Process for acid-catalyzed decomposition of aryl α-hydroperoxide with continuous flow tubular reactor

Abstract

The present disclosure relates to a process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor. The process is a novel process performed in a tubular reactor, taking the aryl -hydroperoxide such as cumene hydroperoxide (CHP) as a raw material and taking acids as a catalyst, performing acid-catalyzed decomposition of the aryl -hydroperoxide solution in a short reaction time ranging from tens of seconds to several minutes, thereby obtaining the phenols; wherein an inert component may be filled in the reactor, so that the effects of heat transmission and mass transfer can be enhanced. The aryl -hydroperoxide and acid are respectively introduced by a metering pump into a mixing module to be mixed, and then enter the tubular reactor to be reacted so as to produce the products such as phenols.

Claims

1. A process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor, wherein the process comprises: respectively forming a homogenous solution of the aryl -hydroperoxide and an acid in a solvent; then synchronously introducing at a flow rate the aryl -hydroperoxide solution and the acid solution by a metering pump into a mixer for mixing, and controlling the flow rate to change the molar ratio of aryl -hydroperoxide to acid to a range of 200:1-1000:1; entering the mixed solution into the tubular reactor for a residence time to carry out reaction to obtain product, controlling temperature of the reaction by an external heat exchanger; after the reaction is completed, flowing product out from an outlet of the reactor and cooling the product; wherein the residence time in the reactor is 40 s-240 s, and the temperature of the reaction is 60 C.-140 C., the aryl of the aryl -hydroperoxide is a phenyl ring, and the aryl -hydroperoxide is a compound containing one or more substituents expressed by the formula I on the phenyl ring: ##STR00006## R1 and R2 each independently represent a C1-C5 alkyl group, and optionally, R1 and R2 are bonded to form a ring, the reactor includes one or more component enhancing effects of mass transfer and heat transmission selected from the group consisting of a Raschig ring, a Pall ring, a Nutter ring, and a Very Special Packing (VSP) ring.

2. The process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor according to claim 1, wherein the aryl -hydroperoxide is at least one selected from the group consisting of cumyl hydroperoxide (CHP), sec-butylbenzene hydroperoxide expressed by Formula I-1, cyclohexylbenzene peroxide expressed by Formula I-2, and m-diisopropylbenzene hydrogen peroxide expressed by Formula I-3: ##STR00007##

3. The process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor according to claim 1, wherein the aryl -hydroperoxide is cumyl hydroperoxide (CHP).

4. The process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor according to claim 1, wherein the process further comprises: analyzing the concentration of each substance in the reaction products by a liquid chromatography external standard method, and the aryl -hydroperoxide is titrated by an iodometric method.

5. The process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor according to claim 3, wherein the CHP is a concentrated oxidation liquid of cumene, the solvent is one of acetone and cumene or a mixture thereof; or the oxidation liquid of cumene is used as a source of the CHP.

6. The process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor according to claim 1, wherein the acid is one or more selected from a group consisting of sulfuric acid, benzenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid.

7. The process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor according to claim 1, wherein the molar ratio of aryl -hydroperoxide to acid is 300:1-1000:1, the mass concentration of aryl -hydroperoxide is 20%-60%, and the mass concentration of acid is 1%-30%.

8. The process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor according to claim 7, wherein the mass concentration of aryl -hydroperoxide is 20%-40%.

9. The process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor according to claim 7, wherein the mass concentration of acid is 1%-15%.

10. The process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor according to claim 1, wherein the residence time in the tubular reactor is 50 s-200 s, and the temperature of the reaction is within a range of 70 C.-130 C.

11. The process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor according to claim 1, wherein the mixer is a micromixer or a static mixer.

12. The process for acid-catalyzed decomposition of aryl -hydroperoxide with a continuous flow tubular reactor according to claim 1, wherein the tubular reactor has an inner diameter of 0.5 mm-30 mm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The FIGURE illustrates a flow chart of the process for preparing phenol by performing acid-catalyzed decomposition of CHP of the invention.

DETAILED DESCRIPTION

(2) In the following Examples 1-13,

(3) selectivity of phenols (phenol, resorcinol)=(molar mass of phenols/molar mass of aryl -hydroperoxide)100%;

(4) selectivity of ketones (butanone, cyclohexanone)=(molar mass of ketones/molar mass of aryl alpha-hydroperoxide)100%.

(5) Examples 1-10 are to illustrate the process for the preparation of phenol by acid-catalyzed decomposition of CHP with a tubular continuous flow reactor. Referring to the technological process of the FIGURE, the following steps are carried out: (1) the CHP solution and the acid solution are respectively introduced by a metering pump into a mixer for mixing, and then introduced into a tubular reactor for reaction, and the system pressure is monitored by a pressure gauge during the whole process; (2) the liquid obtained after the reaction is cooled and collected. The target products and by-products are analyzed by liquid chromatography, and the CHP concentration is titrated by iodometric method.

(6) Examples 11-13 are to illustrate the process for acid-catalyzed decomposition of other aryl -hydroperoxides with a continuous flow tubular reactor. This process is also carried out with reference to the FIGURE, except that the CHP solution in the FIGURE is replaced by a solution of other aryl -hydroperoxide. The target products and by-products are analyzed by the liquid chromatography and optionally the gas chromatography, and the aryl -hydroperoxide concentration is titrated by iodometric method.

Example 1

(7) (1) Apparatus used: a static mixer is used, and the tubular reactor used has an inner diameter of 20 mm.

(8) (2) Acetone is used as a solvent, the mass concentration of the prepared CHP solution is 30%, and the mass concentration of sulfuric acid solution is 2%. The flow rate of the CHP solution is set to 40 mL/min, and the flow rate of the sulfuric acid solution is set to 1 mL/min, both the CHP solution and the sulfuric acid solution are introduced into the mixer to be mixed, and the molar ratio of the CHP to sulfuric acid is 337:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 80 C., and the residence time is 120 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(9) (3) The product is analyzed by liquid chromatography, and the CHP is titrated by iodometric method. The results show that the conversion rate of CHP is 100%, the selectivity of phenol is 99.3%, and the total yield of phenol is 99.3%.

Example 2

(10) (1) Apparatus used: a static mixer is used, and the tubular reactor used has an inner diameter of 30 mm and is filled with Pall rings.

(11) (2) Acetone is used as a solvent, the mass concentration of the prepared CHP solution is 29%, and the mass concentration of sulfuric acid solution is 2%. The flow rate of the CHP solution is set to 36 mL/min, and the flow rate of the sulfuric acid solution is set to 0.9 mL/min, both the CHP solution and the sulfuric acid solution are introduced into the mixer to be mixed, the molar ratio of the CHP to sulfuric acid is 337:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 60 C., and the residence time is 120 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(12) (3) The product is analyzed by liquid chromatography, and the CHP is titrated by iodometric method. The results show that the conversion rate of CHP is 100%, the selectivity of phenol is 98.9%, and the total yield of phenol is 98.9%.

Example 3

(13) (1) Apparatus used: a static mixer is used, the tubular reactor used has an inner diameter of 0.5 mm.

(14) (2) Acetone is used as a solvent, the mass concentration of the prepared CHP solution is 35%, and the mass concentration of sulfuric acid solution is 2.5%. The flow rate of the CHP solution is set to 36 mL/min, and the flow rate of the sulfuric acid solution is set to 0.9 mL/min, both the CHP solution and the sulfuric acid solution are introduced into the mixer to be mixed, and the molar ratio of the CHP to sulfuric acid is 337:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 140 C., and the residence time is 240 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(15) (3) The product is analyzed by liquid chromatography, and the CHP is titrated by iodometric method. The results show that the conversion rate of CHP is 100%, the selectivity of phenol is 97.1%, and the total yield of phenol is 97.1%.

Example 4

(16) (1) Apparatus used: a static mixer is used, and the tubular reactor used has an inner diameter of 8 mm.

(17) (2) Acetone is used as a solvent, the mass concentration of the prepared CHP solution is 30%, and the mass concentration of sulfuric acid solution is 2%. The flow rate of the CHP solution is set to 40 mL/min, and the flow rate of the sulfuric acid solution is set to 0.3 mL/min, both the CHP solution and the sulfuric acid solution are introduced into the mixer to be mixed, and the molar ratio of the CHP to sulfuric acid is 1000:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 110 C., and the residence time is 120 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(18) (3) The product is analyzed by liquid chromatography, and the CHP is titrated by iodometric method. The results show that the conversion rate of CHP is 100%, the selectivity of phenol is 96.2%, and the total yield of phenol is 96.2%.

Example 5

(19) (1) Apparatus used: a micromixer is used, and the tubular reactor used has an inner diameter of 4 mm.

(20) (2) Acetone is used as a solvent, the mass concentration of the prepared CHP solution is 36%, and the mass concentration of sulfuric acid solution is 1%. The flow rate of the CHP solution is set to 29.6 mL/min, and the flow rate of the sulfuric acid solution is set to 3.4 mL/min, both the CHP solution and the sulfuric acid solution are introduced into the micromixer to be mixed, the molar ratio of the CHP to sulfuric acid is 200:1; and the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 80 C., and the residence time is 80 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(21) (3) The product is analyzed by liquid chromatography, and the CHP is titrated by iodometric method. The results show that the conversion rate of CHP is 100%, the selectivity of phenol is 99.6%, and the total yield of phenol is 99.6%.

Example 6

(22) (1) Apparatus used: a static mixer is used, and the tubular reactor used has an inner diameter of 4 mm.

(23) (2) Cumene is used as a solvent, the mass concentration of the prepared CHP solution is 20%, and the mass concentration of sulfuric acid solution is 2%. The flow rate of the CHP solution is set to 29.6 mL/min, and the flow rate of the sulfuric acid solution is set to 0.7 mL/min, both the CHP solution and the sulfuric acid solution are introduced into the mixer to be mixed, the molar ratio of the CHP to sulfuric acid is 242:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 110 C., and the residence time is 136 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(24) (3) The product is analyzed by liquid chromatography, and the CHP is titrated by iodometric method. The results show that the conversion rate of CHP is 100%, the selectivity of phenol is 92.2%, and the total yield of phenol is 92.2%.

Example 7

(25) (1) Apparatus used: a static mixer is used, and the tubular reactor has an inner diameter of 20 mm.

(26) (2) The oxidizing solution of cumene is used as the source of CHP, its mass concentration is 26.4%, and the mass concentration of sulfuric acid is 3% prepared with acetone as a solvent. The flow rate of the CHP solution is set to 40 mL/min, and the flow rate of the sulfuric acid solution is set to 0.7 mL/min, both the CHP solution and the sulfuric acid solution are introduced into to the mixer to be mixed, the molar ratio of the CHP to sulfuric acid is 247:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 80 C., and the residence time is 112 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(27) (3) The product is analyzed by liquid chromatography, and the CHP is titrated by iodometric method. The results show that the conversion rate of CHP is 100%, the selectivity of phenol is 97.1%, and the total yield of phenol is 97.1%.

Example 8

(28) (1) Apparatus used: a static mixer is used, the tubular reactor used has an inner diameter of 20 mm and is filled with Pall rings.

(29) (2) Acetone is used as a solvent, the mass concentration of the prepared CHP solution is 36%, and the mass concentration of methanesulfonic acid is 2%. The flow rate of the CHP solution is set to 40 mL/min, and the flow rate of the methanesulfonic acid solution is set to 1 mL/min, both the CHP solution and the methanesulfonic acid are introduced into the mixer to be mixed, the molar ratio of the CHP to methanesulfonic acid is 337:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 90 C., and the residence time is 120 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(30) (3) The product is analyzed by liquid chromatography, and the CHP is titrated by iodometric method. The results show that the conversion rate of CHP is 100%, the selectivity of phenol is 96.1%, and the total yield of phenol is 96.1%.

Example 9

(31) (1) Apparatus used: a micromixer is used, the tubular reactor used has an inner diameter of 20 mm and is filled with Pall rings.

(32) (2) Acetone is used as a solvent, the mass concentration of the prepared CHP solution is 60%, and the mass concentration of trifluoromethanesulfonic acid solution is 2.5%. The flow rate of the CHP solution is set to 12 mL/min, and the flow rate of the trifluoromethanesulfonic acid solution is set to 0.5 mL/min, both the CHP solution and the trifluoromethanesulfonic acid solution are introduced into the micromixer to be mixed, the molar ratio of the CHP to trifluoromethanesulfonic acid is 535:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 110 C., and the residence time is 136 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(33) (3) The product is analyzed by liquid chromatography, and the CHP is titrated by iodometric method. The results show that the conversion rate of CHP is 100%, the selectivity of phenol is 99.3%, and the total yield of product is 99.3%.

Example 10

(34) (1) Apparatus used: a static mixer is used, the tubular reactor has an inner diameter of 30 mm and is filled with VSP rings.

(35) (2) Acetone is used as a solvent, the mass concentration of the prepared CHP solution is 29%, and the mass concentration of sulfuric acid solution is 30%. The flow rate of the CHP solution is set to 36 mL/min, and the flow rate of the sulfuric acid solution is set to 0.1 mL/min, both the CHP solution and the sulfuric acid solution are introduced into the mixer to be mixed, the molar ratio of the CHP to sulfuric acid is 226:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 60 C., and the residence time is 120 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(36) (3) The product is analyzed by liquid chromatography, and the CHP is titrated by iodometric method. The results show that the conversion rate of CHP is 100%, the selectivity of phenol is 97.9%, and the total yield of phenol is 97.9%.

Example 11

(37) (1) A micro-mixer is used, the tubular reactor has an inner diameter of 30 mm and is filled with Pall rings.

(38) (2) Acetone is used as a solvent, the mass concentration of the prepared sec-butylbenzene hydroperoxide solution is 32%, and the mass concentration of sulfuric acid is 2%. The flow rate of the sec-butylbenzene hydroperoxide solution is set to 32 mL/min, and the flow rate of the sulfuric acid solution is set to 0.8 mL/min, both the sec-butylbenzene hydroperoxide solution and the sulfuric acid solution are introduced into the mixer to be mixed, the molar ratio of the sec-butylbenzene hydroperoxide to sulfuric acid is 337:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 80 C., and the residence time is 135 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(39) (3) The product is analyzed by liquid chromatography and gas chromatography, and the sec-butylbenzene hydroperoxide is titrated by iodometric method. The results show that the conversion rate of sec-butylbenzene hydroperoxide is 100%, the selectivity of phenol is 99.2%, the selectivity of butanone is 99.0%, and the yields of the product phenol and butanone are 99.2% and 99.0%, respectively.

Example 12

(40) (1) A static mixer is used, the tubular reactor has an inner diameter of 20 mm.

(41) (2) Acetone is used as a solvent, the mass concentration of the prepared cyclohyxylbenzene hydroperoxide solution is 40%, and the mass concentration of sulfuric acid solution is 1%. The flow rate of the cyclohyxylbenzene hydroperoxide solution is set to 40 mL/min, and the flow rate of the sulfuric acid solution is set to 0.1 mL/min, both the cyclohyxylbenzene hydroperoxide solution and the sulfuric acid solution are introduced into the mixer to be mixed, the molar ratio of the sec-butylbenzene hydroperoxide to sulfuric acid is 281:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 90 C., and the residence time is 120 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(42) (3) The product is analyzed by liquid chromatography and gas chromatography, and the cyclohyxylbenzene hydroperoxide is titrated by iodometric method. The results show that the conversion rate of cyclohyxylbenzene hydroperoxide is 100%, the selectivity of phenol is 98.8%, the selectivity of cyclohexanone is 99.3%, and the yields of the product phenol and cyclohexanone are 98.8% and 99.3%, respectively.

Example 13

(43) (1) A micro-mixer is used, the tubular reactor has an inner diameter of 20 mm.

(44) (2) Acetone is used as a solvent, the mass concentration of the prepared m-diisopropylbenzene hydroperoxide solution is 11%, and the mass concentration of sulfuric acid solution is 2%. The flow rate of the m-diisopropylbenzene hydroperoxide solution is set to 24 mL/min, and the flow rate of the sulfuric acid solution is set to 0.7 mL/min, both the m-diisopropylbenzene hydroperoxide solution and the sulfuric acid solution are introduced into the mixer to be mixed, the molar ratio of the m-diisopropylbenzene hydroperoxide solution to sulfuric acid solution is 200:1; the mixed raw materials are introduced into the tubular reactor for performing reaction, the reaction temperature is 100 C., and the residence time is 200 s; after the reaction, the obtained product flows out from an outlet of the reactor in a state of continuous flow and is cooled by passing through a coil water bath.

(45) (3) The product is analyzed by liquid chromatography, and the m-diisopropylbenzene hydroperoxide is titrated by iodometric method. The results show that the conversion rate of m-diisopropylbenzene hydroperoxide is 100%, the selectivity of 1,3-dihydroxylbenzene is 95.3%, and the yield of the products is 95.3%.