CN104961632A - Method used for preparing p-ethylacetophenone via catalytic oxidation in presence of loaded molecular sieve - Google Patents
Method used for preparing p-ethylacetophenone via catalytic oxidation in presence of loaded molecular sieve Download PDFInfo
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- CN104961632A CN104961632A CN201510263598.8A CN201510263598A CN104961632A CN 104961632 A CN104961632 A CN 104961632A CN 201510263598 A CN201510263598 A CN 201510263598A CN 104961632 A CN104961632 A CN 104961632A
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- diethylbenzene
- ethylacetophenone
- reaction
- molecular sieve
- solvent
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- NODGRWCMFMEGJH-UHFFFAOYSA-N p-ethylacetophenone Chemical compound CCC1=CC=C(C(C)=O)C=C1 NODGRWCMFMEGJH-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title abstract description 5
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 claims abstract description 184
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 230000035484 reaction time Effects 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 43
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 27
- 229960000583 acetic acid Drugs 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 20
- 230000009466 transformation Effects 0.000 description 18
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- AFZZYIJIWUTJFO-UHFFFAOYSA-N 1,3-diethylbenzene Chemical compound CCC1=CC=CC(CC)=C1 AFZZYIJIWUTJFO-UHFFFAOYSA-N 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method used for preparing p-ethylacetophenone via catalytic oxidation in the presence of a loaded molecular sieve. According to the method, p-diethylbenzene is taken as a raw material, a metal-loaded molecular sieve is taken as a catalyst, an oxidizing agent, an auxiliary agent, and a solvent are added, and stirring reaction is carried out so as to obtain product p-ethylacetophenone, wherein reaction temperature is controlled to be 30 to 100 DEG C, and reaction time is controlled to be 10 to 180min. According to the method, synthesis of p-ethylacetophenone can be realized in relatively short reaction time under mild reaction conditions with high selectivity and high yield; separation of the product and the catalyst is convenient to realize; catalyst performance is stable; the method is green and friendly to the environment; operation is simple and convenient; energy consumption is low; economic benefit is high; and industrialized application prospect is promising.
Description
Technical field
The present invention relates to a kind of preparation method of p-ethylacetophenone, particularly relate to a kind of method that load molecular sieve catalyzed oxidation p-Diethylbenzene prepares p-ethylacetophenone, belong to chemical technique research field.
Background technology
P-ethylacetophenone is in recent years quite by the chemical that domestic and international chemical circles is paid attention to, except there is the general character of general alkylbenzene, because it contains ethanoyl, also have that functional group changes, the function of extensibility of structure, can with nucleophilic reagent generation addition reaction, nucleophilic substitution reaction; Can carry out addition or condensation reaction with alcohol, ammonia, acid amides, aldehyde etc., in medicine, liquid crystal and organic synthesis intermediate etc., tool has been widely used, and exploitation prospect is wide.The domestic large-scale device that there is no produces p-ethylacetophenone at present, and the main dependence on import of p-ethylacetophenone of industrial application, the p-ethylacetophenone synthesis technique of therefore developing green environmental protection, simple economy has huge market outlook.
Producing the traditional method of p-ethylacetophenone is by Friedel-Crafts acylation reaction, and adopt Lewis acid or strong protonic acid catalysis ethylbenzene and acetic anhydride or Acetyl Chloride 98Min. to obtain, common Friedel-Crafts acylation reaction catalyzer has AlCl
3, BF
3, TiCl
4, AlPO
4, SiO
2-AlCl
3the solid acid catalyst of mixture, zeolite-type molecular sieve and perfluorinated sulfonic resin etc.
Patent PL 15908181 discloses a kind of employing AlCl
3catalysis ethylbenzene and acetic anhydride prepare the method for p-ethylacetophenone.The method provided is typical Friedel-Crafts acylation reaction, catalyst A lCl
3be 2 with the mol ratio of acetic anhydride, temperature of reaction 5 ~ 10 DEG C, p-ethylacetophenone yield is 85%.Although the technique p-ethylacetophenone yield provided is higher, catalyst levels is large on the one hand, and is present in waste reaction solution with the form of ion, reclaims difficulty, and causes serious environmental pollution; A large amount of hydrogen chloride gas can be produced in reaction process on the other hand, require high to equipment erosion resistance, considerably increase investment operation cost, and there is potential safety hazard.
S.Sudha`S (Journal of Porous Materials; 2009,16 (2): 215-226) etc. people reports and adopts the synthesising mesoporous MCM-41 of hydrothermal crystallization method (silica alumina ratio is respectively 50 and 100) loaded metal ion (Fe, Al, Zn) to be applied to ethylbenzene alkylation and acylation reaction.Temperature of reaction 250 DEG C; ethylbenzene and ethyl acetate mol ratio are 1:3; reaction times 1h; catalyst A l-MCM-41 (silica alumina ratio is 100) shows best catalytic performance in the acylation reaction of ethylbenzene and ethyl acetate; now conversion of ethylbenzene is 40.2%, and p-ethylacetophenone selectivity is 44.6%.But under this technique p-ethylacetophenone selectivity and yield lower, and have multiple by product to exist, be unfavorable for product separation.And this technological reaction temperature is higher, energy consumption is comparatively large, and production cost is higher.
Patent CN 102267886A discloses a kind of method that catalysis of metalloporphyrin oxygen or air selective oxidation p-Diethylbenzene prepare p-ethylacetophenone.The method provided take p-Diethylbenzene as raw material, the metalloporphyrin of 1 ~ 100ppm is catalyzer, under normal pressure, condition of no solvent, oxygen or air is passed into the flow velocity of 30 ~ 60mL/min, at 150 ~ 160 DEG C, react 1 ~ 2h, gained reaction mixture obtains p-ethylacetophenone through underpressure distillation.P-Diethylbenzene transformation efficiency is 73.8%, and p-ethylacetophenone selectivity is 53.8%, yield is 39.7%.But the technological reaction temperature provided is higher, catalyst structure is complicated, porphyrin metal complexes is expensive, separation and recovery of catalyst cost is high, energy consumption large, complex process, three waste discharge are many, and conversion of ethylbenzene and p-ethylacetophenone yield lower, by product is more, for the separating-purifying of rear thread product is made troubles, production cost is improved greatly.
Kenneth K.Laali (Journal of the Chemical Society, Perkin Transactions 1,2001 (6): 578-583) etc. people reports the catalyzer Ce (OTf) adopting cerous carbonate and trifluoromethanesulfonic acid to prepare
4for p-Diethylbenzene oxidation and NSC 62102 oxidation.This technique is raw material with p-Diethylbenzene, take acetonitrile as solvent, at room temperature synthesizes p-ethylacetophenone.As Ce (OTf)
4be 2:1 with the mol ratio of p-Diethylbenzene, during reaction times 22h, the yield of p-ethylacetophenone is 45.6%; When mol ratio brings up to 4:1, when the reaction times is 25h, p-ethylacetophenone can bring up to 61.3%.But, catalyzer Ce (OTf)
4synthesis cost high, and its water content can affect greatly oxidation susceptibility, and the poisonous and highly volatile of the solvent acetonitrile of employing, has high risks to environment.The problems such as therefore this technique exists high pollution, high cost, the reaction times is long, efficiency is too low.
The people such as Peng M M (Arabian Journal of Chemistry, 2014) report and adopt solvent structure Ce-BTC for ethylbenzene oxidation methyl phenyl ketone.Catalyzer is the Ce-BTC of acicular structure, is typical I class poromerics, specific surface area 778.5m
2/ g, pore volume 0.3346m
3/ g.When temperature of reaction 160 DEG C, reaction times 6h, catalyzer Ce-BTC consumption 0.07g, conversion of ethylbenzene and methyl phenyl ketone selectivity are respectively 84.99% and 95.63%.Although this technique conversion of ethylbenzene and methyl phenyl ketone selectivity higher, temperature of reaction is higher, and the reaction times is longer, and the preparation method of catalyzer is comparatively complicated, and the stability of MOF material still requires study.
In sum, there is following problem in the synthetic method of current p-ethylacetophenone:
(1) method for preparing catalyst is complicated, and price is higher, uses that rear Separation and Recovery cost is higher, energy consumption is larger;
(2) organic solvent toxicity used is comparatively large, and highly volatile, direct exhaust emission environment, waste resource, it is comparatively large to there is solvent recuperation energy consumption in recycle, and recovery process is complicated, causes cost of investment and process cost greatly to increase;
(3) temperature of reaction is high, and energy consumption is too high, substantially increases equipment requirements and running cost, and there is potential safety hazard;
(4) reaction needed uses a large amount of acid or alkali, produces a large amount of brine waste, both wastes resource, again welding, and the existence of a large amount of soda acid also proposes higher requirement to the corrosion resistance nature of equipment;
(5) reaction times is long, and reaction efficiency is low, and oxidized byproduct increases.
Summary of the invention
The object of the invention is to the shortcoming overcoming existing technique, provide that a kind of catalyzer is easy to Separation and Recovery, the reaction times is short, temperature of reaction is low, product yield is high and the load molecular sieve catalyzed oxidation p-Diethylbenzene of environmental protection prepares the method for p-ethylacetophenone.
Object of the present invention is achieved through the following technical solutions: a kind of load molecular sieve catalyzed oxidation p-Diethylbenzene prepares the method for p-ethylacetophenone, the steps include: to take p-Diethylbenzene as raw material, with the molecular sieve of loaded metal for catalyzer, add oxygenant, auxiliary agent and solvent, stirring reaction, obtain product p-ethylacetophenone, wherein temperature of reaction is 30 ~ 100 DEG C, and the reaction times is 10 ~ 180min.
Preferred oxidant charging flow velocity is 5 ~ 360mL/h; The mol ratio of auxiliary agent and p-Diethylbenzene is 0 ~ 10 (namely also can not adding assistant), and more preferably the mol ratio of auxiliary agent and p-Diethylbenzene is 0.2 ~ 10; The volume ratio of solvent and p-Diethylbenzene is 1 ~ 20; Stirring velocity 100 ~ 600r/min.
Preferred catalyst adds quality and p-Diethylbenzene volume ratio is 0.01 ~ 1.0g/mL.
The quality purity of preferred feedstock p-Diethylbenzene is 80 ~ 99.9%.
The metallic element of preferred above-mentioned catalyst cupport is the transition metal of III B ~ II B; The carrier of loaded metal is a kind of molecular sieve in ZSM-5, MCM-41, SBA-15 or SAPO-5; Wherein the mass loading amount of metallic element is 5% ~ 20%.More preferably the metallic element of catalyst cupport is one or both in iron, nickel, manganese, copper or cobalt.
Preferably above-mentioned oxygenant is the one in oxygen, hydrogen peroxide or tertbutyl peroxide.
Preferably above-mentioned auxiliary agent is one or both in Potassium Bromide, sodium-chlor or Sodium Bromide.
Preferably above-mentioned solvent is the one in glacial acetic acid, hexanaphthene or ether.
Beneficial effect:
(1) the present invention adopts the molecular sieve catalyst of loaded metal to prepare p-ethylacetophenone for selective catalytic oxidation p-Diethylbenzene, and method for preparing catalyst is simple, and is easy to Separation and Recovery after reaction;
(2) temperature of reaction of the present invention is 30 ~ 100 DEG C, and temperature of reaction is lower, not only reduces energy consumption, cost-saving, and adds security;
(3) reaction times of the present invention is 10 ~ 180min, and the reaction times is shorter, greatly improves reaction efficiency, reduces energy consumption of reaction and running cost;
(4) the present invention does not use strong acid or highly basic, avoids the generation of a large amount of waste water, reduces environmental pollution, reduces equipment investment cost and three-protection design cost;
(5) the present invention does not use noxious solvent, eliminates the harm that noxious solvent causes environment;
(6) p-Diethylbenzene transformation efficiency of the present invention is high, p-ethylacetophenone selectivity base yield is high, increases Product yields, reduces product separation difficulty and energy consumption;
(7) molecular sieve catalyst of the loaded metal of the present invention's employing, catalytic stability is good, has wide prospects for commercial application.
Embodiment
Embodiment 1
In 50mL there-necked flask, add the p-Diethylbenzene of 1mL purity 80wt%, 0.1g Fe/ZSM-5 catalyzer (charge capacity is 5wt%), passes into O with the flow velocity of 360mL/h
2the mol ratio of auxiliary agent KBr and p-Diethylbenzene is 1, the volume ratio of solvent acetic acid and p-Diethylbenzene is 1, when temperature of reaction 30 DEG C, reaction times 180min, stirring velocity 600r/min, recording p-Diethylbenzene transformation efficiency is 99.2%, and p-ethylacetophenone selectivity is 15.2%, yield is 15.1%.
Embodiment 2
In 100mL there-necked flask, add the p-Diethylbenzene of 2mL purity 80wt%, 1g Fe/ZSM-5 catalyzer (charge capacity is 5wt%), passes into O with the flow velocity of 360mL/h
2the mol ratio of auxiliary agent KBr and p-Diethylbenzene is 5, the volume ratio of solvent hexanaphthene and p-Diethylbenzene is 1, when temperature of reaction 30 DEG C, reaction times 180min, stirring velocity 600r/min, recording p-Diethylbenzene transformation efficiency is 99.4%, and p-ethylacetophenone selectivity is 13.4%, yield is 13.3%.
Embodiment 3
In 250mL there-necked flask, add the p-Diethylbenzene of 10mL purity 90wt%, 0.1g Ni/MCM-41 catalyzer (charge capacity is 5wt%), passes into O with the flow velocity of 360mL/h
2the mol ratio of auxiliary agent KBr and p-Diethylbenzene is 0.2, the volume ratio of solvent acetic acid and p-Diethylbenzene is 10, when temperature of reaction 60 DEG C, reaction times 30min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 44.3%, and p-ethylacetophenone selectivity is 28.2%, yield is 12.5%.
Embodiment 4
In 50mL there-necked flask, add the p-Diethylbenzene of 1mL purity 90wt%, 0.1g Mn/MCM-41 catalyzer (charge capacity is 5wt%), passes into O with the flow velocity of 360mL/h
2the mol ratio of auxiliary agent KBr and p-Diethylbenzene is 0.2, the volume ratio of solvent acetic acid and p-Diethylbenzene is 20, when temperature of reaction 60 DEG C, reaction times 30min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 51.3%, and p-ethylacetophenone selectivity is 37.1%, yield is 19.0%.
Embodiment 5
In 100mL there-necked flask, add the p-Diethylbenzene of 2mL purity 99wt%, 0.1g Co/MCM-41 catalyzer (charge capacity is 5wt%), passes into O with the flow velocity of 360mL/h
2, the volume ratio of solvent acetic acid and p-Diethylbenzene is 1, and when temperature of reaction 60 DEG C, reaction times 30min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 70.2%, and p-ethylacetophenone selectivity is 39.4%, yield is 27.7%.
Embodiment 6
In 50mL there-necked flask, add the p-Diethylbenzene of 1mL purity 90wt%, 0.05g Ni-Co/SAPO-5 catalyzer (charge capacity is 10wt%), passes into O with the flow velocity of 360mL/h
2the mol ratio of auxiliary agent NaCl and p-Diethylbenzene is 0.2, the volume ratio of solvent ether and p-Diethylbenzene is 1, when temperature of reaction 60 DEG C, reaction times 30min, stirring velocity 100r/min, recording p-Diethylbenzene transformation efficiency is 51.3%, and p-ethylacetophenone selectivity is 43.1%, yield is 22.1%.
Embodiment 7
In 50mL there-necked flask, add the p-Diethylbenzene of 1mL purity 99wt%, 0.1g Cu/SAPO-5 catalyzer (charge capacity is 5wt%), passes into O with the flow velocity of 360mL/h
2the mol ratio of auxiliary agent NaBr and p-Diethylbenzene is 0.2, the volume ratio of solvent acetic acid and p-Diethylbenzene is 1, when temperature of reaction 60 DEG C, reaction times 30min, stirring velocity 100r/min, recording p-Diethylbenzene transformation efficiency is 65.3%, and p-ethylacetophenone selectivity is 40.6%, yield is 26.5%.
Embodiment 8
In 50mL there-necked flask, add the p-Diethylbenzene of 1mL purity 99wt%, 1g Cu/SAPO-5 catalyzer (charge capacity is 5wt%), passes into O with the flow velocity of 360mL/h
2the mol ratio of auxiliary agent NaBr and p-Diethylbenzene is 0.2, the volume ratio of solvent acetic acid and p-Diethylbenzene is 1, when temperature of reaction 60 DEG C, reaction times 30min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 79.2%, and p-ethylacetophenone selectivity is 37.6%, yield is 29.8%.
Embodiment 9
In 250mL there-necked flask, add the p-Diethylbenzene of 10mL purity 90wt%, 0.1g Mn/SBA-15 catalyzer (charge capacity is 5wt%), passes into O with the flow velocity of 360mL/h
2the mol ratio of auxiliary agent NaCl-KBr and p-Diethylbenzene is 10, the volume ratio of solvent hexanaphthene and p-Diethylbenzene is 20, when temperature of reaction 60 DEG C, reaction times 60min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 49.4%, and p-ethylacetophenone selectivity is 29.8%, yield is 14.7%.
Embodiment 10
The p-Diethylbenzene of 10mL purity 99wt% is added in 250mL there-necked flask, 1g Cu/SAPO-5 catalyzer (charge capacity is 5wt%), tertbutyl peroxide is passed into the flow velocity of 5mL/h, not adding assistant, solvent ether acid is 10 with the volume ratio of p-Diethylbenzene, when temperature of reaction 60 DEG C, reaction times 120min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 90.4%, and p-ethylacetophenone selectivity is 41.4%, yield is 37.4%.
Embodiment 11
In 50mL there-necked flask, add the p-Diethylbenzene of 1mL purity 99wt%, 0.1g Co/SBA-15 catalyzer (charge capacity is 15wt%), passes into H with the flow velocity of 7mL/h
2o
2the mol ratio of auxiliary agent KBr and p-Diethylbenzene is 0.3, the volume ratio of solvent acetic acid and p-Diethylbenzene is 6, when temperature of reaction 75 DEG C, reaction times 10min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 60.7%, and p-ethylacetophenone selectivity is 65.9%, yield is 40.0%.
Embodiment 12
In 50mL there-necked flask, add the p-Diethylbenzene of 1mL purity 99wt%, 0.1g Co/SBA-15 catalyzer (charge capacity is 15wt%), passes into H with the flow velocity of 7mL/h
2o
2the mol ratio of auxiliary agent KBr and p-Diethylbenzene is 0.3, the volume ratio of solvent acetic acid and p-Diethylbenzene is 6, when temperature of reaction 75 DEG C, reaction times 40min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 91.3%, and p-ethylacetophenone selectivity is 57.8%, yield is 52.8%.
Embodiment 13
In 50mL there-necked flask, add the p-Diethylbenzene of 1mL purity 99wt%, 0.1g Co/SBA-15 catalyzer (charge capacity is 20wt%), passes into H with the flow velocity of 7mL/h
2o
2the mol ratio of auxiliary agent KBr and p-Diethylbenzene is 0.3, the volume ratio of solvent acetic acid and p-Diethylbenzene is 6, when temperature of reaction 75 DEG C, reaction times 50min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 97.5%, and p-ethylacetophenone selectivity is 58.2%, yield is 56.7%.
Embodiment 14
In 50mL there-necked flask, add the p-Diethylbenzene of 1mL purity 99wt%, 0.1g Co/SBA-15 catalyzer (charge capacity is 15wt%), passes into H with the flow velocity of 7mL/h
2o
2the mol ratio of auxiliary agent KBr and p-Diethylbenzene is 0.3, the volume ratio of solvent acetic acid and p-Diethylbenzene is 6, when temperature of reaction 100 DEG C, reaction times 40min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 95.1%, and p-ethylacetophenone selectivity is 51.2%, yield is 48.7%.
Embodiment 15
The p-Diethylbenzene of 1mL purity 99wt% is added in 50mL there-necked flask, 0.1g Co/SBA-15 catalyzer (charge capacity is 5wt%), tertbutyl peroxide is passed into the flow velocity of 5mL/h, the mol ratio of auxiliary agent KBr and p-Diethylbenzene is 0.3, the volume ratio of solvent acetic acid and p-Diethylbenzene is 6, when temperature of reaction 60 DEG C, reaction times 30min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 82.7%, and p-ethylacetophenone selectivity is 49.3%, yield is 40.8%.
Embodiment 16
The p-Diethylbenzene of 1mL purity 99wt% is added in 50mL there-necked flask, 0.1g Co/SBA-15 catalyzer (charge capacity is 5wt%), tertbutyl peroxide is passed into the flow velocity of 10mL/h, the mol ratio of auxiliary agent KBr and p-Diethylbenzene is 0.3, the volume ratio of solvent acetic acid and p-Diethylbenzene is 6, when temperature of reaction 60 DEG C, reaction times 30min, stirring velocity 400r/min, recording p-Diethylbenzene transformation efficiency is 91.2%, and p-ethylacetophenone selectivity is 56.9%, yield is 51.9%.
Under table differential responses condition, Co/SBA-15 is on the impact of p-Diethylbenzene (PDEB) oxidation p-ethylacetophenone processed (EAP)
Note: 1. reaction raw materials is the p-Diethylbenzene of 1mL purity 99wt%;
2. the charge capacity of numeral metal Co before catalyzer, catalyst levels is 0.1g;
3. the mol ratio of auxiliary agent KBr and p-Diethylbenzene is 0.3, and the volume ratio of solvent acetic acid and p-Diethylbenzene is 6;
4. stirring velocity is 400r/min.
Claims (9)
1. a load molecular sieve catalyzed oxidation p-Diethylbenzene prepares the method for p-ethylacetophenone, the steps include: to take p-Diethylbenzene as raw material, with the molecular sieve of loaded metal for catalyzer, add oxygenant, auxiliary agent and solvent, stirring reaction, obtain product p-ethylacetophenone, wherein temperature of reaction is 30 ~ 100 DEG C, and the reaction times is 10 ~ 180min.
2. method according to claim 1, is characterized in that oxidant feed flow velocity is 5 ~ 360mL/h; The mol ratio of auxiliary agent and p-Diethylbenzene is 0 ~ 10; The volume ratio of solvent and p-Diethylbenzene is 1 ~ 20; Stirring velocity 100 ~ 600r/min.
3. method according to claim 1, is characterized in that catalyzer adds quality and p-Diethylbenzene volume ratio is 0.01 ~ 1.0g/mL.
4. method according to claim 1, is characterized in that the quality purity of raw material p-Diethylbenzene is 80 ~ 99.9%.
5. method according to claim 1, is characterized in that the metallic element of catalyst cupport is the transition metal of III B ~ II B; The carrier of loaded metal is a kind of molecular sieve in ZSM-5, MCM-41, SBA-15 or SAPO-5; Wherein the mass loading amount of metallic element is 5% ~ 20%.
6. method according to claim 1, is characterized in that the metallic element of catalyst cupport is one or both in iron, nickel, manganese, copper or cobalt.
7. method according to claim 1, is characterized in that described oxygenant is the one in oxygen, hydrogen peroxide or tertbutyl peroxide.
8. method according to claim 1, is characterized in that described auxiliary agent is one or both in Potassium Bromide, sodium-chlor or Sodium Bromide.
9. method according to claim 1, is characterized in that described solvent is the one in glacial acetic acid, hexanaphthene or ether.
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| CN107286005A (en) * | 2016-04-11 | 2017-10-24 | 中国石化扬子石油化工有限公司 | A kind of p-diethylbenzene homogeneous oxidizing prepares the method to diacetyl benzene |
| CN108435241A (en) * | 2018-03-23 | 2018-08-24 | 盐城工业职业技术学院 | H beta-zeolite catalysts and preparation method thereof and o-nitroethylbenzene prepare the method for ortho-nitroacetophenone, equipment |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107286005A (en) * | 2016-04-11 | 2017-10-24 | 中国石化扬子石油化工有限公司 | A kind of p-diethylbenzene homogeneous oxidizing prepares the method to diacetyl benzene |
| CN107286005B (en) * | 2016-04-11 | 2021-03-19 | 中国石化扬子石油化工有限公司 | Method for preparing p-diacetylbenzene by homogeneous oxidation of p-diethylbenzene |
| CN108435241A (en) * | 2018-03-23 | 2018-08-24 | 盐城工业职业技术学院 | H beta-zeolite catalysts and preparation method thereof and o-nitroethylbenzene prepare the method for ortho-nitroacetophenone, equipment |
| CN108435241B (en) * | 2018-03-23 | 2020-12-11 | 盐城工业职业技术学院 | H beta zeolite catalyst and preparation method thereof, and method and equipment for preparing o-nitroacetophenone from o-nitroethylbenzene |
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