CN102294272A - Catalyst for preparing phenol by hydroxylation of benzene and preparation method - Google Patents

Catalyst for preparing phenol by hydroxylation of benzene and preparation method Download PDF

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CN102294272A
CN102294272A CN2011101940171A CN201110194017A CN102294272A CN 102294272 A CN102294272 A CN 102294272A CN 2011101940171 A CN2011101940171 A CN 2011101940171A CN 201110194017 A CN201110194017 A CN 201110194017A CN 102294272 A CN102294272 A CN 102294272A
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catalyst
benzene
preparation
phenol
reaction
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CN102294272B (en
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张富民
景丽
徐文俊
钟依均
朱伟东
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Zhejiang Normal University CJNU
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Abstract

The invention relates to a catalyst for preparing phenol by hydroxylation of benzene and a preparation method thereof. The component expression of the catalyst provided by the invention is Cs2.5(MIMPS)nH1.5-nPMo11VO40, wherein MIMPS indicates [N-(3-sulfonic)propyl-imidazolium] and n equals to 0.5-1.5. The preparation method provided by the invention comprises the following steps of: (1) preparing pure vanadium substituted heteropolymolybdates; (2) mixing the pure vanadium substituted heteropolymolybdates obtained from the step (1) with deionized water, adding dropwisely an inorganic cesium salt solution into the above solution with stirring, followed by a reaction, removing water from a suspending liquid obtained after the reaction so as to obtain a solid, drying to obtain a heteropolyacid inorganic cesium salt; (3) mixing the heteropolyacid inorganic cesium salt obtained from the step (2) with deionized water, adding dropwisely an MIMPS aqueous solution with stirring, followed by a reaction, removing the solvent from a suspending liquid obtained after the reaction so as to obtain a solid, and drying to obtain the catalyst for preparing phenol by hydroxylation of benzene. By the adoption of the catalyst provided by the invention, the yield of phenol can be obviously raised; in addition, the catalyst is easy to recover and convenient to repeatedly use.

Description

A kind of catalyst and preparation method who is used for benzene hydroxylation system phenol
Technical field
The present invention relates to two heteropolyacid catalyst and the preparation methods that modify of a kind of organic and inorganic, particularly relate to a kind of catalyst and preparation method who is used for benzene hydroxylation system phenol.
Background technology
Phenol is important Organic Chemicals, is widely used in petrochemical industry, agricultural and plastics industry, and the world demand amount is cumulative year after year trend.The industrial process of phenol mainly is a cumene method at present, and this method adopts benzene alkylation to obtain isopropylbenzene, and cumene oxidation obtains dicumyl peroxide, and dicumyl peroxide decomposes generation phenol.The weak point of this technology is that energy consumption is big, phenol yield is low, the peroxide that has the intermediate product-isopropylbenzene of easily blasting, consume national strategy resource propylene, the demand that produces the acetone with the accessory substance acetone of phenol equimolar amounts is much smaller than phenol, and needs to add acid and multiple organic reagent, causes the wasting of resources, operation inconvenience and environmental pollution etc. do not meet STRATEGIES OF SUSTAINABLE DEVELOPMENT.In recent years the Catalytic processes of benzene direct oxidation system phenol has been attracted the extensive concern of academia and industrial quarters.This is one and relates to the direct activation c h bond and make the reaction of hydro carbons functionalization, directly hydroxyl is introduced aromatic ring by the activation c h bond and generated corresponding hydroxy compounds, this is one of the most scabrous problem in the synthetic chemistry, and its key is a high-performance selective oxidation Study of Catalyst.
H 2O 2Oxidant can change the water of direct discharging into, thereby is considered to the green oxidation agent of environmental sound, comes into one's own in hydrocarbon selective oxidation research in recent years.People such as Thangaraj (Thangaraj A, Kumar R, Ratnasamy P, Appl.Catal., 1990,57, L1-L3) reported that benzene and hydrogen peroxide directly carry out hydroxylating system phenol on the TS-1 zeolite.The result shows that reaction has advantages of high catalytic activity and selectivity to the TS-1 molecular sieve to benzene hydroxylation.In reaction system, add an amount of inorganic acid, can improve the selectivity of product phenol; Increase TS-1 and H 2O 2Addition, help the raising of benzene conversion ratio, but cause target product phenol selectivity to descend.
People such as Bhaumik (Bhaumik A, Mukherijee P, Kumar R, J.Catal., 1998,178,101-107) further the TS-1 molecular sieve catalyst is used for phase reaction (solid catalyst+organic substrates+H 2O 2Water).Under condition of no solvent, H 2O 2When carrying out hydroxylating with benzene, activity of such catalysts is high during than traditional, as to adopt cosolvent two-phase (solid catalyst+liquid phase) reaction system.Except that TS-1 molecular sieve and ZSM-5 molecular sieve, the ALPO of cupric 4Molecular sieve to the liquid phase reactor of benzene oxidation system phenol also show higher activity (Cheng S, Chou B, US6180836).
Chinese patent CN1481935A loads on a kind of natural red soil transition metal as catalyst, and is applied in benzene and the reaction of hydrogen peroxide synthesizing phenol.The carrier that discovery is crossed with sulfuric acid treatment is directly produced phenol to benzene during the load vanadic anhydride again obvious facilitation, wherein the mol ratio when benzene and hydrogen peroxide is 1: 1.4, and reaction temperature is 40 ℃, reaction 4h, the conversion ratio of benzene is 12.8%, and the selectivity of phenol is 93.4%.
Chinese patent CN1554630A will directly produce the process of phenol through the activated carbon application that inorganic acid soaks in benzene.When the type of active carbon is the coconut husk type, acetic acid is solvent, and the mass ratio of benzene and hydrogen peroxide is 1: 1～4, and the reaction time is 1～6h, and the yield of phenol can reach 3～13%, and the selectivity of phenol is 70～85%.
The class formation that heteropoly acid is made up of by the coordination of oxygen atom bridging by a fixed structure hetero atom and polyatom is stable, form and simply contain the oxygen polyacid, is a class green, novel solid acid catalyst and oxidation reduction catalyst.The heteropoly acid that particularly contains vanadium because its acidity and oxidisability can be carried out modulation on molecular level, comes into one's own in the reaction of catalytic oxidation benzene system phenol in recent years.People such as Nomiya find that the tungsten vanadium phospha polyacid with Keggin structure is direct oxidation into phenol to benzene and has activity under the effect of hydrogen peroxide, and through reaction 576h, the structure of heteropolyacid catalyst (the Nomiya K that still is kept perfectly, Yanagibayashi H, Nozaki C, Kondoh K, Hiramatsu E, Shimizu Y, J.Mol.Catal.A Chem., 1996,114,181-190).People such as Zhang are to being solvent with the glacial acetic acid, H 3+nPMo 12-nV nO 40The process conditions of liquid phase hydrogen peroxide catalytic oxidation benzene system phenol are optimized, and the highest yield of phenol is 26%, the phenol selectivity be 91% (Zhang J, Tang Y, Li G Y, HuC W, Appl.Catal.AGen., 2005,278,251-261).With pure heteropoly acid is that the significant disadvantages of homogeneous catalyst catalysis benzene liquid phase synthesizing phenol is the catalyst recovery difficulty, at this, Chinese patent CN1788843 adopts sol-gal process to carry out molybdenum vanadium phospha polyacid immobilized, discovery prepared catalyst in benzene and hydrogen peroxide hydroxylating preparation feedback can be reused repeatedly, but this catalyst preparation process is relatively complicated.
Up to now, on the catalyst of open report, the conversion ratio and the phenol yield of benzene are also relative not high in benzene and the hydrogen peroxide hydroxylating system phenol reactant process, and modify simultaneously with organic and inorganic group that molybdenum vanadium phospha polyacid is applied to benzene and hydrogen peroxide hydroxylating process is not appeared in the newspapers as yet.
Summary of the invention
The present invention is directed to the conversion ratio and the not high weak point of phenol yield of benzene in existing benzene and the hydrogen peroxide hydroxylating system phenol reactant process, provide a kind of with respect to pure heteropoly acid, can keep the conversion ratio of benzene constant substantially, can obviously improve the yield of phenol, and have catalyst and this Preparation of catalysts method easy, that repeated use is used for benzene hydroxylation system phenol easily of reclaiming as heterogeneous catalyst.
The present invention finishes by following technical scheme, and a kind of catalyst that is used for benzene hydroxylation system phenol, this catalyst are the two molybdenum vanadium phospha polyacid catalyst of modifying of a kind of organic and inorganic, and the composition of this catalyst represents that mode is Cs 2.5(MIMPS) nH 1.5-nPMo 11VO 40, MIMPS represents [N-(3-sulfonic group) propyl group-imidazole salts], wherein n=0.5～1.5 in the formula.
A kind of Preparation of catalysts method that is used for benzene hydroxylation system phenol of the present invention may further comprise the steps:
(1) preparation of pure molybdenum vanadium phospha polyacid takes by weighing 0.005～0.01mol V by the mol ratio of V and Mo at 1: 11 2O 5With 0.11～0.22mol MoO 3Be dissolved in respectively in the deionized water, then these two kinds of solution mixed and be heated to 353～393K, when stirring, dropwise add the H of 0.01～0.02mol 3PO 4, this suspension is reacted 12～36h under 323～373K, obtain settled solution, will obtain pure molybdenum vanadium phospha polyacid H behind the removal of solvents 4PMo 11VO 40
(2) the pure molybdenum vanadium phospha polyacid 0.001mol that gets preparation in the step (1) mixes with deionized water, and under the heating stirring condition, in the ratio of inorganic cesium salt and heteropoly acid mol ratio 1～4: 1, getting cesium salt concentration is 0.1mol.L -1Inorganic cesiated salt solution 10～40mL dropwise add above-mentioned solution, 303～353K obtains solid with moisture removal in the suspension that obtains after continuing down reaction 3～8h, is dry 5～20h under 323～393K in temperature, obtains the inorganic cesium salt of heteropoly acid;
(3) the acidic cs salts of heteropolyacid 0.001mol that gets step (2) preparation mixes with deionized water, under stirring condition, by Cs in the acidic cs salts of heteropolyacid and MIMPS mol ratio is 2.5: 1～1.5 dropwise to splash into the MIMPS aqueous solution 10～15ml that concentration is 0.1mol.L-1,303～353K is reaction 3～10h down, to obtain solid behind the removal of solvents in the resulting suspension, in temperature is dry 5～20h under 353～393K, promptly obtains a kind of catalyst that is used for benzene hydroxylation system phenol.
In above-mentioned a kind of Preparation of catalysts method that is used for benzene hydroxylation system phenol, used cesium salt is Cs in step (2) 2CO 3, CsNO 3, a kind of among the CsCl.
In above-mentioned a kind of Preparation of catalysts method that is used for benzene hydroxylation system phenol, in step (2), used cesium salt and H 4PMo 11VO 40Mol ratio be 2～3: 1.
In above-mentioned a kind of Preparation of catalysts method that is used for benzene hydroxylation system phenol, preferred temperature conditions is 333～353K in step (3), and the preferred reaction time is 5～7h, and the mol ratio of preferred Cs and MIMPS is 2.5: 0.5～1.
The application of catalyst of the present invention in benzene and the reaction of hydrogen peroxide selective oxidation synthesizing phenol:
Benzene and hydrogen peroxide liquid phase oxidation reaction condition are: when the consumption of benzene and hydrogen peroxide was all 10mmol, the amount of catalyst was 0.05mmol, solvent acetonitrile 6mL, 65 ℃ of reaction temperatures, reaction time 5h.Product is taken out from reactor by syringe, analyzes with U.S. Anjelen Sci. ﹠ Tech. Inc 6820 type gas chromatographs after centrifugal, and chromatographic column is that (0.45mm * 30m), detector is a hydrogen flame detector to the DB-5 capillary column.
A kind of catalyst that is used for benzene hydroxylation system phenol of the present invention, as heterogeneous catalyst, reaction is finished rear catalyst and can be reclaimed by the mode of leaving standstill, reuse conveniently, has overcome pure heteropoly acid as homogeneous catalyst, is dissolved in reaction system and causes reclaiming the problem of reusing difficulty.In addition, the introducing of organic group in the catalyst of the present invention, help nonpolar reactant benzene and be adsorbed in catalyst surface, thereby promote its reaction to improve the benzene conversion ratio, and the phenol of target product polarity easily from the catalyst desorption get off, avoided further deep oxidation, optionally improved thereby help phenol.
Description of drawings
Fig. 1 is Cs 2.5(MIMPS) 1.5PMo 11VO 40The repeat performance comparison diagram of catalyst in benzene and hydrogen peroxide hydroxylating.
The specific embodiment
Below by embodiment the present invention is made further and to specify, but the present invention is not limited to following example.
Embodiment 1
Cs 2.5(MIMPS) 0.5HPMo 11VO 40Preparation and catalytic performance
H 4PMo 11VO 40Preparation: the MoO that takes by weighing 0.11mol 3V with 0.005mol 2O 5Respectively soluble in water, subsequently these two kinds of solution are mixed and be heated to 373K, add the H of 0.01mol under the condition of stirring 3PO 4, and this suspension reacted 24h under 373K, and after the filtration resulting solution being mixed with the standard liquid of 500mL, the concentration of solution is 0.02molL -1
Cs 2.5H 1.5PMo 11VO 40Preparation: the Cs that takes by weighing 0.005mol 2CO 3The formation solution that is dissolved in the water dropwise splashes into the H that pipettes in advance under condition of stirring 4PMo 11VO 40Among the standard liquid 200mL, be heated to 373K, reaction 5～7h is centrifugal and supernatant toppled over to be placed in 100 ℃ of convection oven be drying to obtain Cs with resulting suspension 2.5H 1.5PMo 11VO 40
Cs 2.5(MIMPS) 0.5HPMo 11VO 40Preparation: the Cs that takes by weighing preparation 2.5H 1.5PMo 11VO 400.2mmol be dispersed in the water, form uniform suspension under the stirring condition, take by weighing MIMPS 0.1mmol again and be dissolved in the water, dropwise splash into Cs 2.5H 1.5PMo 11VO 40Suspension in, reaction 5～7h is drying to obtain Cs with the centrifugal back of this suspension under 100 ℃ 2.5(MIMPS) 0.5HPMo 11VO 40
Take by weighing 0.05mmol (being 0.111g) solid catalyst and be applied to the benzene liquid phase oxidation reaction, the results are shown in Table 1.
Embodiment 2
Cs 2.5(MIMPS) 0.75H 0.75PMo 11VO 40Preparation and catalytic performance
The preparation method is with embodiment 1 unanimity, and difference is that the MIMPS amount that adds is 0.15mmol.
Take by weighing 0.05mmol (being 0.113g) solid catalyst and be applied to the benzene liquid phase oxidation reaction, the results are shown in Table 1.
Embodiment 3
Cs 2.5(MIMPS) H 0.5PMo 11VO 40Preparation and catalytic performance
The preparation method is with embodiment 1 unanimity, and difference is that the MIMPS amount that adds is 0.2mmol.
Take by weighing 0.05mmol (being 0.116g) solid catalyst and be applied to the benzene liquid phase oxidation reaction, the results are shown in Table 1.
Embodiment 4
Cs 2.5MIMPS 1.5PMo 11VO 40Preparation and catalytic performance
The preparation method is with embodiment 1 unanimity, and difference is that the MIMPS amount that adds is 0.3mmol.
Take by weighing 0.05mmol (being 0.121g) solid catalyst and be applied to the benzene liquid phase oxidation reaction, the results are shown in Table 1.
Embodiment 5
Select best Cs 2.5(MIMPS) 1.5PMo 11VO 40Solid catalyst has been investigated the repeat performance of catalyst, and the result as shown in Figure 1.As can be known, after catalyst is reused 5 times, reduce, but still show stability preferably though benzene conversion ratio and phenol selectivity all have to a certain degree.
Comparative Examples 1
H 4PMo 11VO 40Catalytic performance
Take by weighing H 4PMo 11VO 400.05mmol (being 0.09g) is used for the benzene liquid phase oxidation reaction, the results are shown in Table 1.
Comparative Examples 2
Cs 2.5H 1.5PMo 11VO 40Catalytic performance
Take by weighing Cs 2.5H 1.5PMo 11VO 400.05mmol (being 0.106g) is used for the benzene liquid phase oxidation reaction, the results are shown in Table 1.
Benzene conversion ratio and phenol optionally compare on table 1 different catalysts

Claims (6)

1. catalyst that is used for benzene hydroxylation system phenol, this catalyst are the two molybdenum vanadium phospha polyacid catalyst of modifying of a kind of organic and inorganic, it is characterized in that the composition of this catalyst represents that mode is Cs 2.5(MIMPS) nH 1.5-nPMo 11VO 40, MIMPS represents [N-(3-sulfonic group) propyl group-imidazole salts], wherein n=0.5～1.5 in the formula.
2. a Preparation of catalysts method that is used for benzene hydroxylation system phenol is characterized in that described a kind of Preparation of catalysts method that is used for benzene hydroxylation system phenol, may further comprise the steps:
(1) preparation of pure molybdenum vanadium phospha polyacid takes by weighing 0.005～0.01mol V by the mol ratio of V and Mo at 1: 11 2O 5With 0.11～0.22mol MoO 3Be dissolved in respectively in the deionized water, then these two kinds of solution mixed and be heated to 353～393K, when stirring, dropwise add the H of 0.01～0.02mol 3PO 4, this suspension is reacted 12～36h under 323～373K, obtain settled solution, will obtain pure molybdenum vanadium phospha polyacid H behind the removal of solvents 4PMo 11VO 40
(2) the pure molybdenum vanadium phospha polyacid 0.001mol that gets preparation in the step (1) mixes with deionized water, and under the heating stirring condition, in the ratio of inorganic cesium salt and heteropoly acid mol ratio 1～4: 1, getting cesium salt concentration is 0.1mol.L -1Inorganic cesiated salt solution 10～40mL dropwise add above-mentioned solution, 303～353K obtains solid with moisture removal in the suspension that obtains after continuing down reaction 3～8h, is dry 5～20h under 323～393K in temperature, obtains the inorganic cesium salt of heteropoly acid;
(3) the acidic cs salts of heteropolyacid 0.001mol that gets step (2) preparation mixes with deionized water, under stirring condition, by Cs in the acidic cs salts of heteropolyacid and MIMPS mol ratio is 2.5: 1～1.5 dropwise to splash into the MIMPS aqueous solution 10～15ml that concentration is 0.1mol.L-1,303～353K is reaction 3～10h down, to obtain solid behind the removal of solvents in the resulting suspension, in temperature is dry 5～20h under 353～393K, promptly obtains a kind of catalyst that is used for benzene hydroxylation system phenol.
3. according to the described a kind of Preparation of catalysts method that is used for benzene hydroxylation system phenol of claim 2, it is characterized in that cesium salt used in step (2) is Cs 2CO 3, CsNO 3, a kind of among the CsCl.
4. according to claim 2 or 3 described a kind of Preparation of catalysts methods that are used for benzene hydroxylation system phenol, it is characterized in that in step (2) used cesium salt and H 4PMo 11VO 40Mol ratio be 2～3: 1.
5. according to the described a kind of Preparation of catalysts method that is used for benzene hydroxylation system phenol of claim 2, it is characterized in that preferred temperature conditions is 333～353K in step (3), the preferred reaction time is 5～7h, and the mol ratio of preferred Cs and MIMPS is 2.5: 0.5～1.
6. application that is used for the catalyst of benzene hydroxylation system phenol in benzene and the reaction of hydrogen peroxide selective oxidation synthesizing phenol, it is characterized in that benzene and hydrogen peroxide liquid phase oxidation reaction condition are in described application: when the consumption of benzene and hydrogen peroxide is all 10mmol, the amount of catalyst is 0.05mmol, solvent acetonitrile 6mL, 65 ℃ of reaction temperatures, reaction time 5h.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102641746A (en) * 2012-04-05 2012-08-22 中国科学院青岛生物能源与过程研究所 Heteropolyacid modified catalyst, and preparation and catalyst catalytic hydrolysis reaction system thereof
CN103566969A (en) * 2012-07-31 2014-02-12 中国科学院大连化学物理研究所 Preparation method of vanadium-base catalytic material for catalyzing benzene hydroxylation to prepare phenol
CN105080533A (en) * 2014-05-14 2015-11-25 中国石油化工股份有限公司 Catalyst for benzene oxidation to synthesize phenol
CN107754854A (en) * 2017-11-12 2018-03-06 闽江学院 The preparation and its application of hydroxyl/sulfonic group difunctionality vanadium doping heteropoly acid ion hybrid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MARLEN GUTJAHR ET AL.: "A Q- and X-Band Pulsed Electron Nuclear Double Resonance Study of the Structure and Location of the Vanadyl Ions in the Cs Salt of Heteropolyacid PVMo11O40", 《J. AM. CHEM. SOC.》 *
杨爽等: "磷钨杂多酸盐催化苯甲醇选择氧化性能的研究", 《石油化工高等学校学报》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102641746A (en) * 2012-04-05 2012-08-22 中国科学院青岛生物能源与过程研究所 Heteropolyacid modified catalyst, and preparation and catalyst catalytic hydrolysis reaction system thereof
CN103566969A (en) * 2012-07-31 2014-02-12 中国科学院大连化学物理研究所 Preparation method of vanadium-base catalytic material for catalyzing benzene hydroxylation to prepare phenol
CN105080533A (en) * 2014-05-14 2015-11-25 中国石油化工股份有限公司 Catalyst for benzene oxidation to synthesize phenol
CN105080533B (en) * 2014-05-14 2017-12-15 中国石油化工股份有限公司 Catalyst for benzene oxidatoin synthesizing phenol
CN107754854A (en) * 2017-11-12 2018-03-06 闽江学院 The preparation and its application of hydroxyl/sulfonic group difunctionality vanadium doping heteropoly acid ion hybrid
CN107754854B (en) * 2017-11-12 2020-05-05 闽江学院 Preparation and application of hydroxyl/sulfonic bifunctional vanadium-doped heteropoly acid ion hybrid

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