CN1212300C - Method for producing dihydroxy-benzene - Google Patents
Method for producing dihydroxy-benzene Download PDFInfo
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- CN1212300C CN1212300C CN 02112451 CN02112451A CN1212300C CN 1212300 C CN1212300 C CN 1212300C CN 02112451 CN02112451 CN 02112451 CN 02112451 A CN02112451 A CN 02112451A CN 1212300 C CN1212300 C CN 1212300C
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Abstract
The present invention relates to a method for producing dihydroxy-benzene. The present invention mainly solves the problems of short catalyst use period and complicated and intermittent operation existing in the technology using a slurry bed in the previous technique, and disposable catalyst use and difficult holding of continuous and stable operation existing in the technology using a homogeneous catalyst continuous reactor. The present invention uses the technical scheme that a reaction zone is composed of at least one fixed bed reactor and a reactor without loading a catalyst. At least one fixed bed reactor and the reactor without loading a catalyst are connected in series when working. After reacting materials firstly enter at least one fixed bed reactor, the materials are supplemented into the reactor without loading a catalyst. After the reaction, the dihydroxy-benzene is obtained. Thus, the present invention perfectly solves the problems and can be used in the industrial production of the dihydroxy-benzene.
Description
Technical field
The present invention relates to a kind of production method that is used for dihydroxy-benzene, particularly about the production method of phenol and the continuous hydroxylation preparing benzenediol of hydrogen peroxide.
Background technology
Dihydroxy-benzene (comprising pyrocatechol, Resorcinol) is an important chemical material, has wide application field.Pyrocatechol has another name called pyrocatechol, is used for industries such as medicine, agricultural chemicals, spices, photograph, resin, coating.Methyl catechol with the pyrocatechol preparation is the important source material of producing vanillin food grade,1000.000000ine mesh; Tert-butyl catechol by the pyrocatechol preparation is divinyl and cinnamic stopper; Can improve the stability of nylon fiber with the synthetic resins of pyrocatechol and all kinds of aldehyde polycondensations.Resorcinol has another name called quinhydrones, and is a large amount of as photographic developer in sensitization industry, also as anticoagulant, catalytic desulfurizing agent etc.Resorcinol is the important source material of anthraquinone dye and azoic dyestuff, or the important source material of essence and greasy oxidation inhibitor, be easy to react with the peroxidation radical and be used as the inhibitor of oxidation inhibitor and autoxidation, Resorcinol and alkylate thereof also can be used as the stopper of monomer accumulating simultaneously.
A lot, the traditional dihydroxy-benzene production technique of dihydroxy-benzene (comprising pyrocatechol, Resorcinol) production method is eliminated as ortho chloro phenol hydrolysis method, disulfonic acid phenol alkali fusion method, aniline oxidation style, benzoquinones reduction method etc.With the hydrogen peroxide is the phenol hydroxylation preparing benzenediol of oxygenant, because technical process is simple, and the reaction conditions gentleness, hydrogen peroxide is inexpensive, and oxidized byproduct is a water and pollution-free, becomes the research focus.Have only French Luo Na-Rhone-Poulenc, Italian ENI company, successfully industrialization of Ube Industries Ltd. at present.The Rhone-Poulenc method is with HClO
4Catalyzer and H
3PO
4Promotor, 70% hydrogen peroxide are oxygenant, three placed in-line reaction process of reactor.The Brichima method is with molysite and cobalt salt (Fe
(II)/ Co
(II)) mixed catalyst, 60% hydrogen peroxide is an oxygenant, forms the reaction process of Fenton reagent.Though can continuous production, have the shortcoming that homogeneous reaction itself is difficult to overcome, there is the disposable use of catalyzer, is difficult to keep continuous quiet run, raw material consumption height, problem that the dihydroxy-benzene selectivity is low.The Ube method is a catalyzer with sulfuric acid etc., adopts 60% hydrogen peroxide and the ketogenesis ketone peroxide reaction process as oxygenant, but the flow process complexity.The Enichem method is with titanium-silicon molecular sieve catalyst, the lower concentration hydrogen peroxide is an oxygenant, the reaction process of slurry bed, though indexs such as yield are better, molecular sieve synthesizes the cost height, and catalyst recovery requires high, use the lower concentration hydrogen peroxide and make dehydration energy consumption height, production operation is loaded down with trivial details, and work under bad environment has a strong impact on this technological competitiveness.Therefore, still in the technology of actively seeking a kind of high-level efficiency CR production dihydroxy-benzene.
What people were developing has: the reaction system of hetero-atom molecular-sieve; The reaction system of heteropoly compound such as document be in " SCIs " 1996 such as sword cutting edges of a knife or a sword, Vol.17, and No.3 has synthesized serial Dawson structure heteropoly compound P among the p126
2Mo
18-nV
n(n=0～3), phenol-hydrogen peroxide hydroxylation in acetonitrile solvent, but hydrogen peroxide decomposition is serious, and solvent acetonitrile toxicity is big.What effect was more satisfactory is the reaction system of metal oxide or metal-salt.As " Chinese science (B collect) " 1997 such as Liu Chibiao, Vol.27, No.5 has synthesized Ln among the p385
2CuO
4The perovskite-like composite oxide catalysts is used for the phenol-hydrogen peroxide hydroxylation.But water is excessive too many, poor catalytic activity.Zhang Xinfang etc. " petrochemical technology " 1999, Vol.6, No.2 adopts coprecipitation method to prepare load-type iron-based O composite metallic oxide catalyst among the p81, be used for the phenol-hydrogen peroxide hydroxylation.Chinese patent application 00115800.7 " phenyl hydroxylating catalyst ", Chinese patent application 00116532.1 " catalyzer of preparing benzene diphenol by means of oxidation of phenol ", Chinese patent application 00116537.2 " catalyzer of preparing benzene diphenol by means of direct oxidation of phenol " etc. have been reported iron Si composite oxide catalyzer, are used for the phenol-hydrogen peroxide hydroxylation.
Metal oxide catalyst research is nearly all carried out in batch reactor." chemistry worlds " 2000 such as document Zhang Chun are only arranged, and No.11 has reported among the p590 with iron content O composite metallic oxide catalyst hydroxylated reaction process of catalysis of phenol hydrogen peroxide in continuous perfectly mixed reactor.Along with the increase of series connection still number, the average activity of O composite metallic oxide catalyst is difficult to improve, and should adopt single still flow process.Its catalyzer reuse ratio should be less than 0.6, otherwise catalyst activity declines to a great extent.
Existing in the reaction process of above-mentioned Enichem titanium-silicon molecular sieve catalyst slurry bed can not continuous production, catalyzer and reaction product separation difficulty, and phenol conversion is not high, and production operation is loaded down with trivial details, the shortcoming of work under bad environment; Exist can not continuous production for the continuous perfectly mixed reactor of iron Si composite oxide catalyzer in the above-mentioned document, and the catalyst abrasion heavy losses are big, and strainer switches and cleans frequently, and hydrogen peroxide is easy to decompose the shortcoming of influence technique economic target.
Summary of the invention
Technical problem to be solved by this invention is to overcome to use slurry bed technology to exist the catalyzer life cycle to lack, operate intermittently loaded down with trivial details in the conventional art, use homogeneous catalyst flow reactor technology to have the disposable use of catalyzer, be difficult to keep the shortcoming of continuous quiet run, a kind of new production method that is used for dihydroxy-benzene is provided.This method has can make reaction process realize continuous operation, and production operation is simple, can improve catalyst productivity, prolongs optionally characteristics of catalyzer work-ing life and raising effective utilization ratio of hydrogen peroxide and dihydroxy-benzene.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of production method that is used for dihydroxy-benzene, its reaction zone by at least one fixed-bed reactor and one not the reactor of loading catalyst form, be arranged in series during the reactor work of fixed-bed reactor and loading catalyst, after the mixture of partial reaction raw material phenol and hydrogen peroxide is introduced into fixed-bed reactor, add surplus stock again and enter the not reactor of loading catalyst, get dihydroxy-benzene after the reaction.
In the technique scheme, the number preferred version of fixed-bed reactor is 1～3, is arranged in series, and more preferably scheme is 1 fixed-bed reactor.The fixed-bed reactor preferred version is its top feed bottom discharge or bottom feed top discharge; The reactor preferred version of loading catalyst is not its top feed bottom discharge or bottom feed top discharge; More preferably scheme is that fixed-bed reactor are the bottom feed top discharge, and the reactor of loading catalyst is not the bottom feed top discharge.
Among the present invention, reaction zone is made up of first reactor and second reactor, and wherein first reactor is the fixed-bed reactor of at least one loading catalyst, and second reactor is a not reactor of loading catalyst.Reaction raw materials reacts under the catalyst action of filling in first reactor, in second reactor, continue reaction with adding raw material then, generate dihydroxy-benzene, realized that phenol prepares the serialization of dihydroxy-benzene process with the hydrogen peroxide hydroxylation, production operation is simple.
Because first reactor adopts the fixed-bed reactor of loading catalyst, second reactor is loading catalyst not.The first reactor reaction product in second reactor with add the raw material hybrid reaction, make dihydroxy-benzene content raising in the phenol-hydrogen peroxide hydroxylating product, reduce the phenol internal circulating load, therefore improved phenyl hydroxylating catalyst throughput, also improved the phenol selectivity.Because adding raw material joins in second reactor, needn't reduce the catalyst loading of first reactor charge significantly through first reactor, has suppressed side reactions such as hydrogen peroxide deep oxidation, therefore prolonged the work-ing life of phenyl hydroxylating catalyst.
Among the present invention, for reactor content flowed to, first reactor was its top feed bottom discharge or bottom feed top discharge.Second reactor is its top feed bottom discharge or bottom feed top discharge.Often adopting first reactor is the bottom feed top discharge, and second reactor is the bottom feed top discharge.At second reactor outlet strainer is set and removes solid impurity, to stop the side reaction in the separation circuit.
Among the present invention, catalyzer can be metal oxide, composite oxide of metal, metal-salt, iron Si composite oxide especially, and it comprises following general formula with atomic ratio measuring:
A
aB
bC
cFe
1.0O
x
A is selected from least a among Ca, Mg, Sr, Be, Cr, Mn, Co, Cd, Zn or the Cu in the formula;
B is Si;
C is selected from least a among Sn, Ge, Pb, Al, Mo, V or the Ti;
The span of a is 0～5;
The span of b is＞0～5;
The span of c is 0～5;
X is the sum that satisfies other element valence requisite oxygen atom.
Above-mentioned method for preparing catalyst is seen the method for Chinese patent application 00115800.7, Chinese patent application 00116532.1, Chinese patent application 00116537.2.
The present invention has realized the serialization of phenol and hydrogen peroxide hydroxylation preparing benzenediol, have the phenyl hydroxylating catalyst of raising throughput, prolong its work-ing life, production operation is simple, improves optionally characteristics of effective utilization ratio of hydrogen peroxide and dihydroxy-benzene, has obtained better technical effect.
The present invention is further illustrated below by embodiment, and still, scope of the present invention has more than and is limited to following explanation.
Embodiment
[embodiment 1]
After the water of 1000 milliliters/hour commercial-grade phenol, 30 milliliters/hour 30 weight % hydrogen peroxide and 500 milliliters/hour mixes, enter fixed-bed reactor, it is the bottom feed top discharge.At 50 milliliters of 2.0MPa, 70 ℃, liquid phase air speed/gram catalyzer hour, react under the iron Si composite oxide catalyst action with embodiment 5 in the Chinese patent application 00115800.7.Reaction product with add raw material and enter the not reactor of loading catalyst, it is the bottom feed top discharge.Add raw material and be 60 milliliters/hour commercial-grade phenol, 150 milliliters/hour 30 weight % hydrogen peroxide, under normal pressure, 90 ℃ of conditions, continue reaction.Total phenol-hydrogen peroxide hydroxylating result: effective utilization ratio of hydrogen peroxide 73.3%, dihydroxy-benzene selectivity 73.8%, 700 hours work-ing life of catalyzer.Through separation circuit, obtain pyrocatechol, Resorcinol product.
[embodiment 2]
After the water of 1000 milliliters/hour commercial-grade phenol, 15 milliliters/hour 30 weight % hydrogen peroxide and 500 milliliters/hour mixes, enter fixed-bed reactor, it is the bottom feed top discharge.In 200 milliliters of 0.8MPa, 80 ℃, liquid phase air speed/gram catalyzer hour, react under the iron Si composite oxide catalyst action with use among the embodiment 1.Reaction product with add raw material and enter the not reactor of loading catalyst, it is the bottom feed top discharge.Add raw material and be 60 milliliters/hour commercial-grade phenol, 255 milliliters/hour 30 weight % hydrogen peroxide, in 0.8MPa,, continue reaction under 80 ℃ of conditions.Total phenol-hydrogen peroxide hydroxylating result: effective utilization ratio of hydrogen peroxide 76.1%, dihydroxy-benzene selectivity 72.1%, 700 hours work-ing life of catalyzer.Through separation circuit, obtain pyrocatechol, Resorcinol product.
[comparative example 1]
After the water of 1000 milliliters/hour commercial-grade phenol, 180 milliliters/hour 30 weight % hydrogen peroxide and 450 milliliters/hour mixes, enter reactor, at 120 milliliters of normal pressures, 85 ℃, liquid phase air speed/gram catalyzer hour, with use among the embodiment 1 iron Si composite oxide catalyst action under react.Total phenol-hydrogen peroxide hydroxylating result: effective utilization ratio of hydrogen peroxide 58.3%, dihydroxy-benzene selectivity 54.2%, 168 hours work-ing life of catalyzer.Through separation circuit, obtain pyrocatechol, Resorcinol product.
Claims (6)
1, a kind of production method that is used for dihydroxy-benzene, it is characterized in that reaction zone by at least one fixed-bed reactor and one not the reactor of loading catalyst form, be arranged in series during the reactor work of fixed-bed reactor and loading catalyst, after the mixture of partial reaction raw material phenol and hydrogen peroxide is introduced into fixed-bed reactor, add surplus stock again and enter the not reactor of loading catalyst, get dihydroxy-benzene after the reaction.
2,, it is characterized in that fixed-bed reactor have 1～3, are arranged in series according to the described production method that is used for dihydroxy-benzene of claim 1.
3,, it is characterized in that fixed-bed reactor are 1 according to the described production method that is used for dihydroxy-benzene of claim 2.
4,, it is characterized in that fixed-bed reactor are bottom feed top discharge or its top feed bottom discharge according to the described production method that is used for dihydroxy-benzene of claim 1.
5,, it is characterized in that the reactor of loading catalyst is not bottom feed top discharge or its top feed bottom discharge according to the described production method that is used for dihydroxy-benzene of claim 1.
6, according to claim 4 or the 5 described production methods that are used for dihydroxy-benzene, it is characterized in that fixed-bed reactor are the bottom feed top discharge, the reactor of loading catalyst is not the bottom feed top discharge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02112451 CN1212300C (en) | 2002-07-10 | 2002-07-10 | Method for producing dihydroxy-benzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02112451 CN1212300C (en) | 2002-07-10 | 2002-07-10 | Method for producing dihydroxy-benzene |
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| Publication Number | Publication Date |
|---|---|
| CN1467190A CN1467190A (en) | 2004-01-14 |
| CN1212300C true CN1212300C (en) | 2005-07-27 |
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| CN 02112451 Expired - Fee Related CN1212300C (en) | 2002-07-10 | 2002-07-10 | Method for producing dihydroxy-benzene |
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| CN104003847B (en) * | 2014-05-16 | 2016-06-29 | 华南理工大学 | A kind of directional synthesis method of 2,5 di tert butyl hydroquinone |
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