CN109096096A - The free radical protective agent of hexamethylene direct oxidation adipic acid - Google Patents
The free radical protective agent of hexamethylene direct oxidation adipic acid Download PDFInfo
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- adipic acid
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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Abstract
The present invention relates to the free radical protective agent of hexamethylene direct oxidation adipic acid, mainly solve the problem of that free radical catalyst is easy inactivated decomposition in hexamethylene direct oxidation adipic acid reaction existing in the prior art.By using the free radical protective agent of hexamethylene direct oxidation adipic acid, including at least one of citric acid and/or the substituted phenol being shown below；Wherein, X and Y is independently selected from H or tert-butyl, and X and Y are not the technical solution of H simultaneously, preferably solve the problems, such as this, can be used for the industrial production of hexamethylene direct oxidation adipic acid.
Description
Technical field
The present invention relates to the free radical protective agents of hexamethylene direct oxidation adipic acid.
Background technique
Adipic acid (adipic acid), also known as adipic acid are a kind of important organic dibasic acids, are to prepare polyurethane and Buddhist nun
The important source material of dragon 66.Adipic acid is more than 70% for the field of nylon66 fiber in the world, and China's adipic acid is for polyurethane
Field is even more to reach 78%.The production method of adipic acid has phynol method, hexamethylene method, the cyclohexene method and butadiene in the world at present
Four kinds of method etc..Before the fifties, the production of adipic acid is a kind of ratio with phynol method production adipic acid mainly using phenol as raw material
More classic method, this method advantage are product purity height, and production technology is mature, is not required to stainless steel material.But phenol resource is limited
And it is expensive, product cost is high, eliminates substantially at present.Modern industrial production mainly uses hexamethylene method, and yield accounts for about
The 93% of total output, the method are largely divided into two step synthesizing adipic acids.First step oxidizing ethyle alkyl generates cyclohexanol and cyclohexanone (KA
Oil), then reaction mixture is separated, unreacted hexamethylene is recycled, and and then second step nitric acid is oily by KA
It is oxidized to adipic acid.The advantages of method, is: technical maturity, occupies an leading position in adipic acid production, by-product is mainly fourth two
Acid and glutaric acid, easily separated, product is purer.Shortcoming is: for the technique during synthesizing KA oil, conversion per pass is lower,
Conversion ratio needs a large amount of strong acid and strong base solution generally in 5%-12%, corrodes equipment, pollutes environment；Second step KA oil oxygen
During changing adipic acid processed, oxidant used is nitric acid, the nitric acid 1.3t of every production 1t adipic acid product consumption 68%, to equipment
Corrode more serious, and can generate and largely have the oxynitrides seriously polluted to environment.
In order to solve this problem, researcher is explored using hexamethylene as raw material using air or oxygen as oxidant
The process route of one more environmentally protective succinct synthesizing adipic acid.
Chinese invention patent CN 1247501C (denomination of invention: catalyst oxdie cyclohexane process), CN 1218922C (invention
Title: the method for preparing adipic acid by air-oxidating hexacarbocyclic compound) and CN 1231449C (denomination of invention: biomimetic-catalysis oxygen
The method that oxidizing ethyle alkyl prepares adipic acid) it discloses and makees catalyst using metalloporphyrin, air oxidation of cyclohexane prepares oneself two
The method of acid.A kind of Chinese invention patent CN 101239899B (denomination of invention: preparing adipic acid by using cyclohexane catalytic oxidation one-step
Method) and CN 101337878B (a kind of denomination of invention: method of directly producing adipic acid by cyclohexane catalytic oxidation) disclose
It is a kind of as carrier loaded nanometer titanium dioxide ruthenium catalyst or to be directly used as catalyst using carbon material hexamethylene is aoxidized
The method that one step prepares adipic acid.
Document Organic Process Research&Development 1998,2,255-260. (article title:
Direct Conversion of Cyclohexane into Adipic Acid with Molecular Oxygen
Catalyzed by N-Hydroxyphthalimide Combined with Mn(acac)2and Co(OAc)2) in, Ishii
Deng using free radical catalyst NHPI, and a small amount of transition metal promoter is added, directly use dioxygen oxidation hexamethylene to oneself two
Acid.In acetic acid solvent, make catalyst with NHPI (10mol%) and manganese acetylacetonate (1mol%), reaction carries out at 100 DEG C
20 hours, cyclohexane conversion reached 73%, and the yield of adipic acid is 53%.
These above-mentioned methods are all from all angles very good solution composition problem of adipic acid, and however, there are also one
Some insufficient and disadvantages, such as the preparation method of many adipic acids at present, cyclohexane conversion is lower, the selectivity of adipic acid also compared with
Low, the carrier that some methods are used is more expensive to be not easy to be made, and also some use small organic molecule as free radical catalyst to urge
Change and aoxidize adipic acid processed, although the conversion ratio of hexamethylene and the selectivity of adipic acid all increase, free radical used is urged
Agent easy in inactivation is decomposed, and can not be reused, there are also certain distances for the industrialized production apart from adipic acid.
Summary of the invention
The first technical problem to be solved by the present invention is hexamethylene direct oxidation adipic acid existing in the prior art
In reaction, free radical catalyst be easy inactivated decomposition the problem of, provide hexamethylene direct oxidation adipic acid free radical protection
Agent has the characteristics that reduce free radical catalyst resolution ratio using the protective agent.
The second technical problem to be solved by the present invention is using the protectant hexamethylene direct oxidation system of above-mentioned free radical
The method of adipic acid.
To solve one of present invention problem, technical scheme is as follows:
The free radical protective agent of hexamethylene direct oxidation adipic acid, including citric acid and/or substituted phenol shown in formula I
At least one of:
Wherein, X and Y is independently selected from H or tert-butyl, and X and Y are not H simultaneously.
The relative position of X, Y and OH are not particularly limited, technical effect of the invention can be obtained.
In above-mentioned technical proposal, the free radical protective agent preferably includes citric acid and substituted phenol simultaneously, and the two is reducing
There is synergistic effect in terms of the resolution ratio of free radical catalyst.
In above-mentioned technical proposal, the substituted phenol preferably is selected from p-tert-butylphenol and 2, in 6- DI-tert-butylphenol compounds extremely
Few one kind.
In above-mentioned technical proposal, with molar ratio computing citric acid: substituted phenol is preferably (0.1~1): (0.1~1).
In above-mentioned technical proposal, the free radical protective agent further preferably includes (R1O)(R2O)(R3O) the phosphorous acid that P is indicated
Sour three esters, wherein R1~R3It is independently selected from the aryl of C6~C10 or the alkyl of C1~C10.Citric acid and phosphorous acid acid at this time
Three esters and sour three esters of substituted phenol and phosphorous acid have synergistic effect in terms of reducing free radical catalyst resolution ratio, and frightened
Surprise finds there is preferably combination association when free radical protective agent of the present invention includes citric acid, substituted phenol and phosphorous acid three ester of acid simultaneously
Same effect.
In above-mentioned technical proposal, with molar ratio computing citric acid: substituted phenol: phosphorous acid three esters of acid: preferred (0.1~1): (0.1
~1) (0.1~1.5).
To solve above-mentioned technical problem two, technical scheme is as follows:
The method of hexamethylene direct oxidation adipic acid, including using acetic acid or acetonitrile as solvent, be with oxygenous gas
Oxidant, the in the above-mentioned technical solutions presence of any one free radical protective agent, metallic catalyst and free radical catalyst
Under, hexamethylene occurs oxidation reaction and obtains adipic acid.
In above-mentioned technical proposal, the metallic catalyst is optional those of commonly used in the art, such as, but not limited to Co, Cu and
At least one of Mn, more preferable above-mentioned three kinds of metallic elements.
In above-mentioned technical proposal, the free radical catalyst is not particularly limited, can select it is those of commonly used in the art,
Such as, but not limited to selected from n-Hydroxyphthalimide (NHPI), n-hydroxysuccinimide (NHS) or using them as bone
At least one of the derivative of frame structure.
In above-mentioned technical proposal, reaction temperature is preferably 70-120 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 1-5MPa in terms of gauge pressure.
Pressure of the present invention is gauge pressure, and product adipic acid of the present invention selectively passes through liquid phase HPLC and detects
It arrives.Cyclohexane oxidation adipic acid reaction gained solid-liquid mix products are with water: the dissolution of methanol=90:10 (V/V) electromagnetic agitation, mistake
Filter is diluted to be detected into efficient liquid phase.Chromatographiccondition: column model is 5 μ of ZORBAX SAX 4.6mm × 250mm
M, mobile phase are methanol: 50mmol/L KH2PO4: aqueous solution=5:95 (V/V), column temperature are 25 DEG C, flow velocity 1.0mL/min, into
Sample amount is 20 μ L, Detection wavelength 210nm.
Using technical solution of the present invention, the inactivation rate of free radical catalyst NHS is lower than 20%, and the year-on-year prior art
The inactivation rate of NHS is but up to 70% or more, achieves preferable technical effect, can be used for hexamethylene direct oxidation adipic acid
In industrial production.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
By 5mol acetic acid, 0.02mol NHS, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate, 1mol
Hexamethylene, 0.01mol p-tert-butylphenol, 0.01mol citric acid and 0.01mol triphenyl phosphite are added to 1 raising pressure
In reaction kettle (there is reflux condensate device, reflux condensate device is communicated by standby pressure valve with atmosphere), it is sealed stirring, is heated
To 90 DEG C, it is continuously passed through air with 5 liters/min, pressure in kettle is controlled and is always held at 3MPa, after reacting 5 hours, be cooled to room
Temperature takes out reaction mixture analysis, analyzes result: cyclohexane conversion 52%, adipic acid selectivity 83%, NHS points after reaction
Solution rate is 6%, for main reaction condition and reaction result are listed in table 1 convenient for comparing.
[embodiment 2]
By 5mol acetic acid, 0.02mol NHPI, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate,
1mol hexamethylene 0.01mol p-tert-butylphenol, 0.01mol triphenyl phosphite, which are added to 1 liter of autoclave, (has reflux
Condensing unit, reflux condensate device are communicated by standby pressure valve with atmosphere) in, it is sealed stirring, is heated to 90 DEG C, with 5 liters/min
Clock is continuously passed through air, controls pressure in kettle and is always held at 3MPa, after reacting 5 hours, be cooled to room temperature, takes out reaction mixing
Result: cyclohexane conversion 47% is analyzed in object analysis, and adipic acid selectivity 81%, NHS resolution ratio is 12% after reaction.For just
Main reaction condition and reaction result are listed in table 1 in comparing.
[embodiment 3]
By 5mol acetic acid, 0.02mol NHS, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate, 1mol
Hexamethylene, 0.01mol citric acid and 0.01mol triphenyl phosphite, which are added to 1 liter of autoclave, (has reflux condensation mode dress
Set, reflux condensate device is communicated by standby pressure valve with atmosphere) in, it is sealed stirring, is heated to 90 DEG C, it is continuous with 5 liters/min
It is passed through air, pressure in kettle is controlled and is always held at 3MPa, after reacting 5 hours, be cooled to room temperature, take out reaction mixture point
Analysis, analyze result: cyclohexane conversion 42%, adipic acid selectivity 78%, after reaction NHS resolution ratio be 18%, for convenient for than
Table 1 is listed in compared with by main reaction condition and reaction result.
[embodiment 4]
By 5mol acetic acid, 0.02mol NHS, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate, 1mol
Hexamethylene, 0.01mol p-tert-butylphenol, 0.01mol tris(nonyl phenyl) phosphate, which are added to 1 liter of autoclave, (has returned cold
Solidifying device, reflux condensate device are communicated by standby pressure valve with atmosphere) in, it is sealed stirring, is heated to 90 DEG C, with 5 liters/min
It is continuously passed through air, pressure in kettle is controlled and is always held at 3MPa, after reacting 5 hours, be cooled to room temperature, take out reaction mixture
Analysis, analyze result: cyclohexane conversion 45%, adipic acid selectivity 76%, after reaction NHS resolution ratio be 15%, for convenient for
Compare and main reaction condition and reaction result are listed in table 1.
[embodiment 5]
By 5mol acetic acid, 0.02mol NHS, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate, 1mol
Hexamethylene, 0.05mol p-tert-butylphenol, 0.01mol citric acid and 0.01mol triphenyl phosphite are added to 1 raising pressure
In reaction kettle (there is reflux condensate device, reflux condensate device is communicated by standby pressure valve with atmosphere), it is sealed stirring, is heated
To 90 DEG C, it is continuously passed through air with 5 liters/min, pressure in kettle is controlled and is always held at 3MPa, after reacting 5 hours, be cooled to room
Temperature takes out reaction mixture analysis, analyzes result: cyclohexane conversion 48%, adipic acid selectivity 82%, NHS points after reaction
Solution rate is 8%, for main reaction condition and reaction result are listed in table 1 convenient for comparing.
[embodiment 6]
By 5mol acetic acid, 0.02mol NHS, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate, 1mol
Hexamethylene, 0.01mol p-tert-butylphenol, 0.05mol citric acid and 0.01mol triphenyl phosphite are added to 1 raising pressure
In reaction kettle (there is reflux condensate device, reflux condensate device is communicated by standby pressure valve with atmosphere), it is sealed stirring, is heated
To 90 DEG C, it is continuously passed through air with 5 liters/min, pressure in kettle is controlled and is always held at 3MPa, after reacting 5 hours, be cooled to room
Temperature takes out reaction mixture analysis, analyzes result: cyclohexane conversion 46%, adipic acid selectivity 79%, NHS points after reaction
Solution rate is 10%, for main reaction condition and reaction result are listed in table 1 convenient for comparing.
[embodiment 7]
By 5mol acetic acid, 0.02mol NHS, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate, 1mol
Hexamethylene, 0.01mol p-tert-butylphenol, 0.01mol citric acid be added to 1 liter of autoclave (have reflux condensate device,
Reflux condensate device is communicated by standby pressure valve with atmosphere) in, it is sealed stirring, is heated to 90 DEG C, it is continuous logical with 5 liters/min
Enter air, control pressure in kettle and be always held at 3MPa, after reacting 5 hours, be cooled to room temperature, take out reaction mixture analysis,
Analyze result: cyclohexane conversion 40%, adipic acid selectivity 82%, after reaction NHS resolution ratio be 13%, for convenient for compare by
Main reaction condition and reaction result are listed in table 1.
[embodiment 8]
By 5mol acetic acid, 0.02mol NHS, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate, 1mol
Hexamethylene, 0.01mol 2,6 di t butyl phenol, 0.01mol triphenyl phosphite, which are added to 1 liter of autoclave, (to be had back
Flow condensing unit, reflux condensate device passes through standby pressure valve and communicates with atmosphere) it is interior, be sealed stirring, be heated to 90 DEG C, with 5 liters/
Minute is continuously passed through air, controls pressure in kettle and is always held at 3MPa, after reacting 5 hours, be cooled to room temperature, takes out and react mixed
Object analysis is closed, result: cyclohexane conversion 42% is analyzed, adipic acid selectivity 76%, NHS resolution ratio is 16% after reaction, is
Main reaction condition and reaction result are listed in table 1 convenient for comparing.
[embodiment 9]
By 5mol acetic acid, 0.02mol NHS, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate, 1mol
Hexamethylene, 0.01mol triphenyl phosphite, which are added to 1 liter of autoclave, (has reflux condensate device, reflux condensate device is logical
Cross and communicated for pressure valve with atmosphere) in, it is sealed stirring, is heated to 90 DEG C, air is continuously passed through with 5 liters/min, controls in kettle
Pressure is always held at 3MPa and is cooled to room temperature after reaction 5 hours, takes out reaction mixture analysis, analyzes result: hexamethylene
Conversion ratio 32%, adipic acid selectivity 77%, NHS resolution ratio is 58% after reaction, for convenient for comparing main reaction condition
Table 1 is listed in reaction result.
[embodiment 10]
By 5mol acetic acid, 0.02mol NHS, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate, 1mol
Hexamethylene, 0.01mol p-tert-butylphenol, which are added to 1 liter of autoclave, (has reflux condensate device, reflux condensate device is logical
Cross and communicated for pressure valve with atmosphere) in, it is sealed stirring, is heated to 90 DEG C, air is continuously passed through with 5 liters/min, controls in kettle
Pressure is always held at 3MPa and is cooled to room temperature after reaction 5 hours, takes out reaction mixture analysis, analyzes result: hexamethylene
Conversion ratio 36%, adipic acid selectivity 76%, NHS resolution ratio is 62% after reaction, for convenient for comparing main reaction condition
Table 1 is listed in reaction result.
[embodiment 11]
By 5mol acetic acid, 0.02mol NHS, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate, 1mol
Hexamethylene, 0.01mol citric acid, which are added to 1 liter of autoclave, (has reflux condensate device, reflux condensate device passes through standby pressure
Valve is communicated with atmosphere) in, it is sealed stirring, is heated to 90 DEG C, air is continuously passed through with 5 liters/min, controls pressure one in kettle
It is directly maintained at 3MPa to be cooled to room temperature after reaction 5 hours, takes out reaction mixture analysis, analyze result: cyclohexane conversion
35%, adipic acid selectivity 78%, NHS resolution ratio is 64% after reaction, for convenient for comparing main reaction condition and reaction
As a result it is listed in table 1.
[comparative example 1]
By 5mol acetic acid, 0.02mol NHS, 0.01mol cobalt acetate, 0.01mol manganese acetate, 0.01mol copper acetate, 1mol
Hexamethylene is added to 1 liter of autoclave (having reflux condensate device, reflux condensate device is communicated by standby pressure valve with atmosphere)
It is interior, it is sealed stirring, is heated to 90 DEG C, is continuously passed through air with 5 liters/min, pressure in kettle is controlled and is always held at 3MPa,
It after reaction 5 hours, is cooled to room temperature, takes out reaction mixture analysis, analyze result: cyclohexane conversion 28%, adipic acid choosing
Selecting property 74%, NHS resolution ratio is 75% after reaction, for main reaction condition and reaction result are listed in table 1 convenient for comparing.
Table 1
Note: in test acetic acid be 5mol, NHS 0.02mol, cobalt acetate 0.01mol, manganese acetate 0.01mol, acetic acid
Copper is 0.01mol, hexamethylene 1mol.
Claims (8)
1. the free radical protective agent of hexamethylene direct oxidation adipic acid, including in citric acid and/or substituted phenol shown in formula I
At least one:
Wherein, X and Y is independently selected from H or tert-butyl, and X and Y are not H simultaneously.
2. free radical protective agent according to claim 1, it is characterised in that the substituted phenol is selected from p-tert-butylphenol
At least one of with 2,6 di t butyl phenol.
3. free radical protective agent according to claim 1, it is characterised in that with molar ratio computing citric acid: substituted phenol is (0.1
~1): (0.1~1).
4. the method for hexamethylene direct oxidation adipic acid, including using acetic acid or acetonitrile as solvent, using oxygenous gas as oxygen
Agent, described in any one of claims 1 to 3 in the presence of free radical protective agent, metallic catalyst and free radical catalyst,
Hexamethylene occurs oxidation reaction and obtains adipic acid.
5. according to the method described in claim 4, it is characterized in that the metallic catalyst in Co, Cu and Mn at least one
Kind.
6. according to the method described in claim 4, it is characterized in that the free radical catalyst is selected from N- hydroxyl phthalyl
Imines (NHPI), n-hydroxysuccinimide (NHS) or using them as at least one of derivative of skeleton structure.
7. according to the method described in claim 4, it is characterized in that reaction temperature is 70-120 DEG C.
8. according to the method described in claim 4, it is characterized in that reaction pressure is 1-5MPa in terms of gauge pressure.
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