CN103044226B - Method for preparing cyclopentanone from adipic acid - Google Patents
Method for preparing cyclopentanone from adipic acid Download PDFInfo
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- CN103044226B CN103044226B CN201210571398.5A CN201210571398A CN103044226B CN 103044226 B CN103044226 B CN 103044226B CN 201210571398 A CN201210571398 A CN 201210571398A CN 103044226 B CN103044226 B CN 103044226B
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- cyclopentanone
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- hexanodioic acid
- adipic acid
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Abstract
The invention discloses a method for preparing cyclopentanone from adipic acid. The method comprises the following steps: (1) filling heat conduction oil in a reaction kettle, stirring, slowly adding a composite catalyst after heating to 100 DEG C, continuously dropping melted adipic acid after continuously heating to 250 DEG C, and controlling the reaction temperature to be 250 to 260 DEG C during the dropping process; (2) after condensing cyclopentanone generated during the reaction and water, collecting the condensed matter as hydrated ketone, and exhausting CO2 gas generated during the reaction from high altitude after being condensed; and (3) rectifying hydrated ketone obtained in the step (2) at normal pressure after being neutralized and salted out through sodium bicarbonate and sodium chloride to obtain a cyclopentanone finished product. The composite catalyst is prepared by mixing stannous oxide, borax, strontium carbonate and sodium dodecyl benzene sulfonate according to the mass ratio of 1:2:(6-8):0.05. According to the invention, the composite catalyst is adopted, so that the yield of cyclopentanone is improved, the polymerization and the carbonization of organic matters such as cyclopentanone and the like are reduced, produced hydrated ketone can reach more than 98%, and the unit consumption of adipic acid is low.
Description
Technical field
The present invention relates to a kind of production method of cyclopentanone, relate to specifically a kind of production method of preparing cyclopentanone with hexanodioic acid.
Background technology
Cyclopentanone (English name: Cyclopentanone), outward appearance is colourless liquid, has the smell of similar spearmint oil.Molecular formula is C
5h
8o, molecular weight is 84.12, fusing point-58.2 ℃, 130.6 ℃ of boiling points, miscible with alcohol, ether.Easily polymerization, particularly easier polymerization under Determining Micro Acid exists.Cyclopentanone is important fine-chemical intermediate, is widely used as the intermediate of solvent, medicine, spices, synthetic rubber, agricultural chemicals, and perfume industry is for the preparation of novel fragrance methyl dihydrojasmonate, also for Biochemical Research with as sterilant.
The industrial making method of cyclopentanone mainly contains cyclopentanol dehydriding, cyclopentene oxidizing, hexanodioic acid cyclisation method etc., and the current domestic hexanodioic acid cyclisation method that substantially all adopts.
It is typical decarboxylation, dehydration reaction that cyclopentanone is prepared in hexanodioic acid cyclisation, need under high temperature, high boiling solvent and catalyzer condition, carry out.Reaction is generally carried out continuously in tank reactor, and the carbon dioxide producing after hexanodioic acid decarboxylation, dehydration is easy to discharge, and the cyclopentanone and the water that produce need ceaselessly steam.Cyclopentanone is easy to occur autohemagglutination and poly under the existence of high temperature and catalyzer, in addition the organism charing at high temperature such as hexanodioic acid, cyclopentanone and solvent, therefore, prolongation along with the time, polymkeric substance and carbide are cumulative, to the viscosity of material in reactor be increased gradually, cause the most at last stirring and stop because of excess load.
Above-mentioned hexanodioic acid cyclisation legal system for the shortcoming of cyclopentanone is:
(1) because of autohemagglutination and poly and the organic charing of cyclopentanone, cause the yield of cyclopentanone to decline, the unit consumption of hexanodioic acid is higher, and at present general unit consumption is all in 2.1～2.2 levels;
(2), because of polymer build-up, the water ketone content of output can only reach 90～92%;
(3) time of successive reaction can only reach 20～25 days;
(4) the residual slagging scorification of still is harder, cleaning difficulty.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing cyclopentanone with hexanodioic acid, this generation method is by adopting composite catalyst to increase the surface-area of transition state intermediate, material in dispersion reactor, after cyclopentanone is generated, can by liquid internal, be diffused into surface rapidly and be steamed in time, reduce organic polymerization and the charings such as cyclopentanone, thereby improve the yield of cyclopentanone.In the method, hexanodioic acid unit consumption water ketone content low, output is high, continuous reaction time is long, the residual not slagging scorification of still.
The present invention is achieved through the following technical solutions:
A method of preparing cyclopentanone with hexanodioic acid, comprises the following steps:
(1) in reactor, drop into thermal oil, stir, be warming up to after 100 ℃, slowly add composite catalyst, continue to be warming up to after 250 ℃, drip continuously the hexanodioic acid after melting, in dropping process, control temperature of reaction at 250 ℃～260 ℃;
(2) reaction produces cyclopentanone and water are collected as water ketone after condensation, carbon dioxide high altitude discharge after condensation that reaction produces;
(3) the water ketone that step (2) obtains is after sodium bicarbonate and sodium-chlor neutralization, saltouing, and atmospheric distillation obtains cyclopentanone finished product.
Composite catalyst be by tin protoxide, borax, Strontium carbonate powder, Sodium dodecylbenzene sulfonate in mass ratio 1:2:6～8:0.05 mix.
The mass ratio of described thermal oil and composite catalyst is 10:0.9～1.1.
300 ℃ of described thermal oil boiling point >.
The present invention compares tool with current technology and has the following advantages:
(1) because adopting composite catalyst, improved the yield of cyclopentanone.
(2) because adopting composite catalyst, reduce organic polymerization and the charings such as cyclopentanone, the water ketone of output can reach more than 98%.
(3) hexanodioic acid unit consumption is low.
(4) continuous reaction time is long, and one-period can reach more than 35 days.
(5) the residual not slagging scorification of still, has saved the clear still time, has improved efficiency.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but scope of the present invention is not had to any restriction.
Embodiment mono-:
Composite catalyst preparation: 5kg tin protoxide, 10kg borax, 35kg Strontium carbonate powder, 2.5kg Sodium dodecylbenzene sulfonate are mixed.
In reactor, drop into 500kg thermal oil, stir, be warming up to 100 ℃, slowly add 50kg composite catalyst, continue to be warming up to 250 ℃, with the speed of about 40kg per hour, drip continuously the hexanodioic acid after thawing, in dropping process, control temperature of reaction at 250 ℃～260 ℃.Cyclopentanone and water that reaction produces are collected as water ketone after condensation, carbon dioxide high altitude discharge after condensation that reaction produces.The about 27.5kg of collection water ketone per hour, cyclopentanone content 98.3% in water ketone.Continuous dosing reaches 35 days, and agitator motor electric current obviously increases, stop feeding intake, and in still during not discharging, by still temperature drop to 50 ℃ left and right, not slagging scorification in still, emptying still is residual.
Water ketone is after sodium bicarbonate and sodium-chlor are neutralized to neutrality, saltout, and atmospheric distillation obtains cyclopentanone finished product.
Continuous dosing 35 days, drops into hexanodioic acid 33600kg altogether, produces the about 23200kg of water ketone, through neutralizing, saltout, rectifying obtains cyclopentanone significant quantity 17680kg.Finished product content > 99.5%, hexanodioic acid unit consumption 1.9.
Embodiment bis-:
Composite catalyst preparation: 5kg tin protoxide, 10kg borax, 40kg Strontium carbonate powder, 2.5kg Sodium dodecylbenzene sulfonate are mixed.
In reactor, drop into 500kg thermal oil, stir, be warming up to 100 ℃, slowly add 55kg composite catalyst, continue to be warming up to 250 ℃, with the speed of about 40kg per hour, drip continuously the hexanodioic acid after thawing, in dropping process, control temperature of reaction at 250 ℃～260 ℃.Cyclopentanone and water that reaction produces are collected as water ketone after condensation, carbon dioxide high altitude discharge after condensation that reaction produces.The about 27.6kg of collection water ketone per hour, cyclopentanone content 98.1% in water ketone.Continuous dosing reaches 35 days, and agitator motor electric current obviously increases, stop feeding intake, and in still during not discharging, by still temperature drop to 50 ℃ left and right, not slagging scorification in still, emptying still is residual.
Water ketone is after sodium bicarbonate and sodium-chlor are neutralized to neutrality, saltout, and atmospheric distillation obtains cyclopentanone finished product.
Continuous dosing 35 days, drops into hexanodioic acid 33600kg altogether, produces the about 23300kg of water ketone, through neutralizing, saltout, rectifying obtains cyclopentanone significant quantity 17670kg.Finished product content > 99.5%, hexanodioic acid unit consumption 1.902.
Embodiment tri-:
Composite catalyst preparation: 5kg tin protoxide, 10kg borax, 30kg Strontium carbonate powder, 2.5kg Sodium dodecylbenzene sulfonate are mixed.
In reactor, drop into 500kg thermal oil, stir, be warming up to 100 ℃, slowly add 45kg composite catalyst, continue to be warming up to 250 ℃, with the speed of about 40kg per hour, drip continuously the hexanodioic acid after thawing, in dropping process, control temperature of reaction at 250 ℃～260 ℃.Cyclopentanone and water that reaction produces are collected as water ketone after condensation, carbon dioxide high altitude discharge after condensation that reaction produces.The about 27.4kg of collection water ketone per hour, cyclopentanone content 98.2% in water ketone.Continuous dosing reaches 35 days, and agitator motor electric current obviously increases, stop feeding intake, and in still during not discharging, by still temperature drop to 50 ℃ left and right, not slagging scorification in still, emptying still is residual.
Water ketone is after sodium bicarbonate and sodium-chlor are neutralized to neutrality, saltout, and atmospheric distillation obtains cyclopentanone finished product.
Continuous dosing 35 days, drops into hexanodioic acid 33600kg altogether, produces the about 23100kg of water ketone, through neutralizing, saltout, rectifying obtains cyclopentanone significant quantity 17660kg.Finished product content > 99.5%, hexanodioic acid unit consumption 1.903.
Claims (3)
1. with hexanodioic acid, prepare the method for cyclopentanone, it is characterized in that comprising the following steps:
(1) in reactor, drop into thermal oil, stir, be warming up to after 100 ℃, slowly add composite catalyst, continue to be warming up to after 250 ℃, drip continuously the hexanodioic acid after melting, in dropping process, control temperature of reaction at 250 ℃～260 ℃;
(2) reaction produces cyclopentanone and water are collected as water ketone after condensation, carbon dioxide high altitude discharge after condensation that reaction produces;
(3) the water ketone that step (2) obtains is after sodium bicarbonate and sodium-chlor neutralization, saltouing, and atmospheric distillation obtains cyclopentanone finished product;
Composite catalyst be by tin protoxide, borax, Strontium carbonate powder, Sodium dodecylbenzene sulfonate in mass ratio 1:2:6～8:0.05 mix.
2. a kind of method of preparing cyclopentanone with hexanodioic acid as claimed in claim 1, is characterized in that: the mass ratio of described thermal oil and composite catalyst is 10:0.9～1.1.
3. a kind of method of preparing cyclopentanone with hexanodioic acid as claimed in claim 1, is characterized in that: 300 ℃ of described thermal oil boiling point >.
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| CN201210571398.5A CN103044226B (en) | 2012-12-26 | 2012-12-26 | Method for preparing cyclopentanone from adipic acid |
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| CN105195063B (en) * | 2015-09-29 | 2017-10-27 | 山东国润生物医药有限公司 | A kind of decarboxylation device that cyclopentanone is prepared for adipic acid |
| CN105418342A (en) * | 2015-11-09 | 2016-03-23 | 贝利化学（张家港）有限公司 | High-temperature decarboxylation method |
| CN105585827A (en) | 2016-03-07 | 2016-05-18 | 金发科技股份有限公司 | Biodegradable polyester composition |
| CN105585826A (en) | 2016-03-07 | 2016-05-18 | 金发科技股份有限公司 | Biodegradable polyester composition |
| CN105585825A (en) | 2016-03-07 | 2016-05-18 | 杨红梅 | Biodegradable polyester composition |
| CN105713356B (en) | 2016-03-07 | 2017-05-31 | 杨红梅 | A kind of Biodegradable polyester composition |
| CN105585824A (en) | 2016-03-07 | 2016-05-18 | 金发科技股份有限公司 | Biodegradable polyester composition |
| CN108912081A (en) * | 2018-06-18 | 2018-11-30 | 苏州盖德精细材料有限公司 | A kind of synthetic method of medicine intermediate Tetrahydro-pyran-4-one |
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| CN1284761C (en) * | 2004-06-21 | 2006-11-15 | 沈阳工业大学 | Method for producing cyclopentanone, cyclopentanol |
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