CN111889134A - Supported catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation and application thereof - Google Patents
Supported catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation and application thereof Download PDFInfo
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- RANCECPPZPIPNO-UHFFFAOYSA-N 2,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC=C1Cl RANCECPPZPIPNO-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 36
- 230000003647 oxidation Effects 0.000 title claims abstract description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 29
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims abstract description 25
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 13
- 238000005070 sampling Methods 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 5
- 239000005504 Dicamba Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- IWEDIXLBFLAXBO-UHFFFAOYSA-N dicamba Chemical compound COC1=C(Cl)C=CC(Cl)=C1C(O)=O IWEDIXLBFLAXBO-UHFFFAOYSA-N 0.000 description 4
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010812 external standard method Methods 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 2
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- CYNFEPKQDJHIMV-UHFFFAOYSA-N 1-(2,5-dichlorophenyl)ethanone Chemical compound CC(=O)C1=CC(Cl)=CC=C1Cl CYNFEPKQDJHIMV-UHFFFAOYSA-N 0.000 description 1
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 description 1
- 239000005496 Chlorsulfuron Substances 0.000 description 1
- 239000005584 Metsulfuron-methyl Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VJYIFXVZLXQVHO-UHFFFAOYSA-N chlorsulfuron Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)Cl)=N1 VJYIFXVZLXQVHO-UHFFFAOYSA-N 0.000 description 1
- 238000012272 crop production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- KWBJSXHLCAHGRB-UHFFFAOYSA-N methanol;pentane-2,4-dione Chemical compound OC.CC(=O)CC(C)=O KWBJSXHLCAHGRB-UHFFFAOYSA-N 0.000 description 1
- RSMUVYRMZCOLBH-UHFFFAOYSA-N metsulfuron methyl Chemical group COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(C)=NC(OC)=N1 RSMUVYRMZCOLBH-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a vanadium oxide/TS-1 heterogeneous catalyst obtained by combining vanadyl acetylacetonate with a TS-1 type titanium silicalite molecular sieve, namely VO (vanadium oxide/TS-1 heterogeneous catalyst) with the vanadium content of 1-5% is obtained by dissolving vanadyl acetylacetonate in methanol, adding the TS-1 type titanium silicalite molecular sieve, stirring, dipping, filtering, freeze drying, roasting and the likeXThe preparation method of the/TS-1 supported catalyst is simple and low in cost, and the yield is 100 percent based on vanadium. The vanadium oxide/TS-1 is used as a catalyst, so that the catalytic efficiency can be improved, the excessive oxidation of 2, 5-dichlorophenol can be effectively inhibited, the excessive oxidation product can be controlled to be below 5%, the 2, 5-dichlorophenol selectivity can reach more than 95%, especially the isomer 2, 4-dichlorophenol can be obviously inhibited, the 2, 4-dichlorophenol selectivity is less than 0.1%, and meanwhile, the supported type vanadium oxide/TS-1 is used as a catalystThe catalyst has the advantages of easy recovery and reuse.
Description
Technical Field
The invention belongs to the technical field of preparation of 2, 5-dichlorophenol, and particularly relates to a supported catalyst and application thereof in preparation of 2, 5-dichlorophenol by catalytic oxidation of 1, 4-dichlorobenzene.
Background
The 2, 5-dichlorophenol is mainly used as intermediates of medicines, dyes and the like, herbicide dicamba intermediates, nitrogen fertilizer synergists, leather mildewproof agents and the like, and is especially a main organic intermediate for preparing pesticide herbicide dicamba. In recent years, with the continuous improvement of greenhouse gas emission reduction and environmental protection requirements and the banning and limited use of chlorsulfuron and metsulfuron-methyl preparations, the demand of low-toxicity pesticide dicamba widely applied to crop production is continuously increased, and the market prospect is good. Therefore, the research and development of the 2, 5-dichlorophenol intermediate have important function on developing dicamba which is a low-toxicity and high-efficiency herbicide.
The prior related patent technologies are as follows:
1. in patent US 2799714, 1,2, 4-trichlorobenzene is used as a raw material, and mixed dichlorophenol is prepared under an alkaline condition, and then 2, 5-dichlorophenol is obtained by separation. The process has the advantages of simple process route and low investment, but the method uses a large amount of acid and alkali, the reaction conditions are harsh, a large amount of acid-base waste liquid and solid salt are generated in the generation process, the problem of serious environmental pollution exists, and the separation of byproducts is difficult.
2. Patent US 4326882 discloses the preparation of 2, 5-dichlorophenol from 2, 5-dichloroaniline as a starting material by diazotization and hydrolysis; the method is mature in technology and widely applied to industry, but a large amount of organic and inorganic reagents are needed, the waste water amount is large, and about 10 tons of phenol-containing waste water is generated for each ton of 2, 5-dichlorophenol.
3. CN 104591973A discloses a preparation method of 2, 5-dichlorophenol, which comprises the steps of firstly, carrying out Friedel-crafts acylation reaction on p-dichlorobenzene and acetyl chloride under the catalysis of anhydrous aluminum trichloride to generate an intermediate 2, 5-dichloroacetophenone, and then carrying out Bayer-Villiger oxidation to obtain the 2, 5-dichlorophenol. The synthesis route has mild conditions, high temperature and high pressure are not needed, and a large amount of organic acid and alkali are not used, but the method generates more aluminum-containing wastewater by using anhydrous aluminum trichloride as a catalyst in the friedel-crafts acylation stage, and generates peroxy acid in the Bayer-Villiger oxidation stage, so that the industrial safety is poor, the cost is high, and no industrial production public report is found at present.
Aiming at the problems, the prior art also provides a method for preparing 2, 5-dichlorophenol by directly catalyzing and oxidizing 1, 4-dichlorobenzene by one step, and the method is widely researched due to the advantages of short process route, good economic benefit, environmental protection, greenness and the like, is expected to become a mainstream method for producing 2, 5-dichlorophenol, but is not reported industrially at present, and the difficulty is mainly in the development of catalysts. The existing method for preparing 2, 5-dichlorophenol by taking 1, 4-dichlorobenzene as a raw material through catalytic oxidation adopts heteropoly acid, copper porphyrin, iron oxide or a supported type heteropoly acid, copper porphyrin and iron oxide as a catalyst, and has the advantages of short reaction route, simple operation and almost no environmental pollution. But the catalytic effect is not ideal and the product selectivity is low. For example, chinese patent CN107129426A discloses a method for preparing 2, 5-dichlorophenol, which is prepared by using 1, 4-dichlorobenzene as a raw material and one or more of water, methanol, acetonitrile and acetic acid as a solvent through catalytic oxidation under the action of an oxidant, a metalloporphyrin catalyst and a cocatalyst; the method achieves the purpose of improving the efficiency and the yield of the oxidation reaction by a catalytic system consisting of the metalloporphyrin catalyst and the cocatalyst, and the catalytic effect is still not ideal when the metalloporphyrin catalyst is used alone. Therefore, in the method for preparing 2, 5-dichlorophenol by catalytic oxidation of 1, 4-dichlorobenzene, the development of a catalyst which is high in efficiency, good in selectivity, low in by-product and easy to recover is very necessary.
Disclosure of Invention
One of the purposes of the invention is to provide a vanadium oxide/TS-1 heterogeneous catalyst obtained by combining vanadyl acetylacetonate with a TS-1 type titanium silicalite molecular sieve, namely VO obtained by dissolving vanadyl acetylacetonate in methanol, adding the TS-1 type titanium silicalite molecular sieve, stirring, dipping, filtering, freeze drying, roasting and the likeXThe preparation method of the/TS-1 supported catalyst is simple, low in cost and high in yieldThe vanadium content can reach 100%, which provides a useful reference value for preparing 2, 5-dichlorophenol by catalytic oxidation.
The second purpose of the invention is to provide the application of the vanadium oxide/TS-1 supported catalyst in the preparation of 2, 5-dichlorophenol by catalytic oxidation, in the process of preparing 2, 5-dichlorophenol by catalytic oxidation of 1, 4-dichlorobenzene, the vanadium oxide/TS-1 is used as the catalyst, the excessive oxidation of 2, 5-dichlorophenol can be effectively inhibited while the catalytic efficiency is improved, the excessive oxidation product can be controlled below 5%, the selectivity of 2, 5-dichlorophenol can reach more than 95%, especially the isomer 2, 4-dichlorophenol can be obviously inhibited, the selectivity of 2, 4-dichlorophenol is less than 0.1%, and meanwhile, the supported catalyst has the advantages of easy recovery and reutilization.
The purpose of the invention is realized by the following technical scheme:
a supported catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation is a vanadium oxide/TS-1 heterogeneous catalyst obtained by combining vanadyl acetylacetonate with a TS-1 type titanium silicalite molecular sieve, namely dissolving vanadyl acetylacetonate in methanol to obtain a methanol solution of vanadyl acetylacetonate, then adding the TS-1 type titanium silicalite molecular sieve, stirring and dipping at room temperature, filtering, freeze-drying a filter cake to remove methanol, then placing the filter cake in a muffle furnace, roasting at 500-600 ℃ for 1-3 h to obtain a brown-gray powdery vanadium oxide/TS-1 supported catalyst product, wherein the vanadium content in the product is 1-5% measured by ICP-AES.
Further, the methanol solution of vanadyl acetylacetonate is obtained by dissolving vanadyl acetylacetonate in 20-30 times of methanol by weight.
Furthermore, the addition amount of the TS-1 type titanium silicalite molecular sieve is 6-25 times of the weight of the vanadyl acetylacetonate.
Further, the stirring and dipping time at room temperature is 2-3 h.
The method for preparing 2, 5-dichlorophenol by catalytic oxidation by using the vanadium oxide/TS-1 supported catalyst comprises the following steps:
(1) sequentially adding 1, 4-dichlorobenzene and 5-15 times of acetic acid by weight into a reaction container, and stirring for dissolving;
(2) push buttonAdding 5 percent by weight of 1, 4-dichlorobenzene as vanadium oxide-TS-1 supported catalyst, and then dripping 0.3eq of H with the mass concentration of 30 percent within 1-3H at the temperature of 60 DEG C2O2And continuously preserving the temperature for 1h after dripping to obtain a 2, 5-dichlorophenol product, sampling and carrying out HPLC detection to obtain the product with the conversion rate of 1, 4-dichlorobenzene of 10-15%, the selectivity of 2, 5-dichlorophenol of more than 95% and the selectivity of 2, 4-dichlorophenol of less than 0.1%.
In the step (2), the H2O2Is added in an amount of 0.3 times mole of 1, 4-dichlorobenzene.
The invention has the advantages and beneficial effects that:
1. the vanadium oxide/TS-1 supported catalyst provided by the invention is a heterogeneous catalyst with vanadium content of 1-5% obtained by combining vanadyl acetylacetonate with a TS-1 type titanium silicalite molecular sieve and performing dissolution, impregnation, filtration, freeze drying, roasting and the like, the yield can reach 100% by vanadium, the catalyst efficiency is improved, the selectivity to a product is high, and the excessive oxidation of 2, 5-dichlorophenol can be effectively controlled.
2. Aiming at the problem that in the prior art, in the process of synthesizing 2, 5-dichlorophenol by one-step catalytic oxidation of 1, 4-dichlorobenzene serving as a raw material, most of catalysts cannot effectively inhibit the over-oxidation of 2, 5-dichlorophenol, so that the selectivity of 2, 5-dichlorophenol is not high, the invention finds that when a complex pyridine-2, 6-vanadyl phthalate (Py-V, the structural formula is shown as formula I) formed by the reaction of pyridine-2, 6-dicarboxylic acid and vanadyl acetylacetonate is used as a catalyst, the over-oxidation product can be remarkably inhibited, the selectivity of 2, 5-dichlorophenol can reach over 90 percent, but the generation of isomer 2, 4-dichlorophenol cannot be well inhibited, and the maximum amount of 2 can be 5 percent, 4-dichlorophenol (see patent application No. 202010753097.9). Meanwhile, when the TS-1 type titanium silicalite molecular sieve is used as a catalyst, although the excessive oxidation of the product cannot be well inhibited, the generation of isomer 2, 4-dichlorophenol can be effectively avoided, and the ratio of 2, 5-dichlorophenol to 2, 4-dichlorophenol is more than 1000/1. Therefore, the complex pyridine-2, 6-vanadyl dicarboxylate and TS-1 are chemically connected to prepare the catalyst Py-V-TS-1 (the structural formula is shown as formula II), and the surprising discovery that the catalyst Py-V-TS-1 can effectively inhibit the over-oxidation of the product and the generation of the isomer 2, 4-dichlorophenol (see the patent application No. 202010751268.4).
Based on the above research results, the inventors tried to directly combine vanadyl acetylacetonate with TS-1 to prepare supported catalyst VOX(ii)/TS-1. Although the two catalysts shown in the formulas I and II have ideal catalytic effects (Py-V: the conversion rate is more than 20%, the selectivity is more than 90%, Py-V-TS-1: the conversion rate is more than 15%, and the selectivity is more than 90%), the two catalysts also have various defects, the Py-V is not a complete heterogeneous catalyst, the recovery process is complicated and is not beneficial to the reuse of the catalyst, and the Py-V-TS-1 is a complete heterogeneous catalyst but needs to be connected with the TS-1 through two-step chemical reaction, so the synthetic route is longer, and the cost is higher. In contrast, VOXthe/TS-1 is a heterogeneous catalyst and can be prepared by an isometric impregnation method, the preparation process is simple, and the catalyst is more convenient to reuse compared with Py-V. Further research proves that VO with vanadium content of 1-5% is adoptedXIn the process of preparing 2, 5-dichlorophenol from 1, 4-dichlorobenzene by one-step catalytic oxidation of the/TS-1, the conversion rate of the 1, 4-dichlorobenzene can reach 10-15%, the selectivity of the 2, 5-dichlorophenol can reach more than 95%, the over-oxidation product can be controlled below 5%, and the isomer 2, 4-dichlorophenol can be obviously inhibited (the selectivity of the 2, 4-dichlorophenol is less than 0.1%). Albeit VOXThe catalytic efficiency of the/TS-1 is not very high, but the catalyst has obvious inhibiting effect on the over-oxidation of the product and the formation of isomer 2, 4-dichlorophenol, and the selectivity of the 2, 5-dichlorophenol is high, so the vanadium oxide/TS-1 supported catalyst can replace two catalysts of Py-V or Py-V-TS-1, and provides a beneficial reference for preparing the 2, 5-dichlorophenol by catalytic oxidationAnd (4) value.
Drawings
FIG. 1 is an HPLC chromatogram of the 2, 5-dichlorophenol product prepared in example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples. It should be noted, however, that the following examples are not to be construed as limiting the scope of the present invention, and that many insubstantial modifications and variations of the invention can be made by those skilled in the art without departing from the spirit and scope of the invention as set forth herein.
Example 1
A supported catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation is a vanadium oxide/TS-1 heterogeneous catalyst obtained by combining vanadyl acetylacetonate with a TS-1 type titanium silicalite molecular sieve, namely 5g of vanadyl acetylacetonate is dissolved by 125g of methanol to obtain a methanol solution of vanadyl acetylacetonate, 30g of the TS-1 type titanium silicalite molecular sieve is added, the solution is stirred and soaked for 2.5 hours at room temperature and then filtered, a filter cake is subjected to freeze drying to remove the methanol and then is placed in a muffle furnace for roasting at 550 ℃ for 2 hours to obtain a brown gray powdery vanadium oxide/TS-1 supported catalyst product, the vanadium content in the product is 4.93 percent as measured by ICP-AES, and the yield is 100 percent calculated by vanadium.
Example 2
A catalytic oxidation preparation 2, 5-dichlorophenol supported catalyst, this catalyst is vanadium oxide/TS-1 heterogeneous catalyst obtained by acetylacetone vanadyl and TS-1 type titanium silicalite molecular sieve combination, dissolve 3g acetylacetone vanadyl with 90g methanol and get acetylacetone methanol solution of vanadyl, then add TS-1 type titanium silicalite molecular sieve of 22.5g, stir and soak 2h at room temperature, filter cake, freeze-dry, remove methanol, place in muffle furnace and roast 1h at 600 duC, get brown gray powdery vanadium oxide/TS-1 supported catalyst product, ICP-AES finds vanadium content in the product is 2.96%, the yield is 100% counted by vanadium.
Example 3
A supported catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation is a vanadium oxide/TS-1 heterogeneous catalyst obtained by combining vanadyl acetylacetonate with a TS-1 type titanium silicalite molecular sieve, namely, 1g of vanadyl acetylacetonate is dissolved by 20g of methanol to obtain a methanol solution of vanadyl acetylacetonate, 25g of the TS-1 type titanium silicalite molecular sieve is added, the mixture is stirred and soaked for 3 hours at room temperature and then filtered, a filter cake is frozen and dried to remove the methanol and then is placed in a muffle furnace to be roasted for 3 hours at 500 ℃ to obtain a brown-gray powdery vanadium oxide/TS-1 supported catalyst product, the vanadium content in the product is 1.07 percent by ICP-AES, and the yield is 100 percent by vanadium.
Example 4
The vanadium oxide/TS-1 supported catalyst prepared in example 1 is used for preparing 2, 5-dichlorophenol by catalytic oxidation, and the specific method is as follows:
(1) adding 1, 4-dichlorobenzene (100 g, 0.68 mol) and 10 times of acetic acid into a reaction vessel in sequence, and stirring for dissolving;
(2) adding vanadium oxide/TS-1 supported catalyst (5 g) according to the weight ratio, and then dropping H with the mass concentration of 30 percent within 2 hours at the temperature of 60 DEG C2O2(23.12 g, 0.20 mol), continuing to preserve heat for 1h after dripping to obtain 2, 5-dichlorophenol product, sampling for HPLC detection (as shown in figure 1), and detecting
The conversion of 1, 4-dichlorobenzene was 12.63% (calculation method: 87.37g as the amount of 1, 4-dichlorobenzene in the reaction mixture quantitatively determined by HPLC external standard method, the conversion of 1, 4-dichlorobenzene was: ((100-87.37)/100 × 100% = 12.63%);
the selectivity of 2, 5-dichlorophenol is 98.93 percent (calculated by measuring the amount of 2, 5-dichlorophenol in the reaction solution by HPLC external standard method to be 13.88g (0.085 mol), and the selectivity of 2, 5-dichlorophenol is 0.085/(12.63/147) × 100% =98.93 percent);
the selectivity of 2, 4-dichlorophenol was 0.06% (calculation method: the amount of 2, 4-dichlorophenol in the reaction mixture, which was quantitatively determined by HPLC external standard method, was 8.40 mg (0.052 mmol), and the selectivity of 2, 4-dichlorophenol was 0.017/1000/(12.63/147) × 100% = 0.06%
Example 5
The vanadium oxide/TS-1 supported catalyst prepared in example 2 is used for preparing 2, 5-dichlorophenol by catalytic oxidation, and the specific method is as follows:
(1) adding 1, 4-dichlorobenzene (147.00 g, 1.00 mol) and 15 times of acetic acid into a reaction vessel in sequence, and stirring for dissolving;
(2) adding vanadium oxide/TS-1 supported catalyst (7.35 g) according to the weight ratio, and then dripping 30 percent H within 3 hours at 60 DEG C2O2(34.0 g, 0.30 mol), continuing to preserve heat for 1h after dripping to obtain a 2, 5-dichlorophenol product, sampling for HPLC detection, and measuring that the conversion rate of 1, 4-dichlorobenzene is 14.11%, the selectivity of 2, 5-dichlorophenol is 99.10% and the selectivity of 2, 4-dichlorophenol is 0.03%.
Example 6
The vanadium oxide/TS-1 supported catalyst prepared in example 3 is used for preparing 2, 5-dichlorophenol by catalytic oxidation, and the specific method is as follows:
(1) adding 1, 4-dichlorobenzene (73.50 g, 0.50 mol) and 5 times of acetic acid into a reaction container in sequence, and stirring for dissolving;
(2) adding vanadium oxide/TS-1 supported catalyst (3.68 g) according to the weight ratio, and then dripping 30 percent H within 1 hour at 60 DEG C2O2(17.00 g, 0.15 mol), continuing to preserve heat for 1h after dripping to obtain a 2, 5-dichlorophenol product, sampling for HPLC detection, and measuring the conversion rate of 1, 4-dichlorobenzene, the selectivity of 2, 5-dichlorophenol to 99.27 percent and the selectivity of 2, 4-dichlorophenol to 0.02 percent.
Comparative example 1
The same procedure as in example 4 was repeated except that a vanadium oxide/TS-1 supported catalyst having a vanadium content of 0.52% was used for the preparation of 2, 5-dichlorophenol by catalytic oxidation. And sampling the obtained 2, 5-dichlorophenol product, and detecting by HPLC (high performance liquid chromatography), wherein the conversion rate of 1, 4-dichlorobenzene is 5.75%, the selectivity of 2, 5-dichlorophenol is 91.38%, and the selectivity of 2, 4-dichlorophenol is 0.05%.
Comparative example 2
The same procedure as in example 4 was repeated except that a vanadium oxide/TS-1 supported catalyst having a vanadium content of 5.5% was used for the preparation of 2, 5-dichlorophenol by catalytic oxidation. And sampling the obtained 2, 5-dichlorophenol product, and detecting by HPLC (high performance liquid chromatography), wherein the conversion rate of 1, 4-dichlorobenzene is 19.53%, the selectivity of 2, 5-dichlorophenol is 93.44%, and the selectivity of 2, 4-dichlorophenol is 4.08%.
Claims (6)
1. A supported catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation is characterized in that: the catalyst is a vanadium oxide/TS-1 heterogeneous catalyst obtained by combining vanadyl acetylacetonate with a TS-1 type titanium silicalite molecular sieve, namely, vanadyl acetylacetonate is dissolved by methanol to obtain a methanol solution of vanadyl acetylacetonate, then the TS-1 type titanium silicalite molecular sieve is added, stirring and dipping are carried out at room temperature, then filtration is carried out, a filter cake is subjected to freeze drying to remove methanol and then is placed in a muffle furnace to be roasted for 1-3 h at 500-600 ℃, thus obtaining a brown-gray powdery vanadium oxide/TS-1 supported catalyst product, and the vanadium content in the product is 1-5% by ICP-AES.
2. The supported catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation according to claim 1, wherein: the methanol solution of vanadyl acetylacetonate is obtained by dissolving vanadyl acetylacetonate in 20-30 times of methanol by weight.
3. The supported catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation according to claim 1, wherein: the addition amount of the TS-1 type titanium silicalite molecular sieve is 6-25 times of the weight of vanadyl acetylacetonate.
4. The supported catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation according to claim 1, wherein: and stirring and dipping at room temperature for 2-3 h.
5. The supported catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation according to claim 1, wherein: the method for preparing 2, 5-dichlorophenol by catalytic oxidation by using the vanadium oxide/TS-1 supported catalyst comprises the following steps:
(1) sequentially adding 1, 4-dichlorobenzene and 5-15 times of acetic acid by weight into a reaction container, and stirring for dissolving;
(2) adding a vanadium oxide-TS-1 supported catalyst with the weight ratio of 5 percent of 1, 4-dichlorobenzene, and then dripping 0.3eq to the mixture within 1 to 3 hours at the temperature of 60 DEG CH concentration of 30%2O2And continuously preserving the temperature for 1h after dripping to obtain a 2, 5-dichlorophenol product, sampling and carrying out HPLC detection to obtain the product with the conversion rate of 1, 4-dichlorobenzene of 10-15%, the selectivity of 2, 5-dichlorophenol of more than 95% and the selectivity of 2, 4-dichlorophenol of less than 0.1%.
6. The supported catalyst for preparing 2, 5-dichlorophenol by catalytic oxidation according to claim 5, wherein: in the step (2), the H2O2Is added in an amount of 0.3 times mole of 1, 4-dichlorobenzene.
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|---|---|---|---|---|
| US5648562A (en) * | 1994-08-03 | 1997-07-15 | Sandoz Ltd. | Oxidation process |
| CN103537313A (en) * | 2013-10-11 | 2014-01-29 | 南京工业大学 | Catalyst for preparing phenol by benzene hydroxylation and preparation method thereof |
| CN104909993A (en) * | 2015-06-15 | 2015-09-16 | 江苏蓝丰生物化工股份有限公司 | Industrial synthesis method of dicamba key intermediate 2,5-dichlorophenol |
| CN105921161A (en) * | 2016-04-27 | 2016-09-07 | 常州大学 | Catalyst used in p-dichlorobenzene hydroxylate for preparing 2,5-dichlorophenol, and preparation method thereof |
| CN108940370A (en) * | 2018-08-01 | 2018-12-07 | 常州大学 | A kind of synthesis of the mesoporous catalyst for benzene Synthesis of Phenol via Direct Catalytic Hydroxylation |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648562A (en) * | 1994-08-03 | 1997-07-15 | Sandoz Ltd. | Oxidation process |
| CN103537313A (en) * | 2013-10-11 | 2014-01-29 | 南京工业大学 | Catalyst for preparing phenol by benzene hydroxylation and preparation method thereof |
| CN104909993A (en) * | 2015-06-15 | 2015-09-16 | 江苏蓝丰生物化工股份有限公司 | Industrial synthesis method of dicamba key intermediate 2,5-dichlorophenol |
| CN105921161A (en) * | 2016-04-27 | 2016-09-07 | 常州大学 | Catalyst used in p-dichlorobenzene hydroxylate for preparing 2,5-dichlorophenol, and preparation method thereof |
| CN108940370A (en) * | 2018-08-01 | 2018-12-07 | 常州大学 | A kind of synthesis of the mesoporous catalyst for benzene Synthesis of Phenol via Direct Catalytic Hydroxylation |
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