Method and apparatus for separating and recovering anthracene alkylation catalyst

Abstract

This invention relates to the field of alkyl anthracene production technology, specifically to a method and apparatus for separating and recovering anthracene alkylation catalyst. The method includes: sequentially extracting, electrodialyzing, and vacuum distilling a mixture of acidic oil containing the anthracene alkylation catalyst to obtain a recovered anthracene alkylation catalyst with a purity ≥98 wt%; wherein the vacuum distillation includes vacuum distillation-I and vacuum distillation-II. This method employs extraction, electrodialysis, and vacuum distillation sequentially, and combines these techniques, resulting in high purity and high yield of the recovered anthracene alkylation catalyst.

Description

Technical Field

[0001] This invention relates to the field of alkyl anthracene production technology, specifically to a method and apparatus for separating and recovering anthracene alkylation catalysts. Background Technology

[0002] Currently, the main process technology for producing hydrogen peroxide both domestically and internationally is the anthraquinone process; in this process, 2-alkylanthraquinone acts as a "carrier," directly affecting the quality and yield of hydrogen peroxide.

[0003] The process route for preparing 2-alkylanthraquinone via the oxidation of 2-alkylanthracene is considered a green production technology with broad application prospects due to its advantages such as simple process flow, wide availability of raw materials, and low environmental pollution. Under acid catalysis, anthracene undergoes an alkylation reaction with an alkylating agent. After separation, the product system yields the target product, 2-alkylanthracene. Then, using specific oxidation techniques, the efficient preparation of 2-alkylanthraquinone from 2-alkylanthracene can be achieved.

[0004] The key raw material for the above process, 2-alkylanthracene, can be prepared by heterogeneous liquid acid alkylation technology. This technology has the advantages of simple process flow and the required acid catalyst is inexpensive, readily available, and has excellent catalytic performance.

[0005] US4255343A, CN111825512A, CN109574779A, and CN111825510A all disclose methods for anthracene alkylation using heterogeneous liquid acid catalysis, but none of them involve the reuse of the catalyst. Because the strong acid-catalyzed alkylation process produces acid-soluble oil as a byproduct, the continuous accumulation of this oil during the reaction leads to a decrease in acidity and an increase in viscosity, which in turn reduces the catalytic activity of the catalyst.

[0006] Currently, high-temperature cracking is commonly used in industry to process alkylation catalysts. Taking sulfuric acid as an example, it first undergoes heating, sedimentation, and degassing to remove acid-soluble oils, followed by incineration cracking, sulfur dioxide conversion, cooling, and sulfuric acid condensation to produce fresh sulfuric acid. The obvious drawbacks of this method are high energy consumption, complex processes, and high costs. Therefore, to achieve catalyst reuse, efficient separation technologies must be developed.

[0007] Therefore, a new method for separating and recovering anthracene alkylation catalysts is urgently needed. Summary of the Invention

[0008] The purpose of this invention is to overcome the problems of complex processes, high energy consumption, and environmental pollution in the separation and recovery of existing anthracene alkylation catalysts, as well as the low purity and low yield of the recovered anthracene alkylation catalyst. This invention provides a new method and apparatus for separating and recovering anthracene alkylation catalysts. The recovered anthracene alkylation catalyst obtained by this method has high purity and high yield. At the same time, this method has the characteristics of simplified process flow, low energy consumption, and environmental friendliness.

[0009] To achieve the above objectives, the first aspect of the present invention provides a method for separating and recovering anthracene alkylation catalyst, the method comprising: sequentially extracting, electrodialyzing and vacuum distilling an acid oil mixture containing anthracene alkylation catalyst to obtain a recovered anthracene alkylation catalyst with a purity ≥98wt%;

[0010] The vacuum distillation includes vacuum distillation-I and vacuum distillation-II.

[0011] Preferably, the method includes the following steps:

[0012] (1) The acid oil mixture is mixed with water and the extraction is performed to obtain an aqueous solution containing anthracene alkylation catalyst as the extraction phase;

[0013] (2) The aqueous solution containing anthracene alkylation catalyst is subjected to electrodialysis to obtain a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of ≥8wt%;

[0014] (3-i) The concentrated alkylation catalyst aqueous solution is subjected to vacuum distillation-I to obtain crude anthracene alkylation catalyst with a water content ≤0.1wt% and catalyst with a water content ≤0.1wt%;

[0015] (3-ii) The crude anthracene alkylation catalyst is subjected to vacuum distillation-II to obtain the recovered anthracene alkylation catalyst and impurities with a catalyst content ≤0.1wt%.

[0016] A second aspect of the present invention provides an apparatus for separating and recovering anthracene alkylation catalysts, the apparatus comprising: an extraction unit, an electrodialysis unit, and a vacuum distillation unit connected in sequence;

[0017] The extraction unit is used to mix and extract an acid oil mixture containing anthracene alkylation catalyst and water, and the resulting aqueous solution containing anthracene alkylation catalyst is used as the extraction phase.

[0018] The electrodialysis unit is used to electrodialyze the aqueous solution containing anthracene alkylation catalyst to obtain a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of ≥8wt%.

[0019] The vacuum distillation unit includes vacuum distillation column I and vacuum distillation column II connected in sequence, used to perform vacuum distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain a recovered anthracene alkylation catalyst with a purity ≥98wt%.

[0020] Compared with the prior art, the present invention has the following advantages:

[0021] (1) The method provided by the present invention uses an acid oil mixture containing anthracene alkylation catalyst as raw material, and sequentially employs extraction, electrodialysis and vacuum distillation (including vacuum distillation-I and vacuum distillation-II) techniques, and combines the coupling of extraction, electrodialysis and vacuum distillation to achieve high purity and high yield of the recovered anthracene alkylation catalyst, that is, the purity of the recovered anthracene alkylation catalyst is ≥98wt% and the yield is ≥90%.

[0022] (2) The method provided by the present invention divides vacuum distillation into vacuum distillation-I and vacuum distillation-II, which respectively dehydrate the aqueous solution containing anthracene alkylation catalyst and remove impurities from the concentrated alkylation catalyst aqueous solution, thereby further improving the purity of the recovered anthracene alkylation catalyst; at the same time, the method also has the characteristics of simple process, low energy consumption, environmental friendliness and low cost, which is convenient for industrial production. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of an apparatus for separating and recovering anthracene alkylation catalysts provided by the present invention.

[0024] Explanation of reference numerals in the attached figures

[0025] I. Extraction Unit II. Electrodialysis Unit III. Vacuum Distillation Unit

[0026] III-1, Vacuum Distillation Column-I III-2, Vacuum Distillation Column-II

[0027] 1. Acid-oil mixture; 2. Water; 3. Aqueous solution containing anthracene alkylation catalyst.

[0028] 4. Acid-containing oil phase; 5. Concentrated anthracene alkylation catalyst aqueous solution; 6. Crude anthracene alkylation catalyst.

[0029] 7. Moisture 8. Recovery of anthracene alkylation catalyst 9. Impurities Detailed Implementation

[0030] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0031] The first aspect of the present invention provides a method for separating and recovering anthracene alkylation catalyst, the method comprising: sequentially extracting, electrodialyzing and vacuum distilling an acid oil mixture containing anthracene alkylation catalyst to obtain a recovered anthracene alkylation catalyst with a purity ≥98wt%;

[0032] The vacuum distillation includes vacuum distillation-I and vacuum distillation-II.

[0033] The inventors of this invention discovered that, theoretically, liquid acid and acid-soluble oil can be separated by vacuum distillation based on the difference in boiling points. However, they found that vacuum distillation cannot separate the liquid acid and acid-soluble oil. For example, with methanesulfonic acid, under a certain vacuum pressure, when the liquid phase temperature reaches the boiling point of methanesulfonic acid (but not its decomposition temperature), methanesulfonic acid cannot be collected at the top of the column. This is likely because side reactions occur between the organic liquid acid and the acid-soluble oil. Therefore, the acid catalyst cannot be separated and recovered using a single vacuum distillation method. Therefore, the inventors combined extraction, electrodialysis, and vacuum distillation (i.e., vacuum distillation-I and vacuum distillation-II) techniques for the separation and recovery of anthracene alkylation catalysts, resulting in high-purity and high-yield recovered anthracene alkylation catalysts.

[0034] In this invention, unless otherwise specified, the acid oil mixture containing anthracene alkylation catalyst is simply referred to as the acid oil mixture.

[0035] In some embodiments of the present invention, preferably, the method includes the following steps:

[0036] (1) The acid oil mixture is mixed with water and the extraction is performed to obtain an aqueous solution containing anthracene alkylation catalyst as the extraction phase;

[0037] (2) The aqueous solution containing anthracene alkylation catalyst is subjected to electrodialysis to obtain a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of ≥8wt%;

[0038] (3-i) The concentrated alkylation catalyst aqueous solution is subjected to vacuum distillation-I to obtain crude anthracene alkylation catalyst with a water content ≤0.1wt% and catalyst with a water content ≤0.1wt%;

[0039] (3-ii) The crude anthracene alkylation catalyst is subjected to vacuum distillation-II to obtain the recovered anthracene alkylation catalyst and impurities with a catalyst content ≤0.1wt%.

[0040] In some embodiments of the present invention, preferably, in step (1), the concentration of the anthracene alkylation catalyst in the acid oil mixture is 80-95 wt%, for example, 80 wt%, 85 wt%, 88 wt%, 90 wt%, 95 wt%, and any value within the range of any two values, preferably 85-90 wt%.

[0041] In this invention, unless otherwise specified, the acid-oil mixture contains acid-soluble oil and impurities in addition to the anthracene alkylation catalyst.

[0042] In this invention, the source of the acid-oil mixture is subject to a wide range of selection, as long as the anthracene alkylation catalyst in the acid-oil mixture meets the above-mentioned limitations. Preferably, the acid-oil mixture is selected from the lower layer solution of the anthracene alkylation reaction solution, wherein the anthracene alkylation reaction process conditions include: a temperature of 80-150°C, a mechanical stirring rate of 200-500 r / min, and an alkylating agent olefin feeding time of 6-15 h.

[0043] In some embodiments of the present invention, preferably, the anthracene alkylation catalyst is selected from liquid acid catalysts; more preferably, the anthracene alkylation catalyst is selected from C1-C5 alkyl sulfonic acids and / or C1-C5 perfluorinated substituted alkyl sulfonic acids.

[0044] In one specific embodiment of the present invention, preferably, the anthraquinone alkylation catalyst is selected from at least one of methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, perfluoromethane sulfonic acid, perfluoroethane sulfonic acid, perfluoropropane sulfonic acid, and perfluorobutane sulfonic acid.

[0045] In this invention, the extraction aims to avoid the influence of acid-soluble oil in the acid-oil mixture on subsequent vacuum distillation, i.e., to prevent side reactions between the acid-soluble oil and the anthracene alkylation catalyst. Preferably, in step (1), the weight ratio of the acid-oil mixture to water, based on the anthracene alkylation catalyst, is 1:5-30, for example, 1:5, 1:8, 1:10, 1:12, 1:15, 1:18, 1:20, 1:30, and any value within any range of two such values, preferably 1:10-20. Using this preferred weight ratio is more conducive to removing the acid-soluble oil from the acid-oil mixture, thereby improving the purity of the recovered anthracene alkylation catalyst.

[0046] In this invention, the mixing aims to homogenize the acid-oil mixture and water, thereby improving the extraction effect. Preferably, the mixing conditions include: a temperature of 20-100°C, more preferably 30-80°C; and a time of 0.25-1 h, more preferably 0.3-0.8 h.

[0047] In this invention, the extraction aims to separate the anthracene alkylation catalyst and the acid-soluble oil in the acid-oil mixture, i.e., to obtain an extract phase containing an aqueous solution of the anthracene alkylation catalyst and a raffinate phase containing the acid-soluble oil. Preferably, the extraction conditions include: a temperature of 20-100°C, more preferably 30-80°C; and a time of 0.5-3 h, more preferably 0.5-1 h. Using these preferred conditions is more advantageous for achieving stratification of the extract phase and the raffinate phase, i.e., obtaining an extract phase in the lower layer and a raffinate phase in the upper layer.

[0048] In this invention, compared with directly subjecting the extracted phase to vacuum distillation, electrodialysis can significantly reduce the energy consumption of subsequent vacuum distillation and dehydration. This advantage is particularly pronounced for aqueous solutions containing anthracene alkylation catalysts at very low concentrations.

[0049] In this invention, the purpose of the electrodialysis is to perform preliminary dehydration to obtain a concentrated aqueous solution of anthracene alkylation catalyst with a high concentration. Preferably, in step (2), the electrodialysis conditions include a current density of 1-10000 A / m³. 2 Preferably 100-5000 A / m 2 The voltage is 0-80V, preferably 5-50V; the time is 2-10h, preferably 3-8h. The current density parameter is the ratio of the current applied to the counter electrode of the electrodialysis device to the cross-sectional area of ​​the membrane stack of the electrodialysis device.

[0050] In some embodiments of the present invention, preferably, the concentration of the concentrated anthracene alkylation catalyst aqueous solution is 8-20 wt%, for example, 8 wt%, 10 wt%, 13 wt%, 15 wt%, 20 wt%, and any value within a range of any two values, preferably 8-15 wt%.

[0051] In this invention, the vacuum distillation is intended to further remove moisture and impurities from the concentrated anthracene alkylation catalyst aqueous solution.

[0052] In this invention, unless otherwise specified, the vacuum distillation-I is carried out in vacuum distillation column-I, at which point a crude anthracene alkylation catalyst containing almost no water but impurities is obtained at the bottom of the column, and at the top of the column a water containing almost no catalyst is obtained.

[0053] In some embodiments of the present invention, preferably, in step (3-i), the conditions for vacuum distillation-I include: a liquid phase temperature of 50-100°C, preferably 60-80°C; a gas phase temperature of 25-75°C, preferably 40-60°C; a pressure of 0-5 kPa, preferably 1-3 kPa; and a reflux ratio of 0.2-5, preferably 0.4-3. In the present invention, the liquid phase temperature refers to the temperature of the aqueous solution of the crude anthracene alkylation catalyst in the bottom of the column under a specific pressure; the gas phase temperature refers to the vaporization temperature of water under the same specific pressure.

[0054] In this invention, unless otherwise specified, all pressure parameters refer to gauge pressure.

[0055] In this invention, unless otherwise specified, the vacuum distillation-II is carried out in vacuum distillation column-II, at the bottom of the column to obtain impurities that are almost free of catalyst, such as black solid residue; and at the top of the column to obtain high-purity recovered anthracene alkylation catalyst.

[0056] In some embodiments of the present invention, preferably, in step (3-ii), the conditions for vacuum distillation-II include: a liquid phase temperature of 150-250°C, preferably 180-220°C; a gas phase temperature of 100-200°C, preferably 130-180°C; a pressure of 0.1-4 kPa, preferably 0.5-2 kPa; and a reflux ratio of 0.1-4, preferably 0.2-2. In the present invention, the liquid phase temperature is the temperature of the crude anthracene alkylation catalyst at the bottom of the column under a specific pressure; the gas phase temperature is the vaporization temperature of the anthracene alkylation catalyst under the same specific pressure.

[0057] A second aspect of the present invention provides an apparatus for separating and recovering anthracene alkylation catalysts, the apparatus comprising: an extraction unit, an electrodialysis unit, and a vacuum distillation unit connected in sequence;

[0058] The extraction unit is used to mix and extract an acid oil mixture containing anthracene alkylation catalyst and water, and the resulting aqueous solution containing anthracene alkylation catalyst is used as the extraction phase.

[0059] The electrodialysis unit is used to electrodialyze the aqueous solution containing anthracene alkylation catalyst to obtain a concentrated aqueous solution of anthracene alkylation catalyst with a concentration ≥10wt%.

[0060] The vacuum distillation unit includes vacuum distillation column I and vacuum distillation column II connected in sequence, used to perform vacuum distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain a recovered anthracene alkylation catalyst with a purity ≥98wt%.

[0061] In this invention, there is a wide range of choices for the types of extraction units, which include, but are not limited to, mixing tanks and extraction towers.

[0062] In this invention, the electrodialysis unit has a wide range of selection, and the electrodialysis unit is an electrodialysis device.

[0063] In some embodiments of the present invention, preferably, the vacuum distillation column-I is used to perform vacuum distillation-I on the concentrated alkylation catalyst aqueous solution to obtain crude anthracene alkylation catalyst with a water content ≤0.1wt% and water with a catalyst content ≤0.1wt%; wherein, the vacuum distillation column-II is used to perform vacuum distillation-II on the crude anthracene alkylation catalyst to obtain the recovered anthracene alkylation catalyst and impurities with a catalyst content ≤0.1wt%.

[0064] The present invention provides a schematic diagram of an apparatus for separating and recovering anthracene alkylation catalysts, as shown below. Figure 1 As shown, the device includes: an extraction unit I, an electrodialysis unit II, a vacuum distillation column-I III-1, and a vacuum distillation column-II III-2 connected in sequence;

[0065] Among them, extraction unit I is used to mix and extract an acid oil mixture 1 containing anthracene alkylation catalyst and water 2, and the resulting aqueous solution 3 containing anthracene alkylation catalyst is used as the extraction phase and the acid-soluble oil phase 4 is used as the raffinate phase.

[0066] Among them, the electrodialysis unit II is used to electrodialyze the aqueous solution 3 containing anthracene alkylation catalyst to obtain a concentrated aqueous solution 5 of anthracene alkylation catalyst with a concentration of ≥8wt%.

[0067] Among them, vacuum distillation column-I III-1 is used to perform vacuum distillation-I on concentrated alkylation catalyst aqueous solution 5 to obtain crude anthracene alkylation catalyst 6 with water content ≤0.1wt% and water 7 with catalyst content ≤0.1wt%;

[0068] Among them, vacuum distillation column-II III-2 is used to perform vacuum distillation-II on crude anthracene alkylation catalyst 6 to obtain recovered anthracene alkylation catalyst 8 and impurities 9 with a catalyst content ≤0.1wt%.

[0069] According to a particularly preferred embodiment of the present invention, a method for separating and recovering anthracene alkylation catalysts, the method comprising:

[0070] (1) The acid oil mixture is mixed with water and the extraction is performed to obtain an aqueous solution containing anthracene alkylation catalyst as the extraction phase;

[0071] (2) The aqueous solution containing anthracene alkylation catalyst is subjected to electrodialysis to obtain a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of ≥8wt%;

[0072] (3-i) The concentrated alkylation catalyst aqueous solution is subjected to vacuum distillation-I to obtain crude anthracene alkylation catalyst with a water content ≤0.1wt% and catalyst with a water content ≤0.1wt%;

[0073] (3-ii) The crude anthracene alkylation catalyst is subjected to vacuum distillation-II to obtain a recovered anthracene alkylation catalyst with a purity ≥99wt% and impurities with a catalyst content ≤0.1wt%;

[0074] In step (1), the weight ratio of the acid oil mixture to water, calculated based on the anthracene alkylation catalyst, is 1:10-20.

[0075] The present invention will be described in detail below through embodiments.

[0076] The concentration of anthracene alkylation catalyst (methanesulfonic acid) in the acid oil mixture containing anthracene alkylation catalyst (hereinafter referred to as acid oil mixture A1) is 87 wt%.

[0077] The concentration of the anthracene alkylation catalyst (perfluoroethane sulfonic acid) in the acid oil mixture containing the anthracene alkylation catalyst (hereinafter referred to as acid oil mixture A2) is 91 wt%.

[0078] Example 1

[0079] (1) A mixture of acid oil A1 based on anthracene alkylation catalyst and water was mixed at a weight ratio of 1:19 (temperature 30℃, time 0.3h) and extracted (temperature 30℃, time 1h) to obtain an aqueous solution containing anthracene alkylation catalyst with a mass of 1kg and a concentration of 5wt% as the extraction phase.

[0080] (2) The above aqueous solution containing anthracene alkylation catalyst was subjected to electrodialysis (current density 300 A / m). 2 (At a voltage of 20V and a time of 4h), a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of 8.32wt% was obtained.

[0081] (3-i) The above concentrated alkylation catalyst aqueous solution was subjected to vacuum distillation-I (liquid phase temperature 78℃, gas phase temperature 58℃, distillation pressure 3kPa, and top reflux ratio 2) to obtain crude anthracene alkylation catalyst with a water content of 0.09wt% and catalyst with a water content of 0.01wt%.

[0082] (3-ii) The above crude anthracene alkylation catalyst was subjected to vacuum distillation-II (liquid phase temperature 218℃, gas phase temperature 178℃, distillation pressure 2kPa, and top reflux ratio 1) to obtain the recovered anthracene alkylation catalyst S1.

[0083] The purity of the recovered anthracene alkylation catalyst S1 was 99.7 wt%, and the yield was 90.89%.

[0084] Comparative Example 1

[0085] According to Example 1, the difference is that in step (2), the above-mentioned aqueous solution containing anthracene alkylation catalyst is subjected to vacuum distillation (liquid phase temperature is 78°C, gas phase temperature is 58°C, distillation pressure is 3 kPa, and reflux ratio at the top of the column is 2) to obtain a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of 8.32 wt%.

[0086] Compared to Comparative Example 1, which consumed 972.46 kJ using vacuum distillation, Example 1, which consumed 25.92 kJ to obtain the same concentration of concentrated anthracene alkylation catalyst aqueous solution using electrodialysis, consumed only 2.67% of the energy consumption of Comparative Example 1. Therefore, the method provided by this invention effectively reduces energy consumption while ensuring high purity and high yield of the recovered anthracene alkylation catalyst.

[0087] Example 2

[0088] (1) A mixture of acid oil A1 based on anthracene alkylation catalyst and water were mixed at a weight ratio of 1:17 (temperature 40℃, time 0.4h) and extracted (temperature 40℃, time 0.6h) to obtain an aqueous solution containing anthracene alkylation catalyst with a concentration of 5.56wt% as the extraction phase.

[0089] (2) The above aqueous solution containing anthracene alkylation catalyst was subjected to electrodialysis (current density 400 A / m). 2 (At a voltage of 25V and a time of 3h), a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of 9.89wt% was obtained.

[0090] (3-i) The above concentrated alkylation catalyst aqueous solution was subjected to vacuum distillation-I (liquid phase temperature 71℃, gas phase temperature 53℃, distillation pressure 2.5kPa, and top reflux ratio 2) to obtain crude anthracene alkylation catalyst with a water content of 0.07wt% and catalyst with a water content of 0.07wt%.

[0091] (3-ii) The above crude anthracene alkylation catalyst was subjected to vacuum distillation-II (liquid phase temperature 202℃, gas phase temperature 169℃, distillation pressure 1.8kPa, and top reflux ratio 1) to obtain the recovered anthracene alkylation catalyst S2.

[0092] The purity of the recovered anthracene alkylation catalyst S2 was 99.6 wt%, and the yield was 91.7%.

[0093] Comparative Example 2

[0094] According to Example 2, the difference is that in step (2), the above-mentioned anthracene alkylation catalyst aqueous solution is subjected to vacuum distillation (liquid phase temperature is 71°C, gas phase temperature is 53°C, distillation pressure is 2.5 kPa, and top reflux ratio is 2) to obtain a concentrated anthracene alkylation catalyst aqueous solution with a concentration of 9.89 wt%.

[0095] Compared to Comparative Example 2, which consumed 1066.95 kJ using vacuum distillation, Example 2, which consumed 32.4 kJ to obtain the same concentration of concentrated anthracene alkylation catalyst aqueous solution using electrodialysis, consumed only 3.04 kJ. Therefore, the energy consumption of Example 2 is 3.04% of that of Comparative Example 2. This demonstrates that the method provided by the present invention effectively reduces energy consumption while ensuring high purity and high yield of the recovered anthracene alkylation catalyst.

[0096] Example 3

[0097] (1) A mixture of acid oil A1 based on anthracene alkylation catalyst and water was mixed at a weight ratio of 1:15 (temperature 50℃, time 0.5h) and extracted (temperature 50℃, time 0.7h) to obtain an aqueous solution containing anthracene alkylation catalyst with a concentration of 6.25wt% as the extraction phase;

[0098] (2) The above aqueous solution containing anthracene alkylation catalyst was subjected to electrodialysis (current density 400 A / m). 2 (At a voltage of 30V and a time of 3h), a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of 11.28wt% was obtained.

[0099] (3-i) The above concentrated alkylation catalyst aqueous solution was subjected to vacuum distillation-I (liquid phase temperature 64℃, gas phase temperature 48℃, distillation pressure 2kPa, and top reflux ratio 2) to obtain crude anthracene alkylation catalyst with a water content of 0.06wt% and catalyst with a water content of 0.04wt%.

[0100] (3-ii) The above crude anthracene alkylation catalyst was subjected to vacuum distillation-II (liquid phase temperature 194℃, gas phase temperature 161℃, distillation pressure 1.5kPa, and top reflux ratio 1) to obtain the recovered anthracene alkylation catalyst S3.

[0101] The purity of the recovered anthracene alkylation catalyst S3 was 99.4 wt%, and the yield was 92.3%.

[0102] Comparative Example 3

[0103] According to Example 3, the difference is that in step (2), the above-mentioned anthracene alkylation catalyst aqueous solution is subjected to vacuum distillation (liquid phase temperature is 64°C, gas phase temperature is 48°C, distillation pressure is 2kPa, and top reflux ratio is 2) to obtain a concentrated anthracene alkylation catalyst aqueous solution with a concentration of 11.28wt%.

[0104] Compared to Comparative Example 3, which consumed 1086.71 kJ using vacuum distillation, Example 3, which consumed 38.88 kJ to obtain the same concentration of concentrated anthracene alkylation catalyst aqueous solution using electrodialysis, consumed only 3.58% of the energy consumption of Comparative Example 3. Therefore, the method provided by this invention effectively reduces energy consumption while ensuring high purity and high yield of the recovered anthracene alkylation catalyst.

[0105] Example 4

[0106] (1) A mixture of acid oil A1 based on anthracene alkylation catalyst and water was mixed at a weight ratio of 1:13 (temperature 60℃, time 0.6h) and extracted (temperature 60℃, time 0.8h) to obtain an aqueous solution containing anthracene alkylation catalyst with a concentration of 7.14wt% as the extraction phase;

[0107] (2) The above aqueous solution containing anthracene alkylation catalyst was subjected to electrodialysis (current density of 500 A / m). 2 (At a voltage of 30V and a time of 3h), a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of 13.45wt% was obtained.

[0108] (3-i) The above concentrated alkylation catalyst aqueous solution was subjected to vacuum distillation-I (liquid phase temperature 58℃, gas phase temperature 45℃, distillation pressure 1.5kPa, and top reflux ratio 2) to obtain crude anthracene alkylation catalyst with a water content of 0.05wt% and catalyst with a water content of 0.05wt%.

[0109] (3-ii) The above crude anthracene alkylation catalyst was subjected to vacuum distillation-II (liquid phase temperature 189℃, gas phase temperature 157℃, distillation pressure 1.2kPa, and top reflux ratio 1) to obtain the recovered anthracene alkylation catalyst S4.

[0110] The purity of the recovered anthracene alkylation catalyst S4 was 99.3 wt%, and the yield was 93.1%.

[0111] Comparative Example 4

[0112] According to Example 4, the difference is that in step (2), the above-mentioned anthracene alkylation catalyst aqueous solution is subjected to vacuum distillation (liquid phase temperature is 58°C, gas phase temperature is 45°C, distillation pressure is 1.5 kPa, and top reflux ratio is 2) to obtain a concentrated anthracene alkylation catalyst aqueous solution with a concentration of 13.45 wt%.

[0113] Compared to Comparative Example 4, which consumed 1143.31 kJ using vacuum distillation, Example 4, which consumed 48.6 kJ to obtain the same concentration of concentrated anthracene alkylation catalyst aqueous solution using electrodialysis, consumed only 4.25% of the energy consumption of Comparative Example 4. Therefore, the method provided by this invention effectively reduces energy consumption while ensuring high purity and high yield of the recovered anthracene alkylation catalyst.

[0114] Example 5

[0115] (1) A mixture of acid oil A1 based on anthracene alkylation catalyst and water were mixed at a weight ratio of 1:11 (temperature 70℃, time 0.8h) and extracted (temperature 70℃, time 0.9h) to obtain an aqueous solution containing anthracene alkylation catalyst with a concentration of 8.33wt% as the extraction phase;

[0116] (2) The above aqueous solution containing anthracene alkylation catalyst was subjected to electrodialysis (current density 700 A / m). 2 (At a voltage of 15V and a time of 5h), a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of 14.56wt% was obtained.

[0117] (3-i) The above concentrated alkylation catalyst aqueous solution was subjected to vacuum distillation-I (liquid phase temperature 52℃, gas phase temperature 42℃, distillation pressure 1kPa, and top reflux ratio 2) to obtain crude anthracene alkylation catalyst with a water content of 0.04wt% and catalyst with a water content of 0.06wt%.

[0118] (3-ii) The above crude anthracene alkylation catalyst was subjected to vacuum distillation-II (liquid phase temperature 185℃, gas phase temperature 151℃, distillation pressure 1kPa, and top reflux ratio 1) to obtain the recovered anthracene alkylation catalyst S5.

[0119] The purity of the recovered anthracene alkylation catalyst S5 was 99.1 wt%, and the yield was 93.5%.

[0120] Comparative Example 5

[0121] According to Example 5, the difference is that in step (2), the above-mentioned anthracene alkylation catalyst aqueous solution is subjected to vacuum distillation (liquid phase temperature is 52°C, gas phase temperature is 42°C, distillation pressure is 1 kPa, and top reflux ratio is 2) to obtain a concentrated anthracene alkylation catalyst aqueous solution with a concentration of 14.56 wt%.

[0122] Compared to Comparative Example 5, which consumed 1042.75 kJ using vacuum distillation, Example 5, which consumed 58.32 kJ to obtain the same concentration of concentrated anthracene alkylation catalyst aqueous solution using electrodialysis, consumed only 5.59% of the energy consumption of Comparative Example 5. Therefore, the method provided by this invention effectively reduces energy consumption while ensuring high purity and high yield of the recovered anthracene alkylation catalyst.

[0123] Example 6

[0124] The method of Example 1 is followed, except that in step (1), acid oil mixture A1 is replaced with acid oil mixture A2, and the other conditions are the same, to obtain the recovered anthracene alkylation catalyst S6;

[0125] The purity of the recovered anthracene alkylation catalyst S6 was 98.7 wt%, and the yield was 94.2%.

[0126] Example 7

[0127] The method of Example 1 is followed, except that in step (1), the weight ratio of acid oil mixture A1 and water based on anthracene alkylation catalyst is replaced with 1:8, and the other conditions are the same, to obtain the recovered anthracene alkylation catalyst S7.

[0128] The purity of the recovered anthracene alkylation catalyst S7 was 98.9 wt%, and the yield was 93.9%.

[0129] Example 8

[0130] The method is the same as in Example 1, except that in step (2), the conditions for electrodialysis are replaced with a current density of 90 A / m. 2 The voltage was 4V and the time was 2h, with all other conditions being the same, to obtain the recovered anthracene alkylation catalyst S8.

[0131] The purity of the recovered anthracene alkylation catalyst S8 was 99.0 wt%, and the yield was 93.7%.

[0132] Comparative Example 1

[0133] When the acid-oil mixture A1 was directly subjected to vacuum distillation (liquid phase temperature 189℃, gas phase temperature 175℃, distillation pressure 1kPa, and reflux ratio at the top of the column 1), methanesulfonic acid could not be collected at the top of the column. Instead, a dark green liquid with a foul odor and insoluble in water was obtained, proving that the single vacuum distillation method cannot recover the methanesulfonic acid catalyst.

[0134] Comparative Example 2

[0135] The method is the same as in Example 1, except that steps (3-i) and (3-ii) are omitted, i.e., the concentrated anthracene alkylation catalyst aqueous solution obtained in step (2) is further subjected to electrodialysis (current density of 800 A / m). 2 (At a voltage of 15V and a time of 5h), the concentration of the anthracene alkylation catalyst remained unchanged after reaching 35wt%. This is because after the concentration of methanesulfonic acid in the electrodialysis concentration chamber reached its limit, water from the feed chamber began to permeate through the membrane, causing the acid concentration in the concentration chamber to stop increasing.

[0136] Comparative Example 3

[0137] The method is the same as in Example 1, except that step (3-ii) is omitted, that is, the crude anthracene alkylation catalyst is directly used as the recovered anthracene alkylation catalyst DS3;

[0138] The purity of the recovered anthracene alkylation catalyst DS3 was 89.7 wt%, and the yield was 95.4%.

[0139] Comparative Example 4

[0140] The method of Example 1 is the same except that step (3-i) is omitted, that is, the above-mentioned concentrated alkylation catalyst aqueous solution is directly subjected to vacuum distillation (liquid phase temperature is 218°C, gas phase temperature is 178°C, distillation pressure is 2 kPa, and reflux ratio at the top of the column is 1), and the other conditions are the same, so the anthracene alkylation catalyst cannot be recovered; since the above-mentioned concentrated alkylation catalyst aqueous solution is directly distilled, the water and the catalyst are mixed together, which is equivalent to no distillation.

[0141] Compared to Comparative Examples 1-4, the recovered anthracene alkylation catalyst prepared by the method provided in this invention has higher purity and yield, wherein the purity of the recovered anthracene alkylation catalyst is ≥98wt% and the yield is ≥90%. Compared to Comparative Examples 3-4, Example 1 achieves high purity and high yield of the recovered anthracene alkylation catalyst by controlling the vacuum distillation scheme, including vacuum distillation-I and vacuum distillation-II.

[0142] Compared to Example 6, Example 1, by adjusting the concentration of the anthracene alkylation catalyst in the acid-oil mixture within the preferred protection range, is more conducive to improving the purity of the recovered anthracene alkylation catalyst. Examples 1 and 6 demonstrate that different concentrations of the anthracene alkylation catalyst in the acid-oil mixture have little impact on the purity and yield of the recovered anthracene alkylation catalyst.

[0143] Compared to Example 7, Example 1, by adjusting the weight ratio of the acid-oil mixture and water (based on the anthracene alkylation catalyst) within the preferred protection range, is more conducive to improving the purity of the recovered anthracene alkylation catalyst.

[0144] Compared to Example 8, Example 1, by adjusting the electrodialysis conditions within the preferred protection range, is more conducive to improving the purity of the recovered anthracene alkylation catalyst.

[0145] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for separating and recovering anthracene alkylation catalyst, characterized in that, The method includes: sequentially extracting, electrodialyzing, and vacuum distilling an acid oil mixture containing anthracene alkylation catalyst to obtain a recovered anthracene alkylation catalyst with a purity ≥98wt%; The vacuum distillation includes vacuum distillation-I and vacuum distillation-II; The method includes the following steps: (1) The acid oil mixture is mixed with water and the extraction is performed to obtain an aqueous solution containing anthracene alkylation catalyst as the extraction phase; (2) The aqueous solution containing anthracene alkylation catalyst is subjected to electrodialysis to obtain a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of ≥8wt%; (3-i) The concentrated alkylation catalyst aqueous solution is subjected to vacuum distillation-I to obtain crude anthracene alkylation catalyst with a water content ≤0.1wt% and catalyst with a water content ≤0.1wt%; (3-ii) The crude anthracene alkylation catalyst is subjected to vacuum distillation-II to obtain the recovered anthracene alkylation catalyst and impurities with a catalyst content ≤0.1wt%.

2. The method according to claim 1, wherein, In step (1), the concentration of anthracene alkylation catalyst in the acid oil mixture is 80-95 wt%.

3. The method according to claim 2, wherein, In step (1), the concentration of anthracene alkylation catalyst in the acid oil mixture is 85-90 wt%.

4. The method according to claim 1, wherein, The anthraquinone alkylation catalyst is selected from liquid acid catalysts.

5. The method according to claim 4, wherein, The anthraquinone alkylation catalyst is selected from C1-C5 alkyl sulfonic acids and / or C1-C5 perfluorinated substituted alkyl sulfonic acids.

6. The method according to claim 5, wherein, The anthraquinone alkylation catalyst is selected from at least one of methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, perfluoromethane sulfonic acid, perfluoroethane sulfonic acid, perfluoropropane sulfonic acid, and perfluorobutane sulfonic acid.

7. The method according to claim 1, wherein, In step (1), the weight ratio of the acid oil mixture to water, based on the anthracene alkylation catalyst, is 1:5-30.

8. The method according to claim 7, wherein, In step (1), the weight ratio of the acid oil mixture to water, based on the anthracene alkylation catalyst, is 1:10-20.

9. The method according to claim 1, wherein, In step (1), the mixing conditions include: temperature of 20-100℃ and time of 0.25-1h.

10. The method according to claim 9, wherein, In step (1), the mixing conditions include: a temperature of 30-80℃ and a time of 0.3-0.8h.

11. The method according to claim 1, wherein, The extraction conditions include: a temperature of 20-100℃ and a time of 0.5-3h.

12. The method according to claim 11, wherein, The extraction conditions include: a temperature of 30-80℃ and a time of 0.5-1h.

13. The method according to claim 1, wherein, In step (2), the conditions for electrodialysis include: a current density of 1-10000 A / m 2 Voltage: 0-80V; Time: 2-10h.

14. The method according to claim 13, wherein, In step (2), the conditions for electrodialysis include: a current density of 100-5000 A / m 2 Voltage: 5-50V; Duration: 3-8h.

15. The method according to claim 1, wherein, The concentration of the concentrated anthracene alkylation catalyst aqueous solution is 8-20 wt%.

16. The method according to claim 15, wherein, The concentration of the concentrated anthracene alkylation catalyst aqueous solution is 8-15 wt%.

17. The method according to claim 1, wherein, In step (3-i), the conditions for vacuum distillation-I include: liquid phase temperature of 50-100℃; gas phase temperature of 25-75℃; pressure of 0-5kPa; and reflux ratio at the top of the column of 0.2-5.

18. The method according to claim 17, wherein, In step (3-i), the conditions for vacuum distillation-I include: liquid phase temperature of 60-80℃; gas phase temperature of 40-60℃; pressure of 1-3kPa; and reflux ratio at the top of the column of 0.4-3.

19. The method according to claim 1, wherein, In step (3-ii), the conditions for vacuum distillation-II include: liquid phase temperature of 150-250℃; gas phase temperature of 100-200℃; pressure of 0.1-4kPa; and reflux ratio at the top of the column of 0.1-4.

20. The method according to claim 19, wherein, In step (3-ii), the conditions for vacuum distillation-II include: liquid phase temperature of 180-220℃; gas phase temperature of 130-180℃; pressure of 0.5-2kPa; and reflux ratio at the top of the column of 0.2-2.

21. The method according to any one of claims 1-20, wherein, The method is carried out in an apparatus for separating and recovering anthracene alkylation catalyst, the apparatus comprising: an extraction unit, an electrodialysis unit, and a vacuum distillation unit connected in sequence; The extraction unit is used to mix and extract an acid oil mixture containing anthracene alkylation catalyst and water, and the resulting aqueous solution containing anthracene alkylation catalyst is used as the extraction phase. The electrodialysis unit is used to electrodialyze the aqueous solution containing anthracene alkylation catalyst to obtain a concentrated aqueous solution of anthracene alkylation catalyst with a concentration of ≥8wt%. The vacuum distillation unit includes vacuum distillation column I and vacuum distillation column II connected in sequence, used to perform vacuum distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain a recovered anthracene alkylation catalyst with a purity ≥98wt%.

22. The method according to claim 21, wherein, The vacuum distillation column-I is used to perform vacuum distillation-I on the concentrated alkylation catalyst aqueous solution to obtain crude anthracene alkylation catalyst with a water content ≤0.1wt% and catalyst with a water content ≤0.1wt%. The vacuum distillation column-II is used to perform vacuum distillation-II on the crude anthracene alkylation catalyst to obtain the recovered anthracene alkylation catalyst and impurities with a catalyst content ≤0.1wt%.

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