CN1288881A - Tar-free catalytic oxidation of arene utilizing coupling reaction - Google Patents
Tar-free catalytic oxidation of arene utilizing coupling reaction Download PDFInfo
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- CN1288881A CN1288881A CN00130719A CN00130719A CN1288881A CN 1288881 A CN1288881 A CN 1288881A CN 00130719 A CN00130719 A CN 00130719A CN 00130719 A CN00130719 A CN 00130719A CN 1288881 A CN1288881 A CN 1288881A
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Abstract
The present invention uses benzene or phenol as reactant, uses hydrogen peroxide as oxidant, and uses molecular sieve or Cu2(OH)PO4 as catalyst to make hydroxylation to synthesize phenol or benzene diphenol. In the course of reaction th proper quantity of methyl-sulfoxide or dimethyl sulfide can be added as coupling reaction reagent. Said invention introduces coupling reaction so as to supperss production of tar. At the same time it can raise effective utilization rate of reactant, and the product obtained by coupling reaction is a useful chemical product which can be easily separated from main product, it can prolong the service life and catalyst. Said invention has no tar, low cost and hight yield, so it can be extensively used for catalytic reaction of arenes.
Description
The invention belongs to catalytic chemistry, particularly a kind of clean catalyzed oxidation technology of aromatic hydrocarbons.
The eighties, people such as Italian Enichem company's T amasso have synthesized titaniferous TS-1 molecular sieve catalyst, utilize hydrogen peroxide to realize clean catalyzed oxidation to aromatic hydrocarbons.See United States Patent (USP) U.S.Patent, 2116974 (1985).Its reactant is a phenol, uses hydrogen peroxide as oxygenant, is being under the condition of catalyzer with TS-1, produces dihydroxy-benzene, and productive rate reaches 25.5%.But there is a large amount of tar in the method for the clean catalyzed oxidation of this aromatic hydrocarbons in the product system, also have following deficiency thus: the first, reduced the effective rate of utilization of reactant benzene or phenol and hydrogen peroxide; The second, the separation of product has suitable inconvenience, so that is difficult to realize industrialized production; The 3rd, the reaction life-span of catalyzer is short.
The objective of the invention is to use a kind of method of couling process, restrain the generation of the tar in the system.In the generation that reduces refuse, improve the effective rate of utilization of reactant, product is separated easily, the catalyst reaction life-span prolongs.
The coupled reaction that the present invention uses is to introduce a side reaction in reaction system, to original reaction effect of competing, thereby restrain disadvantageous side reaction, restrain the generation of tar, and new side reaction of introducing is useful reaction, the effective rate of utilization of reactant is improved, and do not have deleterious side reaction in the system.
The catalysed oxidation processes of realizing no tar particularly is, is reactant with the aromatic hydroxy compound, is oxygenant with the hydrogen peroxide, is solvent with acetonitrile or water, with molecular sieve or Cu
2(OH) PO
4Be catalyzer, adding methyl-sulphoxide or dimethyl thioether are made coupled reaction reagent, hydroxylation synthesizing phenol or dihydroxy-benzene in reaction.The mol ratio of coupled reaction reagent and reactant is controlled at (3-7): 10.
Aforesaid reactant aromatic hydroxy compound comprises benzene and phenol.The catalyst molecule sieve comprises TS-1, Me-MCM-41, Me-ZSM-5, Me-APO-n etc., n=5 wherein, 8,11, metals such as Me=Ti, Fe, Cu, Co, V.Except that coupled reaction reagent, reactant are followed the proportioning of oxygenant, the proportioning of remaining reactant and catalyzer, and reaction conditions is roughly same as the prior art.
Owing to introduced coupled reaction reagent methyl-sulphoxide or dimethyl thioether in the reaction, it can become the intermediate of tar to interact by similar shape, reaches the purpose that does not have tar to produce in the product.Dimethyl thioether wherein generates methyl-sulphoxide with hydroperoxidation after adding reaction system, therefore, reaction effect is identical with methyl-sulphoxide.The mol ratio of coupled reaction reagent dosage and reactant is with (3-7): 10 is comparatively suitable, this is because add very fewly, also have a spot of tar and generate, and add-on is excessive, make the oxidizing reaction of methyl-sulphoxide become main reaction, and be unfavorable for the hydroxylation reaction of benzene or phenol.When not adding coupled reaction reagent, the mol ratio of reactant aromatic hydroxy compound and hydrogen peroxide be 3: 1 for good, when the present invention adds coupled reaction reagent, increase the consumption of hydrogen peroxide in right amount, that is, the mol ratio of reactant and hydrogen peroxide is controlled at (2.5-0.4): 1 for well.
The product of coupled reaction reagent oxidation gained is a dimethyl sulfone, and it also is a kind of useful Chemicals, and adopts common cooling separation method just can separate from aromatic hydrocarbons hydroxylation product.
Embodiment 1
Reactant is a benzene, and solvent is an acetonitrile, and catalyzer is the TS-1 molecular sieve, and coupled reaction reagent is methyl-sulphoxide.Benzene/hydrogen peroxide=1: 1 (mol ratio), benzene/TS-1=10 (mass ratio).60 ℃ of temperature of reaction, reaction product are phenol.Add the coupled reaction reagent of different amounts, its result as shown in Table 1.
The amount of table one, methyl-sulphoxide is to TS-1 being the influence of product of hydroxylation of the benzene of catalyzer
| Methyl-sulphoxide/benzene (mol ratio) | The transformation efficiency of benzene (%) | The effective rate of utilization of hydrogen peroxide (%) | The productive rate of phenol (%) | The productive rate of tar (%) |
| ??????0 ????1：8 ????2：8 ????3：8 ????4：8 ????5：8 | ????22.85 ????15.01 ????24.56 ????42.6 ????34.98 ????13.72 | ????27.65 ????21.9 ????36.46 ????86.12 ????94：62 ????96.33 | ????7.74 ????9.43 ????22.04 ????42.6 ????34.98 ????13.72 | 10.75 5.58 2.56 do not have |
By above-mentioned experimental result as can be known, when methyl-sulphoxide/benzene be (3-5): do not have tar to produce in the time of 8 in the reaction product.During beginning, along with the increase of the amount of methyl-sulphoxide, the transformation efficiency of benzene and the effective rate of utilization of hydrogen peroxide are also along with increase.This mainly is because because the generation of tar is suppressed gradually, make the main reaction of benzene hydroxylation synthesizing phenol obtain enhancing, and do not have the generation of tar.And the methyl-sulphoxide oxidation generates dimethyl sulfone, and these make the effective rate of utilization of hydrogen peroxide increase significantly.After the mol ratio of methyl-sulphoxide and benzene reached 3: 8, the generation of tar was suppressed fully.When the amount of methyl-sulphoxide continues to increase, the transformation efficiency of benzene begins to reduce, but the effective rate of utilization of hydrogen peroxide continues to increase, and mainly is because the amount of methyl-sulphoxide when increasing gradually, the oxidation substituted benzene of methyl-sulphoxide be oxidized into main reaction.Therefore the amount of methyl-sulphoxide must be controlled in certain scope, could on the basis of eliminating tar fully, obtain the transformation efficiency of maximum benzene.Obviously, methyl-sulphoxide/benzene is at (3-5): 10 (mol ratios) are advisable.Methyl-sulphoxide is excessive, influences the transformation efficiency and the phenol yield of benzene, and the methyl-sulphoxide amount is too little, is not enough to suppress the generation of tar.
Embodiment 2
Reactant is a benzene, and solvent is an acetonitrile, and catalyzer is Cu
2(OH) PO
4, coupled reaction reagent is methyl-sulphoxide.Benzene/hydrogen peroxide=1: 1 (mol ratio).Benzene/catalyzer=20 (mass ratio).60 ℃ of temperature of reaction.Reaction product is a phenol, adds the coupled reaction reagent of different amounts, and its result as shown in Table 2.
The amount of table two, methyl-sulphoxide is to Cu
2(OH) PO
4Product influence for the hydroxylation of the benzene of catalyzer
| Methyl-sulphoxide/benzene (mol ratio) | The transformation efficiency of benzene (%) | The effective rate of utilization of hydrogen peroxide (%) | The productive rate of phenol (%) | The productive rate of tar (%) |
| ??????0 ????1：8 ????2：8 ????3：8 ????4：8 ????5：8 | ????47.90 ????19.05 ????2.72 ????4.38 ????3.16 ????1.86 | ????49.65 ????36.06 ????24.67 ????21.64 ????48.97 ????69.1 | ????16.50 ????1.72 ????1.92 ????4.38 ????3.16 ????1.86 | 21.40 16.33 0.8 do not have |
As shown in Table 2, methyl-sulphoxide/benzene=2: 8 o'clock does not almost have tar and produces in the product, and promptly methyl-sulphoxide/benzene=3: 10 o'clock can have been assert no tar generation.Consider the transformation efficiency of benzene and the productive rate of phenol simultaneously, the mol ratio of the two can not be greater than 5: 10.
Comparison sheet two and table one are with Cu
2(OH) PO
4During for catalyzer, reaction result be that catalyzer is different with the TS-1 molecular sieve.Main difference is when the transformation efficiency of benzene is catalyzer than TS-1 much smaller.This is because with Cu
2(OH) PO
4During for catalyzer, the oxidation of methyl-sulphoxide is more faster than the hydroxylation of benzene, thereby has replaced the hydroxylation reaction of benzene, becomes main reaction.This also is the reason that the hydrogen peroxide utilization ratio raises gradually with the increase of the add-on of methyl-sulphoxide.
Embodiment 3
Reactant is a phenol, and solvent is a water, and catalyzer is the TS-1 molecular sieve, and coupled reaction reagent is methyl-sulphoxide.Phenol/hydrogen peroxide=2.5: 1 (mol ratio), phenol/TS-1 molecular sieve=20 (mass ratio).80 ℃ of temperature of reaction.Reaction product is a dihydroxy-benzene.Add the methyl-sulphoxide of different amounts, its result as shown in Table 3.
The amount of table three, methyl-sulphoxide is to TS-1 being the influence of hydroxylation product of the phenol of catalyzer.
| Methyl-sulphoxide/phenol (mol ratio) | Phenol conversion (%) | Effective utilization ratio of hydrogen peroxide (%) | Dihydroxy-benzene productive rate (%) | The productive rate of tar (%) |
| ??????0 ????2：10 ????3：10 ????4：10 ????6：10 | ????27.7 ????18.04 ????14.08 ????8.05 ????1.32 | ????83.2 ????71.9 ????76.46 ????76.12 ????76.33 | ????75.3 ????46.32 ????42.24 ????24.15 ????3.96 | 7.9 7.8 do not have |
As can be seen, when the amount of the methyl-sulphoxide that adds reached 30% (mol ratio) of benzene, the generation of tar was restrained fully from the data of table three.Owing to the many and methyl-sulphoxide oxidizing reaction rate that the speed of reaction of phenol hydroxylation is faster than the hydroxylation of benzene is similar, be not a lot of so the transformation efficiency of phenol reduces, and the effective rate of utilization of hydrogen peroxide does not have special obvious variation yet.But the generation of tar is restrained fully.The productive rate of phenol conversion and dihydroxy-benzene descends bigger when the ratio of coupled reaction reagent and reactant is above at 6: 10.
Embodiment 4
Reactant, solvent, coupled reaction reagent, and their proportioning temperature of reaction is identical with embodiment 3, just catalyzer uses Cu
2(OH) PO
4Its result provides table four.
The amount of table four, methyl-sulphoxide is to Cu
2(OH) PO
4Influence for the phenol hydroxylation reaction product of catalyzer
| Methyl-sulphoxide/phenol (mol ratio) | Phenol conversion (%) | Effective utilization ratio of hydrogen peroxide (%) | Dihydroxy-benzene productive rate (%) | The productive rate of tar (%) |
| ??????0 ????2：10 ????4：10 ????6：10 ????8：10 | ????28.9 ????28.28 ????26.26 ????16.84 ????8.3 | ????86.8 ????88.23 ????86.77 ????85.64 ????88.97 | ????78.6 ????7836 ????75.9 ????50.52 ????24.9 | 8.2 6529 do not have |
From the data of table four as can be seen, when with Cu
2(OH) PO
4During for catalyzer, phenol reactant speed is very fast, when the amount of the methyl-sulphoxide that adds is 40% (mol ratio) of phenol, the transformation efficiency of phenol changes little, the amount of tar just reduces a little, when the amount of methyl-sulphoxide greater than 60% the time, the generation of tar is just restrained fully, the effective rate of utilization of hydrogen peroxide is some increase a little.When the add-on of methyl-sulphoxide was 60%, the generation of tar was restrained fully, and the effective rate of utilization of the transformation efficiency of phenol and hydrogen peroxide can be accepted, and can think the conditions suitable of phenol hydroxylation reaction.
Embodiment 5
Reactant, solvent, coupled reaction reagent, and their proportioning, temperature of reaction are identical substantially with embodiment 2, coupled reaction reagent/reactant=3: 8 (mol ratio) just, catalyzer uses some other catalyzer.
Table five, different catalysts are used the effect of coupling reagent at benzene hydroxylation reaction product
| Catalyzer | Benzene transformation efficiency (%) | Effective utilization ratio of hydrogen peroxide (%) | Phenol yield (%) | The productive rate of tar (%) |
| ?Cu-MCM-41 ?Fe-ZSM-5 ?Fe-APO 4-5 ?Fe-APO 4-11 ?Fe-VPI-5 | ????3.32 ????1.12 ????2.25 ????2.36 ????2.14 | ????20.71 ????21.35 ????23.32 ????24.43 ????22.17 | ????3.32 ????1.12 ????2.25 ????2.36 ????2.14 | Do not have |
From the data of table five as can be seen, utilize being created in the most catalyzer of tar of coupled reaction control all to be suitable for, but the just relatively lower change by certain method and condition of the transformation efficiency of benzene still can change the effective rate of utilization of the transformation efficiency of benzene and hydrogen peroxide.
Embodiment 6.
With the coupled reaction reagent methyl-sulphoxide of dimethyl thioether replacement previous embodiment, reaction effect is basic identical, can suppress the generation of tar fully, and improves the effective rate of utilization of hydrogen peroxide.On consumption proportion, the reaction that is oxidized to methyl-sulphoxide according to dimethyl thioether is calculated, and relatively Shi Yi amount ratio is: dimethyl thioether/reactant=(3-5): 10 (mol ratios), reactant/hydrogen peroxide=(1-0.4): 1,
Utilization of the present invention selects coupling reaction to realize the method without the clean catalytic oxidation of tar to aromatic hydrocarbons, can produce following effect: first, because the coupling reaction reagent of introducing in the reaction system is to become the intermediate of tar product to interact by similar shape, thereby the generation of the tar in inhibition or the complete inhibitory reaction product. Experimentation shows that when not adding coupling reaction reagent in the reaction system, after adding hydrogen peroxide, reactant liquor reddens very soon, and palm fibre, final blackening in final product, can find to have produced a large amount of tar. After adding a certain amount of coupling reaction reagent, solution is nondiscolouring all the time, does not also have the generation of tar in the end product. Product analysis shows there is not the generation of benzoquinones in the benzene system simultaneously, and the growing amount of benzoquinones seldom in the phenol system. The second, the dimethyl sulfone that the methyl-sulfoxide oxidation obtains also is a kind of useful chemical products, and separates from product easily. Thereby the effective rate of utilization of hydrogen peroxide also can improve. And product is easily separated. The 3rd, the generation of the tar catalytic reaction center of covering catalyst usually in the existing catalytic reaction, and in reaction of the present invention owing to there is not the generation of tar, catalytic center can keep the permanent reaction life-span. The 4th, the present invention can be used in the catalytic oxidation of the aromatic compound of hydrogen peroxide existence widely, can realize the effect without tar. In a word, use coupling reaction can restrain the tar that produces in the hydroxylation reaction of phenol and benzene fully, thereby solved the difficult problem in the industrial production. The method cost is low, and product yield is good, and is easily separated, thereby is adapted at extensive use on the chemical industry.
Claims (2)
1. a method of utilizing the coupled reaction realization to the clean catalyzed oxidation of the no tar of aromatic hydrocarbons is a reactant with the aromatic hydroxy compound, is oxygenant with the hydrogen peroxide, is solvent with acetonitrile or water, with molecular sieve or Cu
2(OH) PO
4Be catalyzer, hydroxylation synthesizing phenol or dihydroxy-benzene; It is characterized in that adding methyl-sulphoxide or dimethyl thioether are made coupled reaction reagent in the catalytic oxidation; The mol ratio of coupled reaction reagent and reactant is controlled at (3-7): 10.
2. according to the described method of utilizing that coupled reaction realizes of claim 1, it is characterized in that the mol ratio of reactant and hydrogen peroxide is controlled at (2.5-0.4): 1 to the clean catalyzed reaction of the no tar of aromatic hydrocarbons.
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| CN00130719A CN1104405C (en) | 2000-10-11 | 2000-10-11 | Tar-free catalytic oxidation of arene utilizing coupling reaction |
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| CN00130719A CN1104405C (en) | 2000-10-11 | 2000-10-11 | Tar-free catalytic oxidation of arene utilizing coupling reaction |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792372A (en) * | 2010-04-07 | 2010-08-04 | 四川大学 | Method for preparing phenol and diphenol by direct hydroxylation of benzene and hydrogen peroxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060970C (en) * | 1996-07-18 | 2001-01-24 | 吉林大学 | Process for preparing aromatic hydrocarbon oxidation catalyst |
| CN1076724C (en) * | 1999-03-30 | 2001-12-26 | 中国石油化工集团公司 | Method for hydroxylation of phenol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792372A (en) * | 2010-04-07 | 2010-08-04 | 四川大学 | Method for preparing phenol and diphenol by direct hydroxylation of benzene and hydrogen peroxide |
| 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 |
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