CN109092375B - Free radical stabilizer for preparing adipic acid by direct oxidation of cyclohexane - Google Patents
Free radical stabilizer for preparing adipic acid by direct oxidation of cyclohexane Download PDFInfo
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 235000011037 adipic acid Nutrition 0.000 title claims abstract description 56
- 239000001361 adipic acid Substances 0.000 title claims abstract description 55
- 150000003254 radicals Chemical class 0.000 title claims abstract description 17
- 239000003381 stabilizer Substances 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 13
- 230000003647 oxidation Effects 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 150000002989 phenols Chemical class 0.000 claims abstract description 11
- -1 phosphoric acid triesters Chemical class 0.000 claims abstract description 10
- 239000011953 free-radical catalyst Substances 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 35
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 28
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 12
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 9
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000005691 triesters Chemical class 0.000 claims description 3
- QUTZUATVZPXUJR-UHFFFAOYSA-N trinonyl phosphite Chemical compound CCCCCCCCCOP(OCCCCCCCCC)OCCCCCCCCC QUTZUATVZPXUJR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 33
- 238000000354 decomposition reaction Methods 0.000 description 14
- 229940011182 cobalt acetate Drugs 0.000 description 13
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 13
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 13
- 229940071125 manganese acetate Drugs 0.000 description 13
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000007789 sealing Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VNNDVNZCGCCIPA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VNNDVNZCGCCIPA-FDGPNNRMSA-N 0.000 description 1
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical class O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YVSCCMNRWFOKDU-UHFFFAOYSA-N hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCC(O)=O YVSCCMNRWFOKDU-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a free radical stabilizer for preparing adipic acid by directly oxidizing cyclohexane, which mainly solves the problem that a free radical catalyst is easy to deactivate and decompose in the reaction for preparing adipic acid by directly oxidizing cyclohexane in the prior art. Free radical stabilizers for the preparation of adipic acid by direct oxidation of cyclohexane include substituted phenols and/or (R) as shown in formula I1O)(R2O)(R3O) at least one of phosphoric acid triesters represented by P; wherein X and Y are independently selected from H or tert-butyl, and X and Y are not H at the same time; r1～R3Independently selected from aryl of C6-C10 or alkyl of C1-C10, better solves the problem, and can be used for the industrial production of adipic acid by directly oxidizing cyclohexane.
Description
Technical Field
The invention relates to a free radical stabilizer for preparing adipic acid by directly oxidizing cyclohexane.
Background
Adipic acid (adipic acid), also known as adipic acid, is an important organic diacid, and is an important raw material for preparing polyurethane and nylon 66. The international application field of adipic acid in nylon 66 is over 70 percent, and the international application field of adipic acid in polyurethane is 78 percent. At present, the world has four methods for producing adipic acid, namely a phenol method, a cyclohexane method, a cyclohexene method, a butadiene method and the like. Before the fifty years, the production of adipic acid mainly uses phenol as a raw material, and the production of adipic acid by using a phenol method is a more classical method. But the phenol resource is limited, the price is expensive, the product cost is high, and the phenol is basically eliminated at present. The modern industrial production mainly adopts a cyclohexane method, the yield of which accounts for about 93 percent of the total yield, and the method mainly comprises two steps of adipic acid synthesis. The first step of oxidizing cyclohexane to give cyclohexanol and cyclohexanone (KA oil), followed by separation of the reaction mixture, recycling of unreacted cyclohexane, and the second step of oxidizing the KA oil to adipic acid with nitric acid. The method has the advantages that: the process is mature, the process is dominant in the production of adipic acid, byproducts are mainly succinic acid and glutaric acid, the separation is easy, and the product is relatively pure. The disadvantages are as follows: in the process of synthesizing KA oil, the conversion per pass is low, the conversion rate is generally 5% -12%, and a large amount of strong acid and strong alkali solution is needed, so that equipment is corroded, and the environment is polluted; in the second step, in the process of preparing adipic acid by oxidizing KA oil, the used oxidant is nitric acid, 68 percent of nitric acid is consumed for producing 1t of adipic acid product, the corrosion to equipment is serious, and a large amount of nitrogen oxide compounds which seriously pollute the environment can be generated.
In order to solve the problem, researchers explore a more environment-friendly and simple process route for synthesizing adipic acid by taking cyclohexane as a raw material and air or oxygen as an oxidant.
Chinese invention patents CN 1247501C (title of the invention: cyclohexane catalytic oxidation process), CN 1218922C (title of the invention: method for preparing adipic acid by air oxidation of hexacyclic carbon ring compound) and CN 1231449C (title of the invention: method for preparing adipic acid by biomimetic catalytic oxygen oxidation of cyclohexane) disclose methods for preparing adipic acid by air oxidation of cyclohexane using metalloporphyrin as a catalyst. Chinese invention patents CN 101239899B (title of the invention: a method for preparing adipic acid by one-step catalytic oxidation of cyclohexane) and CN 101337878B (title of the invention: a method for directly producing adipic acid by catalytic oxidation of cyclohexane) disclose a method for preparing adipic acid by one-step oxidation of cyclohexane by using a carbon material as a carrier to load a nano ruthenium dioxide catalyst or directly as a catalyst.
In the literature Organic Process Research&Development 1998,2,255-260 (article title: Direct Conversion of cyclic hexane in o-adaptive Acid with Molecular oxygenated catalyst bound by N-Hydroxyphthalimide bound with Mn (acac)2 and Co(OAc)2) In Ishii et al used a free radical catalyst NHPI with the addition of a small amount of a transition metal promoter to oxidize cyclohexane directly to adipic acid with oxygen. In acetic acid solvent, NHPI (10 mol%) and manganese acetylacetonate (1 mol%) are used as catalystsAt 100 ℃ for 20 hours, the cyclohexane conversion reached 73% and the yield of adipic acid was 53%.
The methods well solve the problem of synthesis of adipic acid from various angles, but have some defects and shortcomings, for example, in the existing preparation methods of many adipic acids, the conversion rate of cyclohexane is low, the selectivity of adipic acid is low, carriers used in some methods are expensive and difficult to prepare, organic small molecules are used as free radical catalysts to catalyze and oxidize the adipic acid, although the conversion rate of cyclohexane and the selectivity of adipic acid are improved, the used free radical catalysts are volatile and active to decompose and cannot be recycled, and the like, and a certain distance is left from industrial production of adipic acid.
Disclosure of Invention
The invention provides a free radical stabilizer for preparing adipic acid by directly oxidizing cyclohexane, which aims to solve the technical problem that a free radical catalyst is easy to deactivate and decompose in the reaction for preparing adipic acid by directly oxidizing cyclohexane in the prior art.
The second technical problem to be solved by the invention is a method for preparing adipic acid by directly oxidizing cyclohexane by using the free radical stabilizer.
In order to solve one of the technical problems of the invention, the technical scheme of the invention is as follows:
the free radical stabilizer for preparing adipic acid by direct oxidation of cyclohexane comprises substituted phenol and/or (R) shown in formula I1O)(R2O)(R3O) at least one of the phosphorous acid triesters represented by P:
wherein X and Y are independently selected from H or tert-butyl, and X and Y are not H at the same time; r1～R3Independently selected from aryl of C6-C10 or alkyl of C1-C10.
The relative positions of X, Y and OH are not particularly limited, and the technical effects of the present invention can be obtained.
In the above technical solution, the radical stabilizer preferably includes both the substituted phenol and the phosphite triester, and both have a synergistic effect in reducing the decomposition rate of the radical catalyst.
In the above technical scheme, the substituted phenol is preferably at least one of p-tert-butylphenol and 2, 6-di-tert-butylphenol.
In the above technical solution, the phosphite triester is preferably at least one selected from triphenyl phosphite and trinonyl phosphite.
In the above technical scheme, the molar ratio of the substituted phenol to the triester phosphite is preferably (0.1-1) to (0.1-1).
In the above technical solution, the radical stabilizer preferably further comprises citric acid, and in this case, the citric acid and the substituted phenol, and the citric acid and the phosphorous acid triester have synergistic effects in reducing the decomposition rate of the radical catalyst, and it has been surprisingly found that the radical stabilizer of the present invention has better combined synergistic effects when the substituted phenol, the phosphorous acid triester and the citric acid are simultaneously included.
In the above technical scheme, the molar ratio of the substituted phenol, the triester phosphite and the citric acid is preferably (0.1-1): 0.1-1) (0.1-1).
To solve the second technical problem, the technical solution of the present invention is as follows:
a method for preparing adipic acid by directly oxidizing cyclohexane comprises the steps of taking acetic acid or acetonitrile as a solvent, taking oxygen-containing gas as an oxidizing agent, and carrying out an oxidation reaction on cyclohexane in the presence of a free radical stabilizer, a metal catalyst and a free radical catalyst in the technical scheme to obtain the adipic acid.
In the above technical solution, the metal catalyst may be selected from those commonly used in the art, such as but not limited to at least one of Co, Cu and Mn, and more preferably the above three metal elements.
In the above technical scheme, the radical catalyst is not particularly limited, and those commonly used in the art can be selected, for example, but not limited to, at least one selected from N-hydroxyphthalimide (NHPI), N-hydroxysuccinimide (NHS), and derivatives having these as a skeleton structure.
In the above technical scheme, the reaction temperature is preferably 70-120 ℃.
In the above-mentioned technical means, the reaction pressure is preferably 1 to 5MPa in terms of gauge pressure.
The pressure of the invention is gauge pressure, and the selectivity of the product adipic acid is obtained by liquid phase HPLC detection. The solid-liquid mixed product obtained by the reaction of preparing adipic acid by oxidizing cyclohexane is electromagnetically stirred and dissolved by water and methanol in a ratio of 90:10(V/V), and is filtered and diluted into a high-efficiency liquid phase for detection. Chromatographic analysis conditions: the chromatography column model is ZORBAX SAX 4.6mm X250 mm 5 μm, and the mobile phase is methanol: 50mmol/L KH2PO4The column temperature was 25 ℃, the flow rate was 1.0mL/min, the amount of sample was 20 μ L, and the detection wavelength was 210 nm.
By adopting the technical scheme of the invention, the deactivation rate of the free radical catalyst NHS is lower than 20 percent, and is higher than 70 percent compared with the deactivation rate of NHS in the prior art, so that the technical effect is better, and the method can be used for industrial production of adipic acid by directly oxidizing cyclohexane.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Adding 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate, 1mol of cyclohexane, 0.01mol of p-tert-butylphenol, 0.01mol of citric acid and 0.01mol of triphenyl phosphite into a 1-step-up pressure reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 90 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 3MPa all the time, cooling to room temperature after reacting for 5 hours, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 52%, adipic acid selectivity was 83%, and NHS decomposition rate after the reaction was 6%, and the main reaction conditions and the reaction results are shown in table 1 for convenience of comparison.
[ example 2 ]
Adding 5mol of acetic acid, 0.02mol of NHPI, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate, 1mol of cyclohexane, 0.01mol of p-tert-butylphenol and 0.01mol of triphenyl phosphite into a 1-step pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 90 ℃, continuously introducing air at 5 liters per minute, controlling the pressure in the kettle to be kept at 3MPa, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: the cyclohexane conversion was 47%, the adipic acid selectivity was 81%, and the NHS decomposition rate after the reaction was 12%. The main reaction conditions and the reaction results are shown in Table 1 for convenience of comparison.
[ example 3 ]
Adding 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate, 1mol of cyclohexane, 0.01mol of citric acid and 0.01mol of triphenyl phosphite into a 1-step-up pressure reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 90 ℃, continuously introducing air at 5 liters per minute, controlling the pressure in the kettle to be kept at 3MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 42%, adipic acid selectivity was 78%, and NHS decomposition rate after reaction was 18%, and the main reaction conditions and the reaction results are shown in table 1 for convenience of comparison.
[ example 4 ]
Adding 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate, 1mol of cyclohexane, 0.01mol of p-tert-butylphenol and 0.01mol of trinonyl phosphite into a 1-liter pressure reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 90 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 3MPa, cooling to room temperature after 5 hours of reaction, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion of 45%, adipic acid selectivity of 76% and NHS decomposition of 15% after the reaction, the main reaction conditions and the reaction results are shown in table 1 for convenience of comparison.
[ example 5 ]
Adding 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate, 1mol of cyclohexane, 0.05mol of p-tert-butylphenol, 0.01mol of citric acid and 0.01mol of triphenyl phosphite into a 1-step-up pressure reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 90 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 3MPa all the time, cooling to room temperature after reacting for 5 hours, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 48%, adipic acid selectivity was 82%, and NHS decomposition rate after reaction was 8%, and the main reaction conditions and the reaction results are shown in table 1 for convenience of comparison.
[ example 6 ]
Adding 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate, 1mol of cyclohexane, 0.01mol of p-tert-butylphenol, 0.05mol of citric acid and 0.01mol of triphenyl phosphite into a 1-step-up pressure reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 90 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 3MPa all the time, cooling to room temperature after reacting for 5 hours, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 46%, adipic acid selectivity was 79%, and NHS decomposition rate after the reaction was 10%, and the main reaction conditions and the reaction results are shown in table 1 for convenience of comparison.
[ example 7 ]
Adding 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate, 1mol of cyclohexane, 0.01mol of p-tert-butylphenol and 0.01mol of citric acid into a 1-liter high-pressure reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 90 ℃, continuously introducing air at 5 liters per minute, controlling the pressure in the kettle to be kept at 3MPa, cooling to room temperature after 5 hours of reaction, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 40%, adipic acid selectivity was 82%, and NHS decomposition rate after the reaction was 13%, and the main reaction conditions and the reaction results are shown in table 1 for convenience of comparison.
[ example 8 ]
Adding 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate, 1mol of cyclohexane, 0.01mol of 2, 6-di-tert-butylphenol and 0.01mol of triphenyl phosphite into a 1-step-up pressure reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 90 ℃, continuously introducing air at 5 liters per minute, controlling the pressure in the kettle to be kept at 3MPa, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 42%, adipic acid selectivity was 76%, and NHS decomposition rate after reaction was 16%, and the main reaction conditions and the reaction results are shown in table 1 for convenience of comparison.
[ example 9 ]
Adding 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate, 1mol of cyclohexane and 0.01mol of triphenyl phosphite into a 1-step-up pressure reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 90 ℃, continuously introducing air at 5 liters/minute, controlling the pressure in the kettle to be kept at 3MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 32%, adipic acid selectivity was 77%, and NHS decomposition rate after reaction was 58%, and the main reaction conditions and the reaction results are shown in table 1 for convenience of comparison.
[ example 10 ]
Adding 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate, 1mol of cyclohexane and 0.01mol of p-tert-butylphenol into a 1-step pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), hermetically stirring, heating to 90 ℃, continuously introducing air at 5 liters/minute, controlling the pressure in the kettle to be kept at 3MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion 36%, adipic acid selectivity 76%, NHS decomposition 62% after the reaction, and the prevailing reaction conditions and reaction results are presented in table 1 for comparison.
[ example 11 ]
Adding 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate, 1mol of cyclohexane and 0.01mol of citric acid into a 1-liter high-pressure reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), hermetically stirring, heating to 90 ℃, continuously introducing air at 5 liters/minute, controlling the pressure in the kettle to be kept at 3MPa all the time, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 35%, adipic acid selectivity was 78%, and NHS decomposition rate after reaction was 64%, and the main reaction conditions and the reaction results are shown in table 1 for convenience of comparison.
[ COMPARATIVE EXAMPLE 1 ]
Adding 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate and 1mol of cyclohexane into a 1-step pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 90 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 3MPa, reacting for 5 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 28%, adipic acid selectivity was 74%, and NHS decomposition rate after reaction was 75%, and the main reaction conditions and the reaction results are shown in table 1 for convenience of comparison.
TABLE 1
Note: in the test, 5mol of acetic acid, 0.02mol of NHS, 0.01mol of cobalt acetate, 0.01mol of manganese acetate, 0.01mol of copper acetate and 1mol of cyclohexane were used.
Claims (7)
1. A method for preparing adipic acid by directly oxidizing cyclohexane comprises the steps of taking acetic acid or acetonitrile as a solvent, taking oxygen-containing gas as an oxidant, and carrying out an oxidation reaction on cyclohexane in the presence of a free radical stabilizer, a metal catalyst and a free radical catalyst to obtain adipic acid; the free radicalA stabilizer comprising (R)1O)(R2O)(R3O) at least one of the phosphorous triesters represented by P, or both of the substituted phenol represented by the formula I and (R)1O)(R2O)(R3O) a phosphite triester represented by P:
wherein X and Y are independently selected from H or tert-butyl, and X and Y are not H at the same time; r1～R3Independently selected from aryl of C6-C10, or alkyl of C1-C10;
wherein the molar ratio of the substituted phenol to the phosphite triester is (0.1-1) to (0.1-1).
2. The method of claim 1, wherein the substituted phenol is selected from at least one of p-tert-butylphenol and 2, 6-di-tert-butylphenol.
3. The method according to claim 1, wherein (R) is1O)(R2O)(R3O) the triester of phosphorous acid represented by P is at least one selected from the group consisting of triphenyl phosphite and trinonyl phosphite.
4. The method according to claim 1, characterized in that the metal catalyst is selected from at least one of Co, Cu and Mn.
5. The process according to claim 1, characterized in that the radical catalyst is selected from at least one of N-hydroxyphthalimide, N-hydroxysuccinimide or derivatives with their skeletal structure.
6. The process according to claim 1, wherein the reaction temperature is from 70 to 120 ℃.
7. The process according to claim 1, wherein the reaction pressure is from 1 to 5MPa in gauge.
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