CN101176852A - Catalyzer for synthesizing p-aminophenol by nitrobenzene catalytic hydrogenation as well as method for preparing and applying the same - Google Patents
Catalyzer for synthesizing p-aminophenol by nitrobenzene catalytic hydrogenation as well as method for preparing and applying the same Download PDFInfo
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- CN101176852A CN101176852A CNA2007101510001A CN200710151000A CN101176852A CN 101176852 A CN101176852 A CN 101176852A CN A2007101510001 A CNA2007101510001 A CN A2007101510001A CN 200710151000 A CN200710151000 A CN 200710151000A CN 101176852 A CN101176852 A CN 101176852A
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Abstract
The invention relates to a catalyst used for synthesis of p-aminophenol by catalytic hydrogenation of nitrobenzene, a preparation method and an application method, belonging to catalyst containing both platinum and organic compound field. The catalyst is a supported and bi-functional catalyst, and comprises room temperature ionic liquid of N, N, N-trimethyl-N-sulfobutyl-ammonium bisulfate which is one component of the active components, active metal Pt which is the other component of the active components, and silica gel carrier; wherein, the loading of the room temperature ionic liquid of N, N, N-trimethyl-N-sulfobutyl-ammonium bisulfate is 5 to 50%, while the loading of the active metal Pt is 0.01 to 1.5%. The invention has the advantages that: as a highly active heterogeneous catalyst, the catalyst overcomes the shortcomings that the homogeneous catalyst in prior art can not be used repeatedly, the reaction conditions of the heterogeneous catalyst in prior art are severe and the activity is low, and the problems that the equipment is liable to corrosion and the discharge of wastewater pollutes environment are solved.
Description
Technical field
Technical scheme of the present invention relates to the catalyst of while platiniferous and organic compound, specifically a kind of catalyst and methods for making and using same thereof that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
Technical background
By the method for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, in the current direction that is generally believed the future development that is synthetic para-aminophenol.Nitrobenzene catalytic hydrogenation technology have one step of reaction finish, method is simple, step is few, equipment and process conditions advantage such as gentleness relatively, is suitable for the large-scale industrial production para-aminophenol.
The mechanism of the synthetic para-aminophenol reaction of nitrobenzene catalytic hydrogenation is:
The first step of this reaction, promptly the nitrobenzene catalytic hydrogenation generates phenylhydroxylamine, adopts the metal platinum catalyst of support type; In second step of this reaction, promptly phenylhydroxylamine is reset and is generated para-aminophenol, then adopts acidic catalyst.
(Takayuki Komatsu such as Takayuki, Tatsuo Hirose.Applied Catalysis A:General, 2004,276:95-102) adopt Pt/ZSM-5 as bifunctional catalyst, from the synthetic para-aminophenol of nitrobenzene gas-phase catalytic hydrogenation, but reaction condition is very harsh, and the para-aminophenol yield only is 17%, selectivity is 42%, and catalyst is not reused; CN1562465 discloses the catalyst that a kind of nitrobenzene selective hydrogenation is reset the system para-aminophenol, and it is to be carrier (being again the acid activated centre of catalyst simultaneously) with the solid acid, is the heterogeneous bifunctional catalyst of hydrogenation main active with the noble metal platinum.Because solid acid does not have flowability, acidic site density is low and the acid strength distribution is even inadequately; The use of solid acid also causes the formation of carbon deposit on it easily, causes the solid acid rapid deactivation, can't reuse, and also causes the catalyst integral body can not be recycling; In addition, this invention has just reduced the consumption of sulfuric acid, and does not stop to use sulfuric acid, thereby can't solve a series of problem of environmental pollutions such as equipment corrosion, discharge of wastewater.
Because the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation needs metal active center and acid activated centre, how to prepare reusable, acid activated centre of highly active, free from corrosion collection and metal active center are arranged is the bifunctional catalyst of the Collaborative Control of one, is the key of improving the synthetic para-aminophenol production technology of nitrobenzene catalytic hydrogenation.
Summary of the invention
Technical problem to be solved by this invention is: a kind of catalyst and methods for making and using same thereof that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation is provided, this catalyst is a kind of highly active heterogeneous catalysis, both having overcome existing homogeneous catalyst can not reusable shortcoming, overcome severe reaction conditions and active low shortcoming that existing heterogeneous catalysis exists again, also overcome equipment corrosion and discharge of wastewater environmental pollution problems.
The present invention solves this technical problem the technical scheme that is adopted:
The catalyst that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, it is a loaded dual-function type catalyst, its composition comprises the ionic liquid at room temperature N of one of active component, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate, two reactive metal Pt and carrier silica gel of active component, ionic liquid at room temperature N wherein, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 5～50%, the loading of reactive metal Pt is 0.01～1.5%, loading is meant ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate and the reactive metal Pt weight percent content in loaded dual-function type catalyst integral body, above-mentioned ionic liquid at room temperature N, N, the preparation method of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is: getting mol ratio is trimethylamine: 1, the trimethylamine aqueous solution and 1 of 4-butane sultone=1: 1.1, the 4-butane sultone places there-necked flask, after reacting 8～48 hours under ℃ condition of room temperature～60, reactant liquor is taken out, carrying out decompression distillation dewaters, obtain the amphion solid of white, with this amphion solid absolute ethyl alcohol, toluene and absolute ether wash successively, then 80 ℃ of following vacuum drying to constant weight, obtain amphion N, N, N-trimethyl-N-sulphur butyl ammonium; Get the amphion N that makes thus, N, N-trimethyl-N-sulphur butyl ammonium is put into a four-hole boiling flask, keeping temperature slowly to drip the concentrated sulfuric acid under less than 10 ℃ condition, amphion N, N, the mol ratio of the N-trimethyl-N-sulphur butyl ammonium and the concentrated sulfuric acid is 1: 0.96～1.04, be warming up to 70 ℃ then, reacted 6 hours, and promptly obtained target product ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate, the weight content of trimethylamine 〉=33% in the above-mentioned trimethylamine aqueous solution.
The above-mentioned catalyst that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, ionic liquid at room temperature N, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is preferably 10～30%, and the loading of reactive metal Pt is preferably 0.05～1.2%.
The above-mentioned catalyst that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, reactive metal Pt and carrier silica gel make with known technology.
The above-mentioned Preparation of catalysts method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, select in the following method any one for use:
Method I, its step is as follows:
The first step, getting mol ratio is trimethylamine: 1, the trimethylamine aqueous solution and 1 of 4-butane sultone=1: 1.1, the 4-butane sultone places there-necked flask, after reacting 8～48 hours under ℃ condition of room temperature～60, reactant liquor is taken out, carry out decompression distillation and dewater, obtain the amphion solid of white, this amphion solid is washed successively with absolute ethyl alcohol, toluene and absolute ether, then 80 ℃ of following vacuum drying to constant weight, obtain amphion N, N, N-trimethyl-N-sulphur butyl ammonium; Get the amphion N that makes thus, N, N-trimethyl-N-sulphur butyl ammonium is put into a four-hole boiling flask, keeping temperature slowly to drip the concentrated sulfuric acid under less than 10 ℃ condition, amphion N, N, the mol ratio of the N-trimethyl-N-sulphur butyl ammonium and the concentrated sulfuric acid is 1: 0.96～1.04, be warming up to 70 ℃ then, reacted 6 hours, and promptly obtained product ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate, the weight content of trimethylamine 〉=33% in the above-mentioned trimethylamine aqueous solution;
In second step, the ethyl orthosilicate that takes by weighing aequum places reactor, adds absolute ethyl alcohol and deionized water, and wherein, volume ratio is an ethyl orthosilicate: absolute ethyl alcohol: deionized water=1: 0.2～4: 0.4～3 stir in 30～90 ℃ of water-baths;
The 3rd step, according to following weight ratio: the ionic liquid at room temperature N that makes by the first step, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate: platinum: ethyl orthosilicate=0.015～0.3: 0.00003～0.009: 1, with ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate and chloroplatinic acid join in the reactor in second step, stir, until forming gel, ℃ aging 10～24 hours then in room temperature～100;
In the 4th step, go on foot prepared material in 30～100 ℃ of vacuum drying 0.5～24 hour with the 3rd;
In the 5th step, the 4th step dried matter is adopted 120～250 ℃ of roastings 1～5 hour in Muffle furnace of nitrogen atmosphere or air atmosphere;
The 6th step placed tubular reactor with prepared material of the 5th step, and adopting volume ratio is N
2: H
2=10～100: 0.5～10 N
2And H
2Gaseous mixture as reducing gases, in 120～250 ℃ of down reduction 1～10 hour, under protection of nitrogen gas, lower the temperature then, from tubular reactor, take out product, promptly make the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation;
Method II, its step is as follows:
The first step is with the method I first step;
Second step is with second step of method I;
The 3rd step, according to following weight ratio: the ionic liquid at room temperature N that makes by the first step, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate: ethyl orthosilicate=0.015～0.3: 1, with ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate joins in second reactor that goes on foot and stirs, adding volume ratio again is ethyl orthosilicate: the concentrated hydrochloric acid of concentrated hydrochloric acid=1: 0.02～0.3 reacts, until forming gel, and ℃ aging 10～24 hours then in room temperature～100;
In the 4th step, the 3rd material that make of step in 120～180 ℃ of vacuum drying 0.5～10 hour, is made catalyst precarsor;
The 5th step, adopt equi-volume impregnating, according to the weight ratio metal platinum: ethyl orthosilicate=0.00003～0.009: 1 ratio takes by weighing chloroplatinic acid, be dissolved in deionized water or weight percent concentration and be in 20～50% the ethanol water and form maceration extract, the catalyst precarsor that the 4th step was made places this maceration extract as carrier, floods 5～30 hours;
In the 6th step, the material that the 5th step dipping is good was in 40～120 ℃ of vacuum drying 5～24 hours;
In the 7th step, the 6th step dried matter is adopted 120～250 ℃ of roastings 1～5 hour in Muffle furnace of nitrogen atmosphere or air atmosphere;
In the 8th step, the material that the 7th step was made places tubular reactor, and adopting volume ratio is N
2: H
2=10～100: 0.5～10 N
2And H
2Gaseous mixture as reducing gases, in 120～250 ℃ of down reduction 1～10 hour, under protection of nitrogen gas, lower the temperature then, from tubular reactor, take out product, promptly make the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
The above-mentioned Application of Catalyst method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, the steps include: nitrobenzene, the catalyst that solvent and this are used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation places autoclave, the weight ratio of nitrobenzene and solvent is 1: 10～30, this catalyst consumption that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation is that 0.01～5% of nitrobenzene weight is determined by the metal Pt weight of this catalyst, go out air in the autoclave with nitrogen replacement, reaction temperature is risen to 60～130 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure is 0.1～0.7MPa, reaction time is 1～7 hour, and nitrobenzene is through the synthetic para-aminophenol of catalytic hydrogenation.
In the above-mentioned Application of Catalyst method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, in autoclave, add in this catalyst, nitrobenzene and solvent that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, add consumption and be 0.2～5% surfactant of above-mentioned used nitrobenzene weight, used surfactant is NPE, softex kw, DTAC or TBAB, and other process conditions all remain unchanged.
Add some surfactants, played the effect of emulsification, dispersion and phase transfer, water can fully be contacted mutually with nitrobenzene, accelerate the synthetic para-aminophenol reaction speed of nitrobenzene catalytic hydrogenation, help the carrying out that react and the high selectivity of synthetic para-aminophenol more.
In the above-mentioned Application of Catalyst method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, solvent for use is deionized water, methyl alcohol, ethanol, butanols, diethylene glycol (DEG), triethylene glycol or tetraethylene glycol.
In the above-mentioned Application of Catalyst method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, the preferred catalyst amount that this is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation is that 0.02～3% of nitrobenzene weight is determined by the metal Pt weight of this catalyst, reaction temperature is 80～100 ℃, hydrogen partial pressure is 0.3～0.6MPa, reaction time is 2～6 hours, in autoclave, add the catalyst that this is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, in the time of nitrobenzene and solvent, add consumption and be 0.2～5% surfactant of above-mentioned used nitrobenzene weight, used surfactant is a NPE, softex kw, DTAC or TBAB.
In the above-mentioned Application of Catalyst method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, after synthetic reaction is finished, utilize filtration under diminished pressure to isolate the catalyst that this is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, after the absolute ethyl alcohol cleaning, 60 ℃ of following vacuum drying 5 hours, drop into and reuse again.
The invention has the beneficial effects as follows:
(1) catalyst that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of the present invention is a loaded dual-function type catalyst, has advantages of high catalytic activity, the nitrobenzene conversion ratio reaches as high as 90%, and the para-aminophenol yield is up to 49%, and the para-aminophenol selectivity is up to 68%.And the Pt/ZSM-5 bifunctional catalyst of the existing catalytic activity the best that adopts at present, its para-aminophenol yield only is 17%, selectivity is 42%.
(2) method for preparing catalyst that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of the present invention is simple, and mechanical strength is big, wear-resistant, the active component loss is less, and recyclable number of times reaches more than 10 times, and cost is lower.And the existing Pt/ZSM-5 bifunctional catalyst that adopts is not at present reused.
(3) catalyst stability that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of the present invention is good, can reuse more than 4 times, only needs simply to see embodiment 30 for details with carrying out use next time after the absolute ethyl alcohol flushing drying.
(4) in the reaction of the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, the catalyst that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of the present invention all has catalytic activity preferably at multiple solvent, and the Pt/ZSM-5 bifunctional catalyst of the existing catalytic activity the best that adopts at present only just has catalytic activity under solvent is the situation of water.
(5) catalyst that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of the present invention is used for the process conditions gentleness, simple to operation of the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
The specific embodiment
Embodiment 1
Ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate synthetic:
The first step, get 1 of the trimethylamine aqueous solution that contains trimethylamine 0.50mol and 0.55mol, the 4-butane sultone, place the there-necked flask of 250ml, after reacting 8～48 hours under ℃ condition of room temperature～60, dewater carrying out decompression distillation after the reactant liquor taking-up, obtain the amphion solid of white, this amphion solid is washed successively with absolute ethyl alcohol, toluene and absolute ether, then 80 ℃ of following vacuum drying to constant weight, obtain amphion N, N, N-trimethyl-N-sulphur butyl ammonium, the weight content of trimethylamine 〉=33% in the above-mentioned trimethylamine aqueous solution.
Second step, get the amphion N that the 0.50mol first step makes, N, N-trimethyl-N-sulphur butyl ammonium is put into a four-hole boiling flask, keep temperature less than 10 ℃ of conditions under, slowly drip the concentrated sulfuric acid of 0.48～0.52mol, be warming up to 70 ℃ then, reacted 6 hours, promptly obtain product ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate.The test data of this product is: 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 2～8 synthesizes one of Preparation of catalysts method of para-aminophenol for being used for the nitrobenzene catalytic hydrogenation.
Embodiment 2
The first step takes by weighing ethyl orthosilicate 10ml (9.356g) and places reactor, adds absolute ethyl alcohol 2ml and deionized water 30ml, stirs in 90 ℃ of water-baths;
Second step, take by weighing the ionic liquid at room temperature N that makes by embodiment 1, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate 0.142g and chloroplatinic acid 0.754mg (amounting to metal platinum is 0.284mg), it is joined in the reactor of the first step, stir, until forming gel, at room temperature aging 24 hours then;
In the 3rd step, go on foot prepared material in 100 ℃ of following vacuum drying 0.5 hour with second;
In the 4th step, the 3rd step dried matter is adopted the 120 ℃ of following roastings 5 hours in Muffle furnace of nitrogen atmosphere or air atmosphere;
In the 5th step, the material that the 4th step was made places tubular reactor, and adopting volume ratio is N
2: H
2=2: 1 N
2And H
2Gaseous mixture as reducing gases, in 120 ℃ down reduction under protection of nitrogen gas, lower the temperature after 10 hours, from tubular reactor, take out, make the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
In this product, active component ionic liquid at room temperature N, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 5%, the loading of metal Pt is 0.01%.Loading is meant ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate and the reactive metal Pt weight percent content (down together) in loaded dual-function type catalyst integral body.Computational methods are: known ethyl orthosilicate complete hydrolysis can obtain 2.7g silica gel, therefore, ionic liquid at room temperature N, N, loading=0.142g/ (2.7+0.142) g * 100%=5% of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate, loading=0.000284g/ of metal Pt (2.7+0.142) g * 100%=0.01% because metal Pt is very micro-, ignores its weight into the total amount of this catalyst in computational process.
Embodiment 3
The first step takes by weighing ethyl orthosilicate 10ml (9.356g) and places reactor, adds absolute ethyl alcohol 40ml and deionized water 4ml, stirs in 30 ℃ of water-baths;
Second step, take by weighing the ionic liquid at room temperature N that makes by embodiment 1, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate 2.7g and chloroplatinic acid 0.215g (amounting to metal platinum is 0.081g), it is joined in the reactor of the first step, stir,, wore out 10 hours down at 100 ℃ then until forming gel;
In the 3rd step, go on foot prepared material in 30 ℃ of following vacuum drying 24 hours with second;
In the 4th step, the 3rd step dried matter is adopted the 250 ℃ of following roastings 1 hour in Muffle furnace of nitrogen atmosphere or air atmosphere;
In the 5th step, the material that the 4th step was made places tubular reactor, and adopting volume ratio is N
2: H
2=2: 1 N
2And H
2Gaseous mixture as reducing gases, in 250 ℃ down reduction under protection of nitrogen gas, lower the temperature after 1 hour, from tubular reactor, take out, make the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
In this product, active component ionic liquid at room temperature N, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 50%, the loading of metal Pt is 1.5%.Computational methods are with embodiment 2.
Embodiment 4
The first step takes by weighing ethyl orthosilicate 10ml (9.356g) and places reactor, adds absolute ethyl alcohol 10ml and deionized water 10ml, stirs in 70 ℃ of water-baths;
Second step, take by weighing the ionic liquid at room temperature N that makes by embodiment 1, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate 0.3g and chloroplatinic acid 3.98mg (amounting to metal platinum is 1.5mg), it is joined in the reactor of the first step, stir,, wore out 16 hours down at 70 ℃ then until forming gel;
In the 3rd step, go on foot prepared material in 80 ℃ of following vacuum drying 12 hours with second;
In the 4th step, the 3rd step dried matter is adopted the 250 ℃ of following roastings 2 hours in Muffle furnace of nitrogen atmosphere or air atmosphere;
In the 5th step, the material that the 4th step was made places tubular reactor, and adopting volume ratio is N
2: H
2=2: 1 N
2And H
2Gaseous mixture as reducing gases, in 250 ℃ down reduction under protection of nitrogen gas, lower the temperature after 4 hours, from tubular reactor, take out, make the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
In this product, active component ionic liquid at room temperature N, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 10%, the loading of metal Pt is 0.05%.Computational methods are with embodiment 2.
Embodiment 5
The first step takes by weighing ethyl orthosilicate 10ml (9.356g) and places reactor, adds absolute ethyl alcohol 20ml and deionized water 20ml, stirs in 60 ℃ of water-baths;
Second step, take by weighing the ionic liquid at room temperature N that makes by embodiment 1, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate 0.675g and chloroplatinic acid 0.108g (amounting to metal platinum is 0.041g), it is joined in the reactor of the first step, stir,, wore out 16 hours down at 60 ℃ then until forming gel;
In the 3rd step, go on foot prepared material in 80 ℃ of following vacuum drying 12 hours with second;
In the 4th step, the 3rd step dried matter is adopted the 200 ℃ of following roastings 3 hours in Muffle furnace of nitrogen atmosphere or air atmosphere;
In the 5th step, the material that the 4th step was made places tubular reactor, and adopting volume ratio is N
2: H
2=2: 1 N
2And H
2Gaseous mixture as reducing gases, in 250 ℃ down reduction under protection of nitrogen gas, lower the temperature after 3 hours, from tubular reactor, take out, make the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
In this product, active component ionic liquid at room temperature N, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 20%, the loading of metal Pt is 1.2%.Computational methods are with embodiment 2.
Embodiment 6
The first step takes by weighing ethyl orthosilicate 10ml (9.356g) and places reactor, adds absolute ethyl alcohol 20ml and deionized water 10ml, stirs in 60 ℃ of water-baths;
Second step, take by weighing the ionic liquid at room temperature N that makes by embodiment 1, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate 1.157g and chloroplatinic acid 0.05g (amounting to metal platinum is 0.019g), it is joined in the reactor of the first step, stir,, wore out 16 hours down at 60 ℃ then until forming gel;
Other makes the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation with embodiment 5.
In this product, active component ionic liquid at room temperature N, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 30%, the loading of metal Pt is 0.5%.Computational methods are with embodiment 2.
Embodiment 7
The first step takes by weighing ethyl orthosilicate 10ml (9.356g) and places reactor, adds absolute ethyl alcohol 15ml and deionized water 10ml, stirs in 80 ℃ of water-baths;
Second step, take by weighing the ionic liquid at room temperature N that makes by embodiment 1, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate 0.675g and chloroplatinic acid 13.4mg (amounting to metal platinum is 5.05mg), it is joined in the reactor of the first step, stir,, wore out 12 hours down at 80 ℃ then until forming gel;
Other makes the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation with embodiment 5.
In this product, active component ionic liquid at room temperature N, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 20%, the loading of metal Pt is 0.15%.Computational methods are with embodiment 2.
Embodiment 8
The first step takes by weighing ethyl orthosilicate 10ml (9.356g) and places reactor, adds absolute ethyl alcohol 20ml and deionized water 10ml, stirs in 80 ℃ of water-baths;
Second step, take by weighing the ionic liquid at room temperature N that makes by embodiment 1, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate 0.675g and chloroplatinic acid 9.02mg (amounting to metal platinum is 3.4mg), it is joined in the reactor of the first step, stir,, wore out 16 hours down at 50 ℃ then until forming gel;
Other makes the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation with embodiment 5.
In this product, active component ionic liquid at room temperature N, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 20%, the loading of metal Pt is 0.1%.Computational methods are with embodiment 2.
Embodiment 9～11 is two of the Preparation of catalysts method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
Embodiment 9
The first step takes by weighing ethyl orthosilicate 10ml (9.356g) and places reactor, adds absolute ethyl alcohol 2ml and deionized water 30ml, stirs in 90 ℃ of water-baths;
In second step, take by weighing the ionic liquid at room temperature N that makes by embodiment 1, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate 0.142g joins it in reactor of the first step, stirs, the concentrated hydrochloric acid that adds 3ml again reacts, until forming gel, and at room temperature aging 24 hours then;
In the 3rd step, prepared material of second step in 120 ℃ of vacuum drying 10 hours, is made catalyst precarsor;
The 4th step, adopt equi-volume impregnating, take by weighing chloroplatinic acid 0.754mg (amounting to metal platinum is 0.284mg), be dissolved in deionized water and form maceration extract, the catalyst precarsor that the 3rd step was made places this maceration extract as carrier, floods 5 hours;
In the 5th step, the material that the 4th step that dipping is good makes was in 40 ℃ of following vacuum drying 24 hours;
In the 6th step, the 5th material that make of step is adopted the 120 ℃ of roastings 5 hours in Muffle furnace of nitrogen atmosphere or air atmosphere;
In the 7th step, the material that the 6th step was made places tubular reactor, and adopting volume ratio is N
2: H
2=2: 1 N
2And H
2Gaseous mixture as reducing gases, in 120 ℃ down reduction under protection of nitrogen gas, lower the temperature after 10 hours, from tubular reactor, take out, make the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
In this product, active component ionic liquid at room temperature N, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 5%, the loading of metal Pt is 0.01%.Computational methods are with embodiment 2.
Embodiment 10
The first step takes by weighing ethyl orthosilicate 10ml (9.356g) and places reactor, adds absolute ethyl alcohol 40ml and deionized water 4ml, stirs in 30 ℃ of water-baths;
In second step, take by weighing the ionic liquid at room temperature N that makes by embodiment 1, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate 2.7g joins it in reactor of the first step, stirs, the concentrated hydrochloric acid that adds 0.2ml again reacts, and until forming gel, wears out 10 hours down at 100 ℃ then;
In the 3rd step, prepared material of second step in 180 ℃ of vacuum drying 0.5 hour, is made catalyst precarsor;
The 4th step, adopt equi-volume impregnating, take by weighing chloroplatinic acid 0.215g (amounting to metal platinum is 0.081g), be dissolved in weight percent concentration and be 20% ethanol water and form maceration extract, the catalyst precarsor that the 3rd step was made places this maceration extract as carrier, floods 30 hours;
In the 5th step, the material that the 4th step that dipping is good makes was in 120 ℃ of following vacuum drying 5 hours;
In the 6th step, the 5th material that make of step is adopted the 250 ℃ of roastings 1 hour in Muffle furnace of nitrogen atmosphere or air atmosphere;
In the 7th step, the material that the 6th step was made places tubular reactor, and adopting volume ratio is N
2: H
2=2: 1 N
2And H
2Gaseous mixture as reducing gases, in 250 ℃ down reduction under protection of nitrogen gas, lower the temperature after 1 hour, from tubular reactor, take out, make the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
In this product, active component ionic liquid at room temperature N, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 50%, the loading of metal Pt is 1.5%.Computational methods are with embodiment 2.
Embodiment 11
The first step takes by weighing ethyl orthosilicate 10ml (9.356g) and places reactor, adds absolute ethyl alcohol 20ml and deionized water 10ml, stirs in 80 ℃ of water-baths;
In second step, take by weighing the ionic liquid at room temperature N that makes by embodiment 1, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate 0.675g joins it in reactor of the first step, stirs, the concentrated hydrochloric acid that adds 0.5ml again reacts, and until forming gel, wears out 12 hours down at 50 ℃ then;
In the 3rd step, prepared material of second step in 150 ℃ of vacuum drying 5 hours, is made catalyst precarsor;
The 4th step, adopt equi-volume impregnating, take by weighing chloroplatinic acid 9.02mg (amounting to metal platinum is 3.4mg), be dissolved in weight percent concentration and be 50% ethanol water and form maceration extract, prepared catalyst precarsor of the 3rd step is placed this maceration extract as carrier, flooded 24 hours;
In the 5th step, the material that the 4th step that dipping is good makes was in 100 ℃ of following vacuum drying 10 hours;
In the 6th step, the 5th material that make of step is adopted the 250 ℃ of roastings 1 hour in Muffle furnace of nitrogen atmosphere or air atmosphere;
In the 7th step, the material that the 6th step was made places tubular reactor, and adopting volume ratio is N
2: H
2=2: 1 N
2And H
2Gaseous mixture as reducing gases, in 200 ℃ down reduction under protection of nitrogen gas, lower the temperature after 3 hours, from tubular reactor, take out, make the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
In this product, active component ionic liquid at room temperature N, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 20%, the loading of metal Pt is 0.1%.Computational methods are with embodiment 2.
Embodiment 12～30th, and the catalyst of the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation is used for the embodiment of the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
Embodiment 12
Get catalyst 1.2g, nitrobenzene 1.2g, deionized water 12ml and NPE 2.4mg by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 2 preparations, place autoclave, go out air in the autoclave with nitrogen replacement, reaction temperature rises to 60 ℃ then, feeds hydrogen again and react hydrogen partial pressure 0.1MPa in autoclave, 7 hours reaction time, reaction result is that nitrobenzene conversion ratio 40.5%, para-aminophenol yield are 10.2%.
Embodiment 13
Get catalyst 4.0g, nitrobenzene 1.2g, deionized water 36ml and NPE 60mg by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 3 preparations, place autoclave, go out air in the autoclave with nitrogen replacement, reaction temperature rises to 130 ℃ then, feeds hydrogen again and react hydrogen partial pressure 0.7MPa in autoclave, 1 hour reaction time, reaction result is that nitrobenzene conversion ratio 55%, para-aminophenol yield are 21%.
Embodiment 14
Get catalyst 1.5g, nitrobenzene 1.2g, deionized water 20ml and softex kw 20mg by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 4 preparations, place autoclave, go out air in the autoclave with nitrogen replacement, reaction temperature rises to 100 ℃ then, feeds hydrogen again and react hydrogen partial pressure 0.3MPa in autoclave, 6 hours reaction time, reaction result is that nitrobenzene conversion ratio 77%, para-aminophenol yield are 38.5%.
Embodiment 15
Get catalyst 2.0g, nitrobenzene 1.2g, deionized water 20ml and softex kw 15mg by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 5 preparations, place autoclave, go out air in the autoclave with nitrogen replacement, reaction temperature rises to 80 ℃ then, feeds hydrogen again and react hydrogen partial pressure 0.6MPa in autoclave, 2 hours reaction time, reaction result is that nitrobenzene conversion ratio 79%, para-aminophenol yield are 47.5%.
Embodiment 16
Get catalyst 2.0g, nitrobenzene 1.2g, deionized water 20ml and DTAC 50mg by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 6 preparations, place autoclave, go out air in the autoclave with nitrogen replacement, reaction temperature rises to 80 ℃ then, feeds hydrogen again and react hydrogen partial pressure 0.4MPa in autoclave, 4 hours reaction time, reaction result is that nitrobenzene conversion ratio 72%, para-aminophenol yield are 49%.
Embodiment 17
Get catalyst 3.0g and TBAB 50mg by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 7 preparations, other is with embodiment 16, and reaction result is that nitrobenzene conversion ratio 88%, para-aminophenol yield are 48%.
Embodiment 18
Get catalyst 2.0g and TBAB 20mg by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 8 preparations, other is with embodiment 16, and reaction result is that nitrobenzene conversion ratio 90%, para-aminophenol yield are 49%.
Embodiment 19
Get catalyst 3.0g and softex kw 20mg by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 9 preparations, other is with embodiment 16, and reaction result is that nitrobenzene conversion ratio 52%, para-aminophenol yield are 16%.
Embodiment 20
Get the catalyst 1.0g by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 10 preparations, other is with embodiment 19, and reaction result is that nitrobenzene conversion ratio 53%, para-aminophenol yield are 21%.
Embodiment 21
Get the catalyst 2.0g by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 11 preparations, other is with embodiment 19, and reaction result is that nitrobenzene conversion ratio 58%, para-aminophenol yield are 28%.
Embodiment 22
Get catalyst 2.0g, nitrobenzene 1.2g and deionized water 20ml by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 8 preparations, place autoclave, go out air in the autoclave with nitrogen replacement, reaction temperature rises to 80 ℃ then, feeds hydrogen again and react hydrogen partial pressure 0.4MPa in autoclave, 4 hours reaction time, reaction result is that nitrobenzene conversion ratio 85%, para-aminophenol yield are 32%.
Embodiment 23
Get the catalyst 2.0g by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 11 preparations, other is with embodiment 22, and reaction result is that nitrobenzene conversion ratio 51%, para-aminophenol yield are 20%.
Embodiment 24
Get catalyst 2.0g, methyl alcohol 20g, nitrobenzene 1.2g and softex kw 20mg by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 8 preparations, place autoclave, go out air in the autoclave with nitrogen replacement, reaction temperature rises to 80 ℃ then, feeds hydrogen again and react hydrogen partial pressure 0.4MPa in autoclave, 4 hours reaction time, reaction result is that nitrobenzene conversion ratio 86%, para-aminophenol yield are 15%.
Embodiment 25
Get catalyst 2.0g and ethanol 20g by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 8 preparations, other is with embodiment 24, and reaction result is that nitrobenzene conversion ratio 81%, para-aminophenol yield are 21%.
Embodiment 26
Get catalyst 2.0g and butanols 20g by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 8 preparations, other is with embodiment 24, and reaction result is that nitrobenzene conversion ratio 76%, para-aminophenol yield are 26.5%.
Embodiment 27
Get catalyst 2.0g and diethylene glycol (DEG) 20g by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 8 preparations, other is with embodiment 24, and reaction result is that nitrobenzene conversion ratio 87%, para-aminophenol yield are 40.5%.
Embodiment 28
Get catalyst 2.0g and triethylene glycol 20g by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 8 preparations, other is with embodiment 24, and reaction result is that nitrobenzene conversion ratio 85%, para-aminophenol yield are 35.5%.
Embodiment 29
Get catalyst 2.0g and tetraethylene glycol 20g by the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of embodiment 8 preparations, other is with embodiment 24, and reaction result is that nitrobenzene conversion ratio 76%, para-aminophenol yield are 31%.
Embodiment 30
The catalyst that embodiment 18 used nitrobenzene catalytic hydrogenations is synthesized para-aminophenol, after each synthetic reaction is finished, wash with the absolute ethyl alcohol of 30ml, again 60 ℃ of following vacuum drying 5 hours, under same reaction condition, carry out the repeated use more than 4 times then.The nitrobenzene conversion ratio is between 85～90%, and the para-aminophenol yield is between 42～49%.This result shows that the activity of such catalysts and the selectivity of the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of the present invention have only small amount of attenuation.
Claims (8)
1. the catalyst that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, it is characterized in that: it is a loaded dual-function type catalyst, its composition comprises the ionic liquid at room temperature N of one of active component, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate, two reactive metal Pt and carrier silica gel of active component, ionic liquid at room temperature N wherein, N, the loading of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is 5～50%, the loading of reactive metal Pt is 0.01～1.5%, loading is meant ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate and the reactive metal Pt weight percent content in loaded dual-function type catalyst integral body, above-mentioned ionic liquid at room temperature N, N, the preparation method of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate is: getting mol ratio is trimethylamine: 1, the trimethylamine aqueous solution and 1 of 4-butane sultone=1: 1.1, the 4-butane sultone places there-necked flask, after reacting 8～48 hours under ℃ condition of room temperature～60, reactant liquor is taken out, carrying out decompression distillation dewaters, obtain the amphion solid of white, with this amphion solid absolute ethyl alcohol, toluene and absolute ether wash successively, then 80 ℃ of following vacuum drying to constant weight, obtain amphion N, N, N-trimethyl-N-sulphur butyl ammonium; Get the amphion N that makes thus, N, N-trimethyl-N-sulphur butyl ammonium is put into a four-hole boiling flask, keeping temperature slowly to drip the concentrated sulfuric acid under less than 10 ℃ condition, amphion N, N, the mol ratio of the N-trimethyl-N-sulphur butyl ammonium and the concentrated sulfuric acid is 1: 0.96～1.04, be warming up to 70 ℃ then, reacted 6 hours, and promptly obtained target product ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate, the weight content of trimethylamine 〉=33% in the above-mentioned trimethylamine aqueous solution.
2. according to the described catalyst that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of claim 1, it is characterized in that: ionic liquid at room temperature N, N, the loading 10～30% of N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate, the loading 0.05～1.2% of reactive metal Pt.
3. the described Preparation of catalysts method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of claim 1 is characterized in that: select in the following method any one for use:
Method I, its step is as follows:
The first step, getting mol ratio is trimethylamine: 1, the trimethylamine aqueous solution and 1 of 4-butane sultone=1: 1.1, the 4-butane sultone places there-necked flask, after reacting 8～48 hours under ℃ condition of room temperature～60, reactant liquor is taken out, carry out decompression distillation and dewater, obtain the amphion solid of white, this amphion solid is washed successively with absolute ethyl alcohol, toluene and absolute ether, then 80 ℃ of following vacuum drying to constant weight, obtain amphion N, N, N-trimethyl-N-sulphur butyl ammonium; Get the amphion N that makes thus, N, N-trimethyl-N-sulphur butyl ammonium is put into a four-hole boiling flask, keeping temperature slowly to drip the concentrated sulfuric acid under less than 10 ℃ condition, amphion N, N, the mol ratio of the N-trimethyl-N-sulphur butyl ammonium and the concentrated sulfuric acid is 1: 0.96～1.04, be warming up to 70 ℃ then, reacted 6 hours, and promptly obtained product ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate, the weight content of trimethylamine 〉=33% in the above-mentioned trimethylamine aqueous solution;
In second step, the ethyl orthosilicate that takes by weighing aequum places reactor, adds absolute ethyl alcohol and deionized water, and wherein, volume ratio is an ethyl orthosilicate: absolute ethyl alcohol: deionized water=1: 0.2～4: 0.4～3 stir in 30～90 ℃ of water-baths;
The 3rd step, according to following weight ratio: the ionic liquid at room temperature N that makes by the first step, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate: platinum: ethyl orthosilicate=0.015～0.3: 0.00003～0.009: 1, with ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate and chloroplatinic acid join in the reactor in second step, stir, until forming gel, ℃ aging 10～24 hours then in room temperature～100;
In the 4th step, go on foot prepared material in 30～100 ℃ of vacuum drying 0.5～24 hour with the 3rd;
In the 5th step, the 4th step dried matter is adopted 120～250 ℃ of roastings 1～5 hour in Muffle furnace of nitrogen atmosphere or air atmosphere;
The 6th step placed tubular reactor with prepared material of the 5th step, and adopting volume ratio is N
2: H
2=10～100: 0.5～10 N
2And H
2Gaseous mixture as reducing gases, in 120～250 ℃ of down reduction 1～10 hour, under protection of nitrogen gas, lower the temperature then, from tubular reactor, take out product, promptly make the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation;
Method II, its step is as follows:
The first step is with the method I first step;
Second step is with second step of method I;
The 3rd step, according to following weight ratio: the ionic liquid at room temperature N that makes by the first step, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate: ethyl orthosilicate=0.015～0.3: 1, with ionic liquid at room temperature N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate joins in second reactor that goes on foot and stirs, adding volume ratio again is ethyl orthosilicate: the concentrated hydrochloric acid of concentrated hydrochloric acid=1: 0.02～0.3 reacts, until forming gel, and ℃ aging 10～24 hours then in room temperature～100;
In the 4th step, the 3rd material that make of step in 120～180 ℃ of vacuum drying 0.5～10 hour, is made catalyst precarsor;
The 5th step, adopt equi-volume impregnating, according to the weight ratio metal platinum: ethyl orthosilicate=0.00003～0.009: 1 ratio takes by weighing chloroplatinic acid, be dissolved in deionized water or weight percent concentration and be in 20～50% the ethanol water and form maceration extract, the catalyst precarsor that the 4th step was made places this maceration extract as carrier, floods 5～30 hours;
In the 6th step, the material that the 5th step dipping is good was in 40～120 ℃ of vacuum drying 5～24 hours;
In the 7th step, the 6th step dried matter is adopted 120～250 ℃ of roastings 1～5 hour in Muffle furnace of nitrogen atmosphere or air atmosphere;
In the 8th step, the material that the 7th step was made places tubular reactor, and adopting volume ratio is N
2: H
2=10～100: 0.5～10 N
2And H
2Gaseous mixture as reducing gases, in 120～250 ℃ of down reduction 1～10 hour, under protection of nitrogen gas, lower the temperature then, from tubular reactor, take out product, promptly make the catalyst prod that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation.
4. the described Application of Catalyst method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of claim 1, it is characterized in that the steps include: with nitrobenzene, the catalyst that solvent and this are used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation places autoclave, the weight ratio of nitrobenzene and solvent is 1: 10～30, this catalyst consumption that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation is that 0.01～5% of nitrobenzene weight is determined by the metal Pt weight of this catalyst, go out air in the autoclave with nitrogen replacement, reaction temperature is risen to 60～130 ℃, feeding hydrogen again in autoclave reacts, hydrogen partial pressure is 0.1～0.7MPa, reaction time is 1～7 hour, and nitrobenzene is through the synthetic para-aminophenol of catalytic hydrogenation.
5. according to the described Application of Catalyst method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of claim 4, it is characterized in that: in autoclave, add in this catalyst, nitrobenzene and solvent that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, add consumption and be 0.2～5% surfactant of above-mentioned used nitrobenzene weight, used surfactant is NPE, softex kw, DTAC or TBAB, and other process conditions all remain unchanged.
6. according to the described Application of Catalyst method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of claim 4, it is characterized in that: solvent for use is deionized water, methyl alcohol, ethanol, butanols, diethylene glycol (DEG), triethylene glycol or tetraethylene glycol.
7. according to the described Application of Catalyst method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of claim 4, it is characterized in that: the catalyst amount that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation is that 0.02～3% of nitrobenzene weight is determined by the metal Pt weight of this catalyst, reaction temperature is 80～100 ℃, hydrogen partial pressure is 0.3～0.6MPa, reaction time is 2～6 hours, in autoclave, add the catalyst that this is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, in the time of nitrobenzene and solvent, add consumption and be 0.2～5% surfactant of above-mentioned used nitrobenzene weight, used surfactant is a NPE, softex kw, DTAC or TBAB.
8. according to the described Application of Catalyst method that is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation of claim 4, it is characterized in that: after synthetic reaction is finished, utilize filtration under diminished pressure to isolate the catalyst that this is used for the synthetic para-aminophenol of nitrobenzene catalytic hydrogenation, after the absolute ethyl alcohol cleaning, 60 ℃ of following vacuum drying 5 hours, drop into and reuse again.
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Assignee: Jilin Wutai Gankang Pharmacy Co., Ltd. Assignor: Hebei University of Technology Contract record no.: 2011120000191 Denomination of invention: Catalyzer for synthesizing p-aminophenol by nitrobenzene catalytic hydrogenation as well as method for preparing and applying the same Granted publication date: 20091021 License type: Exclusive License Open date: 20080514 Record date: 20111013 |
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