Reaction system, catalyst and method for preparing β-phenylethanol

Abstract

Disclosed is a method for preparing β-phenylethanol. The method comprises the following steps: (1) reducing a catalyst in a reactor in advance; (2) introducing pre-heated hydrogen gas to warm the reactor to a predetermined temperature; and (3) introducing a raw material styrene oxide to perform a hydrogenation reaction so as to obtain the β-phenylethanol. The catalyst is Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst. The reactor is an ultrasonic field micro-packed bed reactor. The method of the present invention enables the selectivity of the β-phenylethanol to reach 99% or more.

Claims

1. A reaction system for preparing β-phenylethanol, wherein the reaction system comprises: a micro reaction channel for loading a catalyst, wherein the micro reaction channel is a coiled tube having a microsized diameter and used as a reaction site; a Y-shaped channel communicated with one end of the micro reaction channel, the Y-shaped channel comprising two channels, wherein the two channels of the Y-shaped channel are respectively one gas channel for introducing a gas reaction raw material and one liquid channel for introducing a liquid reaction raw material; an outlet filtration unit communicated with the other end of the micro reaction channel, wherein the outlet filtration unit is used for preventing the catalyst in the micro reaction channel from passing through and allowing liquid product and gas to flow out; a gas-liquid separation system communicated with the outlet filtration unit, wherein the gas-liquid separation system is used for separating the liquid product from the gas; and an ultrasonic field generator for applying an ultrasonic field to the micro reaction channel.

2. The reaction system according to claim 1, wherein the ultrasonic field generator has an ultrasonic power of 50-600 W.

3. The reaction system according to claim 1, wherein the Y-shaped channel has at least one channel with a channel diameter of 5-50 μm; the gas channel and the liquid channel of the Y-shaped channel are both composed of a plurality of evenly distributed thin tubes; the number of the thin tubes per channel is 1-20; the number and distribution of the thin tubes of the gas channel and the number and distribution of the thin tubes of the liquid channel are the same; the micro reaction channel has a diameter of 5-500 μm; the outlet filtration unit is an etched silicon column having an average pore diameter of 0.1-15 μm.

4. A catalyst for preparing β-phenylethanol, wherein the catalyst is a nanosized self-assembled catalyst with Al.sub.2O.sub.3 as a carrier, Ni element and Cu element as active components; wherein, based on the mass of the catalyst, the content of the Ni element is 5-30 wt %; the content of the Cu element is 0.5-3.5 wt %; the balance is Al.sub.2O.sub.3 carrier.

5. The catalyst according to claim 4, wherein the catalyst has an average pore diameter of 10-350 nm.

6. The catalyst according to claim 4, wherein the catalyst is obtained by the preparation method comprising the following steps: {circle around (1)} under an uniform stirring condition, mixing 0.001-0.015 mol/L polyisobutylene maleic acid triethanolamine ester and 0.05-0.25 mol/L base oil for lubricating oil fully with a volume ratio of (5-8):1 and raising the temperature slowly to 90-100° C. to obtain mixture A; under an uniform stirring condition, mixing 1-5.5 mol/L aqueous solution of urea and 0.5-1.5 mol/L aqueous solution of Al(NO.sub.3).sub.3.9H.sub.2O with a volume ratio of 1:(3-5) and heating the mixture to 90-100° C. to obtain mixture B; {circle around (2)} mixing the mixtures A and B with a mass ratio of 1:1 to form a super solubility micelle to obtain a primary super solubility micelle self-assembled body; reacting the primary super solubility micelle self-assembled body at 100-110° C., washing the product with water and drying to obtain a secondary nanosized self-assembled body; baking and pulverizing the secondary nanosized self-assembled body to obtain Al.sub.2O.sub.3 carrier; {circle around (3)} mixing 0.01-0.1 mol/L aqueous solution of Ni(NO.sub.3).sub.2 and 0.01-0.05 mol/L aqueous solution of Cu(NO.sub.3).sub.2 to obtain an immersion liquid; adding the Al.sub.2O.sub.3 carrier powder obtained in step {circle around (2)} to the immersion liquid and mixing them evenly by stirring to form a fluid slurry; {circle around (4)} drying and calcining the fluid slurry obtained in step {circle around (3)} to obtain the catalyst.

7. The catalyst according to claim 6, wherein in step {circle around (2)}, the reaction time of the primary super solubility micelle self-assembled body is 2-4 h, the drying temperature of the primary super solubility micelle self-assembled body is 150-200° C., the calcination temperature of the secondary nanosized self-assembled body is 550-600° C., the calcination time of the secondary nanosized self-assembled body is 6-8 h, and the particle diameter of the pulverized Al.sub.2O.sub.3 carrier is 10-30 μm; in step {circle around (4)}, the drying temperature is 110-130° C., the drying time is 8-10 h, the calcination temperature is 300° C.-500° C., and the calcination time is 3-5 h; in step {circle around (4)}, the calcination is performed by injecting the fluid slurry obtained in step {circle around (3)} into the micro reaction channel of the reaction system according to claim 1.

8. A method for preparing β-phenylethanol, comprising the following steps: (1) heating a reactor loaded with catalyst by introducing pre-heated hydrogen gas; (2) introducing styrene oxide to perform a hydrogenation reaction to obtain β-phenylethanol; wherein, the catalyst is the catalyst according to claim 4, the reactor used is the reaction system according to claim 1.

9. The method according to claim 8, wherein prior to step (1), the method comprises a step of reducing the catalyst in the reactor.

10. The method according to claim 9, wherein the reduction step is: firstly raising the temperature of the micro reaction channel to 120-130° C., keeping for 2-2.5 h, then raising the temperature to 200-220° C., and keeping for 18-24 h, to complete the reduction, wherein the hydrogen gas space velocity during the reduction is 300-500 h.sup.−1, the pressure is 0.5-1.5 MPa, and then lowering the temperature to room temperature in hydrogen atmosphere.

11. The method according to claim 8, wherein the temperature of the pre-heated hydrogen gas in step (1) is 25-60° C.

12. The method according to claim 8, wherein in step (2), the flow rate of hydrogen gas is 0.5-13 Nm.sup.3/h; the feed rate of styrene oxide is 1-35 Kg/h; the molar ratio of hydrogen gas to styrene oxide is 2-69.

13. The method according to claim 8, wherein in step (2), the reaction temperature is 30-120° C.; the reaction pressure is 0.3-10 Mpa.

14. The reaction system according to claim 2, wherein the Y-shaped channel has at least one channel having a channel diameter of 5-50 μm; the gas channel and the liquid channel of the Y-shaped channel are both composed of a plurality of evenly distributed thin tubes; the number of the thin tubes per channel is 1-20; the number and distribution of the thin tubes of the gas channel and the number and distribution of the thin tubes of the liquid channel are exactly the same; the micro reaction channel has a diameter of 5-500 μm; the outlet filtration unit is an etched silicon column having an average pore diameter of 0.1-15 μm.

15. The method according to claim 9, wherein the temperature of the pre-heated hydrogen gas in step (1) is 25-60° C.

16. The method according to claim 10, wherein the temperature of the pre-heated hydrogen gas in step (1) is 25-60° C.

17. The method according to claim 9, wherein in step (2), the flow rate of hydrogen gas is 0.5-13 Nm.sup.3/h; the feed rate of styrene oxide is 1-35 Kg/h; the molar ratio of hydrogen gas to styrene oxide is 2-69.

18. The method according to claim 10, wherein in step (2), the flow rate of hydrogen gas is 0.5-13 Nm.sup.3/h; the feed rate of styrene oxide is 1-35 Kg/h; the molar ratio of hydrogen gas to styrene oxide is 2-69.

19. The method according to claim 11, wherein in step (2), the flow rate of hydrogen gas is 0.5-13 Nm.sup.3/h; the feed rate of styrene oxide is 1-35 Kg/h; the molar ratio of hydrogen gas to styrene oxide is 2-69.

20. The method according to claim 9, wherein in step (2), the reaction temperature is 30-120° C.; the reaction pressure is 0.3-10 Mpa.

Description

DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the reaction results of Example 5.

(2) FIG. 2 shows the reaction results of Comparative example 4.

(3) FIG. 3 shows the reaction results of Comparative example 5.

(4) FIG. 4 shows the reaction results of Comparative example 6.

(5) FIG. 5 is a top view of the ultrasonic field micro-packed bed reactor of the present invention, wherein 1 represents: Y-shaped channel, 2 represents: micro reaction channel, 3 represents: ultrasonic field generator, 4 represents: outlet filtration unit, 5 represents: gas-liquid separation system, 6 represents: micro reaction channel heater, 7 represents:

(6) FIG. 6 is a schematic view showing the structure of the micro reaction channel.

(7) FIG. 7 is a schematic view showing the structure of the Y-shaped channel and a cross-sectional view of the gas channel and liquid channel.

DETAILED DESCRIPTION OF THE INVENTION

(8) The present invention will now be described in the following with reference to specific embodiments. It is to be noted herein that the examples are only used to further illustrate the present invention, and are not to be construed as limiting the protection scope of the present invention. Any non-substantial improvement or adjustment made to the present invention according to its contents shall be included in the protection of the present invention.

(9) The following are the sources of the main raw materials and instruments used in the examples:

(10) Polyisobutylene maleic acid triethanolamine ester: SINOPEC Fushun Research Institute of Petroleum and petrochemicals; Base oil for lubricating oil: South Korea SK Lubricating Oil Company; Urea: Panjin Zhongrun Chemical Co., Ltd.; Al(NO.sub.3).sub.3.9H.sub.2O: Huainan Kedi-chem Technology Co., Ltd.; Cu(NO.sub.3).sub.2.3H.sub.2O: Shanghai Aladdin Bio-chem Technology Co., Ltd.; Ni(NO.sub.3).sub.2.6H.sub.2O: Shanghai Aladdin Bio-chem Technology Co., Ltd.; styrene oxide: Aladdin Industrial Corporation; hydrogen gas: Yantai Wanhua Huasheng Gas Co., Ltd.; sodium hydroxide: Xilong Chemical Co., Ltd.; etched silicon column: Suzhou CSE Semiconductor Equipment Technology Co., Ltd.; ultrasonic field generator: Nanjing Hanzhou Technology Co., Ltd.

(11) The average pore diameter can be measured by nitrogen adsorption-desorption method (BET), and the content of the metal component in the catalyst can be measured by ICP (Ion-Coupling Broad Spectrum Method).

(12) The sample was diluted with HPLC grade ethanol and then subject to GC analysis on SHIMADZU AOC-20i using HP-88 (88%-cyanopropyl-aryl-polysiloxane, 100 m×0.25 mm×0.20 μm) capillary chromatographic column, FID detector. The inlet temperature is 280° C., the detector temperature is 300° C., and the column temperature is controlled by programmed temperature: the initial column temperature is maintained at 50° C. for 0.5 min, and the temperature is raised to 120° C. at 3° C./min for 5 min and the temperature is raised to 220° C. at 20° C./min. The column pressure is 77.3 kpa, the column flow rate is 1.1 ml/min, the split ratio is 1:50, and the injection volume is 0.2 μL. Conversion rate and selectivity were calculated using the area normalization method.

(13) The gas reaction raw material and the liquid reaction raw material are respectively divided into a plurality of streams through the two ends of the Y-shaped channel 1, and then collected into the micro reaction channel 2 loaded with catalyst, and the outlet filtration unit 4 is filled with an etched silicon column for filtering the catalyst and the ultrasonic field generator 3 applies an ultrasonic field to the micro reaction channel.

(14) As shown in FIG. 5, the reaction system for preparing β-phenylethanol in the following examples comprises: a micro reaction channel 2, which is a coiled tube having a microsized diameter and used as reaction site; a Y-shaped channel 1 communicated with one end of the micro reaction channel, wherein the two channels of the Y-shaped channel 1 are respectively one gas channel for introducing a gas reaction raw material and one liquid channel for introducing a liquid reaction raw material; an outlet filtration unit 4 communicated with the other end of the micro reaction channel, wherein the outlet filtration unit 4 is used for preventing the catalyst in the micro reaction channel 2 from passing through and allowing liquid product and gas to flow out; a gas-liquid separation system 5 communicated with the outlet filtration unit 4, wherein the gas-liquid separation system 5 is used for separating the liquid product from the gas; an ultrasonic field generator 3 for applying an ultrasonic field to the micro reaction channel 2; a preheater 7 for preheating the gas reaction raw material and the liquid reaction raw material and a heater 6 for heating the micro reaction channel.

(15) Wherein, the ultrasonic field generator 3 is a box, the micro reaction channel 2 is horizontally fixed in the box; the Y-shaped channel 1 and the outlet filtration unit 4 are respectively located outside the box, and respectively located in the middle of the back side and the middle of the front side of the box; the gas channel and the liquid channel of the Y-shaped channel are located at the same height and are disposed in parallel with the bottom surface of the box; the heaters 6 are jacket type heaters and have a total of three sets, the heating elements are placed on the outside of the box by being respectively clamped on the left side and right side of the box, and preheater 7 has two preheaters which are respectively clamped on the gas channel and the liquid channel of the Y-shaped channel.

(16) As shown in FIG. 6, the micro reaction channel 2 is a coiled tube; as shown in FIG. 7, the gas channel and the liquid channel of the Y-shaped channel are composed of a plurality of evenly distributed thin tubes, and the number and distribution of the thin tubes of the gas channel and the number and distribution of the thin tubes of the liquid channel are exactly the same.

(17) Some specific parameters of the reaction system, such as ultrasonic power, the diameters of the Y-shaped channel and the micro reaction channel, etc., will be given in the specific examples.

Example 1

(18) Catalyst Preparation:

(19) Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst CAT-1: based on the mass of the catalyst, the content of Ni was 9.06 wt %, the content of Cu was 1.64 wt %, and the average pore diameter of the catalyst was 33.27 nm.

(20) The Preparation Process of the Catalyst was as Follows:

(21) {circle around (1)} Under an uniform stirring condition, 0.008 mol/L polyisobutylene maleic acid triethanolamine ester and 0.15 mol/L base oil for lubricating oil were fully mixed with a volume ratio of 5:1, and the temperature was slowly raised to 100° C., to obtain mixture A; at the same time, 2.5 mol/L aqueous solution of urea and 0.7 mol/L aqueous solution of Al(NO.sub.3).sub.3.9H.sub.2O were fully mixed with a volume ratio of 1:5 and the mixture was heated to 95° C., stirred evenly during this process, to obtain mixture B; then, the mixtures A and B were slowly mixed with a mass ratio of 1:1 to form a super solubility micelle to obtain a primary super solubility micelle self-assembled body; then the primary super solubility micelle self-assembled body was reacted at 105° C. for 3.5 h, the product was washed with water and dried at 200° C. for 2 h to obtain a secondary nanosized self-assembled body, and then the secondary nanosized self-assembled body was baked at 580° C. for 6 h, and pulverized to obtain a macroporous Al.sub.2O.sub.3 carrier having an average particle diameter of 13.58 μm.

(22) {circle around (2)} 0.02 mol/L aqueous solution of Ni(NO.sub.3).sub.2 and 0.03 mol/L aqueous solution of Cu(NO.sub.3).sub.2 were mixed with a ratio of 9:1 (volume ratio), to obtain an immersion liquid; the macroporous Al.sub.2O.sub.3 carrier powder obtained in step {circle around (1)} was added to the immersion liquid and mixed evenly by stirring, to form a fluid slurry.

(23) {circle around (3)} The fluid slurry obtained in step {circle around (2)} was injected into the micro reaction channel 2 of the aforementioned reaction system, and then dried at 125° C. for 8 h and calcined at 350° C. for 5 h under the effect of the heater 6 of the reaction system, to obtain Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst.

(24) Preparation of β-phenylethanol:

(25) (1) The Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst in the reaction system (the number of streams per channel of the Y-shaped channel 1 was 8, the diameter of the channel was 17.35 μm, the diameter of the micro reaction channel 2 was 228.86 μm, and the average pore diameter of the silicon column of the outlet filtration unit 4 was 3.52 μm) was reduced in advance: at first hydrogen gas was introduced into the micro reaction channel through the gas channel of the Y-shaped channel, and then the temperature of the micro reaction channel was raised to 125° C. by the heater 6, staying for 2 h, then raised to 220° C., staying for 18 h, to compete the reduction, and then the temperature was lowered to room temperature in hydrogen atmosphere, the hydrogen gas space velocity during the reduction process was 320 h.sup.−1, and the pressure was 1.5 Mpa (gauge pressure).

(26) (2) After the reduction of the catalyst was completed, the ultrasonic generator was turned on and the ultrasonic power was set to 300 W, and the micro reaction channel was heated by the hydrogen gas which was introduced by the gas channel of the Y-shaped channel and preheated by the preheater 7, wherein the preheating temperature of the hydrogen gas was 35° C.

(27) (3) After the temperature of the micro reaction channel was raised to 35° C., the raw material styrene oxide was fed at a rate of 10 Kg/h for hydrogenation reaction, the flow rate of hydrogen gas was 6.5 Nm.sup.3/h, the reaction temperature was controlled to 70° C. and the reaction pressure was 1.5 Mpa. After the reaction was carried out for 8 h, the reaction solution was sampled and the composition of the reaction solution was analyzed, and the results are shown in Table 1.

Example 2

(28) Catalyst Preparation:

(29) Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst CAT-2: based on the mass of the catalyst, the content of Ni was 17.82 wt %, the content of Cu was 3.17 wt %, and the average pore diameter of the catalyst was 208.69 nm.

(30) The Preparation Process of the Catalyst was as Follows:

(31) {circle around (1)} Under an uniform stirring condition, 0.003 mol/L polyisobutylene maleic acid triethanolamine ester and 0.24 mol/L base oil for lubricating oil were fully mixed with a volume ratio of 7:1, and the temperature was slowly raised to 100° C., to obtain mixture A; at the same time, 5.2 mol/L aqueous solution of urea and 1.1 mol/L aqueous solution of Al(NO.sub.3).sub.3.9H.sub.2O were fully mixed with a volume ratio of 1:3.3 and the mixture was heated to 90° C., stirred evenly during this process, to obtain mixture B; then, the mixtures A and B were slowly mixed with a mass ratio of 1:1 to form a super solubility micelle to obtain a primary super solubility micelle self-assembled body; the primary super solubility micelle self-assembled body was reacted at 105° C. for 3 h, the product was washed with water and dried at 185° C. for 1.5 h to obtain a secondary nanosized self-assembled body, and then the secondary nanosized self-assembled body was baked at 550° C. for 8 h, and pulverized to obtain a macro porous Al.sub.2O.sub.3 carrier having an average particle diameter of 19.36 μm.

(32) {circle around (2)} 0.034 mol/L aqueous solution of Ni(NO.sub.3).sub.2 and 0.05 mol/L aqueous solution of Cu(NO.sub.3).sub.2 were mixed with a ratio of 9:1 (volume ratio), to obtain an immersion liquid; the macro porous Al.sub.2O.sub.3 carrier powder obtained in step {circle around (1)} was added to the immersion liquid and mixed evenly by stirring, to form a fluid slurry.

(33) {circle around (3)} The fluid slurry obtained in step {circle around (2)} was injected into the micro reaction channel 2 of the aforementioned reaction system, and then dried at 110° C. for 8 h and calcined at 500° C. for 5 h under the effect of the heater 6 of the reaction system, to obtain Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst.

(34) Preparation of β-phenylethanol:

(35) (1) The Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst in the reaction system (the number of streams per channel of the Y-shaped channel 1 was 14, the diameter of the channel was 25.56 μm, the diameter of the micro reaction channel 2 was 342.87 μm, and the average pore diameter of the silicon column of the outlet filtration unit 4 was 1.63 μm) was reduced in advance: at first hydrogen gas was introduced into the micro reaction channel through the gas channel of the Y-shaped channel, and then the temperature of the micro reaction channel was raised to 120° C. by the heater 6, staying for 2.5 h, then raised to 200° C., staying for 18 h to complete the reduction, and then the temperature was lowered to room temperature in hydrogen atmosphere, the hydrogen gas space velocity during the reduction process was 500 h.sup.−1, and the pressure was 0.5 Mpa (gauge pressure).

(36) (2) After the reduction of the catalyst was completed, the ultrasonic generator was turned on and the ultrasonic power was set to 200 W, and the micro reaction channel was heated by the hydrogen gas which was introduced by the gas channel of the Y-shaped channel and pre-heated by the preheater 7, wherein the preheating temperature of the hydrogen gas was 40° C.

(37) (3) After the temperature of the micro reaction channel was raised to 40° C., the raw material styrene oxide was fed at a rate of 5 Kg/h for hydrogenation reaction, the flow rate of hydrogen gas was 2 Nm.sup.3/h, the reaction temperature was controlled to 50° C. and the reaction pressure was 0.5 Mpa. After the reaction was carried out for 8 h, the reaction solution was sampled and the composition of the reaction solution was analyzed, and the results are shown in Table 1.

Example 3

(38) Catalyst Preparation:

(39) Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst CAT-3: based on the mass of the catalyst, the content of Ni was 24.88 wt %, the content of Cu was 1.36 wt %, and the average pore diameter of the catalyst was 146.21 nm.

(40) The Preparation Process of the Catalyst was as Follows:

(41) {circle around (1)} Under an uniform stirring condition, 0.015 mol/L polyisobutylene maleic acid triethanolamine ester and 0.06 mol/L base oil for lubricating oil were fully mixed with a volume ratio of 7:1, and the temperature was slowly raised to 95° C., to obtain mixture A; at the same time, 2.6 mol/L aqueous solution of urea and 0.75 mol/L aqueous solution of Al(NO.sub.3).sub.3.9H.sub.2O were fully mixed with a volume ratio of 1:4.7 and the mixture was heated to 100° C., stirred evenly during this process, to obtain mixture B; then, the mixtures A and B were slowly mixed with a mass ratio of 1:1 to form a super solubility micelle to obtain a primary super solubility micelle self-assembled body; then the primary super solubility micelle self-assembled body was reacted at 110° C. for 2 h, the product was washed with water and dried at 150° C. for 2 h to obtain a secondary nanosized self-assembled body, and then the secondary nanosized self-assembled body was baked at 600° C. for 6 h, and pulverized to obtain a macro porous Al.sub.2O.sub.3 carrier having an average particle diameter of 28.36 μm.

(42) {circle around (2)} 0.044 mol/L aqueous solution of Ni(NO.sub.3).sub.2 and 0.02 mol/L aqueous solution of Cu(NO.sub.3).sub.2 were mixed with a ratio of 9:1 (volume ratio), to obtain an immersion liquid; the macroporous Al.sub.2O.sub.3 carrier powder obtained in step {circle around (1)} was added to the immersion liquid, to form a fluid slurry.

(43) {circle around (3)} The fluid slurry obtained in step {circle around (2)} was injected into the micro reaction channel 2 of the aforementioned reaction system, and then dried at 130° C. for 9 h and calcined at 450° C. for 5 h under the effect of the heater 6 of the reaction system, to obtain Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst.

(44) Preparation of β-phenylethanol:

(45) (1) The Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst in the reaction system (the number of streams per channel of the Y-shaped channel 1 was 17, the diameter of the channel was 7.32 μm, the diameter of the micro reaction channel 2 was 48.62 μm, and the average pore diameter of the silicon column of the outlet filtration unit 4 was 11.33 μm) was reduced in advance: at first hydrogen gas was introduced into the micro reaction channel through the gas channel of the Y-shaped channel, and then the temperature of the micro reaction channel was raised to 125° C. by the heater 6, staying for 2.5 h, then raised to 210° C., staying for 22 h to complete the reduction, and then the temperature was lowered to room temperature in hydrogen atmosphere, the hydrogen gas space velocity during the reduction process was 450 h.sup.−1, and the pressure was 1.0 Mpa (gauge pressure).

(46) (2) After the reduction of the catalyst was completed, the ultrasonic generator was turned on and the ultrasonic power was set to 250 W, and the reactor was heated by the hydrogen gas which was introduced by the gas channel of the Y-shaped channel and pre-heated by the preheater 7, wherein the preheating temperature of the hydrogen gas was 25° C.

(47) (3) After the temperature of the micro reaction channel was raised to 25° C., the raw material styrene oxide was fed at a rate of 7.5 Kg/h for hydrogenation reaction, the flow rate of hydrogen gas was 4.5 Nm.sup.3/h, the reaction temperature was controlled to 35° C. and the reaction pressure was 7 Mpa. After the reaction was carried out for 8 h, the reaction solution was sampled and the composition of the reaction solution was analyzed, and the results are shown in Table 1.

Example 4

(48) Catalyst Preparation:

(49) Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst CAT-4: based on the mass of the catalyst, the content of Ni was 22.37 wt %, the content of Cu was 1.71 wt %, and the average pore diameter of the catalyst was 311.58 nm.

(50) The Preparation Process of the Catalyst was as Follows:

(51) {circle around (1)} Under an uniform stirring condition, 0.002 mol/L polyisobutylene maleic acid triethanolamine ester and 0.22 mol/L base oil for lubricating oil were fully mixed with a volume ratio of 8:1, and the temperature was slowly raised to 95° C., to obtain mixture A; at the same time, 1.1 mol/L aqueous solution of urea and 1.35 mol/L aqueous solution of Al(NO.sub.3).sub.3.9H.sub.2O were fully mixed with a volume ratio of 1:3.5 and the mixture was heated to 100° C., stirred evenly during this process, to obtain mixture B; then, the mixtures A and B were slowly mixed with a mass ratio of 1:1 to form a super solubility micelle to obtain a primary super solubility micelle self-assembled body; then the primary super solubility micelle self-assembled body was reacted at 110° C. for 4 h, the product was washed with water and dried at 200° C. for 1.5 h to obtain a secondary nanosized self-assembled body, and then the secondary nanosized self-assembled body was baked at 560° C. for 7.5 h, and pulverized to obtain a macroporous Al.sub.2O.sub.3 carrier having an average particle diameter of 19.64 μm.

(52) {circle around (2)} 0.047 mol/L aqueous solution of Ni(NO.sub.3).sub.2 and 0.03 mol/L aqueous solution of Cu(NO.sub.3).sub.2 were mixed with a ratio of 9:1 (volume ratio), to obtain an immersion liquid; the macroporous Al.sub.2O.sub.3 carrier powder obtained in step {circle around (1)} was added to the immersion liquid, to form a fluid slurry.

(53) {circle around (3)} The fluid slurry obtained in step {circle around (2)} was injected into the micro reaction channel 2 of the aforementioned reaction system, and then dried at 118° C. for 10 h and calcined at 500° C. for 5 h under the effect of the heater 6 of the reaction system, to obtain Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst.

(54) Preparation of β-phenylethanol:

(55) (1) The Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst in the reaction system (the number of streams per channel of the Y-shaped channel 1 was 8, the diameter of the channel was 15.98 μm, the diameter of the micro reaction channel 2 was 256.76 μm, and the average pore diameter of the silicon column of the outlet filtration unit 4 was 8.52 μm) was reduced in advance: at first hydrogen gas was introduced into the micro reaction channel through the gas channel of the Y-shaped channel, and then the temperature of the micro reaction channel was raised to 120° C. by the heater 6, staying for 2.5 h, then raised to 220° C., staying for 20 h to complete the reduction, and then the temperature was lowered to room temperature in hydrogen atmosphere, the hydrogen gas space velocity during the reduction process was 400 h.sup.−1, and the pressure was 0.8 Mpa (gauge pressure).

(56) (2) After the reduction of the catalyst was completed, the ultrasonic generator was turned on and the ultrasonic power was set to 400 W, and the micro reaction channel was heated by the hydrogen gas which was introduced by the gas channel of the Y-shaped channel and pre-heated by the preheater 7, wherein the preheating temperature of the hydrogen gas was 40° C.

(57) (3) After the temperature of the micro reaction channel was raised to 40° C., the raw material styrene oxide was fed at a rate of 5 Kg/h for hydrogenation reaction, the flow rate of hydrogen gas was 3 Nm.sup.3/h, the reaction temperature was controlled to 65° C. and the reaction pressure was 0.8 Mpa. After the reaction was carried out for 8 h, the reaction solution was sampled and the composition of the reaction solution was analyzed, and the results are shown in Table 1.

Example 5

(58) Catalyst Preparation:

(59) Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst CAT-5: based on the mass of the catalyst, the content of Ni was 23.09 wt %, the content of Cu was 1.82 wt %, and the average pore diameter of the catalyst was 136.59 nm.

(60) The Preparation Process of the Catalyst was:

(61) {circle around (1)} Under an uniform stirring condition, 0.003 mol/L polyisobutylene maleic acid triethanolamine ester and 0.24 mol/L base oil for lubricating oil were fully mixed with a volume ratio of 8:1, and the temperature was slowly raised to 95° C., to obtain mixture A; at the same time, 3.5 mol/L aqueous solution of urea and 1.35 mol/L aqueous solution of Al(NO.sub.3).sub.3.9H.sub.2O were fully mixed with a volume ratio of 1:4 and the mixture was heated to 100° C., stirred evenly during this process, to obtain mixture B; then, the mixtures A and B were slowly mixed with a mass ratio of 1:1 to form a super solubility micelle to obtain a primary super solubility micelle self-assembled body; then the primary super solubility micelle self-assembled body was reacted at 110° C. for 3 h, the product was washed with water and dried at 180° C. for 2 h to obtain a secondary nanosized self-assembled body, and then the secondary nanosized self-assembled body was baked at 600° C. for 7 h, and pulverized to obtain a macroporous Al.sub.2O.sub.3 carrier having an average particle diameter of 25.71 μm.

(62) {circle around (2)} 0.054 mol/L aqueous solution of Ni(NO.sub.3).sub.2 and 0.035 mol/L aqueous solution of Cu(NO.sub.3).sub.2 were mixed with a ratio of 9:1 (volume ratio), to obtain an immersion liquid; the macroporous Al.sub.2O.sub.3 carrier powder obtained in step {circle around (1)} was added to the immersion liquid, to form a fluid slurry.

(63) {circle around (3)} The fluid slurry obtained in step {circle around (2)} was injected into the micro reaction channel 2 of the aforementioned reaction system, and then dried at 125° C. for 9 h and calcined at 500° C. for 4 h under the effect of the heater 6 of the reaction system, to obtain Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst.

(64) Preparation of β-phenylethanol:

(65) (1) The Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst in the reaction system (the number of streams per channel of the Y-shaped channel 1 was 10, the diameter of the channel was 45.85 μm, the diameter of the micro reaction channel 2 was 208.61 μm, and the average pore diameter of the silicon column of the outlet filtration unit 4 was 1.53 μm) was reduced in advance: at first hydrogen gas was introduced into the micro reaction channel through the gas channel of the Y-shaped channel, and then the temperature of the micro reaction channel was raised to 130° C. by the heater 6, staying for 2.5 h, then raised to 220° C., staying for 24 h to complete the reduction, and then the temperature was lowered to room temperature in hydrogen atmosphere, the hydrogen gas space velocity during the reduction process is 450 h.sup.−1, the pressure is 1.5 Mpa (gauge pressure).

(66) (2) After the reduction of the catalyst was completed, the ultrasonic generator was turned on and the ultrasonic power was set to 350 W, and the micro reaction channel was heated by the hydrogen gas which was introduced by the gas channel of the Y-shaped channel and pre-heated by the preheater 7, wherein the preheating temperature of the hydrogen gas was 45° C.

(67) (3) After the temperature of the micro reaction channel was raised to 45° C., the raw material styrene oxide was fed at a rate of 7.5 Kg/h for hydrogenation reaction, the flow rate of hydrogen gas was 6 Nm.sup.3/h, the reaction temperature was controlled to 110° C. and the reaction pressure was 1.0 Mpa. After the reaction was carried out for 8 h, the reaction solution was sampled and the composition of the reaction solution was analyzed at intervals. The catalyst performance change during the long-term operation was investigated, and the total operation was 4500 h, and the results are shown in Table 1.

(68) As can be seen from the figure, under the process conditions of the present invention, the catalyst had a stable performance, long life and high product selectivity.

Comparative Example 1

(69) 10 g Raney6800 catalyst (Grace), 50 g styrene oxide and 450 g ethanol were added to a reactor (model GSH-1, material 316L, the manufacturer is Weihai Chemical Machinery Co., Ltd.), and after the reactor was closed to replace the air while the pressure was maintained, hydrogen gas was introduced to perform the reaction, wherein the reaction temperature was 80° C., the reaction pressure was 6 Mpa, the stirring speed was 700 rpm and the reaction time was 3 h. After the reaction was completed, the reaction solution was sampled and analyzed, and the results are shown in Table 1.

Comparative Example 2

(70) 10 g Raney6800 catalyst (Grace), 50 g styrene oxide, 450 g ethanol and 0.2 g NaOH were added to a reactor (model GSH-1, material 316L, the manufacturer is Weihai Chemical Machinery Co., Ltd.), and after the reactor was closed to replace the air while the pressure was maintained, hydrogen gas was introduced to perform the reaction, wherein the reaction temperature was 60° C., the reaction pressure was 1 Mpa, the stirring speed was 700 rpm, and the reaction time was 3 h. After the reaction was completed, the reaction solution was sampled and analyzed, and the results are shown in Table 1. As can be seen from the table, the selectivity of β-phenylethanol is not ideal even under the condition of adding auxiliary agent NaOH, and the addition of the auxiliary agent will cause the bottom of the fractionating tower to be blocked during the separation process, and meanwhile will affect the product quality.

Comparative Example 3

(71) 30 g Raney6800 catalyst (Grace) and 500 g styrene oxide were added to a reactor (model GSH-1, material 316L, the manufacturer is Weihai Chemical Machinery Co., Ltd.), and after the reactor was closed to replace the air while the pressure was maintained and exchanged, hydrogen gas was introduced to perform the reaction, wherein the reaction temperature was 80° C., the reaction pressure was 6 MPa, the stirring speed was 700 rpm, and the reaction time was 4.5 h. After the reaction was completed, the reaction solution was sampled and analyzed, and the results are shown in Table 1.

Comparative Example 4

(72) The hydrogenation reaction of styrene oxide was carried out in a common fixed bed with a diameter of 20 mm (model TORCH, material 316SS, manufacturer is Beijing Tuochuan Petrochemical Evaluation Device Technology Development Co., Ltd., reaction tube length is 1400 mm), wherein the catalyst, catalyst reduction procedure, reaction temperature, pressure and space velocity were all the same as that in Example 5, and the operation was continued for 4500 h. The reaction results are shown in FIG. 2.

(73) As can be seen from the figure, with the common fixed bed reactor, the reaction effect was significantly worse than that of the ultrasonic micro-packed bed reactor, and the selectivity of the product β-phenylethanol was obviously decreased.

Comparative Example 5

(74) The Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst in Example 5 was replaced with Raney 6800 (Grace), and the other process parameters were all the same as that in Example 5, and the operation was continued for 4500 h. The reaction results are shown in FIG. 3.

(75) As can be seen from the figure, the performance of the catalyst Raney 6800 was significantly inferior to that of the Ni—Cu/Al.sub.2O.sub.3 nanosized self-assembled catalyst described in this patent.

Comparative Example 6

(76) The styrene oxide was hydrogenated without ultrasonic field and the other process parameters were all the same as that in Example 5, and the operation was continued for 4500 h. The reaction results are shown in FIG. 4.

(77) As can be seen from the figure, after the ultrasonic field was removed, the reaction effect was significantly deteriorated and the catalyst stability was lowered.

(78) TABLE-US-00001 TABLE 1 Conversion Selectivity of Selectivity rate of styrene β-phenyl- of ethyl- No. oxide/% ethanol/% benzene/% Example 1 100 99.34 0.51 Example 2 100 99.07 0.73 Example 3 100 99.52 0.36 Example 4 100 99.35 0.48 Comparative 100 91.42 8.05 example 1 Comparative 100 98.57 1.26 example 2 Comparative 100 79.67 20.15 example 3