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CN113304771B - Catalyst for preparing glycol ether and method for preparing glycol ether by using same - Google Patents

Catalyst for preparing glycol ether and method for preparing glycol ether by using same Download PDF

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CN113304771B
CN113304771B CN202110652591.0A CN202110652591A CN113304771B CN 113304771 B CN113304771 B CN 113304771B CN 202110652591 A CN202110652591 A CN 202110652591A CN 113304771 B CN113304771 B CN 113304771B
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molecular sieve
catalyst
carbonate
earth metal
reaction
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CN113304771A (en
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牟新东
刘晓然
李慧
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Shanghai Suntian Technology Co ltd
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Shanghai Suntian Technology Co ltd
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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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/087—X-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • 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
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • 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
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present disclosure relates to a catalyst for preparing glycol ether and a method for preparing glycol ether using the same. The catalyst is a molecular sieve containing alkali metal, alkaline earth metal and/or rare earth metal. The method comprises the following steps: 1) filling the catalyst into a fixed bed reactor, heating to a reaction temperature under nitrogen purging, and keeping a certain pressure, 2) pumping the dihydric alcohol and the carbonate raw material into a preheater respectively by using a plunger pump for preheating, then entering the reactor for reaction, and 3) enabling a reaction product to enter a collector after passing through a condenser. The method has the advantages of easily obtained raw materials, greener route, simple process, high efficiency and continuous operation.

Description

Catalyst for preparing glycol ether and method for preparing glycol ether by using same
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for preparing glycol ether, and more particularly relates to a method for continuously preparing glycol ether by using carbonate as an alkylating reagent.
Background
Monoethers and diethers of dihydric alcohols are widely used as organic solvents and organic synthetic block compounds in the fields of organic synthesis and medicine due to their unique physicochemical properties.
The current methods for synthesizing glycol ether mainly comprise the following steps: firstly, epoxy compounds and alcohol react under the catalysis of acid to obtain ether, but the selectivity of the product is generally not high. One is the Williamson synthesis, which produces large amounts of waste water by reacting alkyl halides with metal alkoxides to give the corresponding ethers. One is the catalytic dehydration of alcohols to synthesize the corresponding ethers, which can synthesize both symmetric and asymmetric ethers. For example, CN105585459 and CN105585455 describe the use of ethylene glycol and A, respectively, in a fixed bed reactor using a solid acid catalystThe etherification reaction of alcohol has the yield of ethylene glycol monoether and ethylene glycol diether of only 55 percent at 250 ℃ and 0.5 MPa. Japanese patent JP 2004196783 describes that etherification of ethylene glycol and 1, 2-propylene glycol can be achieved at 300 ℃ and 8.2MPa over a Cs-P-Si composite catalyst, with a monoether selectivity of 77% and a diether selectivity of 1% at a conversion of 53%. However, the ultra-high temperatures and pressures certainly increase costs. In addition, in the case of methylation using dimethyl sulfate as the methylating agent in the presence of a base, CN200310112773.0 discloses a process using dimethyl sulfate as the methylating agent, but dimethyl sulfate is too toxic and the process is generally carried out only intermittently. WO 2015095710 discloses a method for methylating fatty alcohol by using dimethyl carbonate as a methylating agent, wherein the selectivity of ethylene glycol monoether reacted by dimethyl carbonate and ethylene glycol is 15% under the catalysis of potassium carbonate. The method for synthesizing the fatty alcohol monoether is a batch method and has low yield. CN 107108645A describes a process for the oxyalkylation of glycols with dimethyl carbonate as methylating agent, in which methanol is used as solvent and CO is present at high pressure 2 The weak acid formed in situ by hydration is a catalyst and can realize high-selectivity oxygen methylation of dihydric alcohol. However, the relatively high reaction pressure (up to 11MPa) makes the method face equipment cost problem in industrial process, and the reaction is carried out in a reaction kettle intermittently, and continuous production is not possible. In summary, there is no report on the single-side or double-side etherification of aliphatic diols by using a continuous carbonate as an alkylating agent.
Disclosure of Invention
The invention provides a catalyst for preparing glycol ether and a method for continuously preparing glycol ether, aiming at the current situation of the prior art.
According to one aspect of the present invention, there is provided a catalyst for the preparation of glycol ethers, said catalyst being an alkali, alkaline earth and/or rare earth metal modified molecular sieve, wherein said catalyst is prepared by a process comprising the steps of:
1) soaking the molecular sieve into 0.5-2mol/L aqueous solution of alkali metal and/or alkaline earth metal compounds, refluxing and stirring at 110-120 ℃ for 5-12h, standing overnight, filtering, washing, vacuum drying at 80-95 ℃ for 10-15h, such as 12h, roasting at 500-550 ℃ for 6-8h to obtain the alkali metal and/or alkaline earth metal ion exchange molecular sieve;
2) soaking the molecular sieve in 1-4 wt% concentration RE compound water solution, reflux stirring at 110-120 deg.c for 10-15 hr, standing overnight, heating to distill most of the liquid, cooling, freezing with liquid nitrogen, drying in a vacuum drier for 12-20 hr, grinding into powder, and roasting at 550 deg.c for 6-8 hr to obtain the RE modified catalyst.
The molecular sieve is one or more selected from Y-type molecular sieve, X-type molecular sieve, beta-type molecular sieve and A-type molecular sieve.
The alkali metal compound can be one or more selected from hydroxide, carbonate or acetate of Na, K and Cs; and the alkaline earth metal compound may be one or more selected from acetates of Mg, Ca, Ba.
The doping amount of the alkali metal and/or the alkaline earth metal can be 1 to 30wt percent of the mass of the molecular sieve.
The rare earth metal compound may be one or more selected from halide salts, nitrate salts, and acetate salts of yttrium (Y), neodymium (Nd), cerium (Ce), and lanthanum (La).
The doping amount of the rare earth metal can be 1-10 wt% of the mass of the molecular sieve.
According to another aspect of the present invention, there is provided a method for preparing a glycol ether, the method comprising the steps of:
1) filling the catalyst into a fixed bed reactor, heating to reaction temperature under nitrogen purging, maintaining a certain pressure,
2) respectively pumping the raw materials of the dihydric alcohol and the carbonic ester into a preheater by using a plunger pump for preheating, then entering the reactor for reaction,
3) the reaction product enters a collector after passing through a condenser.
The reaction conditions in the step 1) include: the reaction temperature is 90-600 deg.C, such as 100 deg.C, 200 deg.C, 250 deg.C, 300 deg.C, 350 deg.C, 400 deg.C, etc., and the reaction pressure is 0.1-8MPa, such as 0.2, 0.3, 0.4, 0.5, 0.6, 1,2, 3MPa, etc.
The dihydric alcohol in the step 2) comprises ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 2-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol.
The carbonic ester in the step 2) comprises dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate and dibutyl carbonate.
The step 2) can be carried out in a solvent or without a solvent. If a solvent is used, the solvent is mixed with a dihydric alcohol and is pumped into the reactor by a plunger pump after being dissolved, wherein the solvent is one or more selected from methanol, ethanol, propanol, isopropanol, butanol and water, and the volume ratio of the dihydric alcohol to the solvent is 1:100-1: 1.
The molar ratio of the starting diol to the carbonate described in step 2) above may be in the range of from 1:0.5 to 1:20, for example in the range of from 1:1 to 1:5, or in the range of from 1:1.5 to 1: 4.5.
The space velocity of the feed pumped into the reactor in the step 2) is 0.01 to 8h -1 。
The temperature of the preheater in the step 2) can be 100-400 ℃, for example, 150-250 ℃.
Advantageous effects
The method for preparing the glycol ether provided by the invention has the advantages of simple process, easily available raw materials, high efficiency and greener route.
Detailed Description
In one embodiment, the catalyst for the preparation of glycol ethers of the present invention is prepared by a process comprising the steps of:
1) soaking 10g of molecular sieve into 50ml of aqueous solution of alkali metal or alkaline earth metal compound with the concentration of 1mol/L, refluxing and stirring at 120 ℃ for 10h, standing overnight, filtering, washing, vacuum drying at 80 ℃ for 12h, and roasting at 500 ℃ for 6h to obtain the molecular sieve exchanged with alkali metal or alkaline earth metal ions;
2) soaking the molecular sieve in 50ml of 1 wt% rare earth metal compound solution, refluxing and stirring at 120 ℃ for 10h, standing overnight, heating and distilling most of liquid, cooling, freezing and molding by using liquid nitrogen, drying in a vacuum drier for 12h, taking out, grinding into powder, and roasting at 500 ℃ for 6h to obtain the rare earth modified catalyst.
The molecular sieve can be one or more selected from Y-type molecular sieve, X-type molecular sieve, beta-type molecular sieve and A-type molecular sieve.
The alkali metal compound can be one or more selected from hydroxide, carbonate or acetate of Na, K and Cs; and the alkaline earth metal compound may be one or more selected from acetates of Mg, Ca, Ba.
The rare earth metal compound is one or more of halide, nitrate and acetate of yttrium (Y), neodymium (Nd), cerium (Ce) and lanthanum (La). For example, the catalyst modified by rare earth is La-NaY molecular sieve, La-KX molecular sieve or Nd-KX molecular sieve.
The dosage of the rare earth metal compound is 1-10% of the mass of the molecular sieve.
According to one embodiment of the present invention, the method for preparing glycol ether comprises the steps of:
1) filling the catalyst modified by the rare earth, such as La-NaY molecular sieve, La-KX molecular sieve or Nd-KX molecular sieve catalyst, into a fixed bed reactor, raising the temperature to the reaction temperature under nitrogen purging, and keeping a certain pressure;
2) the dihydric alcohol and the carbonic ester are respectively pumped into a preheater through a plunger pump for preheating and then enter a reactor;
3) and (3) collecting and separating the reaction product in the step 2) after passing through a condenser and a gas-liquid separator.
In the method for preparing the glycol ether, glycol and carbonate are used as raw materials, and the glycol ether is obtained through etherification reaction.
The reaction conditions in the step 1) include: the reaction temperature is 90 to 600 ℃, for example, 100 ℃, 200 ℃, 220 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃ and the like, and the reaction pressure is 0.1 to 8MPa, for example, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 1MPa, 2MPa, 3MPa and the like.
The dihydric alcohol in the step 2) comprises ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 2-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol.
The carbonic ester in the step 2) comprises dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate and dibutyl carbonate.
The step 2) can be carried out in a solvent or without a solvent. If a solvent is used, the solvent is mixed with a dihydric alcohol and is pumped into the reactor by a plunger pump after being dissolved, wherein the solvent is one or more selected from methanol, ethanol, propanol, isopropanol, butanol and water, and the volume ratio of the dihydric alcohol to the solvent is 1:100-1: 1.
The molar ratio of the starting diol to the carbonate described in step 2) above may be in the range of from 1:0.5 to 1:20, for example in the range of from 1:1 to 1:5, or in the range of from 1:1.5 to 1: 4.5.
The space velocity of the feed pumped into the reactor in the step 2) is 0.01 to 8h -1 。
The temperature of the preheater in the step 2) can be 100 ℃ to 400 ℃, for example, 150 ℃ to 250 DEG C
The product obtained after separation in step 3) was passed through a 0.22 μm filter and analyzed by Gas Chromatography (GC). And (3) qualitatively analyzing the low-boiling-point products by gas chromatography-mass spectrometry (GC-MS) and standard substance GC retention time contrast, and determining that the reaction products are mainly glycol ethers. The product was quantified by Shimazu-GC 2010plus gas chromatography and analyzed quantitatively by comparison with standard retention time and peak area size. The yield of the liquid product was calculated as (molar amount of the target product)/(molar amount of glycol) × 100%, and the associated calculation formula was as follows:
conversion (%) of glycol (n) Post-reaction dihydric alcohol /(n Glycol before reaction -n Post-reaction dihydric alcohol ))×100％
Yield (%) of glycol ether ═ n Glycol ethers /n Diol before reaction )×100％
Glycol ether selectivity (%). glycol ether yield/conversion of glycol × 100%
Wherein n is Glycol ethers Is the molar amount of glycol ether, n Glycol before reaction Is the molar amount of diol before reaction, n Post-reaction dihydric alcohol Is the molar amount of diol after the reaction.
Examples
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention.
Except for special description, the raw materials used in the invention are all purchased from the company Tianjin Ministry catalysis (such as 13X type molecular sieve and NKF-8 type Y molecular sieve), and the raw materials of the invention are sodium hydroxide, lanthanum nitrate, potassium hydroxide, neodymium nitrate, 1, 3-propylene glycol, 1, 4-butanediol, dimethyl carbonate and diethyl carbonate are purchased from the company chemical reagents of national medicine group.
Gas Chromatography (GC) detection conditions: the instrument comprises the following steps: shimadzu GC2010Plus, column: Intercap-FFAP, 30m × 0.25mm × 0.25um, vaporization chamber temperature 250 ℃, FID temperature 300 ℃, column oven temperature program: keeping at 60 deg.C for 1min, and heating to 230 deg.C at 15 deg.C/min for 10 min.
Except where specifically stated, all methods and apparatus used are conventional in the art.
Preparation of the catalyst
Preparation example 1: preparation of La-NaY molecular sieve catalyst
1) Soaking a 10g Y type molecular sieve into 50ml of aqueous solution of sodium hydroxide with the concentration of 1mol/L, refluxing and stirring at 120 ℃ for 10h, standing overnight, filtering, washing, vacuum drying at 80 ℃ for 12h, and roasting at 500 ℃ for 6h to obtain a NaY molecular sieve;
2) placing the NaY molecular sieve in the step 1) in 50ml of lanthanum nitrate (La (NO) with the concentration of 1 wt% 3 ) 3 ·6H 2 O) soaking in water solution, refluxing at 120 deg.C, stirring for 10 hr, standing overnight, heating to distill most of the liquid, cooling, freezing with liquid nitrogen, molding, and standingDrying in a vacuum drier for 12h, taking out and grinding into powder. Roasting at 500 deg.c for 6 hr to obtain La-NaY molecular sieve catalyst.
Preparation example 2: preparation of La-KX molecular sieve catalyst
The La-KX molecular sieve catalyst was prepared in the same manner as the preparation of the La-NaY molecular sieve catalyst in preparation example 1, except that the Y-type molecular sieve was replaced with the X-type molecular sieve and the sodium hydroxide solution was replaced with the potassium hydroxide solution.
Preparation example 3: preparation of Nd-KX molecular sieve catalyst
Except that the lanthanum nitrate solution was replaced with neodymium nitrate (Nd (NO) 3 ) 3 ·6H 2 O), an Nd-KX molecular sieve catalyst was prepared in the same manner as the preparation of the La-KX molecular sieve catalyst in preparation example 2.
Preparation example 4: LaY preparation of molecular sieve catalyst
Placing 10g Y type molecular sieve in 50ml lanthanum nitrate (La (NO) with concentration of 1 wt% 3 ) 3 ·6H 2 O) soaking in water solution, refluxing at 120 deg.C, stirring for 10 hr, standing overnight, heating to distill most of the liquid, cooling, freezing with liquid nitrogen, drying in vacuum drier for 12 hr, taking out, and grinding into powder. The LaY molecular sieve catalyst is obtained after roasting for 6 hours at 500 ℃.
Example 1
1) 2g of the NaY molecular sieve prepared in step 1) of preparation example 1 were charged into a fixed bed reactor, and the temperature was raised to 250 ℃ under nitrogen purge and the pressure was maintained at 0.5 MPa.
2) Respectively pumping a 1, 3-propylene glycol raw material and dimethyl carbonate into a preheater (preheating temperature is 220 ℃) by using a plunger pump for preheating, and then feeding the preheated 1, 3-propylene glycol raw material and dimethyl carbonate into a reactor, wherein the molar ratio of the 1, 3-propylene glycol to the dimethyl carbonate is 1:4, and the feeding airspeed is 0.1h -1 。
3) GC detection results of the reaction products show that the conversion rate of 1, 3-propylene glycol is 43%, the selectivity of 3-methoxy-1-propanol in the products is 37%, the selectivity of 1, 3-dimethoxypropane is 11%, the selectivity of 3-hydroxypropyl methyl carbonate is 50%, and the selectivity of dipropylene glycol is 3%.
Example 2
1) 2g of the La-NaY molecular sieve prepared in preparation example 1 was charged into a fixed bed reactor, and heated to 250 ℃ under nitrogen purge while maintaining a pressure of 0.5 MPa.
2) Pumping the 1, 3-propylene glycol raw material and dimethyl carbonate into a preheater respectively by using a plunger pump for preheating (the preheating temperature is 220 ℃), then feeding the preheated raw material and the dimethyl carbonate into a reactor, wherein the molar ratio of the 1, 3-propylene glycol to the dimethyl carbonate is 1:4, and the feeding airspeed is 0.1h -1 。
3) The reaction product enters a collector after passing through a condenser, and GC detection results show that the conversion rate of 1, 3-propylene glycol is 85%, the selectivity of 3-methoxy-1-propanol in the product is 61%, the selectivity of 1, 3-dimethoxypropane is 21%, the selectivity of 3-hydroxypropyl methyl carbonate is 10% and the selectivity of dipropylene glycol is 2%.
Example 3
1) 2g of the La-KX molecular sieve prepared in preparation example 2 was charged into a fixed bed reactor, and heated to 250 ℃ under nitrogen purge while maintaining a pressure of 0.5 MPa.
2) Pumping the 1, 3-propylene glycol raw material and dimethyl carbonate into a preheater respectively by using a plunger pump for preheating (the preheating temperature is 220 ℃), then feeding the preheated raw material and the dimethyl carbonate into a reactor, wherein the molar ratio of the 1, 3-propylene glycol to the dimethyl carbonate is 1:2, and the feeding airspeed is 0.1h -1 。
3) The reaction product enters a collector after passing through a condenser, and GC detection results show that the conversion rate of 1, 3-propylene glycol is 81%, the selectivity of 3-methoxy-1-propanol in the product is 65%, the selectivity of 1, 3-dimethoxypropane is 15%, the selectivity of 3-hydroxypropyl methyl carbonate is 13% and the selectivity of dipropylene glycol is 2%.
Example 4
1) 2g of the KX molecular sieve prepared in step 1) of preparation example 2 were charged into a fixed-bed reactor, and the temperature was raised to 250 ℃ under nitrogen purge and the pressure was maintained at 0.5 MPa.
2) Respectively pumping the 1, 4-butanediol raw material and diethyl carbonate into a preheater by using a plunger pump for preheating (the preheating temperature is 220 ℃), then feeding the preheated raw material and diethyl carbonate into a reactor, wherein the molar ratio of the 1, 4-butanediol to the diethyl carbonate is 1:2, and the feeding airspeed is 0.1h -1 。
3) The reaction product enters a collector after passing through a condenser, and GC detection results show that the conversion rate of 1, 4-butanediol is 33%, the selectivity of 4-ethoxy-1-butanol in the product is 31%, the selectivity of 1, 4-diethoxybutane is 9%, the selectivity of 3-hydroxybutyl ethyl carbonate is 49%, and the selectivity of dibutylene glycol is 7%.
Example 5
2) 2g of the Nd-KX molecular sieve prepared in preparation example 3 was charged into a fixed bed reactor, and the temperature was raised to 250 ℃ under nitrogen purge and the pressure was maintained at 0.5 MPa.
2) Respectively pumping the 1, 4-butanediol raw material and diethyl carbonate into a preheater by using a plunger pump for preheating (the preheating temperature is 220 ℃), then feeding the preheated raw material and diethyl carbonate into a reactor, wherein the molar ratio of the 1, 4-butanediol to the diethyl carbonate is 1:2, and the feeding airspeed is 0.1h -1 。
3) The reaction product enters a collector after passing through a condenser, and GC detection results show that the conversion rate of 1, 4-butanediol is 73%, the selectivity of 4-ethoxy-1-butanol in the product is 61%, the selectivity of 1, 4-diethoxybutane is 12%, the selectivity of 3-hydroxybutyl ethyl carbonate is 9%, and the selectivity of dibutylene glycol is 7%.
Example 6
1) 2g of the LaY molecular sieve from preparation 4 were charged into a fixed bed reactor, and the temperature was raised to 250 ℃ under a nitrogen purge while maintaining a pressure of 0.5 MPa.
2) Respectively pumping the 1, 3-propylene glycol raw material and dimethyl carbonate into a preheater (preheating temperature of 220 ℃) by using a plunger pump for preheating, and then feeding the preheated raw material and the dimethyl carbonate into a reactor, wherein the molar ratio of the 1, 3-propylene glycol to the dimethyl carbonate is 1:4, and the feeding airspeed is 0.1h -1 。
3) GC detection results of the reaction products show that the conversion rate of the 1, 3-propylene glycol is only 2.1 percent, and no target product, namely 3-methoxy-1-propanol, is generated.
The method for preparing the alcohol ether has simple process and can realize continuous reaction, and the rare earth metal is doped to obviously improve the conversion rate of the dihydric alcohol and the selectivity of the glycol ether in the product.

Claims (10)

1. A method of making a glycol ether, wherein the method comprises the steps of:
1) filling the catalyst into a fixed bed reactor, heating to reaction temperature under nitrogen purging, maintaining a certain pressure,
wherein the catalyst is a molecular sieve containing alkali metals, alkaline earth metals and/or rare earth metals, wherein the catalyst is prepared by a method comprising the steps of:
a) immersing molecular sieve in 0.5-2mol/L aqueous solution of alkali metal and/or alkaline earth metal compound at 110-120- o Stirring under reflux for 5-12 hr, standing overnight, filtering, washing at 80-95 deg.C o C after vacuum drying for 10-15h, at 500-550- o Roasting for 6-8h under C to obtain the molecular sieve exchanged by alkali metal and/or alkaline earth metal ions;
b) the molecular sieve obtained in the step a) is put into a rare earth metal compound solution with the concentration of 1-4wt percent for dipping in 110- o C, refluxing and stirring for 10-15h, standing overnight, heating and distilling most of liquid, cooling, freezing with liquid nitrogen, drying in a vacuum drier for 12-20h, grinding, and purifying with 500-550- o Roasting for 6-8h under C to obtain a rare earth modified catalyst;
2) respectively pumping the dihydric alcohol and the carbonic ester raw material into a preheater by using a plunger pump for preheating, then entering the reactor for reaction,
3) the reaction product enters a collector after passing through a condenser.
2. The method of claim 1, wherein the reaction conditions in step 1) comprise: the reaction temperature is 90-600% o C, the reaction pressure is 0.1-8 MPa.
3. The method of claim 1, wherein,
the dihydric alcohol in the step 2) comprises ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 2-pentanediol, 1, 6-hexanediol and 1, 7-heptanediol; and/or
The carbonic ester in the step 2) comprises dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate and dibutyl carbonate.
4. The method of any one of claims 1 to 3,
the molar ratio of the raw material dihydric alcohol to the carbonate in the step 2) is in the range of 1:0.5-1: 20; and/or
The space velocity of the feeding of the raw materials pumped into the reactor in the step 2) is 0.01 to 8h -1 。
5. The method as claimed in any one of claims 1 to 3, wherein the preheater temperature in step 2) is 100- o C。
6. The method of claim 1, wherein the molecular sieve is one or more selected from the group consisting of a Y-type molecular sieve, an X-type molecular sieve, a β -type molecular sieve, and an a-type molecular sieve.
7. The method according to claim 1, wherein the alkali metal compound is one or more selected from a hydroxide, a carbonate or an acetate of Na, K, Cs; and the alkaline earth metal compound is one or more of acetates of Mg, Ca and Ba.
8. The method of claim 1, wherein the alkali and/or alkaline earth metal doping is in the range of 1-30 wt% of the mass of the molecular sieve.
9. The method of claim 1, wherein the rare earth metal compound is one or more selected from the group consisting of halide salts, nitrate salts, and acetate salts of yttrium, neodymium, cerium, and lanthanum.
10. The process of claim 9 wherein the rare earth metal compound is present in an amount of 1 to 10 wt% based on the mass of the molecular sieve.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120259132A1 (en) * 2011-04-06 2012-10-11 Universiteit Leiden Process to prepare an ethanol-derivate
US20170334818A1 (en) * 2014-12-22 2017-11-23 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method for preparing double-sealed-end glycol ether

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CN1034276C (en) * 1991-11-20 1997-03-19 中国石化金陵石化公司烷基苯厂 Solid acid catalyst for olefine hydrocarbons and phenyl alkylate
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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120259132A1 (en) * 2011-04-06 2012-10-11 Universiteit Leiden Process to prepare an ethanol-derivate
US20170334818A1 (en) * 2014-12-22 2017-11-23 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Method for preparing double-sealed-end glycol ether

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