CN117919778A - Method and apparatus for separating and recovering anthracene alkylation catalyst - Google Patents
Method and apparatus for separating and recovering anthracene alkylation catalyst Download PDFInfo
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- CN117919778A CN117919778A CN202211310511.4A CN202211310511A CN117919778A CN 117919778 A CN117919778 A CN 117919778A CN 202211310511 A CN202211310511 A CN 202211310511A CN 117919778 A CN117919778 A CN 117919778A
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- alkylation catalyst
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title claims abstract description 416
- 239000003054 catalyst Substances 0.000 title claims abstract description 230
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 219
- 230000029936 alkylation Effects 0.000 title claims abstract description 215
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000004821 distillation Methods 0.000 claims abstract description 182
- 239000012528 membrane Substances 0.000 claims abstract description 123
- 239000007864 aqueous solution Substances 0.000 claims abstract description 68
- 239000002253 acid Substances 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000012071 phase Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 27
- 239000007791 liquid phase Substances 0.000 claims description 25
- 238000000605 extraction Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 22
- 238000010992 reflux Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 19
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000004907 flux Effects 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 10
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000110 cooling liquid Substances 0.000 claims description 6
- -1 perfluoro Chemical group 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 4
- GKNWQHIXXANPTN-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000012466 permeate Substances 0.000 claims description 3
- XBWQFDNGNOOMDZ-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F XBWQFDNGNOOMDZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 2
- 239000012510 hollow fiber Substances 0.000 claims description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of alkylanthracene production, in particular to a method for separating and recycling an anthracene alkylation catalyst and a device for separating and recycling the anthracene alkylation catalyst. The method comprises the following steps: (1) Extracting an acid oil mixture containing an anthracene alkylation catalyst to obtain an aqueous solution containing the anthracene alkylation catalyst; (2) Performing membrane distillation on the anthracene-containing alkylation catalyst aqueous solution to obtain a concentrated anthracene alkylation catalyst aqueous solution with the concentration of more than or equal to 22 wt%; (3) And (3) sequentially carrying out first reduced pressure distillation and second reduced pressure distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain the recovered anthracene alkylation catalyst with the purity of more than or equal to 98 wt%. The recovered anthracene alkylation catalyst prepared by the method has high purity and high yield.
Description
Technical Field
The invention relates to the technical field of alkylanthracene production, in particular to a method for separating and recycling an anthracene alkylation catalyst and a device for separating and recycling the anthracene alkylation catalyst.
Background
Hydrogen peroxide is an important green base chemical and has a very wide range of industrial applications. The technology for producing hydrogen peroxide at home and abroad mainly adopts an anthraquinone method, and 2-alkylanthraquinone in the process is used as a carrier in the process, so that the quality and the yield of the hydrogen peroxide are directly affected.
The process route for preparing the 2-alkylanthraquinone by oxidizing the 2-alkylanthracene has the advantages of simple process flow, wide raw material sources, small environmental pollution and the like, is considered as a green production process technology, and has wide application prospect. The anthracene can be subjected to alkylation reaction with an alkylating reagent under the action of acid catalysis, and a target product 2-alkylanthracene can be obtained after the reaction product system is treated by a separation technology. Then, a specific oxidation technology is adopted to realize the purpose of efficiently preparing the 2-alkylanthracene from the 2-alkylanthracene.
The key raw material 2-alkylanthracene of the process can be prepared by a heterogeneous liquid acid alkylation technology, and the technology has the characteristics of simple process flow, low-cost and easily-obtained required acid catalyst, excellent catalytic performance and the like.
US4255343A, CN111825512B, CN109574779B and CN111825510B disclose heterogeneous liquid acid catalyzed anthracene alkylation processes, but neither involves catalyst reuse. The acid-soluble oil is byproduct in the process of catalyzing alkylation by strong acid, so that the acid-soluble oil continuously accumulated in the reaction process reduces acidity and increases viscosity, and further the catalytic activity of the catalyst is reduced.
High temperature cracking processes are currently commonly employed in the industry to treat alkylation catalysts. Taking sulfuric acid as an example, firstly, the acid-soluble oil contained in the sulfuric acid is removed through steps of heating, sedimentation, degassing and the like, and then fresh sulfuric acid is generated through procedures of incineration cracking, sulfur dioxide conversion, cooling, sulfuric acid condensation and the like. The obvious disadvantages of the method are high energy consumption, complex procedures and high cost. Therefore, in order to achieve the recycling of the catalyst, efficient separation techniques must be developed.
Disclosure of Invention
The invention aims to solve the problems of complex process, high energy consumption, environmental pollution and the like in the separation and recovery of the existing anthracene alkylation catalyst, low purity and low yield of the recovered anthracene alkylation catalyst and provides a novel method for separating and recovering the anthracene alkylation catalyst and a novel device for separating and recovering the anthracene alkylation catalyst.
To achieve the above object, a first aspect of the present invention provides a method for separating and recovering an anthracene alkylation catalyst, the method comprising the steps of:
(1) Extracting an acid oil mixture containing an anthracene alkylation catalyst to obtain an aqueous solution containing the anthracene alkylation catalyst;
(2) Performing membrane distillation on the anthracene-containing alkylation catalyst aqueous solution to obtain a concentrated anthracene alkylation catalyst aqueous solution with the concentration of more than or equal to 22 wt%;
(3) And (3) sequentially carrying out first reduced pressure distillation and second reduced pressure distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain the recovered anthracene alkylation catalyst with the purity of more than or equal to 98 wt%.
In a second aspect, the present invention provides an apparatus for separating and recovering an anthracene alkylation catalyst, the apparatus comprising: the extraction unit, the membrane distillation unit and the reduced pressure distillation unit are sequentially communicated;
the extraction unit is used for mixing and extracting the acid oil mixture containing the anthracene alkylation catalyst with water to obtain an aqueous solution containing the anthracene alkylation catalyst;
The membrane distillation unit is used for carrying out membrane distillation on the anthracene-containing alkylation catalyst aqueous solution to obtain a concentrated anthracene alkylation catalyst aqueous solution with the concentration of more than or equal to 22 wt%;
The reduced pressure distillation unit comprises a first reduced pressure distillation tower and a second reduced pressure distillation tower which are sequentially communicated, and is used for sequentially carrying out first reduced pressure distillation and second reduced pressure distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain recovered anthracene alkylation catalyst with purity of more than or equal to 98wt%.
Compared with the prior art, the invention has the following advantages:
(1) According to the method provided by the invention, the acid oil mixture containing the anthracene alkylation catalyst is used as a raw material, and the technical means of extraction, membrane distillation, first reduced pressure distillation and second reduced pressure distillation are sequentially adopted, so that the recovered anthracene alkylation catalyst has high purity and high yield, namely, the purity of the recovered anthracene alkylation catalyst is more than or equal to 98wt%, and the yield is more than or equal to 90%;
(2) According to the method provided by the invention, the extraction, the membrane distillation, the first reduced pressure distillation and the second reduced pressure distillation are coupled to obtain the recovered anthracene alkylation catalyst with high purity and high yield, namely, the acid-oil mixture is extracted firstly, so that side reactions of acid-soluble oil in the acid-oil mixture are avoided; then membrane distillation is carried out, so that the purposes of energy conservation and consumption reduction are achieved; finally, carrying out two-step reduced pressure distillation, and respectively carrying out dehydration and impurity removal; meanwhile, the method has the characteristics of simple process, low energy consumption, environmental friendliness and low cost, and is convenient for industrial production.
Drawings
FIG. 1 is a schematic diagram of an apparatus for separating and recovering an anthracene alkylation catalyst according to the present invention.
Description of the reference numerals
I. Extraction unit II, membrane distillation unit III and reduced pressure distillation unit
III-1, first vacuum distillation column III-2, second vacuum distillation column
1. Acid oil mixture 2, water 3, and an aqueous solution of an anthracene-containing alkylation catalyst
4. Acid-containing oil phase 5, concentrated aqueous anthracene alkylation catalyst solution 6, crude anthracene alkylation catalyst
7. Moisture 8, recovery of anthracene alkylation catalyst 9, impurities
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless specifically stated otherwise, the terms "first" and "second" do not denote a sequential order, nor do they denote a limitation of individual materials or steps, but are used solely to distinguish one from another. For example, "first" and "second" in "first reduced pressure distillation" and "second reduced pressure distillation" are used only to indicate that this is not the same reduced pressure distillation; the "first" and "second" of the "first vacuum distillation column" and the "second vacuum distillation column" are used only to indicate that this is not the same vacuum distillation column.
In a first aspect, the present invention provides a process for the separation and recovery of an anthracene alkylation catalyst, the process comprising the steps of:
(1) Extracting an acid oil mixture containing an anthracene alkylation catalyst to obtain an aqueous solution containing the anthracene alkylation catalyst;
(2) Performing membrane distillation on the anthracene-containing alkylation catalyst aqueous solution to obtain a concentrated anthracene alkylation catalyst aqueous solution with the concentration of more than or equal to 22 wt%;
(3) And (3) sequentially carrying out first reduced pressure distillation and second reduced pressure distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain the recovered anthracene alkylation catalyst with the purity of more than or equal to 98 wt%.
The inventors of the present invention studied and found that: according to the difference of boiling points of the liquid acid catalyst and the acid-soluble oil, the liquid acid and the acid-soluble oil can be separated theoretically by a reduced pressure distillation method; however, the inventors have found that the reduced pressure distillation method cannot separate the liquid acid from the acid-soluble oil, for example, methane sulfonic acid, and that when the liquid phase temperature reaches the boiling point of methane sulfonic acid (this temperature does not reach the decomposition temperature of methane sulfonic acid) under a certain vacuum pressure, methane sulfonic acid cannot be collected at the top of the column, probably because the organic liquid acid and the acid-soluble oil undergo side reactions, and therefore the acid catalyst cannot be separated and recovered by a single reduced pressure distillation method. Therefore, the inventors have combined the technical means of extraction, membrane distillation, first reduced pressure distillation and second reduced pressure distillation for separation and recovery of anthracene alkylation catalyst, and can obtain recovered anthracene alkylation catalyst with high purity and high yield.
In the present invention, the acid-oil mixture containing the anthracene alkylation catalyst is simply referred to as an acid-oil mixture unless otherwise specified.
In some embodiments of the invention, preferably, in step (1), the concentration of anthracene alkylation catalyst in the acid oil mixture is from 80 to 95wt%, e.g., from 80wt%, 85wt%, 88wt%, 90wt%, 95wt%, and any value in the range of any two values, preferably from 85 to 90wt%.
In the present invention, the acid oil mixture contains acid-soluble oil and impurities in addition to the anthracene alkylation catalyst, unless otherwise specified.
In the present invention, there is a wide selection range of the source of the acid-oil mixture, as long as the anthracene alkylation catalyst in the acid-oil mixture satisfies the above-described limitations. Preferably, the acid oil mixture is selected from a lower solution of an anthracene alkylation reaction solution, wherein anthracene alkylation reaction process conditions include: the temperature is 80-150 ℃, the mechanical stirring speed is 200-500r/min, and the feeding time of the alkylating agent olefin is 6-15h.
In some embodiments of the invention, preferably, the anthracene alkylation catalyst is selected from liquid acid catalysts; further preferably, the anthracene alkylation catalyst is selected from the group consisting of C 1-C5 alkylsulfonic acids and/or C 1-C5 perfluoro substituted alkylsulfonic acids.
In one embodiment of the present invention, preferably, the anthracene 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.
In the present invention, the extraction is intended to avoid the influence of acid-soluble oil in the acid-oil mixture on the subsequent distillation under reduced pressure, i.e., to prevent side reactions of the acid-soluble oil and the anthracene alkylation catalyst. Preferably, in step (1), the extraction process comprises: the acid oil mixture containing the anthracene alkylation catalyst is mixed with water and the extraction is performed.
In some embodiments of the present invention, preferably, in step (1), the weight ratio of the acid oil mixture to water calculated as anthracene alkylation catalyst is 1:2-20, e.g., 1:2, 1:3, 1:5, 1:6, 1:8, 1:10, 1:15, 1:20, and any value in the range of any two values, preferably 1:5-10. The preferred weight ratio is more advantageous for removing acid soluble oil from the acid oil mixture, thereby improving the purity of the recovered anthracene alkylation catalyst.
In the invention, the mixing aims to uniformly mix the acid oil mixture and water, thereby improving the extraction effect. Preferably, the mixing conditions include: the temperature is 20-100deg.C, preferably 40-80deg.C; the time is 0.1-1h, preferably 0.25-0.8h.
In the present invention, the extraction aims to achieve separation of the anthracene alkylation catalyst and the acid-soluble oil in the acid-oil mixture, i.e., to obtain an extract phase containing an aqueous anthracene alkylation catalyst solution and a raffinate phase containing an acid-soluble oil phase. Preferably, the conditions of the extraction include: the temperature is 20-100deg.C, preferably 40-80deg.C; the time is 0.1-3h, preferably 0.5-2h. The layering of the extract phase and the raffinate phase is more advantageously achieved by adopting the preferred conditions, namely, the extract phase positioned at the lower layer and the raffinate phase positioned at the upper layer are obtained.
In the invention, compared with the method that the extracted phase is directly subjected to reduced pressure distillation, the technical means of membrane distillation can greatly reduce the energy consumption of subsequent reduced pressure distillation dehydration, and particularly has more obvious advantages of energy conservation and consumption reduction for the aqueous solution containing anthracene alkylation catalyst with low concentration.
In the invention, the membrane distillation realizes the concentration of the anthracene-containing alkylation catalyst aqueous solution through dehydration to obtain the concentrated anthracene alkylation catalyst aqueous solution with the concentration of more than or equal to 22 wt%.
In some embodiments of the present invention, preferably, in step (2), the conditions of the membrane distillation include: the feed liquid feeding temperature is 30-80 ℃, the feed flow rate is 0.1-2L/min, the membrane inlet side pressure is 0-0.2MPa, the membrane permeation side pressure is-0.1-0.06 MPa, the temperature of the cooling liquid at the membrane permeation side is 0-10 ℃, the average membrane permeation flux is 0.5-2 L.m -2·h-1, and the separation time is 3-20h.
In some embodiments of the present invention, further preferably, in step (2), the conditions of the membrane distillation include: the feed temperature of the feed liquid is 40-70 ℃, the feed flow rate is 0.5-1.5L/min, the membrane inlet side pressure is 0.05-0.1MPa, the membrane permeation side pressure is-0.1-0.08 MPa, the temperature of the cooling liquid at the membrane permeation side is 2-8 ℃, the average permeation flux of the membrane is 0.7-1.5 L.m -2·h-1, and the separation time is 7-15h.
In some embodiments of the invention, preferably, the membrane permeate side cooling liquid is selected from the group consisting of circulating condensate and/or liquid nitrogen.
In some embodiments of the invention, it is further preferred that the concentration of the concentrated aqueous anthracene alkylation catalyst solution is 22-32wt%. Membrane distillation is carried out in the concentration range, so that the energy consumption is the lowest for the whole separation process; when the concentration of the concentrated anthracene alkylation catalyst aqueous solution is less than 22wt%, then more water needs to be distilled under reduced pressure; when the concentration of the concentrated anthracene alkylation catalyst aqueous solution is higher than 32wt%, more energy is consumed for membrane distillation.
In the present invention, the mode of the membrane distillation has a wide range of options. Preferably, in step (2), the membrane distillation is selected from direct contact membrane distillation or air gap membrane distillation.
In one embodiment of the present invention, when the membrane distillation is a direct contact membrane distillation, both the membrane feed solution (hot side) and the membrane permeate (condensing side) are in direct contact with the membrane; when the membrane distillation is an air gap type membrane distillation, the membrane raw material liquid (hot side) is contacted with the membrane, and an air gap exists between the membrane permeation liquid (condensation side) and the membrane. In the invention, when the direct contact type membrane distillation is adopted, the membrane has high flux, but the retention rate is relatively low, the membrane is easier to wet, and the membrane distillation is invalid; when air gap type membrane distillation is adopted, the method has the advantages of higher rejection rate, longer membrane service life, low membrane flux and high energy consumption.
In some embodiments of the present invention, preferably, the membrane material of the membrane distillation is selected from at least one of polytetrafluoroethylene, polyvinylidene fluoride, and polypropylene.
In some embodiments of the invention, preferably the membrane distillation has a membrane pore size of 1 μm or less, preferably 0.1 to 1 μm. By adopting the preferable conditions, the higher membrane flux can be ensured on the premise of ensuring higher rejection rate.
In some embodiments of the invention, preferably, the membrane of the membrane distillation is selected from flat plate type or hollow fiber type.
In the present invention, the first reduced pressure distillation is performed in a first reduced pressure distillation column, and a crude anthracene alkylation catalyst containing almost no water but impurities is obtained at the bottom of the column, and a water containing almost no catalyst is obtained at the top of the column, unless otherwise specified.
In some embodiments of the present invention, preferably, in step (3), the first reduced pressure distillation process includes: and carrying out the first reduced pressure distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain a crude anthracene alkylation catalyst with the water content less than or equal to 1wt% and water with the catalyst content less than or equal to 0.1 wt%.
In some embodiments of the present invention, preferably, in step (3), the conditions of the first reduced pressure distillation include: the liquid phase temperature is 50-100 ℃; the gas phase temperature is 25-75 ℃; the pressure is 0-5kPa; the theoretical plate number is 10-30; the reflux ratio of the top of the tower is 0.2-5. In the invention, the liquid phase temperature refers to the temperature of the aqueous solution of the crude anthracene alkylation catalyst at the tower bottom under a specific pressure; the gas phase temperature refers to the vaporization temperature of water at the same specific pressure.
In the present invention, the pressure parameters are all referred to as gauge pressure unless otherwise specified.
In some embodiments of the present invention, further preferably, in step (3), the conditions of the first reduced pressure distillation include: the liquid phase temperature is 55-80 ℃; the gas phase temperature is 40-60 ℃; the pressure is 1-3kPa; the theoretical plate number is 15-25; the reflux ratio of the top of the tower is 0.4-3.
In the present invention, the second reduced pressure distillation is performed in a second reduced pressure distillation column, and impurities containing almost no catalyst, for example, black solid pot residues are obtained at the bottom of the column; the recovered anthracene alkylation catalyst of high purity is obtained at the top of the column.
In some embodiments of the present invention, preferably, in step (3), the second reduced pressure distillation process includes: and carrying out the second reduced pressure distillation on the crude anthracene alkylation catalyst to obtain the recovered anthracene alkylation catalyst and impurities with the catalyst content less than or equal to 5 wt%.
In some embodiments of the present invention, preferably, in step (3), the conditions of the second reduced pressure distillation include: the liquid phase temperature is 150-300 ℃; the gas phase temperature is 100-200 ℃; the pressure is 0.1-4kPa; the theoretical plate number is 30-50; the reflux ratio of the top of the tower is 0.1-4. In the invention, the liquid phase temperature is the temperature of the crude anthracene alkylation catalyst at a specific pressure; the gas phase temperature is the vaporization temperature of the anthracene alkylation catalyst at the same specific pressure.
In some embodiments of the present invention, further preferably, in step (3), the conditions of the second reduced pressure distillation include: the liquid phase temperature is 180-280 ℃; the gas phase temperature is 130-180 ℃; the pressure is 0.5-2kPa; the theoretical plate number is 35-45; the reflux ratio of the top of the tower is 0.2-2.
In a second aspect, the present invention provides an apparatus for separating and recovering an anthracene alkylation catalyst, the apparatus comprising: the extraction unit, the membrane distillation unit and the reduced pressure distillation unit are sequentially communicated;
the extraction unit is used for mixing and extracting the acid oil mixture containing the anthracene alkylation catalyst with water to obtain an aqueous solution containing the anthracene alkylation catalyst;
The membrane distillation unit is used for carrying out membrane distillation on the anthracene-containing alkylation catalyst aqueous solution to obtain a concentrated anthracene alkylation catalyst aqueous solution with the concentration of more than or equal to 22 wt%;
The reduced pressure distillation unit comprises a first reduced pressure distillation tower and a second reduced pressure distillation tower which are sequentially communicated, and is used for sequentially carrying out first reduced pressure distillation and second reduced pressure distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain recovered anthracene alkylation catalyst with purity of more than or equal to 98wt%.
In the present invention, the kinds of the extraction units including, but not limited to, a mixing tank and an extraction tower have a wide selection range.
In the invention, the membrane distillation unit has a wider selection range, and is a membrane distillation device.
In some embodiments of the present invention, preferably, the first reduced pressure distillation column is used to subject the concentrated aqueous alkylation catalyst solution to a first reduced pressure distillation to obtain a crude anthracene alkylation catalyst having a water content of less than or equal to 1wt% and a moisture content of less than or equal to 0.1wt% of the catalyst; the second reduced pressure distillation tower is used for carrying out second reduced pressure distillation on the crude anthracene alkylation catalyst to obtain recovered anthracene alkylation catalyst with purity of more than or equal to 98wt% and impurities with catalyst content of less than or equal to 5wt%.
The invention provides a schematic diagram of an apparatus for separating and recovering anthracene alkylation catalyst, as shown in fig. 1, comprising: the extraction unit I, the membrane distillation unit II, the first reduced pressure distillation tower III-1 and the second reduced pressure distillation tower III-2 are sequentially communicated;
The extraction unit I is used for mixing and extracting the acid oil mixture 1 containing the anthracene alkylation catalyst and water 2, and the obtained anthracene alkylation catalyst-containing aqueous solution 3 is used as an extraction phase and the acid-containing oil-soluble oil phase 4 is used as a raffinate phase;
wherein the membrane distillation unit II is used for carrying out membrane distillation on the anthracene-containing alkylation catalyst aqueous solution 3 to obtain a concentrated anthracene alkylation catalyst aqueous solution 5 with the concentration of more than or equal to 22 wt%;
Wherein the first reduced pressure distillation tower III-1 is used for carrying out first reduced pressure distillation on the concentrated alkylation catalyst aqueous solution 5 to obtain a crude anthracene alkylation catalyst 6 with the water content less than or equal to 1wt% and water 7 with the catalyst content less than or equal to 0.1 wt%;
Wherein the second reduced pressure distillation tower III-2 is used for carrying out second reduced pressure distillation on the crude anthracene alkylation catalyst 6 to obtain recovered anthracene alkylation catalyst 8 with purity of more than or equal to 98wt% and impurity 9 with catalyst content of less than or equal to 5wt%.
According to a particularly preferred embodiment of the present invention, a process for the separation and recovery of an anthracene alkylation catalyst, the process comprising:
(1) Extracting an acid oil mixture containing an anthracene alkylation catalyst with water to obtain an aqueous solution containing the anthracene alkylation catalyst;
(2) Performing membrane distillation on the anthracene-containing alkylation catalyst aqueous solution to obtain a concentrated anthracene alkylation catalyst aqueous solution with the concentration of more than or equal to 22 wt%;
(3) Performing first reduced pressure distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain a crude anthracene alkylation catalyst with the water content less than or equal to 1wt% and water with the catalyst content less than or equal to 0.1 wt%; performing second reduced pressure distillation on the crude anthracene alkylation catalyst to obtain recovered anthracene alkylation catalyst with purity of more than or equal to 98wt% and impurities with catalyst content of less than or equal to 5 wt%;
wherein; the weight ratio of the acid oil mixture to water calculated by the anthracene alkylation catalyst is 1:5-10.
The present invention will be described in detail by examples.
The concentration of the anthracene alkylation catalyst (methane sulfonic acid) in the acid-oil mixture containing anthracene alkylation catalyst (acid-oil mixture A1 for short) was 88.6wt%;
The concentration of the anthracene alkylation catalyst (perfluoroethane sulfonic acid) in the acid oil mixture containing anthracene alkylation catalyst (acid oil mixture A2 for short) was 92.4wt%.
Example 1
(1) Acid oil mixture A1 calculated by anthracene alkylation catalyst and water are mixed according to the weight ratio of 1:10 (the temperature is 30 ℃ C., the time is 0.3 h) and extracted (the temperature is 30 ℃ C., the time is 0.5 h), and 1kg of aqueous solution containing anthracene alkylation catalyst with the concentration of 9.09wt% is obtained;
(2) Performing membrane distillation on the anthracene-containing alkylation catalyst aqueous solution by adopting a direct contact membrane distillation method, wherein a flat plate type PTFE membrane with the aperture of 0.22 mu m is used for performing membrane distillation, the feeding temperature is 60 ℃, the feeding flow rate is 0.2L/min, the membrane inlet side pressure is 0MPa, the membrane permeation side pressure is-0.1 MPa, the permeation side liquid is condensed by liquid nitrogen at the temperature of 6 ℃, the average membrane permeation flux is 0.8L.m -2·h-1, the separation time is 5 hours, and the concentrated anthracene alkylation catalyst aqueous solution with the concentration of 22.5wt% is obtained;
(3) Subjecting the concentrated aqueous alkylation catalyst solution to a first reduced pressure distillation (liquid phase temperature: 78 ℃ C., vapor phase temperature: 58 ℃ C., distillation pressure: 3kPa, theoretical plate number: 18, overhead reflux ratio: 2) to obtain a crude anthracene alkylation catalyst having a water content of 0.8% by weight and a water content of 0.01% by weight;
Performing second reduced pressure distillation (liquid phase temperature is 217 ℃, gas phase temperature is 178 ℃, distillation pressure is 2kPa, theoretical plate number is 35, tower top reflux ratio is 1) on the crude anthracene alkylation catalyst to obtain a recovered anthracene alkylation catalyst S1;
wherein the purity of the recovered anthracene alkylation catalyst S1 was 99.6wt%, and the yield was 90.3%.
Comparative example 1
In the same manner as in example 1 except that in step (2), the above-mentioned anthracene-containing alkylation catalyst aqueous solution was subjected to reduced pressure distillation (liquid phase temperature: 78 ℃ C., gas phase temperature: 58 ℃ C., distillation pressure: 3kPa, theoretical plate number: 18 pieces, overhead reflux ratio: 2), to obtain a concentrated anthracene alkylation catalyst aqueous solution having a concentration of 22.5% by weight.
The energy consumption of the concentrated anthracene alkylation catalyst aqueous solution obtained in example 1 was 1452kJ by membrane distillation, which is the same concentration as that obtained in comparative example 1, compared to 4357kJ by reduced pressure distillation, i.e., the energy consumption of example 1 was 33.3% of that of comparative example 1. Therefore, the method provided by the invention can more effectively reduce the energy consumption on the premise of ensuring that the recovered anthracene alkylation catalyst has high purity and high yield.
Example 2
(1) Acid oil mixture A1 calculated by anthracene alkylation catalyst and water are mixed according to the weight ratio of 1:9 (the temperature is 40 ℃ C., the time is 0.4 h) and extracted (the temperature is 40 ℃ C., the time is 0.6 h), and 1kg of aqueous solution containing anthracene alkylation catalyst with the concentration of 10wt% is obtained;
(2) Performing membrane distillation on the anthracene-containing alkylation catalyst aqueous solution by adopting a direct contact membrane distillation method, wherein a flat plate type PTFE membrane with the aperture of 0.45 mu m is used for performing membrane distillation, the feeding temperature is 60 ℃, the feeding flow rate is 0.2L/min, the membrane inlet side pressure is 0MPa, the membrane permeation side pressure is-0.1 MPa, the permeation side liquid is condensed by liquid nitrogen at the temperature of 5 ℃, the average membrane permeation flux is 1.2 L.m -2·h-1, the separation time is 5 hours, and the concentrated anthracene alkylation catalyst aqueous solution with the concentration of 28.6wt% is obtained;
(3) Subjecting the concentrated aqueous alkylation catalyst solution to a first reduced pressure distillation (liquid phase temperature: 71 ℃ C., vapor phase temperature: 53 ℃ C., distillation pressure: 2.5kPa, theoretical plate number: 18, overhead reflux ratio: 2) to obtain a crude anthracene alkylation catalyst having a water content of 0.6% by weight and a water content of 0.02% by weight;
Subjecting the crude anthracene alkylation catalyst to second reduced pressure distillation (liquid phase temperature is 202 ℃, gas phase temperature is 169 ℃, distillation pressure is 1.8kPa, theoretical plate number is 35, and overhead reflux ratio is 1) to obtain a recovered anthracene alkylation catalyst S2;
Wherein the purity of the recovered anthracene alkylation catalyst S2 was 99.5wt%, and the yield was 91.5%.
Comparative example 2
According to example 2, except that in step (2), the above-mentioned anthracene-containing alkylation catalyst aqueous solution was subjected to reduced pressure distillation (liquid phase temperature: 71 ℃ C., gas phase temperature: 53 ℃ C., distillation pressure: 2.5kPa, theoretical plate number: 18 pieces, overhead reflux ratio: 1.8), to obtain a concentrated anthracene alkylation catalyst aqueous solution having a concentration of 28.6% by weight.
The energy consumption of example 2 was 1662kJ, which is 35.7% of the energy consumption of comparative example 2, compared to the energy consumption of comparative example 2 by distillation under reduced pressure, which was 4654kJ, and the energy consumption of example 2 by membrane distillation, which gave the concentrated anthracene alkylation catalyst aqueous solution of the same concentration. Therefore, the method provided by the invention can more effectively reduce the energy consumption on the premise of ensuring that the recovered anthracene alkylation catalyst has high purity and high yield.
Example 3
(1) Acid oil mixture A1 calculated by anthracene alkylation catalyst and water are mixed according to the weight ratio of 1:8 (the temperature is 50 ℃ C., the time is 0.5 h) and extracted (the temperature is 50 ℃ C., the time is 0.7 h), and 1kg of water solution containing anthracene alkylation catalyst with the concentration of 11.11wt% is obtained;
(2) Performing membrane distillation on the anthracene-containing alkylation catalyst aqueous solution by adopting a direct contact membrane distillation method, wherein a flat plate type PTFE membrane with the aperture of 0.22 mu m is used for performing membrane distillation, the feeding temperature is 70 ℃, the feeding flow rate is 0.2L/min, the membrane inlet side pressure is 0MPa, the membrane permeation side pressure is-0.1 MPa, the permeation side liquid is condensed by liquid nitrogen at the temperature of 3 ℃, the membrane average permeation flux is 0.83 L.m -2·h-1, the separation time is 5 hours, and the concentrated anthracene alkylation catalyst aqueous solution with the concentration of 23.1wt% is obtained;
(3) Subjecting the concentrated aqueous alkylation catalyst solution to a first reduced pressure distillation (liquid phase temperature: 64 ℃ C., gas phase temperature: 48 ℃ C., distillation pressure: 2kPa, theoretical plate number: 18, overhead reflux ratio: 2) to obtain a crude anthracene alkylation catalyst having a water content of 0.5% by weight and a water content of 0.04% by weight;
Subjecting the crude anthracene alkylation catalyst to second reduced pressure distillation (liquid phase temperature is 194 ℃, gas phase temperature is 161 ℃, distillation pressure is 1.5kPa, theoretical plate number is 35, and overhead reflux ratio is 1) to obtain recovered anthracene alkylation catalyst S3;
wherein the purity of the recovered anthracene alkylation catalyst S3 was 99.3wt%, and the yield was 92.2%.
Comparative example 3
According to example 3, except that in step (2), the above-mentioned anthracene-containing alkylation catalyst aqueous solution was subjected to reduced pressure distillation (liquid phase temperature: 64 ℃ C., gas phase temperature: 48 ℃ C., distillation pressure: 2kPa, theoretical plate number: 18 pieces, overhead reflux ratio: 1.5), to obtain a concentrated anthracene alkylation catalyst aqueous solution having a concentration of 23.1% by weight.
The energy consumption by distillation under reduced pressure was 3695kJ compared with comparative example 3, and the energy consumption by membrane distillation for example 3 to obtain a concentrated anthracene alkylation catalyst aqueous solution of the same concentration was 1478kJ, i.e., the energy consumption for example 3 was 40% of that for comparative example 3. Therefore, the method provided by the invention can more effectively reduce the energy consumption on the premise of ensuring that the recovered anthracene alkylation catalyst has high purity and high yield.
Example 4
(1) Acid oil mixture A1 calculated by anthracene alkylation catalyst and water are mixed according to the weight ratio of 1:7 (the temperature is 60 ℃ C., the time is 0.6 h) and extracted (the temperature is 60 ℃ C., the time is 0.8 h), and 1kg of aqueous solution containing anthracene alkylation catalyst with the concentration of 12.5wt% is obtained;
(2) Performing air gap membrane distillation on the anthracene-containing alkylation catalyst aqueous solution, and performing membrane distillation on a flat plate type PTFE membrane with the aperture of 0.22 mu m, wherein the feeding temperature is 60 ℃, the feeding flow rate is 0.2L/min, the membrane inlet side pressure is 0MPa, the membrane permeation side pressure is-0.1 MPa, the permeation side liquid is condensed by liquid nitrogen at 8 ℃, the average permeation flux of the membrane is 0.65 L.m -2·h-1, the separation time is 5 hours, and the concentrated anthracene alkylation catalyst aqueous solution with the concentration of 30.2wt% is obtained;
(3) Subjecting the concentrated aqueous alkylation catalyst solution to a first reduced pressure distillation (liquid phase temperature: 58 ℃ C., gas phase temperature: 45 ℃ C., distillation pressure: 1.5kPa, theoretical plate number: 18, overhead reflux ratio: 2) to obtain a crude anthracene alkylation catalyst having a water content of 0.2% by weight and a water content of 0.05% by weight;
Subjecting the crude anthracene alkylation catalyst to second reduced pressure distillation (liquid phase temperature is 189 ℃, gas phase temperature is 157 ℃, distillation pressure is 1.2kPa, theoretical plate number is 35, overhead reflux ratio is 1), to obtain recovered anthracene alkylation catalyst S4;
wherein the purity of the recovered anthracene alkylation catalyst S4 was 99.1wt%, and the yield was 93.4%.
Comparative example 4
According to example 4, except that in step (2), the above-mentioned anthracene-containing alkylation catalyst aqueous solution was subjected to reduced pressure distillation (liquid phase temperature: 58 ℃ C., gas phase temperature: 45 ℃ C., distillation pressure: 1.5kPa, theoretical plate number: 18 pieces, overhead reflux ratio: 1.2), to obtain a concentrated anthracene alkylation catalyst aqueous solution having a concentration of 30.2% by weight.
The energy consumption by distillation under reduced pressure was 3747kJ compared to comparative example 4, and the energy consumption by membrane distillation for example 4 to obtain a concentrated anthracene alkylation catalyst aqueous solution of the same concentration was 1703kJ, i.e., the energy consumption for example 4 was 45.4% of that for comparative example 4. Therefore, the method provided by the invention can more effectively reduce the energy consumption on the premise of ensuring that the recovered anthracene alkylation catalyst has high purity and high yield.
Example 5
The procedure of example 1 was followed except that in step (1), acid oil mixture A1 was replaced with acid oil mixture A2, and the remaining conditions were the same, to obtain recovered anthracene alkylation catalyst S5;
Wherein the purity of the recovered anthracene alkylation catalyst S5 was 99.2wt%, and the yield was 91.8%.
Example 6
The procedure of example 1 was followed except that in step (1), the weight ratio of the acid oil mixture A1 to water based on the anthracene alkylation catalyst was replaced with 1:4, and the other conditions were the same, to obtain a recovered anthracene alkylation catalyst S6;
Wherein the purity of the recovered anthracene alkylation catalyst S6 was 98.2wt%, and the yield was 95.4%.
Example 7
The procedure of example 1 was followed except that in step (2), the conditions of the membrane distillation were replaced with: the feed temperature is 35 ℃, the feed flow rate is 0.1L/min, the membrane inlet side pressure is 0MPa, the membrane permeation side pressure is-0.1 MPa, permeation side liquid is condensed by liquid nitrogen at 0 ℃, the average permeation flux of the membrane is 0.45 L.m -2·h-1, the separation time is 5h, and the rest conditions are the same, so as to obtain the recovered anthracene alkylation catalyst S7;
Wherein the purity of the recovered anthracene alkylation catalyst S7 was 99.5wt%, and the yield was 90.6%.
Comparative example 1
The acid oil mixture A1 was directly subjected to reduced pressure distillation (liquid phase temperature: 189 ℃ C., gas phase temperature: 175 ℃ C., distillation pressure: 1kPa, overhead reflux ratio: 1), methane sulfonic acid was not collected at the top of the column, and a dark green liquid having a malodorous taste and insoluble in water was obtained, which proved that the methane sulfonic acid catalyst could not be recovered by the single reduced pressure distillation method.
Comparative example 2
The procedure of example 1 was followed except that step (3) was not carried out, i.e., the concentrated aqueous anthracene alkylation catalyst solution obtained in step (2) was used as recovered anthracene alkylation catalyst DS2;
Wherein the purity of the recovered anthracene alkylation catalyst DS2 was 22.5wt%, and the yield was 90.5%.
Comparative example 3
The procedure of example 1 was followed except that there was no second reduced pressure distillation, i.e., the crude anthracene alkylation catalyst was directly used as recovered anthracene alkylation catalyst DS3;
wherein the purity of the recovered anthracene alkylation catalyst DS3 was 95.8wt% and the yield was 95.3%.
Comparative example 4
According to the method of example 1, except that the concentrated aqueous alkylation catalyst solution was directly subjected to reduced pressure distillation (liquid phase temperature: 217 ℃ C., gas phase temperature: 178 ℃ C., distillation pressure: 2kPa, theoretical plate number: 35 pieces, overhead reflux ratio: 1) without first reduced pressure distillation, the remaining conditions were the same, and no recovered anthracene alkylation catalyst was obtained; since the concentrated aqueous alkylation catalyst solution is distilled directly, this is equivalent to no distillation because the water and catalyst are mixed together.
Compared with comparative examples 1-4, the recovered anthracene alkylation catalyst prepared by the method provided by the invention has higher purity and yield, wherein the purity of the recovered anthracene alkylation catalyst is more than or equal to 98wt%, and the yield is more than or equal to 90%. In comparison with comparative examples 3 to 4, example 1 enables recovery of anthracene alkylation catalyst with high purity and high yield by regulating the scheme of reduced pressure distillation including first reduced pressure distillation and second reduced pressure distillation.
Compared with example 5, example 1 is more beneficial to improving the purity of the recovered anthracene alkylation catalyst by regulating the concentration of the anthracene alkylation catalyst in the acid oil mixture within a preferred protection range. It is seen from examples 1 and 5 that the different concentration levels of the anthracene alkylation catalyst in the acid oil mixture have little effect on the purity and yield of the recovered anthracene alkylation catalyst.
Compared with example 6, example 1 is more advantageous in improving the purity of recovered anthracene alkylation catalyst by controlling the weight ratio of acid oil mixture and water to anthracene alkylation catalyst within the preferred protective range.
Compared with example 7, example 1 is more advantageous in improving the purity of the recovered anthracene alkylation catalyst by adjusting the conditions of electrodialysis to a scheme within the preferred protective range.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method for separating and recovering an anthracene alkylation catalyst, the method comprising the steps of:
(1) Extracting an acid oil mixture containing an anthracene alkylation catalyst to obtain an aqueous solution containing the anthracene alkylation catalyst;
(2) Performing membrane distillation on the anthracene-containing alkylation catalyst aqueous solution to obtain a concentrated anthracene alkylation catalyst aqueous solution with the concentration of more than or equal to 22 wt%;
(3) And (3) sequentially carrying out first reduced pressure distillation and second reduced pressure distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain the recovered anthracene alkylation catalyst with the purity of more than or equal to 98 wt%.
2. The process according to claim 1, wherein in step (1) the concentration of anthracene alkylation catalyst in the acid oil mixture is 80-95wt%, preferably 85-90wt%;
Preferably, the anthracene alkylation catalyst is selected from liquid acid catalysts, preferably from C 1-C5 alkylsulfonic acids and/or C 1-C5 perfluoro substituted alkylsulfonic acids;
Further preferably, the anthracene 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.
3. The method according to claim 1 or 2, wherein in step (1), the process of extraction comprises: mixing the acid oil mixture containing the anthracene alkylation catalyst with water and performing the extraction;
Preferably, the weight ratio of the acid oil mixture to water, calculated as anthracene alkylation catalyst, is 1:2-20, preferably 1:5-10;
preferably, the mixing conditions include: the temperature is 20-100deg.C, preferably 40-80deg.C; the time is 0.1-1h, preferably 0.25-0.8h;
Preferably, the conditions of the extraction include: the temperature is 20-100deg.C, preferably 40-80deg.C; the time is 0.1-3h, preferably 0.5-2h.
4. A process according to any one of claims 1 to 3, wherein in step (2), the conditions of the membrane distillation comprise: the feed liquid feeding temperature is 30-80 ℃, the feed flow rate is 0.1-2L/min, the membrane inlet side pressure is 0-0.2MPa, the membrane permeation side pressure is-0.1-0.06 MPa, the temperature of the cooling liquid at the membrane permeation side is 0-10 ℃, the average membrane permeation flux is 0.5-2 L.m -2·h-1, and the separation time is 3-20h;
Preferably, the conditions of the membrane distillation include: the feed temperature of the feed liquid is 40-70 ℃, the feed flow rate is 0.5-1.5L/min, the membrane inlet side pressure is 0.05-0.1MPa, the membrane permeation side pressure is-0.1-0.08 MPa, the temperature of the cooling liquid at the membrane permeation side is 2-8 ℃, the average permeation flux of the membrane is 0.7-1.5 L.m -2·h-1, and the separation time is 7-15h;
And/or the membrane permeate side cooling liquid is selected from circulating condensed water and/or liquid nitrogen.
5. The process according to any one of claims 1-4, wherein in step (2), the membrane distillation is selected from direct contact membrane distillation or air gap membrane distillation;
preferably, the membrane material of the membrane distillation is selected from at least one of polytetrafluoroethylene, polyvinylidene fluoride and polypropylene;
Preferably, the membrane pore size of the membrane distillation is less than or equal to 1 μm, preferably 0.1-1 μm;
preferably, the membrane of the membrane distillation is selected from the group consisting of flat plate type and hollow fiber type.
6. The method according to any one of claims 1 to 5, wherein in step (3), the first reduced pressure distillation process comprises: and carrying out the first reduced pressure distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain a crude anthracene alkylation catalyst with the water content less than or equal to 1wt% and water with the catalyst content less than or equal to 0.1 wt%.
7. The method according to any one of claims 1 to 6, wherein in step (3), the conditions of the first reduced pressure distillation include: the liquid phase temperature is 50-100 ℃; the gas phase temperature is 25-75 ℃; the pressure is 0-5kPa; the theoretical plate number is 10-30; the reflux ratio of the tower top is 0.2-5;
Preferably, the conditions of the first reduced pressure distillation include: the liquid phase temperature is 55-80 ℃; the gas phase temperature is 40-60 ℃; the pressure is 1-3kPa; the theoretical plate number is 15-25; the reflux ratio of the top of the tower is 0.4-3.
8. The method according to any one of claims 1 to 7, wherein in step (3), the second reduced pressure distillation process comprises: and carrying out the second reduced pressure distillation on the crude anthracene alkylation catalyst to obtain the recovered anthracene alkylation catalyst and impurities with the catalyst content less than or equal to 5 wt%.
9. The method according to any one of claims 1 to 8, wherein in step (3), the conditions of the second reduced pressure distillation include: the liquid phase temperature is 150-300 ℃; the gas phase temperature is 100-200 ℃; the pressure is 0.1-4kPa; the theoretical plate number is 30-50; the reflux ratio of the tower top is 0.1-4;
Preferably, the conditions of the second reduced pressure distillation include: the liquid phase temperature is 180-280 ℃; the gas phase temperature is 130-180 ℃; the pressure is 0.5-2kPa; the theoretical plate number is 35-45; the reflux ratio of the top of the tower is 0.2-2.
10. An apparatus for separating and recovering an anthracene alkylation catalyst, the apparatus comprising: the extraction unit, the membrane distillation unit and the reduced pressure distillation unit are sequentially communicated;
the extraction unit is used for mixing and extracting the acid oil mixture containing the anthracene alkylation catalyst with water to obtain an aqueous solution containing the anthracene alkylation catalyst;
The membrane distillation unit is used for carrying out membrane distillation on the anthracene-containing alkylation catalyst aqueous solution to obtain a concentrated anthracene alkylation catalyst aqueous solution with the concentration of more than or equal to 22 wt%;
The reduced pressure distillation unit comprises a first reduced pressure distillation tower and a second reduced pressure distillation tower which are sequentially communicated, and is used for sequentially carrying out first reduced pressure distillation and second reduced pressure distillation on the concentrated anthracene alkylation catalyst aqueous solution to obtain recovered anthracene alkylation catalyst with purity of more than or equal to 98wt%.
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