CN114471704A - Preparation of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material and application of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material in removal of trace olefins in aromatic hydrocarbons - Google Patents
Preparation of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material and application of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material in removal of trace olefins in aromatic hydrocarbons Download PDFInfo
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- CN114471704A CN114471704A CN202011148635.8A CN202011148635A CN114471704A CN 114471704 A CN114471704 A CN 114471704A CN 202011148635 A CN202011148635 A CN 202011148635A CN 114471704 A CN114471704 A CN 114471704A
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- montmorillonite
- trifluoromethanesulfonic acid
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 63
- 239000002135 nanosheet Substances 0.000 title claims abstract description 43
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title abstract description 16
- 239000000463 material Substances 0.000 title description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000011973 solid acid Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000004927 clay Substances 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 2
- 239000011148 porous material Substances 0.000 claims 2
- 238000004299 exfoliation Methods 0.000 claims 1
- 239000013335 mesoporous material Substances 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 17
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000007848 Bronsted acid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- 238000005303 weighing Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
Abstract
The invention relates to a preparation method of a solid acid catalyst for removing trace olefin in aromatic hydrocarbon. The invention also provides a preparation method and application of the solid acid catalyst. In the invention, the montmorillonite nanosheet is used as a carrier to load the Bronsted acid trifluoromethanesulfonic acid, and the catalyst has excellent performance for removing trace olefins in mixed aromatic hydrocarbons, thereby improving the quality of oil products and reducing environmental pollution.
Description
Technical Field
The invention relates to a strong acid solid acid catalyst, in particular to a preparation method of a load trifluoromethanesulfonic acid material and application thereof in removing trace olefin in aromatic hydrocarbon. The strong-acid solid acid catalyst is prepared by taking montmorillonite nanosheets as a carrier and trifluoromethanesulfonic acid as an acid modifier by adopting an impregnation method.
Background
Aromatic hydrocarbons are used as important basic organic raw materials in chemical production, and the yield and the demand of the aromatic hydrocarbons are increased year by year. However, processes for producing mixed aromatics by naphtha reforming typically contain trace amounts of olefin impurities. These olefin impurities are easily polymerized to form colloids, which affects the quality of aromatic hydrocarbon products and also has adverse effects on subsequent processes, such as reducing the service effect and the service life of the adsorption separation agent in the adsorption separation tower, and therefore, measures must be taken to deeply remove these impurities.
The existing processes for removing olefin impurities in aromatic hydrocarbon mainly comprise a hydrofining process and a clay refining process.
(1) The hydrofining process is effective for removing olefin, but the process can cause partial aromatics to be hydrogenated and saturated, so that the loss of aromatics is caused, and the use range of the hydrofining process is greatly influenced by the danger coefficient of hydrogen storage and transportation.
(2) The clay refining process has simple operation, low production cost and high olefin removal rate, and is a suitable method for removing olefin impurities. But the catalyst has the problems of quick inactivation, short service cycle, no regeneration, frequent replacement, increased aromatic hydrocarbon loss, serious environmental pollution caused by a large amount of inactivated clay and the like.
In order to solve the contradiction, a solid acid catalyst which can effectively reduce the bromine index in the mixed aromatic hydrocarbon, has long service life and low pollutant emission in the preparation process needs to be designed and developed.
The montmorillonite nano-sheet prepared by stripping montmorillonite can increase the specific surface and improve the adsorption performance, and meanwhile, the modifier is used for acid modification to increase the acid sites on the clay surface, so that olefin is promoted to generate polymerization and alkylation reactions, and the generated high-boiling-point polymer is removed.
At present, no relevant report is found for the preparation of the montmorillonite nanosheet supported trifluoromethanesulfonic acid material.
Disclosure of Invention
The invention provides a strong acid solid catalyst montmorillonite nanosheet loaded trifluoromethanesulfonic acid.
The invention also aims to provide a preparation method of the catalyst.
The invention also provides the application of the catalyst.
In order to achieve the above object, the preparation method comprises the steps of:
(1) and preparing the montmorillonite nanosheet by adopting a gas phase stripping method.
(2) And (3) loading trifluoromethanesulfonic acid on the montmorillonite nanosheets by using water as a solvent and adopting an isometric impregnation method, drying and calcining to obtain the montmorillonite nanosheet loaded trifluoromethanesulfonic acid.
In the step (1), the preparation of the montmorillonite nanosheet specifically comprises the following operations: weighing 5g of montmorillonite, placing in a muffle furnace at 300 ℃ for 10min, pouring into liquid nitrogen for quenching, collecting montmorillonite after the liquid nitrogen volatilizes, and repeating the operation for 15 times. Dispersing the obtained montmorillonite powder in an ethanol solution, performing ultrasonic treatment for 0.5h, centrifuging at 2000 rpm for 5min, and evaporating the obtained supernatant to obtain montmorillonite nanosheets.
In the step (2), the montmorillonite nanosheets are immersed in 10-20 mL of 2-10% by mass trifluoromethanesulfonic acid solution, stirred for 3h, dried, and calcined to obtain 2-10% TfOH/MMTNS.
The montmorillonite nanosheet loaded trifluoromethanesulfonic acid is used for removing trace olefin in mixed aromatic hydrocarbon. The montmorillonite nanosheet loaded trifluoromethanesulfonic acid is used as a catalyst and reacts at 150 ℃ for 2h under normal pressure, and the olefin removal rate can be 86%.
The specific application method is as follows: adding a certain amount of mixed aromatic hydrocarbon and montmorillonite nanosheet loaded trifluoromethanesulfonic acid catalyst into a three-neck flask, stirring at a certain temperature for reaction, and absorbing supernatant after a certain time for bromine number determination. Wherein the reaction time is 2h, the reaction temperature is 150 ℃, and m (catalyst)/V (oil) is 1g:50 mL.
The invention provides a novel active solid acid catalyst montmorillonite nanosheet loaded trifluoromethanesulfonic acid, which has the advantages of large specific surface area, high olefin removal efficiency and simple preparation method.
The invention has the following advantages:
(1) the montmorillonite nanosheet prepared by the gas phase stripping method has the advantages of no pollution, high yield and the like.
(2) The supported trifluoromethanesulfonic acid material prepared by using trifluoromethanesulfonic acid as an acid modifier has excellent olefin removal performance.
Drawings
FIG. 1 shows N of montmorillonite nanosheets obtained in example 12Adsorption-desorption isotherm diagram;
FIG. 2 is a scanning electron micrograph and a high-resolution transmission electron micrograph of the montmorillonite nanosheet obtained in example 1;
FIG. 3 shows the removal efficiency of olefin in aromatic hydrocarbon by the montmorillonite nanosheet supported trifluoromethanesulfonic acid material obtained in example 1.
Detailed Description
The present invention is described by the following examples, but the present invention is not limited to the following examples, and variations and implementations are included in the technical scope of the present invention without departing from the spirit of the invention described above and below. The invention is further described with reference to the following drawings and specific embodiments.
Example 1
Weighing 5g of montmorillonite, placing in a muffle furnace at 300 ℃ for 10min, rapidly transferring to a beaker filled with liquid nitrogen for quenching, after the liquid nitrogen is completely volatilized, transferring the montmorillonite to the crucible again, and repeating the process for 15 times. Dispersing the obtained argil powder in an ethanol solution, performing ultrasonic treatment for 0.5h, centrifuging at the rotating speed of 2000rmp, transferring the upper-layer solution to a culture dish, and evaporating to dryness to obtain the montmorillonite nanosheet A. And soaking the obtained montmorillonite nano-sheet A in 10mL of 5% TfOH aqueous solution, stirring for 3h, evaporating to dryness, and calcining in a muffle furnace at 150 ℃ for 2h to obtain the montmorillonite nano-sheet loaded trifluoromethanesulfonic acid B.
The nitrogen desorption curve and the scanning-transmission electron microscope image of the solid acid catalyst sample obtained in example 1 are shown in fig. 1 to 2, respectively.
Wherein the nitrogen desorption curve and table 1 show that the catalyst prepared in example 1 falls within the type IV physical adsorption isotherm proposed by the International Union of Pure and Applied Chemistry (IUPAC). The specific surface of the montmorillonite nanosheet obtained by the gas phase stripping method is obviously increased.
TABLE 1
The scanning electron microscope and the transmission electron microscope illustrate that the montmorillonite nanosheet is successfully obtained, and the montmorillonite surface is slightly etched after the trifluoromethanesulfonic acid is loaded.
Pyridine red surface 2 shows that the acid sites are increased after the montmorillonite is sequentially subjected to gas phase stripping and acid modification.
TABLE 2
Example 2
Weighing 5g of montmorillonite, placing in a muffle furnace at 250 ℃ for 10min, rapidly transferring to a beaker filled with liquid nitrogen for quenching, after the liquid nitrogen is completely volatilized, transferring the montmorillonite to the crucible again, and repeating the process for 15 times. Dispersing the obtained argil powder in an ethanol solution, performing ultrasonic treatment for 0.5h, centrifuging at the rotating speed of 2000rmp, transferring the upper-layer solution to a culture dish, and evaporating to dryness to obtain montmorillonite nanosheets C.
Example 3
Weighing 5g of montmorillonite, placing in a muffle furnace at 300 ℃ for 10min, rapidly transferring to a beaker filled with liquid nitrogen for quenching, after the liquid nitrogen is completely volatilized, transferring the montmorillonite to the crucible again, and repeating the process for 15 times. Dispersing the obtained argil powder in an ethanol solution, performing ultrasonic treatment for 0.5h, centrifuging at the rotating speed of 2000rmp, transferring the upper-layer solution to a culture dish, and evaporating to dryness to obtain the montmorillonite nanosheet D.
Example 4
Weighing 5g of montmorillonite, placing in a muffle furnace at 300 ℃ for 10min, rapidly transferring to a beaker filled with liquid nitrogen for quenching, after the liquid nitrogen is completely volatilized, transferring the montmorillonite to the crucible again, and repeating the process for 10 times. Dispersing the obtained argil powder in an ethanol solution, performing ultrasonic treatment for 0.5h, centrifuging at the rotating speed of 2000rmp, transferring the upper-layer solution to a culture dish, and evaporating to dryness to obtain the montmorillonite nanosheet E.
Example 5
Weighing 5g of montmorillonite, placing in a muffle furnace at 300 ℃ for 10min, rapidly transferring to a beaker filled with liquid nitrogen for quenching, after the liquid nitrogen is completely volatilized, transferring the montmorillonite to the crucible again, and repeating the process for 20 times. Dispersing the obtained argil powder in an ethanol solution, performing ultrasonic treatment for 0.5h, centrifuging at the rotating speed of 2000rmp, transferring the upper-layer solution to a culture dish, and evaporating to dryness to obtain the montmorillonite nanosheet F.
Example 6
The montmorillonite nanosheet loaded trifluoromethanesulfonic acid obtained in example 1 is used for removing trace olefin in mixed aromatic hydrocarbon, and the specific process is as follows, 0.5g of TfOH/MMTNS and 25mL of mixed aromatic hydrocarbon are added into a three-neck flask with a reflux condenser pipe, and then heating and stirring reaction are carried out at 150 ℃. And after the reaction is finished, standing for layering, transferring an upper oil sample, and measuring the bromine index by using a bromine value meter.
Catalyst activity X ═ 100% of [ (feed oil bromine index-discharge oil bromine index)/feed oil bromine index ].
The bromine index of the raw oil is 1025mg Br/100g oil. The bromine index refers to the number of milligrams of elemental bromine consumed for saturating all unsaturated bonds in one hundred grams of oil sample in the unit of mg Br/100g of oil in the potentiometric titration process according to the standard of the petrochemical industry in China (SH/T0630-.
FIG. 3 shows the olefin removal performance of montmorillonite after gas phase stripping and acid modification treatment in sequence, and it can be seen from the figure that the olefin removal performance is gradually improved, because the adsorption and catalysis performance of the catalyst is improved due to the increase of the specific surface and the increase of the acid sites.
Claims (8)
1. A preparation method of montmorillonite nanosheet loaded trifluoromethanesulfonic acid is characterized by comprising the following steps:
1) firstly, preparing montmorillonite nanosheet MMTNS by adopting a gas-phase stripping method;
2) using water as a solvent, and loading a certain amount of trifluoromethanesulfonic acid (TfOH) on a montmorillonite nano-sheet by adopting an immersion method;
3) drying the product obtained in the step 2) in an oven, and then carrying out temperature programming in a muffle furnace to reach the calcining temperature, so as to obtain the montmorillonite nanosheet supported trifluoromethanesulfonic acid solid acid catalyst.
2. The method for preparing a montmorillonite nanosheet-supported trifluoromethanesulfonic acid as claimed in claim 1, wherein the operation of preparing a montmorillonite nanosheet by using a gas phase exfoliation method in step 1) is as follows: heating 5g of activated clay in a muffle furnace at 300 ℃ for several minutes, then quickly transferring the activated clay into a beaker filled with liquid nitrogen for quenching, after the liquid nitrogen is completely volatilized, transferring the activated clay into the crucible again, and repeating the process for 10-20 times. Dispersing the obtained clay powder in an ethanol solution, performing ultrasonic treatment for 0.5h, centrifuging at a rotating speed of 2000rmp, transferring the upper-layer solution to a culture dish, and evaporating to dryness to obtain the montmorillonite nanosheets.
3. The preparation method of montmorillonite nanosheet-supported trifluoromethanesulfonic acid as claimed in claim 1, wherein the loading of the immersion method supported trifluoromethanesulfonic acid in step 2) is 2-10%.
4. The method for preparing trifluoromethanesulfonic acid supported by montmorillonite nanosheets as claimed in claim 1, wherein the impregnation method in step 2) is carried out in an equal volume.
5. The preparation method of montmorillonite nanosheet-supported trifluoromethanesulfonic acid as claimed in claim 1, wherein the drying temperature in step 3) is 80-120 ℃.
6. The method for preparing trifluoromethanesulfonic acid loaded on montmorillonite nanosheets as claimed in claim 1, wherein the temperature programming and drying temperature in step 3) is 150 ℃ and is maintained for 2 hours.
7. A montmorillonite nanosheet supported trifluoromethanesulfonic acid catalyst, characterized by being prepared by the method of claims 1-6, and having a specific surface area of 299m2The mesoporous material has a mesoporous structure with a pore volume of 0.54-0.59 cm3(ii)/g, the pore diameter is 2.2 to 2.8 nm.
8. The application of the montmorillonite nanosheet supported trifluoromethanesulfonic acid catalyst of claims 1-7 in removal of trace olefins in mixed aromatics.
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| CN202011148635.8A CN114471704A (en) | 2020-10-23 | 2020-10-23 | Preparation of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material and application of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material in removal of trace olefins in aromatic hydrocarbons |
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| CN202011148635.8A CN114471704A (en) | 2020-10-23 | 2020-10-23 | Preparation of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material and application of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material in removal of trace olefins in aromatic hydrocarbons |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4795550A (en) * | 1987-04-03 | 1989-01-03 | Uop Inc. | Removal of trace olefins from aromatic hydrocarbons |
| US5171896A (en) * | 1992-03-05 | 1992-12-15 | Texaco Chemical Company | Alkylphenol synthesis using acid-modified inorganic clay catalysts |
| CN102324530A (en) * | 2011-08-29 | 2012-01-18 | 重庆大学 | Preparation method for proton exchange membrane fuel cell catalyst carrier |
| CN104646054A (en) * | 2013-11-19 | 2015-05-27 | 华东理工大学 | Solid acid catalyst supporting methane sulfonic acid, preparation method and application of same |
| CN105080592A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Aromatic olefin-reducing catalyst and use thereof |
| CN105327710A (en) * | 2015-12-04 | 2016-02-17 | 淮阴工学院 | Method for microwave synthesis of pillar type mesoporous activated clay olefin removal catalyst |
| CN105536875A (en) * | 2016-01-22 | 2016-05-04 | 张玲 | Preparation method of carclazyte catalyst of deolefin |
| CN110240172A (en) * | 2019-07-26 | 2019-09-17 | 沈阳工业大学 | A kind of method that gas phase removing prepares montmorillonite-based nano piece |
-
2020
- 2020-10-23 CN CN202011148635.8A patent/CN114471704A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4795550A (en) * | 1987-04-03 | 1989-01-03 | Uop Inc. | Removal of trace olefins from aromatic hydrocarbons |
| US5171896A (en) * | 1992-03-05 | 1992-12-15 | Texaco Chemical Company | Alkylphenol synthesis using acid-modified inorganic clay catalysts |
| CN102324530A (en) * | 2011-08-29 | 2012-01-18 | 重庆大学 | Preparation method for proton exchange membrane fuel cell catalyst carrier |
| CN104646054A (en) * | 2013-11-19 | 2015-05-27 | 华东理工大学 | Solid acid catalyst supporting methane sulfonic acid, preparation method and application of same |
| CN105080592A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Aromatic olefin-reducing catalyst and use thereof |
| CN105327710A (en) * | 2015-12-04 | 2016-02-17 | 淮阴工学院 | Method for microwave synthesis of pillar type mesoporous activated clay olefin removal catalyst |
| CN105536875A (en) * | 2016-01-22 | 2016-05-04 | 张玲 | Preparation method of carclazyte catalyst of deolefin |
| CN110240172A (en) * | 2019-07-26 | 2019-09-17 | 沈阳工业大学 | A kind of method that gas phase removing prepares montmorillonite-based nano piece |
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