CN102816054A - Environment-friendly method for preparing adipic acid by catalytic oxidation - Google Patents
Environment-friendly method for preparing adipic acid by catalytic oxidation Download PDFInfo
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- CN102816054A CN102816054A CN201210314963XA CN201210314963A CN102816054A CN 102816054 A CN102816054 A CN 102816054A CN 201210314963X A CN201210314963X A CN 201210314963XA CN 201210314963 A CN201210314963 A CN 201210314963A CN 102816054 A CN102816054 A CN 102816054A
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Abstract
The invention discloses an environment-friendly method for preparing adipic acid by catalytic oxidation. The method includes: at the beginning of reaction, adding cyclohexane, butanone serving as solvent, cyclohexanone serving as initiators and activated carbon supported nano-gold catalysts into a stainless steel high-pressure reactor; carrying out the catalytic oxidation reaction for 3-14 hours under the pressure of 0.9-2.1MPa at the temperature of 100-150 DEG C; separating after the reaction is completed to obtain the activated carbon supported nano-gold catalysts and reaction liquor, and processing the reaction liquor to obtain adipic acid crystalline solid; collecting the cyclohexanone serving as the initiators by oil-phase vacuum rotary steaming; and washing and drying the activated carbon supported nano-gold catalysts for recycling. By the method, solvent effect of the butanone serving as the solvent is particularly suitable for the nano-gold catalysts to catalyze the cyclohexane to generate the adipic acid by means of selective oxidation, and the problems of low activity and proneness to inactivation of the catalysts in reaction are solved. The method is simple in technological process, convenient for preparing and separating the catalysts, mild in reaction conditions, low in technological cost, economic, efficient and environment-friendly and pollution-free as molecular oxygen substitutes for nitric acid to be used as oxidants.
Description
Technical field
The present invention relates to the method that a kind of environment protection catalytic oxidation prepares hexanodioic acid.
Background technology
Hexanodioic acid is widely used in industrial circles such as chemistry, medicine, food as a kind of important organic intermediate and raw material, and industrial requirement is very big.Existing Production Processes of Adipic Acid is mainly hexanaphthene two-step oxidation method, needs to use nitric acid to be oxygenant, and the oxynitride that produces in the technological process has caused the serious environmental pollution.For replacing nitric acid oxidation method, Chinese scholars has been done number of research projects to one-step catalytic oxidation system hexanodioic acid, but the process method that can accomplish to take into account simultaneously environmental protection and high efficiency, low cost is still demanded urgently finding.
In recent years; For improving the transformation efficiency and the selectivity of single stage method system adipic acid; A large amount of new catalysts are developed; Wherein homogeneous catalyst accounts for the overwhelming majority, prepares hexanodioic acid as using metalloporphyrin to do the catalyst cyclohexane oxidation among use four hydration Cobaltous diacetates, ZL200310110458 and the ZL200310110349 among the Chinese patent CN95195040.1.It below all is homogeneous catalyst; Catalytic effect is remarkable; But, be to solve the problem of homogeneous catalyst separation difficulty, complicated extraction cells also need be set to accomplish separating of product and catalyzer; As proposing the extraction process separating catalyst among patent CN1344240A and the CN1308599A, make the technology cost greatly increase like this.
For overcoming the difficult problem of catalyst separating, heterogeneous catalyst becomes the research focus.Recent research a type of heat is a carrier nanometer catalyst; Wherein load type nano gold catalyst is the great discovery of catalytic field in recent years, has found that at present this catalyzer has a good application prospect in fields such as the elimination of CO LTO, oxynitride, liquid phase selective oxidation, water-gas shift.From 2004, nano catalyst was applied to cyclohexane oxidation, and this heterogeneous catalyst has solved the problem of homogeneous catalyst separation difficulty, shows certain catalytic activity simultaneously.In disclosed patents; Chinese patent CN102060656A adopts hydrothermal synthesis method to prepare that supported nanometer gold catalyst is used for hexanaphthene catalyzed oxidation preparing cyclohexanone on the HTS, patent CN1772723A uses mesopore molecular sieve to come supported nanometer gold catalyst catalysis cyclohexane oxidation preparing cyclohexanone, and two patent gained catalyzer all provide the alcohol ketone selectivity more than 90%.Li.X. etc. (Catal.Lett.2007,114,202-206) reported Au/Au
2O
3The method of catalysis cyclohexane oxidation system hexalin, pimelinketone.Yet because the cyclohexane oxidation of highly selective needs the pyritous severe condition mostly, and the distinctive low temperature active of Au catalyst is restricted this catalyzed reaction and is difficult to play a role.This feasible investigation to nano catalyst all stops at nano gold catalysis cyclohexane oxidation system hexalin and pimelinketone, and can only under extremely low transformation efficiency, could obtain higher selectivity.When being used to the hexanaphthene single stage method, nano catalyst produces hexanodioic acid; Because long reaction time, temperature of reaction height; Nano catalyst just is difficult to show good catalytic activity; And be more prone to inactivation, be not used for the report of hexanaphthene oxidation step system hexanodioic acid so see load type nano gold catalyst up to now.
Summary of the invention
The objective of the invention is in order to overcome the deficiency of prior art, provide a kind of environment protection catalytic oxidation to prepare the method for hexanodioic acid.
Prepare the method for hexanodioic acid, step is following:
When 1) reacting initial, in the stainless steel autoclave, add hexanaphthene, solvent butanone, initiator pimelinketone and activated carbon supported type nano catalyst; Described hexanaphthene and solvent butanone mass ratio are 0.6 ~ 7.7:1, and hexanaphthene and initiator pimelinketone mass ratio are 150 ~ 70:1, and hexanaphthene and activated carbon supported type nano catalyst mass ratio are 138.4 ~ 1245.6:1; Under 100 ~ 150 ℃ of temperature, pressure 0.9 ~ 2.1MPa, be that oxygenant carried out catalytic oxidation 3 ~ 14 hours with oxygen;
2) after reaction finished, spinning obtained activated carbon supported type nano catalyst and reaction solution, and reaction solution obtains oil phase and water after extracting three times with deionized water, and water was cooled off 12 hours down at 0 ℃, obtains the crystallization of adipic acid solid; The oil phase vacuum is revolved steaming, collect the initiator pimelinketone, it is returned reaction kettle react again; Activated carbon supported type nano catalyst is with washing with acetone three times, and 120 ℃ down after dry 5 hours, recycle.
Described activated carbon supported type nano catalyst adopts the chemical reduction method preparation, and gac is 200 ~ 230 order active fruit shell carbons; Nm gold particles is 2 ~ 6nm; Golden amount degree is 0.5 ~ 2.5%, and the quality of activated carbon degree is 97.5 ~ 99.5%.
The beneficial effect that the present invention compared with prior art has:
1) the one-step technology flow process is simple, has saved the operation and the equipment cost of traditional nitric acid oxidation two-step approach;
2) form effective recycle operation, practice thrift cost, efficient is high;
3) oxygen replaces nitric acid as oxygenant, and environmental protection is pollution-free, and equipment is not perishable;
4) use solid catalyst, easily separated recovery can reuse, and absorbent charcoal carrier is cheap and easy to get;
5) the nano catalyst preparation method is simple, and nano particle is shaped good, in the solvent butanone, is used for cyclohexane oxidation system hexanodioic acid, has significant catalytic activity;
6) butanone is as solvent; Not only be beneficial to hexanaphthene and the proportional absorption of molecular oxygen in the catalyzer duct; And be that solid catalyst, liquid cyclohexane and gas molecular oxygen provide good reaction environment---special roles such as its polarization, static, chromatic dispersion to solute; Improved nano catalyst serious problem of inactivation in this reaction greatly; And reducing reaction required temperature, time, pressure condition, both synergistic effects make nano catalyst in cyclohexane oxidation, show significant catalytic activity;
7) with in the primary first-order equation, cyclohexane conversion can reach 44.93%, and the hexanodioic acid selectivity can reach 54.85%, and KA oil (hexalin and pimelinketone) selectivity reaches 27.11% simultaneously.
Description of drawings
Fig. 1 is cyclohexane oxidation product chromatography of gases figure.
Fig. 2 is chromatography of gases figure behind the cyclohexane oxidation product derivatize.
Fig. 3 is the TEM figure of activated carbon supported type nano catalyst.
Fig. 4 is the X-ray diffractogram of activated carbon supported type nano catalyst.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described.
Embodiment 1
In reaction kettle, add 74mmol hexanaphthene, 7ml solvent butanone (hexanaphthene and butanone mass ratio are 1.1:1), (the Au massfraction is 1.25% to the activated carbon supported type nano catalyst of 33mg; Hexanaphthene and catalyst quality are than being 188.7:1), 0.7mmol initiator pimelinketone (hexanaphthene and pimelinketone mass ratio are 90.6:1), magnetic agitation be sub; Open magnetic agitation, under 130 ℃, aerating oxygen; Keep oxygen pressure at 1.5MPa, react 8 hours postcooling to room temperature.Spinning obtains activated carbon supported type nano catalyst and reaction solution; Get a little partial reaction liquid and be used for result's detection; The rest part reaction solution obtains oil phase and water after extracting three times with deionized water, and water was cooled off 12 hours down at 0 ℃, obtains the crystallization of adipic acid solid; The oil phase vacuum is revolved steaming, collect the initiator pimelinketone, it is returned reaction kettle react again; Activated carbon supported type nano catalyst is with washing with acetone three times, and 120 ℃ down after dry 5 hours, recycle.
Described activated carbon supported type nano catalyst adopts the chemical reduction method preparation, and gac is 200 ~ 230 order active fruit shell carbons; Nm gold particles is 2 ~ 6nm; Golden amount degree is 0.5 ~ 3.0%, and the quality of activated carbon degree is 97 ~ 99.5%.The preparation method of said activated carbon supported type nano catalyst is following:
(1) under the normal temperature, in the there-necked flask of cleaning, adds deionized water, magnetic agitation that an amount of resistivity is 18.3M Ω cm, open magnetic agitation;
(2) transfer pipet pipettes 2.1ml concentration and is that the 0.01g/ml chlorauric acid solution adds there-necked flask;
(3), add the 1ml massfraction and be 1% polyvinyl alcohol solution with solution stirring in there-necked flask in (2) after 5 minutes;
(4) solution stirring in the there-necked flask in (3) was slowly added the sodium borohydride solution that 2.05ml concentration is 0.1mol/L after 10 minutes;
Treat that (5) (4) gained solution colour no longer changes, and inwardly adds the 2g gac and gets suspension liquid;
(6) the suspension liquid stirring at normal temperature after 1 hour, is used the sand core funnel suction filtration, the gained solid does not have cl ions with deionized water wash to filtrating;
(7) will wash to the neutral catalyzer and place loft drier, 140 ℃ of dry 8h down, be cooled to room temperature after, grind evenly, the gained solid is activated carbon supported type nano catalyst.
The composition of reaction solution sample is at first through gas chromatography appearance (GC-MS) Analysis and Identification.Confirm that principal product is hexanodioic acid, hexalin, pimelinketone, by product is cyclohexyl hydroperoxide, other organic acid (like pentanedioic acid, Succinic Acid, caproic acid etc.), organic ester (like cyclohexyl, lactone etc.).The principal product quantitative analysis is carried out having on the GC-1690 gas chromatograph of SE-54 capillary column, and detector is a hydrogen flame ionization detector.Directly use residue ring hexane, pimelinketone, hexalin in the chromatogram ration analysis product, like color atlas (Fig. 1); After reaction solution carried out the esterification derivative reaction, the content of quantitative analysis dimethyl adipate was to confirm the content of hexanodioic acid, like color atlas (Fig. 2).By product in the chemistry titration quantitative analysis product.In the present embodiment, cyclohexane conversion 44.93%, hexanodioic acid selectivity 54.85%.
In reaction kettle, add 74mmol hexanaphthene, 7ml butanone, 33mg catalyzer (golden amount per-cent is 1.5%), 0.7mmol pimelinketone and magnetic agitation, open magnetic agitation.Under 130 ℃, aerating oxygen is kept oxygen pressure at 1.5MPa, reacts 8 hours postcooling to room temperature.Product separation and analytical procedure are with embodiment 1.Among the embodiment 2 ~ 8, the golden amount mark of catalyzer is respectively 0.5%, 0.75%, 1.0%, 1.25%, 1.5%, 2.0%, 2.5%.Cyclohexane conversion and hexanodioic acid selectivity are seen table 1.
Table 1 embodiment 2 ~ 8 quantitative analysis results
a
aReaction conditions: 74mmol hexanaphthene, 33mg catalyzer (1.5%Au), 7ml butanone, 0.7mmol pimelinketone, 130 ℃, 1.5MPa, 8h
bKA oil: hexalin and pimelinketone close claims KA oil
Embodiment 9 ~ embodiment 13
In reaction kettle, add 74mmol hexanaphthene, 7ml butanone, 33mg catalyzer (golden amount per-cent is 1.5%); 0.7mmol pimelinketone and magnetic agitation are opened magnetic agitation, at a certain temperature; Aerating oxygen is kept oxygen pressure at 1.5MPa, reacts 8 hours postcooling to room temperature.Product separation and analytical procedure are with embodiment 1.Among the embodiment 9 ~ 13, temperature of reaction is respectively 100 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃.Cyclohexane conversion and hexanodioic acid selectivity are seen table 2.
Table 2 embodiment 9 ~ 13 quantitative analysis results
a
aReaction conditions: 74mmol hexanaphthene, 33mg catalyzer (1.5%Au), 7ml butanone, 0.7mmol pimelinketone, 1.5MPa, 8h
bKA oil: hexalin and pimelinketone close claims KA oil
In reaction kettle, add 74mmol hexanaphthene, 7ml butanone, 33mg catalyzer (golden amount per-cent is 1.5%); 0.7mmol pimelinketone and magnetic agitation are opened magnetic agitation, under 130 ℃; Aerating oxygen is kept oxygen pressure at 1.5MPa, and reaction certain hour postcooling is to room temperature.Product separation and analytical procedure are with embodiment 1.Among the embodiment 14 ~ 18, the reaction times is respectively 3h, 5h, 8h, 11h, 14h.Cyclohexane conversion and hexanodioic acid selectivity are seen table 3.
Table 3 embodiment 14 ~ 18 quantitative analysis results
a
aReaction conditions: 74mmol hexanaphthene, 33mg catalyzer (1.5%Au), 7ml butanone, 0.7mmol pimelinketone, 130 ℃, 1.5MPa
bKA oil: hexalin and pimelinketone close claims KA oil
Embodiment 19 ~ embodiment 23
In reaction kettle, add 74mmol hexanaphthene, 7ml butanone, 33mg catalyzer (golden amount per-cent is 1.5%); 0.7mmol pimelinketone and magnetic agitation are opened magnetic agitation, under 130 ℃; Aerating oxygen is kept certain oxygen pressure, reacts 8 hours postcooling to room temperature.Product separation and analytical procedure are with embodiment 1.Among the embodiment 19 ~ 23, oxygen pressure is respectively 0.9MPa, 1.2MPa, 1.5MPa, 1.8MPa, 2.1MPa.Cyclohexane conversion and hexanodioic acid selectivity are seen table 4.
Table 4 embodiment 19 ~ 23 quantitative analysis results
a
aReaction conditions: 74mmol hexanaphthene, 33mg catalyzer (1.5%Au), 7ml butanone, 0.7mmol pimelinketone, 130 ℃, 8h
bKA oil: hexalin and pimelinketone close claims KA oil
Embodiment 24 ~ embodiment 28
In reaction kettle, add the 74mmol hexanaphthene, the 7ml butanone, a certain amount of catalyzer, 0.7mmol pimelinketone and magnetic agitation are opened magnetic agitation, and under 130 ℃, aerating oxygen is kept oxygen pressure 1.5MPa, reacts 5 hours postcooling to room temperature.Product separation and analytical procedure are with embodiment 1.Among the embodiment 24 ~ 28, catalyst levels is respectively 5mg, 15mg, 25mg, 30mg, 45mg.Cyclohexane conversion and hexanodioic acid selectivity are seen table 5.
Table 5 embodiment 24 ~ 28 quantitative analysis results
a
aReaction conditions: the 74mmol hexanaphthene, selecting the Au mass percent for use is 1.5% catalyzer, 7ml butanone, 0.7mmol pimelinketone, 130 ℃, 1.5MPa, 5h
bKA oil: hexalin and pimelinketone close claims KA oil
Embodiment 29 ~ embodiment 35
In reaction kettle, add the 74mmol hexanaphthene, 42mg catalyzer (golden amount per-cent is 1.5%), 0.7mmol pimelinketone and magnetic agitation are opened magnetic agitation, and under 130 ℃, aerating oxygen is kept oxygen pressure 1.5MPa, reacts 8 hours postcooling to room temperature.Product separation and analytical procedure are with embodiment 1.The catalyzer that recovery is obtained repeats this reaction.Among the embodiment 29 ~ 35, the butanone consumption is respectively 0ml, 1ml, 2ml, 5ml, 7ml, 10ml, 12ml.Cyclohexane conversion and hexanodioic acid selectivity are seen table 6.
Table 6 embodiment 29 ~ 35 quantitative analysis results
a
aReaction conditions: 74mmol hexanaphthene, 33mg catalyzer (1.5%Au), 7ml butanone, 0.7mmol pimelinketone, 130 ℃, 1.5MPa, 8h
bKA oil: hexalin and pimelinketone close claims KA oil
Embodiment 36 ~ embodiment 39
In reaction kettle, add 74mmol hexanaphthene, 42mg catalyzer (golden amount per-cent is 1.25%), 7ml butanone; A certain amount of pimelinketone and magnetic agitation are opened magnetic agitation, under 130 ℃; Aerating oxygen is kept oxygen pressure 1.5MPa, reacts 8 hours postcooling to room temperature.Product separation and analytical procedure are with embodiment 1.The catalyzer that recovery is obtained repeats this reaction.Among the embodiment 36 ~ 39, the pimelinketone consumption is respectively 0mmol, 0.1mmol, 0.7mmol, 5mmol.Cyclohexane conversion and hexanodioic acid selectivity are seen table 6.
Table 6 embodiment 36 ~ 39 quantitative analysis results
a
aReaction conditions: 74mmol hexanaphthene, 42mg catalyzer (1.25%Au), 7ml butanone, 130 ℃, 1.5MPa, 8h
bKA oil: hexalin and pimelinketone close claims KA oil.
Claims (2)
1. an environment protection catalytic oxidation prepares the method for hexanodioic acid, it is characterized in that its step is following:
When 1) reacting initial, in the stainless steel autoclave, add hexanaphthene, solvent butanone, initiator pimelinketone and activated carbon supported type nano catalyst; Described hexanaphthene and solvent butanone mass ratio are 0.6 ~ 7.7:1, and hexanaphthene and initiator pimelinketone mass ratio are 12.7 ~ 634.6:1, and hexanaphthene and activated carbon supported type nano catalyst mass ratio are 138.4 ~ 1245.6:1; Under 100 ~ 150 ℃ of temperature, oxygen pressure 0.9 ~ 2.1MPa, carried out catalytic oxidation 3 ~ 14 hours;
2) reaction finishes postcooling to room temperature, and spinning obtains activated carbon supported type nano catalyst and reaction solution, and reaction solution obtains oil phase and water after extracting three times with deionized water, and water was cooled off 12 hours down at 0 ℃, obtains the crystallization of adipic acid solid; The oil phase vacuum is revolved steaming, collect the initiator pimelinketone, it is returned reaction kettle react again; Activated carbon supported type nano catalyst is with washing with acetone three times, and 120 ℃ down after dry 5 hours, recycle.
2. a kind of environment protection catalytic oxidation according to claim 1 prepares the method for hexanodioic acid; It is characterized in that; Described activated carbon supported type nano catalyst adopts the chemical reduction method preparation, and gac is 200 ~ 230 order active fruit shell carbons, and the nm gold particles particle diameter is 2 ~ 6nm; Golden amount degree is 0.5 ~ 2.5%, and the quality of activated carbon degree is 97.5 ~ 99.5 %.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254491A (en) * | 2015-09-29 | 2016-01-20 | 衢州群颖化学科技有限公司 | Adipic acid and KA oil co-production method |
| CN105642214A (en) * | 2016-01-12 | 2016-06-08 | 杭州海虹精细化工有限公司 | Vertical bottom stirring reaction still and environment-friendly process for producing hexanedioic acid through still reaction |
| CN112742367A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Method for catalytic oxidation of cycloalkane |
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| US5756837A (en) * | 1994-07-21 | 1998-05-26 | Rhone-Poulenc Fiber & Resin Intermediates | Method of recycling a catalyst in a reaction involving the direct oxidation of cyclohexane into adipic acid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254491A (en) * | 2015-09-29 | 2016-01-20 | 衢州群颖化学科技有限公司 | Adipic acid and KA oil co-production method |
| CN105642214A (en) * | 2016-01-12 | 2016-06-08 | 杭州海虹精细化工有限公司 | Vertical bottom stirring reaction still and environment-friendly process for producing hexanedioic acid through still reaction |
| CN112742367A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Method for catalytic oxidation of cycloalkane |
| CN112742367B (en) * | 2019-10-29 | 2023-07-11 | 中国石油化工股份有限公司 | Method for catalytic oxidation of cycloalkane |
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