CN103113254B - Technology for directly synthesizing acetaminophen from nitrobenzene - Google Patents
Technology for directly synthesizing acetaminophen from nitrobenzene Download PDFInfo
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- CN103113254B CN103113254B CN201310076366.2A CN201310076366A CN103113254B CN 103113254 B CN103113254 B CN 103113254B CN 201310076366 A CN201310076366 A CN 201310076366A CN 103113254 B CN103113254 B CN 103113254B
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Abstract
The invention provides a technology for directly synthesizing acetaminophen from nitrobenzene. The technology comprises the following steps: placing lewis acid metal salt, a supported Pt metal catalyst, a promoter, the nitrobenzene, cetyl trimethyl ammonium bromide and water into a high-pressure reaction kettle; replacing the air by N2; charging H2; reacting for 1 to 10 hours at 80 to 200 DEG C; filtering the reaction liquid in a hot state; cooling the reaction liquid subjected to reduced pressure distillation to reach 30 to 50 DEG C; adding acetic anhydride to react for 0.2 to 1 hour; concentrating and cooling the obtained reaction liquid to separate crystal; and then filtering to obtain the crystal which is the acetaminophen. According to the process, the reaction is carried out in the trace metal salt solution, and the yield of the acetaminophen still can reach more than 70% if the concentration of the metal salt solution is less than 5mmol/L; the pH (Potential Of Hydrogen) value of the solution is not needed to be regulated by ammonia water during the reaction process; and the crystallization mother liquor in which the acetaminophen is separated can be recycled, so that no waste liquid is drained.
Description
Technical field
Technical scheme of the present invention belongs to organic chemistry filed, specifically a kind of from the direct technique of synthetic paracetamol of oil of mirbane.
Background technology
Paracetamol (being called for short APAP) is a kind of good antipyretic and analgesic, is also the intermediate of synthetic multiple other medicines.Industrial paracetamol is many to be made through acidylate by p-aminophenol and acetic acid or acid anhydrides.According to the preparation of p-aminophenol and paracetamol, whether need independently to carry out being divided into single stage method and two-step approach.
In two-step approach production process; raw material reduction generates p-aminophenol and independently carries out with reacting respectively of paracetamol of p-aminophenol acidylate generation; due to p-aminophenol very easily oxidation stain in production, transportation and transporting procedures; therefore when preparing paracetamol, must refine p-aminophenol, just can produce the former medicine of paracetamol that meets standards of pharmacopoeia.Complex technical process not only, energy consumption is large, and in p-aminophenyl phenol treating and purification process, loss is larger, causes the total recovery of product to reduce.Single stage method is synthesized paracetamol; reduction and acidylate are incorporated in same reactor and are carried out; the p-aminophenol that reaction generates immediately acidylate is paracetamol, has not only reduced production energy consumption, and has avoided the problem of oxidation of transporting procedures p-aminophenol.The synthetic paracetamol of single stage method is raw material mainly with p-NP at present, though can realize the directly synthetic of paracetamol, raw materials cost is higher, uneconomical economically.
Oil of mirbane is large industrial chemicals, take its production of producing p-aminophenol and then carrying out paracetamol as starting raw material to have very significantly raw material advantage.Industrial by the synthetic p-aminophenol of hydrogenation of chloronitrobenzene, conventionally to take the precious metals such as platinum, rhodium, palladium be catalyzer, in 10～20% sulphuric acid soln, carries out.Because reaction is carried out in sulphuric acid soln, the p-aminophenol of generation and by product aniline all exist with the form of vitriol, and this just makes directly to carry out acylation reaction in hydrogenation reaction solution and has certain difficulty.Patent GB1469099 discloses a kind of method that vitriol mixing solutions to p-aminophenol and aniline carries out the synthetic APAP of acidylate; first to regulate pH to 5 left and right with ammonia; then by distillation method, remove aniline; finally at 20 ℃, use aceticanhydride acidylate; with ammonia, maintain pH 5 simultaneously, can obtain content and be 95% APAP.Therefore, for the synthetic p-aminophenol reaction process of the hydrogenation of chloronitrobenzene carrying out in sulphuric acid soln, for carrying out follow-up acylation process, need to reaction solution, carry out neutralizing treatment with a large amount of ammoniacal liquor, cause production process waste liquid amount large, complex process.The invention provides a kind of technique from the synthetic paracetamol of the direct acidylate of By Catalytic Hydrogenation of Nitrobenzene; reaction is carried out in neutral trace metal salts solution; solution after hydrogenation reaction is isolated after aniline and part water through simple evaporation process; can directly add acylating agent to carry out acylation reaction; obtain paracetamol, production process is without waste liquid, waste sludge discharge.
Summary of the invention
Technical problem to be solved by this invention is: provide from oil of mirbane and directly synthesize the technique of paracetamol, this technique can directly be prepared paracetamol from By Catalytic Hydrogenation of Nitrobenzene in neutral trace metal salts solution, technique is simple, product yield is high, and production process is without waste liquid, waste sludge discharge.
The present invention solves this technical problem adopted technical scheme:
From oil of mirbane, directly synthesize a technique for acamol, this technique is from oil of mirbane, directly to synthesize paracetamol in neutral metal salt solution, comprises the steps:
The first step, Lewis acid metal-salt, load type metal Pt catalyzer, promotor, oil of mirbane, tensio-active agent cetyl trimethylammonium bromide and aqueous solvent are put into autoclave, and its quality proportioning is Lewis acid metal-salt: catalyzer: promotor: oil of mirbane: cetyl trimethylammonium bromide: water=0.01～0.49: 0.01～0.3: 0.01～0.3:1～5: 0.01: 50;
Second step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, pass into H
2, to hydrogen partial pressure be 0.1～2.0MPa, temperature of reaction is 80～200 ℃, reacts 1～10 hour, makes oil of mirbane be converted into p-aminophenol;
The 3rd step, after the reaction of second step finishes, while hot by reacting liquid filtering;
The 4th step, the reaction solution leaching steams by product aniline and part water through underpressure distillation;
The 5th step, the reaction solution of the 4th step being isolated to aniline is cooled to 30～50 ℃, adds acylating agent acetic anhydride, and it is 0.5～1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor:, react 0.2～1 hour.
The 6th step, the reaction solution that the 5th step is obtained be concentrated into volume be the first step add volume of water 30%～40%, and be cooled to 0 ℃～5 ℃, crystallization, filters, the crystallization obtaining is paracetamol.
Load type metal Pt catalyzer recited above is Pt/C, Pt/SiO
2, Pt/Al
2o
3, Me-Pt/C, Me-Pt/SiO
2or Me-Pt/Al
2o
3, wherein Pt charge capacity is that the mol ratio of the 0.01%～3%, second metal M e and Pt is Me:Pt=0.01～5:1.
The the second metal M e adding is Mg, Ba or Pb.
Described Lewis acid metal-salt is zinc sulfate, zinc chloride or zinc nitrate.
Described promotor is ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic acid (EDTA) zinc sodium and Zn/SiO
2in a kind of.
The invention has the beneficial effects as follows: the present invention directly synthesizes the technique of paracetamol from By Catalytic Hydrogenation of Nitrobenzene, to react in neutral trace metal salts solution, when metal salt solution concentration is during lower than 5mmol/L, acamol yield still can reach more than 70%.Because concentration of metal ions in reaction solution is low; the p-aminophenol reaction solution that the first step hydrogenation generates can be isolated by product aniline by simple still-process; reaction solution need not neutralize the Crystallizing process with p-aminophenol; can directly carry out the synthetic paracetamol of acylation reaction; simplified the production technique of paracetamol; product yield is high, effectively reduces energy consumption and production cost.Because reaction process is without the pH value with ammoniacal liquor regulator solution, the crystalline mother solution of isolating paracetamol can recycle again in hydrogenation reaction, has avoided the discharge of waste liquid.
Embodiment
With embodiment, further illustrate the present invention below, embodiment only, for describing the present invention in detail, is not considered as the restriction to the claims in the present invention protection domain.
Embodiment 1
The first step, the Pt/SiO that is 0.1% by 0.04g zinc sulfate, 0.1g Pt charge capacity
2catalyzer, 2g oil of mirbane, 0.01g cetyl trimethylammonium bromide, 0.05g promotor ethylenediamine tetraacetic acid (EDTA) and 50ml water are put into autoclave, and wherein zinc ion concentration is 4.9mmol/L;
Second step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, be heated to 180 ℃ and pass into H
2, to hydrogen partial pressure be 1.0MPa, react 6 hours, make oil of mirbane be converted into p-aminophenol;
The 3rd step, after the reaction of second step finishes, while hot by reacting liquid filtering, separated solid-phase catalyst and reaction solution;
The 4th step, the reaction solution leaching, in 40～100 ℃, distills under 0.05～0.1MPa pressure, steams by product aniline and part water;
The 5th step, the reaction solution of the 4th step being isolated to aniline is cooled to 30～50 ℃, adds acylating agent acetic anhydride, and it is 1.0:1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor, reacts 0.5 hour;
The 6th step, it is 15ml that the reaction solution that the 5th step is obtained carries out evaporation concentration to reaction solution volume, is cooled to 0 ℃～5 ℃, and crystallization filters, and the crystallization obtaining is paracetamol, and the yield of paracetamol is 72%.Crystalline mother solution returns to reactor and recycles.
Embodiment 2
The first step, the Pt/Al that is 0.3% by 0.49g zinc nitrate, 0.1g Pt charge capacity
2o
3catalyzer, 2g oil of mirbane, 0.1g promotor ethylenediamine tetraacetic acid (EDTA), 0.01g cetyl trimethylammonium bromide and 50ml water are put into autoclave;
Second step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, be heated to 200 ℃ and pass into H
2, to hydrogen partial pressure be 0.1MPa, react 8 hours, make oil of mirbane be converted into p-aminophenol;
The 3rd step, after the reaction of second step finishes, while hot by reacting liquid filtering, separated solid-phase catalyst and reaction solution;
The 4th step, the reaction solution leaching, in 40～100 ℃, distills under 0.05～0.1MPa pressure, steams by product aniline and part water;
The 5th step, the reaction solution of the 4th step being isolated to aniline is cooled to 30～50 ℃, adds acylating agent acetic anhydride, and it is 1.0:1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor, reacts 0.5 hour;
The 6th step, it is 15ml that the reaction solution that the 5th step is obtained carries out evaporation concentration to reaction solution volume, is cooled to 0 ℃～5 ℃, and crystallization filters, and the crystallization obtaining is paracetamol, and the yield of paracetamol is 75%.Crystalline mother solution returns to reactor and recycles.
Embodiment 3
The first step, the Pt/C catalyzer that is 0.01% by 0.01g zinc sulfate, 0.3g Pt charge capacity, 0.1g promotor ethylenediamine tetraacetic acid (EDTA), 1g oil of mirbane, 0.01g cetyl trimethylammonium bromide and 50ml water are put into autoclave;
Second step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, be heated to 80 ℃ and pass into H
2, to hydrogen partial pressure be 2.0MPa, react 5 hours, make oil of mirbane be converted into p-aminophenol;
The 3rd step, after the reaction of second step finishes, while hot by reacting liquid filtering, separated solid-phase catalyst and reaction solution;
The 4th step, the reaction solution leaching, in 40～100 ℃, distills under 0.05～0.1MPa pressure, steams by product aniline and part water;
The 5th step, the reaction solution of the 4th step being isolated to aniline is cooled to 30～50 ℃, adds acylating agent acetic anhydride, and it is 0.5:1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor, reacts 0.2 hour;
The 6th step, it is 15ml that the reaction solution that the 5th step is obtained carries out evaporation concentration to reaction solution volume, is cooled to 0 ℃～5 ℃, and crystallization filters, and the crystallization obtaining is paracetamol, and the yield of paracetamol is 32%.Crystalline mother solution returns to reactor and recycles.
Embodiment 4
The first step is that 3%, Ba/Pt mol ratio is the Ba-Pt/Al of 5:1 by 0.02g zinc chloride, 0.01g Pt charge capacity
2o
3catalyzer, 5g oil of mirbane, 0.01g cetyl trimethylammonium bromide, 0.05g ethylenediamine tetraacetic acid (EDTA) zinc sodium and 50ml water are put into autoclave;
Second step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, be heated to 180 ℃ and pass into H
2, to hydrogen partial pressure be 0.5MPa, react 10 hours, make oil of mirbane be converted into p-aminophenol;
The 3rd step, after the reaction of second step finishes, while hot by reacting liquid filtering, separated solid-phase catalyst and reaction solution;
The 4th step, the reaction solution leaching, in 40～100 ℃, distills under 0.05～0.1MPa pressure, steams by product aniline and part water;
The 5th step, the reaction solution of the 4th step being isolated to aniline is cooled to 30～50 ℃, adds acylating agent acetic anhydride, and it is 1.0:1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor, reacts 1.0 hours;
The 6th step, it is 15ml that the reaction solution that the 5th step is obtained carries out evaporation concentration to reaction solution volume, is cooled to 0 ℃～5 ℃, and crystallization filters, and the crystallization obtaining is paracetamol, paracetamol 45%.Crystalline mother solution returns to reactor and recycles.
Embodiment 5
The first step is that 3%, Mg/Pt mol ratio is the Mg-Pt/Al of 0.1:1 by 0.04g zinc sulfate, 0.01g Pt charge capacity
2o
3catalyzer, 0.01g promotor ethylenediamine tetraacetic acid (EDTA), 1g oil of mirbane, 0.01g cetyl trimethylammonium bromide and 50ml water are put into autoclave;
Second step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, be heated to 180 ℃ and pass into H
2, to hydrogen partial pressure be 0.5MPa, react 2 hours, make oil of mirbane be converted into p-aminophenol;
The 3rd step, after the reaction of second step finishes, while hot by reacting liquid filtering, separated solid-phase catalyst and reaction solution;
The 4th step, the reaction solution leaching, in 40～100 ℃, distills under 0.05～0.1MPa pressure, steams by product aniline and part water;
The 5th step, the reaction solution of the 4th step being isolated to aniline is cooled to 30～50 ℃, adds acylating agent acetic anhydride, and it is 0.5:1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor, reacts 0.2 hour;
The 6th step, the reaction solution that the 5th step is obtained carries out evaporation concentration and is cooled to 0 ℃～5 ℃, and crystallization filters, and the crystallization obtaining is paracetamol, and the yield of paracetamol is 46%.Crystalline mother solution returns to reactor and recycles.
Embodiment 6
The first step is that 0.1%, Mg/Pt mol ratio is the Mg-Pt/Al of 0.1:1 by 0.04g zinc sulfate, 0.1g Pt charge capacity
2o
3catalyzer, 3g oil of mirbane, 0.01g cetyl trimethylammonium bromide, 0.05g promotor ethylenediamine tetraacetic acid (EDTA) and 50ml water are put into autoclave;
Second step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, be heated to 180 ℃ and pass into H
2, to hydrogen partial pressure be 1.0MPa, react 8 hours, make oil of mirbane be converted into p-aminophenol;
The 3rd step, after the reaction of second step finishes, while hot by reacting liquid filtering, separated solid-phase catalyst and reaction solution;
The 4th step, the reaction solution leaching, in 40～100 ℃, distills under 0.05～0.1MPa pressure, steams by product aniline and part water;
The 5th step, the reaction solution of the 4th step being isolated to aniline is cooled to 30～50 ℃, adds acylating agent acetic anhydride, and it is 1.0:1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor, reacts 0.6 hour;
The 6th step, the reaction solution that the 5th step is obtained carries out evaporation concentration and is cooled to 0 ℃～5 ℃, and crystallization filters, and the crystallization obtaining is paracetamol, and the yield of paracetamol is 75%.Crystalline mother solution returns to reactor and recycles.
Embodiment 7
The first step is that 3%, Pb/Pt mol ratio is the Pb-Pt/Al of 2:1 by 0.1g zinc chloride, 0.01g Pt charge capacity
2o
3catalyzer, 0.05g promotor ethylenediamine tetraacetic acid (EDTA), 2g oil of mirbane, 0.01g cetyl trimethylammonium bromide and 50ml water are put into autoclave;
Second step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, be heated to 180 ℃ and pass into H
2, to hydrogen partial pressure be 0.6MPa, react 8 hours, make oil of mirbane be converted into p-aminophenol;
The 3rd step, after the reaction of second step finishes, while hot by reacting liquid filtering, separated solid-phase catalyst and reaction solution;
The 4th step, the reaction solution leaching, in 40～100 ℃, distills under 0.05～0.1MPa pressure, steams by product aniline and part water;
The 5th step, the reaction solution of the 4th step being isolated to aniline is cooled to 30～50 ℃, adds acylating agent acetic anhydride, and it is 1.0:1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor, reacts 0.5 hour;
The 6th step, the reaction solution that the 5th step is obtained carries out evaporation concentration and is cooled to 0 ℃～5 ℃, and crystallization filters, and the crystallization obtaining is paracetamol, and the yield of paracetamol is 78%.Crystalline mother solution returns to reactor and recycles.
Embodiment 8
1.0g zinc acetate is dissolved in 8ml water, then with 2gSiO
2carrier drip to mix, and floods after 24 hours in 100 ℃ and is dried to constant weight, finally, in 500 ℃ of roastings 2 hours, obtains Zn/SiO
2promotor.
Embodiment 9
By 2gSiO
2carrier, 1.0g zinc acetate, 100ml methylcarbonate is put into autoclave, is heated to 170 ℃ of reactions 2 hours, filters, and the catalyzer after filtering is dried to constant weight in 100 ℃, obtains Zn/SiO
2promotor.
Embodiment 10
The first step is that 0.1%, Mg/Pt mol ratio is the Mg-Pt/SiO of 5:1 by the charge capacity of 0.04g zinc sulfate, 0.1g Pt
2the promotor Zn/SiO of catalyzer, 2g oil of mirbane, 0.01g cetyl trimethylammonium bromide, 0.3g embodiment 8 preparations
2put into autoclave with 50ml water;
Second step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, be heated to 180 ℃ and pass into H
2, to hydrogen partial pressure be 0.6MPa, react 6 hours, make oil of mirbane be converted into p-aminophenol;
After the reaction of the 3rd step second step finishes, while hot by reacting liquid filtering, separated solid-phase catalyst and reaction solution;
The 4th step, the reaction solution leaching, in 40～100 ℃, distills under 0.05～0.1MPa pressure, steams by product aniline and part water;
The 5th step, the reaction solution of the 4th step being isolated to aniline is cooled to 30～50 ℃, adds acylating agent acetic anhydride, and it is 1.0:1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor, reacts 0.5 hour;
The 6th step, the reaction solution that the 5th step is obtained carries out evaporation concentration and is cooled to 0 ℃～5 ℃, and crystallization filters, and the crystallization obtaining is paracetamol, and the yield of paracetamol is 65%.Crystalline mother solution returns to reactor and recycles.
Embodiment 11,
The first step is that 0.1%, Mg/Pt mol ratio is the Mg-Pt/SiO of 5:1 by the charge capacity of 0.04g zinc sulfate, 0.1g Pt
2the promotor Zn/SiO of catalyst agent, 2g oil of mirbane, 0.01g cetyl trimethylammonium bromide and 0.1g embodiment 9 preparations
2put into autoclave with 50ml water;
Second step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, be heated to 180 ℃ and pass into H
2, to hydrogen partial pressure be 0.6MPa, react 6 hours, make oil of mirbane be converted into p-aminophenol;
The 3rd step, after the reaction of second step finishes, while hot by reacting liquid filtering, separated solid-phase catalyst and reaction solution;
The 4th step, the reaction solution leaching, in 40～100 ℃, distills under 0.05～0.1MPa pressure, steams by product aniline and part water;
The 5th step, the reaction solution of the 4th step being isolated to aniline is cooled to 30～50 ℃, adds acylating agent acetic anhydride, and it is 1.0:1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor, reacts 0.5 hour;
The 6th step, the reaction solution that the 5th step is obtained carries out evaporation concentration and is cooled to 0 ℃～5 ℃, and crystallization filters, and the crystallization obtaining is paracetamol, and the yield of paracetamol is 72%.Crystalline mother solution returns to reactor and recycles.
Embodiment 12,
The first step, the solid-phase catalyst (comprising metal catalyst and promotor) that embodiment 11 the 3rd step is filtered out adds in autoclave, and the crystalline mother solution that returns to reactor with the 6th step mixes;
Second step, at above-mentioned autoclave, filling into a certain amount of water to reaction solution volume is 50ml, then adds 2g oil of mirbane;
The 3rd step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, be heated to 180 ℃ and pass into H
2, to hydrogen partial pressure be 0.6MPa, react 6 hours, make oil of mirbane be converted into p-aminophenol;
The 4th step, after the reaction of second step finishes, while hot by reacting liquid filtering, separated solid-phase catalyst and reaction solution;
The 5th step, the reaction solution leaching, in 40～100 ℃, distills under 0.05～0.1MPa pressure, steams by product aniline and part water;
The 6th step, the reaction solution of the 5th step being isolated to aniline is cooled to 30～50 ℃, adds acylating agent acetic anhydride, and it is 1.0:1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor, reacts 0.5 hour;
The 6th step, the reaction solution that the 6th step is obtained carries out evaporation concentration and is cooled to 0 ℃～5 ℃, and crystallization filters, and the crystallization obtaining is paracetamol, and the yield of paracetamol is 72%.Crystalline mother solution returns to reactor and recycles.
The load type metal Pt catalyzer using in above-mentioned whole embodiment, can prepare by existing known technology.As just there being specific descriptions in Chinese patent CN1270821C.
The present invention does not address part and is applicable to prior art.
Claims (4)
1. from oil of mirbane, directly synthesize a technique for acamol, it is characterized by this technique is from oil of mirbane, directly to synthesize paracetamol in neutral metal salt solution, comprises the steps:
The first step, Lewis acid metal-salt, load type metal Pt catalyzer, promotor, oil of mirbane, tensio-active agent cetyl trimethylammonium bromide and aqueous solvent are put into autoclave, and its quality proportioning is Lewis acid metal-salt: catalyzer: promotor: oil of mirbane: cetyl trimethylammonium bromide: water=0.01～0.49: 0.01～0.3: 0.01～0.3:1～5: 0.01: 50;
Second step, in above-mentioned autoclave, with N
2after displaced air 8～12 minutes, pass into H
2, to hydrogen partial pressure be 0.1～2.0MPa, temperature of reaction is 80～200 ℃, reacts 1～10 hour, makes oil of mirbane be converted into p-aminophenol;
The 3rd step, after the reaction of second step finishes, while hot by reacting liquid filtering;
The 4th step, the reaction solution leaching steams by product aniline and part water through underpressure distillation;
The 5th step, the reaction solution of the 4th step being isolated to aniline is cooled to 30～50 ℃, squeezes into acylating agent acetic anhydride, and it is acetic anhydride: oil of mirbane=0.5～1.0:1.0 that acetic anhydride and the first step add the mol ratio of oil of mirbane in reactor, reacts 0.2～1 hour;
The 6th step, the reaction solution that the 5th step is obtained be concentrated into volume be the first step add volume of water 30%～40%, and be cooled to 0 ℃～5 ℃, crystallization, filters, the crystallization obtaining is paracetamol;
Described promotor is ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic acid (EDTA) zinc sodium and Zn/SiO
2in a kind of.
2. as claimed in claim 1 from the direct technique of synthetic acamol of oil of mirbane, it is characterized by described load type metal Pt catalyzer is Pt/C, Pt/SiO
2, Pt/Al
2o
3, Me-Pt/C, Me-Pt/SiO
2or Me-Pt/Al
2o
3, wherein Pt charge capacity is that the mol ratio of the 0.01%～3%, second metal M e and Pt is Me:Pt=0.01～5:1.
3. as claimed in claim 2 from the direct technique of synthetic acamol of oil of mirbane, it is characterized by the second described metal M e is Mg, Ba or Pb.
4. as claimed in claim 1 from the direct technique of synthetic acamol of oil of mirbane, it is characterized by described Lewis acid metal-salt is zinc sulfate, zinc chloride or zinc nitrate.
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| CN104628592B (en) * | 2015-03-02 | 2017-08-01 | 河北工业大学 | Method for directly synthesizing p-acetamidophenol from nitrobenzene in acetic acid solution in one step |
| CN108689871A (en) * | 2018-06-18 | 2018-10-23 | 东莞市联洲知识产权运营管理有限公司 | A kind of synthetic method of the paracetamol of the platinum/carbon aerogel catalyst based on Supported Pt Nanoparticles |
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| CN1285567C (en) * | 2004-04-30 | 2006-11-22 | 河北工业大学 | Process for synthesizing paracetamol |
| CN100594210C (en) * | 2007-11-16 | 2010-03-17 | 河北工业大学 | Process for synthesizing p-aminophenol by nitrobenzene catalytic hydrogenation |
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