CN111841635A - Lewis acid modified strong-acid cation exchange resin and preparation method thereof - Google Patents
Lewis acid modified strong-acid cation exchange resin and preparation method thereof Download PDFInfo
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- CN111841635A CN111841635A CN202010730396.0A CN202010730396A CN111841635A CN 111841635 A CN111841635 A CN 111841635A CN 202010730396 A CN202010730396 A CN 202010730396A CN 111841635 A CN111841635 A CN 111841635A
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- cation exchange
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- lewis acid
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 37
- 239000002253 acid Substances 0.000 title claims abstract description 31
- 239000002841 Lewis acid Substances 0.000 title claims abstract description 16
- 150000007517 lewis acids Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000011324 bead Substances 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- 238000010992 reflux Methods 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 abstract description 32
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract description 16
- 239000011347 resin Substances 0.000 abstract description 16
- 229920005989 resin Polymers 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 26
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006266 etherification reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000003930 superacid Substances 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polyoxymethylene dimethyl ether Polymers 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a Lewis acid modified strong acid cation exchange resin and a preparation method thereof, wherein the strong acid cation exchange resin, dichloroethane and anhydrous AlCl which are subjected to drying treatment are used3Sequentially adding the materials into a reactor, heating in a water bath under the stirring condition until the materials are refluxed, reacting for 2-8h, and cooling to room temperature; the material obtained after cooling is poured into water to hydrolyze the unreacted AlCl3Then carrying out suction filtration, ethanol washing, acetone washing, ether washing and vacuum drying treatment in sequence to obtain milky beads, namely Lewis acid modified strong-acid cation exchange resin. The resin obtained by the invention is a special resin catalyst for synthesizing polymethoxy dimethyl ether (DMMn), has higher loading capacity, simple preparation and easy separation, is water-proof, and has a tool for DMMn synthesis reactionHas better catalytic action and stable catalytic performance, and can be repeatedly used for at least 10 times.
Description
Technical Field
The invention relates to a modified strong-acid cation exchange resin and a preparation method thereof, in particular to a Lewis acid modified strong-acid cation exchange resin and a preparation method thereof, belonging to the technical field of resin catalysts.
Background
At present, with the speed of industrialization of polymethoxy dimethyl ether, the application of polymethoxy dimethyl ether in different fields is also the focus of research. As the application of the dimethyl ether as a diesel additive, the polyoxymethylene dimethyl ether is known as an environment-friendly diesel additive component due to excellent physicochemical properties of the dimethyl ether, DMMn can effectively improve the cetane number and oxygen content of diesel, effectively improve the combustion efficiency of the diesel, and greatly reduce the emission of pollutants such as engine tail gas particles, nitrogen oxides, hydrocarbon substances, carbon monoxide and the like, so that the emission reaches the national V emission standard; DMMn has higher boiling point, is not easy to volatilize, has lower average melting point and better low-temperature property, and can be suitable for areas with high altitude, cold, oxygen deficiency and the like; DMMn as a diesel additive can effectively improve the lubricating property of diesel, reduce the friction loss of an engine and is beneficial to prolonging the service life of the engine; DMMn has higher flash point and high safety performance, and special reconstruction of systems such as an engine, an oil tank and the like is not needed during use; DMMn is mainly synthesized by methanol, formaldehyde and derivatives thereof, can effectively relieve the problem of excess methanol production in China, and has the advantages of cheap and easily available raw materials and good economic benefit.
Since 1970, solid super acidic catalysts have been rapidly developed, and have been applied to many catalytic systems due to their special acidity and high catalytic activity, and because of their advantages of easy separation after use, easy recovery, and regeneration. There are two types of superacids commonly used at present: one is the sulfuric acid catalyst loaded by the composite of rare earth metal oxide and common metal oxide, and the other is the Lewis acid catalyst loaded by the polymer as the carrier.
In recent years, many studies have been made on lewis acid catalysts (AlCl3, BF3, SnCl4, TiCl4) which are supported by polystyrene, and although they have a good catalytic effect in organic synthesis, they have problems in loss of active species and in repeated use.
Currently, the use of AlCl3The research on preparing the super acid by the modified strong acid resin generally adopts a reaction system taking ethanol as a solvent, but the control of the reaction process is not facilitated due to violent heat release in the reaction feeding process; although reaction systems using carbon disulfide as a solvent are also available in such reactions, the solubility of aluminum trichloride is not good enough.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a Lewis acid modified strong-acid cation exchange resin and a preparation method thereof, the obtained resin is a special resin catalyst for synthesizing polymethoxy dimethyl ether (DMMn), the loading capacity is high, the preparation is simple, the separation is easy, the catalyst is water-proof, has good catalytic action on DMMn synthesis reaction, the catalytic performance is stable, and the catalyst can be repeatedly used for at least 10 times.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a Lewis acid modified strong-acid cation exchange resin comprises the following steps:
(1) drying strong acid cation exchange resin, dichloroethane, and anhydrous AlCl3Sequentially adding the materials into a reactor, heating in a water bath under the stirring condition until the materials are refluxed, reacting for 2-8h, and cooling to room temperature;
(2) pouring the material obtained after cooling in the step (1) into water to hydrolyze unreacted AlCl3Then carrying out suction filtration, ethanol washing, acetone washing, ether washing and vacuum drying treatment in sequence to obtain milky beads, namely Lewis acid modified strong-acid cation exchange resin.
In the above technical solution, in the step (1), the strong acid cation exchange resin is preferably a macroporous strong acid cation exchange resin, more preferably a macroporous strong acid polystyrene cation exchange resin, and still more preferably a D006 type resin catalyst produced by the kelvin environmental protection technologies gmbh.
In the above technical scheme, in the step (1), the strong acid cation exchange resin and the anhydrous AlCl are used3And the mass ratio of dichloroethane is (0.5-1.5): (0.5-1.5): (4-10), the mass ratio is preferably 1: 1: 6.
in the above technical scheme, in the step (1), the water bath is heated to reflux, and the reflux temperature is 60-90 ℃, preferably 80 ℃.
In the above technical scheme, in the step (1), the water bath is heated to reflux, and the reaction time is preferably 4-5h, and more preferably 4.5 h.
In the above technical scheme, in the step (2), the vacuum drying is performed at a temperature of 40-90 ℃, preferably 78 ℃.
In the above technical scheme, in the step (2), the vacuum drying is performed for 31-32h, preferably 30 h.
In the technical scheme, the Lewis acid modified strong-acid cation exchange resin contains 2.0-3.0 percent of aluminum (mass fraction).
In the above technical solution, the content of aluminum in the lewis acid modified strong acid cation exchange resin is preferably 2.78% (mass fraction). For example, under the conditions of the reaction temperature of 78 ℃, the reaction time of 6 hours in the step (1) and the drying time of 30 hours in the step (2), the aluminum content of the catalyst can reach 2.78% (mass fraction), and a PS-1 type echelle grating spectrometer is adopted for measuring the aluminum content in the catalyst; according to D006 resin with AlCl3The theoretical complexation amount of aluminum in the reaction can be calculated to be 5.4% by a reaction equation, but actually, because the resin has a framework and the aluminum trichloride solution is difficult to enter all micropores of the resin, the actual complexation rate is far lower than the theoretical complexation rate.
The invention also provides a Lewis acid modified strong-acid cation exchange resin which is prepared by the method.
The invention also provides application of the Lewis acid modified strong-acid cation exchange resin as a catalyst in the synthesis of polymethoxy dimethyl ether (DMMn).
On the basis of a large amount of experimental researches, the invention discovers that a reaction system which takes dichloroethane as a solvent is selected to prepare AlCl3The reaction process of preparing the super acidic catalyst by the modified strong acid resin is stable and has high load capacity. In the invention, macroporous strong-acid polystyrene cation exchange resin and AlCl3At CS2The catalyst is water-proof, has good catalytic action on DMMn synthesis reaction, has stable catalytic performance, and can be repeatedly used for at least 10 times.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:
the invention will now be illustrated with reference to specific examples:
example 1:
a preparation method of Lewis acid modified strong-acid cation exchange resin is prepared by the following steps:
(1) 20g of dried D006 type resin catalyst, 120 g of dichloroethane, 20g of anhydrous AlCl3Sequentially adding the materials into a reactor, heating in a water bath under the stirring condition until the materials are refluxed, reacting at the reflux temperature of 78 ℃ for 4.5 hours, and cooling to the room temperature;
(2) pouring the material obtained after cooling in the step (1) into water to hydrolyze unreacted AlCl3Then, the mixture is sequentially filtered, washed by ethanol, washed by acetone, washed by ether and dried in vacuum (60 ℃ and 30 hours) to obtain milk white beads, namely Lewis acid modified strong acid cation exchange resin.
After passing through a PS-1 echelle grating spectrometer, the aluminum content in the aluminum trichloride modified strong acid cation exchange resin obtained in this example was 2.78% (mass fraction).
Example 2:
a Lewis acid-modified strongly acidic cation exchange resin was prepared in the same manner as in example 1, except that in the step (1), 20g of the resin was passed through a drying sectionPhysical D006 type resin catalyst, 120 g dichloroethane, 16g anhydrous AlCl3Sequentially adding the mixture into a reactor for reaction. After passing through a PS-1 echelle grating spectrometer, the aluminum content in the aluminum trichloride modified strong acid cation exchange resin obtained in this example was 2.65% (mass fraction).
Example 3:
a Lewis acid-modified strongly acidic cation exchange resin was prepared in the same manner as in example 1, except that in the step (1), 20g of a dried D006 type resin catalyst, 140 g of dichloroethane, 20g of anhydrous AlCl3Sequentially adding the mixture into a reactor for reaction. After passing through a PS-1 echelle grating spectrometer, the aluminum content in the aluminum trichloride modified strong acid cation exchange resin obtained in this example was 2.80% (mass fraction).
The application example is as follows: taking etherification reaction as a research object to investigate the application effect of the catalyst
1. Batch reaction process
To a 250mL reaction vessel, 60 g of methylal, 30 g of trioxymethylene and 1.5 g of a catalyst (the Lewis acid-modified strongly acidic cation exchange resin obtained in example 1) were added, mixed, and then the mixture was charged into an autoclave. Reacting at 70 ℃ for 4 hours, stopping stirring and heating after the reaction is finished, and cooling to room temperature. The reaction product was taken out and weighed, and then centrifuged. And taking the supernatant, adding n-octane as an internal standard, taking acetone as a solvent, filtering the obtained solution through a microporous filter membrane, and performing ultrasonic degassing to obtain the solution to be detected. Quantitative analysis is carried out in SP3420 gas chromatography by adopting an internal standard method, and the conversion rate of trioxymethylene and the concentration and selectivity of each component in the product are calculated.
And (3) investigating catalytic activity: taking etherification reaction as a research object, and investigating the stability of repeated application of the catalyst. After each reaction, the filtered off milky catalyst was used in the next reaction without treatment, and the etherification yields were almost unchanged from 1 st 95%, 2 nd 94%, 4 th 94%, 6 th 3%, 8 th 93%, 10 th 93%. The result shows that the catalyst has better reusability, is repeatedly applied for at least 10 times and is a promising high-molecular catalyst.
And (3) stability investigation: the catalyst is applied to the etherification reaction of methylal and trioxymethylene, and has better catalytic reaction activity. Comparison of the amount of aluminum loaded before and after use of the catalyst: 2.54% before use and 2.50% after use. The reduction amount is 1.57% (the percentage of the reduction amount is (2.54-2.50) ÷ 2.54 × 100% ═ 1.57%), the change of the aluminum carrying amount before and after use is 1.0-3.0%, the result can meet the technical requirement of catalyst evaluation, and stability investigation proves that the catalyst of the invention is suitable for an etherification reaction system of methylal and trioxymethylene.
2. The continuous reaction process comprises the following steps:
the technical parameters of the continuous reaction process for preparing polymethoxy dimethyl ether (DMMn) by trioxymethylene and methylal are as follows:
(1) a mixer, a multi-stage fixed bed reactor and a finished product fractionating tower in a patent CN201811323228 are taken as reaction devices: wherein the mixer is provided with a feed inlet 14A, a discharge outlet 14C and a methylal inlet 14B; wherein: the feed port 14A is connected to a device capable of supplying trioxymethylene; the methylal inlet 14B is connected with a device capable of providing methylal;
the top of the multi-section fixed bed reactor is provided with a feeding reflux port 12A, the bottom of the multi-section fixed bed reactor is provided with a discharge port 12C, and the side wall of the multi-section fixed bed reactor is provided with a feeding port 12B; wherein: the feed inlet 12B is connected with a discharge outlet 14C of the mixer; the feeding reflux port 12A is divided into two paths, wherein one path is also connected with the discharge port 14C of the mixer, and the mixed materials are fed from the top and the side wall simultaneously, so that the full chemical reaction can be carried out in the fixed bed reactors of different sections in the multi-section fixed bed reactor; a reboiler II is arranged below the side wall of the multi-section fixed bed reactor;
the top of the finished product fractionating tower is provided with a gas phase outlet 13C, the bottom of the finished product fractionating tower is provided with a discharge hole 13D, a reflux port 13B is arranged above the side wall, a feed port 13A is arranged in the middle of the side wall, and a reboiler III is arranged below the side wall; wherein: the feed inlet 13A is connected with a discharge outlet 12C of the multi-section fixed bed reactor; the gas phase outlet 13C is sequentially connected with a condenser II, a condensing tank II and a reflux pump II; the outlet of the reflux pump II is divided into two paths, one path is connected with the reflux port 13B, and the other path is connected with the other path of the feeding reflux port 12A of the multi-section fixed bed reactor; the discharge port 13D is connected with a device for collecting or receiving the finished product DMM 3-8.
(2) The feeding mode is as follows: introducing high-purity trioxymethylene liquid into a mixer from a feeding hole 14A, and simultaneously introducing methylal with 3 times of mass into the mixer from a methylal inlet 14B, wherein the temperature during mixing is 25-35 ℃; trioxymethylene and methylal are fully mixed in a mixer to obtain a mixture, the mixture is led out from a discharge hole 14C, and is simultaneously led into the multi-section fixed bed reactor from a feeding reflux hole 12A at the top and a feeding hole 12B on the side wall;
(3) synthesizing DMMn: the mass space velocity of the mixture fed is 0.5h-1Under the catalytic action of a catalyst in a multi-section fixed bed reactor, DMMn is synthesized under the conditions that the reaction temperature is 60-70 ℃ and the pressure is 0.15-0.25Mpa, is led out through a discharge port 14C and is led into a finished product fractionating tower through a feed port 13A; wherein:
the number of fixed beds N in the multistage fixed bed reactor was 4, and the catalyst charged in each bed was the aluminum trichloride-modified strongly acidic cation exchange resin obtained in example 1.
(4) And (3) fractionation of a finished product: after entering a fractionating tower, the DMMn product obtained by the reaction is fractionated in a heating state of a reboiler III, and the fractionation conditions are as follows: the tower top temperature: 102 ℃; temperature at the bottom of the column: 150 ℃; operating pressure: 0.6 Mpa; the gas phase at the top of the tower is discharged from a gas phase outlet 13C, and is divided into two paths after sequentially passing through a condenser II, a condensing tank II and a reflux pump II: one path is refluxed into a finished product fractionating tower through a reflux port 13B, the reflux ratio is 0.3 (namely the reflux amount is 8.1 g), the other path is that the residual amount of the methylal after reaction is refluxed into a multi-section fixed bed reactor through a feed reflux port 12A to continue the reaction, and DMM is obtained at the bottom of the tower3-5The yield of the finished product reaches more than 98 percent, and the finished product is superior to unmodified D006 resin, and the purity of the finished product is nearly 100 percent.
Through the continuous investigation of the fixed bed reactor on the catalyst, the technical parameters of the etherification reaction process of the methylal and the trioxymethylene and the operation condition of the catalyst on a device are preliminarily obtained, and the catalyst is proved to be suitable for being used as an industrial catalyst and provides a theoretical basis for further process design.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A preparation method of a Lewis acid modified strong-acid cation exchange resin is characterized by comprising the following steps:
(1) drying strong acid cation exchange resin, dichloroethane, and anhydrous AlCl3Sequentially adding the materials into a reactor, heating in a water bath under the stirring condition until the materials are refluxed, reacting for 2-8h, and cooling to room temperature;
(2) pouring the material obtained after cooling in the step (1) into water to hydrolyze unreacted AlCl3Then carrying out suction filtration, ethanol washing, acetone washing, ether washing and vacuum drying treatment in sequence to obtain milky beads, namely Lewis acid modified strong-acid cation exchange resin.
2. The process according to claim 1, wherein in the step (1), the strongly acidic cation exchange resin is a macroporous strongly acidic cation exchange resin.
3. The method according to claim 1, wherein in step (1), the strong acid cation exchange resin and the anhydrous AlCl are used3And the mass ratio of dichloroethane is (0.5-1.5): (0.5-1.5): (4-10).
4. The method of claim 1, wherein in step (1), the water bath is heated to reflux at a temperature of 60-90 ℃.
5. The method according to claim 1, wherein in step (1), the water bath is heated to reflux for 4-5 h.
6. The method according to claim 1, wherein in the step (2), the vacuum drying is carried out at a temperature of 40 to 90 ℃.
7. The method according to claim 1, wherein in the step (2), the vacuum drying is performed for 31 to 32 hours.
8. The process according to claim 1, wherein the Lewis acid-modified strongly acidic cation exchange resin has an aluminum content of 2.0 to 3.0%.
9. The method according to claim 8, wherein the Lewis acid-modified strongly acidic cation exchange resin preferably contains 2.78% of aluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010730396.0A CN111841635A (en) | 2020-07-27 | 2020-07-27 | Lewis acid modified strong-acid cation exchange resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010730396.0A CN111841635A (en) | 2020-07-27 | 2020-07-27 | Lewis acid modified strong-acid cation exchange resin and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113398991A (en) * | 2021-05-26 | 2021-09-17 | 华东理工大学 | Preparation method and application of hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst |
| CN114394900A (en) * | 2022-01-19 | 2022-04-26 | 山东瑞博龙化工科技股份有限公司 | Preparation method of dicyclopentadiene oxyethyl (meth) acrylate |
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| CA2027664A1 (en) * | 1989-11-13 | 1991-05-14 | John F. Knifton | Systhesis of low molecular weight glycol ethers from oxiranes plus olefins |
| JPH06256476A (en) * | 1993-03-01 | 1994-09-13 | Nippon Zeon Co Ltd | Modified resin and its hydrogenation product |
| CN102320970A (en) * | 2011-06-10 | 2012-01-18 | 四川大学 | With the modified cation-exchange resin is the method for Preparation of Catalyst tributyl citrate |
| CN103506171A (en) * | 2012-06-15 | 2014-01-15 | 华东理工大学 | Modified acidic cation exchange resin and applications thereof |
| CN105833904A (en) * | 2016-04-12 | 2016-08-10 | 沈阳化工大学 | A modifying method of a sulfonic acid resin catalyst for polyoxymethylene dimethyl ethers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CA2027664A1 (en) * | 1989-11-13 | 1991-05-14 | John F. Knifton | Systhesis of low molecular weight glycol ethers from oxiranes plus olefins |
| JPH06256476A (en) * | 1993-03-01 | 1994-09-13 | Nippon Zeon Co Ltd | Modified resin and its hydrogenation product |
| CN102320970A (en) * | 2011-06-10 | 2012-01-18 | 四川大学 | With the modified cation-exchange resin is the method for Preparation of Catalyst tributyl citrate |
| CN103506171A (en) * | 2012-06-15 | 2014-01-15 | 华东理工大学 | Modified acidic cation exchange resin and applications thereof |
| CN105833904A (en) * | 2016-04-12 | 2016-08-10 | 沈阳化工大学 | A modifying method of a sulfonic acid resin catalyst for polyoxymethylene dimethyl ethers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113398991A (en) * | 2021-05-26 | 2021-09-17 | 华东理工大学 | Preparation method and application of hydrophobic zirconium-loaded strong-acid cation exchange resin catalyst |
| CN114394900A (en) * | 2022-01-19 | 2022-04-26 | 山东瑞博龙化工科技股份有限公司 | Preparation method of dicyclopentadiene oxyethyl (meth) acrylate |
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