CN117843468A - Method for oxidizing cycloolefin - Google Patents
Method for oxidizing cycloolefin Download PDFInfo
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- CN117843468A CN117843468A CN202211216284.9A CN202211216284A CN117843468A CN 117843468 A CN117843468 A CN 117843468A CN 202211216284 A CN202211216284 A CN 202211216284A CN 117843468 A CN117843468 A CN 117843468A
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- 150000001925 cycloalkenes Chemical class 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 127
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical class [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 119
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 45
- 239000011574 phosphorus Substances 0.000 claims abstract description 45
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- -1 cyclic olefin Chemical class 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 30
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
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- 238000001035 drying Methods 0.000 claims description 12
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- 239000002243 precursor Substances 0.000 claims description 11
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- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 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 description 9
- 230000008569 process Effects 0.000 claims description 7
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001935 cyclohexenes Chemical class 0.000 claims description 3
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 3
- 239000004913 cyclooctene Substances 0.000 claims description 3
- 150000001941 cyclopentenes Chemical class 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 18
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 239000001361 adipic acid Substances 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910003110 Mg K Inorganic materials 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
Abstract
The present disclosure relates to a method of oxidizing a cyclic olefin, the method comprising: contacting cycloolefin and oxidant with catalyst containing phosphorus modified carbon nitrogen material to make oxidation reaction; the phosphorus-modified carbon-nitrogen material is prepared by adopting a method comprising the following steps: and mixing the carbon-nitrogen material with an acid solution containing a phosphorus source, performing hydrothermal treatment, and taking out the solid to obtain the phosphorus-modified carbon-nitrogen material. The method disclosed by the invention can realize the oxidation of cycloolefin under mild conditions, and the selectivity of a target product is high.
Description
Technical Field
The present disclosure relates to a method of oxidizing a cyclic olefin.
Background
The oxidation of olefins plays an important role in chemical production, wherein the products of the oxidation of cycloolefins play a unique role in modern chemical engineering. Such as the preparation of adipic acid by oxidation of cyclohexene, is of great significance in chemical production. However, the existing oxidation process has serious corrosion pollution, such as oxidation by nitric acid.
Development of new environment-friendly technology for the existing cycloolefin oxidation reaction is urgently needed.
Disclosure of Invention
The invention aims to provide a method for oxidizing cycloolefin, which has high raw material conversion rate and high selectivity of target products.
In order to achieve the above object, the present disclosure provides a method for oxidizing cycloolefin, the method comprising: contacting cycloolefin and oxidant with catalyst containing phosphorus modified carbon nitrogen material to make oxidation reaction;
the phosphorus-modified carbon-nitrogen material is prepared by adopting a method comprising the following steps:
and mixing the carbon-nitrogen material with an acid solution containing a phosphorus source, performing hydrothermal treatment, and taking out the solid to obtain the phosphorus-modified carbon-nitrogen material.
Optionally, the carbon nitrogen material has a nitrogen content of 30 to 75 wt% based on the dry weight of the carbon nitrogen material;
the content of phosphorus element in the phosphorus-modified carbon nitrogen material is 0.1-20 wt% based on the dry weight of the phosphorus-modified carbon nitrogen material.
Optionally, the weight ratio of the carbon-nitrogen material to the amount of the acid solution containing the phosphorus source is 1: (0.2 to 80), preferably 1: (2 to 40), more preferably 1: (5-20);
optionally, the acid solution containing a phosphorus source contains a phosphorus element and an acid;
the content of the phosphorus source in the acid solution containing the phosphorus source is 0.5 to 50% by weight, preferably 2 to 25% by weight, more preferably 4 to 20% by weight;
the content of the acid is 1 to 40 wt%, preferably 2 to 20 wt%;
the phosphorus source is selected from one or more of phosphoric acid, phosphorous acid, pyrophosphoric acid, metaphosphoric acid and phosphorus pentoxide;
the acid is selected from one or more of phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid and phosphorous acid.
Optionally, the average particle size of the phosphorus-modified carbon nitrogen material is 20 to 800nm, preferably 40 to 400nm;
the weight of the phosphorus-modified carbon nitrogen material having a particle size of 40 to 100nm is 2 to 50%, preferably 4 to 40%, more preferably 8 to 25% of the total weight of the phosphorus-modified carbon nitrogen material.
Optionally, the conditions of the hydrothermal treatment include: the temperature is 100-300 ℃ and the time is 0.1-48 h;
the removing of the solids to obtain the phosphorus-modified carbon nitrogen material comprises: drying the taken solid to obtain the phosphorus-modified carbon-nitrogen material;
the drying conditions may include: the temperature is 60-200 ℃ and the time is 1-12 h; preferably, the temperature is 80-180 ℃ and the time is 2-10 h.
Optionally, the carbon-nitrogen material is prepared by a method comprising the following steps:
roasting a precursor of a nitrogen-containing carbon compound at 500-1000 ℃ for 1-12 h in an inert atmosphere;
the precursor of the nitrogen-containing carbon compound is a nitrogen-containing carbon compound with the nitrogen content of 30-75 weight percent;
preferably, the precursor of the nitrogen-containing carbon compound is selected from one or more of urea, dicyandiamide and melamine.
Alternatively, the cyclic olefin is selected from substituted or unsubstituted cyclic olefins having 5 to 10 ring-forming carbon atoms; the substituent in the substituted cycloolefin is selected from one or more of halogen groups and alkyl groups with 1-5 carbon atoms;
alternatively, the cyclic olefin is cyclohexene, cyclopentene, cyclooctene, cycloheptene, methylcyclohexene, halogenated cyclopentene, or halogenated cyclohexene, or a combination of two or three thereof;
the oxidant is oxygen-containing gas, the oxygen-containing gas is air or oxygen, and the molar ratio of the cycloolefin to the oxygen in the oxygen-containing gas is 1: (1 to 15), preferably 1: (3-8).
Optionally, the method for oxidizing cycloolefin comprises: contacting the cycloolefin with the oxidant in the presence of a solvent and the catalyst to perform the oxidation reaction;
the solvent is deionized water, C1-C6 alcohol, C3-C8 ketone or C2-C6 nitrile, or the combination of two or three of the above;
the weight ratio of the cycloolefin to the solvent is 1: (1 to 200), preferably 1: (5-100).
Optionally, the weight hourly space velocity of the cycloolefin is 0.2 to 200h -1 Preferably 0.5 to 100h -1 The method comprises the steps of carrying out a first treatment on the surface of the Or,
the catalyst is used in an amount of 5 to 1000mg, preferably 10 to 500mg, based on 100mL of the cycloolefin.
Optionally, the oxidation reaction conditions include: the temperature is 100-250 ℃, the pressure is 0.1-5 MPa, and the time is 1-24 h;
preferably, the temperature is 120-220 ℃, the pressure is 0.2-2 MPa, and the time is 2-12 h.
Through the technical scheme, compared with the catalyst containing the unmodified carbon-nitrogen material, the catalyst containing the phosphorus-modified carbon-nitrogen material can be used for realizing the oxidation of cycloolefin under mild conditions, and the selectivity of a target product is high.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
The present disclosure provides a method of oxidizing a cyclic olefin, the method comprising: contacting cycloolefin and oxidant with catalyst containing phosphorus modified carbon nitrogen material to make oxidation reaction;
the phosphorus-modified carbon-nitrogen material is prepared by adopting a method comprising the following steps:
and mixing the carbon-nitrogen material with an acid solution containing a phosphorus source, performing hydrothermal treatment, and taking out the solid to obtain the phosphorus-modified carbon-nitrogen material.
The target product of the oxidation of cycloolefins of the present disclosure is a dicarboxylic acid.
According to an embodiment of the present disclosure, the method for removing the solid is not particularly limited, and for example, filtration, centrifugal separation, etc. may be employed, and preferably, the removed solid is dried under the conditions including: the temperature is 60-200 ℃ and the time is 1-12 h; preferably, the temperature is 80-180 ℃ and the time is 2-10 h. Drying is a chemical operation well known to those skilled in the art and may be performed, for example, in a constant temperature oven or in a muffle furnace.
According to one embodiment of the present disclosure, the carbon nitrogen material has a nitrogen content of 30 to 75 wt%, preferably 35 to 70 wt%, based on the dry weight of the carbon nitrogen material; the content of the phosphorus element in the phosphorus-modified carbon nitrogen material is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the dry weight of the phosphorus-modified carbon nitrogen material. The nitrogen content of the carbon nitrogen material and the content of the phosphorus element in the phosphorus-modified carbon nitrogen material can be detected by adopting an XPS method.
The catalyst may also contain other materials conventionally employed by those skilled in the art for the oxidation of cycloolefins, such as one or more of transition metal oxides, noble metals, and heteroatom molecular sieves, in accordance with an embodiment of the present disclosure. In a preferred embodiment, the catalyst is a 100% phosphorus modified carbon nitrogen material.
According to one embodiment of the present disclosure, the carbon-nitrogen material may be obtained by firing a precursor of a nitrogen-containing carbon compound, specifically as follows: calcining the precursor of the nitrogen-containing carbon compound at 500-1000 ℃ for 1-12 h, preferably at 700-900 ℃ for 2-6 h in a sealed heat-resistant container under inert atmosphere; the closed heat-resistant container can be conventionally adopted by those skilled in the art, and can be, for example, a quartz tube, a quartz crucible (high-temperature-resistant vacuum oil ester seal) or a stainless steel reaction kettle. The inert gas species in the inert atmosphere for calcination is not particularly limited, and may be argon, helium, nitrogen, or the like, and the inert gas content in the inert atmosphere is more than 85% by volume, preferably more than 90% by volume. The nitrogen-containing carbon compound prepared by the method can be used in the oxidation process of cycloolefin, so that the conversion rate of raw materials and the selectivity of target products can be further improved. The precursor of the nitrogen-containing carbon compound is a nitrogen-containing carbon compound with a nitrogen content of 30-75 wt%; preferably, the precursor of the nitrogen-containing carbon compound is selected from one or more of urea, dicyandiamide and melamine; more preferably, the precursor of the nitrogen-containing carbon compound is a nitrogen-containing carbon compound having a nitrogen content of 35 to 70 wt%, more preferably urea. The firing is a well-known technique to those skilled in the art, and may be performed in a muffle furnace or a tube furnace, for example, and the atmosphere for firing is not particularly limited in the present disclosure, and is generally an inert atmosphere, for example, a carbon dioxide atmosphere, a nitrogen atmosphere, or an inert gas atmosphere.
According to the present disclosure, the acid solution of the phosphorus source may be any form of acid solution that dissolves or contains elemental phosphorus.
According to one embodiment of the present disclosure, the phosphorus source is conventional in the art, and may be various inorganic matters containing phosphorus elements, and nontoxic organic phosphorus sources such as phospholipids, preferably, the phosphorus source is selected from one or more of phosphoric acid, phosphorous acid, pyrophosphoric acid, metaphosphoric acid and phosphorus pentoxide; the acid is selected from one or more of phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid and phosphorous acid, wherein the phosphoric acid and the phosphorous acid can be used as a phosphorus source and the acid at the same time, that is, the acid solution containing the phosphorus source can be a phosphoric acid solution or a phosphorous acid solution.
According to one embodiment of the present disclosure, the weight ratio of the amounts of carbon-nitrogen material and the acid solution containing the phosphorus source may vary within a wide range, for example, may be 1: (0.2 to 80), preferably 1: (2 to 40), more preferably 1: (5-20), the carbon-nitrogen material and the phosphorus source acid solution are used in the weight ratio in the above range, so that the phosphorus-modified carbon-nitrogen material with better catalytic performance can be prepared.
According to one embodiment of the present disclosure, the content of the phosphorus source in the acid solution containing the phosphorus source may vary within a wide range, and may be, for example, 0.5 to 50 wt%, preferably 2 to 25 wt%, more preferably 4 to 20 wt%; the content of the acid is 1 to 40% by weight, preferably 2 to 20% by weight.
According to one embodiment of the present disclosure, the average particle size of the carbon nitrogen material may be 20 to 800nm, preferably 40 to 400nm. In this disclosure, "particle size" refers to the distance between two points on a particle where the distance is greatest. The inventors of the present application have unexpectedly found that when the carbon-nitrogen material having a particle size of 40 to 100nm accounts for 2 to 50%, preferably 4 to 40%, more preferably 8 to 25% by weight of the total weight of the carbon-nitrogen material, the phosphorus-modified carbon-nitrogen material prepared within the above-mentioned preferred range has more excellent properties of catalyzing the oxidation of cycloolefins. The phosphorus-modified carbon nitrogen material has proper particle size and excellent catalytic performance, and is especially suitable for the catalytic oxidation of cycloolefin.
According to one embodiment of the present disclosure, the conditions of the hydrothermal treatment may include: the temperature is 100-300 ℃ and the time is 0.1-48 h; preferably, the temperature is 150-250 ℃ and the time is 2-24 h. The pressure of the hydrothermal treatment is not particularly limited, and may be autogenous pressure or applied pressure, preferably autogenous pressure.
According to one embodiment of the present disclosure, the cyclic olefin is selected from substituted or unsubstituted cyclic olefins having 5 to 10 ring-forming carbon atoms; the substituent in the substituted cycloolefin is selected from one or more of halogen groups and alkyl groups with 1-5 carbon atoms; preferably, the cyclic olefin is cyclohexene, cyclopentene, cyclooctene, cycloheptene, methylcyclohexene, halogenated cyclopentene or halogenated cyclohexene, or a combination of two or three thereof.
According to one embodiment of the present disclosure, the oxidizing agent is an oxygen-containing gas, the oxygen-containing gas is air or oxygen, and the molar ratio of cycloolefin to oxygen in the oxygen-containing gas is 1: (1 to 15), preferably 1: (3-8).
In order to improve the uniformity between the reaction materials, according to one embodiment of the present disclosure, a method of oxidizing a cycloolefin may include: the cycloolefin is contacted with an oxidizing agent in the presence of a solvent and a catalyst to perform an oxidation reaction. The solvent may be any liquid capable of dissolving both the cycloolefin and the peroxide or promoting the mixing of both, and promoting the dissolution of the target product, and may be, for example, an organic solvent and/or deionized water. The organic solvent is well known to those skilled in the art and may be, for example, a C1-C6 alcohol, a C3-C8 ketone or a C2-C6 nitrile, or a combination of two or three thereof, preferably, the solvent is one or more of methanol, acetone and deionized water. The weight ratio of cycloolefin to solvent used may vary within a wide range, for example 1: (1 to 200), preferably 1: (5 to 100), more preferably 1: (5-50).
According to one embodiment of the present disclosure, the oxidation reaction may be carried out in any catalytic reactor known to those skilled in the art, for example, in a batch tank reactor, a fixed bed reactor, a moving bed reactor, a suspended bed reactor, or a slurry bed reactor. In one embodiment, the catalytic oxidation is carried out in a fixed bed reactor, the weight hourly space velocity of the cycloolefin being from 0.2 to 200h -1 Preferably 0.5 to 100h -1 The method comprises the steps of carrying out a first treatment on the surface of the In another embodiment, the catalytic oxidation is carried out in a slurry bed reactor, the catalyst being used in an amount of 5 to 1000mg, preferably 10 to 500mg, more preferably 20 to 250mg, based on 100mL of cycloolefin.
According to one embodiment of the present disclosure, the conditions of the oxidation reaction may include: the temperature is 100-250 ℃, the pressure is 0.1-5 MPa, and the time is 1-24 h; preferably, the temperature is 120-220 ℃, the pressure is 0.2-2 MPa, and the time is 2-12 h.
In a preferred embodiment, the oxidation reaction is carried out under stirring conditions, and the specific form of stirring is not limited, and common stirring forms may be, for example, mechanical stirring or magnetic stirring.
The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby.
The reagents used in the examples and comparative examples were all analytically pure and were commercially available.
In the preparation examples, the average particle size (particle diameter) of the carbon-nitrogen material was determined by using TECNAIG from FEI Co 2 F20 The (200 kv) type transmission electron microscope was used for measurement under the following conditions: accelerating voltage is 20kV, a suspension method is adopted to prepare a sample, the sample is placed into a 2mL glass bottle, absolute ethyl alcohol is used for dispersing, vibration is uniform, a drop is taken by a dropper, the drop is dropped on a sample net with the diameter of 3mm, after the drop is dried, the sample is placed into a sample injector, then an electron microscope is inserted for observation, and particle size statistics is carried out on 100 carbon-nitrogen material particles at random.
The particle ratio of the particles with the particle size of 40-100 nm in the carbon-nitrogen material is separated by a membrane separation device (model BONA-GM-05) of Jinan Bona biotechnology Co, the particle size of 40-100 nm, and the ratio of the weight of the carbon-nitrogen material with the particle size of 40-100 nm to the total weight of the carbon-nitrogen material is calculated according to the weight of the carbon-nitrogen material with the particle size of 40-100 nm and the total weight of the carbon-nitrogen material.
The method for testing the content of the nitrogen element and the phosphorus element is X-ray photoelectron spectroscopy (XPS), is carried out on a VGESCA-LABSX-ray photoelectron spectrometer, and is mainly used for analyzing the existence state of the element on the surface of a sample and the interaction between the elements. Test conditions: adopts Mg K alpha rays as a laser source (hν= 1253.6eV, detection sensitivity)>1%, vacuum degree 10 -7 Pa)。
Preparation examples are provided to illustrate phosphorus modified carbon nitrogen materials prepared by the method of the present invention and comparative examples are provided to illustrate carbon nitrogen materials prepared by methods of the prior art.
Preparation example 1
In a nitrogen atmosphere, 50g of urea is placed in a 100mL crucible, the crucible is covered and sealed by vacuum sealing ester, the crucible is placed in a muffle furnace at 700 ℃ for roasting for 3 hours, a carbon-nitrogen material (the nitrogen content is 56 wt%) is obtained after natural cooling at room temperature (20 ℃, the following is the same), and then the carbon-nitrogen material is added into a phosphoric acid aqueous solution (the concentration is 5 wt%) to be mixed, wherein the weight ratio of the carbon-nitrogen material to the phosphoric acid aqueous solution is 1:5, carrying out hydrothermal treatment at 200 ℃ for 12 hours, and then drying at 120 ℃ for 6 hours to obtain the phosphorus-modified carbon-nitrogen material A1, wherein the content of phosphorus element is 1.7 weight percent.
The average particle size of the phosphorus-modified carbon nitrogen material A1 is 310nm, wherein the weight of the carbon nitrogen material with the particle size of 40-100 nm accounts for 24% of the total weight of the carbon nitrogen material.
Preparation example 2
In a nitrogen atmosphere, placing 40g of urea in a 100mL crucible, sealing the crucible with a vacuum sealing ester, placing the crucible in a muffle furnace at 800 ℃ for roasting for 5 hours, naturally cooling at room temperature to obtain a carbon-nitrogen material (the nitrogen content is 63 wt%), and then adding the carbon-nitrogen material into a phosphoric acid aqueous solution (the concentration is 10 wt%) for mixing, wherein the weight ratio of the carbon-nitrogen material to the phosphoric acid aqueous solution is 1:10, carrying out hydrothermal treatment at 150 ℃ for 12 hours, and then drying at 100 ℃ for 6 hours to obtain the phosphorus-modified carbon-nitrogen material A2, wherein the content of phosphorus element is 5.3 weight percent.
The average particle size of the phosphorus-modified carbon nitrogen material A2 is 160nm, wherein the weight of the carbon nitrogen material with the particle size of 40-100 nm accounts for 21% of the total weight of the carbon nitrogen material.
Preparation example 3
In nitrogen atmosphere, 100g of urea is placed in a 200mL crucible, the crucible is capped and sealed by vacuum sealing ester, the crucible is placed in a muffle furnace at 550 ℃ for roasting for 8 hours, a carbon-nitrogen material (the nitrogen content is 53 wt%) is obtained after natural cooling at room temperature, and then the carbon-nitrogen material is added into a phosphoric acid aqueous solution (the concentration is 5 wt%) for mixing, wherein the weight ratio of the carbon-nitrogen material to the phosphoric acid aqueous solution is 1:20, carrying out hydrothermal treatment at 100 ℃ for 24 hours, and then drying at 120 ℃ for 6 hours to obtain the phosphorus-modified carbon-nitrogen material A3, wherein the content of phosphorus element is 1.1 weight percent.
The average particle size of the phosphorus-modified carbon nitrogen material A3 is 60nm, wherein the weight of the carbon nitrogen material with the particle size of 40-100 nm accounts for 41% of the total weight of the carbon nitrogen material.
Preparation example 4
In a nitrogen atmosphere, 60g of melamine is placed in a 100mL crucible, the crucible is capped and sealed by vacuum sealing ester, the crucible is placed in a muffle furnace at 900 ℃ for roasting for 2 hours, a carbon-nitrogen material (the nitrogen content is 67 wt%) is obtained after natural cooling at room temperature, then the carbon-nitrogen material is added into a phosphoric acid aqueous solution (the concentration is 0.5 wt%) for mixing, and the weight ratio of the carbon-nitrogen material to the phosphoric acid aqueous solution is 1:15, carrying out hydrothermal treatment at 280 ℃ for 6 hours, and then drying at 150 ℃ for 6 hours to obtain the phosphorus-modified carbon nitrogen material A4, wherein the content of phosphorus element is 0.6 weight percent.
The average particle size of the phosphorus-modified carbon nitrogen material A4 is 520nm, wherein the weight of the carbon nitrogen material with the particle size of 40-100 nm accounts for 3% of the total weight of the carbon nitrogen material.
Preparation example 5
In a nitrogen atmosphere, 50g of urea is placed in a 100mL crucible, the crucible is covered and sealed by vacuum sealing ester, the crucible is placed in a muffle furnace at 650 ℃ for roasting for 6 hours, a carbon-nitrogen material (nitrogen content is 55 wt%) is obtained after natural cooling at room temperature (20 ℃, the following is the same), and then the carbon-nitrogen material is added into a phosphorous acid solution (concentration is 5 wt%) to be mixed, wherein the weight ratio of the carbon-nitrogen material to the water solution is 1:5, carrying out hydrothermal treatment at 200 ℃ for 12 hours, and then drying at 120 ℃ for 6 hours to obtain the phosphorus-modified carbon-nitrogen material A5, wherein the content of phosphorus element is 2.1 weight percent.
The average particle size of the phosphorus-modified carbon nitrogen material A5 is 180nm, wherein the weight of the carbon nitrogen material with the particle size of 40-100 nm accounts for 9% of the total weight of the carbon nitrogen material.
Preparation example 6
In a nitrogen atmosphere, 50g of melamine is placed in a 100mL crucible, the crucible is capped and sealed by vacuum sealing ester, the crucible is placed in a muffle furnace at 1000 ℃ for roasting for 1h, a carbon-nitrogen material (the nitrogen content is 69 wt%) is obtained after natural cooling at room temperature (20 ℃, the following is the same), and then the carbon-nitrogen material is added into a phosphoric acid aqueous solution (the concentration is 5 wt%) to be mixed, wherein the weight ratio of the carbon-nitrogen material to the phosphoric acid aqueous solution is 1:5, carrying out hydrothermal treatment at 280 ℃ for 12 hours, and then drying at 120 ℃ for 6 hours to obtain the phosphorus-modified carbon-nitrogen material A6, wherein the content of phosphorus element is 2.2 weight percent.
The average particle size of the phosphorus-modified carbon nitrogen material A6 is 620nm, wherein the weight of the carbon nitrogen material with the particle size of 40-100 nm accounts for 4% of the total weight of the carbon nitrogen material.
Preparation example 7
In a nitrogen atmosphere, 50g of urea is placed in a 100mL crucible, the crucible is capped and sealed by vacuum sealing ester, the crucible is placed in a muffle furnace at 450 ℃ for roasting for 8 hours, a carbon-nitrogen material (the nitrogen content is 51 wt%) is obtained after natural cooling at room temperature, and then the carbon-nitrogen material is added into a phosphoric acid aqueous solution (the concentration is 5 wt%) for mixing, wherein the weight ratio of the carbon-nitrogen material to the phosphoric acid aqueous solution is 1:5, carrying out hydrothermal treatment at 200 ℃ for 12 hours, and then drying at 120 ℃ for 6 hours to obtain the phosphorus-modified carbon-nitrogen material A7, wherein the content of phosphorus element is 21 weight percent.
The average particle size of the phosphorus-modified carbon nitrogen material A7 is 19nm, wherein the weight of the carbon nitrogen material with the particle size of 40-100 nm accounts for 0% of the total weight of the carbon nitrogen material.
Preparation of comparative example 1
In a nitrogen atmosphere, 50g of urea is placed in a 100mL crucible, the crucible is capped and sealed by vacuum sealing ester, the crucible is placed in a muffle furnace at 450 ℃ for roasting for 8 hours, and carbon-nitrogen material particles a (the nitrogen content is 51 wt%) are obtained after natural cooling at room temperature.
The average particle size of the carbon-nitrogen material particles a is 400nm, wherein the weight of the carbon-nitrogen material with the particle size of 40-100 nm accounts for 1% of the total weight of the carbon-nitrogen material.
Examples are provided to illustrate the process of the invention for the oxidation of cycloolefins.
In the following examples and comparative examples, the oxidation products were analyzed by gas chromatography (GC: agilent, 7890A) and gas chromatography-mass spectrometry (GC-MS: thermo Fisher Trace ISQ).
The following formulas were used to calculate the feedstock conversion and target product selectivity:
% cycloolefin conversion = (molar amount of cycloolefin added before reaction-molar amount of cycloolefin remaining after reaction)/molar amount of cycloolefin added before reaction x 100%;
target product selectivity% = (molar amount of target product formed after reaction)/molar amount of cycloolefin added before reaction x 100%.
Example 1
80mL of cyclohexene and 0.25g of phosphorus-modified carbon nitrogen material A1 as a catalyst were added to a 250mL autoclave, the autoclave was sealed after the reaction mass was formed, then oxygen gas (molar ratio of oxygen gas to cyclohexene: 8:1) was introduced, and after the mixture was stirred at 130℃and 2MPa for 2 hours, the catalyst was separated by centrifugation and filtration. The results of analysis of the resulting oxidation products are shown in Table 1.
Examples 2 to 7
The oxidation of cyclohexene was carried out in the same manner as in example 1, except that the same amounts of phosphorus-modified carbon nitrogen materials A2 to A7 were used as the catalyst in place of A1, respectively. The results of analysis of the resulting oxidation products are shown in Table 1.
Example 8
Cyclohexene is fed into the reaction zone from a feed inlet at the top of a small laboratory fixed bed reactor, and oxygen is fed into the reaction zone from a feed inlet at the bottom of the fixed bed reactor to be contacted with phosphorus-modified carbon nitrogen material A1 serving as a catalyst, wherein the molar ratio of cyclohexene to oxygen is 1:4, the reaction temperature is 120 ℃, the pressure is 0.8MPa, and the weight hourly space velocity of cyclohexene is 2h -1 . The reaction mixture obtained after the reaction was allowed to proceed for 2 hours was analyzed by on-line gas chromatography, and the results are shown in Table 1.
Example 9
Cyclohexene was oxidized as in example 1, except that acetone was added to the reaction vessel as a solvent, the weight ratio of cyclohexene to solvent being 1:5, the results are set forth in table 1.
Comparative example 1
Cyclohexene was oxidized as in example 1, except that no phosphorus-modified carbon nitrogen material was added as a catalyst. The results of analysis of the oxidation products are shown in Table 1.
Comparative example 2
Cyclohexene is oxidized as in example 1, except that a is added as a catalyst. The results of analysis of the oxidation products are shown in Table 1.
TABLE 1
| Catalyst numbering | Cycloolefin conversion% | Adipic acid selectivity of the target product% | |
| Example 1 | A1 | 46 | 88 |
| Example 2 | A2 | 35 | 83 |
| Example 3 | A3 | 31 | 73 |
| Example 4 | A4 | 29 | 71 |
| Example 5 | A5 | 38 | 79 |
| Example 6 | A6 | 34 | 75 |
| Example 7 | A7 | 25 | 69 |
| Example 8 | A1 | 27 | 90 |
| Example 9 | A1 | 48 | 85 |
| Comparative example 1 | - | 4 | 62 |
| Comparative example 2 | a | 22 | 65 |
From the data in table 1, it can be seen that the process of cyclohexene oxidation of the present disclosure has higher feedstock conversion and selectivity to the desired product adipic acid. Further, as can be seen from comparison of examples 3, 4, 6, and 7 with examples 1, 2, and 5, the phosphorus-modified carbon nitrogen material has more excellent performance of catalyzing the oxidation of cycloolefin when the weight of the carbon nitrogen material having a particle size of 40 to 100nm is 8 to 25% of the total weight of the carbon nitrogen material.
The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations are not described further in this disclosure in order to avoid unnecessary repetition.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (10)
1. A process for the oxidation of cycloolefins, characterized in that it comprises: contacting cycloolefin and oxidant with catalyst containing phosphorus modified carbon nitrogen material to make oxidation reaction;
the phosphorus-modified carbon-nitrogen material is prepared by adopting a method comprising the following steps:
and mixing the carbon-nitrogen material with an acid solution containing a phosphorus source, performing hydrothermal treatment, and taking out the solid to obtain the phosphorus-modified carbon-nitrogen material.
2. The method of claim 1, wherein the carbon nitrogen material has a nitrogen content of 30 to 75 wt% based on the dry weight of the carbon nitrogen material;
the content of phosphorus element in the phosphorus-modified carbon nitrogen material is 0.1-20 wt% based on the dry weight of the phosphorus-modified carbon nitrogen material.
3. The method of claim 1, wherein the carbon-nitrogen material and the phosphorous source-containing acid solution are used in an amount of 1 by weight: (0.2 to 80), preferably 1: (2 to 40), more preferably 1: (5-20);
optionally, the acid solution containing a phosphorus source contains a phosphorus element and an acid;
the content of the phosphorus source in the acid solution containing the phosphorus source is 0.5 to 50% by weight, preferably 2 to 25% by weight, more preferably 4 to 20% by weight;
the content of the acid is 1 to 40 wt%, preferably 2 to 20 wt%;
the phosphorus source is selected from one or more of phosphoric acid, phosphorous acid, pyrophosphoric acid, metaphosphoric acid and phosphorus pentoxide;
the acid is selected from one or more of phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid and phosphorous acid.
4. A method according to claim 1, wherein the average particle size of the phosphorus-modified carbon nitrogen material is 20-800 nm, preferably 40-400 nm;
the weight of the phosphorus-modified carbon nitrogen material having a particle size of 40 to 100nm is 2 to 50%, preferably 4 to 40%, more preferably 8 to 25% of the total weight of the phosphorus-modified carbon nitrogen material.
5. The method of claim 1, wherein the hydrothermal treatment conditions comprise: the temperature is 100-300 ℃ and the time is 0.1-48 h;
the removing of the solids to obtain the phosphorus-modified carbon nitrogen material comprises: drying the taken solid to obtain the phosphorus-modified carbon-nitrogen material;
the drying conditions may include: the temperature is 60-200 ℃ and the time is 1-12 h; preferably, the temperature is 80-180 ℃ and the time is 2-10 h.
6. The method of claim 1, wherein the carbon-nitrogen material is prepared by a method comprising:
roasting a precursor of a nitrogen-containing carbon compound at 500-1000 ℃ for 1-12 h in an inert atmosphere;
the precursor of the nitrogen-containing carbon compound is a nitrogen-containing carbon compound with the nitrogen content of 30-75 weight percent;
preferably, the precursor of the nitrogen-containing carbon compound is selected from one or more of urea, dicyandiamide and melamine.
7. The process according to claim 1, wherein the cycloolefin is selected from substituted or unsubstituted cycloolefins having 5 to 10 ring-forming carbon atoms; the substituent in the substituted cycloolefin is selected from one or more of halogen groups and alkyl groups with 1-5 carbon atoms;
alternatively, the cyclic olefin is cyclohexene, cyclopentene, cyclooctene, cycloheptene, methylcyclohexene, halogenated cyclopentene, or halogenated cyclohexene, or a combination of two or three thereof;
the oxidant is oxygen-containing gas, the oxygen-containing gas is air or oxygen, and the molar ratio of the cycloolefin to the oxygen in the oxygen-containing gas is 1: (1 to 15), preferably 1: (3-8).
8. The method of claim 1, wherein the method of oxidizing the cyclic olefin comprises: contacting the cycloolefin with the oxidant in the presence of a solvent and the catalyst to perform the oxidation reaction;
the solvent is deionized water, C1-C6 alcohol, C3-C8 ketone or C2-C6 nitrile, or the combination of two or three of the above;
the weight ratio of the cycloolefin to the solvent is 1: (1 to 200), preferably 1: (5-100).
9. The process according to claim 1, wherein the cycloolefin has a weight hourly space velocity of 0.2 to 200h -1 Preferably 0.5 to 100h -1 The method comprises the steps of carrying out a first treatment on the surface of the Or,
the catalyst is used in an amount of 5 to 1000mg, preferably 10 to 500mg, based on 100mL of the cycloolefin.
10. The method of claim 1, wherein the oxidation reaction conditions comprise: the temperature is 100-250 ℃, the pressure is 0.1-5 MPa, and the time is 1-24 h;
preferably, the temperature is 120-220 ℃, the pressure is 0.2-2 MPa, and the time is 2-12 h.
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