zeolite molecular sieve2/Al2O3Molar ratio is
120-350, preferably 140-320, more preferable 150-300.
A small amount of sodium metal salt such as sodium sulphate, sodium chloride, sodium fluoride, sodium carbonate, sodium bicarbonate can also be added in step (i)
And/or sodium acetate etc., wherein preferably sulfuric acid sodium and/or sodium chloride.The present invention does not limit the amount of sodium metal salt used particularly
It is fixed, it can be selected according to actual needs.
The present invention can be conventional preparation FER zeolite molecules without particular/special requirement to crystallization condition described in step (ii)
The crystallization condition of sieve.For example, the temperature of crystallization can be 50-250 DEG C；Preferably 100-200 DEG C；The time of crystallization is 12-120
Hour, preferably 24-96 hours.The crystallization well known to those skilled in the art carries out generally in water heating kettle, no longer superfluous herein
It states.The solid containing FER zeolite molecular sieve ingredient and template is obtained after crystallization.
The present invention to after crystallization described in step (ii) filtering and drying condition there is no particular/special requirement, be referred to existing
Technology carries out.For example, filtering after the crystallization and dry generally comprise will be containing FER zeolite molecular sieve ingredient and templates
Solid is separated with mother liquor, and the solid of the ingredient of zeolite molecular sieve containing FER and template is washed with deionized to neutrality, in 70-150
DEG C air drying 3-15 hours.
Those skilled in the art could be aware that, the step of template is usually carried out after crystallization and drying steps
Suddenly.The present invention can be various methods well known in the art without particular/special requirement to the method for removing template, such as can be
It is roasted after drying.To roasting condition described in step (ii) without particular/special requirement, the temperature of the preferably described roasting is the present invention
400-650 DEG C, preferably 500-600 DEG C；The time of roasting is 3-16 hours, preferably 4-8 hours；Calcination atmosphere is air.
It, can to the molar ratio of Na type FER zeolite molecular sieve and ammonium salt in terms of silicon without particular/special requirement in step (iii)
To select in a wider scope.It is preferred that the molar ratio of the Na type FER zeolite molecular sieve and ammonium salt in terms of silicon is 1:0.1-
0.2, more preferably 1:0.12-0.18.Exchange temperature is -90 DEG C of room temperature, preferably -70 DEG C of room temperature.Swap time is that 2-10 is small
When, preferably 3-6 hours.
Ammonium salt usually uses as an aqueous solution.Generally, the concentration of ammonium salt is 0.5-1.5mol/L, preferably 0.75-
1.2mol/L。
Ammonium salt of the invention can be ammonium salt known in those skilled in the art, preferably ammonium nitrate, ammonium chloride and sulphur
At least one of sour ammonium.
The present invention is to the condition of roasting described in step (iii) without particular/special requirement.It is preferred that the temperature of the roasting is 400-
650 DEG C, preferably 500-600 DEG C；The time of roasting is 3-16 hours, preferably 4-8 hours.
It is accounted for from the selectivity of glycol dimethyl ether, metal described in instant component a) is preferably selected from Fe, Ni, Zn
At least one of with Zr, it is more preferably selected from least one of Fe, Ni and Zr, most preferably Ni and/or Zr.
There is no particular limitation for type of the present invention to the carrier of used catalyst, can be selected according to actual needs
It selects.Such as carrier can be selected from least one of aluminium oxide and silica.
Another aspect of the present invention provides a kind of method for preparing catalyst of the present invention, method includes the following steps:
(1) SiO is provided2/Al2O3Molar ratio is the H-type zeolite molecular sieve of 120-350；
(2) after contacting the aqueous solution of water-soluble metal salt with the zeolite molecular sieve of step (1), be filtered, washed, dry and
Roasting, obtains modified zeolite molecular sieve, wherein the metal is selected from least one of Fe, Co, Ni, Cu, Zn and Zr；
(3) zeolite molecular sieve for the modification that step (2) obtains is pinched with carrier or precursor carrier, shaping assistant, water and acid
It closes, then forms, is dry, roasting, being crushed and sieve later, obtain solid particle；
The wherein total weight that the dosage of each component makes with catalyst, the catalyst include following components:
A) SiO of 20-90 weight %2/Al2O3Molar ratio is the metal of 120-350 and/or the zeolite of its oxide modifying
Molecular sieve；Wherein total weight of the content of metal and/or its oxide based on catalyst is 0.01-5 weight %, the metal choosing
From at least one of Fe, Co, Ni, Cu, Zn and Zr；With
B) carrier of 10-80 weight %,
Wherein the summation of each component adds up as 100 weight %.
According to the present invention, the type of water-soluble metal salt used can be selected in the larger context in step (2)
It selects.For example, the water-soluble metal salt can be selected from least one of the water soluble salt of Fe, Co, Ni, Cu, Zn and Zr；From second
The selectivity of glycol dimethyl ether accounts for, and the preferably described water-soluble metal salt is in the water soluble salt of Zr, Fe, Ni, Zn
It is at least one.Specifically, the water-soluble metal salt can be selected from nitrate, carbonate, the phosphorus of Fe, Co, Ni, Cu, Zn and Zr
At least one of hydrochlorate, phosphite and hydrochloride, be preferably selected from the nitrate of Fe, Ni, Zn and Zr, carbonate, phosphate,
At least one of phosphite and hydrochloride.
The present invention is in step (2) contacting the aqueous solution of water-soluble metal salt with the H-type zeolite molecular sieve of step (1)
Condition does not specially require, and generally, the condition of contact may include: that the temperature of contact is 50-150 DEG C, and the time of contact is
2-10 hours, the temperature preferably contacted was 50-120 DEG C, and the time of contact is 2-8 hours.
The present invention does not specially require other operations in step (2), and method well known in the art can be used and carry out.
The present invention does not specially require the condition mediated in step (3), and generally, the condition of kneading may include: to pinch
The temperature of conjunction is 20-50 DEG C, and the time of kneading is 20-90 minutes；It is preferred that the temperature mediated is 25-45 DEG C, the time of kneading is
25-45 minutes.
The invention also includes molding, drying and the calcination steps after mediating in step (3).Molding method, drying side
Method and the method for roasting can be used method well known in the art and carry out.
Drying can be the drying condition of conventional preparation H-type zeolite molecular sieve in step (3) of the present invention, specifically, do
Dry temperature can be 50-250 DEG C；Preferably 100-200 DEG C；The dry time can be 12-120 hours, preferably 24-96
Hour.
Roasting can be the roasting condition of conventional preparation H-type zeolite molecular sieve in step (3) of the present invention.For example, roasting
Temperature can be 500-750 DEG C；Preferably 500-650 DEG C；The time of roasting can be 1-10 hours, preferably 3-8 hours.
The broken and screening step in step (3) is not particularly limited in the present invention, can be used well known in the art any
Method.
Acid used in step (3) is not particularly limited in the present invention, including inorganic acid (such as nitric acid, hydrochloric acid, sulfuric acid
At least one of Deng) or organic acid (formic acid, acetic acid, propionic acid, oxalic acid etc.).Shaping assistant can be selected from field mountain valley with clumps of trees and bamboo powder, polyethylene
At least one of pure and mild polyethylene glycol.
In the preparation process in accordance with the present invention, the type and dosage of H-type zeolite molecular sieve, SiO2/Al2O3Molar ratio, carrier
Type and dosage are as described above, details are not described herein.For precursor carrier, Aluminum sol, boehmite, silica solution can be selected from
At least one of with clay.
Further aspect of the present invention provides a kind of method using catalyst preparation glycol dimethyl ether of the present invention, this method
It include: to connect material a and material b with catalyst of the present invention or catalyst prepared according to the methods of the invention under etherification conditions
Touching, wherein the material a is ethylene glycol and/or glycol monoethyl ether, the material b is methanol and/or dimethyl ether.
According to the present invention, material b and the molar ratio of material a are not particularly limited, for example, the material b and material a
Molar ratio can be 0.1-20:1, preferably 1-10:1, more preferably 4-8:1.
According to the present invention, the raw material not only can also use the ethylene glycol in reaction product with spent glycol and methanol
Monomethyl ether substitutes a part of ethylene glycol as raw material；In addition, since methanol is excessive, most of methanol in reaction in the feed
Be converted into dimethyl ether, use by-product dimethyl ether recycle instead of a part of methanol as raw material, it is non-to recycling for by-product
Chang Youli.
According to the present invention, material a and material the b condition contacted with catalyst are not particularly limited, such as described connect
The condition of touching may include: that the temperature of contact is 100-400 DEG C, and the pressure of contact is 1.0-10.0MPa, with material a and material b
Mass flow meters mass space velocity be 0.05-15h-1.It is examined from the angle of reaction conversion ratio and glycol dimethyl ether selectivity
Consider, the temperature preferably contacted is 140-180 DEG C, and the pressure of contact is 3.0-7.0MPa, with the mass flow meters of material a and material b
Mass space velocity be 0.5-10h-1。
It is not special to the form of the reactor of contact progress in the method for preparing glycol dimethyl ether of the invention
It limits, the reactor can be fixed bed reactors, paste state bed reactor, intermittent kettle reactor, fluidized-bed reactor, movement
The combination of bed reactor and at least one of only stone reactor.In the present invention, only stone reactor refers to using foam
The reactor of only stone integral catalyst, the preferably described reactor are fixed bed.
Another aspect of the invention provides the catalyst for being used to prepare glycol dimethyl ether in preparing glycol dimethyl ether
Application.
Below by embodiment and comparative example the present invention is described in detail, but the scope of the present invention is not limited to these realities
Apply example.
Embodiment
In the present invention, it using the analysis respectively formed in gas-chromatography carry out system, is quantified by correcting normalization method,
It can refer to prior art progress, calculate the evaluations such as the conversion ratio of reactant, the yield of product and selectivity on this basis and refer to
Mark.
In the present invention, the conversion ratio calculation formula of ethylene glycol is as follows:
CEthylene glycol molar concentration in raw materialIndicate the molar concentration of ethylene glycol in raw material, CEthylene glycol molar concentration in productEthylene glycol rubs in expression product
That concentration.
The calculation formula of the selectivity of each component is as follows in product:
Wherein, nGlycol monoethyl ether mole in raw materialIndicate the mole of glycol monoethyl ether in raw material, nGlycol monoethyl ether mole in productIt indicates to produce
The mole of glycol monoethyl ether, M in objectGlycol monoethyl etherIndicate the molecular weight of glycol monoethyl ether, niIndicate that each component (includes second
Glycol monomethyl ether, glycol dimethyl ether, ethylene glycol, dioxanes and more glycol ethers) mole, MiIndicate the molecule of each component
Amount.
Embodiment 1
The present embodiment is used to illustrate the preparation of catalyst of the present invention.
(1) preparation of H-type FER zeolite molecular sieve
By 4.91g Al2(SO4)3·18H2O is dissolved in 480ml deionized water, and 88.0g pyridine and 384g waterglass is added
(SiO2Content is 28.8 weight %), 68.8g Na is added2SO4, it is sufficiently mixed with vigorous stirring, addition 38g concentration is 98 weights
The concentrated sulfuric acid for measuring %, is subsequently added into 5.0g SiO2/Al2O3The FER zeolite molecular sieve crystal seed that molar ratio is 250 stirs 30 minutes,
Obtain uniform gel reaction mixture.Above-mentioned reaction mixture is transferred to the height of the stainless steel with polytetrafluoroethyllining lining
It presses in kettle, crystallization 72 hours at 150 DEG C, is filtered after the completion of crystallization, 2-4 is washed with deionized in the solid being obtained by filtration
It is secondary, until the pH value of solution is 8-9, it is then that the solid after washing is 12 hours dry at 120 DEG C, it is small that 5 are roasted at 550 DEG C
When, obtain SiO2/Al2O3The Na type FER zeolite molecular sieve 105.0g that molar ratio is 250.
By the NH of gained 105g Na type FER zeolite molecular sieve 1000ml 1mol/L at 25 DEG C4NO3Solion is handed over
It changes 240 minutes, then filters, and be washed with deionized 3 times, it is 3 hours dry at 120 DEG C, then 5 are roasted at 550 DEG C
Hour, repetition ion exchange, drying and roasting process 3 times obtain SiO2/Al2O3The H-type FER zeolite molecules that molar ratio is 250
Sieve.
(2) preparation of the modified FER zeolite molecular sieve of nickel
By the Ni (NO of 5.0g3)2·6H2O is dissolved in 500ml deionized water, and 100g H-type FER zeolite produced above is added
Molecular sieve stirs 4 hours at 60 DEG C, then filters, rinsed with deionized water, filtered again, does in baking oven at 120 DEG C
Dry 12 hours, in Muffle kiln roasting 5 hours at 550 DEG C, obtain modified Ni-FER zeolite molecular sieve.
(3) preparation of catalyst
Ni-FER zeolite molecular sieve, the 45g boehmite (Al for taking 70g produced above2O3Weight content be 67%),
5g field mountain valley with clumps of trees and bamboo powder and 60ml H2O is added 5g concentrated nitric acid, mediates 30 minutes at 25 DEG C, the mold extrusion for being 3.0 millimeters with diameter
Molding, dries, and is placed in 120 DEG C of baking oven 12 hours, then roasting 5 is small at 550 DEG C under air atmosphere in Muffle furnace
When.Then it is crushed, sieves, obtaining partial size is 0.75-1.17mm catalyst solid particle.
With the total weight of gained catalyst, which includes the SiO of 70 weight %2/Al2O3Molar ratio is 250
The Al of Ni-FER zeolite molecular sieve and 30 weight %2O3。
Embodiment 2
The present embodiment uses experiment condition same as Example 1, unlike, it (is come from H-type beta-zeolite molecular sieve
The CP811C-300 of Zeolyst company, SiO2/Al2O3By 300) replacing H-type FER zeolite molecular sieve.
Embodiment 3
The present embodiment use experiment condition same as Example 1, unlike, with H-type ZSM-5 zeolite molecular sieve (come
From the CBV28014 of Zeolyst company, SiO2/Al2O3By 280) replacing H-type FER zeolite molecular sieve.
Embodiment 4
The present embodiment uses experiment condition same as Example 1, unlike, the Al in step (1)2(SO4)3·
18H2The dosage of O is 8.18g, in addition, the SiO of FER zeolite molecular sieve crystal seed2/Al2O3Molar ratio becomes 150, obtained Na type
The SiO of FER zeolite molecular sieve2/Al2O3Molar ratio is 150.
Embodiment 5
The present embodiment uses experiment condition same as Example 1, unlike, the Al in step (1)2(SO4)3·
18H2The dosage of O is 6.14g, the SiO of FER zeolite molecular sieve crystal seed2/Al2O3Molar ratio becomes 200, obtained Na type FER boiling
The SiO of stone molecular sieve2/Al2O3Molar ratio is 200.
Embodiment 6
The present embodiment uses experiment condition same as Example 1, unlike, the Al in step (1)2(SO4)3·
18H2The dosage of O is 4.09g, the SiO of FER zeolite molecular sieve crystal seed2/Al2O3Molar ratio becomes 300, obtained Na type FER boiling
The SiO of stone molecular sieve2/Al2O3Molar ratio is 300.
Embodiment 7
The present embodiment uses experiment condition same as Example 1, unlike, with 5.5g Fe (NO3)3·6H2O is replaced
5.0g Ni(NO3)2·6H2O。
Embodiment 8
The present embodiment uses experiment condition same as Example 1, unlike, with 5.0g Zn (NO3)2·6H2O is replaced
5.0g Ni(NO3)2·6H2O。
Embodiment 9
The present embodiment uses experiment condition same as Example 1, unlike, with 5.0g Zr (NO3)4·5H2O is replaced
5.0g Ni(NO3)2·6H2O。
Embodiment 10
The present embodiment uses experiment condition same as Example 1, unlike, with silica solution (Nissan Chemical Industries strain
The Colloidal Sillica, SiO of formula commercial firm2Content 30%) replace boehmite.
Gained catalyst includes the SiO of 70 weight %2/Al2O3The Ni-FER zeolite molecular sieve and 30 weights that molar ratio is 250
Measure the SiO of %2。
Embodiment 11
The present embodiment use experiment condition same as Example 1, unlike, with clay (Kanto Kagaku K. K.,
Fullers earth) replace boehmite.
Gained catalyst includes the SiO of 70 weight %2/Al2O3The Ni-FER zeolite molecular sieve and 30 weights that molar ratio is 250
Measure the mixture of the alumina silica of %.
Embodiment 12
The present embodiment uses experiment condition same as Example 1, unlike, during kneaded and formed, Ni-FER
Zeolite molecular sieve is 50g, boehmite 75g.
With the total weight of gained catalyst, which includes the SiO of 50 weight %2/Al2O3Molar ratio is 250
The Al of Ni-FER zeolite molecular sieve and 50 weight %2O3。
Embodiment 13
The present embodiment uses experiment condition same as Example 1, unlike, during kneaded and formed, Ni-FER
Zeolite molecular sieve is 60g, boehmite 60g.
With the total weight of gained catalyst, which includes the SiO of 60 weight %2/Al2O3Molar ratio is 250
The Al of Ni-FER zeolite molecular sieve and 40 weight %2O3。
Embodiment 14
The present embodiment uses experiment condition same as Example 1, unlike, during kneaded and formed, Ni-FER
Zeolite molecular sieve is 80g, boehmite 30g.
With the total weight of gained catalyst, which includes the SiO of 80 weight %2/Al2O3Molar ratio is 250
The Al of Ni-FER zeolite molecular sieve and 20 weight %2O3。
Comparative example 1
This comparative example uses experiment condition same as Example 1, unlike, with H-type mordenite molecular sieve
(CBV21A from Zeolyst company, SiO2/Al2O3By 20) replacing H-type FER zeolite molecular sieve.
Comparative example 2
This comparative example uses experiment condition same as Example 1, unlike, the SiO of FER zeolite molecular sieve2/
Al2O3Molar ratio is 100 (HSZ-770NAA of Tosoh company), and with 5.00g Ca (NO3)4·4H2O replaces 5.0g Ni
(NO3)2·6H2O。
Application Example 1
This application embodiment is used to illustrate using catalyst of the present invention by ethylene glycol and/or glycol monoethyl ether and methanol
And/or dimethyl ether reaction prepares glycol dimethyl ether.
In the quartz tube reactor that internal diameter is 10 millimeters, catalyst prepared by filling 2.0g embodiment 1,5.0MPa's
Under pressure, with 1.2h-1Mass space velocity be passed through molar ratio be 4:2:0.3:0.7 dimethyl ether/methanol/glycol monoethyl ether/second
Diol mixture as reaction raw materials, and make reaction raw materials 165 DEG C at a temperature of react.
Experimental result is as shown in table 1.
Application Example 2-14
Repeated application embodiment 1, unlike, used catalyst is replaced with to the catalysis of embodiment 2-14 preparation respectively
Agent.
Experimental result is listed in Table 1 below.
Compare Application Example 1-2
Repeated application embodiment 1, unlike, used catalyst is replaced with to urging for the preparation of comparative example 1 and 2 respectively
Agent.
Experimental result is listed in Table 1 below.
Compare Application Example 3
Repeated application embodiment 1, unlike, used catalyst is replaced with into γ-Al2O3。
Experimental result is listed in Table 1 below.
Compare Application Example 4
Repeated application embodiment 1, unlike, used catalyst is replaced with into H-type perfluorinated sulfonic resin.
Experimental result is listed in Table 1 below.
Application Example 15
Repeated application embodiment 1, unlike, by reaction raw materials be changed to molar ratio be 0:6:0:1 dimethyl ether/methanol/
Glycol monoethyl ether/ethylene glycol mixture.
Experimental result is listed in Table 2 below.
Application Example 16
Repeated application embodiment 1, unlike, by reaction raw materials be changed to molar ratio be 4:2:0:1 dimethyl ether/methanol/
Glycol monoethyl ether/ethylene glycol mixture.
Experimental result is listed in Table 2 below.
Application Example 17
Repeated application embodiment 1, unlike, reaction raw materials are changed to dimethyl ether/first that molar ratio is 6:0:0.3:0.7
Alcohol/glycol monoethyl ether/ethylene glycol mixture.
Experimental result is listed in Table 2 below.
Application Example 18
Repeated application embodiment 1, unlike, by reaction raw materials be changed to molar ratio be 6:0:0:1 dimethyl ether/methanol/
Glycol monoethyl ether/ethylene glycol mixture.
Experimental result is listed in Table 2 below.
Application Example 19-22
Repeated application embodiment 1, unlike, temperature is changed into 150 DEG C, 155 DEG C, 160 DEG C and 170 DEG C respectively.
Experimental result is as shown in table 3.
Application Example 23-28
Repeated application embodiment 1, unlike, pressure is changed into respectively 0.1MPa, 3.0MPa, 4.0MPa, 4.5MPa,
5.5MPa and 6.0MPa.
Experimental result is as shown in table 3.
Application Example 29-31
Repeated application embodiment 1, unlike, mass space velocity is changed into 0.8h respectively-1、2.4h-1And 5.6h-1。
Experimental result is as shown in table 3.
Claims (11)
1. a kind of catalyst for being used to prepare glycol dimethyl ether, with the total weight of catalyst, the catalyst includes following
Component:
A) 20-90 weight %, preferably 30-85 weight %, the SiO of more preferable 40-80 weight %2/Al2O3Molar ratio is 120-
350, preferably 140-320, the metal of more preferable 150-300 and/or the zeolite molecular sieve of its oxide modifying；Wherein metal and/
Or total weight of the content of its oxide based on catalyst is 0.01-5 weight %, preferably 0.1-3 weight %, the metal is selected from
At least one of Fe, Co, Ni, Cu, Zn and Zr；With
B) 10-80 weight %, preferably 15-70 weight %, the carrier of more preferable 20-60 weight %,
Wherein the summation of each component adds up as 100 weight %.
2. catalyst according to claim 1, wherein the zeolite molecular sieve is selected from USY, FER, ZSM-5, ZSM-11, ZSM-
23, at least one of MCM-22 and beta-zeolite molecular sieve, at least one be preferably selected from ZSM-5, FER and beta-zeolite molecular sieve
Kind, more preferably FER and/or beta-zeolite molecular sieve, most preferably FER zeolite molecular sieve.
3. catalyst according to claim 1 or 2, wherein the metal is selected from least one of Fe, Ni, Zn and Zr, it is more excellent
Choosing is selected from least one of Fe, Ni and Zr, most preferably Ni and/or Zr.
4. catalyst as claimed in one of claims 1-3, wherein the carrier in aluminium oxide and silica extremely
Few one kind.
5. a kind of method for preparing catalyst as claimed in one of claims 1-4, the described method comprises the following steps:
(1) SiO is provided2/Al2O3Molar ratio is 120-350, preferably 140-320, the H-type zeolite molecular sieve of more preferable 150-300；
(2) it after contacting the aqueous solution of water-soluble metal salt with the zeolite molecular sieve of step (1), is filtered, washed, dries and roasts
It burns, obtains modified zeolite molecular sieve, wherein the metal is selected from least one of Fe, Co, Ni, Cu, Zn and Zr；
(3) zeolite molecular sieve Yu carrier of the modification for obtaining step (2) or precursor carrier, shaping assistant, water and acid are mediated, so
It forms afterwards, is dry, roasting, being crushed and sieve later, obtain solid particle.
6. method according to claim 5, wherein the carrier is selected from least one of aluminium oxide and silica；The load
Body precursor is selected from least one of Aluminum sol, boehmite, silica solution and clay；The shaping assistant be selected from field mountain valley with clumps of trees and bamboo powder,
At least one of polyvinyl alcohol and polyethylene glycol.
7. according to the method for claim 5 or 6, wherein the water soluble salt be selected from Fe, Co, Ni, Cu, Zn and Zr nitrate,
At least one of carbonate, hydrochloride, phosphate and phosphite.
8. a kind of method for preparing glycol dimethyl ether, which comprises under etherification conditions, make material a and material b and root
It is contacted according to the catalyst of any one of claim 1-4 or according to the catalyst of the method for any one of claim 5-7 preparation,
Wherein material a is ethylene glycol and/or glycol monoethyl ether, and material b is methanol and/or dimethyl ether.
9. method according to claim 8, wherein the molar ratio of material b and material a is 0.1-20:1, preferably 1-10:1, more
Preferably 4-8:1.
10. it is 100-400 DEG C that wherein etherification conditions, which include: the temperature of contact, the pressure of contact according to the method for claim 8 or 9
Power is 1.0-10.0MPa, and the mass space velocity with the mass flow meters of material a and material b is 0.05-15h-1；It is preferred that the temperature contacted
It is 140-180 DEG C, the pressure of contact is 3.0-7.0MPa, and the mass space velocity with the mass flow meters of material a and material b is 0.5-
10h-1。
11. catalyst as claimed in one of claims 1-4 or urging according to the preparation of the method for any one of claim 5-7
Agent is preparing the application in glycol dimethyl ether.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710468616.5A CN109092349A (en) | 2017-06-20 | 2017-06-20 | It is used to prepare the catalyst and its preparation method and application of glycol dimethyl ether |
| EA202090101A EA202090101A1 (en) | 2017-06-20 | 2018-06-14 | CATALYST FOR PRODUCING DIMETOXYETHANE, METHOD FOR ITS PRODUCTION AND APPLICATION |
| PCT/CN2018/091296 WO2018233550A1 (en) | 2017-06-20 | 2018-06-14 | Catalyst for preparing ethylene glycol dimethyl ether and preparation method therefor and use thereof |
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| CN201710468616.5A CN109092349A (en) | 2017-06-20 | 2017-06-20 | It is used to prepare the catalyst and its preparation method and application of glycol dimethyl ether |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113210009A (en) * | 2021-04-20 | 2021-08-06 | 中山大学 | Catalyst for synthesizing anisole from phenol-methanol and preparation method thereof |
| CN114621063A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Device and method for preparing glycol dimethyl ether by reactive distillation |
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| JP2009179609A (en) * | 2008-01-31 | 2009-08-13 | Sanyo Chem Ind Ltd | Method for producing dialkyl ether |
| CN105585459A (en) * | 2014-11-17 | 2016-05-18 | 中国科学院大连化学物理研究所 | Method of preparing glycol dimethyl ether through continuous etherification in fixed bed |
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| CN1634659A (en) * | 2004-10-15 | 2005-07-06 | 浙江大学 | Low temperature high activity catalyst for directly synthesizing dimethyl ether and its preparation process |
| US20090023958A1 (en) * | 2004-10-15 | 2009-01-22 | Ki-Won Jun | Process for preparing dimethyl ether from crude methanol in an adiabatic reactor |
| US20100076227A1 (en) * | 2007-03-30 | 2010-03-25 | China Petroleum & Chemical Corporation | Fluidized catalytic process for production of dimethyl ether from methanol |
| WO2016187773A1 (en) * | 2015-05-25 | 2016-12-01 | 高化学株式会社 | Catalyst for preparing glycol ether and preparation method and application thereof |
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| CN113210009A (en) * | 2021-04-20 | 2021-08-06 | 中山大学 | Catalyst for synthesizing anisole from phenol-methanol and preparation method thereof |
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| WO2018233550A1 (en) | 2018-12-27 |
| EA202090101A1 (en) | 2020-10-12 |
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