CN1291961C - Process for preparing phenol from benzene by one step directly hydoxylation - Google Patents
Process for preparing phenol from benzene by one step directly hydoxylation Download PDFInfo
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- CN1291961C CN1291961C CNB2003101041091A CN200310104109A CN1291961C CN 1291961 C CN1291961 C CN 1291961C CN B2003101041091 A CNB2003101041091 A CN B2003101041091A CN 200310104109 A CN200310104109 A CN 200310104109A CN 1291961 C CN1291961 C CN 1291961C
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- benzene
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Abstract
The present invention relates to a method for preparing phenol from benzene by one step direct hydoxylation with benzene as raw material, hydrogen peroxide as oxidizing agents, lower fatty acid as solvent and active carbon as catalysts. The present invention has the advantages of simple preparing technology, low cost, repeated use, mild condition of hydroxylation reaction and high phenol yield, and raw material of catalysts is easy to obtain. The present invention is an environment protective synthesizing method with low investment and high yield.
Description
The invention belongs to the method for direct hydroxylation system phenol of one step of benzene.
Phenol is important basic Organic Chemicals, has a purposes widely industrial, and demand is big, and the world demand amount had surpassed 66Mt in 2000.The synthetic main cumene method that adopts of the industry of phenol at present, this method will could realize the synthetic of phenol through three-step reaction, at first is that benzene and propylene are at 200-250 ℃ and 14-20kg/cm
2Pressure, alkylation obtains isopropyl benzene under catalyst action, the transformation efficiency of benzene is approximately 20%, second step was that cumene oxidation gets dicumyl peroxide, the transformation efficiency of isopropyl benzene is about 25%, final step is dicumyl peroxide such as is decomposed at amount of substance under the vitriolic effect phenol and an acetone, the transformation efficiency of dicumyl peroxide is about 95%, transformation efficiency according to each step reaction, one step yield of phenol is no more than 5%, and this method exists reactions steps many, the technical process complexity, and equipment corrosion is serious, shortcomings such as by product is many, and is big for environment pollution.So the single step reaction that directly benzene hydroxylation is prepared in recent years, phenol has attracted various countries investigators' extensive concern.This is one and relates to the direct activation c h bond and make the reaction of hydro carbons functionalization, directly hydroxyl is introduced aromatic ring by the activation c h bond to generate corresponding oxy-compound, and this is one of the most scabrous problem in the synthetic chemistry.Capture this difficulty, selection of catalysts and preparation are the most key factors.
United States Patent (USP) U.S.Pat.Nos.6 in 2002,355,847B1 has reported people's such as Tsuruya S Method of Manufacturing Phenol by Direct Oxidation ofbenzene.The catalyzer that this method is used is V/Al
2O
3Or Zn-V/Al
2O
3Or Cu/HZSM-5.Use V/Al
2O
3Or Zn-V/Al
2O
3When making catalyzer, the oxygenant that uses is molecular oxygen, and molecular oxygen is as reactant, and raw material is easy to get, and cost is low, and the by product of generation is mainly water, not only helps product separation, and can not produce pollution to environment.Use V/Al
2O
3When making catalyzer, molecular oxygen is made oxygenant, and xitix is made reductive agent, and acetic acid is made solvent, and the yield of phenol is higher, has reached 8%.Use N
2O does the system of oxygenant, and for benzene, the selectivity of phenol is very high, generally all greater than 90%.But these methods also come with some shortcomings:
1. catalyzer is made loaded down with trivial details.At first to select carrier, and to carry out activation treatment to it, be then with active constituent loading on carrier, the method of taking is ion exchange method, pickling process or sol-gel method etc. normally, there is the carrier of corresponding active ingredient salt dry in a vacuum load, at high temperature it is carried out roasting at last, just can obtain loaded catalyst.
2. the active ingredient of this loaded catalyst is wanted the part solution-off in the catalyzed reaction, even use this patent to think best Al
2O
3Carrier, active ingredient V also can be from V/Al
2O
3Solution-off 40%, this has influenced the recycling of catalyzer to a great extent, and the solution-off of active ingredient is purified to product separation and all can be produced detrimentally affect to environment.
3. use V/Al
2O
3Make catalyzer, molecular oxygen is made oxygenant, and acetic acid is made solvent, though the yield of phenol has reached 8%, and, it has used expensive reductive agent---xitix, and the consumption of xitix is very big and the maximum amount of substance ratio of benzene feedstock is 0.5.
4. if do not use expensive xitix to make reductive agent, use the loaded catalyst Zn-V/Al of dual-active component
2O
3, can catalytic molecular oxygen be phenol also by the coordinative role of two active ingredients, but the yield of phenol only be 0.1% with the direct hydroxylation of benzene.
5. reaction will be carried out in encloses container, needs certain pressure.
Reaction times longer, to react usually 24 hours.
7. using Cu/HZSM-5 to make catalyzer, by gas-phase reaction, can be phenol with the direct catalytic hydroxylation of benzene also, though phenol yield also can reach 6.3%, a large amount of N that costs an arm and a leg has been used in this reaction
2O makees oxygenant and a large amount of nitrogen is done carrier gas, and in this gas-phase reaction system, the easy coking of catalyzer and inactivation.
8. if use cheap oxygen to replace N
2O makees oxygenant, and phenol yield has only 0.8% so.
Niwa S in 2002, Eswaramoorthy M, Nair J etc. are at Science[2002,295 (5552): 105] be reported to they achievement in research " A One-step Conversion of Benzene to Phenol with aPalladium Membrane " they adopt the Pd film device, with O
2, H
2Feed the inside and outside both sides of film respectively, reduced O
2And H
2The blended explosion potential is reflected under 250 ℃ and carries out, and the transformation efficiency of benzene is 2%-13%, and the phenol selectivity is 85%-96%.But this catalyzer has used precious metals pd, and catalyst P d film production and catalyzed reaction operation difficulty comparatively all, simultaneously, and the catalyst reaction device more complicated.
United States Patent (USP) U.S.Pat.Nos.6 in 2002,437,197B1 has reported that " Process For Catalytic Hydroxylation of Aromatic Hydrocarbons " this method of people such as David MorrisHamilton adopts the catalytic distillation device to carry out benzene through N
2The reaction of O oxidation synthesizing phenol is because reactant N
2The duration of contact of O and benzene and catalyzer is shorter, product leaves catalysis region once forming, reduced the probability that further reacts greatly, effectively stoped the carbon distribution on the catalyzer, improved the stability of catalyzer, thereby the selectivity that has guaranteed phenol does not descend, and the selectivity of phenol generally can reach more than 90%.But the catalyzer that this method is used is molecular sieve or loaded catalyst, and the making of catalyzer is comparatively loaded down with trivial details, and the catalytic distillation energy consumption is higher, catalytic distillation device relative complex, N
2The cost height of O, side reaction is to N
2The consumption of O is also very big.
In addition, in the method for existing phenol by directly hydroxylating benzene, more representational catalyzer has: U.S.Pat.Nos.5,672,777; 5,808,167; 5,110,995; 5,874,646; 4,683,217; 4,758,419; 5,912,391; EP 0043562; 0158976, molecular sieve, heteropolyacid, molysite (FeCl
2, FeCl
3) load on the silica gel, precious metal (Pd, Rh, Ir, Pt) loads on SiO
2On, Pd/TS-1, Pd-Cu/ sepiolite, VOx/SiO
2, V
4Mo
8Ox/SiO
2And V
8Mo
4Ox/SiO
2, Fe (NO
3)
39H
2O catalyzer etc. use these catalyzer the direct catalytic hydroxylation of benzene can both be become phenol under certain conditions, and the yield of phenol is between 2%-25%, and the selectivity of phenol is between 60%-95%.But the making difficulty that these catalyzer have equally, the cost height, what have at all can not recycling, the catalytic reaction condition harshness that has etc.
The method that the purpose of this invention is to provide a kind of simple and effective phenol by directly hydroxylating benzene.
Technical scheme of the present invention: granularity is that 20-100 purpose gac soaked 2-6 hour with the 5%-15% mineral acid, filter, after drying under 100-120 ℃, by quality than gac: lower fatty acid: benzene==1: 10-50: 2-10 puts into three-necked bottle, under normal pressure, 20-80 ℃ condition, dropwise add 30% hydrogen peroxide then, wherein quality is than benzene: hydrogen peroxide==1: 1-4, stirring reaction 1-6 hour simultaneously constantly, separate product phenol.The yield of phenol is 3%-13%, and the selectivity of phenol is 70%-85%.
As the activity of such catalysts charcoal can be cocoanut active charcoal, almond gac, peach-pit gac, Semen Crataegi gac, fiber-reactive charcoal and coal mass active carbon.Best gac is cocoanut active charcoal, peach-pit gac.Granularity of activated carbon is preferably the 40-80 order, and the best mineral acid of immersion treatment gac is nitric acid or hydrochloric acid, and soaking optimal temperature is 20-30 ℃, and soaking suitable time is 3-5 hour.The optimum temperature of reaction of direct hydroxylation system phenol is 50-70 ℃ as one step of activated carbon catalysis benzene, the suitable reaction times is 3-5 hour, lower fatty acid refers to formic acid, acetate, propionic acid or butyric acid, best lower fatty acid is an acetate, optimum gac: lower fatty acid: benzene: hydrogen peroxide=1: 15-30: 3-6: 6-10 (mass ratio).
The present invention is catalyzer with the gac, and lower fatty acid is a solvent, and the method for the phenol by directly hydroxylating benzene of hydrogen peroxide as oxidant has following outstanding characteristics:
(1) the catalyzer raw material is easy to get, and is inexpensive, cost is low.
(2) catalyst performance stabilised, the life-span is long, and is reusable.
(3) catalytic reaction condition gentleness just can be carried out under normal pressure and lesser temps.
(4) H
2O
2After finishing oxidizing reaction as oxygenant, change environmentally acceptable water into, can think the green oxidation agent of environmental sound.
(5) the catalyzed reaction time is shorter.
(6) catalyst reaction device is simple.
(7) phenol yield height can reach 13%, and the phenol selectivity is good, can reach 85%.
Therefore, the present invention has considerable application prospect.
Embodiment 1: take by weighing 20 gram 40-80 purpose cocoanut active charcoals respectively in two beakers, add the nitric acid of 25ml10% and the hydrochloric acid soln of 25ml 10% respectively and soak 3h, filter, dry down for 120 ℃ and promptly get catalyzer: 1#, 2#.
Embodiment 2: take by weighing 20 gram 20-40 orders and 80-100 purpose cocoanut active charcoal respectively in two beakers, the salpeter solution that adds 25ml10% respectively soaks 3h, filters, and dries down for 120 ℃ and promptly gets catalyzer: 3#, 4#.
Embodiment 3: take by weighing two part of 20 gram 40-80 purpose cocoanut active charcoal in two beakers, the salpeter solution that adds 25ml5% and 25ml 15% respectively soaks 3h, filters, and dries down for 120 ℃ and promptly gets catalyzer: 5#, 6#.
Embodiment 4: take by weighing two part of 20 gram 40-80 purpose cocoanut active charcoal in two beakers, all add the salpeter solution of 25ml10%, soaked respectively 2 hours and 6 hours, filter, dry down for 120 ℃ and promptly get catalyzer: 7#, 8#.
Embodiment 5: take by weighing 20 and restrain 40-80 purpose peach-pit gacs in beaker, the salpeter solution that adds 25ml10% soaks 3h, filters, and dries down for 120 ℃ and promptly gets catalyzer: 9#.
Embodiment 6: take by weighing 1#-9# catalyzer 0.6 respectively and restrain in the three-necked bottle of 9 50ml, the benzene that each adds 10ml acetate and 2ml is stirred and heated to 60 ℃, dropwise adds 30%H
2O
25ml reacted 4 hours, and getting different catalysts Pyrogentisinic Acid yield and phenol optionally influences.The results are shown in Table one
The different preparation method's gained of table one catalyzer Pyrogentisinic Acid's yield and optionally influence
| Catalyzer | 1# | 2# | 3# | 4# | 5# | 6# | 7# | 8# | 9# |
| Phenol yield % | 13.0 | 12.2 | 12.0 | 12.8 | 11.6 | 12.6 | 12.0 | 12.8 | 11.8 |
| Phenol selectivity % | 80 | 75 | 76 | 80 | 76 | 78 | 76 | 78 | 74 |
Embodiment 7: get 1# catalyzer 0.6 gram, the benzene of 10ml acetate and 2ml has in the three-necked bottle of magnetic agitation in 50ml, stirs and be heated to 60 ℃, dropwise adds 30% hydrogen peroxide 5ml, react 1 hour, must phenol yield be 4.8% and the phenol selectivity be 85%.
Embodiment 8: get 1# catalyzer 0.6 gram, the benzene of 10ml acetate and 2ml has in the three-necked bottle of magnetic agitation in 50ml, stirs and be heated to 60 ℃, dropwise adds 30% hydrogen peroxide 5ml, react 6 hours, must phenol yield be 12.8% and the phenol selectivity be 78%.
Embodiment 9: get 1# catalyzer 0.2 gram, the benzene of 10ml acetate and 2ml has in the three-necked bottle of magnetic agitation in 50ml, stirs and be heated to 60 ℃, dropwise adds 30% hydrogen peroxide 5ml, react 4 hours, must phenol yield be 6.8% and the phenol selectivity be 76%.
Embodiment 10: get 1# catalyzer 0.8 gram, the benzene of 10ml acetate and 2ml has in the three-necked bottle of magnetic agitation in 50ml, stirs and be heated to 60 ℃, dropwise adds 30% hydrogen peroxide 5ml, react 4 hours, must phenol yield be 13.0% and the phenol selectivity be 78%.
Embodiment 11: get 1# catalyzer 0.6 gram, the benzene of 10ml acetate and 2ml has in the three-necked bottle of magnetic agitation in 50ml, stirs and be heated to 60 ℃, dropwise adds 30% hydrogen peroxide 2ml, react 4 hours, must phenol yield be 6.6% and the phenol selectivity be 80%.
Embodiment 12: get 1# catalyzer 0.6 gram, the benzene of 10ml acetate and 2ml has in the three-necked bottle of magnetic agitation in 50ml, stirs and be heated to 30 ℃, dropwise adds 30% hydrogen peroxide 5ml, react 4 hours, must phenol yield be 3.2% and the phenol selectivity be 85%.
Embodiment 13: get 1# catalyzer 0.6 gram, the benzene of 10ml acetate and 4ml has in the three-necked bottle of magnetic agitation in 50ml, stirs and be heated to 60 ℃, dropwise adds 30% hydrogen peroxide 10ml, react 4 hours, must phenol yield be 8.8% and the phenol selectivity be 78%.
Embodiment 14: get 1# catalyzer 0.6 gram, the benzene of 10ml butyric acid and 2ml has in the three-necked bottle of magnetic agitation in 50ml, stirs and be heated to 60 ℃, dropwise adds 30% hydrogen peroxide 5ml, react 4 hours, must phenol yield be 8.2% and the phenol selectivity be 70%.
Embodiment 15: the benzene of getting 1# catalyzer 0.6 gram and 2ml has in the three-necked bottle of magnetic agitation in 50ml, stirs and be heated to 60 ℃, dropwise adds 30% hydrogen peroxide 5ml, reacts 4 hours, must phenol yield be 3.0% and the phenol selectivity be 70%.
Embodiment 16: with the 1# catalyst recovery in [embodiment 6], carry out catalyzed reaction by each condition in [embodiment 6], reuse and reclaim catalyzer 10 times, experimental result shows that catalyst activity does not subtract, phenol yield is 12%-13%, phenol selectivity 75%-80%.
Embodiment 17: with the 9# catalyst recovery in [embodiment 6], carry out catalyzed reaction by each condition in [embodiment 6], reuse and reclaim catalyzer 10 times, experimental result shows that catalyst activity does not subtract, phenol yield is 11%-12%, phenol selectivity 70%-76%.
Claims (7)
1. method by direct hydroxylation system phenol of benzene one step, it is characterized in that granularity is that 20-100 purpose gac soaked 2-6 hour with the 5%-15% mineral acid, filter, after drying under 100-120 ℃, by quality than gac: formic acid, acetate, propionic acid or butyric acid: benzene==1: 10-50: 2-10 puts into three-necked bottle, then under normal pressure, 20-80 ℃ condition, dropwise add 30% hydrogen peroxide, wherein quality is than benzene: hydrogen peroxide==1: 1-4, stirring reaction 1-6 hour simultaneously constantly, separate product phenol.
2. according to claims 1 described method, it is characterized in that gac is cocoanut active charcoal, peach-pit gac.
3. according to claims 1 described method, it is characterized in that granularity of activated carbon is meant the 40-80 order.
4. according to claims 1 described method, it is characterized in that said mineral acid is nitric acid or hydrochloric acid.
5. according to claims 1 described method, it is characterized in that quality is than gac: formic acid, acetate, propionic acid or butyric acid: benzene==1: 15-30: 3-6.
6. according to claims 1 described method, it is characterized in that temperature of reaction is 50-70 ℃.
7. according to claims 1 described method, it is characterized in that the reaction times is 3-5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101041091A CN1291961C (en) | 2003-12-25 | 2003-12-25 | Process for preparing phenol from benzene by one step directly hydoxylation |
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|---|---|---|---|
| CNB2003101041091A CN1291961C (en) | 2003-12-25 | 2003-12-25 | Process for preparing phenol from benzene by one step directly hydoxylation |
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| CN1291961C true CN1291961C (en) | 2006-12-27 |
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| CN101733098B (en) * | 2008-11-07 | 2012-08-08 | 中国石油天然气股份有限公司 | Catalyst for preparing phenol by benzene hydroxylation as well as preparation method and application thereof |
| CN101792372B (en) * | 2010-04-07 | 2012-12-12 | 四川大学 | Method for preparing phenol and diphenol by direct hydroxylation of benzene and hydrogen peroxide |
| CN102731266B (en) * | 2012-07-09 | 2014-04-16 | 河北工业大学 | Method for synthesizing p-xylenol in ionic liquid catalytic system |
| CN106045820B (en) * | 2016-07-04 | 2019-03-12 | 中石化炼化工程（集团）股份有限公司 | A kind of method that catalytic distillation produces phenol and/or benzenediol |
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