Method for catalyzing O2 to oxidize hydrocarbon compounds by metalloporphyrin based on continuous flow tubular reaction without tail gas emission

Abstract

The invention discloses a method for catalyzing O2 to oxidize hydrocarbon compounds by metalloporphyrin based on continuous flow tubular reaction without tail gas emission, which comprises the following steps: feeding a raw material solution containing a catalyst and O2 into a 1 # mixer, feeding the mixed solution into a reaction pipeline to carry out catalytic oxidation reaction, uniformly arranging n 2 # mixers in the reaction pipeline at intervals, and n being an integer greater than or equal to 1; and cooling the reaction liquid after the reaction, and introducing the cooled reaction liquid into a gas-liquid separator for gas-liquid separation to obtain a reaction mixture containing part of oxidation products alcohol and ketone. According to the hydrocarbon continuous flow oxidation method provided by the invention, the yield of partial oxidation products (alcohol and ketone) is high, and the selectivity is high. Compared with the traditional kettle reaction, the continuous flow reaction involved in the invention is more efficient and safer. Compared with other continuous flow tubular reactions, the continuous flow reaction involved in the invention has no tail gas emission and is more environment-friendly. The method is a safe, efficient and environment-friendly hydrocarbon oxidation method.

Description

Technical Field

[0001] The present invention relates to a metal porphyrin catalyzed O-catalyzed catalyst without tail gas emission based on continuous flow tubular reaction. 2 The invention discloses a method and a device for oxidizing hydrocarbon compounds, belonging to the field of organic catalysis and fine organic synthesis. Background Art

[0002] Catalytic oxidation of hydrocarbon compounds can convert hydrocarbons widely present in fossil resources into high value-added alcohol compounds and ketone compounds, and has a wide range of applications in the chemical industry (ZL 202111006432.X; ZL202010884408.5; ZL 201911161924.9). However, since the chemical activity of the generated partial oxidation products (alcohols and ketones) is higher than that of the substrate hydrocarbons, the partial oxidation products are very likely to undergo deep oxidation to generate aliphatic carboxylic acids and their derivatives, which not only reduces the selectivity of the partial oxidation products and increases the energy consumption and equipment requirements for separation and purification, but also the generated aliphatic carboxylic acids and their derivatives are easy to crystallize, blocking the production pipeline, causing great difficulties for industrial production. For example, in the industrial catalytic oxidation of cyclohexane, in order to ensure better selectivity of partial oxidation products (cycloalkanols and cycloalkanones) and prevent the formation of over-oxidation product adipic acid, the conversion rate of cyclohexane is often controlled at about 5% to obtain a partial oxidation product selectivity of about 85% (Chemical Engineering Journal, 2022, 443: 136126; Chemical Engineering Science, 2022, 260: 117825; Molecular Catalysis, 2023, 535: 112853). Further improving the substrate conversion rate will significantly reduce the selectivity of partial oxidation products (cyclohexanol and cyclohexanone), generate a large amount of adipic acid and its derivatives, and it is impossible to achieve simultaneous improvement of substrate conversion rate and partial oxidation product selectivity. The root cause of the above problems, in addition to the high reactivity of the oxidation products (cycloalkyl alcohols and cycloalkyl ketones), is another important reason that in the intermittent reactor reaction, the generated partial oxidation products are severely back-mixed and have a long residence time, which is easy to cause deep oxidation.

[0003] Continuous flow tubular reactions, especially microchannel reactions, have attracted widespread attention due to their advantages of high area-to-volume ratio, high safety, excellent mass transfer and heat transfer performance, and have been widely used in some highly exothermic liquid-phase reactions, gas-phase reactions, and rapid gas-liquid reactions (Chemical Engineering Science, 1990, 45(5): 1281-1287; Journal of Catalysis, 2000, 191(2): 282-293; Chemical Engineering Journal, 2010, 160(3): 873-881; Chemical Review, 2011, 111(5): 3508-3576). In continuous flow tubular reactions, the back-mixing phenomenon of the partially oxidized products is suppressed. 2 The selectivity of the partial oxidation products of oxidized hydrocarbon compounds has been significantly improved. However, in the continuous flow tube gas-liquid phase oxidation reaction, the excess gas raw material not only causes a large amount of tail gas emissions, but also carries a certain amount of organic liquid phase substances, causing serious pollution to the atmospheric environment, and the tail gas treatment device is cumbersome. How to apply the advantages of continuous flow tube reaction to O 2 Oxidation of hydrocarbon compounds and avoiding the generation of tail gas containing a large amount of organic compounds, becoming a continuous flow tubular reactor, O 2 The oxidation of hydrocarbons is an urgent problem. Therefore, the development of continuous flow tubular reactors without tail gas emissions of O 2 Method for oxidizing hydrocarbon compounds, to achieve O 2 Efficient, selective and environmentally friendly oxidation of hydrocarbon compounds has important application value. Summary of the invention

[0004] In view of the above problems existing in the prior art, the object of the present invention is to provide a metalloporphyrin-catalyzed catalyst for the production of oxygen based on a continuous flow tube reaction without tail gas emission. 2 Method and device for oxidizing hydrocarbon compounds. The present invention uses a continuous flow tubular reactor as a reaction device, and uses the continuous flow tubular reactor to eliminate the back-mixing phenomenon while providing a certain confined environment, limiting the disordered diffusion of free radicals, preventing deep oxidation of partial oxidation products, and improving the selectivity of partial oxidation products. By designing multiple mixers in the reactor pipeline, the gas-liquid mass transfer contact in the oxidation process is strengthened, and the O 2 Complete reaction, so that the entire reaction system has no tail gas emissions. 2 The method for oxidizing hydrocarbon compounds not only has high selectivity for partial oxidation product alcohols and ketones, but also has no tail gas emissions, less material loss, and is environmentally friendly and green. It is an efficient, feasible, safe and environmentally friendly method for catalytic oxidation of hydrocarbon compounds to synthesize partial oxidation product alcohols and ketones.

[0005] The technical solution adopted by the present invention is as follows:

[0006] A novel metalloporphyrin-catalyzed O catalysis system based on a continuous flow tubular reaction without tail gas emissions 2 A method for oxidizing hydrocarbon compounds, characterized in that it comprises the following steps:

[0007] 1) mixing a hydrocarbon compound and a metal porphyrin catalyst and dissolving them by ultrasonication to obtain a raw material liquid containing the catalyst;

[0008] 2) Step 1) The raw material liquid is introduced into the 1# mixer, and at the same time 2 Also introduced into the 1# mixer, the raw material liquid and O 2 After being mixed in the 1# mixer, the mixture enters the reaction pipeline, and the reaction system in the reaction pipeline is heated to the reaction temperature to perform a catalytic oxidation reaction; wherein n 2# mixers are evenly spaced in the reaction pipeline and n+1 reaction sections are evenly divided by the 2# mixers, where n is an integer ≥1;

[0009] 3) The reaction liquid discharged from the outlet of the reaction pipeline is first cooled by a cooler, and then passed into a gas-liquid separator for gas-liquid separation. The reaction liquid discharged from the bottom liquid outlet of the gas-liquid separator is passed into a product collection tank to obtain a reaction mixture containing partial oxidation product alcohols and ketones.

[0010] Further, in step 1), the metal porphyrin catalyst is: 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin cobalt (TFPFPP-Co), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin manganese (TFPFPP-Mn), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin copper (TFPFPP-Cu), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin nickel (TFPFPP-Ni), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin iron (TFPFPP-Fe), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin 5,10,15,20-tetrakis(2,4,6-trifluoro)porphyrin cobalt (T(2,4,6-triF)PP-Co), 5,10,15,20-tetrakis(2,3,6-trichloro)porphyrin cobalt (T(2,3,6-triCl)PP-Co), 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin cobalt (T(4-Cl)PP-Co), 5,10,15,20-tetrakis(4-ester)porphyrin cobalt (T(4-COOCH 3 )PP-Co), 5,10,15,20-tetrakis(4-carboxyl)porphyrin cobalt (T(4-COOH)PP-Co), or any combination thereof;

[0011] The dispersion concentration of the metal porphyrin catalyst in the hydrocarbon compound is 0.005-0.04 mmol / L, preferably 0.01-0.03 mmol / L.

[0012] Furthermore, the inner diameter of the reaction pipeline is 0.5-3.0 mm, the length of the reaction pipeline is 20.0-150.0 m, and 1-8 2# mixers are arranged in the reaction pipeline.

[0013] Preferably, the inner diameter of the reaction pipe is 0.6-1.0 mm, the length of the reaction pipe is 90.0 m-120.0 m, and 2-6 2# mixers are arranged in the reaction pipe, preferably 4-6 2# mixers are arranged.

[0014] Furthermore, the standard flow rate of oxygen introduced is 5.0-99.0 mL / min, the liquid flow rate of raw material liquid introduced is 0.5-10.0 mL / min, and the ratio of the standard flow rate of oxygen to the liquid flow rate of the raw material is 5-50:1.

[0015] Preferably, the standard flow rate of oxygen introduced is 30-60.0 mL / min, the liquid flow rate of raw material liquid introduced is 2.4-3.0 mL / min, and the ratio of the standard flow rate of oxygen to the liquid flow rate of raw material is 10-25:1, preferably 12.5-25:1.

[0016] Furthermore, the reaction temperature is 100 to 200°C, preferably 150 to 200°C.

[0017] Furthermore, the hydrocarbon compound is an alkyl-substituted benzene or a C5-C8 cycloalkane, the substituent on the benzene ring of the alkyl-substituted benzene is H, halogen or nitro, the alkyl on the benzene ring of the alkyl-substituted benzene is a C1-C4 alkyl, and the corresponding partial oxidation products are substituted benzalkanols, substituted benzalkonones and peroxides, or C5-C8 cycloalkanols and C5-C8 cycloalkanones.

[0018] The method of the present invention adopts the following device: comprising an oxygen cylinder, an air flow meter, a liquid storage tank containing hydrocarbon compound raw materials and a catalyst, a liquid flow pump, a 1# mixer, a reaction pipeline and a post-processing system, wherein the inlet of the 1# mixer is divided into two paths, one path is connected to the gas outlet of the oxygen cylinder through a pipeline through the air flow meter, and the other path is connected to the liquid storage tank through a pipeline through the liquid flow pump, a plurality of 2# mixers are evenly arranged in the reaction pipeline and are evenly divided into a plurality of reaction sections by the 2# mixers, the outlet of the 1# mixer is connected to the inlet of the reaction pipeline, and the outlet of the reaction pipeline is further connected to the post-processing system; the post-processing system comprises a cooler, a gas-liquid separator and a product collection tank, the reaction liquid discharged from the outlet of the reaction pipeline is first cooled by the cooler, and then passed into the gas-liquid separator for gas-liquid separation, an exhaust pipeline with a back pressure valve is arranged at the top of the gas-liquid separator, and the liquid outlet at the bottom of the gas-liquid separator is connected to the product collection tank through a pipeline.

[0019] The technical concept of the present invention is: the present invention uses a continuous flow tubular reactor as a basic device to achieve metal porphyrin catalysis without tail gas emission. 2 Partial oxidation of hydrocarbon compounds to prepare partial oxidation product alcohols and ketones. Using a continuous flow tubular reactor, the back-mixing phenomenon of partial oxidation products is eliminated while providing a certain confined environment to limit the disordered diffusion of free radicals, prevent deep oxidation of partial oxidation products, and improve the selectivity of partial oxidation products. By designing multiple mixers in the reactor pipeline, the gas-liquid mass transfer contact in the oxidation process is strengthened to promote O 2 The complete reaction makes the entire reaction system free of tail gas emissions. Therefore, the method for partial oxidation of hydrocarbon compounds of the present invention not only has high selectivity for partial oxidation product alcohols and ketones, but also has no tail gas emissions, less material loss, no environmental pollution, and is green and environmentally friendly. 2 The oxidation method not only has important industrial application value and theoretical research value, but also has certain reference value for improving the selectivity and environmental protection of other catalytic oxidation systems.

[0020] The beneficial effects of the present invention are mainly reflected in: the present invention uses a continuous flow tubular reactor as a reaction device and metal porphyrin as a catalyst to achieve the production of hydrocarbon compounds without tail gas emission. 2 Oxidation, ingenious design, high efficiency and environmental protection, wide application range and strong practicality. In the partial oxidation reaction of hydrocarbon compounds, alcohol and ketone have high selectivity, which effectively inhibits the deep oxidation of partial oxidation products and the formation of aliphatic carboxylic acids and their derivatives. The low selectivity of aliphatic carboxylic acids and their derivatives is also conducive to the continuous partial oxidation process of hydrocarbons and the low-energy separation of products. By designing multiple mixers in the reactor pipeline, the gas-liquid mass transfer contact in the oxidation process is enhanced, and the O 2Complete reaction makes the whole reaction system free of tail gas emission and environmental pollution. The present invention is an environmentally friendly production method, which not only has important industrial application value and theoretical research value, but also has certain reference value for improving the selectivity and environmental protection degree of other catalytic oxidation systems. The present invention is a new method for selective catalytic oxidation of hydrocarbon compounds that is efficient, feasible and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is a schematic diagram of the structure of the reaction device used in Example 1 of the present invention. DETAILED DESCRIPTION

[0022] The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0023] Example 1-46: Metalloporphyrin Catalyzed O in a Continuous Flow Tubular Reactor without Tail Gas Emissions 2 A method for oxidizing hydrocarbon compounds.

[0024] The metal porphyrin catalyst used in the present invention is prepared by conventional techniques, and the present invention is prepared by referring to the preparation methods in existing literature (Chemical Engineering Journal, 2022, 443: 136126; Chemical Engineering Science, 2022, 260: 117825). All other reagents used are commercially available analytically pure.

[0025] The full names and abbreviations of the metal porphyrins used in the present invention are as follows. For the convenience of subsequent description, the abbreviations are used. 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin cobalt (TFPFPP-Co), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin manganese (TFPFPP-Mn), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin copper (TFPFPP-Cu), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin nickel (TFPFPP-Ni), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin iron (TFPFPP-Fe), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin zinc (TFPFPP-Zn ... copper (TFPFPP-Cu), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin nickel (TFPFPP-Ni P-Zn), 5,10,15,20-tetrakis(2,4,6-trifluoro)porphyrin cobalt (T(2,4,6-triF)PP-Co), 5,10,15,20-tetrakis(2,3,6-trichloro)porphyrin cobalt (T(2,3,6-triCl)PP-Co), 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin cobalt (T(4-Cl)PP-Co), 5,10,15,20-tetrakis(4-ester)porphyrin cobalt (T(4-COOCH 3)PP-Co), 5,10,15,20-tetrakis(4-carboxy)porphyrin cobalt (T(4-COOH)PP-Co).

[0026] Taking cyclohexane as an example, the main reaction equation involved in the invention is as follows:

[0027]

[0028] The reaction device used in Example 1 of the present invention is as follows Figure 1 As shown, it includes an oxygen cylinder 2, an air flow meter 4, a liquid storage tank 1 containing hydrocarbon compound raw materials and catalysts, a liquid flow pump 3, a 1# mixer 5, a reaction pipeline and a post-processing system. The inlet of the 1# mixer 5 is divided into two paths, one of which is connected to the gas outlet of the oxygen cylinder 2 by a pipeline through the air flow meter 4, and the other is connected to the liquid storage tank 1 by a pipeline through the liquid flow pump 3. A plurality of 2# mixers 6 are evenly spaced in the reaction pipeline and are evenly divided into a plurality of reaction sections by the 2# mixers 6. The outlet of the 1# mixer 5 is connected to the inlet of the reaction pipeline, and the outlet of the reaction pipeline is further connected to the post-processing system.

[0029] Comparison Figure 1 The post-treatment system includes a cooler 8, a gas-liquid separator 9 and a product collection tank 11. The reaction liquid discharged from the outlet of the reaction pipeline is first cooled by the cooler 8, and then passed into the gas-liquid separator 9 for gas-liquid separation. An exhaust pipeline with a back pressure valve 10 is provided on the top of the gas-liquid separator 9, and the liquid outlet at the bottom of the gas-liquid separator 9 is connected to the product collection tank 11 through a pipeline.

[0030] The model of the gas flow meter 4 of the present invention is D08-1F, which is purchased from Beijing Qixing Huachuang Flow Meter Co., Ltd. The gas flow rate detected by the gas flow meter is the flow rate under standard conditions and is not affected by the pressure of the oxygen cylinder.

[0031] Example 1

[0032] Accurately measure 200.0 mL of dry cyclohexane, add (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst, dissolve by ultrasonication to fully dissolve the metal porphyrin in the cyclohexane, filter, and prepare a raw material liquid containing the catalyst for use.

[0033] Before catalytic oxidation, the reaction pipeline was rinsed with dry cyclohexane at a flow rate of 3.0 mL / min for 10 min, and the above-prepared "raw material liquid containing catalyst" was transported with a plunger pump at a flow rate of 2.0 mL / min after air was removed. At the same time, the air flow meter 4 connected to the oxygen cylinder 2 was opened, and oxygen was transported at a flow rate of 20.0 mL / min under standard conditions. The two entered the mixer and mixed. After mixing, it flowed into the reaction pipeline, which was a 316L stainless steel pipeline with a length of 60.0 m and an inner diameter of 0.6 mm (six mixers were evenly spaced in the reaction pipeline, so that the 316L stainless steel pipeline was evenly divided into 7 reaction sections, and the total length of the 7 reaction sections was 60.0 m. The 7 reaction sections were connected by 6 mixers, that is, two adjacent reaction sections were connected by a mixer respectively). By adjusting the opening degree of the back pressure valve of the exhaust pipeline on the gas-liquid separator, the back pressure value of the reaction was adjusted, and the back pressure valve was closed after the reaction was stable. After the temperature was raised to 170°C and the back pressure reached 1.6MPa, the reaction was stabilized for 15 minutes. The back pressure valve of the exhaust pipe on the gas-liquid separator remained stable under the closed state, and no tail gas emission was required. Samples were taken from the gas-liquid separator for analysis and testing, and 8.42g of oxidation product was taken each time (subject to the actual mass taken).

[0034] Triphenylphosphine (0.6657g, 2.50mmol) was added to the sampled oxidation product and stirred at room temperature for 30min, and the mixture was settled to a 50mL volumetric flask with acetone. 10mL of the constant volume solution was accurately pipetted, and internal standard toluene (0.1843g, 2.0mmol) was added for GC analysis to determine the substrate cyclohexane conversion rate, the yield and selectivity of the partial oxidation products cyclohexanol and cyclohexanone; 10mL of the constant volume solution was accurately pipetted, and internal standard benzoic acid (0.1221g, 1.0mmol) was added for HPLC analysis to determine the yield and selectivity of the deep oxidation products adipic acid and glutaric acid. GC, HPLC analysis showed that the cyclohexane conversion rate was 7.761%, the cyclohexanol selectivity was 59.98%, the cyclohexanone selectivity was 33.32%, the cyclohexyl hydroperoxide selectivity was 3.64%, the adipic acid selectivity was 3.06%, and glutaric acid and other byproducts were not detected.

[0035] Example 2

[0036] The experimental process of Example 2 repeats Example 1, except that "six mixers are evenly spaced in the reaction pipeline" is replaced by "one mixer is evenly spaced in the reaction pipeline", and the other conditions are the same as Example 1. The experimental results of Example 2 are: cyclohexane conversion rate 3.881%, cyclohexanol selectivity 62.03%, cyclohexanone selectivity 31.03%, cyclohexyl hydroperoxide selectivity 6.93%, partial oxidation product total selectivity greater than 99%, and no acid and other by-products are detected. Example 1 Under the condition of this one mixer connected, the back pressure valve is closed, the back pressure will slowly rise, and tail gas discharge is required.

[0037] Example 3

[0038] The experimental process of Example 3 repeats Example 1, except that "6 mixers are evenly spaced in the reaction pipe" is replaced by "8 mixers are evenly spaced in the reaction pipe", and the other conditions are the same as Example 1. The experimental results of Example 3 are: cyclohexane conversion rate 6.832%, cyclohexanol selectivity 59.81%, cyclohexanone selectivity 33.82%, cyclohexyl hydroperoxide selectivity 3.73%, adipic acid selectivity 2.64%, and glutaric acid and other by-products are not detected. In Example 3, when there are more mixers, the back pressure valve is closed, and the back pressure remains stable, and no tail gas emission is required.

[0039] Example 4

[0040] The experimental process of Example 4 repeats Example 1, the only difference is that "six mixers are evenly spaced in the reaction pipe" is replaced by "four mixers are evenly spaced in the reaction pipe", and the other conditions are the same as Example 1. The experimental results of Example 4 are: cyclohexane conversion rate 5.385%, cyclohexanol selectivity 60.06%, cyclohexanone selectivity 33.75%, cyclohexyl hydroperoxide selectivity 4.23%, adipic acid selectivity 1.96%, and glutaric acid and other by-products are not detected.

[0041] Example 5

[0042] The experimental process of Example 5 repeats Example 1, except that:

[0043] 1) The oxygen flow rate under standard conditions of 20.0 mL / min was replaced by the oxygen flow rate under standard conditions of 5.0 mL / min;

[0044] 2) Replace “6 mixers are evenly spaced in the reaction pipeline” with “0 mixers are evenly spaced in the reaction pipeline”.

[0045] The remaining conditions of Example 5 are the same as those of Example 1. The experimental results of Example 5 are as follows: cyclohexane conversion rate is 1.462%, cyclohexanol selectivity is 48.85%, cyclohexanone selectivity is 35.48%, cyclohexyl hydroperoxide selectivity is 15.67%, the total selectivity of partial oxidation products is greater than 99%, and glutaric acid and other by-products are not detected. In Example 5, under the condition that no mixer is connected, at a low oxygen flow rate, no excess oxygen overflows during the reaction, and no tail gas emission is required.

[0046] Example 6

[0047] The experimental process of Example 6 repeats Example 1, except that:

[0048] 1) The oxygen flow rate under standard conditions of 20.0 mL / min was replaced by the oxygen flow rate under standard conditions of 56.0 mL / min;

[0049] 2) Replace “6 mixers are evenly spaced in the reaction pipeline” with “0 mixers are evenly spaced in the reaction pipeline”.

[0050] During the experiment of Example 6, the back pressure valve was still kept in an open state, and the other conditions were the same as those of Example 1. The experimental results of Example 6 were: cyclohexane conversion rate 3.447%, cyclohexanol selectivity 57.11%, cyclohexanone selectivity 34.28%, cyclohexyl hydroperoxide selectivity 8.61%, total selectivity of partial oxidation products greater than 99%, and no glutaric acid and other by-products were detected. In Example 6, under the condition that there is no mixer connected and the oxygen flow rate is large, the back pressure will rise when the back pressure valve is closed, and tail gas discharge is required, so the back pressure valve is kept in an open state during the experiment.

[0051] Example 7

[0052] The experimental process of Example 7 repeats Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (30.88 mg, 0.03 mmol) of TPFPP-Mn catalyst", and the other conditions are the same as those of Example 1. The experimental results of Example 7 are: cyclohexane conversion rate 7.183%, cyclohexanol selectivity 59.72%, cyclohexanone selectivity 33.46%, cyclohexyl hydroperoxide selectivity 3.87%, adipic acid selectivity 2.95%, and glutaric acid and other by-products are not detected.

[0053] Example 8

[0054] The experimental process of Example 8 is repeated in Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (31.14 mg, 0.03 mmol) of TPFPP-Cu catalyst", and the other conditions are the same as those in Example 1. The experimental results of Example 8 are: cyclohexane conversion rate 6.548%, cyclohexanol selectivity 62.21%, cyclohexanone selectivity 30.85%, cyclohexyl hydroperoxide selectivity 4.18%, adipic acid selectivity 2.76%, and no glutaric acid and other by-products were detected.

[0055] Example 9

[0056] The experimental process of Example 9 repeats Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (31.19 mg, 0.03 mmol) of TPFPP-Zn catalyst", and the other conditions are the same as those of Example 1. The experimental results of Example 9 are: cyclohexane conversion rate 6.374%, cyclohexanol selectivity 58.74%, cyclohexanone selectivity 34.29%, cyclohexyl hydroperoxide selectivity 4.09%, adipic acid selectivity 2.88%, and glutaric acid and other by-products are not detected.

[0057] Example 10

[0058] The experimental process of Example 10 is repeated in Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (30.99 mg, 0.03 mmol) of TPFPP-Ni catalyst", and the other conditions are the same as those in Example 1. The experimental results of Example 10 are: cyclohexane conversion rate 6.519%, cyclohexanol selectivity 59.53%, cyclohexanone selectivity 33.44%, cyclohexyl hydroperoxide selectivity 3.94%, adipic acid selectivity 3.09%, and glutaric acid and other by-products were not detected.

[0059] Embodiment 11

[0060] The experimental process of Example 11 is repeated in Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (30.91 mg, 0.03 mmol) of TPFPP-Fe catalyst", and the other conditions are the same as those in Example 1. The experimental results of Example 11 are: cyclohexane conversion rate 6.832%, cyclohexanol selectivity 60.62%, cyclohexanone selectivity 32.57%, cyclohexyl hydroperoxide selectivity 3.57%, adipic acid selectivity 3.24%, and glutaric acid and other by-products are not detected.

[0061] Example 12

[0062] The experimental process of Example 12 repeats Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (32.61 mg, 0.03 mmol) of T(2,4,6-triF)-Co catalyst", and the remaining conditions are the same as those of Example 1. The experimental results of Example 12 are: cyclohexane conversion rate 7.32%, cyclohexanol selectivity 59.68%, cyclohexanone selectivity 33.13%, cyclohexyl hydroperoxide selectivity 4.08%, adipic acid selectivity 3.11%, and glutaric acid and other by-products are not detected.

[0063] Embodiment 13

[0064] The experimental process of Example 13 repeats Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (30.88 mg, 0.03 mmol) of T(2,3,6-triCl)-Co catalyst", and the other conditions are the same as those of Example 1. The experimental results of Example 13 are: cyclohexane conversion rate 7.07%, cyclohexanol selectivity 59.67%, cyclohexanone selectivity 33.28%, cyclohexyl hydroperoxide selectivity 4.17%, adipic acid selectivity 2.88%, and no glutaric acid and other by-products are detected.

[0065] Embodiment 14

[0066] The experimental process of Example 14 was repeated in Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" was changed to "addition of (27.15 mg, 0.03 mmol) of T(4-COOCH 3 )-Co catalyst", and the other conditions were the same as in Example 1. The experimental results of Example 14 were: cyclohexane conversion rate 5.764%, cyclohexanol selectivity 58.09%, cyclohexanone selectivity 34.93%, cyclohexyl hydroperoxide selectivity 4.46%, adipic acid selectivity 2.52%, and glutaric acid and other by-products were not detected.

[0067] Embodiment 15

[0068] The experimental process of Example 15 repeats Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (24.34 mg, 0.03 mmol) of T(4-Cl)-Co catalyst", and the other conditions are the same as those of Example 1. The experimental results of Example 15 are: cyclohexane conversion rate 5.556%, cyclohexanol selectivity 57.66%, cyclohexanone selectivity 35.36%, cyclohexyl hydroperoxide selectivity 4.51%, adipic acid selectivity 2.47%, and no glutaric acid and other by-products are detected.

[0069] Example 16

[0070] The experimental process of Example 16 repeats Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (19.81 mg, 0.03 mmol) of TPP-Co catalyst", and the remaining conditions are the same as those of Example 1. The experimental results of Example 16 are: cyclohexane conversion rate 5.198%, cyclohexanol selectivity 60.17%, cyclohexanone selectivity 32.67%, cyclohexyl hydroperoxide selectivity 4.94%, adipic acid selectivity 2.22%, and glutaric acid and other by-products are not detected.

[0071] Embodiment 17

[0072] The experimental process of Example 17 repeats Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (26.73 mg, 0.03 mmol) of T(4-COOH)-Co catalyst", and the remaining conditions are the same as those of Example 1. The experimental results of Example 17 are: cyclohexane conversion rate 4.954%, cyclohexanol selectivity 58.66%, cyclohexanone selectivity 34.19%, cyclohexyl hydroperoxide selectivity 4.87%, adipic acid selectivity 2.28%, and no glutaric acid and other by-products are detected.

[0073] Embodiment 18

[0074] The experimental process of Example 18 is repeated in Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (5.21 mg, 0.005 mmol) of TPFPP-Co catalyst", and the other conditions are the same as in Example 1. The experimental results of Example 18 are: cyclohexane conversion rate 4.473%, cyclohexanol selectivity 59.63%, cyclohexanone selectivity 33.76%, cyclohexyl hydroperoxide selectivity 4.55%, adipic acid selectivity 2.06%, and glutaric acid and other by-products are not detected.

[0075] Embodiment 19

[0076] The experimental process of Example 19 repeats Example 1, except that "addition of (31.25 mg, 0.03 mmol) of TPFPP-Co catalyst" is changed to "addition of (41.67 mg, 0.04 mmol) of TPFPP-Co catalyst", and the remaining conditions are the same as those of Example 1. The experimental results of Example 19 are: cyclohexane conversion rate 7.553%, cyclohexanol selectivity 59.94%, cyclohexanone selectivity 33.27%, cyclohexyl hydroperoxide selectivity 3.84%, adipic acid selectivity 2.95%, and glutaric acid and other by-products are not detected.

[0077] Embodiment 20

[0078] The experimental process of Example 20 repeats that of Example 1, with the only difference being that "a 316L stainless steel pipeline with a length of 60.0 m and an inner diameter of 0.6 mm (the pipeline is connected by 6 mixers)" is changed to "a 316L stainless steel pipeline with a length of 60.0 m and an inner diameter of 0.5 mm (the pipeline is connected by 6 mixers)", and the remaining conditions are the same as those of Example 1. The experimental results of Example 20 are: cyclohexane conversion rate 6.844%, cyclohexanol selectivity 60.18%, cyclohexanone selectivity 33.09%, cyclohexyl hydroperoxide selectivity 3.92%, adipic acid selectivity 2.81%, and glutaric acid and other by-products were not detected.

[0079] Embodiment 21

[0080] The experimental process of Example 21 repeats that of Example 1, with the only difference being that “a 316L stainless steel pipeline with a length of 60.0 m and an inner diameter of 0.6 mm (the pipeline is connected by 6 mixers)” is changed to “a 316L stainless steel pipeline with a length of 60.0 m and an inner diameter of 3.0 mm (the pipeline is connected by 6 mixers)”, and the remaining conditions are the same as those of Example 1. The experimental results of Example 21 are: cyclohexane conversion rate 4.811%, cyclohexanol selectivity 58.15%, cyclohexanone selectivity 34.92%, cyclohexyl hydroperoxide selectivity 4.77%, adipic acid selectivity 2.16%, and glutaric acid and other by-products were not detected.

[0081] Embodiment 22

[0082] The experimental process of Example 22 repeats that of Example 1, with the only difference being that the "316L stainless steel pipeline with a length of 60.0 m and an inner diameter of 0.6 mm (the pipeline is connected by 6 mixers)" is changed to "316L stainless steel pipeline with a length of 20.0 m and an inner diameter of 0.6 mm (the pipeline is connected by 6 mixers)", and the remaining conditions are the same as those of Example 1. The experimental results of Example 22 are: cyclohexane conversion rate 2.566%, cyclohexanol selectivity 30.51%, cyclohexanone selectivity 30.82%, cyclohexyl hydroperoxide selectivity 38.67%, the total selectivity of partial oxidation products is greater than 99%, and no acid or other by-products are detected.

[0083] Embodiment 23

[0084] The experimental process of Example 23 repeats that of Example 1, with the only difference being that the "316L stainless steel pipeline with a length of 60.0 m and an inner diameter of 0.6 mm (the pipeline is connected by 6 mixers)" is changed to "316L stainless steel pipeline with a length of 150.0 m and an inner diameter of 0.6 mm (the pipeline is connected by 6 mixers)", and the remaining conditions are the same as those of Example 1. The experimental results of Example 23 are: cyclohexane conversion rate 10.088%, cyclohexanol selectivity 57.68%, cyclohexanone selectivity 34.58%, cyclohexyl hydroperoxide selectivity 2.66%, adipic acid selectivity 5.08%, and glutaric acid and other by-products were not detected.

[0085] Embodiment 24

[0086] The experimental process of Example 24 repeats that of Example 1, with the only difference being that the "316L stainless steel pipeline with a length of 60.0 m and an inner diameter of 0.6 mm (the pipeline is connected by 6 mixers)" is changed to "316L stainless steel pipeline with a length of 90.0 m and an inner diameter of 0.6 mm (the pipeline is connected by 6 mixers)", and the remaining conditions are the same as those of Example 1. The experimental results of Example 24 are: cyclohexane conversion rate 11.484%, cyclohexanol selectivity 59.59%, cyclohexanone selectivity 34.39%, cyclohexyl hydroperoxide selectivity 2.56%, adipic acid selectivity 5.46%, and glutaric acid and other by-products were not detected.

[0087] Embodiment 25

[0088] The experimental process of Example 25 repeats Example 24, except that:

[0089] 1) The delivery flow rate of "raw material liquid containing catalyst" is changed from 2.0 mL / min to 0.5 mL / min;

[0090] 2) The oxygen flow rate under standard conditions of 20.0 mL / min was replaced by the oxygen flow rate under standard conditions of 5.0 mL / min.

[0091] The rest of the conditions in Example 25 are the same as those in Example 24. The experimental results in Example 25 are as follows: cyclohexane conversion rate 6.635%, cyclohexanol selectivity 59.01%, cyclohexanone selectivity 34.07%, cyclohexyl hydroperoxide selectivity 3.88%, adipic acid selectivity 3.04%, and no glutaric acid and other by-products were detected.

[0092] Embodiment 26

[0093] The experimental process of Example 26 repeats Example 24, except that:

[0094] 1) The delivery flow rate of "raw material liquid containing catalyst" is changed from 2.0 mL / min to 4.0 mL / min;

[0095] 2) The oxygen flow rate under standard conditions was changed from 20.0 mL / min to 40.0 mL / min.

[0096] The rest of the conditions in Example 26 are the same as those in Example 24. The experimental results in Example 26 are as follows: cyclohexane conversion rate 9.241%, cyclohexanol selectivity 58.31%, cyclohexanone selectivity 34.27%, cyclohexyl hydroperoxide selectivity 3.23%, adipic acid selectivity 4.19%, and no glutaric acid and other by-products were detected.

[0097] Embodiment 27

[0098] The experimental process of Example 27 repeats Example 24, except that:

[0099] 1) The delivery flow rate of "raw material liquid containing catalyst" is changed from 2.0 mL / min to 3.0 mL / min;

[0100] 2) The oxygen flow rate under standard conditions was changed from 20.0 mL / min to 30.0 mL / min.

[0101] The remaining conditions of Example 27 are the same as those of Example 24. The experimental results of Example 27 are: cyclohexane conversion rate 12.037%, cyclohexanol selectivity 56.99%, cyclohexanone selectivity 34.24%, cyclohexyl hydroperoxide selectivity 2.66%, adipic acid selectivity 6.11%, and no glutaric acid and other by-products were detected.

[0102] Embodiment 28

[0103] The experimental process of Example 28 repeats Example 27, with the only difference being that the delivery flow rate of the "catalyst-containing raw material liquid" is replaced from 3.0 mL / min to 0.5 mL / min.

[0104] The remaining conditions of Example 28 are the same as those of Example 27. The experimental results of Example 28 are: cyclohexane conversion rate 5.139%, cyclohexanol selectivity 59.75%, cyclohexanone selectivity 33.58%, cyclohexyl hydroperoxide selectivity 4.05%, adipic acid selectivity 2.62%, and no glutaric acid and other by-products were detected.

[0105] Embodiment 29

[0106] The experimental process of Example 29 repeats Example 27, with the only difference being that the delivery flow rate of the "catalyst-containing raw material liquid" is replaced from 3.0 mL / min to 10.0 mL / min.

[0107] Example 29 The remaining conditions are the same as those of Example 27. The experimental results of Example 29 are: cyclohexane conversion rate 6.542%, cyclohexanol selectivity 59.23%, cyclohexanone selectivity 34.05%, cyclohexyl hydroperoxide selectivity 3.85%, adipic acid selectivity 2.87%, and no glutaric acid and other by-products are detected. Example 29 Under the condition that there are six mixers in the pipeline, when the liquid flow rate is large, the pressure of the back pressure valve of the gas outlet pipeline on the gas-liquid separator will rise slightly when it is closed, and tail gas discharge is also required.

[0108] Embodiment 30

[0109] The experimental process of Example 30 repeats Example 27, with the only difference being that the delivery flow rate of the "catalyst-containing raw material liquid" is replaced from 3.0 mL / min to 2.4 mL / min.

[0110] The remaining conditions of Example 30 are the same as those of Example 27. The experimental results of Example 30 are: cyclohexane conversion rate 12.667%, cyclohexanol selectivity 57.65%, cyclohexanone selectivity 33.28%, cyclohexyl hydroperoxide selectivity 2.53%, adipic acid selectivity 6.54%, and no glutaric acid and other by-products were detected.

[0111] Embodiment 31

[0112] The experimental process of Example 31 repeats Example 30, with the only difference being that the flow rate of oxygen delivered under standard conditions of 30.0 mL / min is replaced by the flow rate of oxygen delivered under standard conditions of 5.0 mL / min.

[0113] The rest of the conditions in Example 31 are the same as those in Example 30. The experimental results in Example 31 are as follows: cyclohexane conversion rate 5.413%, cyclohexanol selectivity 58.81%, cyclohexanone selectivity 34.66%, cyclohexyl hydroperoxide selectivity 4.55%, adipic acid selectivity 1.98%, and no glutaric acid and other by-products were detected.

[0114] Embodiment 32

[0115] The experimental process of Example 32 repeats Example 30, with the only difference being that the flow rate of oxygen delivered under standard conditions of 30.0 mL / min is replaced by the flow rate of oxygen delivered under standard conditions of 99.0 mL / min.

[0116] Example 32 The remaining conditions are the same as those of Example 30. The experimental results of Example 32 are: cyclohexane conversion rate 8.462%, cyclohexanol selectivity 59.45%, cyclohexanone selectivity 34.04%, cyclohexyl hydroperoxide selectivity 3.27%, adipic acid selectivity 3.24%, and no glutaric acid and other by-products were detected. Example 32 Under the condition that there are six mixers in the pipeline, when the gas flow rate is large, the pressure of the back pressure valve of the gas outlet pipeline on the gas-liquid separator will rise slightly when it is closed, and tail gas discharge is also required.

[0117] Embodiment 33

[0118] The experimental process of Example 33 repeats Example 30, with the only difference being that the flow rate of oxygen delivered under standard conditions of 30.0 mL / min is replaced by the flow rate of oxygen delivered under standard conditions of 60.0 mL / min.

[0119] The rest of the conditions in Example 33 are the same as those in Example 30. The experimental results in Example 33 are as follows: cyclohexane conversion rate is 13.845%, cyclohexanol selectivity is 57.09%, cyclohexanone selectivity is 33.45%, cyclohexyl hydroperoxide selectivity is 2.52%, adipic acid selectivity is 6.94%, and glutaric acid and other by-products are not detected.

[0120] Embodiment 34

[0121] The experimental process of Example 34 repeats Example 30, with the only difference being that the flow rate of oxygen delivered under standard conditions of 30.0 mL / min is replaced by the flow rate of oxygen delivered under standard conditions of 56.0 mL / min.

[0122] The rest of the conditions in Example 34 are the same as those in Example 30. The experimental results in Example 34 are as follows: cyclohexane conversion rate is 14.683%, cyclohexanol selectivity is 56.65%, cyclohexanone selectivity is 33.14%, cyclohexyl hydroperoxide selectivity is 2.37%, adipic acid selectivity is 7.84%, and glutaric acid and other by-products are not detected.

[0123] Embodiment 35

[0124] The experimental process of Example 35 is the same as that of Example 34, except that the reaction temperature is changed from 170° C. to 100° C. The other conditions are the same as those of Example 34, and the experimental results of Example 35 are as follows: cyclohexane conversion rate is 2.795%, cyclohexanol selectivity is 62.28%, cyclohexanone selectivity is 30.99%, cyclohexyl hydroperoxide selectivity is 6.15%, the total selectivity of partial oxidation products is greater than 99%, and glutaric acid and other by-products are not detected.

[0125] Embodiment 36

[0126] The experimental process of Example 36 is the same as that of Example 34, except that the reaction temperature is changed from 170° C. to 200° C. The other conditions are the same as those of Example 34, and the experimental results of Example 36 are: cyclohexane conversion rate 17.655%, cyclohexanol selectivity 47.98%, cyclohexanone selectivity 25.38%, cyclohexyl hydroperoxide selectivity 2.68%, adipic acid selectivity 15.47%, glutaric acid selectivity 8.49%, and no other by-products are detected.

[0127] Embodiment 37

[0128] The experimental process of Example 37 is the same as that of Example 34, except that the reaction temperature is changed from 170° C. to 150° C. The other conditions are the same as those of Example 34. The experimental results of Example 37 are as follows: cyclohexane conversion rate is 8.147%, cyclohexanol selectivity is 59.26%, cyclohexanone selectivity is 33.79%, cyclohexyl hydroperoxide selectivity is 3.58%, adipic acid selectivity is 3.37%, and glutaric acid and other by-products are not detected.

[0129] Embodiment 38

[0130] The experimental process of Example 38 is repeated in Example 34, except that "measure 200.0 mL of dry cyclohexane" is replaced by "measure 200.0 mL of toluene". The remaining conditions are the same as those of Example 34. The experimental results of Example 38 are: toluene conversion rate 38.768%, benzyl alcohol selectivity 10.75%, benzaldehyde selectivity 24.28%, benzyl hydroperoxide selectivity 45.19%, acid selectivity 19.78%, and no other by-products are detected.

[0131] Embodiment 39

[0132] The experimental process of Example 39 is repeated in Example 34, except that "measure 200.0 mL of dry cyclohexane" is replaced by "measure 200.0 mL of p-chlorotoluene". The remaining conditions are the same as those of Example 34. The experimental results of Example 39 are: p-chlorotoluene conversion rate 39.735%, p-chlorobenzyl alcohol selectivity 17.24%, p-chlorobenzaldehyde selectivity 26.94%, p-chlorobenzyl hydroperoxide selectivity 40.64%, acid selectivity 15.18%, and no other by-products are detected.

[0133] Embodiment 40

[0134] The experimental process of Example 40 is repeated in Example 34, except that "measure 200.0 mL of dry cyclohexane" is replaced by "measure 200.0 mL of dry ethylbenzene". The remaining conditions are the same as those of Example 34. The experimental results of Example 40 are: ethylbenzene conversion rate 38.716%, phenylethanol selectivity 15.61%, acetophenone selectivity 21.75%, phenylethyl hydroperoxide selectivity 62.64%, and no acid or other byproducts are detected.

[0135] Embodiment 41

[0136] The experimental process of Example 41 is repeated in Example 34, except that "measure 200.0 mL of dry cyclohexane" is replaced by "measure 200.0 mL of dry p-ethylnitrobenzene". The remaining conditions are the same as those of Example 34. The experimental results of Example 41 are: p-ethylnitrobenzene conversion rate 40.332%, p-nitrobenzene ethanol selectivity 16.81%, p-nitroacetophenone selectivity 24.73%, p-nitrophenylethyl hydroperoxide selectivity 58.46%, and no acid or other byproducts are detected.

[0137] Embodiment 42

[0138] The experimental process of Example 42 repeats Example 34, except that "measure 200.0 mL of dry cyclohexane" is replaced by "measure 200.0 mL of dry 1,3-diisopropylbenzene". The remaining conditions are the same as those of Example 34. The experimental results of Example 42 are: 1,3-diisopropylbenzene conversion rate 50.346%, Α,Α'-dihydroxy-1,3-diisopropylbenzene selectivity 5.75%, 1,3-diacetylbenzene selectivity 19.28%, hydroperoxide isopropylbenzene selectivity 55.19%, and no other by-products are detected.

[0139] Embodiment 43

[0140] The experimental process of Example 43 is repeated in Example 34, except that "measure 200.0 mL of dry cyclohexane" is replaced by "measure 200.0 mL of dry p-nitroisopropylbenzene". The remaining conditions are the same as those of Example 34. The experimental results of Example 43 are: p-nitroisopropylbenzene conversion rate is 25.246%, and p-nitrohydroperoxide isopropylbenzene selectivity is 98.36%.

[0141] Embodiment 44

[0142] The experimental process of Example 44 is repeated in Example 34, except that "measure 200.0 mL of dry cyclohexane" is changed to "measure 200.0 mL of dry cyclopentane". The remaining conditions are the same as those of Example 34. The experimental results of Example 44 are: cyclopentane conversion rate 12.768%, cyclopentanol selectivity 57.75%, cyclopentanone selectivity 34.28%, cyclopentyl hydroperoxide selectivity 2.19%, glutaric acid selectivity 5.78%, and no succinic acid and other by-products are detected.

[0143] Embodiment 45

[0144] The experimental process of Example 45 is the same as that of Example 34, except that "measure 200.0 mL of dry cyclohexane" is changed to "measure 200.0 mL of dry cycloheptane". The remaining conditions are the same as those of Example 34. The experimental results of Example 45 are: cycloheptane conversion rate 18.94%, cycloheptanol selectivity 55.64%, cycloheptanone selectivity 34.19%, cycloheptyl hydroperoxide selectivity 3.23%, pimelic acid selectivity 5.94%, and no adipic acid and other by-products were detected.

[0145] Embodiment 46

[0146] The experimental process of Example 46 was repeated in Example 34 except that "measure 200.0 mL of dry cyclohexane" was changed to "measure 200.0 mL of dry cyclooctane". The remaining conditions were the same as those of Example 34. The results of Example 46 were: cyclooctane conversion rate 38.24%, cyclooctanol selectivity 55.58%, cyclooctanone selectivity 35.07%, cyclooctyl hydroperoxide selectivity 2.64%, suberic acid selectivity 6.71%, and no pimelic acid and other byproducts were detected.

[0147] The contents described in this specification are merely an enumeration of implementation forms of the inventive concept, and the protection scope of the present invention should not be regarded as being limited to the specific forms described in the embodiments.

Claims

1. A method for the oxidation of hydrocarbon compounds by metalloporphyrin-catalyzed O2 without tail gas emission based on a continuous flow tubular reaction, characterized in that The following steps are involved: 1) The hydrocarbon compound and the metal porphyrin catalyst are mixed and dissolved by ultrasonication to obtain a raw material liquid containing the catalyst; 2) Step 1) The raw material liquid is introduced into the 1# mixer (5), and O2 is also introduced into the 1# mixer (5). The raw material liquid and O2 are mixed in the 1# mixer (5) and then enter the reaction pipe. The reaction system in the reaction pipe is heated to the reaction temperature to perform a catalytic oxidation reaction. The reaction pipe is evenly spaced n 2# mixers (6) and evenly divided into n+1 reaction sections by the 2# mixers (6), where n is an integer ≥1. 3) The reaction liquid discharged from the outlet of the reaction pipeline is first cooled by a cooler (8) and then passed into a gas-liquid separator (9) for gas-liquid separation. The reaction liquid discharged from the bottom liquid outlet of the gas-liquid separator (9) is passed into a product collection tank (11) to obtain a reaction mixture containing partial oxidation product alcohols and ketones.

2. A method for the oxidation of hydrocarbon compounds by metalloporphyrin-catalyzed O2 without tail gas emission based on a continuous flow tubular reaction as claimed in claim 1, characterized in that In step 1), the metal porphyrin catalyst is: 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin cobalt (TFPFPP-Co), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin manganese (TFPFPP-Mn), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin copper (TFPFPP-Cu), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin nickel (TFPFPP-Ni), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin iron (TFPFPP-Fe), 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin zinc (TFPFPP-Zn), 5,10,15,20-tetrakis(2,4 ,6-trifluoro) porphyrin cobalt (T(2,4,6-triF)PP-Co), 5,10,15,20-tetrakis(2,3,6-trichloro) porphyrin cobalt (T(2,3,6-triCl)PP-Co), 5,10,15,20-tetrakis(4-chlorophenyl) porphyrin cobalt (T(4-Cl)PP-Co), 5,10,15,20-tetrakis(4-ester) porphyrin cobalt (T(4-COOCH3)PP-Co), 5,10,15,20-tetrakis(4-carboxyl) porphyrin cobalt (T(4-COOH)PP-Co), any one of them or any combination thereof; The dispersion concentration of the metal porphyrin catalyst in the hydrocarbon compound is 0.005-0.04 mmol / L, preferably 0.01-0.03 mmol / L.

3. A method for the oxidation of hydrocarbon compounds by metalloporphyrin-catalyzed O2 without tail gas emission based on a continuous flow tubular reaction as claimed in claim 1, characterized in that The inner diameter of the reaction pipeline is 0.5-3.0 mm, the length of the reaction pipeline is 20.0-150.0 m, and 1-8 2# mixers (6) are arranged in the reaction pipeline.

4. A method for the oxidation of hydrocarbon compounds by metalloporphyrin-catalyzed O2 without tail gas emission based on a continuous flow tubular reaction as claimed in claim 3, characterized in that The inner diameter of the reaction pipeline is 0.6-1.0 mm, the length of the reaction pipeline is 90.0 m-120.0 m, and 2-6 2# mixers (6) are arranged in the reaction pipeline, preferably 4-6 2# mixers (6) are arranged.

5. A method for the oxidation of hydrocarbon compounds by metalloporphyrin catalysis with O2 without tail gas emission based on continuous flow tubular reaction as claimed in claim 3, characterized in that The standard flow rate of oxygen introduced is 5.0-99.0 mL / min, the liquid flow rate of raw material liquid introduced is 0.5-10.0 mL / min, and the ratio of the standard flow rate of oxygen to the liquid flow rate of raw material is 5-50:

1.

6. A method for the oxidation of hydrocarbon compounds by metalloporphyrin-catalyzed O2 without tail gas emission based on a continuous flow tubular reaction as claimed in claim 5, characterized in that The standard flow rate of oxygen is 30-60.0 mL / min, the liquid flow rate of raw material liquid is 2.4-3.0 mL / min, and the ratio of the standard flow rate of oxygen to the liquid flow rate of raw material is 10-25:1, preferably 12.5-25:

1.

7. A method for the oxidation of hydrocarbon compounds by metalloporphyrin-catalyzed O2 without tail gas emission based on a continuous flow tubular reaction as claimed in claim 1, characterized in that The reaction temperature is 100 to 200°C, preferably 150 to 200°C.

8. A method for the oxidation of hydrocarbon compounds by metalloporphyrin-catalyzed O2 without tail gas emission based on a continuous flow tubular reaction as claimed in claim 1, characterized in that The hydrocarbon compound is an alkyl-substituted benzene or a C5-C8 cycloalkane, the substituent on the benzene ring of the alkyl-substituted benzene is H, halogen or nitro, the alkyl on the benzene ring of the alkyl-substituted benzene is a C1-C4 alkyl, and the corresponding partial oxidation products are substituted phenylalkanols, substituted phenylalkanones and peroxides, or C5-C8 cycloalkanols and C5-C8 cycloalkanones.

9. A method for the oxidation of hydrocarbon compounds by metalloporphyrin-catalyzed O2 without tail gas emission based on a continuous flow tubular reaction as claimed in claim 1, characterized in that The method adopts the following device: comprising an oxygen cylinder (2), an air flow meter (4), a liquid storage tank (1) containing a hydrocarbon compound raw material and a catalyst, a liquid flow pump (3), a 1# mixer (5), a reaction pipeline and a post-processing system, wherein the inlet of the 1# mixer (5) is divided into two paths, one of which is connected to the gas outlet of the oxygen cylinder (2) through a pipeline via the air flow meter (4), and the other of which is connected to the liquid storage tank (1) through a pipeline via the liquid flow pump (3), and a plurality of 2# mixers (6) are evenly spaced in the reaction pipeline and are connected to the 2# mixers. (6) multiple reaction sections are evenly separated, the outlet of the 1# mixer (5) is connected to the inlet of the reaction pipeline, and the outlet of the reaction pipeline is further connected to a post-processing system; the post-processing system comprises a cooler (8), a gas-liquid separator (9) and a product collection tank (11), the reaction liquid discharged from the outlet of the reaction pipeline is first cooled by the cooler (8), and then passed into the gas-liquid separator (9) for gas-liquid separation, an exhaust pipeline with a back pressure valve (10) is provided at the top of the gas-liquid separator (9), and the liquid outlet at the bottom of the gas-liquid separator (9) is connected to the product collection tank (11) through a pipeline.

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