CN2581449Y - Reactor for producing phenylene diphenol by phenol hydroxylation - Google Patents
Reactor for producing phenylene diphenol by phenol hydroxylation Download PDFInfo
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- CN2581449Y CN2581449Y CN 02261515 CN02261515U CN2581449Y CN 2581449 Y CN2581449 Y CN 2581449Y CN 02261515 CN02261515 CN 02261515 CN 02261515 U CN02261515 U CN 02261515U CN 2581449 Y CN2581449 Y CN 2581449Y
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- phenol hydroxylation
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Abstract
The utility model relates to a reactor for producing phenylene diphenol by phenol hydroxylation. The utility model mainly solves the problems that continuous and stable operation is difficult to keep, and the unit consumption of raw materials is high in the use of the technology of homogeneous catalyst flow reactor in the old technology, when a complete mixed flow reactor is used, the production can not be continuous, the operation is troublesome, and the technical economical indexes are poor. The utility model better solves problems by taking the measures that the complete mixed flow reactor is adopted, a heat insulating jacket which is arranged outside the reactor can be filled with vapor to be exchanged with cooling water, metallic nets are arranged in the reactor from top to bottom, and the reactor is divided by the metallic nets into an inner circle and an outer circle. The utility model can be used for the industrial production of producing the phenylene diphenol by the phenol hydroxylation.
Description
Technical field
The utility model relates to a kind of reactor that is used for the phenol hydroxylation preparing benzenediol, particularly about being used for the reactor that the continuous hydroxylation of phenol and hydrogen peroxide prepares dihydroxy-benzene.
Background technology
Dihydroxy-benzene (comprising Resorcinol, pyrocatechol) is an important chemical material, has wide application field.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; Owing to itself and peroxidation radical are easy to react the inhibitor that is used as oxidation inhibitor and autoxidation; Resorcinol and alkylate thereof also are used as the stopper of monomer accumulating in addition.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.
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 one 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 are 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.
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.Temperature of reaction, hydrogen peroxide/phenol mol ratio have been inquired into to the influence in sexual cycle of pyrocatechol in the reaction product/Resorcinol ratio, catalyst activity.But the perfectly mixed reactor in the document exists can not continuous production, and production operation is loaded down with trivial details, 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 in the utility model is to use the existence of homogeneous catalyst flow reactor technology to be difficult to keep continuous quiet run in the document in the past, the raw material consumption height, using the complete mixing flow reactor to exist can not continuous production, troublesome poeration, the problem of technico-economical comparison difference provides a kind of new reactor that is used for the phenol hydroxylation preparing benzenediol.This reactor has can keep production serialization quiet run, and easy and simple to handle, the characteristics that reaction effect is good.
For solving the problems of the technologies described above, the technical solution adopted in the utility model is as follows: a kind of reactor that is used for the phenol hydroxylation preparing benzenediol, comprise reactor shell, the reactor capping, stirring rake, insulation jacket, material inlet, the product discharge port, entrance of cooling water, cooling water outlet, steam inlet and vapour outlet, wherein insulation jacket is positioned at the reactor enclosure external body, entrance of cooling water is positioned at insulation jacket top, cooling water outlet is positioned at the insulation jacket bottom, steam inlet is positioned at the insulation jacket bottom, vapour outlet is positioned at insulation jacket top, stirring rake is positioned at the reactor central part, material inlet is positioned in the reactor capping, the product discharge port is positioned at reactor bottom, wherein in reactor also by the wire netting that is equipped with from top to bottom, reactor is separated into inside and outside two circles, stirring rake is positioned at inner ring.
In the technique scheme, the wire netting preferred version is 60～300 purpose Stainless Steel Wire Meshes, and more preferably scheme is 160～180 purpose Stainless Steel Wire Meshes; The product discharge port is positioned at inner ring.
In the utility model, when reactor was used to react, catalyzer can be loaded into the reactor outer ring, can avoid catalyzer directly to contact with stirring rake and broken, also can eat dishes without rice or wine and discharge port by putting respectively in the top and the bottom of reactor.
The insulation jacket of reactor outside has been communicated with the import and export pipeline of steam and water coolant respectively, can require to switch at any time according to reaction.
Inside reactor from top to bottom is separated into inside and outside two portions with Stainless Steel Wire Mesh, and the order number of Stainless Steel Wire Mesh is 60～300 orders, and wherein optimum is 160～180 orders.
A drain is arranged at the top of reactor, is positioned at Stainless Steel Wire Mesh inner ring top, reacts under certain pressure condition as need, it can be closed.
Two opening for feeds are arranged at the top of reactor, are positioned at top, Stainless Steel Wire Mesh outer ring, are respectively the opening for feed of phenol water and hydrogen peroxide.
The bottom of reactor is positioned at Stainless Steel Wire Mesh inner ring place, and a reaction solution discharge port is arranged, and on this place's material mouth 200 purpose strainers is housed.
The bottom of reactor is positioned at the Stainless Steel Wire Mesh outside, and a catalyzer discharge port is arranged, and old catalyzer can be developed from this mouth.
The employed catalyzer of reactor can be liquid, pulverous or solid granular, but be suitable for using granular catalyzer most, 40～80 purpose solid granular catalysts preferably, the reaction result at intermittence of the result of its continuous reaction and powder catalyst is suitable.
Owing in the utility model, catalyzer can be separated with product by wire netting, allow product pass through the inner ring discharge port then and discharge, loaded down with trivial details troublesome poeration when having avoided in the past preparing dihydroxy-benzene can be realized continuous production simultaneously; Owing to designed steam heating and water quench switching port in the reactor shell insulation jacket, make the reactor reaction temperature be easy to keep homogeneous in addition, kept the quiet run of producing, the effect that can improve reaction effect has simultaneously obtained better technical effect.
Description of drawings
Fig. 1 is a structural representation of the present utility model.
Among Fig. 1: 1 is phenol water opening for feed, and 2 is entrance of cooling water, and 3 is insulation jacket, 4 is steam inlet, and 5 are reaction solution place material mouth, and 6 is the catalyzer discharge port, 7 is cooling water outlet, 8 is vapour outlet, and 9 is the hydrogen peroxide opening for feed, and 10 is drain, 11 is stirring rake, 12 is Stainless Steel Wire Mesh, and 13 is the reactor capping, and 14 is reactor shell.
Below by embodiment the utility model is further elaborated.
Embodiment [embodiment 1]
Fig. 1 reactor volume is 1000 milliliters, at first a certain amount of iron series composite oxide catalysts (40～60 order) is thrown between Stainless Steel Wire Mesh 12 and reactor wall, and is kept drain to open.Feed phenol and water by phenol water opening for feed, stir and keep 80 rev/mins, feed steam by steam inlet simultaneously, feed temperature in the reactor is risen to 75 ± 2 ℃ and keep, feed hydrogen peroxide then in proportion.
Question response liquid has obvious intensification, illustrates to finish inductive phase, stops to feed steam, changes the feeding water coolant into, and by regulating cooling water flow, keeping reacting liquid temperature is 80 ± 2 ℃.
Proportionally drop into phenol water and hydrogen peroxide respectively by two opening for feeds, discharge reaction solution at the reaction solution discharge port simultaneously, discharging speed is identical with input speed, keeps the serialization of entire reaction to carry out.
Finish the following technical parameter of also need of above-mentioned reaction process:
Condition of normal pressure, the feeding temperature of phenol water are about 60 ℃, 50 milliliters of liquid phase air speeds/gram catalyzer hour, and the mol ratio of phenol and hydrogen peroxide is 6: 1, and the concentration of the hydrogen peroxide of use is 30 weight %, and water-content is 40% (weight) in the reaction solution.
Successive reaction 24 hours, reaction process temperature, input and output material are steady.
Reaction product dihydroxy-benzene HP efficient liquid phase chromatographic analysis.Reaction result is, is that the selectivity of dihydroxy-benzene is 72.5% when initial, and the effective rate of utilization of hydrogen peroxide is 54.5%, and the selectivity of dihydroxy-benzene is 72.0% during end, and the effective rate of utilization of hydrogen peroxide is 54.2%.[comparative example 1]
In the fixed-bed reactor of 1 centimetre of internal diameter, dose into a certain proportion of iron series composite oxide catalysts (40～60 order) and quartz sand, form about 10 centimetres catalyst layer bed, after being warming up to about 75 ℃ by heating muff, continuously feeding then, question response begin to switch water of condensation again after the heat release.
Reaction raw materials was according to phenol/hydrogen peroxide mol ratio 6: 1, and the concentration of the hydrogen peroxide of use is 30 weight %, water-content 40% (weight) preparation.The opening for feed temperature is about 60 ℃, and the liquid phase air speed is 50 a milliliters/gram catalyzer hour.
Successive reaction 24 hours.The reaction starting stage, the rapid exothermic phenomenon of the local generation of catalyst layer bed, temperature fluctuation has to lower the temperature by reducing air speed or stopping up to 25 ℃.
Reaction result is to be the selectivity 71.0% of dihydroxy-benzene the starting stage, and the effective rate of utilization of hydrogen peroxide is 54.0%; Ending phase is the selectivity 43.1% of dihydroxy-benzene, and the effective rate of utilization of hydrogen peroxide is 32.4%.
The advantage of the utility model reactor:
1, reaction can be carried out under the condition of serialization, and catalyst keeps suspended state, contacts fully reaction with reactant liquor The result is suitable with the reaction result at intermittence that uses fine catalyst.
2, carry out because of the reaction serialization, operation is simpler, convenient than the intermittenceization reaction.
3, can obviously save energy and reduce the cost. Only need before decomposition induction time finishes, logical steam insulation only needs later on logical cooling water to inhale Receive exothermic heat of reaction, keep reaction temperature; And the intermittenceization reaction needed heats up repeatedly, cooling, not only energy consumption height, and operation Loaded down with trivial details.
4, the liquid-solid separation of reactant liquor is simple, and product need not to refilter.
Claims (4)
1, a kind of reactor that is used for the phenol hydroxylation preparing benzenediol, comprise reactor shell, the reactor capping, stirring rake, insulation jacket, material inlet, the product discharge port, entrance of cooling water, cooling water outlet, steam inlet and vapour outlet, wherein insulation jacket is positioned at the reactor enclosure external body, entrance of cooling water is positioned at insulation jacket top, cooling water outlet is positioned at the insulation jacket bottom, steam inlet is positioned at the insulation jacket bottom, vapour outlet is positioned at insulation jacket top, stirring rake is positioned at the reactor central part, material inlet is positioned in the reactor capping, the product discharge port is positioned at reactor bottom, it is characterized in that in reactor also by the wire netting that is equipped with from top to bottom, reactor is separated into inside and outside two circles, and stirring rake is positioned at inner ring.
2,, it is characterized in that wire netting is 60～300 purpose Stainless Steel Wire Meshes according to the described reactor that is used for the phenol hydroxylation preparing benzenediol of claim 1.
3,, it is characterized in that wire netting is 160～180 purpose Stainless Steel Wire Meshes according to the described reactor that is used for the phenol hydroxylation preparing benzenediol of claim 2.
4,, it is characterized in that the product discharge port is positioned at inner ring according to the described reactor that is used for the phenol hydroxylation preparing benzenediol of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02261515 CN2581449Y (en) | 2002-11-13 | 2002-11-13 | Reactor for producing phenylene diphenol by phenol hydroxylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02261515 CN2581449Y (en) | 2002-11-13 | 2002-11-13 | Reactor for producing phenylene diphenol by phenol hydroxylation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN2581449Y true CN2581449Y (en) | 2003-10-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02261515 Expired - Fee Related CN2581449Y (en) | 2002-11-13 | 2002-11-13 | Reactor for producing phenylene diphenol by phenol hydroxylation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024356A (en) * | 2021-03-31 | 2021-06-25 | 嘉兴市中华化工有限责任公司 | Reaction system and method for producing benzenediol by phenol hydroxylation |
-
2002
- 2002-11-13 CN CN 02261515 patent/CN2581449Y/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024356A (en) * | 2021-03-31 | 2021-06-25 | 嘉兴市中华化工有限责任公司 | Reaction system and method for producing benzenediol by phenol hydroxylation |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20031022 Termination date: 20111113 |