CN105884598A - Method for performing biomimetic catalysis and air oxidation on cyclohexane with pure natural preparation - Google Patents
Method for performing biomimetic catalysis and air oxidation on cyclohexane with pure natural preparation Download PDFInfo
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- CN105884598A CN105884598A CN201510011352.1A CN201510011352A CN105884598A CN 105884598 A CN105884598 A CN 105884598A CN 201510011352 A CN201510011352 A CN 201510011352A CN 105884598 A CN105884598 A CN 105884598A
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- haemachrome
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- adipic acid
- hexalin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The invention relates to a new method for performing selective catalytic oxidation on cyclohexane to successfully prepare cyclohexanone, cyclohexanol and adipic acid with the pure natural biochemical preparation protoheme as a catalyst and air as an oxidizing agent. According to the method, technological conditions are mild, only the air pressure of 0.6-2 MPa and the temperature of 110-165 DEG C are needed, no solvent needs to be added, and the selectivity of products is 90% or above. Protoheme with a mono-metalloporphyrin structure is a natural bio-enzyme active centre and is very suitable for being used in a biomimetic catalysis chemical reaction system as a high-efficiency and high-selectivity catalyst; besides, protoheme is extremely small in dosage and can be reused. Due to the special structure, protoheme can be easily prepared into various immobilized catalysts. The cost of the catalyst in the technology is reduced to the minimum, and the technology is simple and environmentally friendly.
Description
Technical field
The present invention relates to a kind of method being prepared Ketohexamethylene, Hexalin and adipic acid by air oxidation of cyclohexane, particularly to a kind of method using biochemical preparation haemachrome catalytic air oxidation hexamethylene to prepare Ketohexamethylene, Hexalin and adipic acid.
Technical background
Ketohexamethylene and the mixture of Hexalin that hexamethylene is prepared through air oxidation are commonly called as KA oil, are industrial production caprolactam and the base stock of adipic acid.Caprolactam is the monomer producing polyamide nylon-6, and adipic acid is then the monomer producing nylon-66.In addition KA oil and adipic acid also all have important application in solvent, resin and other many field of chemicals.
Cyclohexane oxidation technique the most conventional mainly has the cobalt salt catalytic oxidation developed by DuPont and the non-catalyst oxidation method of DSM N. V. of Holland exploitation.But the hexamethylene conversion per pass of both approaches is the highest, general control is 4～about 5%, and the selectivity of KA oil the most also only has 80%, or more slightly higher.This just makes the production cost of KA oil remain high always.For changing this situation, selecting both at home and abroad before and after 2000NovelCatalyst, change reaction condition have done substantial amounts of research work to improve the aspects such as selectivity and the conversion per pass of KA oil；And achieve bigger progress.The most prominent has the multiple molecular sieve catalyst having loaded metal ion, and the catalyst system and catalyzing of multiple use metalloporphyrin, is also called ' bionical ' catalyst system and catalyzing.A kind of μ-oxygen bimetallic porphyrin and the catalyst system and catalyzing of monometallic porphyrin is selected as CN 1405131A discloses.These new methods improve selectivity and the conversion per pass of cyclohexane oxidation technique the most to varying degrees.But above new method there is also some problems, generally there is obscission in the metal ion such as molecular sieve catalyst, decreases its cyclic utilization rate.The catalyst of metalloporphyrin then has preparation cost higher, and can produce a large amount of reluctant asphalt waste during preparation, and the problem such as the cyclic utilization rate of catalyst is the highest.
Summary of the invention
Present invention employs the biochemical preparation haemachrome catalyst as catalysis air oxidation of cyclohexane reaction of pure natural；The conversion ratio with hexamethylene is high, and the yield of oxidation product Ketohexamethylene, Hexalin and the adipic acid of good reaction selectivity and reaction all compares high feature.Shown in haemachrome structure such as formula (I),
It contains a natural porphyrin ring, thus is undertaken multinomial important physiological function in vivo, as fixed oxygen molecule, transport and activation etc..So haemachrome natural just have preferably be catalyzed activity and selectivity than the catalysis of metalloporphyrin agent of ' bionical '.Haemachrome originates from natural simultaneously, is not required to synthesis thus the preparation cost that produces during also avoiding to prepare catalysis of metalloporphyrin agent is high, waste residue is difficult to the problems such as process.In addition from haemachrome structure it can also be seen that it is prone to be processed to loaded catalyst, thus higher cyclic utilization rate is obtained.
The present invention uses air oxidation in technique, it is not necessary to relatively costly oxygen or oxygen-enriched air, has the function of higher capture and activating oxygen molecule because haemachrome is natural.Have only to a little site catalyst, be just adequate to bring about the free radical circulation coupled reaction of reaction system relative to the catalyst of raw material hexamethylene 0.01～10PPM.Compared to conventional cobalt salt catalytic oxidation and non-catalyst oxidation method also gentleness how reaction condition, it is only necessary to the air pressure of 0.6～2MPa, and the temperature of 110～185 DEG C, is not required to add any solvent, reacts 35～175 minutes；Can be product Ketohexamethylene, Hexalin and adipic acid by the cyclohexane oxidation of about more than 15% in response system, the selectivity of product be more than 90%.
The present invention has bigger degree of freedom to the selection of consersion unit, it is not necessary to special special equipment.Using conventional cobalt salt catalytic oxidation and the old equipment of non-catalyst oxidation method if having, using the new technology of the present invention, it is not necessary to add new equipment, it is only necessary to old equipment does some little changes can put into production.The older technique of reaction conversion ratio that typically can make hexamethylene is enhanced about more than once, and the selectivity of product Ketohexamethylene improves 10% or more preferable.In production process, reaction condition becomes gentleer simultaneously, saves energy consumption, reduces pollution, production cost is also greatly reduced, thus has good application prospect.
The haemachrome catalyst low price that the present invention uses, and consumption is few, general 1PPM (1/1000000th) i.e. has good effect, thus can be used alone as disposable catalyst.But fromFormula (I) structural formula of haemachrome can be seen that, haemachrome is easy to be supported on general carrier and is prepared as loaded catalyst, thus forms the catalytic center with certain complementary micro structure, improves the selectivity of catalysis further.Simultaneously the user of carrier the recovery of catalyst and being recycled for multiple times；The most further reduce production cost.Can be a lot of as the material of carrier, such as molecular sieve, aluminium oxide, resin, silica gel, porous ceramics, cotton products, gunny products, bamboo product, lignin, chitosan, kieselguhr, cyclodextrin, biomembrane, nano-particle and high molecular polymer etc..Carrying method can use simple infusion process, it would however also be possible to employ the method for the chemical bondings such as heating and chemical catalysis.
This reaction can add a small amount of promoter, to improve the selectivity of reaction, the conversion ratio of reaction further and to reduce the temperature of reaction.These additives include radical initiator, surfactant, organic complexing agent, ionic liquid, the salt of transition metal and metallo-organic compound.
The activity of this catalyst is the highest, as long as therefore extending the time of reaction further, raising reaction temperature or increase catalyst amount can improve the conversion ratio of hexamethylene further；But at this moment it is also possible to cause some side reactions thus reduces the selectivity of product.Thus it is necessary that the conversion ratio suitably controlling hexamethylene is to ensure that product is our required specific products.
Detailed description of the invention
Below in conjunction with being embodied as example, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
[embodiment 1]
In the stainless steel cauldron that volume is a liter, add hexamethylene 350 grams, chlorhematin 2 milligrams, build and this response system airtight.Temperature is also controlled at 135 DEG C by stirring, intensification, is imported air by reactor bottom simultaneously, and reactor top is provided with tail gas outlet, makes the pressure in reactor be maintained at 1.5MPa；Reaction 2 hours is continued after temperature, pressure reach designated value；Stopped reaction.Detection reaction solution；The conversion ratio of hexamethylene is 11.3%；The selectivity 95% of Ketohexamethylene, Hexalin and adipic acid.
[embodiment 2]
In the stainless steel cauldron that volume is 1 liter, add hexamethylene 350 grams, chlorhematin 6 milligrams, build and this response system airtight.Temperature is also controlled at 160 DEG C by stirring, intensification, is imported air by reactor bottom simultaneously, and reactor top is provided with tail gas outlet, makes the pressure in reactor be maintained at 1.8MPa；Reaction 2 hours is continued after temperature, pressure reach designated value；Stopped reaction.Detection reaction solution；The conversion ratio of hexamethylene is 15.2%；The selectivity 92% of Ketohexamethylene, Hexalin and adipic acid.
[embodiment 3]
In the stainless steel cauldron that volume is 1 liter, add hexamethylene 350 grams, chlorhematin 12 milligrams, build and this response system airtight.Temperature is also controlled at 165 DEG C by stirring, intensification, is imported air by reactor bottom simultaneously, and reactor top is provided with tail gas outlet, makes the pressure in reactor be maintained at 1.8MPa；Reaction 2 hours is continued after temperature, pressure reach designated value；Stopped reaction.Detection reaction solution；The conversion ratio of hexamethylene is 17.5%；The selectivity 91% of Ketohexamethylene, Hexalin and adipic acid.
[embodiment 4]
In the rustless steel bubble tower type reactor that volume is 3 liters, add hexamethylene 1800 grams, chlorhematin 3 milligrams, build and this response system airtight.Temperature is also controlled at 135 DEG C by stirring, intensification, is imported air by reactor bottom simultaneously, and reactor top is provided with tail gas outlet, makes the pressure in reactor be maintained at 1.6MPa；Reaction 5 hours is continued after temperature, pressure reach designated value；Stopped reaction.Detection reaction solution；The conversion ratio of hexamethylene is 23.5%；The selectivity 96% of Ketohexamethylene, Hexalin and adipic acid.
[embodiment 5]
In the rustless steel bubble tower type reactor that volume is 3 liters, add hexamethylene 1800 grams, chlorhematin 15 milligrams, build and this response system airtight.Temperature is also controlled at 165 DEG C by stirring, intensification, is imported air by reactor bottom simultaneously, and reactor top is provided with tail gas outlet, makes the pressure in reactor be maintained at 1.6MPa；Reaction 5 hours is continued after temperature, pressure reach designated value；Stopped reaction.Detection reaction solution；The conversion ratio of hexamethylene is 25.7%；The selectivity 93% of Ketohexamethylene, Hexalin and adipic acid.
[embodiment 6]
In the rustless steel bubble tower type reactor that volume is 3 liters, add hexamethylene 1800 grams, chlorhematin 5 milligrams, build and this response system airtight.Temperature is also controlled at 165 DEG C by stirring, intensification, is imported air by reactor bottom simultaneously, and reactor top is provided with tail gas outlet, makes the pressure in reactor be maintained at 1.8MPa；Reaction 3 hours is continued after temperature, pressure reach designated value；Discharged partial reaction solution about 800g by bottom, close outlet, continue reaction 2 hours, stopped reaction.Discharge remaining reactant liquor, merge with the previous reactant liquor discharged, detect reaction solution；The conversion ratio of hexamethylene is 32.6%；The selectivity 91% of Ketohexamethylene, Hexalin and adipic acid.
[embodiment 7]
In the rustless steel bubble tower type reactor that volume is 3 liters, add hexamethylene 1800 grams, add the Catalysis by Hemin agent 80 milligrams that wood flour is immobilized, build and this response system airtight.Temperature is also controlled at 145 DEG C by stirring, intensification, is imported air by reactor bottom simultaneously, and reactor top is provided with tail gas outlet, makes the pressure in reactor be maintained at 1.8MPa；Reaction 3 hours is continued after temperature, pressure reach designated value；Discharged partial reaction solution about 800g by bottom, close outlet, continue reaction 2 hours, stopped reaction.Discharge remaining reactant liquor, merge with the previous reactant liquor discharged, detect reaction solution；The conversion ratio of hexamethylene is 35.1%；The selectivity 94% of Ketohexamethylene, Hexalin and adipic acid.
[embodiment 8]
In the rustless steel bubble tower type reactor that volume is 3 liters, add hexamethylene 1800 grams, add the Catalysis by Hemin agent 60 milligrams that bamboo bits are immobilized, build and this response system airtight.Temperature is also controlled at 145 DEG C by stirring, intensification, is imported air by reactor bottom simultaneously, and reactor top is provided with tail gas outlet, makes the pressure in reactor be maintained at 1.6MPa；Reaction 3 hours is continued after temperature, pressure reach designated value；Discharged partial reaction solution about 800g by bottom, close outlet, continue reaction 2 hours, stopped reaction.Discharge remaining reactant liquor, merge with the previous reactant liquor discharged, detect reaction solution；The conversion ratio of hexamethylene is 33.1%；The selectivity 92% of Ketohexamethylene, Hexalin and adipic acid.
Claims (9)
1. use the method that pure natural preparation bionic catalysis air oxidation of cyclohexane prepares Ketohexamethylene, Hexalin and adipic acid, its
Being characterised by the biochemical preparation haemachrome that catalyst is pure natural, described haemachrome contains a natural porphyrin ring, and it is common
Dosage form be chlorhematin, its chemical structural formula such as formula (I)
Chloride ion therein is alternatively other halogens or acid radical anion, and the iron ion at the porphyrin ring center of same haemachrome can also use it
His metal ion replaces, such as the transition metal such as Co, Cu, Cr, Mn, Mo, Zn, Ni, Ru, Rh and Pd or rare earth gold
The cation belonged to.Natural haemachrome extracts mostly from the fresh blood of animal, many biochemical preparations of therefore being prepared by blood and
The semi-finished product of medicine, finished product and mixture all contain the composition of haemachrome；Haemachrome can also through simple oxidation, reduction,
Or the organic chemical reactions such as esterification, addition is prepared as the derivant of multiple haemachrome, above preparation can serve as this method to be made
Catalyst；The derivant of haemachrome and above-mentioned multiple haemachrome can be carried on multiple different carrier simultaneously,
It is prepared as loaded catalyst, is applied to the reaction of the bionic catalysis air oxidation of cyclohexane that the present invention relates to.
2. catalytic air oxidation hexamethylene as claimed in claim 1 prepare Ketohexamethylene, Hexalin and adipic acid method, its feature
Being, the carrier of supported catalyst can be molecular sieve, silica gel, aluminium oxide, zeolite, kieselguhr, porous ceramics, glass fibers
Dimension, resin, straw, wood flour, lignin, cotton products, fibre, chitosan, cyclodextrin, nano-particle, biology
Film, high molecular polymer and polymeric film etc..
3. the method that catalytic air oxidation hexamethylene as claimed in claim 1 prepares Ketohexamethylene, Hexalin and adipic acid, its feature exists
In, described carrying method includes infusion process, thermal chemical reaction and catalytic reaction bonding method.
4. the method that catalytic air oxidation hexamethylene as claimed in claim 1 prepares Ketohexamethylene, Hexalin and adipic acid, its feature exists
In, start material is the hexamethylene that liquid is pure, is not required to add any solvent.
5. the method that catalytic air oxidation hexamethylene as claimed in claim 1 prepares Ketohexamethylene, Hexalin and adipic acid, its feature exists
In, reaction need to be heated in pressure vessel and be carried out；Its Stress control is 0.6～2MPa, and temperature controls at 110～185 DEG C, instead
Control between Ying Shi at 35～175 minutes.
6. the method that catalytic air oxidation hexamethylene as claimed in claim 1 prepares Ketohexamethylene, Hexalin and adipic acid, its feature exists
In, reaction need to be heated in pressure vessel and be carried out；This pressure vessel can be conventional tank reactor, it is also possible to be bubble tower
Formula reactor；In general tower reactor can obtain higher cyclohexane conversion.
7. the method that catalytic air oxidation hexamethylene as claimed in claim 1 prepares Ketohexamethylene, Hexalin and adipic acid, its feature exists
In, this reaction can add a small amount of promoter, to improve the selectivity of reaction further, and the conversion ratio of reaction and reduction
The temperature of reaction；These additives include radical initiator, surfactant, organic complexing agent, ionic liquid, transition gold
The salt belonged to and metallo-organic compound.
8. the method that catalytic air oxidation hexamethylene as claimed in claim 1 prepares Ketohexamethylene, Hexalin and adipic acid, its feature exists
In, described haemachrome contains a natural porphyrin ring, and its common dosage form is chlorhematin；Wherein in porphyrin ring
The iron ion of the heart can by heating or acid adding, add alkali, the method that adds the simple reactions such as slaine is taken by other metal ion
Generation；Here include the transition metal such as Co, Cu, Cr, Mn, Mo, Zn, Ni, Ru, Rh and Pd or rare earth metal just from
Son, the haemachrome replaced by these metal ions still has good catalytic performance, but the most different to the selectivity of product.
9. the method that catalytic air oxidation hexamethylene as claimed in claim 1 prepares Ketohexamethylene, Hexalin and adipic acid, its feature exists
In, described catalyst is biochemical preparation haemachrome, but when using other biochemical preparations such as medicine containing heme moiety
Semi-finished product, finished product and relevant mixture are as catalyst, or are simply aoxidized by some by haemachrome, reduce or ester
When the organic chemical reactionses such as change, addition are prepared as the derivant of multiple haemachrome later as the above catalyst reacted, for institute
The amount of the catalyst used needs to do corresponding adjustment.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823758A (en) * | 2017-02-28 | 2017-06-13 | 中国矿业大学 | A kind of method that haemachrome solution ultrasonic atomizatio spray eliminates the CO in restricted clearance |
| CN109575036A (en) * | 2018-12-11 | 2019-04-05 | 怀化学院 | Two ester type compound of Metal hematoporphyrins bis ether, catalyst and preparation method thereof and catalytic oxidation of cyclohexane method |
-
2015
- 2015-01-09 CN CN201510011352.1A patent/CN105884598A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106823758A (en) * | 2017-02-28 | 2017-06-13 | 中国矿业大学 | A kind of method that haemachrome solution ultrasonic atomizatio spray eliminates the CO in restricted clearance |
| CN106823758B (en) * | 2017-02-28 | 2019-04-09 | 中国矿业大学 | A kind of method that haemachrome solution ultrasonic atomizatio spray eliminates the CO in restricted clearance |
| CN109575036A (en) * | 2018-12-11 | 2019-04-05 | 怀化学院 | Two ester type compound of Metal hematoporphyrins bis ether, catalyst and preparation method thereof and catalytic oxidation of cyclohexane method |
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