CN112479832B - Method for preparing ethylene glycol monoether by taking titanium silicalite molecular sieve as catalyst - Google Patents

Method for preparing ethylene glycol monoether by taking titanium silicalite molecular sieve as catalyst Download PDF

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CN112479832B
CN112479832B CN202011386480.1A CN202011386480A CN112479832B CN 112479832 B CN112479832 B CN 112479832B CN 202011386480 A CN202011386480 A CN 202011386480A CN 112479832 B CN112479832 B CN 112479832B
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ethylene glycol
molecular sieve
titanium silicalite
catalyst
silicalite molecular
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CN112479832A (en
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王志钢
孙红影
王贤彬
王炳春
李进
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China Catalyst Holding Co ltd
Zhonghaiya Environmental Protection Material Co ltd
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China Catalyst Holding Co ltd
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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
    • 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
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/34—Reaction with organic or organometallic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst. The method takes ethylene glycol and low-carbon fatty alcohol as raw materials, takes a titanium silicalite molecular sieve as a catalyst, and carries out catalytic reaction after the titanium silicalite molecular sieve is treated by chloropropene to obtain the product ethylene glycol monoether. The preparation method provided by the invention has the advantages of simple process, renewable and reusable catalyst, high conversion rate of ethylene glycol and high selectivity of ethylene glycol monoether.

Description

Method for preparing ethylene glycol monoether by using titanium silicalite molecular sieve as catalyst
Technical Field
The invention relates to the field of catalytic reaction, in particular to a method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst.
Background
The ethylene glycol monoether series product is a universal green solvent. The structure of the dye contains ether bond, hydroxyl and different alkyl, so that the dye can dissolve organic molecules, synthetic polymers and natural macromolecules, has certain water solubility, and is widely used for industrial solvents, antifreeze solutions, surfactants, printed circuit board binders, skin care product additives and the like, wherein ethylene glycol monomethyl ether is used for dissolving acetate fibers, moistureproof cellophane, gas purification and the like, and can improve the permeability and level-dyeing property of the dye; the ethylene glycol monoethyl ether is mainly used as a solvent of grease, nitrocellulose and paint, a textile dyeing auxiliary agent, a metal and glass cleaning agent and the like; ethylene glycol monobutyl ether is widely used in water-based coatings and paint thinners.
The glycol ether can also be used for clean fuel, mainly comprising: (1) an oxygen-containing fuel: the glycol ether is taken as the oxygen-containing fuel and contained in the diesel fuel, so that the exhaust emission can be greatly improved, especially the soot particles can be greatly reduced, and the emission of PM2.5 can be reduced. (2) Pour point depressant: the condensation point of glycol ether is generally lower than-60 ℃, and the freezing point can be reduced by adding the glycol ether into fuel oil, so that the glycol ether is a good antifreezing agent for military jet fuel. (3) And (3) improving the cetane number: the cetane number of glycol dimethyl ether is as high as 98, and the cetane number can be improved by adding glycol ether into fuel oil.
Currently, typical synthetic routes for glycol ether compounds include Williamson synthesis, ethylene oxide ring opening etherification, ethylene addition, and the like. Among them, the method for industrial scale production is mainly the Williamson synthesis method, but the method produces a large amount of sodium chloride or sodium sulfate, has serious pollution and difficult post-treatment, and becomes a bottleneck of the current industrial production.
The ethylene oxide ring-opening etherification method is to synthesize glycol ether by taking ethylene oxide and low-carbon fatty alcohol as raw materials, and Chinese patent CN101190876B discloses a method for preparing glycol ether by the reaction of ethylene oxide and low-carbon fatty alcohol, wherein the conversion rate of ethylene glycol is more than 99 percent, and the selectivity of ethylene glycol riddle is more than 82 percent. The ethylene addition method is an extension of the ring-opening etherification method of ethylene oxide in essence.
Chinese patent CN100554231C uses Tween 80, aluminum isopropoxide and benzene 80 modified titanium silicalite molecular sieve to catalyze ethylene, hydrogen peroxide and n-butyl alcohol to react in one step to prepare the ethylene glycol monobutyl ether, the utilization rate of the hydrogen peroxide is about 80%, and the ethylene glycol monobutyl ether can reach 100%. The developed process routes are essentially petrochemical routes based on ethylene as an original substrate and ethylene oxide as an intermediate, and at the present day that the petroleum reserves are increasingly tense, the development of non-petroleum-based raw materials for preparing glycol ether is urgently needed to supplement the petrochemical process. At present, the technical schemes of 'glycol prepared from coal' and 'glycol prepared from cellulose' are developed successively, so that non-petroleum sources of glycol are realized. Therefore, the preparation of glycol ether by using glycol as a raw material is a new synthetic method in a non-petrochemical process.
Chinese patent CN 107042A discloses a method for synthesizing glycol ether by catalyzing low-carbon alcohol and ethylene glycol or ethylene glycol monoether with a metal oxide modified zeolite molecular sieve, but the conversion rate of ethylene glycol is low.
Chinese patent CN104250206B discloses a method for preparing glycol ether. Glycol is used as a raw material, low-carbon fatty alcohol is used as an etherification reagent and a reaction solvent, and acid is used as a catalyst, but the selectivity of monoether is low.
Chinese patent CN102452908B discloses a method for preparing ethylene glycol monoether from ethylene, in the presence of a titanium silicalite molecular sieve composite catalyst, ethylene, hydrogen peroxide and low carbon alcohol directly undergo epoxidation and ring-opening etherification one-step reaction to prepare glycol ether, and the catalyst consists of a titanium silicalite molecular sieve, an acidic molecular sieve and resin.
Disclosure of Invention
Based on the above, the invention aims to provide a method for preparing ethylene glycol monoether with high conversion rate and high selectivity.
The preparation method of the ethylene glycol monoether uses a titanium silicalite molecular sieve as a catalyst to prepare the ethylene glycol monoether, adopts ethylene glycol and low-carbon fatty alcohol as raw materials, and carries out catalytic reaction on the raw materials after the catalyst is treated by chloropropene to obtain the product of the ethylene glycol monoether, and comprises the following specific steps:
(1) Filling a titanium silicalite molecular sieve catalyst with the particle size of 20-40 meshes into the middle position of a reaction tube, controlling the temperature of a catalyst bed layer to be 30-60 ℃, and controlling the mass space velocity of chloropropene relative to the titanium silicalite molecular sieve to be 3-8h-1Treating the catalyst for 24-48 h;
(2) Purging with nitrogen, cleaning with low-carbon fatty alcohol, raising the temperature of a catalyst bed to 150-250 ℃, reacting at 2-5 MPa, feeding ethylene glycol and the low-carbon fatty alcohol together, reacting for 24 hours, and sampling for analysis.
Further, the lower fatty alcohol is any one of methanol, ethanol, n-propanol and n-butanol.
Further, the titanium silicalite molecular sieve is one or two of titanium silicalite TS-1 and titanium silicalite Ti-MWW.
The preparation method of the titanium silicalite TS-1 comprises the following steps: taking silica sol as a silicon source, tetrabutyl titanate as a titanium source and tetrapropyl ammonium bromide as a template agent, crystallizing at 150-200 ℃ for 12-48h, and filtering, washing, drying and roasting to obtain the titanium-silicon molecular sieve TS-1 raw powder. And (3) uniformly mixing the raw powder of the titanium silicalite TS-1 with sesbania powder, adding silica sol, further uniformly mixing, extruding and molding by using an extruding machine, drying the molded sample at 100 ℃ for 12 hours, and then roasting to obtain the strip-shaped titanium silicalite TS-1.
The preparation method of the titanium silicalite Ti-MWW comprises the following steps: using boric acid as a boron source, silica sol as a silicon source and piperidine as a template agent, crystallizing at 90-100 ℃ for 24-48h, filtering, washing and drying to obtain B-MWW, carrying out acid treatment and boron removal on the B-MWW, then carrying out secondary hydrothermal crystallization by using tetrabutyl titanate as a titanium source, crystallizing at 150-180 ℃ for 48-72h, filtering, washing, drying and roasting to obtain raw powder of the Ti-MWW molecular sieve, uniformly mixing the raw powder and sesbania powder, adding the silica sol, further uniformly mixing, extruding by using an extruding machine to form strips, drying the formed sample at 100 ℃ for 12h, and roasting to obtain the strip Ti-MWW molecular sieve.
Further, the crystallinity of the titanium silicalite molecular sieve is greater than 95%.
Further, the titanium dioxide content of the titanium silicalite molecular sieve is 0.1wt% -10wt%.
Furthermore, the titanium dioxide content of the titanium silicalite molecular sieve is 1wt% -5wt%.
Further, the mass space velocity of the ethylene glycol in the step (2) is 1.0-5.0h-1The mol ratio of the lower fatty alcohol to the glycol is 1-3:1.
further, in the step (2), the molar ratio of the lower fatty alcohol to the glycol is 1.5-2.0:1.
further, the catalyst is regenerated by adopting an in-situ roasting mode after being deactivated, and the roasting temperature is 450-500 ℃.
The preparation method of the ethylene glycol monoether takes ethylene glycol and low-carbon fatty alcohol as raw materials, and takes a titanium silicalite molecular sieve as a catalyst to carry out reaction, so as to obtain the ethylene glycol monoether.
The reaction formula is as follows:
Figure BDA0002809844370000031
r can be methyl, ethyl, n-propyl and n-butyl.
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst is characterized in that ethylene glycol and lower fatty alcohol are selected from any commercially available reagents, and the purity is not less than 99%; the catalyst titanium-silicon molecular sieve is selected from self-made or commercial, and the relative crystallinity of the titanium-silicon molecular sieve is more than 95 percent.
The synthetic reaction indexes of the ethylene glycol monoether are the conversion rate of the ethylene glycol (X), the selectivity of the ethylene glycol monoether (S) and the selectivity of the ethylene glycol diether (S)T) The calculation method of each reaction index is as follows:
the ethylene glycol conversion X = moles of ethylene glycol reacted/total moles of ethylene glycol 100%;
ethylene glycol monoether selectivity S = mole of ethylene glycol monoether produced by the reaction/mole of ethylene glycol reacted x 100%;
ethylene glycol diether selectivity ST= moles of ethylene glycol diether formed by reaction/moles of ethylene glycol reacted x 100%;
the XRD characterization of the catalyst was determined by X-ray diffraction analyzer (Pasnake, X' Pert3 Powder).
The preparation method provided by the invention has the advantages of simple process, high conversion rate of ethylene glycol and high selectivity of ethylene glycol monoether.
Drawings
FIG. 1 is an XRD spectrum of titanium silicalite TS-1;
FIG. 2 is an XRD spectrum of Ti-MWW molecular sieve.
Detailed Description
The invention provides a method for obtaining a product ethylene glycol monoether by catalytic reaction after chloropropene treatment by using ethylene glycol and low-carbon fatty alcohol as raw materials and a titanium silicalite molecular sieve as a catalyst, which comprises the following specific steps:
(1) Filling a titanium silicalite molecular sieve catalyst with the particle size of 20-40 meshes into the middle position of a reaction tube, controlling the temperature of a catalyst bed layer to be 30-60 ℃, and controlling the mass space velocity of chloropropene relative to the titanium silicalite molecular sieve to be 3-8h-1And treating the catalyst for 24-48 h.
(2) Purging with nitrogen, cleaning with low-carbon fatty alcohol, raising the temperature of a catalyst bed to 150-250 ℃, reacting at 2-5 MPa, feeding ethylene glycol and the low-carbon fatty alcohol together, reacting for 24 hours, and sampling for analysis.
In the embodiment of the present application, the lower fatty alcohol is any one of methanol, ethanol, n-propanol and n-butanol. The titanium-silicon molecular sieve is one or two of titanium-silicon molecular sieve TS-1 and titanium-silicon molecular sieve Ti-MWW.
The preparation method of the titanium silicalite TS-1 comprises the following steps: taking silica sol as a silicon source, tetrabutyl titanate as a titanium source and tetrapropylammonium bromide as a template agent, crystallizing at 150-200 ℃ for 12-48h, and filtering, washing, drying and roasting to obtain raw powder of the titanium-silicon molecular sieve TS-1. And (3) uniformly mixing the raw powder of the titanium silicalite TS-1 with sesbania powder, adding silica sol, further uniformly mixing, extruding and molding by using an extruding machine, drying the molded sample at 100 ℃ for 12 hours, and then roasting to obtain the strip-shaped titanium silicalite TS-1.
The preparation method of the titanium silicalite Ti-MWW comprises the following steps: using boric acid as a boron source, silica sol as a silicon source and piperidine as a template agent, crystallizing at 90-100 ℃ for 24-48h, filtering, washing and drying to obtain B-MWW, carrying out acid treatment and boron removal on the B-MWW, then carrying out secondary hydrothermal crystallization by using tetrabutyl titanate as a titanium source, crystallizing at 150-180 ℃ for 48-72h, filtering, washing, drying and roasting to obtain raw powder of the Ti-MWW molecular sieve, uniformly mixing the raw powder and sesbania powder, adding the silica sol, further uniformly mixing, extruding by using an extruding machine to form strips, drying the formed sample at 100 ℃ for 12h, and roasting to obtain the strip Ti-MWW molecular sieve.
The method for preparing ethylene glycol monoethers provided by the present invention is further illustrated below with reference to examples.
Example 1
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) 6g of titanium silicalite TS-1 catalyst (20-40 meshes) is filled in the middle of the reaction tube, the temperature of the catalyst bed is controlled to be 40 ℃, chloropropene is fed at the speed of 18g/h, and the catalyst is treated for 48h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 220 ℃, the reaction pressure is 3.5MPa, the ethylene glycol and the n-butanol are co-fed, and the mass space velocity of the ethylene glycol is 3.0h-1The mol ratio of the n-butyl alcohol to the ethylene glycol is 2:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 2
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) Filling 6g of titanium silicalite TS-1 catalyst (20-40 meshes) into the middle position of a reaction tube, controlling the temperature of a catalyst bed layer to be 50 ℃, feeding chloropropene at the speed of 36g/h, and treating the catalyst for 24h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 220 ℃, the reaction pressure is 3.5MPa, the ethylene glycol and the n-butanol are co-fed, and the mass space velocity of the ethylene glycol is 3.0h-1The mol ratio of the n-butyl alcohol to the ethylene glycol is 2:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 3
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) Filling 6g of titanium silicalite TS-1 catalyst (20-40 meshes) into the middle position of a reaction tube, controlling the temperature of a catalyst bed layer to be 50 ℃, feeding chloropropene at the speed of 36g/h, and treating the catalyst for 48h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 220 ℃, the reaction pressure is 3.5MPa, the ethylene glycol and the n-butyl alcohol are fed together, and the mass space velocity of the ethylene glycol is 3.0h-1The mol ratio of the n-butyl alcohol to the ethylene glycol is 2:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 4
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) 6g of titanium silicalite TS-1 catalyst (20-40 meshes) is filled in the middle of the reaction tube, the temperature of the catalyst bed is controlled at 50 ℃, chloropropene is fed at the speed of 36g/h, and the catalyst is treated for 24h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 180 ℃, the reaction pressure is 3.5MPa, the ethylene glycol and the n-butanol are co-fed, and the mass space velocity of the ethylene glycol is 3.0h-1The mol ratio of the n-butyl alcohol to the ethylene glycol is 2:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 5
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) 6g of titanium silicalite TS-1 catalyst (20-40 meshes) is filled in the middle of the reaction tube, the temperature of the catalyst bed is controlled at 50 ℃, chloropropene is fed at the speed of 36g/h, and the catalyst is treated for 24h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 250 ℃, the reaction pressure is 3.5MPa, the ethylene glycol and the n-butanol are co-fed, and the mass space velocity of the ethylene glycol is 3.0h-1The mol ratio of the n-butyl alcohol to the ethylene glycol is 2:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 6
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) Filling 6g of titanium silicalite TS-1 catalyst (20-40 meshes) into the middle position of a reaction tube, controlling the temperature of a catalyst bed layer to be 50 ℃, feeding chloropropene at the speed of 36g/h, and treating the catalyst for 24h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 220 ℃, the reaction pressure is 2.5MPa, the ethylene glycol and the n-butanol are co-fed, and the mass space velocity of the ethylene glycol is 3.0h-1The mol ratio of the n-butyl alcohol to the ethylene glycol is 2:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 7
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) Filling 6g of titanium silicalite TS-1 catalyst (20-40 meshes) into the middle position of a reaction tube, controlling the temperature of a catalyst bed layer to be 50 ℃, feeding chloropropene at the speed of 36g/h, and treating the catalyst for 24h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 220 ℃, the reaction pressure is 4.5MPa, the ethylene glycol and the n-butanol are co-fed, and the mass space velocity of the ethylene glycol is 3.0h-1The mol ratio of n-butyl alcohol to ethylene glycol is 2:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 8
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) 6g of titanium silicalite TS-1 catalyst (20-40 meshes) is filled in the middle of the reaction tube, the temperature of the catalyst bed is controlled at 50 ℃, chloropropene is fed at the speed of 36g/h, and the catalyst is treated for 24h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 220 ℃, the reaction pressure is 3.5MPa, the ethylene glycol and the n-butanol are co-fed, and the mass space velocity of the ethylene glycol is 1.0h-1The mol ratio of the n-butyl alcohol to the ethylene glycol is 2:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 9
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) 6g of titanium silicalite TS-1 catalyst (20-40 meshes) is filled in the middle of the reaction tube, the temperature of the catalyst bed is controlled at 50 ℃, chloropropene is fed at the speed of 36g/h, and the catalyst is treated for 24h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 220 ℃, the reaction pressure is 3.5MPa, the ethylene glycol and the n-butanol are co-fed, and the mass space velocity of the ethylene glycol is 5.0h-1The mol ratio of the n-butyl alcohol to the ethylene glycol is 2:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 10
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) Filling 6g of titanium silicalite TS-1 catalyst (20-40 meshes) into the middle position of a reaction tube, controlling the temperature of a catalyst bed layer to be 50 ℃, feeding chloropropene at the speed of 36g/h, and treating the catalyst for 24h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 220 ℃, the reaction pressure is 3.5MPa, the ethylene glycol and the n-butanol are co-fed, and the mass space velocity of the ethylene glycol is 3.0h-1The mol ratio of n-butyl alcohol to ethylene glycol is 1:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 11
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) Filling 6g of titanium silicalite TS-1 catalyst (20-40 meshes) into the middle position of a reaction tube, controlling the temperature of a catalyst bed layer to be 50 ℃, feeding chloropropene at the speed of 36g/h, and treating the catalyst for 24h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 220 ℃, the reaction pressure is 3.5MPa, the ethylene glycol and the n-butanol are co-fed, and the mass space velocity of the ethylene glycol is 3.0h-1The mol ratio of n-butyl alcohol to ethylene glycol is 3:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 12
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) 6g of titanium silicalite TS-1 catalyst (20-40 meshes) is filled in the middle of the reaction tube, the temperature of the catalyst bed is controlled at 50 ℃, chloropropene is fed at the speed of 36g/h, and the catalyst is treated for 24h.
(2) Purged with nitrogen and then purged with n-propanol. The temperature of a catalyst bed layer is raised to 210 ℃, the reaction pressure is 3.5MPa, the ethylene glycol and the n-propanol are co-fed, and the mass space velocity of the ethylene glycol is 3.0h-1The molar ratio of the n-propanol to the ethylene glycol is 2:1, the results of sampling and analysis after 24 hours of reaction time are shown in Table 1.
Example 13
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) 6g of titanium silicalite TS-1 catalyst (20-40 meshes) is filled in the middle of the reaction tube, the temperature of the catalyst bed is controlled at 50 ℃, chloropropene is fed at the speed of 36g/h, and the catalyst is treated for 24h.
(2) Purging with nitrogen and then washing with ethanol. The temperature of a catalyst bed layer is raised to 200 ℃, the reaction pressure is 3.0MPa, the ethylene glycol and the ethanol are fed together, and the mass space velocity of the ethylene glycol is 3.0h-1The molar ratio of ethanol to ethylene glycol is 1.5:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 14
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) 6g of titanium silicalite TS-1 catalyst (20-40 meshes) is filled in the middle of the reaction tube, the temperature of the catalyst bed is controlled at 50 ℃, chloropropene is fed at the speed of 36g/h, and the catalyst is treated for 24h.
(2) Purged with nitrogen and then purged with methanol. The temperature of a catalyst bed layer is raised to 180 ℃, the reaction pressure is 3.0MPa, the ethylene glycol and the methanol are co-fed, and the mass space velocity of the ethylene glycol is 4.0h-1The molar ratio of methanol to ethylene glycol is 1.5:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 15
A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst comprises the following specific steps:
(1) Filling 6g of Ti-Si molecular sieve Ti-MWW catalyst (20-40 meshes) into the middle position of a reaction tube, controlling the temperature of a catalyst bed layer to be 50 ℃, feeding chloropropene at the speed of 36g/h, and treating the catalyst for 24h.
(2) Purging with nitrogen, and washing with n-butanol. The temperature of a catalyst bed layer is raised to 220 ℃, the reaction pressure is 3.5MPa, the ethylene glycol and the n-butanol are co-fed, and the mass space velocity of the ethylene glycol is 3.0h-1N-butanolThe molar ratio of ethylene glycol to ethylene glycol is 2:1, the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Example 16
After the reaction in example 2 was carried out for 3000 hours, the conversion rate of ethylene glycol was less than 95%, and the catalyst was regenerated in situ at a calcination temperature of 550 ℃. After calcination, the same treatment was carried out, and the results of sampling analysis after 24 hours of reaction are shown in Table 1.
Table 1: results of sampling analysis
Figure BDA0002809844370000081
The above-mentioned embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (8)

1. A method for preparing ethylene glycol monoether by taking a titanium silicalite molecular sieve as a catalyst is characterized in that ethylene glycol and low-carbon fatty alcohol are taken as raw materials, the titanium silicalite molecular sieve is taken as the catalyst, and the catalyst is subjected to catalytic reaction after chloropropene treatment to obtain the product ethylene glycol monoether, and the method comprises the following specific steps:
(1) Filling a titanium silicalite molecular sieve catalyst with the particle size of 20-40 meshes into the middle position of a reaction tube, controlling the temperature of a catalyst bed layer to be 30-60 ℃, and controlling the mass space velocity of chloropropene relative to the titanium silicalite molecular sieve to be 3-8h-1Treating the catalyst for 24-48 h;
(2) Purging with nitrogen, cleaning with low-carbon fatty alcohol, raising the temperature of a catalyst bed to 150-250 ℃, reacting at 2-5 MPa, feeding ethylene glycol and the low-carbon fatty alcohol together, reacting for 24 hours, and sampling for analysis;
the titanium silicalite molecular sieve is one or two of titanium silicalite molecular sieve TS-1 and titanium silicalite molecular sieve Ti-MWW.
2. The method for preparing ethylene glycol monoether by using the titanium silicalite molecular sieve as the catalyst according to claim 1, wherein the lower fatty alcohol is any one of methanol, ethanol, n-propanol and n-butanol.
3. The method for preparing ethylene glycol monoethers by using the titanium silicalite molecular sieve as the catalyst according to claim 1, wherein the crystallinity of the titanium silicalite molecular sieve is more than 95%.
4. The method for preparing ethylene glycol monoether by using the titanium silicalite molecular sieve as the catalyst according to claim 1, wherein the titanium dioxide content of the titanium silicalite molecular sieve is 0.1wt% -10wt%.
5. The method for preparing ethylene glycol monoether by using the titanium silicalite molecular sieve as the catalyst according to claim 4, wherein the titanium dioxide content in the titanium silicalite molecular sieve is 1wt% -5wt%.
6. The method for preparing ethylene glycol monoethers by using the titanium silicalite molecular sieve as the catalyst according to claim 1, wherein the mass space velocity of the ethylene glycol in the step (2) is 1.0-5.0h-1The mol ratio of the lower fatty alcohol to the glycol is 1-3:1.
7. the method for preparing ethylene glycol monoether by using a titanium silicalite molecular sieve as a catalyst according to claim 1, wherein the molar ratio of the lower fatty alcohol to the ethylene glycol in the step (2) is 1.5-2.0:1.
8. the method for preparing ethylene glycol monoether by using the titanium silicalite molecular sieve as the catalyst according to claim 1, wherein the catalyst is regenerated by in-situ roasting after being deactivated, and the roasting temperature is 450-500 ℃.
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