CN101613262A - The preparation facilities of cyclohexenyl hexamethylene ketone and method thereof - Google Patents
The preparation facilities of cyclohexenyl hexamethylene ketone and method thereof Download PDFInfo
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- CN101613262A CN101613262A CN200910025978A CN200910025978A CN101613262A CN 101613262 A CN101613262 A CN 101613262A CN 200910025978 A CN200910025978 A CN 200910025978A CN 200910025978 A CN200910025978 A CN 200910025978A CN 101613262 A CN101613262 A CN 101613262A
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Abstract
The present invention relates to a kind of preparation facilities and method of intermediate cyclohexenyl hexamethylene ketone of orthoxenol, this device is made up of tower still 6, tower reactor 5, total reflux condenser 1 and water-and-oil separator 2, and wherein reactor 5 is made up of Reaction Separation section 3 and segregation section 4; Catalyst pack is placed in the catalyzer frame on tower reactor Reaction Separation section 3 column plates, the pimelinketone heating steams in the tower still, enter on Reaction Separation section 3 column plates by segregation section 4 and to form liquid layer, make that catalyzer is immersed in the pimelinketone liquid in the frame, pimelinketone generation condensation reaction generates cyclohexenyl hexamethylene ketone and water under catalyst action, under the centrifugation of column plate, cyclohexenyl hexamethylene ketone leaves conversion zone and moves to the tower bottom and enter the tower still at last, the water and the pimelinketone that generate steam phase-splitting in water-and-oil separator after the condensation together from cat head.The pimelinketone per pass conversion can reach more than 95%, and the selectivity of cyclohexenyl hexamethylene ketone can reach more than 98%.
Description
Technical field
The present invention relates to a kind of preparation facilities and method of intermediate cyclohexenyl hexamethylene ketone of orthoxenol, relating in particular to a kind of is the preparation method and the device thereof of raw material high conversion, highly-selective preparation cyclohexenyl hexamethylene ketone with the pimelinketone.
Background technology
Orthoxenol (OPP) is purposes fine chemicals and an organic intermediate very widely, can be used as anticorrosion, mould inhibitor, wide-spectrum bactericide, be used for fruit freshness preserving, makeup, the preservation of timber against decay, and the sterilization of family, public place, swimming pool and hospital, also can be used for synthesizing new macromolecular compound, stablizer and flame retarded polymeric material intermediate etc. in recent years more and more by its produce oil dissolubility O-SyL formaldehyde resin, nonionic emulsifier, synthetic dyestuff, water-base cutting fluid etc.Main both at home and abroad at present employing pimelinketone is a raw material, obtains intermediate-cyclohexenyl hexamethylene ketone through the condensation dehydration, again through catalytic dehydrogenation, the refining OPP that obtains.
About more existing researchs of pimelinketone condensation cyclohexene basic ring hexanone and report, USP 4002693 adopts sulfuric acid to make catalyzer, and 500g pimelinketone and 100g 50% sulfuric acid mix, at N
2Gas bell or stirring keep 20min at 90-100 ℃ down, can obtain 170g cyclohexenyl hexamethylene ketone.JP 7791846 adopts molecular sieve, heteropolyacid, Al
2O
3Gels etc. are made catalyzer, 1000g pimelinketone, 50g hexanaphthene and 100gAl
2O
3Gel backflow azeotropic band water 7h, reaction conversion ratio is 82%, reaction preference is 91%.Yue Lili, Jiang Wenwei etc. have tested acid, the influence of alkaline catalysts to reacting respectively, NaOH is 0.5% (mole) of raw material as its consumption of catalyzer, 155 ℃ of temperature of reaction, reacted 1.5-2 hour, will react the water that generates by pimelinketone and take system out of, the pimelinketone circulation continues to participate in reaction, obtain heavy-gravity dark brown red crude product, obtain dipolymer through underpressure distillation, the transformation efficiency of pimelinketone can reach 71.5%, and the reaction preference of dipolymer is 89.5%.Chen Hongyan etc. have studied the application of dealuminzation ultra-steady Y molecular sieve DUSY catalyzer in the pimelinketone condensation reaction, react 4 hours down for 138 ℃ at the DUSY-2 (silica alumina ratio is 8.95) that uses 5%, use the band aqua, and the one-pass yield of dimer can reach 49.5%.Defend Yan'an etc. in the research synthesizing o-phenylphenol, adopt 98% the vitriol oil to make the pimelinketone condensation catalyst, be reflected at 112-115 ℃ of reaction 2 hours, reaction product is distilled under normal pressure, collects 270-272 ℃ cut, and total recovery can reach 90%.People such as Chen Yao have studied the solid acid catalyst of pimelinketone condensation, and compare as catalyzer with the vitriol oil, preferably solid acid catalyst, be 3% in add-on, 40 minutes reaction times, the pimelinketone transformation efficiency reaches 52%, and yield is 49%, and selectivity still remains on more than 94%; Chen Yao etc. have also studied the kinetics of pimelinketone condensation reaction.With the pimelinketone is the domestic existing three pieces of patents of raw material synthesizing o-phenylphenol, and wherein CN1371897A newspaper and two pieces of patents of CN1490293A do not relate to pimelinketone condensation reaction transformation ratio and selectivity; CN101003471 relates to the method for pimelinketone continuous production cyclohexenyl hexamethylene ketone under solid superacid as catalyst, and the pimelinketone per pass conversion is lower than 50%, and cyclohexenyl hexamethylene ketone selectivity is below 97%.
The research method of above-mentioned classics all is that catalyzer is added in reaction at a certain temperature in the pimelinketone, and reaction product and reactant are in the same system.Along with the carrying out of reaction, moisture and product cyclohexenyl hexamethylene ketone concentration constantly increase in the system, and the water concentration height increases reversed reaction speed, thereby the pimelinketone per pass conversion is not high; Product cyclohexenyl hexamethylene ketone concentration improves in the system, has increased cyclohexenyl hexamethylene ketone and pimelinketone and has further reacted the chance that generates by product, so selectivity is descended; Reaction will be told catalyzer after finishing, and generally will handle through washing and alkali cleaning, produces a certain amount of organic waste water that contains, and environment is polluted.
Summary of the invention
The objective of the invention is in order to overcome above-mentioned shortcoming, the device of a kind of pimelinketone condensation high conversion, highly-selective preparation cyclohexenyl hexamethylene ketone is proposed, another object of the present invention is to utilize this device to prepare the method for cyclohexenyl hexamethylene ketone, and reacted product needn't just can be sent to refining through washing and alkali cleaning processing.
Technical scheme of the present invention is: by the research to reaction rule, following reaction network is pressed in the major and minor reaction of pimelinketone condensation prepared cyclohexenyl hexamethylene ketone:
A wherein: pimelinketone, P: cyclohexenyl hexamethylene ketone, S: represent 2,6-two (1-cyclohexenyl) pimelinketone etc. the by product that contracts more.
The pimelinketone condensation reaction is reversible consecutive reaction, and the water that generates in the system can make the pimelinketone transformation efficiency descend, and product cyclohexenyl hexamethylene ketone concentration height generates by product easily, and selectivity is descended.Shift out reaction system as if the water that will react generation and help improving speed of reaction and per pass conversion; The cyclohexenyl hexamethylene ketone that generates in reaction also can further react with pimelinketone, generation three is contracted or is contracted compound more, the cyclohexenyl hexamethylene ketone of therefore managing to generate shifts out reaction system immediately, make that cyclohexenyl hexamethylene ketone remains under the lower concentration in the reaction system, the cyclohexenyl hexamethylene ketone that can suppress to generate further further reacts with pimelinketone and generates the compound that contracts more, helps improving the selectivity of purpose product cyclohexenyl hexamethylene ketone.
The present invention is according to above-mentioned reaction characteristics, and at the problem that existing research exists, it is as follows to propose concrete technical scheme of the present invention:
A kind of preparation facilities of cyclohexenyl hexamethylene ketone, it is characterized in that forming by tower still 6, tower reactor 5, total reflux condenser 1 and water-and-oil separator 2, wherein reactor 5 is made up of Reaction Separation section 3 and segregation section 4, and reactor 5 tops are Reaction Separation section 3, and the bottom is a segregation section 4; Segregation section 4 can be with common column plate layer or high efficiency packing layer, and number of theoretical plate is the 15-20 piece; Wherein said Reaction Separation section 3 for the 10-15 piece all with the sieve plate of a downtake, downtake portion onboard highly is 10-15cm; On a part of sieve plate of Reaction Separation section 3 the catalyzer frame is housed, frame only adds up to 5-10, can be determined in the residence time of Reaction Separation section by turnout and material.
The catalyzer frame is made by multihole lamina, and end uncovered is arranged, and the frame diameter is less than reactor inside diameter, and the catalyzer frame is enclosed within on the downtake, and the distance with sieve plate at the bottom of its frame is 3-5cm.
The present invention also provides the method for utilizing said apparatus to prepare cyclohexenyl hexamethylene ketone, it is characterized in that catalyst pack is placed in the catalyzer frame on tower reactor Reaction Separation section 3 column plates, the pimelinketone heating steams in the tower still, enter on Reaction Separation section 3 column plates by segregation section 4 and to form liquid layer, make that catalyzer is immersed in the pimelinketone liquid in the frame, pimelinketone generation condensation reaction generates cyclohexenyl hexamethylene ketone and water under catalyst action, under the centrifugation of column plate, cyclohexenyl hexamethylene ketone leaves conversion zone and moves to the tower bottom and enter the tower still at last, the water and the pimelinketone that generate steam from cat head together, phase-splitting in water-and-oil separator after the condensation, pimelinketone is on the upper strata, and continuous overflow enters on the cat head first deblocking reaction plate; Water is in lower floor, and regularly discharging or continuous overflow are discharged.
Described solid catalyst bag is placed on 60-80 order silk screen by solid acid catalyst and makes, and wherein said solid acid catalyst is activated carbon supported phospho-wolframic acid, resin cation (R.C.) load FeCl
3Or SiO
2Load FeCl
3, particle diameter is the 20-40 order.
All placed catalyst pack in every catalyzer frame, under operational condition, the pimelinketone heating steams in the tower still, enter on the Reaction Separation section column plate by segregation section and to form liquid layer, make that catalyzer is immersed in the pimelinketone liquid in the frame, pimelinketone generation condensation reaction generates cyclohexenyl hexamethylene ketone and water under catalyst action, under the centrifugation of column plate, cyclohexenyl hexamethylene ketone leaves conversion zone and moves to the tower bottom and enter the tower still at last, the water and the pimelinketone that generate steam from cat head together, phase-splitting in water-and-oil separator after the condensation, pimelinketone return again tower enter the Reaction Separation section proceed the reaction, water is emitted.Condensation reaction with separate the coupled condition under preparation cyclohexenyl hexamethylene ketone.
Placed catalyst pack in every catalyzer frame, catalyst pack is immersed in the liquid on the column plate, and catalytic amount is the 1-10% of liquid weight on the column plate on every block of column plate of Reaction Separation section; Pimelinketone apparent residence time in the liquid layer of Reaction Separation section of refluxing is 0.1-1 hour, is entered in the material of segregation section cyclohexenyl hexamethylene ketone weight percentage by the Reaction Separation section at 10-30%.
Pimelinketone condensation reaction of the present invention is under atmospheric pressure carried out, and perhaps carries out under 10-100kPa pressure; Under atmospheric pressure descending the tower reactor head temperature is 120-155 ℃, and the tower still is the material boiling temperature, at 170-280 ℃.
Contain the water that the pimelinketone condensation reaction generates in the material under the whole condensations of above-mentioned cat head, phase-splitting in water-and-oil separator, pimelinketone is on the upper strata, and continuous overflow enters on the cat head first deblocking reaction plate; Water is in lower floor, and regularly discharging or continuous overflow are discharged.
Reaction finishes back pimelinketone per pass conversion and can reach more than 95%, and the selectivity of cyclohexenyl hexamethylene ketone can reach more than 98%, but product needn't go to make with extra care through washing and alkali cleaning step direct sending, the purity of cyclohexenyl hexamethylene ketone reaches more than 99.5%.
Beneficial effect:
1) solid acid catalyst is made catalyst pack and is placed in the frame on the tower reactor column plate, condensation reaction with separate the coupled condition and be issued to the purpose that high conversion, highly selective prepare cyclohexenyl hexamethylene ketone.
2) pimelinketone condensation reaction device is by being made up of tower still, tower kettle heater, reaction tower, total reflux condenser and several parts of water-and-oil separator.The pimelinketone per pass conversion can reach more than 95%, and the selectivity of cyclohexenyl hexamethylene ketone can reach more than 98%.
3) reaction finishes after product and needn't reduce wastewater discharge through washing and alkali cleaning step.
Description of drawings
Condensation of Fig. 1 pimelinketone and the setting drawing that separates coupling preparation cyclohexenyl hexamethylene ketone; Wherein: 1, total reflux condenser, 2, water-and-oil separator, 3, the Reaction Separation section, 4, segregation section, 5, tower reactor, 6, the tower still; A is a water, and B is a pimelinketone.
The tower plate structure synoptic diagram of Fig. 2 band catalyzer frame; A, flange, b, sieve plate, c, catalyzer frame, d, downtake, e, catalyst pack, f, liquid.
Embodiment
The present invention can be illustrated more clearly in from following embodiment, but it is not the restriction that the present invention is made.
The condensation of Fig. 1 pimelinketone with separate coupling preparation cyclohexenyl hexamethylene ketone device in the tower still be 1000L, charged heating; The tower internal diameter is Φ 300mm, and segregation section is loaded efficient screen waviness packings, highly is 3m; 10 sieve plates of Reaction Separation Duan Gongshe are being provided with the catalyzer frame on the 1st, 3,5,7,9 sieve plate from top to bottom, and the catalyzer frame is made by the thick porous plate of 1mm, and external diameter is Φ 290mm, the high 8cm of frame, at the bottom of the frame from column plate 3cm, the high 12cm of downtake.In every frame catalyst pack is housed, the activated carbon supported phospho-wolframic acid solid acid catalyst of dress 20-40 order 1kg adorns catalyzer 5kg in five frames altogether in the catalyst pack.In 1000 L tower stills 1, add pimelinketone 700kg, under normal pressure, be heated to boiling, the pimelinketone steam that rises after the total reflux condenser condenses from the trim the top of column to the tower in, and progressively on Reaction Separation section column plate, form liquid level, liquid flows downward from first plate block-by-block of cat head by upflow tube on the column plate, enter the segregation section packing layer then and flow to the tower still again, enter in the liquid of segregation section packing layer cyclohexenyl hexamethylene ketone about 25%.
After forming liquid level on the column plate, catalyst pack is immersed in the pimelinketone liquid in the catalyzer frame, condensation reaction takes place and generates cyclohexenyl hexamethylene ketone and water in pimelinketone under catalyst action, under the centrifugation of column plate, the high boiling point cyclohexenyl hexamethylene ketone that generates leaves conversion zone and moves to the tower bottom and enter the tower still at last, the water and the pimelinketone that generate steam from cat head together, after the total reflux condenser condenses, enter water-and-oil separator, pimelinketone is on the upper strata, overflows back cat head and enters the Reaction Separation section and proceed reaction again; Water is intermittently emitted in lower floor.The unreacted pimelinketone constantly steams in the tower still, and the effect by the segregation section filler separates with cyclohexenyl hexamethylene ketone and enters the Reaction Separation section and constantly react, and substantially all steams and stays the basic cyclohexenyl hexamethylene ketone that is up to tower still pimelinketone.Along with the carrying out of reaction, tower still temperature progressively rises from reacting about 165 ℃ of beginning, and the reaction later stage is near 280 ℃.Tower top temperature is from 125 ℃ of beginning, and reaction is about 160 ℃ when finishing.
After finishing, reaction stops heating, sampling adopts the gas chromatographic analysis condensation product to consist of: pimelinketone 4.40%, cyclohexenyl hexamethylene ketone 94.55%, the compound that contracts is 1.05% more, the pimelinketone per pass conversion is about 96%, reaction preference is 98.5%, and cyclohexenyl hexamethylene ketone purity reaches 99.6% after the direct rectifying of condensation product.
With embodiment 1 same device, in every frame catalyst pack is housed, dress 20-40 order resin cation (R.C.) load FeCl in the catalyst pack
3Solid acid catalyst 0.5kg adorns catalyzer 2.5kg in five frames altogether, and other condition is all identical.
After finishing, reaction stops heating, sampling adopts the gas chromatographic analysis condensation product to consist of: pimelinketone 3.0%, cyclohexenyl hexamethylene ketone 96.15%, the compound that contracts is 0.85% more, the pimelinketone per pass conversion is about 96.5%, reaction preference is 98.8%, and cyclohexenyl hexamethylene ketone purity reaches 99.7% after the direct rectifying of condensation product.
Claims (7)
1. the preparation facilities of cyclohexenyl hexamethylene ketone, it is characterized in that forming by tower still (6), tower reactor (5), total reflux condenser (1) and water-and-oil separator (2), wherein reactor (5) is made up of Reaction Separation section (3) and segregation section (4), reactor (5) top is Reaction Separation section (3), and the bottom is segregation section (4).
2. device according to claim 1 is characterized in that segregation section (4) with common column plate layer or high efficiency packing layer, and number of theoretical plate is the 15-20 piece.
3. device according to claim 1, it is characterized in that described Reaction Separation section (3) for the 10-15 piece all with the sieve plate of a downtake, downtake portion onboard highly is 10-15cm; On the part sieve plate of Reaction Separation section (3) the catalyzer frame is housed, frame only adds up to 5-10; The catalyzer frame has end uncovered, is made by multihole lamina, and catalyzer frame diameter is enclosed within on the downtake less than reactor inside diameter, and the distance with sieve plate at the bottom of its frame is 3-5cm.
4. the method for a pimelinketone condensation prepared cyclohexenyl hexamethylene ketone, it is characterized in that catalyst pack is placed in the catalyzer frame on tower reactor Reaction Separation section (3) column plate, the pimelinketone heating steams in the tower still, enter on Reaction Separation section (3) column plate by segregation section (4) and to form liquid layer, make that catalyzer is immersed in the pimelinketone liquid in the frame, pimelinketone generation condensation reaction generates cyclohexenyl hexamethylene ketone and water under catalyst action, under the centrifugation of column plate, cyclohexenyl hexamethylene ketone leaves conversion zone and moves to the tower bottom and enter the tower still at last, the water and the pimelinketone that generate steam from cat head together, phase-splitting in water-and-oil separator after the condensation, pimelinketone is on the upper strata, continuous overflow enters on the cat head first deblocking reaction plate, and water is in lower floor, and regularly discharging or continuous overflow are discharged.
5. method according to claim 4 is characterized in that the solid catalyst bag is placed on 60-80 order silk screen by solid acid catalyst and makes, and wherein said solid acid catalyst is activated carbon supported phospho-wolframic acid, resin cation (R.C.) load FeCl
3Or SiO
2Load FeCl
3, particle diameter is the 20-40 order.
6. method according to claim 4 is characterized in that having placed catalyst pack in every catalyzer frame, and catalyst pack is immersed in the liquid on the column plate, and catalytic amount is the 1-10% of liquid weight on the column plate on every block of column plate of Reaction Separation section; Pimelinketone apparent residence time in the liquid layer of Reaction Separation section of refluxing is 0.1-1 hour, is entered in the material of segregation section cyclohexenyl hexamethylene ketone weight percentage by the Reaction Separation section at 10-30%.
7. method according to claim 5 is characterized in that the pimelinketone condensation reaction under atmospheric pressure carries out, and perhaps carries out under 10-100kPa pressure; Under atmospheric pressure descending the tower reactor head temperature is 120-155 ℃, and the tower still is the material boiling temperature, at 170-280 ℃.
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| CN200910025978A CN101613262B (en) | 2009-03-16 | 2009-03-16 | Device and method for preparing cyclohexenyl cyclohexanone |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311326A (en) * | 2010-07-06 | 2012-01-11 | 东营远大化工有限公司 | Method for preparing cyclohexenyl cyclohexanone with high conversion rate |
| CN104437265A (en) * | 2014-11-19 | 2015-03-25 | 济南大学 | Self-condensation reaction preparation device of cyclohexanone |
| CN110066679A (en) * | 2018-01-24 | 2019-07-30 | 中国石油天然气股份有限公司 | The method of fatty alcohol liquid fuel was prepared |
| CN110845321A (en) * | 2019-11-27 | 2020-02-28 | 宿迁南翔化学品制造有限公司 | Tower type method and equipment for preparing malonic acid |
| CN114377424A (en) * | 2022-01-24 | 2022-04-22 | 国家能源集团宁夏煤业有限责任公司 | Suspension concentration evaporation device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7500549A (en) * | 1975-01-17 | 1976-07-20 | Stamicarbon | PROCESS FOR THE PREPARATION OF 2- (1-CYCLO-HEXENYL) -CYCLOHEXANONE. |
| CN1535945A (en) * | 2003-04-08 | 2004-10-13 | 上海应用技术学院 | Method for preparing 2-(1-cyclohexenyl) cyclohexanone by utilizing reduced pressure resin catalytic condensation |
| CN101121640A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Method for producing ethylene glycol by catalysis rectification |
| CN101003471B (en) * | 2006-11-02 | 2010-05-12 | 盐城市华业医药化工有限公司 | Method for producing cyclohexenyl anone from continuous condensating anone |
-
2009
- 2009-03-16 CN CN200910025978A patent/CN101613262B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311326A (en) * | 2010-07-06 | 2012-01-11 | 东营远大化工有限公司 | Method for preparing cyclohexenyl cyclohexanone with high conversion rate |
| CN104437265A (en) * | 2014-11-19 | 2015-03-25 | 济南大学 | Self-condensation reaction preparation device of cyclohexanone |
| CN104437265B (en) * | 2014-11-19 | 2017-03-01 | 济南大学 | The preparation facilitiess of cyclohexanone self-condensation reaction |
| CN110066679A (en) * | 2018-01-24 | 2019-07-30 | 中国石油天然气股份有限公司 | The method of fatty alcohol liquid fuel was prepared |
| CN110845321A (en) * | 2019-11-27 | 2020-02-28 | 宿迁南翔化学品制造有限公司 | Tower type method and equipment for preparing malonic acid |
| CN110845321B (en) * | 2019-11-27 | 2022-06-03 | 宿迁南翔化学品制造有限公司 | Tower type method and equipment for preparing malonic acid |
| CN114377424A (en) * | 2022-01-24 | 2022-04-22 | 国家能源集团宁夏煤业有限责任公司 | Suspension concentration evaporation device |
| CN114377424B (en) * | 2022-01-24 | 2023-04-14 | 国家能源集团宁夏煤业有限责任公司 | Suspension concentration evaporation device |
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