A process for the preparation of tetraethylene glycol ether

Abstract

The present application relates to the field of aromatic hydrocarbon extraction solvent, and particularly to a preparation method of tetraethylene glycol ether; the present application adopts anion polymerization reaction, and utilizes diethylene glycol and ethylene oxide to synthesize tetraethylene glycol ether; a great breakthrough is made in the refining process, so that the product purity and color reach the level of foreign similar products; the prepared tetraethylene glycol ether has the characteristics of high treatment capacity, high selectivity, high thermal stability, low corrosion, low toxicity, high density and the like, and its small specific heat is more conducive to energy saving and consumption reduction; the present application has low investment, a relatively simple reaction process and low requirement on equipment conditions; the prepared tetraethylene glycol ether solvent has the same extraction effect as the imported solvent.

Description

Technical Field

[0001] This invention relates to the field of aromatic hydrocarbon extraction solvents, and in particular to a method for preparing tetraethylene glycol ether. Background Technology

[0002] With the rapid development of my country's chemical industry, the demand for essential basic chemical raw materials such as benzene, toluene, and xylene (BTX) is increasing. These three components mainly originate from the aromatics extraction of reformate from oil refineries. According to surveys, solvents used for aromatics extraction abroad generally include: sulfolane, N-methylpyrrolidone, dimethyl sulfoxide, N-formylmorpholine, triethylene glycol ether, and tetraethylene glycol ether. Tetraethylene glycol ether was already widely used as an aromatics extraction solvent abroad in the 1960s. The Fushun Petrochemical Company's No. 2 Oil Refinery in my country was the first to switch from triethylene glycol ether to imported tetraethylene glycol ether for aromatics extraction, resulting in significant economic benefits.

[0003] CN03134153.5: Belonging to the field of surfactants, this paper specifically relates to a mixed-type ether-alcohol surfactant and its preparation method; characterized in that it contains: an ether compound; wherein the ether compound molecule has one or more —CH2CH2O— structural units. The ether compound is ethylene glycol ether, diethylene glycol ether, or triethylene glycol ether. The preparation process of the above-mentioned mixed-type ether-alcohol surfactant is characterized by: using industrial by-products containing ether-alcohol compounds as raw materials, and obtaining the finished product after filtration separation, extraction separation, and distillation column separation; during the distillation column separation process, the temperature at the top of the column is controlled between 140℃ and 260℃.

[0004] CN201780048779.6: A method for preparing ethylene glycol ethers by means of the following steps: providing a mixture of diethylene glycol ether column bottoms comprising triethylene glycol ether, tetraethylene glycol ether and an ethylene glycol ether catalyst; separating the column bottoms mixture into a triethylene glycol ether vapor top distillate and a liquid substrate in a stripping column; and separating the liquid substrate into a residue containing about 80% to about 90% tetraethylene glycol ether and an evaporator top distillate containing at least about 60% tetraethylene glycol ether in an evaporator.

[0005] CN201710853976.7: This invention relates to the field of aromatic hydrocarbon extraction and discloses a method for purifying aromatic hydrocarbon extraction solvents. The method includes: (1) mixing an extraction solvent containing impurities, water, and an absorbent to obtain a mixture, and then performing a first separation on the mixture to obtain stream a and stream b. Stream a contains the absorbent, impurities, and a small amount of extraction solvent and water, while stream b contains water and the extraction solvent; (2) performing a second separation on stream a to obtain stream c and stream d. Stream c contains the absorbent and impurities, while stream d contains the extraction solvent and water. The absorbent is selected from at least one of C5-C8 hydrocarbons. The purification method provided by this invention can not only effectively remove impurities from aromatic hydrocarbon extraction solvents and achieve purification of aromatic hydrocarbon extraction solvents, but also has low energy consumption.

[0006] However, the aforementioned patents and existing technologies generally suffer from technical problems such as high investment, complex reaction processes, stringent requirements for equipment, and relatively low product yields. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a method for preparing tetraethylene glycol ether. The tetraethylene glycol ether prepared by this invention has the characteristics of high processing capacity, high selectivity, high thermal stability, low corrosion, low toxicity, and high density. At the same time, its low specific heat is more conducive to energy saving and consumption reduction.

[0008] The following solutions are provided:

[0009] A method for preparing a tetraethylene glycol ether, comprising the following steps:

[0010] S1: Weigh a certain proportion of diethylene glycol and ethylene oxide, and 0.2-0.6 parts of organometallic supported catalyst by weight, and react them in a reactor.

[0011] S2: After the reaction is complete, add 20-40 parts of azeotropic agent and evaporate the water generated in the reaction via azeotropic distillation to obtain crude tetraethylene glycol ether;

[0012] S3: Crude tetraethylene glycol ether is purified by passing it through a light component removal tower, a purification tower, and a decolorization tower to obtain high-purity tetraethylene glycol ether.

[0013] Furthermore, in the above-mentioned method for preparing tetraethylene glycol ether, the azeotropic agent is xylene.

[0014] Furthermore, in the above-mentioned method for preparing tetraethylene glycol ether, the ratio of diethylene glycol to ethylene oxide is 1:1-2.

[0015] Furthermore, in the above-mentioned method for preparing tetraethylene glycol ether, the reaction pressure is 0.2-0.9 MPa.

[0016] Furthermore, in the above-mentioned method for preparing tetraethylene glycol ether, the reaction temperature is 85-100℃ and the time is 1-3h.

[0017] Furthermore, in the above-mentioned method for preparing tetraethylene glycol ether, atomized n-dodecane, n-tridecane, or n-tetradecane is added to the decolorization tower.

[0018] Furthermore, in the above-mentioned method for preparing tetraethylene glycol ether, the method for preparing the organometallic supported catalyst is as follows:

[0019] S1: Place montmorillonite in an oven and dry it at 180-200℃ for 20-24 hours to remove organic impurities;

[0020] S2: Weigh 100-300 parts of dried montmorillonite, put it into 1000-1500 parts of aqueous solution, add 5-8 parts of acrylic silane, stir at room temperature for 20-100 minutes, filter under pressure, and dry to obtain acrylic montmorillonite.

[0021] S3: Weigh 3-7 parts of metal chloride salt and 10-16 parts of 2-aminoterephthalic acid, dissolve them in 500-1000 parts of N,N-dimethylformamide, and sonicate at room temperature to mix the reactants evenly; heat to the reaction temperature and react for 2-5 hours, then add 100-300 parts of acrylate-based montmorillonite and 0.05-0.5 parts of cerium methacrylate, react for 10-20 hours, and cool to room temperature; filter, wash with water until pH is neutral, and dry to obtain the organometallic supported catalyst.

[0022] Furthermore, in the above-mentioned method for preparing organometallic supported catalysts, the metal chloride salt is ZnCl2, FeCl3, or AlCl3.

[0023] Furthermore, in the above-mentioned method for preparing organometallic supported catalysts, the acrylate silane is γ-(methacryloyloxy)propyltrimethoxysilane or 3-methacryloyloxypropylmethyldiethoxysilane.

[0024] Furthermore, in the above-mentioned method for preparing organometallic supported catalysts, the reaction temperature in S3 is 80-100℃.

[0025] Reaction mechanism:

[0026] Metal chloride salts react with 2-aminoterephthalic acid to form organometallic compounds, which then undergo amino addition reactions with acrylate-based montmorillonite and cerium methacrylate. This process produces an organic-inorganic hybrid material with an intramolecular porous structure, formed by the self-assembly of organic ligands and metal ions or clusters through coordination bonds, thus yielding organometallic supported catalysts.

[0027] Technical effects:

[0028] The present invention provides a method for preparing tetraethylene glycol ether, which, compared with the prior art, has the following significant advantages:

[0029] 1. The tetraethylene glycol ether prepared by this invention has the characteristics of high processing capacity, high selectivity, high thermal stability, low corrosion, low toxicity, and high density. At the same time, its low specific heat is more conducive to energy saving and consumption reduction.

[0030] 2. This invention requires low investment, has a relatively simple reaction process, low equipment requirements, and the product purity and color reach the level of similar foreign products.

[0031] 3. The organometallic supported catalyst prepared by this invention has the characteristics of improved stability, easy recovery, and reusability. Detailed Implementation

[0032] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0033] Example 1

[0034] A method for preparing a tetraethylene glycol ether, comprising the following steps:

[0035] S1: Weigh a certain proportion of diethylene glycol and ethylene oxide, and 0.2g of organometallic supported catalyst into a reaction vessel and carry out the reaction.

[0036] S2: After the reaction is complete, add 20g of azeotropic agent and evaporate the water generated in the reaction to obtain crude tetraethylene glycol ether.

[0037] S3: Crude tetraethylene glycol ether is purified by passing it through a light component removal tower, a purification tower, and a decolorization tower to obtain high-purity tetraethylene glycol ether.

[0038] The azeotropic agent is xylene.

[0039] The ratio of diethylene glycol to ethylene oxide is 1:1.

[0040] The reaction pressure is 0.2 MPa.

[0041] The reaction temperature was 85℃ and the reaction time was 1 hour.

[0042] Atomized n-dodecane is added to the decolorization tower.

[0043] The method for preparing the organometal supported catalyst is as follows:

[0044] S1: Place montmorillonite in an oven and dry it at 180℃ for 20 hours to remove organic impurities;

[0045] S2: Weigh 100g of dried montmorillonite, put it into 1000g of aqueous solution, add 5g of acrylic silane, stir at room temperature for 20min, filter under pressure, and dry to obtain acrylic montmorillonite.

[0046] S3: Weigh 3g of metal chloride salt and 10g of 2-aminoterephthalic acid, dissolve them in 500g of N,N-dimethylformamide, and sonicate at room temperature to mix the reactants evenly; the reaction temperature is 80℃ and the reaction time is 2h. Then add 100g of acrylate-based montmorillonite and 0.05g of cerium methacrylate, and the reaction time is 10h. Cool to room temperature; filter, wash with water until pH is neutral, and dry to obtain the organometallic supported catalyst.

[0047] The metal chloride salt mentioned is ZnCl2.

[0048] The acrylate silane is γ-(methacryloyloxy)propyltrimethoxysilane.

[0049] Example 2

[0050] A method for preparing a tetraethylene glycol ether, comprising the following steps:

[0051] S1: Weigh a certain proportion of diethylene glycol and ethylene oxide, and 0.3g of organometallic supported catalyst, and react them in a reactor;

[0052] S2: After the reaction is complete, add 25g of azeotropic agent and evaporate the water generated in the reaction via azeotropic distillation to obtain crude tetraethylene glycol ether;

[0053] S3: Crude tetraethylene glycol ether is purified by passing it through a light component removal tower, a purification tower, and a decolorization tower to obtain high-purity tetraethylene glycol ether.

[0054] The azeotropic agent is xylene.

[0055] The ratio of diethylene glycol to ethylene oxide is 1:1.

[0056] The reaction pressure is 0.5 MPa.

[0057] The reaction temperature was 90℃ and the reaction time was 2 hours.

[0058] Atomized n-tetane is added to the decolorization tower.

[0059] The method for preparing the organometal supported catalyst is as follows:

[0060] S1: Place montmorillonite in an oven and dry it at 185℃ for 21 hours to remove organic impurities;

[0061] S2: Weigh 150g of dried montmorillonite, put it into 1100g of aqueous solution, add 6g of acrylic silane, stir at room temperature for 50min, filter under pressure, and dry to obtain acrylic montmorillonite;

[0062] S3: Weigh 4g of metal chloride salt and 12g of 2-aminoterephthalic acid, dissolve them in 600g of N,N-dimethylformamide, and sonicate at room temperature to mix the reactants uniformly; the reaction temperature is 85℃ and the reaction time is 3h. Then add 150g of acrylic montmorillonite and 0.2g of cerium methacrylate, and the reaction time is 14h. Cool to room temperature; filter, wash with water until pH is neutral, and dry to obtain organometallic supported catalyst.

[0063] The metal chloride salt mentioned is FeCl3.

[0064] The acrylate silane is γ-(methacryloyloxy)propyltrimethoxysilane.

[0065] Example 3

[0066] A method for preparing a tetraethylene glycol ether, comprising the following steps:

[0067] S1: Weigh a certain proportion of diethylene glycol and ethylene oxide, and 0.5g of organometallic supported catalyst, and react them in a reactor;

[0068] S2: After the reaction is complete, add 35g of azeotropic agent and evaporate the water generated in the reaction to obtain crude tetraethylene glycol ether.

[0069] S3: Crude tetraethylene glycol ether is purified by passing it through a light component removal tower, a purification tower, and a decolorization tower to obtain high-purity tetraethylene glycol ether.

[0070] The azeotropic agent is xylene.

[0071] The ratio of diethylene glycol to ethylene oxide is 1:2.

[0072] The reaction pressure is 0.8 MPa.

[0073] The reaction temperature was 95℃ and the reaction time was 2 hours.

[0074] Atomized n-tetane is added to the decolorization tower.

[0075] The method for preparing the organometal supported catalyst is as follows:

[0076] S1: Place montmorillonite in an oven and dry it at 195℃ for 23 hours to remove organic impurities;

[0077] S2: Weigh 250g of dried montmorillonite, put it into 1400g of aqueous solution, add 7g of acrylic silane, stir at room temperature for 80min, filter under pressure, and dry to obtain acrylic montmorillonite;

[0078] S3: Weigh 6g of metal chloride salt and 14g of 2-aminoterephthalic acid, dissolve them in 900g of N,N-dimethylformamide, and sonicate at room temperature to mix the reactants uniformly; the reaction temperature is 95℃ and the reaction time is 4h. Then add 250g of acrylic montmorillonite and 0.4g of cerium methacrylate, and the reaction time is 18h. Cool to room temperature; filter, wash with water until pH is neutral, and dry to obtain the organometallic supported catalyst.

[0079] The metal chloride salt mentioned is AlCl3.

[0080] The acrylate silane is 3-methacryloyloxypropylmethyldiethoxysilane.

[0081] Example 4

[0082] A method for preparing a tetraethylene glycol ether, comprising the following steps:

[0083] S1: Weigh a certain proportion of diethylene glycol and ethylene oxide, and 0.6g of organometallic supported catalyst, and react them in a reactor;

[0084] S2: After the reaction is complete, add 40g of azeotropic agent and evaporate the water generated in the reaction to obtain crude tetraethylene glycol ether.

[0085] S3: Crude tetraethylene glycol ether is purified by passing it through a light component removal tower, a purification tower, and a decolorization tower to obtain high-purity tetraethylene glycol ether.

[0086] The azeotropic agent is xylene.

[0087] The ratio of diethylene glycol to ethylene oxide is 1:2.

[0088] The reaction pressure is 0.9 MPa.

[0089] The reaction temperature was 100℃ and the reaction time was 3 hours.

[0090] Atomized n-tetradecane is added to the decolorization tower.

[0091] The method for preparing the organometal supported catalyst is as follows:

[0092] S1: Place montmorillonite in an oven and dry it at 200℃ for 24 hours to remove organic impurities;

[0093] S2: Weigh 300g of dried montmorillonite, put it into 1500g of aqueous solution, add 8g of acrylic silane, stir at room temperature for 100min, filter under pressure, and dry to obtain acrylic montmorillonite;

[0094] S3: Weigh 7g of metal chloride salt and 16g of 2-aminoterephthalic acid, dissolve them in 1000g of N,N-dimethylformamide, and sonicate at room temperature to mix the reactants evenly; the reaction temperature is 100℃ and the reaction time is 5h. Then add 300g of acrylic montmorillonite and 0.5g of cerium methacrylate, and the reaction time is 20h. Cool to room temperature; filter, wash with water until pH is neutral, and dry to obtain organometallic supported catalyst.

[0095] The metal chloride salt mentioned is AlCl3.

[0096] The acrylate silane is 3-methacryloyloxypropylmethyldiethoxysilane.

[0097] Comparative Example 1

[0098] A method for preparing a tetraethylene glycol ether, comprising the following steps:

[0099] S1: Weigh a certain proportion of diethylene glycol and ethylene oxide, and 0.2g of organometallic supported catalyst into a reaction vessel and carry out the reaction.

[0100] S2: After the reaction is complete, add 20g of azeotropic agent and evaporate the water generated in the reaction to obtain crude tetraethylene glycol ether.

[0101] S3: Crude tetraethylene glycol ether is purified by passing it through a light component removal tower, a purification tower, and a decolorization tower to obtain high-purity tetraethylene glycol ether.

[0102] The azeotropic agent is xylene.

[0103] The ratio of diethylene glycol to ethylene oxide is 1:1.

[0104] The reaction pressure is 0.2 MPa.

[0105] The reaction temperature was 85℃ and the reaction time was 1 hour.

[0106] Atomized n-dodecane is added to the decolorization tower.

[0107] The catalyst is niobium oxide.

[0108] Comparative Example 2

[0109] A method for preparing a tetraethylene glycol ether, comprising the following steps:

[0110] S1: Weigh a certain proportion of diethylene glycol and ethylene oxide, and 0.2g of organometallic supported catalyst into a reactor and carry out the reaction.

[0111] S2: After the reaction is complete, add 20g of azeotropic agent and evaporate the water generated in the reaction to obtain crude tetraethylene glycol ether.

[0112] S3: Crude tetraethylene glycol ether is purified by passing it through a light component removal tower, a purification tower, and a decolorization tower to obtain high-purity tetraethylene glycol ether.

[0113] The azeotropic agent is xylene.

[0114] The ratio of diethylene glycol to ethylene oxide is 1:1.

[0115] The reaction pressure is 0.2 MPa.

[0116] The reaction temperature was 85℃ and the reaction time was 1 hour.

[0117] Atomized n-dodecane is added to the decolorization tower.

[0118] The method for preparing the organometal supported catalyst is as follows:

[0119] S1: Place montmorillonite in an oven and dry it at 180℃ for 20 hours to remove organic impurities;

[0120] S2: Weigh 100g of dried montmorillonite, put it into 1000g of aqueous solution, add 5g of acrylic silane, stir at room temperature for 20min, filter under pressure, and dry to obtain acrylic montmorillonite.

[0121] S3: Weigh 3g of metal chloride salt and dissolve it in 500g of N,N-dimethylformamide. Sonicate at room temperature to mix the reactants evenly. The reaction temperature is 80℃ and the reaction time is 2h. Then add 100g of acrylic montmorillonite and 0.05g of cerium methacrylate and react for 10h. Cool to room temperature. Filter and wash with water until the pH is neutral. Dry to obtain the organometallic supported catalyst.

[0122] The metal chloride salt mentioned is ZnCl2.

[0123] The acrylate silane is γ-(methacryloyloxy)propyltrimethoxysilane.

[0124] Comparative Example 3

[0125] A method for preparing a tetraethylene glycol ether, comprising the following steps:

[0126] S1: Weigh a certain proportion of diethylene glycol and ethylene oxide, and 0.2g of organometallic supported catalyst into a reactor and carry out the reaction.

[0127] S2: After the reaction is complete, add 20g of azeotropic agent and evaporate the water generated in the reaction to obtain crude tetraethylene glycol ether.

[0128] S3: Crude tetraethylene glycol ether is purified by passing it through a light component removal tower, a purification tower, and a decolorization tower to obtain high-purity tetraethylene glycol ether.

[0129] The azeotropic agent is xylene.

[0130] The ratio of diethylene glycol to ethylene oxide is 1:1.

[0131] The reaction pressure is 0.2 MPa.

[0132] The reaction temperature was 85℃ and the reaction time was 1 hour.

[0133] Atomized n-dodecane is added to the decolorization tower.

[0134] The method for preparing the organometal supported catalyst is as follows:

[0135] S1: Place montmorillonite in an oven and dry it at 180℃ for 20 hours to remove organic impurities;

[0136] S2: Weigh 100g of dried montmorillonite, put it into 1000g of aqueous solution, add 5g of acrylic silane, stir at room temperature for 20min, filter under pressure, and dry to obtain acrylic montmorillonite.

[0137] S3: Weigh 3g of metal chloride salt and 10g of 2-aminoterephthalic acid, dissolve them in 500g of N,N-dimethylformamide, and sonicate at room temperature to mix the reactants evenly; the reaction temperature is 80℃ and the reaction time is 2h, then add 100g of acrylic montmorillonite, and the reaction time is 10h. Cool to room temperature; filter, wash with water until pH is neutral, and dry to obtain organometallic supported catalyst.

[0138] The metal chloride salt mentioned is ZnCl2.

[0139] The acrylate silane is γ-(methacryloyloxy)propyltrimethoxysilane.

[0140] The methods for calculating the purity and reaction yield of tetraethylene glycol ether in the above specific implementation scheme are as follows:

[0141] 1. Purity: Purity of tetraethylene glycol ether = mass of tetraethylene glycol ether in the mixture ÷ mass of the mixture × 100%;

[0142] 2. Yield: The yield of tetraethylene glycol ether = actual amount of tetraethylene glycol ether produced / theoretical amount of tetraethylene glycol ether produced × 100%.

[0143] purity / % Yield / % Example 1 99.5 92.8 Example 2 99.6 93.1 Example 3 99.8 95.5 Example 4 99.9 93.6 Comparative Example 1 85.6 75.9 Comparative Example 2 93.3 88.4 Comparative Example 3 94.5 89.6

[0144] The above embodiments are merely a limited number of preferred implementations of the present invention, and their descriptions are quite specific and detailed, but they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. A method for preparing tetraethylene glycol ether, comprising the following steps: S1: Weigh a certain proportion of diethylene glycol and ethylene oxide, and 0.2-0.6 parts of organometallic supported catalyst by weight, and react them in a reactor. S2: After the reaction is complete, add 20-40 parts of azeotropic agent and evaporate the water generated in the reaction via azeotropic distillation to obtain crude tetraethylene glycol ether; S3: Crude tetraethylene glycol ether, after being purified by a light component removal tower, a purification tower, and a decolorization tower, yields high-purity tetraethylene glycol ether. The method for preparing the organometal supported catalyst is as follows: A1: Place montmorillonite in an oven and dry it at 180-200℃ for 20-24 hours to remove organic impurities; A2: Weigh 100-300 parts of dried montmorillonite, put it into 1000-1500 parts of aqueous solution, add 5-8 parts of acrylic silane, stir at room temperature for 20-100 minutes, filter under pressure, and dry to obtain acrylic montmorillonite. A3: Weigh 3-7 parts of metal chloride salt and 10-16 parts of 2-aminoterephthalic acid, dissolve them in 500-1000 parts of N,N-dimethylformamide, and sonicate at room temperature to ensure uniform mixing of the reactants; heat to the reaction temperature and react for 2-5 hours, then add 100-300 parts of acrylate-based montmorillonite and 0.05-0.5 parts of cerium methacrylate, react for 10-20 hours, and cool to room temperature; filter, wash with water until pH is neutral, and dry to obtain the organometallic supported catalyst; The metal chloride salt is ZnCl2, FeCl3, or AlCl3; The acrylate silane is γ-(methacryloyloxy)propyltrimethoxysilane or 3-methacryloyloxypropylmethyldiethoxysilane; The reaction temperature in A3 is 80-100℃ during the preparation of the organometallic supported catalyst.

2. The method for preparing a tetraethylene glycol ether according to claim 1, characterized in that: The azeotropic agent is xylene.

3. The method for preparing a tetraethylene glycol ether according to claim 1, characterized in that: The ratio of diethylene glycol to ethylene oxide is 1:1-2.

4. The method for preparing a tetraethylene glycol ether according to claim 1, characterized in that: The reaction pressure is 0.2-0.9 MPa.

5. The method for preparing a tetraethylene glycol ether according to claim 1, characterized in that: The reaction temperature is 85-100℃, and the time is 1-3 hours.

6. The method for preparing a tetraethylene glycol ether according to claim 1, characterized in that: Atomized n-dodecane, n-tetrazane, or n-tetradecane are added to the decolorization tower.