CN101182300B - Quaternary ammonium ionic liquid as well as preparation and application method thereof - Google Patents
Quaternary ammonium ionic liquid as well as preparation and application method thereof Download PDFInfo
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- CN101182300B CN101182300B CN2007101510016A CN200710151001A CN101182300B CN 101182300 B CN101182300 B CN 101182300B CN 2007101510016 A CN2007101510016 A CN 2007101510016A CN 200710151001 A CN200710151001 A CN 200710151001A CN 101182300 B CN101182300 B CN 101182300B
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Abstract
The present invention provides a quaternary ammonium salt ionic liquid, a preparation and an application method thereof and belongs to a quaternary ammonium compound, the molecular component of whichis N, N, N-trimethyl-N-sulfobutyl-ammonium hydrogen sulfate, a molecular formula is [HSO3-b-N(CH3) 3]HSO4, and a structural formula is as follows. The quaternary ammonium salt ionic liquid of the present invention does not erode equipments and is friendly to the environment; the catalyst of the quaternary ammonium salt ionic liquid of the present invention is used for nitrobenzene catalytic hydrogenation synthesis towards amino phenol reaction, which is the liquid phase method, the reaction temperature is 60 DEG C to 130 DEG C, the PAP yield is 19.5 percent to 88 percent.
Description
Technical field
Technical scheme of the present invention relates to quaternary ammonium compound, specifically a kind of quaternary ammonium salt ionic liquid and methods for making and using same thereof.
Technical background
By the synthetic p-aminophenol of the oil of mirbane shortening method of (p-Aminophenol is called for short PAP), be the direction of future development current generally believing.Oil of mirbane shortening technology have one step of reaction finish, method is simple, step is few, equipment and processing condition advantage such as gentleness relatively, is suitable for large-scale industrial production.
The mechanism of this reaction is:
In the first step of reaction, promptly the oil of mirbane shortening generates in the phenylhydroxylamine process, adopts the metal platinum catalyzer of loading type; In second step of reaction, promptly phenylhydroxylamine is reset and is generated p-aminophenol, then adopts an acidic catalyst.
The selection of an acidic catalyst is the important factor that influences the synthetic p-aminophenol of oil of mirbane shortening.Industrial 10%～20% dilute sulphuric acid that generally all adopts carries out catalysis.Adopt that dilute sulphuric acid catalysis meeting causes that subsequent technique is complicated, equipment corrosion and discharge of wastewater cause environmental pollution problems.The alternative dilute sulphuric acid of solid acid can solve equipment corrosion, discharge of wastewater causes environmental pollution problem though adopt,, few to adopting solid acid to replace vitriolic research to report both at home and abroad at present on the one hand.(Chaudhari R V such as Chaudhari, Diveher S S, Vaidya M J, et al.US, 6028227.2000) propose to adopt solid acid catalyst and Pt-S/AC to use simultaneously, oil of mirbane is mixed the synthetic p-aminophenol of back shortening with water, used solid acid catalyst is ion exchange resin (Indion 130), consumption is 3%～7%, and oil of mirbane is 1: 5～7 with the amount of substance ratio of water, and temperature of reaction is 50～100 ℃, reaction pressure is 2.0～2.5MPa, in 3～7 hours reaction times, the oil of mirbane transformation efficiency reaches 97%, and the p-aminophenol yield only is 13.9%; (TakayukiKomatsu such as Takayuki, Tatsuo Hirose. Applied Catalysis A:General, 2004,276:95-102) adopt Pt/ZSM-5 as dual-function catalyst, from the synthetic p-aminophenol of oil of mirbane gas-phase catalytic hydrogenation, but reaction conditions is very harsh, and the p-aminophenol yield only is 17%, and selectivity is 42%.This shows the use of these solid acid catalysts, all have the low problem of p-aminophenol yield.CN1562465 discloses the catalyzer that a kind of nitrobenzene selective hydrogenation is reset the system p-aminophenol, and it is to be carrier (being again the acid active centre of catalyzer simultaneously) with the solid acid, is the heterogeneous dual-function catalyst of hydrogenation main active ingredient with the noble metal platinum.Because solid acid does not have flowability, acidic site density is low and the strength of acid distribution is even inadequately; The use of solid acid easily causes the formation of carbon deposit on it, can cause the rapid deactivation of solid acid, can't reuse, and causes the catalyzer integral body can not recycle; In addition, this invention has just reduced the vitriolic consumption, and does not stop to use sulfuric acid, thereby can't solve equipment corrosion and the disagreeableness problem of environment.
The functionalization acidic ionic liquid body is because have the advantage of solid acid and liquid acid concurrently, and do not have volatilization, the low corrosion, shows very big potentiality in eco-friendly acid catalysis application facet.From domestic and international research, also acidic ion liquid is not applied to the report in the synthetic p-aminophenol reaction of oil of mirbane shortening at present.Therefore, synthetic prepare the advantage, good fluidity, the acidic site density height that have solid acid and liquid acid concurrently, strength of acid is evenly distributed and do not have volatilization, free from corrosion highly active ion liquid acidic catalyst, in order to substitute dilute sulphuric acid, then can realize the greenization of p-aminophenol production process.
Summary of the invention
Technical problem to be solved by this invention is: a kind of quaternary ammonium salt ionic liquid and methods for making and using same thereof are provided, overcome the problem that the dilute sulphuric acid Application of Catalyst that exists can cause and equipment corrosion unfriendly to environment in prior art, and the severe reaction conditions that exists in using of solid acid catalyst, the problem that the p-aminophenol yield is low.
The present invention solves this technical problem the technical scheme that is adopted:
A kind of quaternary ammonium salt ionic liquid is provided, and its molecular composition is N, N, and N-trimethylammonium-N-sulphur butyl-monoammonium sulfate, molecular formula is [HSO
3-b-N (CH
3)
3] HSO
4, structural formula is as follows:
Above-mentioned a kind of quaternary ammonium salt preparation method of ionic liquid, its synthesis step is as follows:
The first step, N, N, N-trimethylammonium-N-sulphur butyl ammonium is zwitterionic synthetic
According to Trimethylamine 99: 1, the mol ratio of 4-butane sultone=1: 0.8～1.2, with trimethylamine aqueous solution and 1, the 4-butane sultone places reactor, after reacting 8～72 hours under ℃ condition of room temperature～70, dewater carrying out underpressure distillation after the reaction solution taking-up, obtain the zwitter-ion solid of white, with this zwitter-ion solid dehydrated alcohol, toluene and anhydrous diethyl ether wash successively, then 50～110 ℃ of following vacuum-dryings to constant weight, the pure zwitter-ion solid that obtains, its molecular weight is 195.11, standby, the weight content of Trimethylamine 99 〉=33% in the trimethylamine aqueous solution wherein;
Second step, N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate is ion liquid synthetic
Get the N that makes by the first step, N, N-trimethylammonium-N-sulphur butyl ammonium zwitter-ion is put into reactor, slowly drip the vitriol oil, its mol ratio is this zwitter-ion: the vitriol oil=1: 0.7～1.1, and keep temperature to be no more than 10 ℃ during dropping, be warming up to 40～90 ℃ then, reacted 3～10 hours, obtain product quaternary ammonium salt ionic liquid, i.e. N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid, its molecular weight is 293.11.
The ion liquid application method of above-mentioned quaternary ammonium salt: with this quaternary ammonium salt ionic liquid as an acidic catalyst, be used for the reaction of the synthetic p-aminophenol of oil of mirbane shortening, in second step of this reaction, be that phenylhydroxylamine is reset in the process that generates p-aminophenol, this quaternary ammonium salt ionic liquid plays the effect of an acidic catalyst, concrete steps are: it is 10～40% quaternary ammonium salt ionic liquid solution that this quaternary ammonium salt ionic liquid and solvent are mixed with weight percent concentration, with this quaternary ammonium salt ionic liquid solution, oil of mirbane and load type metal platinum catalyst add in the autoclave, the weight ratio of solvent is 1: 5～30 in oil of mirbane and this quaternary ammonium salt ionic liquid solution, load type metal platinum catalyst consumption is that 0.01～5% of oil of mirbane weight is determined by the metal platinum weight in this catalyzer, go out air in the autoclave with nitrogen replacement, temperature of reaction is risen to 60～130 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure is 0.1～0.7Mpa, reaction times is 1～8 hour, and oil of mirbane is through the synthetic p-aminophenol of shortening.
In the ion liquid application method of above-mentioned quaternary ammonium salt, in autoclave, add in this quaternary ammonium salt ionic liquid solution, oil of mirbane and the load type metal platinum catalyst, add consumption and be 0.2～5% tensio-active agent of above-mentioned used oil of mirbane weight, used tensio-active agent is polyoxyethylene nonylphenol ether, cetyl trimethylammonium bromide, Dodecyl trimethyl ammonium chloride or Tetrabutyl amonium bromide, and other processing condition all remain unchanged.
Add some tensio-active agents, played the effect of emulsification, dispersion and phase transition, water can fully be contacted mutually with oil of mirbane, accelerate the synthetic p-aminophenol speed of response of oil of mirbane shortening, help the carrying out that react and the highly selective of synthetic p-aminophenol more.
In the ion liquid application method of above-mentioned quaternary ammonium salt, the solvent of described preparation quaternary ammonium salt ionic liquid solution is deionized water, methyl alcohol, ethanol, butanols, glycol ether, triglycol or Tetraglycol 99.
In the ion liquid application method of above-mentioned quaternary ammonium salt, used load type metal platinum catalyst is got by known approach.
In the ion liquid application method of above-mentioned quaternary ammonium salt, the preferable range of the concentration of described quaternary ammonium salt ionic liquid solution is 10～30%, preferred load type metal platinum catalyst consumption is that 0.02～2% of used oil of mirbane weight is determined by the Pt weight in this catalyzer, preferred temperature of reaction is 70～100 ℃, preferred hydrogen partial pressure is 0.3～0.6MPa, and the preferred reaction times is 2～6 hours.
The invention has the beneficial effects as follows: the present invention is applied to this ionic liquid in the reaction of the synthetic p-aminophenol of oil of mirbane shortening first.Ionic liquid generally be constitute by the relative less inorganic anion of the asymmetric organic cation of the relatively large structure of specific volume with volume, in room temperature or be bordering on the material that is in a liquid state under the room temperature.Compare with solid matter, it is liquid; Compare with traditional fluent meterial, it is an ionic.Thereby, compare with other solids or fluent material, ionic liquid can show unique physicochemical property and functions peculiar: non-volatile or " zero " vapour pressure (this should be the important evidence that ionic liquid is considered to green), low corrosion, low melting point (can hang down-90 ℃), wide liquid journey (can reach 200 ℃), strong electrostatic field, wide electrochemical window (even can be greater than 5V, this means in so wide voltage range, electrochemical reaction can not take place in ionic liquid, i.e. degraded, this is the common not available characteristic of electrolytic solution), good ionic conduction (25ms/cm) and thermal conductivity high heat capacity and thermal energy storage density (the thermal energy storage density 9MJ/m of the heat accumulation oil that ratio uses now
3High 6.4 times), high thermal stability (decomposition temperature can be higher than 400 ℃), selective dissolution power, designability.These characteristics make ionic liquid become to have concurrently " solid " liquid of liquid and solid function and characteristic.
(1) adopt quaternary ammonium salt ionic-liquid catalyst of the present invention to overcome the problem that the dilute sulphuric acid Application of Catalyst can cause and equipment corrosion unfriendly to environment:
Similar to solid acid, ionic liquid does not have volatility yet, therefore has eco-friendly advantage equally; It also can have concurrently simultaneously
With Lewis acidity.By contrast, ionic liquid tart modulation is easier, meticulousr, thereby helps the research of catalytic mechanism and the optimization of catalyzer more; Similar to mineral acid, ionic liquid has the advantage of fluent material equally, as: good fluidity, acidic site density height and strength of acid are evenly distributed; By changing and modified ion liquid yin, yang ionic structure, can realize the optimization of heterogeneous reaction system, as the solvability that strengthens substrate, the separation of simplifying product, ion liquid the recycling of promotion.Thereby as can be seen, quaternary ammonium salt ionic liquid of the present invention be not etching apparatus with eco-friendly, this point, the proof that has yet obtained in concrete experiment does not promptly have special protection against corrosion requirement to the use of reactor.
(2) adopt quaternary ammonium salt ionic-liquid catalyst of the present invention to overcome the problem of the severe reaction conditions that exists in the solid acid catalyst application:
Divide in mentioned people's articles such as Chaudhari in above-mentioned background technical division, used solid acid catalyst, in the synthetic p-aminophenol reaction of oil of mirbane shortening, reaction pressure is 2.0MPa～2.5MPa, and quaternary ammonium salt ionic-liquid catalyst of the present invention is used for the synthetic p-aminophenol reaction of oil of mirbane shortening, and reaction pressure is 0.1～0.7MPa.
Divide in mentioned people's articles such as Takayuki in above-mentioned background technical division, metal-zeolite type dual-function catalyst Pt/HZSM-5 is used for the synthetic p-aminophenol reaction of oil of mirbane shortening, temperature of reaction is 250 ℃, it is vapor phase process, and quaternary ammonium salt ionic-liquid catalyst of the present invention is used for the synthetic p-aminophenol reaction of oil of mirbane shortening and is liquid phase method, and temperature of reaction is 60～130 ℃.
(3) adopt quaternary ammonium salt ionic-liquid catalyst of the present invention to overcome the extremely low problem of p-aminophenol yield that in prior art, exists:
Divide in mentioned people's articles such as Chaudhari in above-mentioned background technical division, used solid acid catalyst, in the synthetic p-aminophenol reaction of oil of mirbane shortening, the PAP yield is 13.9%.
Divide in mentioned people's articles such as Takayuki in above-mentioned background technical division, metal-zeolite type dual-function catalyst Pt/HZSM-5 is used for the synthetic p-aminophenol reaction of oil of mirbane shortening, the PAP yield reaches as high as 17%.
Quaternary ammonium salt ionic-liquid catalyst of the present invention is used for the synthetic p-aminophenol reaction of oil of mirbane shortening, and the PAP yield reaches 19.5～88%.
(4) quaternary ammonium salt preparation method of ionic liquid easy handling of the present invention, repeatability is high.
Embodiment
Embodiment 1～8 is quaternary ammonium salt ionic liquid of the present invention, i.e. N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid preparation method's embodiment.
Embodiment 1
The first step, N, N, N-trimethylammonium-N-sulphur butyl ammonium is zwitterionic synthetic
Get 1 of the trimethylamine aqueous solution that contains Trimethylamine 99 1.0mol and 1.2mol, the 4-butane sultone, be placed in the there-necked flask of 500ml, reacted 72 hours down, carry out underpressure distillation after reaction solution is taken out and dewater in room temperature condition, obtain the zwitter-ion solid of white, this zwitter-ion solid is washed successively with dehydrated alcohol, toluene and anhydrous diethyl ether, then 110 ℃ of following vacuum-dryings to constant weight, obtain pure zwitter-ion solid, its molecular weight is 195.11, and is standby.The weight content of Trimethylamine 99 〉=33% in the trimethylamine aqueous solution wherein, following examples 2～8 are identical.
Second step, N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate is ion liquid synthetic
Get the N that makes by the first step, N, N-trimethylammonium-N-sulphur butyl ammonium zwitter-ion 0.50mol puts into a four-hole boiling flask, slowly drips the vitriol oil of 0.55mol, keeps temperature to be no more than 10 ℃ during dropping, be warming up to 40 ℃ then, reacted 10 hours, and promptly obtained N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid, its molecular weight is 293.11.FTIR(KBr)：υ
max：3044，2968，1482，1227，1165，1039，882，727cm
-1。
1HNMR (D
2O, δ, 400.13MHz): 1.536 (m, 2H ,-CH
2-), 1.680 (m, J=7.6Hz, 2H ,-CH
2-), 2.707 (t, J=7.6Hz, 2H ,-N-CH
2-), 2.852 (s, 9H ,-CH
3), 3.099 (t, J=7.2Hz, 2H ,-CH
2-S-), the H on sulfonic group and the bisulfate ion
+With D
2O exchange back disappears.
13CNMR(D
2O，δ，100.62MHz)：65.679，52.674，49.828，21.065，20.866。
Embodiment 2
The first step, N, N, N-trimethylammonium-N-sulphur butyl ammonium is zwitterionic synthetic
Get 1 of the trimethylamine aqueous solution that contains Trimethylamine 99 1.0mol and 0.8mol, the 4-butane sultone, be placed in the there-necked flask of 500ml, reacted 8 hours down, carry out underpressure distillation after reaction solution is taken out and dewater in 70 ℃, obtain the zwitter-ion solid of white, this zwitter-ion is washed successively with dehydrated alcohol, toluene and anhydrous diethyl ether, then 110 ℃ of following vacuum-dryings to constant weight, obtain pure zwitter-ion solid, its molecular weight is 195.11, and is standby.
Second step made N with embodiment 1, N, and N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid, its measurement result and embodiment 1 are just the same.
Embodiment 3
The first step, N, N, N-trimethylammonium-N-sulphur butyl ammonium is zwitterionic synthetic
Get 1 of the trimethylamine aqueous solution that contains Trimethylamine 99 1.0mol and 0.8mol, the 4-butane sultone, be placed in the there-necked flask of 500ml, reacted 24 hours down, carry out underpressure distillation after reaction solution is taken out and dewater in room temperature condition, obtain the zwitter-ion solid of white, this zwitter-ion is washed successively with dehydrated alcohol, toluene and anhydrous diethyl ether, then 50 ℃ of following vacuum-dryings to constant weight, obtain pure zwitter-ion solid, its molecular weight is 195.11, and is standby.
Second step, N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate is ion liquid synthetic
Get the N that makes by the first step, N, N-trimethylammonium-N-sulphur butyl ammonium zwitter-ion 0.50mol puts into a four-hole boiling flask, slowly drips the vitriol oil of 0.35mol, keeps temperature to be no more than 10 ℃ during dropping, be warming up to 90 ℃ then, reacted 3 hours, and promptly obtained N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid, its measurement result and embodiment 1 are just the same.
Embodiment 4
The first step, N, N, N-trimethylammonium-N-sulphur butyl ammonium is zwitterionic synthetic
Get 1 of the trimethylamine aqueous solution that contains Trimethylamine 99 1.0mol and 1.2mol, the 4-butane sultone, be placed in the there-necked flask of 500ml, reacted 16 hours down, carry out underpressure distillation after reaction solution is taken out and dewater in 45 ℃, obtain the zwitter-ion solid of white, this zwitter-ion is washed successively with dehydrated alcohol, toluene and anhydrous diethyl ether, then 50 ℃ of following vacuum-dryings to constant weight, obtain pure zwitter-ion solid, its molecular weight is 195.11, and is standby.
Second step made N with embodiment 3, N, and N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid, its measurement result and embodiment 1 are just the same.
Embodiment 5
The first step, N, N, N-trimethylammonium-N-sulphur butyl ammonium is zwitterionic synthetic
Get 1 of the trimethylamine aqueous solution that contains Trimethylamine 99 1.0mol and 1.1mol, the 4-butane sultone, be placed in the there-necked flask of 500ml, reacted 48 hours down, carry out underpressure distillation after reaction solution is taken out and dewater in room temperature condition, obtain the zwitter-ion solid of white, this zwitter-ion is washed successively with dehydrated alcohol, toluene and anhydrous diethyl ether, then 80 ℃ of following vacuum-dryings to constant weight, obtain pure zwitter-ion solid, its molecular weight is 195.11, and is standby.
Second step, N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate is ion liquid synthetic
Get the N that makes by the first step, N, N-trimethylammonium-N-sulphur butyl ammonium zwitter-ion 0.50mol puts into a four-hole boiling flask, slowly drips the vitriol oil of 0.45mol, keeps temperature to be no more than 10 ℃ during dropping, be warming up to 60 ℃ then, reacted 8 hours, and promptly made N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid, its measurement result and embodiment 1 are just the same.
Embodiment 6
The first step, N, N, N-trimethylammonium-N-sulphur butyl ammonium is zwitterionic synthetic
Get 1 of the trimethylamine aqueous solution that contains Trimethylamine 99 1.0mol and 0.9mol, the 4-butane sultone, be placed in the there-necked flask of 500ml, reacted 10 hours down, carry out underpressure distillation after reaction solution is taken out and dewater in 70 ℃, obtain the zwitter-ion solid of white, this zwitter-ion is washed successively with dehydrated alcohol, toluene and anhydrous diethyl ether, then 70 ℃ of following vacuum-dryings to constant weight, obtain pure zwitter-ion solid, its molecular weight is 195.11, and is standby.
Second step made N with embodiment 5, N, and N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid, its measurement result and embodiment 1 are just the same.
Embodiment 7
The first step, N, N, N-trimethylammonium-N-sulphur butyl ammonium is zwitterionic synthetic
Get 1 of the trimethylamine aqueous solution that contains Trimethylamine 99 1.0mol and 1.06mol, the 4-butane sultone, be placed in the there-necked flask of 500ml, reacted 48 hours down, carry out underpressure distillation after reaction solution is taken out and dewater in room temperature condition, obtain the zwitter-ion solid of white, this zwitter-ion is washed successively with dehydrated alcohol, toluene and anhydrous diethyl ether, then 100 ℃ of following vacuum-dryings to constant weight, obtain pure zwitter-ion solid, its molecular weight is 195.11, and is standby.
Second step, N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate is ion liquid synthetic
Get the N that makes by the first step, N, N-trimethylammonium-N-sulphur butyl ammonium zwitter-ion 0.50mol puts into a four-hole boiling flask, slowly drips the vitriol oil of 0.52mol, keeps temperature to be no more than 10 ℃ during dropping, be warming up to 70 ℃ then, reacted 7 hours, and promptly made N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid, its measurement result and embodiment 1 are just the same.
Embodiment 8
The first step, N, N, N-trimethylammonium-N-sulphur butyl ammonium is zwitterionic synthetic
Get 1 of the trimethylamine aqueous solution that contains Trimethylamine 99 1.0mol and 0.96mol, the 4-butane sultone, be placed in the there-necked flask of 500ml, reacted 20 hours down, carry out underpressure distillation after reaction solution is taken out and dewater in 50 ℃, obtain the zwitter-ion solid of white, this zwitter-ion is washed successively with dehydrated alcohol, toluene and anhydrous diethyl ether, then 80 ℃ of following vacuum-dryings to constant weight, obtain pure zwitter-ion solid, its molecular weight is 195.11, and is standby.
Second step made N with embodiment 7, N, and N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid, its measurement result and embodiment 1 are just the same.
With the N that makes in the foregoing description, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid is used for the following examples 9～23.
Embodiment 9
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 1.33g and deionized water 12ml is mixed with weight percent concentration and is 10% quaternary ammonium salt ionic liquid aqueous solution, places autoclave, adds oil of mirbane 2.4g and Pt/SiO in still
2(wherein the charge capacity of metal Pt is 2% to catalyzer 0.012g, following examples 10～23 are identical) and polyoxyethylene nonylphenol ether 4.8mg, go out air in the autoclave with nitrogen replacement, temperature of reaction is risen to 60 ℃, in autoclave, feed hydrogen again and react hydrogen partial pressure 0.1MPa, 8 hours reaction times, reaction result is that oil of mirbane transformation efficiency 79%, p-aminophenol yield are 58.5%.
Embodiment 10
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 24g and deionized water 36ml is mixed with weight percent concentration and is 40% quaternary ammonium salt ionic liquid aqueous solution, places autoclave, adds oil of mirbane 1.2g, Pt/SiO in still
2Catalyzer 3.0g and polyoxyethylene nonylphenol ether 60mg, go out air in the autoclave with nitrogen replacement, temperature of reaction is risen to 130 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure 0.7MPa, in 1 hour reaction times, reaction result is, oil of mirbane transformation efficiency 100%, p-aminophenol yield are 65%.
Embodiment 11
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 4.0g and deionized water 20ml is mixed with weight percent concentration and is 16.7% quaternary ammonium salt ionic liquid aqueous solution, places autoclave, adds oil of mirbane 2.4g, Pt/SiO in still
2Catalyzer 0.03g and polyoxyethylene nonylphenol ether 40mg, go out air in the autoclave with nitrogen replacement, temperature of reaction is risen to 100 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure 0.6MPa, in 2 hours reaction times, reaction result is, oil of mirbane transformation efficiency 84%, p-aminophenol yield are 65.5%.
Embodiment 12
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 6.0g and deionized water 20ml is mixed with weight percent concentration and is 23.1% quaternary ammonium salt ionic liquid aqueous solution, places autoclave, adds oil of mirbane 2.4g, Pt/SiO in still
2Catalyzer 1.5g and cetyl trimethylammonium bromide 30mg, go out air in the autoclave with nitrogen replacement, temperature of reaction is risen to 80 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure 0.5MPa, in 5 hours reaction times, reaction result is, oil of mirbane transformation efficiency 99%, p-aminophenol yield are 82.5%.
Embodiment 13
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 8.57g and deionized water 20ml is mixed with weight percent concentration and is 30.0% quaternary ammonium salt ionic liquid aqueous solution, places autoclave, adds oil of mirbane 2.4g, Pt/SiO in still
2Catalyzer 1.0g and cetyl trimethylammonium bromide 20mg, go out air in the autoclave with nitrogen replacement, temperature of reaction is risen to 80 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure 0.6MPa, in 3 hours reaction times, reaction result is, oil of mirbane transformation efficiency 99%, p-aminophenol yield are 84%.
Embodiment 14
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 7.5g and deionized water 20ml is mixed with weight percent concentration and is 27.3% quaternary ammonium salt ionic liquid aqueous solution, places autoclave, adds oil of mirbane 2.4g, Pt/SiO in still
2Catalyzer 0.5g and cetyl trimethylammonium bromide 15mg, go out air in the autoclave with nitrogen replacement, temperature of reaction is risen to 70 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure 0.5MPa, in 6 hours reaction times, reaction result is, oil of mirbane transformation efficiency 98%, p-aminophenol yield are 86%.
Embodiment 15
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 6.0g and deionized water 20ml is mixed with weight percent concentration and is 23.1% quaternary ammonium salt ionic liquid aqueous solution, places autoclave, adds oil of mirbane 2.4g, Pt/SiO in still
2Catalyzer 0.1g and Dodecyl trimethyl ammonium chloride 60mg, go out air in the autoclave with nitrogen replacement, temperature of reaction is risen to 100 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure 0.3MPa, in 4 hours reaction times, reaction result is, oil of mirbane transformation efficiency 98%, p-aminophenol yield are 88%.
Embodiment 16
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 4.5g and deionized water 20ml is mixed with weight percent concentration and is 18.4% quaternary ammonium salt ionic liquid aqueous solution, places autoclave, adds oil of mirbane 2.4g, Pt/SiO in still
2Catalyzer 0.08g and Tetrabutyl amonium bromide 50mg, go out air in the autoclave with nitrogen replacement, temperature of reaction is risen to 85 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure 0.5MPa, in 5 hours reaction times, reaction result is, oil of mirbane transformation efficiency 99%, p-aminophenol yield are 87.5%.
Embodiment 17
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 4.5g and deionized water 20ml is mixed with weight percent concentration and is 18.4% quaternary ammonium salt ionic liquid aqueous solution, places autoclave, adds oil of mirbane 2.4g, Pt/SiO in still
2Catalyzer 0.08g goes out air in the autoclave with nitrogen replacement, and temperature of reaction is risen to 85 ℃, in autoclave, feed hydrogen again and react hydrogen partial pressure 0.5MPa, 5 hours reaction times, reaction result is that oil of mirbane transformation efficiency 99%, p-aminophenol yield are 71.5%.
Embodiment 18
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 4.5g and methyl alcohol 20g is mixed with weight percent concentration and is 18.4% quaternary ammonium salt ionic liquid methanol solution, places autoclave, adds oil of mirbane 2.4g, Pt/SiO in still
2Catalyzer 0.08g and cetyl trimethylammonium bromide 20mg, go out air in the autoclave with nitrogen replacement, temperature of reaction is risen to 85 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure 0.5MPa, in 5 hours reaction times, reaction result is, oil of mirbane transformation efficiency 99.5%, p-aminophenol yield are 19.5%.
Embodiment 19
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 4.5g and ethanol 20g is mixed with weight percent concentration and is 18.4% quaternary ammonium salt ionic liquid ethanolic soln, and other is with embodiment 18.Reaction result is that oil of mirbane transformation efficiency 77.5%, p-aminophenol yield are 28.5%.
Embodiment 20
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 4.5g and butanols 20g is mixed with weight percent concentration and is 18.4% quaternary ammonium salt ionic liquid butanol solution, and other is with embodiment 18.Reaction result is that oil of mirbane transformation efficiency 73.5%, p-aminophenol yield are 30.5%.
Embodiment 21
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 4.5g and glycol ether 20g is mixed with weight percent concentration and is 18.4% quaternary ammonium salt ionic liquid diethylene glycol solution, and other is with embodiment 18.Reaction result is that oil of mirbane transformation efficiency 96.5%, p-aminophenol yield are 67.5%.
Embodiment 22
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 4.5g and triglycol 20g is mixed with weight percent concentration and is 18.4% quaternary ammonium salt ionic liquid triglycol solution, and other is with embodiment 18.Reaction result is that oil of mirbane transformation efficiency 81.5%, p-aminophenol yield are 58%.
Embodiment 23
Get N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid 4.5g and Tetraglycol 99 20g is mixed with weight percent concentration and is 18.4% quaternary ammonium salt ionic liquid Tetraglycol 99 solution, and other is with embodiment 18.Reaction result is that oil of mirbane transformation efficiency 65.5%, p-aminophenol yield are 51.5%.
In embodiment 9～23, used load type metal platinum catalyst is got by known approach.
Claims (2)
1. ion liquid application method of quaternary ammonium salt, the molecular composition of this quaternary ammonium salt ionic liquid is N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate, molecular formula is [HSO
3-b-N (CH
3)
3] HSO
4, structural formula is as follows:
It is characterized in that: with this quaternary ammonium salt ionic liquid as an acidic catalyst, be used for the reaction of the synthetic p-aminophenol of oil of mirbane shortening, in second step of this reaction, be that phenylhydroxylamine is reset in the process that generates p-aminophenol, this quaternary ammonium salt ionic liquid plays the effect of an acidic catalyst, concrete steps are: it is 10～40% quaternary ammonium salt ionic liquid solution that this quaternary ammonium salt ionic liquid and solvent are mixed with weight percent concentration, with this quaternary ammonium salt ionic liquid solution, oil of mirbane and load type metal platinum catalyst add in the autoclave, the weight ratio of solvent is 1: 5～30 in oil of mirbane and this quaternary ammonium salt ionic liquid solution, load type metal platinum catalyst consumption is that 0.01～5% of oil of mirbane weight is determined by the metal platinum weight in this catalyzer, go out air in the autoclave with nitrogen replacement, temperature of reaction is risen to 60～130 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure is 0.1～0.7Mpa, reaction times is 1～8 hour, and oil of mirbane is through the synthetic p-aminophenol of shortening;
The solvent of this quaternary ammonium salt ionic liquid solution of wherein said preparation is deionized water, methyl alcohol, ethanol, butanols, glycol ether, triglycol or Tetraglycol 99.
2. according to the ion liquid application method of the described a kind of quaternary ammonium salt of claim 1, it is characterized in that in autoclave, adding in this quaternary ammonium salt ionic liquid solution, oil of mirbane and the load type metal platinum catalyst, add consumption and be 0.2～5% tensio-active agent of above-mentioned used oil of mirbane weight, used tensio-active agent is polyoxyethylene nonylphenol ether, cetyl trimethylammonium bromide, Dodecyl trimethyl ammonium chloride or Tetrabutyl amonium bromide, and other processing condition all remain unchanged.
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| CN102603448B (en) * | 2009-02-11 | 2015-03-04 | 中国科学技术大学 | Method for performing metal catalytic coupling reaction by utilizing organic anion-cation pair |
| CN101475493B (en) * | 2009-02-11 | 2013-01-23 | 中国科学技术大学 | Preparation method of organic cation-anion pair |
| CN102001954B (en) * | 2010-10-22 | 2013-10-16 | 大连理工大学 | Method for preparing paraaminophenol from N-phenylhydroxylamine in pressurized CO2/H2O system |
| CN102259025B (en) * | 2011-06-10 | 2013-12-18 | 河北工业大学 | Catalyst for preparing cyclohexanol by hydration of cyclohexene as well as preparation method and application method thereof |
| CN102441433B (en) * | 2011-09-13 | 2014-07-30 | 昆明理工大学 | Ion liquid catalyst and method for liquefying and gasifying catalytic biomass waste thereof |
| CN102723528B (en) * | 2012-06-06 | 2016-01-20 | 广州中科立新材料科技有限公司 | Amphion liquid electrolyte material and preparation thereof and application in lithium battery electrolytes |
| CN102898318B (en) * | 2012-10-10 | 2013-12-25 | 华东理工大学 | Steric-hindrance amine ionic liquid and preparation thereof |
| CN103193660B (en) * | 2013-03-30 | 2015-03-04 | 浙江工业大学 | Synthetic method of 4-alkoxy phenylamine compound |
| CN103539742B (en) * | 2013-10-15 | 2015-08-05 | 河北工业大学 | A kind of preparation method of ionic liquid type hydroxylamine salt |
| CN103736469B (en) * | 2013-12-19 | 2016-02-17 | 湖北出入境检验检疫局检验检疫技术中心 | A kind of ionic liquid bonding polysiloxane stationary phase and preparation method thereof |
| CN111514941B (en) * | 2019-02-03 | 2023-03-14 | 南京大学 | Catalyst and method for one-step synthesis of p-aminophenol by catalyzing hydrogenation of nitrobenzene |
| CN113030221B (en) * | 2021-04-14 | 2023-03-10 | 武汉理工大学 | Hydrogen sensor and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6403833B1 (en) * | 2001-01-30 | 2002-06-11 | Council Of Scientific And Industrial Research | Single step hydrogenation of nitrobenzene to p-aminophenol |
| CN1562465A (en) * | 2004-03-22 | 2005-01-12 | 四川大学 | Catalyzer for preparing p-aminophenol by using hydrogenation rearrangement through selection of nitrobenzene |
| CN1736979A (en) * | 2005-05-13 | 2006-02-22 | 中国科学院上海有机化学研究所 | The oil of mirbane hydro-reduction prepares the method for p-aminophenol |
-
2007
- 2007-12-12 CN CN2007101510016A patent/CN101182300B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6403833B1 (en) * | 2001-01-30 | 2002-06-11 | Council Of Scientific And Industrial Research | Single step hydrogenation of nitrobenzene to p-aminophenol |
| CN1562465A (en) * | 2004-03-22 | 2005-01-12 | 四川大学 | Catalyzer for preparing p-aminophenol by using hydrogenation rearrangement through selection of nitrobenzene |
| CN1736979A (en) * | 2005-05-13 | 2006-02-22 | 中国科学院上海有机化学研究所 | The oil of mirbane hydro-reduction prepares the method for p-aminophenol |
Non-Patent Citations (2)
| Title |
|---|
| Fang Dong.Mannich reaction in water using acidic ionic liquidasrecoverable and reusable catalyst.Catalysis Letters116 1-2.2007,116(1-2),77页2.2、2.3，Scheme1. |
| Fang Dong.Mannich reaction in water using acidic ionic liquidasrecoverable and reusable catalyst.Catalysis Letters116 1-2.2007,116(1-2),77页2.2、2.3,Scheme1. * |
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