CN102942487B - Method for preparing o-nitrophenol through phenol nitration selectivity - Google Patents

Method for preparing o-nitrophenol through phenol nitration selectivity Download PDF

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CN102942487B
CN102942487B CN201210463229.XA CN201210463229A CN102942487B CN 102942487 B CN102942487 B CN 102942487B CN 201210463229 A CN201210463229 A CN 201210463229A CN 102942487 B CN102942487 B CN 102942487B
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phenol
caesium
heteropolyacid
silicon dioxide
tetraethyl silicate
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CN102942487A (en
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刘丽君
龚树文
李永新
崔庆新
尹汉东
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Liaocheng University
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Liaocheng University
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Abstract

The invention discloses a method for preparing o-nitrophenol, which comprises the following steps: nitrating phenol in mild conditions with silica loaded heteropoly acid cesium as a catalyst and low-concentration nitric acid as a nitrating agent; and successively performing extraction, distillation, steam distillation and recrystallization to obtain the o-nitrophenol. The silica loaded heteropoly acid cesium is formed by loading 1% to 40% (wt%) of heteropoly acid cesium to silica. The method for preparing o-nitrophenol has the advantages of high phenol conversion rate, high o-phenol nitration selectivity, easiness in preparation of the catalyst, high catalytic activity, easy separation of the catalyst after the action, reusability and broad application prospects.

Description

A kind of phenol nitration selectivity is prepared the method for o-NP
Technical field
The present invention relates to a kind of preparation method of o-NP, more specifically, the present invention relates to a kind of method that highly selective is prepared o-NP.
Background technology
O-NP can be used for the intermediate of medicine, dyestuff, rubber ingredients and sensitive materials, also can be used as monochromatic pH value indicator, so the preparation of o-NP is extremely important with regard to what show.The production technique of o-NP is comparatively ripe at present, and still, various technique all exists some defects.
Traditional method is to take nitric acid as nitrating agent, by phenol nitration, but the poor selectivity of the method o-NP, product is the mixture of o-NP and p-NP, through distillation, cooling, crystallization, separation obtains o-NP again, and the method has oxidisability because of concentrated nitric acid, by oxidation of phenol, be quinones, cause o-NP productive rate lower.Take o-Nitrochlorobenzene in addition as raw material, be hydrolyzed and react with sodium hydroxide solution, then through sulfuric acid acidation, cooling, crystallization, separation can prepare o-NP, the method is used alkali lye and acid treatment, causes environmental pollution.Can also produce o-NP with o-Nitrophenyl methyl ether, but the defect such as the method exists o-NP content be difficult to surpass 95%, o-Nitrophenyl methyl ether is difficult to recycle, production wastewater treatment difficulty is large and energy consumption is higher.
Summary of the invention
For above-mentioned the deficiencies in the prior art, it is high and meet the preparation method of the o-NP of " green " production requirement that the present invention proposes a kind of selectivity.
The present invention is achieved by the following technical solutions:
Phenol selective nitration is prepared a method for o-NP, and step is as follows:
(1) nitrated: loading silicon dioxide with heteropoly acid caesium catalyzer and phenol to be added in round-bottomed flask, under agitation nitric acid dropping is entered to round-bottomed flask, stirring reaction;
(2) extraction: take ethyl acetate as extraction agent;
(3) distillation: after extraction, oily liquids is placed in round-bottomed flask, and distillation and concentration, collects 75-85 ℃ of cut;
(4) wet distillation: changing water distilling apparatus is wet distillation, has yellow crystals to separate out after the liquid cooling steaming, finishes during without yellow liquid to prolong, and suction filtration is collected, after dry o-NP crude product;
(5) recrystallization: crude product is dissolved in hot ethanol completely, and splashing into suitable warm water, that it is occurred is muddy, and then splash into ethanol it is dissolved completely, separates out glassy yellow needle crystal after cooling, and suction filtration is collected to obtain o-NP sterling.
Foregoing method, preferred scheme is: step (1) stirring reaction is no less than 1 hour.
Foregoing method, preferred scheme is: step (1) loading silicon dioxide with heteropoly acid caesium catalyst levels is the preferred 3-10% of 1%-15%(of phenol quality, is more preferably 5%).
Foregoing method, preferred scheme is: the mass concentration of step (1) nitric acid is 20-40%(preferably 30%).
Foregoing method, preferred scheme is: the mol ratio of step (1) nitric acid and phenol usage is the preferred 1-4 of 0.5～5(, is more preferably 3).
Foregoing method, preferred scheme is: step (2) extraction times is 2-3 time.
The present invention also provides the preparation method of loading silicon dioxide with heteropoly acid caesium catalyzer, and step is as follows:
(1) heteropolyacid is dissolved in deionized water, obtains the heteropolyacid aqueous solution heating;
(2) get cesium carbonate and be dissolved in deionized water, obtain cesium carbonate aqueous solution;
(3) cesium carbonate aqueous solution is added drop-wise in the heteropolyacid aqueous solution, stirring reaction obtains heteropolyacid caesium suspension;
(4) get tetraethyl silicate, by volume tetraethyl silicate: ethanol: water=1:1-6:1-6 is made into tetraethyl silicate alcohol solution heating;
(5) heteropolyacid caesium suspension agitation is added drop-wise in tetraethyl silicate alcohol solution, is heated to gel and occurs, ageing is drying to obtain loading silicon dioxide with heteropoly acid caesium catalyzer.
Described preparation method, preferred scheme is, and the described heteropolyacid of step (1) is have Keggin structure formed containing oxygen polyacid by the coordination of Sauerstoffatom bridging by heteroatoms P and polyatom Mo, W, V, and molecular formula is H 3+xpM 12-xv xo 40, wherein M is Mo or W, x is 1,2 or 3.Described heteropolyacid is phospho-wolframic acid, phospho-molybdic acid, molybdovanaphosphoric acid or tungstovanadophosphoric acid.Described preparation method, preferred scheme is that the described heating of step (1) is preferably at 50 ℃ of heating 30min at 40～60 ℃ of heating 10～60min().Described preparation method, preferred scheme is, the described stirring reaction of step (3) be temperature at 40～60 ℃ stirring reaction 1～6h(preferably at temperature stirring reaction 5h at 50 ℃).Described preparation method, preferred scheme is that the described heating of step (4) is at 60～90 ℃, to heat 10～60min(preferably at 70 ℃, to heat 30min).Described preparation method, preferred scheme is that the described heating of step (5) is to heat at 60～90 ℃ (preferably 70 ℃).The described digestion time of step (5) is the preferred 24h of 10～36h().Described being dried of step (5) is at 80～130 ℃ dry (preferably 120 ℃).Described loading silicon dioxide with heteropoly acid caesium catalyzer is silicon dioxide carried 1～40% heavy heteropolyacid caesium (preferably 10-30%, more preferably 25%).
The preparation method of carried heteropoly acid caesium catalyzer of the present invention, concrete scheme is: heteropolyacid is dissolved in a deionized water, and 40～60 ℃ are heated 10～60min, are then added dropwise to the deionized water solution of cesium carbonate, stirring reaction 1～6h, obtains the suspension of heteropolyacid caesium; By tetraethyl silicate, be tetraethyl silicate by volume: ethanol: water=1:1～6:1～6 wiring solution-forming, heating at 60～90 ℃, heating 10～60min; Heteropolyacid caesium suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continuation is 60～90 ℃ of heating, until gel occurs, after ageing 10～36h, dry at 80～130 ℃, after being dried, can use, adjust the consumption of tetraethyl silicate, the catalyzer that can obtain different heteropolyacid caesium charge capacity, charge capacity is in the mass ratio of cesium salt and silicon-dioxide.
The present invention adopts loading silicon dioxide with heteropoly acid caesium to make catalyzer, and active phase is dispersed in to be had on high specific surface area silica supports, during reaction, can fully contact with reactant, improves its catalytic activity, and nitrated transformation efficiency is corresponding increase also.
Compared with prior art, phenol conversion phenol nitration thing ortho position selectivity high, that prepare is good in the present invention, without contraposition nitration product, produces, and has avoided the separating step of ortho para isomer; Because catalyzer has certain granularity, after reaction, easily process, and catalyzer used to be stable especially, can reuse, the preparation method of catalyzer, preparation facilities are all very simple, and preparation cycle is short, can efficiently be utilized.The present invention has that transformation efficiency is high, process is simple, required time is short, pollution-free, low cost and other advantages.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of embodiment 1 gained sample.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated:
Embodiment 1: prepare o-NP:
(1) Kaolinite Preparation of Catalyst: by 1gH 4pMo 11vO 40be dissolved in 9g deionized water, be made into mass concentration and be 10% H 4pMo 11vO 40the aqueous solution, 50 ℃ of heating 30min, get 0.091g cesium carbonate and are dissolved in appropriate amount of deionized water, keep 50 ℃ of reaction 5h, obtain heteropolyacid caesium CsH 3pMo 11vO 40suspension; Get the about 39ml of 37g() tetraethyl silicate is tetraethyl silicate: ethanol: water=1:2:2 wiring solution-forming, heating at 60 ℃, heating 30min by volume; By heteropolyacid caesium CsH 3pMo 11vO 40suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 60 ℃ of heating, until gel appearance is after ageing 24h, dry at 120 ℃, after being dried, obtains silicon dioxide carried 10% heteropolyacid caesium CsH 3pMo 11vO 40catalyzer.
(2) 0.2mol phenol joins 50ml1, in 2-ethylene dichloride, adds above-mentioned catalyzer 0.5g, and agitation and dropping 0.2mol nitric acid under 30 ℃ of heating (mass concentration, lower same, 30%), reaction 5h; Take ethyl acetate as extraction agent, extract 2 times, combining extraction liquid, is placed in round-bottomed flask, distillation and concentration, the 75-85 of collection oc cut, ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, steams to prolong and finishes during without yellow liquid, after the liquid cooling steaming, has yellow crystals to separate out, and suction filtration is collected, after dry o-NP crude product; The ethanol of take carries out recrystallization to crude product as solvent, and suction filtration is collected to obtain glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 2: prepare o-NP:
(1) Kaolinite Preparation of Catalyst: by 1gH 5pMo 10v 2o 40be dissolved in 9g deionized water, be made into mass concentration and be 10% H 4pMo 10vO 40the aqueous solution, 50 ℃ of heating 30min, get 0.094g cesium carbonate and are dissolved in appropriate amount of deionized water, keep 40 ℃ of reaction 6h, obtain heteropolyacid caesium CsH 4pMo 10v 2o 40suspension; Get the about 39ml of 37g() tetraethyl silicate is tetraethyl silicate: ethanol: water=1:2:2 wiring solution-forming, heating at 80 ℃, heating 30min by volume; By heteropolyacid caesium CsH 4pMo 10v 2o 40suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 80 ℃ of heating, until gel appearance is after ageing 36h, dry at 110 ℃, after being dried, obtains silicon dioxide carried 10% heteropolyacid caesium CsH 4pMo 10v 2o 40catalyzer.
(2) 0.2mol phenol joins 50ml1, in 2-ethylene dichloride, adds above-mentioned catalyzer 1.0g, agitation and dropping 0.25mol nitric acid (30%) under 30 ℃ of heating, reaction 6h; Take ethyl acetate as extraction agent, extract 2 times, combining extraction liquid, is placed in round-bottomed flask, distillation and concentration, the 75-85 of collection oc cut, ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, after the liquid cooling steaming, has yellow crystals to separate out, and to prolong, finishes during without yellow liquid, and suction filtration is collected, after dry o-NP crude product; The ethanol of take carries out recrystallization to crude product as solvent, and suction filtration is collected to obtain glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 3: prepare o-NP:
(1) Kaolinite Preparation of Catalyst: by 1gH 6pMo 9v 3o 40be dissolved in 9g deionized water, be made into mass concentration and be 10% H 6pMo 9v 3o 40the aqueous solution, 50 ℃ of heating 30min, get 0.096g cesium carbonate and are dissolved in appropriate amount of deionized water, keep 60 ℃ of reaction 4h, obtain heteropolyacid caesium CsH 5pMo 9v 3o 40suspension; Get the about 39ml of 37g() tetraethyl silicate is tetraethyl silicate: ethanol: water=1:2:2 wiring solution-forming, heating at 70 ℃, heating 30min by volume; By heteropolyacid caesium CsH 5pMo 9v 3o 40suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 70 ℃ of heating, until gel appearance is after ageing 24h, dry at 100 ℃, after being dried, obtains silicon dioxide carried 10% heteropolyacid caesium CsH 5pMo 9v 3o 40catalyzer.
(2) 0.2mol phenol joins 50ml1, in 2-ethylene dichloride, adds above-mentioned catalyzer 1.5g, agitation and dropping 0.5mol nitric acid (40%) under 30 ℃ of heating, reaction 4h; Take ethyl acetate as extraction agent, extract 2 times, combining extraction liquid, is placed in round-bottomed flask, distillation and concentration, the 75-85 of collection oc cut, ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, after the liquid cooling steaming, has yellow crystals to separate out, and to prolong, finishes during without yellow liquid, and suction filtration is collected, after dry o-NP crude product; The ethanol of take carries out recrystallization to crude product as solvent, and suction filtration is collected to obtain glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 4: prepare o-NP:
(1) Kaolinite Preparation of Catalyst: by 1gH 4pW 11vO 40be dissolved in 9g deionized water, be made into mass concentration and be 10% H 4pW 11vO 40the aqueous solution, 50 ℃ of heating 30min, get 0.059g cesium carbonate and are dissolved in appropriate amount of deionized water, keep 40 ℃ of reaction 3h, obtain heteropolyacid caesium CsH 3pW 11vO 40suspension; Get the about 38ml of 36g() tetraethyl silicate is tetraethyl silicate: ethanol: water=1:2:2 wiring solution-forming, heating at 90 ℃, heating 30min by volume; By heteropolyacid caesium CsH 3pW 11vO 40suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 90 ℃ of heating, until gel appearance is after ageing 12h, dry at 90 ℃, after being dried, obtains silicon dioxide carried 10% heteropolyacid caesium CsH 3pW 11vO 40catalyzer.
(2) 0.2mol phenol joins 50ml1, in 2-ethylene dichloride, adds above-mentioned catalyzer 1.5g, agitation and dropping 0.75mol nitric acid (30%) under 30 ℃ of heating, reaction 7h; Take ethyl acetate as extraction agent, extract 2 times, combining extraction liquid, is placed in round-bottomed flask, distillation and concentration, the 75-85 of collection oc cut, ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, after the liquid cooling steaming, has yellow crystals to separate out, and to prolong, finishes during without yellow liquid, and suction filtration is collected, after dry o-NP crude product; The ethanol of take carries out recrystallization to crude product as solvent, and suction filtration is collected to obtain glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 5: prepare o-NP:
(1) Kaolinite Preparation of Catalyst: by 1gH 4pMo 11vO 40be dissolved in 9g deionized water, be made into mass concentration and be 10% H 4pMo 11vO 40the aqueous solution, 50 ℃ of heating 30min, get 0.18g cesium carbonate and are dissolved in appropriate amount of deionized water, keep 40 ℃ of reaction 3h, obtain heteropolyacid caesium Cs 2h 2pMo 11vO 40suspension; Get the about 43ml of 40g() tetraethyl silicate is tetraethyl silicate: ethanol: water=1:6:3 wiring solution-forming, heating at 90 ℃, heating 30min by volume; By heteropolyacid caesium Cs 2h 2pMo 11vO 40suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 90 ℃ of heating, until gel appearance is after ageing 12h, dry at 90 ℃, after being dried, obtains silicon dioxide carried 10% heteropolyacid caesium Cs 2h 2pMo 11vO 40catalyzer.
(2) 0.2mol phenol joins 50ml1, in 2-ethylene dichloride, adds above-mentioned catalyzer 1.5g, agitation and dropping 0.6mol nitric acid (20%) under 30 ℃ of heating, reaction 7h; Take ethyl acetate as extraction agent, extract 2 times, combining extraction liquid, is placed in round-bottomed flask, distillation and concentration, the 75-85 of collection oc cut, ethyl acetate and 1,2-ethylene dichloride are reusable; Changing water distilling apparatus is wet distillation, after the liquid cooling steaming, has yellow crystals to separate out, and to phlegma, finishes during without yellow liquid, and suction filtration is collected, after dry o-NP crude product; The ethanol of take carries out recrystallization to crude product as solvent, and suction filtration is collected to obtain glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 6: prepare o-NP:
(1) Kaolinite Preparation of Catalyst: by 1gH 4pMo 11vO 40be dissolved in 9g deionized water, be made into mass concentration and be 10% H 4pMo 11vO 40the aqueous solution, 50 ℃ of heating 30min, get 0.27g cesium carbonate and are dissolved in appropriate amount of deionized water, keep 40 ℃ of reaction 3h, obtain heteropolyacid caesium Cs 3hPMo 11vO 40suspension; Get the about 45ml of 42g() tetraethyl silicate is tetraethyl silicate: ethanol: water=1:2:3 wiring solution-forming, heating at 90 ℃, heating 30min by volume; By heteropolyacid caesium Cs 3hPMo 11vO 40suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 90 ℃ of heating, until gel appearance is after ageing 12h, dry at 90 ℃, after being dried, obtains silicon dioxide carried 10% heteropolyacid caesium Cs 3hPMo 11vO 40catalyzer.
(2) 0.2mol phenol joins 50ml1, in 2-ethylene dichloride, adds above-mentioned catalyzer 1.8g, agitation and dropping 0.75mol nitric acid (30%) under 30 ℃ of heating, reaction 7h; Take ethyl acetate as extraction agent, extract 2 times, combining extraction liquid, is placed in round-bottomed flask, distillation and concentration, the 75-85 of collection oc cut, ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, after the liquid cooling steaming, has yellow crystals to separate out, and to prolong, finishes during without yellow liquid, and suction filtration is collected, after dry o-NP crude product; The ethanol of take carries out recrystallization to crude product as solvent, and suction filtration is collected to obtain glassy yellow needle crystal, i.e. o-NP sterling.
Detect: utilize X-ray powder diffraction to carry out the analysis of purity to embodiment 1,2,3,4,5,6 made sample thiefs, result shows only to present in XRD figure the characteristic diffraction peak of o-NP, with standard diagram JCPDS(08-0752) consistent, illustrate that in embodiment, producing sample is o-NP, the XRD spectra that wherein embodiment 1 produces sample as shown in Figure 1; Take o-NP, p-NP is standard substance, utilizes melting point detector to carry out fusing point test to embodiment 1,2,3,4,5,6 made sample thiefs, and result shows just to dissolve at 45 ℃ of o-NP fusing points; Take o-NP, p-NP is standard substance, utilizes gas-chromatography to embodiment 1,2,3,4,5,6 reaction after product analyses, and result shows all do not have p-NP to generate; Utilize the quality of products obtained therefrom and the ratio of theoretical nitrated output after recrystallization to weigh yield, the results are shown in Table 1.
Table 1
? Phenol conversion (%) Selectivity (%)
Embodiment 1 98.8 100
Embodiment 2 95.6 100
Embodiment 3 92.1 100
Embodiment 4 97.6 100
Embodiment 5 91.6 100
Embodiment 6 93.2 100
As can be seen from Table 1, loading silicon dioxide with heteropoly acid caesium catalyzer Pyrogentisinic Acid nitration reaction of the present invention has high catalytic activity and ortho position selectivity of product.
Embodiment 7: prepare o-NP:
(1) Kaolinite Preparation of Catalyst: by 1gH 4pMo 11vO 40be dissolved in 9g deionized water, be made into mass concentration and be 10% H 4pMo 11vO 40the aqueous solution, 50 ℃ of heating 30min, get 0.091g cesium carbonate and are dissolved in appropriate amount of deionized water, keep 50 ℃ of reaction 5h, obtain heteropolyacid caesium CsH 3pMo 11vO 40suspension; Get the about 78ml of 74g() tetraethyl silicate is tetraethyl silicate: ethanol: water=1:3:6 wiring solution-forming, heating at 60 ℃, heating 30min by volume; By heteropolyacid caesium CsH 3pMo 11vO 40suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 60 ℃ of heating, until gel appearance is after ageing 24h, dry at 120 ℃, after being dried, obtains silicon dioxide carried 5% heteropolyacid caesium CsH 3pMo 11vO 40catalyzer.
(2) 0.2mol phenol joins 50ml1, in 2-ethylene dichloride, adds above-mentioned catalyzer 1.8g, agitation and dropping 1mol nitric acid (30%) under 30 ℃ of heating, reaction 3h; Take ethyl acetate as extraction agent, extract 2 times, combining extraction liquid, is placed in round-bottomed flask, distillation and concentration, the 75-85 of collection oc cut, ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, steams to prolong and finishes during without yellow liquid, after the liquid cooling steaming, has yellow crystals to separate out, and suction filtration is collected, after dry o-NP crude product; The ethanol of take carries out recrystallization to crude product as solvent, and suction filtration is collected to obtain glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 8: prepare o-NP:
(1) Kaolinite Preparation of Catalyst: by 1gH 4pMo 11vO 40be dissolved in 9g deionized water, be made into mass concentration and be 10% H 4pMo 11vO 40the aqueous solution, 50 ℃ of heating 30min, get 0.091g cesium carbonate and are dissolved in appropriate amount of deionized water, keep 50 ℃ of reaction 5h, obtain heteropolyacid caesium CsH 3pMo 11vO 40suspension; Get the about 20ml of 19g() tetraethyl silicate is tetraethyl silicate: ethanol: water=1:1:2 wiring solution-forming, heating at 70 ℃, heating 30min by volume; By heteropolyacid caesium CsH 3pMo 11vO 40suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 70 ℃ of heating, until gel appearance is after ageing 24h, dry at 120 ℃, after being dried, obtains silicon dioxide carried 20% heteropolyacid caesium CsH 3pMo 11vO 40catalyzer.
(2) 0.2mol phenol joins 50ml1, in 2-ethylene dichloride, adds above-mentioned catalyzer 0.75g, agitation and dropping 0.8mol nitric acid (30%) under 30 ℃ of heating, reaction 5h; Take ethyl acetate as extraction agent, extract 2 times, combining extraction liquid, is placed in round-bottomed flask, distillation and concentration, the 75-85 of collection oc cut, ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, steams to prolong and finishes during without yellow liquid, after the liquid cooling steaming, has yellow crystals to separate out, and suction filtration is collected, after dry o-NP crude product; The ethanol of take carries out recrystallization to crude product as solvent, and suction filtration is collected to obtain glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 9: prepare o-NP:
(1) Kaolinite Preparation of Catalyst: by 1gH 4pMo 11vO 40be dissolved in 9g deionized water, be made into mass concentration and be 10% H 4pMo 11vO 40the aqueous solution, 50 ℃ of heating 30min, get 0.091g cesium carbonate and are dissolved in appropriate amount of deionized water, keep 40 ℃ of reaction 3h, obtain heteropolyacid caesium CsH 3pMo 11vO 40suspension; Get the about 13ml of 12g() tetraethyl silicate is tetraethyl silicate: ethanol: water=1:3:6 wiring solution-forming, heating at 50 ℃, heating 30min by volume; By heteropolyacid caesium CsH 3pMo 11vO 40suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 50 ℃ of heating, until gel appearance is after ageing 24h, dry at 120 ℃, after being dried, obtains silicon dioxide carried 30% heteropolyacid caesium CsH 3pMo 11vO 40catalyzer.
(2) 0.2mol phenol joins 50ml1, in 2-ethylene dichloride, adds above-mentioned catalyzer 0.2g, agitation and dropping 0.7mol nitric acid (30%) under 30 ℃ of heating, reaction 5h; Take ethyl acetate as extraction agent, extract 2 times, combining extraction liquid, is placed in round-bottomed flask, distillation and concentration, the 75-85 of collection oc cut, ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, steams to prolong and finishes during without yellow liquid, after the liquid cooling steaming, has yellow crystals to separate out, and suction filtration is collected, after dry o-NP crude product; The ethanol of take carries out recrystallization to crude product as solvent, and suction filtration is collected to obtain glassy yellow needle crystal, i.e. o-NP sterling.
Detect: utilize X-ray powder diffraction to carry out the analysis of purity to embodiment 7,8,9 made sample thiefs, result shows only to present in XRD figure the characteristic diffraction peak of o-NP, with standard diagram JCPDS(08-0752) consistent, illustrate that in embodiment, producing sample is o-NP; Take o-NP, p-NP is standard substance, utilizes melting point detector to carry out fusing point test to embodiment 7,8,9 made sample thiefs, and result shows just to dissolve at 45 ℃ of o-NP fusing points; Take o-NP, p-NP is standard substance, utilizes gas-chromatography to embodiment 7,8,9 reaction after product analyses, and result shows all do not have p-NP to generate; Utilize the quality of products obtained therefrom and the ratio of theoretical nitrated output after recrystallization to weigh yield, the results are shown in Table 2.
Table 2
? Phenol conversion (%) Selectivity (%)
Embodiment 7 79.0 100
Embodiment 8 92.6 100
Embodiment 9 86.4 100
As can be seen from Table 2, the catalyzer of different loads amount has all shown higher catalytic activity, when the catalyst loadings that adopts as the present invention is lower and higher, also can obtain good result.
Embodiment 10:
The method that catalyzer in embodiment 1 is pressed in embodiment (1) (2) is used five times continuously, measures respectively transformation efficiency and selectivity at every turn, the results are shown in Table 3, as can be seen from the table, is repeatedly used after catalyzer, and its active fall is little.
Table 3:
Catalyzer access times O-phenyl phenol transformation efficiency (%) Selectivity (%)
For the first time 98.8 100
For the second time 95.1 100
For the third time 92.9 100
The 4th time 90.2 100
The 5th time 86.3 100

Claims (9)

1. phenol selective nitration is prepared a method for o-NP, it is characterized in that: step is as follows:
(1) nitrated: loading silicon dioxide with heteropoly acid caesium catalyzer and phenol are added in round-bottomed flask, under agitation nitric acid dropping is entered to round-bottomed flask, stirring reaction, loading silicon dioxide with heteropoly acid caesium catalyst levels is the 1%-15% of phenol quality, the mol ratio of nitric acid and phenol usage is 0.5～5;
(2) extraction: take ethyl acetate as extraction agent;
(3) distillation: after extraction, oily liquids is placed in round-bottomed flask, and distillation and concentration, collects 75-85 ℃ of cut;
(4) wet distillation: changing water distilling apparatus is wet distillation, has yellow crystals to separate out after the liquid cooling steaming, finishes during without yellow liquid to prolong, and suction filtration is collected, after dry o-NP crude product;
(5) recrystallization: crude product is dissolved in hot ethanol completely, and splashing into suitable warm water, that it is occurred is muddy, and then splash into ethanol it is dissolved completely, separates out glassy yellow needle crystal after cooling, and suction filtration is collected to obtain o-NP sterling;
The preparation process of loading silicon dioxide with heteropoly acid caesium catalyzer used is as follows:
A, heteropolyacid is dissolved in deionized water, obtains the heteropolyacid aqueous solution heating;
B, get cesium carbonate and be dissolved in deionized water, obtain cesium carbonate aqueous solution;
C, cesium carbonate aqueous solution is added drop-wise in the heteropolyacid aqueous solution, stirring reaction obtains heteropolyacid caesium suspension;
D, get tetraethyl silicate, by volume tetraethyl silicate: ethanol: water=1:1-6:1-6 is made into tetraethyl silicate alcohol solution heating;
E, heteropolyacid caesium suspension agitation is added drop-wise in tetraethyl silicate alcohol solution, is heated to gel and occurs, ageing is drying to obtain loading silicon dioxide with heteropoly acid caesium catalyzer.
2. method according to claim 1, is characterized in that: step (1) stirring reaction is no less than 1 hour.
3. method according to claim 1, is characterized in that: step (1) loading silicon dioxide with heteropoly acid caesium catalyst levels is the 3-10% of phenol quality.
4. method according to claim 3, is characterized in that: loading silicon dioxide with heteropoly acid caesium catalyst levels is 5% of phenol quality.
5. method according to claim 1, is characterized in that: the mass concentration of step (1) nitric acid is 20-40%.
6. method according to claim 5, is characterized in that: mass concentration is 30%.
7. method according to claim 1, is characterized in that: the mol ratio of step (1) nitric acid and phenol usage is 1-4.
8. method according to claim 7, is characterized in that: the mol ratio of nitric acid and phenol usage is 3.
9. method according to claim 1, is characterized in that: step (2) extraction times is 2-3 time.
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