CN102942487A - Method for preparing o-nitrophenol through phenol nitration selectivity - Google Patents
Method for preparing o-nitrophenol through phenol nitration selectivity Download PDFInfo
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- CN102942487A CN102942487A CN201210463229XA CN201210463229A CN102942487A CN 102942487 A CN102942487 A CN 102942487A CN 201210463229X A CN201210463229X A CN 201210463229XA CN 201210463229 A CN201210463229 A CN 201210463229A CN 102942487 A CN102942487 A CN 102942487A
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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
Technical field
The present invention relates to a kind of preparation method of o-NP, more specifically, the present invention relates to the method that a kind of highly selective prepares 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, all there are some defectives in various techniques.
Traditional method is as nitrating agent take nitric acid, with 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, separate obtaining o-NP again, the method has oxidisability because of concentrated nitric acid, be quinones with oxidation of phenol, cause the o-NP productive rate lower.In addition take o-Nitrochlorobenzene as raw material, with the sodium hydroxide solution reaction that is hydrolyzed, again through sulfuric acid acidation, cooling, crystallization, separation can prepare o-NP, and the method is used alkali lye and acid treatment, causes environmental pollution.Can also produce o-NP with o-Nitrophenyl methyl ether, but the defective such as the method exists o-NP content be difficult to surpass 95%, o-Nitrophenyl methyl ether is difficult to recycle, the production wastewater treatment difficulty is large and energy consumption is higher.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the present invention proposes a kind of selectivity height and meets the preparation method of the o-NP of " green " production requirement.
The present invention is achieved by the following technical solutions:
A kind of phenol selective nitration prepares the method for o-NP, and step is as follows:
(1) nitrated: as loading silicon dioxide with heteropoly acid caesium catalyzer and phenol to be added in the round-bottomed flask, under agitation nitric acid dropping is entered round-bottomed flask, stirring reaction;
(2) extraction: take ethyl acetate as extraction agent;
(3) distillation: oily liquids places round-bottomed flask after the extraction, and distillation and concentration is collected 75-85 ℃ of cut;
(4) wet distillation: changing water distilling apparatus is wet distillation, has yellow crystals to separate out after the liquid cooling that steams, and finishes during without yellow liquid to prolong, and suction filtration is collected, after the drying the o-NP crude product;
(5) recrystallization: crude product is dissolved in the hot ethanol fully, and splashing into suitable warm water, that it is occurred is muddy, and then splashes into ethanol it is dissolved fully, separates out glassy yellow needle crystal after the cooling, and suction filtration is collected to get the 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%(preferred 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 the deionized water, gets the heteropolyacid aqueous solution and heating;
(2) get cesium carbonate and be dissolved in the deionized water, get cesium carbonate aqueous solution;
(3) cesium carbonate aqueous solution is added drop-wise in the heteropolyacid aqueous solution, stirring reaction gets 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 and heating;
(5) heteropolyacid caesium suspension agitation is added drop-wise in the 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 be, the described heteropolyacid of step (1) be have the Keggin structure by heteroatoms P and polyatom Mo, W, V by the formed oxygen polyacid that contains of Sauerstoffatom bridging coordination, 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 are 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 be, the described stirring reaction of step (3) be temperature at 40～60 ℃ of lower stirring reaction 1～6h(preferably in temperature at 50 ℃ of lower stirring reaction 5h).Described preparation method, preferred scheme are that the described heating of step (4) is preferably at 70 ℃ of lower heating 30min at 60～90 ℃ of lower heating 10～60min().Described preparation method, preferred scheme is that the described heating of step (5) is to heat at 60～90 ℃ (preferred 70 ℃).The described digestion time of step (5) is the preferred 24h of 10～36h().The described drying of step (5) is at 80～130 ℃ lower dry (preferred 120 ℃).Described loading silicon dioxide with heteropoly acid caesium catalyzer is silicon dioxide carried 1～40% heavy heteropolyacid caesium (preferred 10-30%, more preferably 25%).
The preparation method of carried heteropoly acid caesium catalyzer of the present invention, a kind of concrete scheme is: heteropolyacid is dissolved in deionized water, and 40～60 ℃ are heated 10～60min, then are added dropwise to the deionized water solution of cesium carbonate, stirring reaction 1～6h gets the suspension of heteropolyacid caesium; Be tetraethyl silicate by volume with tetraethyl silicate: ethanol: water=1:1～6:1～6 wiring solution-formings, at 60～90 ℃ of lower heating, 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, behind ageing 10～36h, in 80～130 ℃ of lower dryings, can use after the drying, adjust the consumption of tetraethyl silicate, can obtain the catalyzer of different heteropolyacid caesium charge capacity, charge capacity is in the mass ratio of cesium salt and silicon-dioxide.
The present invention adopts the loading silicon dioxide with heteropoly acid caesium to make catalyzer, and active phase is dispersed in to have on the high specific surface area silica supports, can fully contact with reactant during reaction, improves its catalytic activity, and nitrated transformation efficiency is corresponding increase also.
The present invention compared with prior art, phenol conversion phenol nitration thing ortho position selectivity high, that prepare is good, unmatchful nitrated in position product produces, and has avoided the separating step of ortho para isomer; Because catalyzer has certain granularity, easily process after the reaction, and used catalyzer 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 the transformation efficiency height, process is simple, required time is short, pollution-free, low cost and other advantages.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 gained sample.
Embodiment
The present invention is further illustrated below in conjunction with embodiment:
Embodiment 1: the preparation o-NP:
(1) Kaolinite Preparation of Catalyst: with 1gH
4PMo
11VO
40Be dissolved in the 9g deionized water, be made into mass concentration and be 10% H
4PMo
11VO
40The aqueous solution, 50 ℃ of heating 30min get the 0.091g cesium carbonate and are dissolved in the appropriate amount of deionized water, keep 50 ℃ of reaction 5h, get heteropolyacid caesium CsH
3PMo
11VO
40Suspension; Get the about 39ml of 37g() tetraethyl silicate is tetraethyl silicate: ethanol by volume: water=1:2:2 wiring solution-forming, at 60 ℃ of lower heating, heating 30min; With heteropolyacid caesium CsH
3PMo
11VO
40Suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 60 ℃ of heating, until gel occurs, behind the ageing 24h, in 120 ℃ of lower dryings, namely gets silicon dioxide carried 10% heteropolyacid caesium CsH after the drying
3PMo
11VO
40Catalyzer.
(2) 0.2mol phenol joins 50ml1, in the 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 places round-bottomed flask, distillation and concentration, the 75-85 of collection
oThe C cut, namely ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, steams to prolong and finishes during without yellow liquid, has yellow crystals to separate out after the liquid cooling that steams, and suction filtration is collected, after the drying the o-NP crude product; Take ethanol as solvent crude product is carried out recrystallization, suction filtration is collected to get glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 2: the preparation o-NP:
(1) Kaolinite Preparation of Catalyst: with 1gH
5PMo
10V
2O
40Be dissolved in the 9g deionized water, be made into mass concentration and be 10% H
4PMo
10VO
40The aqueous solution, 50 ℃ of heating 30min get the 0.094g cesium carbonate and are dissolved in the appropriate amount of deionized water, keep 40 ℃ of reaction 6h, get heteropolyacid caesium CsH
4PMo
10V
2O
40Suspension; Get the about 39ml of 37g() tetraethyl silicate is tetraethyl silicate: ethanol by volume: water=1:2:2 wiring solution-forming, at 80 ℃ of lower heating, heating 30min; With 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 occurs, behind the ageing 36h, in 110 ℃ of lower dryings, namely gets silicon dioxide carried 10% heteropolyacid caesium CsH after the drying
4PMo
10V
2O
40Catalyzer.
(2) 0.2mol phenol joins 50ml1, in the 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 places round-bottomed flask, distillation and concentration, the 75-85 of collection
oThe C cut, namely ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, has yellow crystals to separate out after the liquid cooling that steams, and finishes during without yellow liquid to prolong, and suction filtration is collected, after the drying the o-NP crude product; Take ethanol as solvent crude product is carried out recrystallization, suction filtration is collected to get glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 3: the preparation o-NP:
(1) Kaolinite Preparation of Catalyst: with 1gH
6PMo
9V
3O
40Be dissolved in the 9g deionized water, be made into mass concentration and be 10% H
6PMo
9V
3O
40The aqueous solution, 50 ℃ of heating 30min get the 0.096g cesium carbonate and are dissolved in the appropriate amount of deionized water, keep 60 ℃ of reaction 4h, get heteropolyacid caesium CsH
5PMo
9V
3O
40Suspension; Get the about 39ml of 37g() tetraethyl silicate is tetraethyl silicate: ethanol by volume: water=1:2:2 wiring solution-forming, at 70 ℃ of lower heating, heating 30min; With 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 occurs, behind the ageing 24h, in 100 ℃ of lower dryings, namely gets silicon dioxide carried 10% heteropolyacid caesium CsH after the drying
5PMo
9V
3O
40Catalyzer.
(2) 0.2mol phenol joins 50ml1, in the 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 places round-bottomed flask, distillation and concentration, the 75-85 of collection
oThe C cut, namely ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, has yellow crystals to separate out after the liquid cooling that steams, and finishes during without yellow liquid to prolong, and suction filtration is collected, after the drying the o-NP crude product; Take ethanol as solvent crude product is carried out recrystallization, suction filtration is collected to get glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 4: the preparation o-NP:
(1) Kaolinite Preparation of Catalyst: with 1gH
4PW
11VO
40Be dissolved in the 9g deionized water, be made into mass concentration and be 10% H
4PW
11VO
40The aqueous solution, 50 ℃ of heating 30min get the 0.059g cesium carbonate and are dissolved in the appropriate amount of deionized water, keep 40 ℃ of reaction 3h, get heteropolyacid caesium CsH
3PW
11VO
40Suspension; Get the about 38ml of 36g() tetraethyl silicate is tetraethyl silicate: ethanol by volume: water=1:2:2 wiring solution-forming, at 90 ℃ of lower heating, heating 30min; With heteropolyacid caesium CsH
3PW
11VO
40Suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 90 ℃ of heating, until gel occurs, behind the ageing 12h, in 90 ℃ of lower dryings, namely gets silicon dioxide carried 10% heteropolyacid caesium CsH after the drying
3PW
11VO
40Catalyzer.
(2) 0.2mol phenol joins 50ml1, in the 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 places round-bottomed flask, distillation and concentration, the 75-85 of collection
oThe C cut, namely ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, has yellow crystals to separate out after the liquid cooling that steams, and finishes during without yellow liquid to prolong, and suction filtration is collected, after the drying the o-NP crude product; Take ethanol as solvent crude product is carried out recrystallization, suction filtration is collected to get glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 5: the preparation o-NP:
(1) Kaolinite Preparation of Catalyst: with 1gH
4PMo
11VO
40Be dissolved in the 9g deionized water, be made into mass concentration and be 10% H
4PMo
11VO
40The aqueous solution, 50 ℃ of heating 30min get the 0.18g cesium carbonate and are dissolved in the appropriate amount of deionized water, keep 40 ℃ of reaction 3h, get heteropolyacid caesium Cs
2H
2PMo
11VO
40Suspension; Get the about 43ml of 40g() tetraethyl silicate is tetraethyl silicate: ethanol by volume: water=1:6:3 wiring solution-forming, at 90 ℃ of lower heating, heating 30min; With 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 occurs, behind the ageing 12h, in 90 ℃ of lower dryings, namely gets silicon dioxide carried 10% heteropolyacid caesium Cs after the drying
2H
2PMo
11VO
40Catalyzer.
(2) 0.2mol phenol joins 50ml1, in the 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 places round-bottomed flask, distillation and concentration, the 75-85 of collection
oThe C cut, namely ethyl acetate and 1,2-ethylene dichloride are reusable; Changing water distilling apparatus is wet distillation, has yellow crystals to separate out after the liquid cooling that steams, and finishes during without yellow liquid to phlegma, and suction filtration is collected, after the drying the o-NP crude product; Take ethanol as solvent crude product is carried out recrystallization, suction filtration is collected to get glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 6: the preparation o-NP:
(1) Kaolinite Preparation of Catalyst: with 1gH
4PMo
11VO
40Be dissolved in the 9g deionized water, be made into mass concentration and be 10% H
4PMo
11VO
40The aqueous solution, 50 ℃ of heating 30min get the 0.27g cesium carbonate and are dissolved in the appropriate amount of deionized water, keep 40 ℃ of reaction 3h, get heteropolyacid caesium Cs
3HPMo
11VO
40Suspension; Get the about 45ml of 42g() tetraethyl silicate is tetraethyl silicate: ethanol by volume: water=1:2:3 wiring solution-forming, at 90 ℃ of lower heating, heating 30min; With heteropolyacid caesium Cs
3HPMo
11VO
40Suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 90 ℃ of heating, until gel occurs, behind the ageing 12h, in 90 ℃ of lower dryings, namely gets silicon dioxide carried 10% heteropolyacid caesium Cs after the drying
3HPMo
11VO
40Catalyzer.
(2) 0.2mol phenol joins 50ml1, in the 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 places round-bottomed flask, distillation and concentration, the 75-85 of collection
oThe C cut, namely ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, has yellow crystals to separate out after the liquid cooling that steams, and finishes during without yellow liquid to prolong, and suction filtration is collected, after the drying the o-NP crude product; Take ethanol as solvent crude product is carried out recrystallization, suction filtration is collected to get glassy yellow needle crystal, i.e. o-NP sterling.
Detect: utilize X-ray powder diffraction that embodiment 1,2,3,4,5,6 made sample thiefs are carried out the analysis of purity, the result shows the characteristic diffraction peak that only presents o-NP in the XRD figure, with standard diagram JCPDS(08-0752) consistent, illustrate that producing sample among the embodiment is o-NP, wherein embodiment 1 produce sample XRD spectra as shown in Figure 1; Take o-NP, p-NP as standard substance, utilize melting point detector that embodiment 1,2,3,4,5,6 made sample thiefs are carried out fusing point test, the result shows just in 45 ℃ of lower dissolvings of o-NP fusing point; Take o-NP, p-NP as standard substance, utilize gas-chromatography to embodiment 1,2,3,4,5,6 reaction after product analyses, the result shows all do not have p-NP to generate; Utilize the quality of products obtained therefrom behind the recrystallization and the ratio of theoretical nitrated output 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: the preparation o-NP:
(1) Kaolinite Preparation of Catalyst: with 1gH
4PMo
11VO
40Be dissolved in the 9g deionized water, be made into mass concentration and be 10% H
4PMo
11VO
40The aqueous solution, 50 ℃ of heating 30min get the 0.091g cesium carbonate and are dissolved in the appropriate amount of deionized water, keep 50 ℃ of reaction 5h, get heteropolyacid caesium CsH
3PMo
11VO
40Suspension; Get the about 78ml of 74g() tetraethyl silicate is tetraethyl silicate: ethanol by volume: water=1:3:6 wiring solution-forming, at 60 ℃ of lower heating, heating 30min; With heteropolyacid caesium CsH
3PMo
11VO
40Suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 60 ℃ of heating, until gel occurs, behind the ageing 24h, in 120 ℃ of lower dryings, namely gets silicon dioxide carried 5% heteropolyacid caesium CsH after the drying
3PMo
11VO
40Catalyzer.
(2) 0.2mol phenol joins 50ml1, in the 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 places round-bottomed flask, distillation and concentration, the 75-85 of collection
oThe C cut, namely ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, steams to prolong and finishes during without yellow liquid, has yellow crystals to separate out after the liquid cooling that steams, and suction filtration is collected, after the drying the o-NP crude product; Take ethanol as solvent crude product is carried out recrystallization, suction filtration is collected to get glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 8: the preparation o-NP:
(1) Kaolinite Preparation of Catalyst: with 1gH
4PMo
11VO
40Be dissolved in the 9g deionized water, be made into mass concentration and be 10% H
4PMo
11VO
40The aqueous solution, 50 ℃ of heating 30min get the 0.091g cesium carbonate and are dissolved in the appropriate amount of deionized water, keep 50 ℃ of reaction 5h, get heteropolyacid caesium CsH
3PMo
11VO
40Suspension; Get the about 20ml of 19g() tetraethyl silicate is tetraethyl silicate: ethanol by volume: water=1:1:2 wiring solution-forming, at 70 ℃ of lower heating, heating 30min; With heteropolyacid caesium CsH
3PMo
11VO
40Suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 70 ℃ of heating, until gel occurs, behind the ageing 24h, in 120 ℃ of lower dryings, namely gets silicon dioxide carried 20% heteropolyacid caesium CsH after the drying
3PMo
11VO
40Catalyzer.
(2) 0.2mol phenol joins 50ml1, in the 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 places round-bottomed flask, distillation and concentration, the 75-85 of collection
oThe C cut, namely ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, steams to prolong and finishes during without yellow liquid, has yellow crystals to separate out after the liquid cooling that steams, and suction filtration is collected, after the drying the o-NP crude product; Take ethanol as solvent crude product is carried out recrystallization, suction filtration is collected to get glassy yellow needle crystal, i.e. o-NP sterling.
Embodiment 9: the preparation o-NP:
(1) Kaolinite Preparation of Catalyst: with 1gH
4PMo
11VO
40Be dissolved in the 9g deionized water, be made into mass concentration and be 10% H
4PMo
11VO
40The aqueous solution, 50 ℃ of heating 30min get the 0.091g cesium carbonate and are dissolved in the appropriate amount of deionized water, keep 40 ℃ of reaction 3h, get heteropolyacid caesium CsH
3PMo
11VO
40Suspension; Get the about 13ml of 12g() tetraethyl silicate is tetraethyl silicate: ethanol by volume: water=1:3:6 wiring solution-forming, at 50 ℃ of lower heating, heating 30min; With heteropolyacid caesium CsH
3PMo
11VO
40Suspension agitation is added drop-wise to the alcohol solution of tetraethyl silicate, continues 50 ℃ of heating, until gel occurs, behind the ageing 24h, in 120 ℃ of lower dryings, namely gets silicon dioxide carried 30% heteropolyacid caesium CsH after the drying
3PMo
11VO
40Catalyzer.
(2) 0.2mol phenol joins 50ml1, in the 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 places round-bottomed flask, distillation and concentration, the 75-85 of collection
oThe C cut, namely ethyl acetate is reusable; Changing water distilling apparatus is wet distillation, steams to prolong and finishes during without yellow liquid, has yellow crystals to separate out after the liquid cooling that steams, and suction filtration is collected, after the drying the o-NP crude product; Take ethanol as solvent crude product is carried out recrystallization, suction filtration is collected to get glassy yellow needle crystal, i.e. o-NP sterling.
Detect: utilize X-ray powder diffraction that embodiment 7,8,9 made sample thiefs are carried out the analysis of purity, the result shows the characteristic diffraction peak that only presents o-NP in the XRD figure, with standard diagram JCPDS(08-0752) consistent, illustrate that producing sample among the embodiment is o-NP; Take o-NP, p-NP as standard substance, utilize melting point detector that embodiment 7,8,9 made sample thiefs are carried out fusing point test, the result shows just in 45 ℃ of lower dissolvings of o-NP fusing point; Take o-NP, p-NP as standard substance, utilize gas-chromatography to embodiment 7,8,9 reaction after product analyses, the result shows all do not have p-NP to generate; Utilize the quality of products obtained therefrom behind the recrystallization and the ratio of theoretical nitrated output 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 preferably result.
Embodiment 10:
The method that catalyzer among the embodiment 1 is pressed among the embodiment (1) (2) is used five times continuously, is measured respectively transformation efficiency and selectivity at every turn, the results are shown in Table 3, as can be seen from the table, be repeatedly used catalyzer after, its active fall is little.
Table 3:
| The 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 (6)
1. a phenol selective nitration prepares the method for o-NP, and it is characterized in that: step is as follows:
(1) nitrated: as loading silicon dioxide with heteropoly acid caesium catalyzer and phenol to be added in the round-bottomed flask, under agitation nitric acid dropping is entered round-bottomed flask, stirring reaction;
(2) extraction: take ethyl acetate as extraction agent;
(3) distillation: oily liquids places round-bottomed flask after the extraction, and distillation and concentration is collected 75-85 ℃ of cut;
(4) wet distillation: changing water distilling apparatus is wet distillation, has yellow crystals to separate out after the liquid cooling that steams, and finishes during without yellow liquid to prolong, and suction filtration is collected, after the drying the o-NP crude product;
(5) recrystallization: crude product is dissolved in the hot ethanol fully, and splashing into suitable warm water, that it is occurred is muddy, and then splashes into ethanol it is dissolved fully, separates out glassy yellow needle crystal after the cooling, and suction filtration is collected to get the o-NP sterling.
2. method according to claim 1, it is characterized in that: step (1) stirring reaction is no less than 1 hour.
3. method according to claim 1, it is characterized in that: 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%).
4. method according to claim 1, it is characterized in that: the mass concentration of step (1) nitric acid is 20-40%(preferred 30%).
5. method according to claim 1, it is characterized in that: the mol ratio of step (1) nitric acid and phenol usage is the preferred 1-4 of 0.5～5(, is more preferably 3).
6. method according to claim 1, it is characterized in that: step (2) extraction times is 2-3 time.
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|---|---|---|---|
| CN201210463229.XA CN102942487B (en) | 2012-11-17 | 2012-11-17 | Method for preparing o-nitrophenol through phenol nitration selectivity |
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| CN104030926A (en) * | 2014-06-13 | 2014-09-10 | 芜湖职业技术学院 | Method for preparing phenolic nitride by adopting nitration reaction device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410415A (en) * | 2002-11-13 | 2003-04-16 | 中国科学院上海有机化学研究所 | Green nitration method of phenol type compound |
| CN1709856A (en) * | 2005-06-10 | 2005-12-21 | 中国科学院上海有机化学研究所 | Nitrofication method for catalysis of phenol and diphenyl ether compounds using metal salt |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410415A (en) * | 2002-11-13 | 2003-04-16 | 中国科学院上海有机化学研究所 | Green nitration method of phenol type compound |
| CN1709856A (en) * | 2005-06-10 | 2005-12-21 | 中国科学院上海有机化学研究所 | Nitrofication method for catalysis of phenol and diphenyl ether compounds using metal salt |
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| 金明善 等: "负载型杂多酸催化剂用于硝基苯的催化合成", 《分子催化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030926A (en) * | 2014-06-13 | 2014-09-10 | 芜湖职业技术学院 | Method for preparing phenolic nitride by adopting nitration reaction device |
| CN104030926B (en) * | 2014-06-13 | 2016-06-22 | 芜湖职业技术学院 | Adopt the method that nitration reaction device prepares phenols itrated compound |
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