CN117624083A - Method for efficiently and selectively oxidizing styrene - Google Patents
Method for efficiently and selectively oxidizing styrene Download PDFInfo
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- CN117624083A CN117624083A CN202311545795.XA CN202311545795A CN117624083A CN 117624083 A CN117624083 A CN 117624083A CN 202311545795 A CN202311545795 A CN 202311545795A CN 117624083 A CN117624083 A CN 117624083A
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- styrene
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 31
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000004064 recycling Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000007792 addition Methods 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 238000000859 sublimation Methods 0.000 claims description 2
- 230000008022 sublimation Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 6
- 238000011112 process operation Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 8
- 239000005457 ice water Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000006735 epoxidation reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 150000003944 halohydrins Chemical class 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- BXRVAIYLQLSKIJ-UHFFFAOYSA-N 3-iodo-3h-2-benzofuran-1-one Chemical compound C1=CC=C2C(I)OC(=O)C2=C1 BXRVAIYLQLSKIJ-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tertiry butyl alcohol Natural products CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FVTWJXMFYOXOKK-UHFFFAOYSA-N 2-fluoroacetamide Chemical compound NC(=O)CF FVTWJXMFYOXOKK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000003869 acetamides Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000507 anthelmentic effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000000729 antidote Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960005091 chloramphenicol Drugs 0.000 description 1
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 tert-butyl alcohol peroxide Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for oxidizing styrene with high efficiency and high selectivity, which comprises the following steps: adding styrene, acetonitrile, a catalyst and an alkaline substance into a reaction solvent, dropwise adding an oxidant at a certain temperature for oxidation reaction, keeping the temperature for reaction at a certain temperature, filtering a reaction system after the reaction is finished to obtain a filtrate, and recycling the catalyst for the next batch of reaction; the method has the advantages of simple process operation, high selectivity, high yield, high product purity, high styrene conversion rate up to 99%, high styrene oxide selectivity up to 97%, and high social use value and application prospect.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a method for efficiently oxidizing styrene with high selectivity.
Background
The oxidation reaction of the styrene is a classical organic reaction, the double bond of the styrene has high reactivity, and under the action of a catalyst and an oxidant, the double bond of the styrene is broken, and the reactions such as addition, oxidation, polymerization and the like can be carried out to generate products such as benzaldehyde, styrene oxide, benzoic acid, polystyrene and the like.
The styrene oxide is often subjected to selective ring opening to prepare fine chemicals with higher value because the epoxy groups on the side chains of the benzene rings of the styrene oxide are very active. Besides being used for synthesizing beta-phenethyl alcohol, the catalyst can also be used for applications of anthelmintic, namely levorotatory hydrochloride, ultraviolet absorbent, epoxy resin diluent and the like. Styrene oxide is industrially synthesized mainly by a halohydrin method, and there are few reports of preparing styrene oxide by oxidizing styrene with a hydrogen peroxide solution and preparing styrene oxide by using molecular oxygen as an oxidant. The method for preparing the styrene oxide by using the halohydrin method is rapid, but has high material consumption and energy consumption, high cost and serious pollution. The molecular oxygen is used for preparing the styrene oxide, the atom economy is good, but the conversion rate of the styrene is too low, and a high-efficiency catalyst is lacking at present.
Acetamide has a high dielectric constant, is an excellent solvent for many organic and inorganic substances, and is widely used in various industries. Can be used as a solubilizer for substances with low water solubility when dissolved in water, such as a solvent for dye and a solubilizer in the fiber industry, and as a solvent for synthesizing antibiotics such as chloramphenicol and a plasticizer for plastics. N-haloacetamide generated by chlorination or bromination of acetamide is a halogenating reagent for organic synthesis. Acetamides are also raw materials for the manufacture of pharmaceuticals and bactericides. Acetamide is an organic fluorine insecticidal pesticide-a antidote to fluoroacetamide poisoning.
The hydrogen peroxide is used as the byproduct of the oxidant reaction, so that the water is convenient to treat, and the sustainable development concept of current green environmental protection is met. However, hydrogen peroxide has a weak oxidizing ability to styrene, and current reports on styrene oxide are more focused on the design and synthesis of catalysts, so that catalysts with better catalytic performance are obtained.
CN 106565633 discloses a styrene epoxidation process. The method comprises the steps of simultaneously conveying styrene and hydrogen peroxide solution containing a catalyst into a microchannel reactor through conveying equipment, and staying in the reactor for a period of time to obtain a mixture of compounds such as styrene, styrene oxide, phenylacetaldehyde, benzaldehyde, benzoic acid and the like. Under the reaction condition, the single pass conversion rate of the styrene exceeds 10 percent, and the selectivity of the styrene oxide is more than 98 percent. In the method, the solid powder catalyst is easy to cause the blockage of the micro-channel reactor, the single-pass conversion rate of the styrene is low, and a large amount of reaction raw materials need to be separated and recycled.
CN 106699693 discloses a method for epoxidation of styrene, which comprises using hydrogen peroxide as oxidant, salt as auxiliary agent and amorphous MOx/TiO in the presence of organic solvent DMF, THF, toluene, acetonitrile or dichloroethane 2 -SiO 2 As a catalyst, the styrene oxide is prepared through epoxidation reaction. The active component loading is 0.01-20wt% and the active component is at least any one of Pd, ag, W, mo or Co. The temperature condition of the epoxidation reaction is 45-65 ℃, the reaction time is 30-120 min, the mixing mole ratio of the styrene and the hydrogen peroxide is 1:5, the conversion rate of the styrene in the process is 30-80%, and the selectivity of the styrene oxide is more than 85%. The method uses a large amount of noble metal, the excessive hydrogen peroxide is needed to be added with substances for quenching the hydrogen peroxide in the aftertreatment, and the conversion rate is low, so that the cost is too high.
Although the method for preparing the styrene oxide by using the halohydrin method is quick, the oxyhalide used comprises chlorate, perchloric acid, hypohalous acid, hypochlorite and iodophthalide. The use of the iodophthalide has higher cost, the use of the oxyhalide easily causes serious environmental pollution, and the energy consumption is higher (synthetic chemistry, 2000,8 (1): 71-74).
CN 109516966B reports that the use of molecular oxygen for the preparation of styrene oxide is economically advantageous in terms of atoms, but the conversion of styrene is only 38%, the selectivity of styrene oxide is 9%, and there is currently no efficient catalyst.
Accordingly, the inventor has the problem of providing a method for oxidizing styrene with high efficiency and high selectivity, which is expected to achieve the purpose of having more practical value, by keeping the experience of design development and practical production in the related industry for many years and researching and improving the prior art and the deficiency.
Disclosure of Invention
In order to solve the problems mentioned in the background art, the invention provides a method for oxidizing styrene with high efficiency and high selectivity, which is safe, low in cost and pollution-free and is in accordance with the modern green chemical concept.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for oxidizing styrene with high efficiency and high selectivity, which comprises the following specific steps:
s1, sequentially adding a reaction solvent, acetonitrile, an oxidant, an alkaline substance and styrene, dropwise adding the oxidant under the condition of controlling a certain reaction temperature to perform an oxidation reaction, performing heat preservation reaction at 55-60 ℃ after dropwise adding, cooling to room temperature after the reaction is finished, filtering, removing a catalyst, recycling the catalyst for the next batch of reaction, and collecting filtrate;
s2, distilling the filtrate under reduced pressure, separating the solvent, recycling the solvent for the next batch of reaction, and collecting the concentrated solution;
s3, extracting the concentrated solution by using an extracting agent, and respectively collecting an organic phase and a water phase;
s4, collecting a water phase, performing reduced pressure distillation to separate water, and performing reduced pressure sublimation on residual kettle liquid to obtain acetamide crystals, wherein the GC purity is 99.9%;
s5, collecting an organic phase for rectification, and adopting a rectification column filled with 0.5-0.8m glass spring, wherein under a certain vacuum degree and reflux ratio, the styrene oxide with the purity of more than 98.5% can be obtained, and the rectification is stopped.
The chemical reaction equation is shown below:
preferably, styrene and acetonitrile in the step S1 are used as reaction substrates;
the reaction solvent is one or a combination of several of methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane, toluene and tetrahydrofuran;
the oxidant is one or the combination of hydrogen peroxide and tert-butyl peroxide;
the catalyst is one or a combination of a plurality of industrial magnesium oxide and chromium oxide;
the alkaline substance is one or a combination of sodium carbonate, sodium bicarbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate and sodium hydroxide, and is used for stabilizing styrene oxide;
and the extractant in the step S3 is ethyl acetate.
Preferably, the addition amount of the alkaline substance is 0.5-1.5wt% of the total feeding mass.
Preferably, the molar ratio of styrene, acetonitrile, oxidant and catalyst is 1: (1.5-3.5): (2-4): (0.2-0.6).
Preferably, the mass concentration of the hydrogen peroxide solution is 20-50wt%, and the mass concentration of the tert-butyl peroxide is 70wt%.
Preferably, the addition amount of the solvent is 4-7 times of the feeding mass of the styrene.
Preferably, in S1, the reaction temperature is between 0 and 15 ℃ during the addition of the oxidizing agent.
Preferably, in the step S2, the vacuum degree of the reduced pressure distillation system is 2-3KPa, and the temperature is 30-60 ℃.
Preferably, in the step S3, the extractant is extracted 2 to 3 times by ethyl acetate, and the addition amount of each time is 20 to 35 weight percent of the total mass.
Preferably, in S4, the aqueous phase is distilled under reduced pressure (vacuum degree 2-3KPa, kettle temperature 50-95 ℃), sublimated under reduced pressure (vacuum degree 2.5-3.5hPa, kettle temperature 75-95 ℃), and the acetamide purity is 99.9% (GC), yield is 65%.
Preferably, in S5, the vacuum degree of the rectification system is 2.5-3.5hPa, the reflux ratio r=0.5-2, the kettle temperature is 30-80 ℃, and the top temperature is 36-40 ℃.
Preferably, when the oxidant is 30% hydrogen peroxide solution, the styrene conversion is 99% and the styrene oxide selectivity is 97%.
Compared with the prior art, the invention has the beneficial effects that: the invention aims at the problems of low conversion rate of raw material styrene and low selectivity of product styrene oxide in the prior art, and adopts the method that a certain proportion of alkaline substances are added to protect the product styrene oxide, so that the product styrene oxide is prevented from ring-opening reaction to cause selectivity reduction, and the conversion rate of the styrene can reach more than 99 percent by controlling the proportion of the raw materials and the reaction temperature.
The invention uses styrene as initial raw material, hydrogen peroxide as oxidant, industrial magnesium oxide as catalyst, alkaline substance and solvent to increase substrate solubility, and the high purity styrene oxide is obtained through oxidation reaction and separation. The method has the advantages of simple process operation, high selectivity, high yield, high product purity, high styrene conversion rate up to 99%, high styrene oxide selectivity up to 97%, and high social use value and application prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a GC spectrum of styrene oxide;
FIG. 2 is a GC spectrum of acetamide.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of styrene oxide:
to a 2L three-necked flask was successively added 780.0g (500 wt%) of DMF, 156.0g (3.75 mol,100 wt%) of acetonitrile, and oxidized37.5g (0.90 mol,24 wt.%) of magnesium, 7.5g (0.08 mol,0.5 wt.%) of sodium bicarbonate and 156.3g (1.50 mol) of styrene, and a thermometer and a condenser were mounted as required. Under the ice-water bath condition, 280.5g (50% in H) of hydrogen peroxide is added dropwise into the system 2 O, about containing 4.13 mol), controlling the temperature to be not more than 15 ℃, maintaining the temperature for 0.5h in an ice water bath after the dripping is finished, then heating to 55 ℃ and maintaining the temperature for 8h, cooling, stopping the reaction, sampling and detecting to obtain the styrene conversion rate of 93% and the internal standard yield of 89%. The magnesium oxide was separated by filtration using a G3 sand core funnel, and the filtrate was washed three times (700G. Times.3) to remove DMF, acetamide and salts, and the organic phases were combined to give 211.2G of crude styrene oxide as a yellow oil. Taking 211.2g of crude styrene oxide, loading the crude styrene oxide into a rectification column filled with 0.8m glass spring, and obtaining 140.9g of styrene oxide with GC purity of more than 98% at the top temperature of 36-40 ℃ under the vacuum degree of 2.5-3.5hPa, wherein the separation yield is 78.2%, and the front part and the rear part containing the styrene oxide are sleeved into the next batch of rectification raw materials.
Example 2
Preparation of styrene oxide:
to a 2L three-necked flask, 624.0g (500 wt%) of ethanol, 112.8g (2.75 mol,90 wt%) of acetonitrile, 30.0g (0.20 mol,24 wt%) of chromium oxide, 6.4g (0.16 mol,0.5 wt%) of sodium hydroxide and 124.9g (1.20 mol) of styrene were successively added, and a thermometer and a condenser were mounted as required. Under the ice water bath condition, 424.8g of tert-butyl alcohol peroxide (70% in H2O, about 3.30 mol) is dropwise added into the system, the temperature is controlled to be not higher than 15 ℃, the ice water bath is used for heat preservation for 0.5h after the dropwise addition is finished, the temperature is then increased to 55 ℃ for heat preservation for 8h, the temperature is reduced, the reaction is stopped, and the styrene conversion rate, the styrene oxide selectivity and the internal standard yield are obtained by sampling and detecting, and are respectively 84%. Filtering and separating out chromium oxide by using a G3 sand core funnel, separating out ethanol (vacuum degree 2-3KPa, kettle temperature 40-75 ℃) by rotary evaporation, and applying the ethanol to the next batch reaction to obtain concentrated solution. The concentrate was extracted three times with ethyl acetate (400 g. Times.3), the organic phases were washed once with water (700 g. Times.1), the organic phases were combined and the aqueous phases were combined and retained. The organic phase is distilled off to remove the ethyl acetate (vacuum degree 2-3KPa, kettle temperature 40-70 ℃), and the ethyl acetate is used for the next batch reaction to obtain 156.7g of yellow liquid crude styrene oxide. 156.7g of crude styrene oxide is taken and put into a rectification column filled with 0.8m glass spring, the vacuum degree is about 2.5-3.5hPa, 70.9g of styrene oxide with the GC purity of more than 98% can be obtained at the top temperature of 36-40 ℃, the separation yield is 49.2%, and the front part and the rear part containing the styrene oxide are sleeved into the next batch of rectification raw materials.
Example 3
Preparation of styrene oxide:
to a 2L three-necked flask, 624.0g (500 wt%) of methanol, 112.8g (2.75 mol,90 wt%) of acetonitrile, 30.0g (0.71 mol,24 wt%) of magnesium oxide, 6.0g (0.06 mol,0.5 wt%) of disodium hydrogenphosphate and 124.9g (1.20 mol) of styrene were successively added, and a thermometer and a condenser were mounted as required. Under the ice water bath condition, 374.4g (30% in H) of hydrogen peroxide is added dropwise into the system 2 O, about 3.30 mol), controlling the temperature to be not more than 15 ℃, carrying out ice water bath heat preservation for 0.5h after dropwise addition, then heating to 55 ℃ for heat preservation for 5h, cooling, stopping the reaction, sampling and detecting to obtain the styrene conversion rate of 99%, the selectivity of the styrene oxide of 97% and the internal standard yield of 96%. The magnesium oxide is filtered and separated by a G3 sand core funnel, methanol (vacuum degree 2-3KPa, kettle temperature 35-60 ℃) is separated by rotary evaporation, and the methanol is applied to the next batch of reaction to obtain concentrated solution. The concentrate was extracted three times with ethyl acetate (400 g. Times.3), the organic phases were washed once with water (700 g. Times.1), the organic phases were combined and the aqueous phases were combined and retained. The organic phase is distilled off to remove the ethyl acetate (vacuum degree 2-3KPa, kettle temperature 40-70 ℃), and the ethyl acetate is used for the next batch reaction to obtain 169.2g of yellow liquid crude styrene oxide. 169.2g of crude styrene oxide is taken and put into a rectifying column filled with 0.8m glass spring, the vacuum degree is about 2.5-3.5hPa, 125.6g of styrene oxide with the GC purity of more than 98 percent can be obtained at the top temperature of 36-40 ℃, the separation yield is 87.1 percent, and the front part and the rear part containing the styrene oxide are sleeved into the next batch of rectifying raw materials.
Example 4
Preparation of acetamide:
the aqueous phase in example 3 was collected, dried in vacuo to remove water, 181.2g of crude acetamide was obtained, the crude acetamide was sublimated under reduced pressure, the vacuum degree was 2.5-3.5hPa, the pot temperature was 78-95℃to obtain 106.6g of acetamide crystals, the GC purity was 99.9%, and the isolation yield was 65.6%.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (12)
1. A method for oxidizing styrene with high efficiency and high selectivity, which is characterized by comprising the following specific steps:
s1, sequentially adding a reaction solvent, acetonitrile, an oxidant, an alkaline substance and styrene, dropwise adding the oxidant under the condition of controlling a certain reaction temperature to perform an oxidation reaction, performing heat preservation reaction at 55-60 ℃ after dropwise adding, cooling to room temperature after the reaction is finished, filtering, removing a catalyst, recycling the catalyst for the next batch of reaction, and collecting filtrate;
s2, distilling the filtrate under reduced pressure, separating the solvent, recycling the solvent for the next batch of reaction, and collecting the concentrated solution;
s3, extracting the concentrated solution by using an extracting agent, and respectively collecting an organic phase and a water phase;
s4, collecting a water phase, performing reduced pressure distillation to separate water, and performing reduced pressure sublimation on residual kettle liquid to obtain acetamide crystals, wherein the GC purity is 99.9%;
s5, collecting an organic phase for rectification, and adopting a rectification column filled with 0.5-0.8m glass spring, wherein under a certain vacuum degree and reflux ratio, the styrene oxide with the purity of more than 98.5% can be obtained, and the rectification is stopped.
2. The method for oxidizing styrene with high efficiency and high selectivity according to claim 1, wherein styrene and acetonitrile in the step S1 are used as reaction substrates;
the reaction solvent is one or a combination of several of methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane, toluene and tetrahydrofuran;
the oxidant is one or the combination of hydrogen peroxide and tert-butyl peroxide;
the catalyst is one or a combination of a plurality of industrial magnesium oxide and chromium oxide;
the alkaline substance is one or a combination of sodium carbonate, sodium bicarbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate and sodium hydroxide, and is used for stabilizing styrene oxide;
and the extractant in the step S3 is ethyl acetate.
3. The method for efficiently oxidizing styrene with high selectivity according to claim 1, wherein the alkaline substance is added in an amount of 0.5 to 1.5% by weight based on the total charged mass.
4. A method for highly efficient and highly selective oxidation of styrene according to claim 1, wherein the molar ratio of styrene, acetonitrile, oxidant and catalyst is 1: (1.5-3.5): (2-4): (0.2-0.6).
5. A method for highly efficient and highly selective oxidation of styrene according to claim 2, wherein said hydrogen peroxide solution has a mass concentration of 20 to 50% by weight and t-butyl peroxide has a mass concentration of 70% by weight.
6. The method for efficiently oxidizing styrene with high selectivity according to claim 1, wherein the solvent is added in an amount of 4 to 7 times the mass of the styrene charge.
7. A method for the efficient and highly selective oxidation of styrene according to claim 1, wherein said step S1 is carried out at a reaction temperature of 0 to 15 ℃ during said addition of said oxidizing agent.
8. The method for efficiently oxidizing styrene with high selectivity according to claim 1, wherein in said step S2, the vacuum degree of said reduced pressure distillation system is 2 to 3KPa and the temperature is 30 to 60 ℃.
9. A method for highly efficient and highly selective oxidation of styrene according to claim 1, wherein in said S3, said extractant ethyl acetate is extracted 2 to 3 times, each time in an amount of 20 to 35% by weight based on the total mass.
10. The method for efficiently oxidizing styrene with high selectivity according to claim 1, wherein in S4, the aqueous phase is distilled under reduced pressure (vacuum degree 2-3KPa, pot temperature 50-95 ℃) and sublimated under reduced pressure (vacuum degree 2.5-3.5hPa, pot temperature 75-95 ℃), and the purity of the acetamide is 99.9% (GC), and the yield is 65%.
11. The method for oxidizing styrene with high selectivity and high efficiency according to claim 1, wherein in the step S5, the vacuum degree of the rectification system is 2.5-3.5hPa, the reflux ratio r=0.5-2, the kettle temperature is 30-80 ℃, and the top temperature is 36-40 ℃.
12. A method for highly efficient and highly selective oxidation of styrene according to claim 1, wherein said conversion of styrene is 99% and the selectivity of styrene oxide is 97% when said oxidizing agent is 30% hydrogen peroxide solution.
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