WO2018126531A1 - 一种制备β-苯乙醇的反应系统、催化剂及其工艺方法 - Google Patents

一种制备β-苯乙醇的反应系统、催化剂及其工艺方法 Download PDF

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WO2018126531A1
WO2018126531A1 PCT/CN2017/076663 CN2017076663W WO2018126531A1 WO 2018126531 A1 WO2018126531 A1 WO 2018126531A1 CN 2017076663 W CN2017076663 W CN 2017076663W WO 2018126531 A1 WO2018126531 A1 WO 2018126531A1
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catalyst
reaction
channel
temperature
liquid
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French (fr)
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曾伟
陈长生
黎源
杨在刚
杨恒东
胡江林
刘运海
丁可
鲍元野
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万华化学集团股份有限公司
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Priority to EP17889831.8A priority Critical patent/EP3567023A4/en
Priority to JP2019536161A priority patent/JP6856757B2/ja
Priority to US16/475,839 priority patent/US11389780B2/en
Publication of WO2018126531A1 publication Critical patent/WO2018126531A1/zh

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Definitions

  • the invention relates to a reaction system for preparing ⁇ -phenylethanol, a catalyst used, a preparation method of the catalyst and a process for preparing ⁇ -phenylethyl alcohol, in particular to a method for preparing ⁇ -phenylethanol by hydrogenation using styrene oxide as a raw material. Methods.
  • ⁇ -Phenylethanol also known as 2-phenylethanol, phenylethyl alcohol, and ethyl phenylethyl alcohol
  • PDA ⁇ -Phenylethanol
  • 2-phenylethanol phenylethyl alcohol
  • ethyl phenylethyl alcohol is a simple aromatic primary alcohol. It is a colorless liquid at room temperature, with a light, delicate and long-lasting rose aroma. It was first discovered as a characteristic aroma compound in plant flowers, and naturally found in aromatic oils such as neroli, rose oil and geranium oil.
  • ⁇ -phenylethyl alcohol is widely used in various food flavors and tobacco flavors because of its soft, pleasant and long-lasting rose aroma. It is the main raw material for the preparation of rose-flavored food additives and rose-flavor flavors.
  • the use of ⁇ -phenylethyl alcohol as a perfume is second only to vanillin.
  • ⁇ -phenylethyl alcohol is stable in alkali action and insoluble in water, and is often used in lotions and soaps.
  • ⁇ -phenylethyl alcohol has good antibacterial efficacy, it can also be used in aqueous solutions of eye drops and skin care products.
  • ⁇ -phenylethyl alcohol on the market is basically chemically synthesized.
  • the main chemical synthesis methods for ⁇ -phenylethyl alcohol are the benzene-ethylene oxide method (Friedel-Crafts reaction) and the styrene oxide (STO) hydrogenation method.
  • benzene-oxirane products account for about 40%
  • styrene-butadiene hydrogenation products account for about 60%.
  • the products produced by the benzene-ethylene oxide method contain different trace impurities, and the aroma varies greatly, and the quality has not yet reached the standard of the fragrance. Therefore, the styrene styrene hydrogenation process is mainly employed in the perfume industry.
  • Patent US3579593 describes a method for preparing ⁇ -phenylethanol by using skeletons Ni and Pd as catalysts, and the comparative examples show that when Ni alone is used as a catalyst, the by-product ethylbenzene content is as high as 11%; when Pd is used as a catalyst alone, Will produce about 10% phenylacetaldehyde; the yield of ⁇ -phenylethanol is low, only about 85%; meanwhile, if the reaction solution contains a large amount of phenylacetaldehyde, phenylacetaldehyde will further with the product ⁇ -phenylethanol The reaction produces high boilers that block the catalyst channels and cause catalyst deactivation.
  • 6,166,269 and 4,064,186 disclose the addition of NaOH, Na 2 CO 3 , KOH and the like to the reaction system. Although the selectivity and yield of ⁇ -phenylethanol are greatly improved, the addition of the auxiliary base shortens the life of the catalyst. The separation of the later products is difficult, and it is easy to cause many problems such as plugging towers.
  • Patent US2822403 proposes to prepare ⁇ -phenylethyl alcohol under alkaline conditions using water as a solvent, Raney Ni or Co as a catalyst; however, this process requires a large amount of water, and an emulsifier is added to adjust the compatibility of water and styrene oxide. This is a great difficulty for the separation of later products.
  • the hydrogenation of styrene oxide to produce ⁇ -phenylethanol is carried out in a reactor or a tubular reactor. Since hydrogenation of styrene oxide is a strong exothermic reaction, in order to control the heat of reaction, it is often necessary to add a solvent. Solvents are required for the ⁇ -phenylethanol preparation process proposed by the patents CN1111169A, US6979753, US4943667, US2524096, etc., which reduces the production efficiency, complicates the product separation process, and increases the cost of solvent removal.
  • the existing technologies all have certain deficiencies to varying degrees.
  • the poor mass transfer effect leads to the need to add additives to improve the selectivity, but at the same time, the catalyst life is reduced, the product separation is difficult, and even the product quality is affected.
  • the invention provides a reaction system for hydrogenating styrene styrene to prepare ⁇ -phenylethanol; the invention also provides a catalyst for hydrogenating styrene styrene to prepare ⁇ -phenylethanol and a preparation method thereof; In a specific embodiment of the invention, the catalyst has uniform macropores, which can effectively prevent catalyst pore blockage and prolong catalyst life.
  • the present invention still further provides a process for hydrogenating styrene oxide to produce ⁇ -phenylethyl alcohol. In a specific embodiment of the present invention, the process method has relatively mild reaction conditions, simple product separation, and is easy to industrialize and scale up production.
  • a reaction system for preparing ⁇ -phenylethanol comprising a microreaction channel for loading a catalyst, the microreaction channel being a coil of a micron diameter, as a reaction site; and the microreaction a Y-shaped channel communicating with one end of the channel, wherein the two channels of the Y-shaped channel are respectively a gas passage for introducing a gas reaction raw material and a liquid passage for introducing a liquid reaction raw material; and the micro-reaction channel is further An outlet filtration unit communicating at one end, the outlet filtration unit for preventing passage of a catalyst in the microreaction passage to allow liquid product and gas to flow out; a gas-liquid separation system in communication with the outlet filtration unit, the gas-liquid separation a separation system for separating the liquid product and gas; An ultrasonic field generator that applies an ultrasonic field to the microreaction channel.
  • the reaction system also includes a preheater for preheating the gaseous reaction feedstock and the liquid reaction feedstock and a heater for heating the microreaction passage.
  • the ultrasonic field generator has an ultrasonic power of 50 to 600 W, preferably 150 to 400 W, more preferably 200 to 300 W.
  • the Y-shaped channel has a channel diameter of 5 to 50 ⁇ m, preferably 10 to 35 ⁇ m, more preferably 20 to 30 ⁇ m; the gas passage and the liquid passage of the Y-shaped passage are each formed by a plurality of evenly distributed thin tubes (the thin tube is also called a flow)
  • the composition of the strands; the number of streams per channel is from 1 to 20, preferably from 3 to 15, more preferably from 5 to 10; preferably, the number of tubes of the gas passage and the number of tubes of the liquid passage are exactly the same;
  • the reaction raw material and the liquid reaction raw material are respectively divided into a plurality of streams through two channels of the Y-type channel and then collected into the micro-reaction channel; the micro-reaction channel has a diameter of 5 to 500 ⁇ m, preferably 50 to 350 ⁇ m, more preferably 200 to 300 ⁇ m; the outlet filtration unit is filled with an etched silicon column having an average pore diameter of 0.1 to 15 ⁇ m, preferably 0.5 to 10 ⁇ m,
  • reaction system can meet the need to adjust capacity by employing a parallel form.
  • a catalyst for preparing ⁇ -phenylethyl alcohol wherein the catalyst is a nano self-assembled catalyst with Al 2 O 3 as a carrier, Ni element and Cu element as active components; wherein, the content of Ni element is 5 based on the mass of the catalyst ⁇ 30 wt%, preferably 10-27 wt%, more preferably 20-25 wt%; Cu element content is 0.5-3.5 wt%, preferably 1-3 wt%, more preferably 1.5-2 wt%; the balance is an Al 2 O 3 support.
  • the catalyst has an average pore diameter of 10 to 350 nm, preferably 50 to 300 nm, more preferably 100 to 150 nm.
  • the preparation process of the catalyst is:
  • the mixture materials A and B are slowly mixed at a mass ratio of 1:1 to form a super-enriched sol group, and a super-enriched sol group self-assembly is obtained; the primary super-aggregated granule self-assembly is reacted at 100-110 ° C. ⁇ 4h, the product was washed with water and dried at 150-200 ° C for 1-2 h to obtain a secondary nano-self-assembly; the secondary nano-self-assembled body was baked at 550-600 ° C for 6-8 h, and pulverized to obtain a particle size of 10 ⁇ . 30 ⁇ m macroporous Al 2 O 3 carrier;
  • the fluid slurry obtained in the step 3 is dried at 110 ° C to 130 ° C for 8 to 10 h, and calcined at 300 ° C to 500 ° C for 3 to 5 h, preferably the fluidity slurry is injected into the microreaction channel in the reaction system. get on.
  • a process for preparing ⁇ -phenylethyl alcohol comprises the following steps: (1) heating a reactor loaded with a catalyst by introducing preheated hydrogen; (2) introducing styrene oxide to perform hydrogenation reaction to obtain ⁇ - phenylethyl alcohol; the catalyst is the above-mentioned nano self-assembled catalyst having Al 2 O 3 as a carrier, Ni element and Cu element as active components or the catalyst is a catalyst obtained by the aforementioned catalyst preparation method, and the reactor used is The aforementioned reaction system.
  • step (1) Also included prior to said step (1) is the step of reducing the catalyst in the reactor.
  • the reduction step is: firstly raising the micro-reaction channel to 120-130 ° C, staying for 2 to 2.5 h, then heating to 200-220 ° C, staying for 18-24 h, the reduction is completed, wherein the hydrogen space velocity during the reduction process is 300 ⁇ 500h -1 , the pressure is 0.5-1.5Mpa (gauge pressure), and then it is lowered to room temperature in a hydrogen atmosphere.
  • gauge pressure refers to the portion exceeding atmospheric pressure.
  • the temperature of the preheated hydrogen in the step (1) is 25 to 60 ° C, preferably 30 to 50 ° C, more preferably 35 to 45 ° C.
  • the styrene oxide is introduced in step (2) by means of a pump.
  • the flow rate of hydrogen in the step (2) is from 0.5 to 13 Nm 3 /h, preferably from 1.5 to 10 Nm 3 /h, more preferably from 2.5 to 7 Nm 3 /h;
  • the styrene oxide feed rate is from 1 to 35 kg/h, preferably from 3 to 20 kg. /h, more preferably 5 to 10 kg/h;
  • the molar ratio of hydrogen to styrene oxide is 2 to 69, preferably 2.6 to 17, more preferably 3.7 to 14.
  • the reaction temperature in the step (2) is from 30 to 120 ° C, preferably from 40 to 100 ° C, more preferably from 50 to 70 ° C; and the reaction pressure (gauge pressure) is from 0.3 to 10 MPa, preferably from 0.5 to 3 MPa, more preferably from 1 to 1.5 MPa.
  • the ⁇ -phenylethanol preparation technique is carried out in the reaction system with an ultrasonic field, the micro-reaction channel has a large specific surface area, sufficient mass transfer, and another advantage of a large specific surface area is that the heat transfer capability is strong, Styrene styrene hydrogenation heat Rapid removal allows the reaction to be carried out under solvent-free conditions, reducing the solvent removal process during product refining, simplifying the product separation process, reducing production costs, and ensuring a pure aroma of the product; Quality, which makes it possible to ensure high selectivity and high yield without adding additives in the preparation of ⁇ -phenylethanol, and the selectivity of ⁇ -phenylethanol can reach more than 99%.
  • the de-assisting process is reduced, the product separation process is simple, and the cost is low.
  • the extremely large specific surface area of the microreaction channel, coupled with the mass transfer enhancement of the ultrasonic field, allows the reaction to proceed under mild conditions, reducing equipment input and safety risks.
  • the equipment has a small footprint and no amplification effect, and multiple reactors can be connected in parallel to flexibly configure the production capacity.
  • a large-porosity Ni-Cu/Al 2 O 3 nano self-assembling catalyst is adopted, and the catalyst has a large pore size and uniformity, which can effectively prevent high boiling materials such as acetals formed during the reaction from blocking the catalyst pores, and simultaneously ultrasonicizing.
  • the disturbance provided by the field can further prevent the deposition of high boilers on the surface of the catalyst, which greatly prolongs the life of the catalyst and reduces the unit consumption of the catalyst.
  • the addition of Cu in the Ni-Cu/Al 2 O 3 nano self-assembled catalyst will It effectively promotes the hydrogenation of phenylacetaldehyde, reduces the probability of reaction of phenylacetaldehyde with ⁇ -phenylethanol to form high boilers, reduces the high boiler content in the reaction solution, reduces the amount of tar, and prolongs the life of the catalyst.
  • the ultrasonic field power range selected by the invention can not only enhance the mass transfer effect, but also cause the reactor to vibrate violently.
  • the reasonable combination of the number of Y-channels, the diameter and the diameter of the micro-reaction channels ensures the mass transfer heat transfer effect, so that the reaction can be carried out without solvent or additives.
  • the preferred catalyst pore size range ensures catalyst life without affecting catalyst strength and selectivity.
  • Reasonable Cu addition amount can effectively promote the hydrogenation of phenylacetaldehyde, reduce the formation of high boilers, prolong the life of the catalyst, and will not affect the main reaction rate of styrene ring opening.
  • Figure 1 shows the results of the reaction of Example 5.
  • Fig. 3 shows the results of the reaction of Comparative Example 5.
  • Figure 5 is a top plan 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 filter unit, and 5 represents: gas Liquid separation system, 6 Representation: Micro-reaction channel heater, 7 means: gas, liquid raw material preheater.
  • Figure 6 is a schematic view showing the structure of a microreaction channel.
  • Figure 7 is a schematic view showing the structure of a Y-shaped passage and a cross-sectional view of a gas passage and a liquid passage.
  • Polyisobutylene maleic acid triethanolamine ester China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute; Lubricating Base Oil: South Korea SK Lubricating Oil Company; Urea: Panjin Zhongrun Chemical Co., Ltd.; Jiuhui Aluminum Nitrate: Huainan Cody Chemical Technology Co., Ltd.; copper nitrate trihydrate: Shanghai Aladdin Biochemical Technology Co., Ltd.; nickel nitrate hexahydrate: Shanghai Aladdin Biochemical Technology Co., Ltd.; styrene oxide: Aladdin Industrial Corporation; hydrogen: Yantai Wanhua Huasheng Gas Co., Ltd.; sodium hydroxide: Xiqiao Chemical Co., Ltd.; etched silicon column: Suzhou Hualin Kona Semiconductor Equipment Technology Co., Ltd.; ultrasonic field generator: Nanjing Hanzhou Technology Co., Ltd.
  • the average pore diameter can be measured by nitrogen adsorption-desorption (BET), and the content of the metal component in the catalyst can be measured by ICP (Ion-Coupling Broad Spectrum Method).
  • the sample was diluted with chromatographic ethanol and analyzed by GC on SHIMADZU AOC-20i using HP-88 (88%-cyanopropyl-aryl-polysiloxane, 100m ⁇ 0.25mm ⁇ 0.20 ⁇ m) capillary column, FID detection. Device.
  • the inlet temperature is 280 ° C
  • the detector temperature is 300 ° C
  • the column temperature is controlled by programmed temperature: the initial column temperature is 50 ° C for 0.5 minutes, the temperature is raised to 120 ° C at 3 ° C / min, held for 5 minutes, and then heated at 20 ° C / min. To 220 ° C.
  • the column pressure was 77.3 kpa, the column flow rate was 1.1 ml/min, the split ratio was 1:50, and the injection amount was 0.2 ⁇ L. Conversion and selectivity were calculated using the area normalization method.
  • 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-channel 1, and then collected into the micro-reaction channel 2 loaded with the catalyst, and the outlet filter unit 4 is filled with the etched silicon column for filtering the catalyst.
  • An ultrasonic field generator 3 applies an ultrasonic field to the microreaction channel.
  • the reaction system for preparing ⁇ -phenylethanol in the following examples includes: a microreaction channel 2, which is a coil having a diameter of a micron order, used as a reaction site; a Y-channel 1 in which one end of the reaction channel communicates, wherein the two channels of the Y-channel 1 are respectively a gas passage for introducing a gas reaction raw material and a liquid passage for introducing a liquid reaction raw material; An outlet filtration unit 4 communicating with the other end of the reaction passage, the outlet filtration unit 4 for preventing passage of a catalyst in the micro-reaction passage 2 to allow liquid product and gas to flow out; gas communicating with the outlet filtration unit 4 a liquid separation system 5 for separating the liquid product and gas; an ultrasonic field generator 3 for applying an ultrasonic field to the micro-reaction channel 2; for reacting a gas reaction material and a liquid A preheater 7 for preheating the raw material and a heater 6 for heating the microreaction passage.
  • a microreaction channel 2 which is
  • the ultrasonic field generator 3 is a box, the micro-reaction channel 2 is horizontally fixed in the box; the Y-channel 1 and the outlet filter unit 4 are respectively located outside the box, and respectively Located at a rear middle portion and a front middle portion of the tank; the gas passage and the liquid passage of the Y-shaped passage are located at the same height and are disposed in parallel with the bottom surface of the tank; and the heater 6 is a jacket type heating a total of three sets, the heating element is placed on the outside of the box by being respectively clamped on the left and right sides of the box, and two preheaters 7 are respectively clamped in the The gas passage and the liquid passage of the Y-shaped passage.
  • the micro-reaction channel 2 is a disk-shaped tube; as shown in FIG. 7, the gas channel and the liquid channel of the Y-channel are composed of a plurality of evenly distributed thin tubes, and the gas channels are The number and distribution of the tubules and the thin tubes of the liquid passage are exactly the same.
  • reaction system such as ultrasonic power, the diameter of the Y-channel and the microreaction channel, etc., will be given in the specific examples.
  • Ni-Cu/Al 2 O 3 nano self-assembled catalyst CAT-1 The Ni content was 9.06 wt%, the Cu content was 1.64 wt%, and the average pore diameter of the catalyst was 33.27 nm.
  • the catalyst preparation process is:
  • a 0.02 mol/L aqueous solution of Ni(NO 3 ) 2 and a 0.03 mol/L Cu(NO 3 ) 2 aqueous solution were mixed at a ratio of 9:1 (volume ratio) to obtain an immersion liquid;
  • the Al 2 O 3 carrier powder was added to the immersion liquid, stirred and mixed uniformly to form a fluid slurry.
  • the fluid slurry obtained in step 2 is injected into the micro-reaction channel 2 of the foregoing reaction system, and then dried at 125 ° C for 8 h and calcined at 350 ° C for 5 h under the action of the heater 6 of the reaction system to obtain Ni-Cu. /Al 2 O 3 nano self-assembled catalyst.
  • the ultrasonic generator is turned on, the ultrasonic power is set to 300 W, and the micro-reaction channel is carried out from the gas passage of the Y-channel to the hydrogen gas preheated by the preheater 7.
  • the temperature was raised, and the hydrogen preheating temperature was 35 °C.
  • the Ni-Cu/Al 2 O 3 nano self-assembled catalyst CAT-2 has a Ni content of 17.82% by weight, a Cu content of 3.17% by weight, and an average pore diameter of the catalyst of 208.69 nm.
  • the catalyst preparation process is:
  • a 0.034 mol/L aqueous solution of Ni(NO 3 ) 2 and a 0.05 mol/L Cu(NO 3 ) 2 aqueous solution were mixed at a ratio of 9:1 (volume ratio) to obtain an immersion liquid;
  • the Al 2 O 3 carrier powder was added to the immersion liquid, stirred and mixed uniformly to form a fluid slurry.
  • the fluid slurry obtained in the step 2 is injected into the micro-reaction channel 2 of the foregoing reaction system, and then dried at 110 ° C for 8 h and 500 ° C for 5 h under the action of the heater 6 of the reaction system to obtain Ni-Cu. /Al 2 O 3 nano self-assembled catalyst.
  • the reaction system is preliminarily (the number of streams per channel of the Y-channel 1 is 14, the diameter of the channel is 25.56 ⁇ m, the diameter of the micro-reaction channel 2 is 342.87 ⁇ m, and the average pore diameter of the silicon column of the outlet filtration unit 4 is Reduction of the Ni-Cu/Al 2 O 3 nano self-assembled catalyst in 1.63 ⁇ m): first introducing hydrogen into the micro reaction channel through a gas passage of the Y-shaped channel, and then passing the micro through the heater 6 The reaction channel was heated to 120 ° C, stayed for 2.5 h, then heated to 200 ° C, and stayed for 18 h. The reduction was completed and the temperature was lowered to room temperature in a hydrogen atmosphere. The hydrogen space velocity was 500 h -1 and the pressure was 0.5 Mpa (gauge pressure) during the reduction.
  • the ultrasonic generator is turned on, the ultrasonic power is set to 200 W, and the micro-reaction channel is carried out from the gas passage of the Y-channel into the hydrogen gas preheated by the preheater 7.
  • the temperature was raised, and the hydrogen preheating temperature was 40 °C.
  • the Ni-Cu/Al 2 O 3 nano self-assembled catalyst CAT-3 has a Ni content of 24.88 wt%, a Cu content of 1.36 wt%, and an average pore diameter of the catalyst of 146.21 nm.
  • the catalyst preparation process is:
  • a 0.044 mol/L aqueous solution of Ni(NO 3 ) 2 and an aqueous solution of 0.02 mol/L of Cu(NO 3 ) 2 were mixed at a ratio of 9:1 (volume ratio) to obtain an immersion liquid; and the macropores obtained in the step 1 were obtained.
  • the Al 2 O 3 carrier powder was added to the impregnation liquid to form a fluid slurry.
  • the fluidity slurry obtained in the step 2 is injected into the micro-reaction channel 2 of the foregoing reaction system, and then dried at 130 ° C for 9 h and at 450 ° C for 5 h under the action of the heater 6 of the reaction system to obtain Ni-Cu. /Al 2 O 3 nano self-assembled catalyst.
  • the reaction system is preliminarily (the number of streams per channel of the Y-channel 1 is 17, the diameter of the channel is 7.32 ⁇ m, the diameter of the micro-reaction channel 2 is 48.62 ⁇ m, and the average pore diameter of the silicon column of the outlet filtration unit 4 is Reduction of the Ni-Cu/Al 2 O 3 nano self-assembled catalyst in 11.33 ⁇ m): first introducing hydrogen into the micro reaction channel through a gas passage of the Y-shaped channel, and then passing the micro through the heater 6 The reaction channel was heated to 125 ° C, stayed for 2.5 h, then heated to 210 ° C, and stayed for 22 h. The reduction was completed and the temperature was lowered to room temperature in a hydrogen atmosphere. The hydrogen space velocity was 450 h -1 and the pressure was 1.0 Mpa (gauge pressure) during the reduction.
  • the ultrasonic generator is turned on, the ultrasonic power is set to 250 W, and the reactor is heated from the gas passage of the Y-channel to the hydrogen preheated by the preheater 7, and the hydrogen is heated.
  • Preheating temperature is 25 °C.
  • the Ni-Cu/Al 2 O 3 nano self-assembled catalyst CAT-4 has a Ni content of 22.37 wt%, a Cu content of 1.71 wt%, and an average pore diameter of the catalyst of 311.58 nm.
  • the catalyst preparation process is:
  • 1.1 mol / L aqueous urea solution and 1.35 mol / L aqueous solution of aluminum nitrate non-aqueous solution are mixed well in a volume ratio of 1:3.5, heated to 100 ° C, and uniformly stirred in the process to obtain a mixture B;
  • the mixture materials A and B were slowly mixed at a mass ratio of 1:1 to form a super-enriched sol group, and a super-enriched sol group self-assembly was obtained; the primary super-solubilized group self-assembly was reacted at 110 ° C for 4 h, and the product was washed with water.
  • a 0.047 mol/L aqueous solution of Ni(NO 3 ) 2 and a 0.03 mol/L aqueous solution of Cu(NO 3 ) 2 were mixed at a ratio of 9:1 (volume ratio) to obtain an immersion liquid; and the macropores obtained in the step 1 were obtained.
  • the Al 2 O 3 carrier powder was added to the impregnation liquid to form a fluid slurry.
  • the fluid slurry obtained in step 2 is injected into the micro-reaction channel 2 of the foregoing reaction system, and then dried at 118 ° C for 10 h and 500 ° C for 5 h under the action of the heater 6 of the reaction system to obtain Ni-Cu. /Al 2 O 3 nano self-assembled catalyst.
  • the reaction system is preliminarily (the number of streams per channel of the Y-channel 1 is 8, the diameter of the channel is 15.98 ⁇ m, the diameter of the micro-reaction channel 2 is 256.76 ⁇ m, and the average pore diameter of the silicon column of the outlet filter unit 4 is 8.52.
  • the channel was heated to 120 ° C, stayed for 2.5 h, then heated to 220 ° C, stayed for 20 h, the reduction was completed, and the hydrogen atmosphere was lowered to room temperature.
  • the hydrogen space velocity was 400 h -1 and the pressure was 0.8 Mpa (gauge pressure).
  • the ultrasonic generator is turned on, the ultrasonic power is set to 400 W, and the micro-reaction channel is carried out from the gas passage of the Y-channel into the hydrogen gas preheated by the preheater 7.
  • the temperature was raised, and the hydrogen preheating temperature was 40 °C.
  • the Ni-Cu/Al 2 O 3 nano self-assembled catalyst CAT-5 has a Ni content of 23.09 wt%, a Cu content of 1.82 wt%, and an average pore diameter of the catalyst of 136.59 nm.
  • the catalyst preparation process is:
  • a 3.5 mol/L aqueous urea solution and a 1.35 mol/L aqueous solution of aluminum nitrate nonahydrate are thoroughly mixed in a volume ratio of 1:4, and heated to 100 ° C, and uniformly stirred in the process to obtain a mixture B;
  • the mixture materials A and B were slowly mixed at a mass ratio of 1:1 to form a super-enriched sol group, and a super-enriched sol group self-assembly was obtained; the primary super-solubilized group self-assembly was reacted at 110 ° C for 3 h, and the product was washed with water.
  • a 0.054 mol/L aqueous solution of Ni(NO 3 ) 2 and a 0.035 mol/L Cu(NO 3 ) 2 aqueous solution were mixed at a ratio of 9:1 (volume ratio) to obtain an immersion liquid; and the large pore obtained in the step 1 was obtained.
  • the Al 2 O 3 carrier powder was added to the impregnation liquid to form a fluid slurry.
  • the fluidity slurry obtained in the step 2 is injected into the micro-reaction channel 2 of the foregoing reaction system, and then dried at 125 ° C for 9 h under the action of the heater 6 of the reaction system, and calcined at 500 ° C for 4 h to obtain Ni-Cu. /Al 2 O 3 nano self-assembled catalyst.
  • the reaction system is preliminarily (the number of streams per channel of the Y-channel 1 is 10, the diameter of the channel is 45.85 ⁇ m, the diameter of the micro-reaction channel 2 is 208.61 ⁇ m, and the average pore diameter of the silicon column of the outlet filtration unit 4 is 1.53.
  • the channel was heated to 130 ° C, stayed for 2.5 h, then heated to 220 ° C, stayed for 24 h, the reduction was completed, and the hydrogen atmosphere was lowered to room temperature.
  • the hydrogen space velocity was 450 h -1 and the pressure was 1.5 MPa (gauge pressure).
  • the ultrasonic generator is turned on, the ultrasonic power is set to 350 W, and the micro-reaction channel is carried out from the gas passage of the Y-channel to the hydrogen gas preheated by the preheater 7.
  • the temperature was raised, and the hydrogen preheating temperature was 45 °C.
  • the catalyst has stable performance, long life, and high product selectivity.
  • the hydrogenation reaction of styrene oxide is 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 1400 mm), catalyst, catalyst reduction procedure, The reaction temperature, pressure, and space velocity were the same as in Example 5, and the operation was carried out for 4500 hours.
  • the reaction results are shown in Fig. 2.
  • Example 5 The Ni-Cu/Al 2 O 3 nano self-assembled catalyst in Example 5 was replaced with Raney 6800 (Grass), and the remaining process parameters were the same as in Example 5, and the operation was 4500 hours.
  • the reaction results are shown in FIG. 3 .
  • the performance of the catalyst Raney 6800 is significantly inferior to that of the Ni-Cu/Al 2 O 3 nano self-assembled catalyst described in this patent.
  • the oxidized styrene was hydrogenated without ultrasonic field.
  • the other process parameters were the same as in Example 5, and the operation was 4500 hours.
  • the reaction results are shown in Fig. 4.
  • 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 example 1 100 91.42 8.05
  • Comparative example 2 100 98.57 1.26
  • Comparative example 3 100 79.67 20.15

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Abstract

本发明公开了一种制备β-苯乙醇的方法，包括如下步骤：(1)预先对反应器中催化剂进行还原；(2)通入经预热的氢气对反应器进行升温至预定温度；(3)打入原料氧化苯乙烯，进行加氢反应，得到β-苯乙醇。所述催化剂为Ni-Cu/Al2O3纳米自组装催化剂，所述反应器为超声场微填充床反应器。通过本发明的方法，β-苯乙醇的选择性可以达到99％以上。

Description

一种制备β-苯乙醇的反应系统、催化剂及其工艺方法 技术领域
本发明涉及一种制备β-苯乙醇的反应系统、所用的催化剂、催化剂的制备方法及制备β-苯乙醇的工艺方法，具体是一种以氧化苯乙烯为原料，加氢制备β-苯乙醇的方法。
背景技术
β-苯乙醇(PEA)，又称2-苯乙醇、苯乙醇、乙位苯乙醇，是一种简单的芳香族伯醇，常温下为无色液体，具有淡雅、细腻而持久的玫瑰花香气，最早是作为植物鲜花中特征性的香气化合物被发现的，天然存在于橙花油、玫瑰油、香叶油等芳香油中。
β-苯乙醇因其具有柔和、愉快而持久的玫瑰香气而广泛应用于各种食用香精和烟用香精中，是配制玫瑰香型食品添加剂、玫瑰香型香精的主要原料。β-苯乙醇作为香料在全球范围内的使用量仅次于香兰素。同时，β-苯乙醇由于对碱作用稳定，不溶于水，在化妆水、香皂中也经常使用。此外，由于β-苯乙醇有良好的抗菌效能，还可用于眼药水溶液及护肤品中。
目前，市场上的β-苯乙醇基本都是化学合成的。β-苯乙醇的主要化学合成方法是苯-环氧乙烷法(Friedel-Crafts反应)和氧化苯乙烯(STO)加氢法。国际市场上，苯-环氧乙烷法产品约占40％，氧化苯乙烯加氢法产品约占60％。苯-环氧乙烷法生产的产品所含微量杂质不同，香气差异较大，质量尚未达到香料的标准。因此，在香料工业中主要采用氧化苯乙烯加氢法。
对于氧化苯乙烯加氢制备β-苯乙醇，均相法和非均相法均有文献报道。均相法由于存在催化剂回收困难、产物分离难度大等问题，实际生产中几乎不采用。大多专利文献都致力于研究开发非均相催化工艺。在非均相催化工艺中，如何提高β-苯乙醇的选择性及催化剂寿命一直是热点和难点，而提高β-苯乙醇的选择性关键在于保证良好的氢气传质效果。专利US3579593介绍了以骨架Ni和Pd作催化剂制备β-苯乙醇的方法，其对比实施例表明，单独以Ni为催化剂时，副产物乙苯的含量高达11％；单独以Pd作催化剂时，又会产生约10％的苯乙醛；β-苯乙醇的收率均偏低，仅为85％左右；同时，反应液中若含大量苯乙醛，苯乙醛将与产物β-苯乙醇进一步反应生成高沸物，阻塞催化剂孔道，造成催化剂失活。专利US6166269、 US4064186提出向反应体系中加入NaOH、Na2CO3、KOH等助剂，虽然β-苯乙醇的选择性和收率大幅提高，但助剂碱的加入使得催化剂寿命缩短，同时会对后期产物分离造成困难，容易造成堵塔等诸多问题。专利US2822403提出在碱性条件下以水作溶剂、Raney Ni或Co作催化剂制备β-苯乙醇；但该工艺需要大量的水，同时为调节水和氧化苯乙烯的相容性需加入乳化剂，这均为后期产物分离带来巨大困难。目前，氧化苯乙烯加氢制备β-苯乙醇均在反应釜或管式反应器中进行，由于氧化苯乙烯加氢为强放热反应，为控制反应热，常常需要加入溶剂。专利CN1111169A、US6979753、US4943667、US2524096等提出的β-苯乙醇制备工艺均需使用溶剂，这降低了生产效率，使产品分离工序复杂、增加了溶剂脱除等所带来的成本。
综上所述，现有的技术均在不同程度上存在一定的不足，如传质效果不佳导致需添加助剂提高选择性，但同时造成催化剂寿命降低、产物分离困难、甚至影响产品品质等问题；如催化剂结构及性能不佳，导致催化剂易于失活，催化剂寿命短；如因反应器传热限制需采用溶剂，增加了分离成本等等。因此，开发一种高效的反应器及高选择性、长寿命的催化剂对提升β-苯乙醇的制备工艺具有重要意义。
发明内容
本发明提供了一种氧化苯乙烯加氢制备β-苯乙醇所用的反应系统；本发明还提供了一种氧化苯乙烯加氢制备β-苯乙醇所用的催化剂及所述催化剂的制备方法；在本发明的具体实施方式中所述催化剂具有均匀的大孔，可有效防止催化剂孔道阻塞，延长催化剂寿命。本发明还进一步提供了氧化苯乙烯加氢制β-苯乙醇的工艺方法。在本发明的具体实施方式中，所述工艺方法反应条件相对温和、产物分离简单，易于工业化放大生产。
本发明采用如下技术方案：
一种制备β-苯乙醇所用的反应系统，所述反应系统包括，用于装载催化剂的微反应通道，所述微反应通道为直径为微米级的盘管，作为反应场所；与所述微反应通道的一端连通的Y型通道，所述Y型通道的两个通道分别为用于通入气体反应原料的气体通道和用于通入液体反应原料的液体通道；与所述微反应通道的另一端连通的出口过滤单元，所述出口过滤单元用于阻止所述微反应通道中的催化剂穿过而允许液体产物和气体流出；与所述出口过滤单元连通的气液分离系统，所述气液分离系统用于分离所述液体产物和气体；以及用于给所 述微反应通道施加超声场的超声场发生器。
所述反应系统还包括用于给气体反应原料和液体反应原料预热的预热器和用于给所述微反应通道加热的加热器。
所述超声场发生器的超声功率为50～600W，优选150～400W，更优选200～300W。
所述Y型通道的通道直径为5～50μm，优选10～35μm，更优选20～30μm；所述Y型通道的气体通道和液体通道均由若干均匀分布的细管(细管也称为流股)组成；每个通道的流股数为1～20，优选3～15，更优选5～10；优选所述气体通道的细管与所述液体通道的细管数量及分布完全相同；气体反应原料和液体反应原料分别通过Y型通道的两个通道被分成若干流股后汇集进入所述微反应通道；所述微反应通道的直径为5～500μm，优选50～350μm，更优选200～300μm；所述出口过滤单元装填有经刻蚀的硅柱，所述硅柱的平均孔径为0.1～15μm，优选0.5～10μm，更优选1～2μm。其中，所述经刻蚀的硅柱为经过刻蚀形成的具有多孔结构的圆柱形硅材料。
在优选的实施方式中所述反应系统可以通过采用并联形式，满足调节产能的需要。
一种制备β-苯乙醇所用的催化剂，所述催化剂为以Al2O3为载体、Ni元素和Cu元素为活性组分的纳米自组装催化剂；其中，以催化剂质量计，Ni元素含量为5～30wt％，优选10～27wt％，更优选20～25wt％；Cu元素含量为0.5～3.5wt％，优选1～3wt％，更优选1.5～2wt％；余量为Al2O3载体。
所述催化剂的平均孔径为10～350nm，优选50～300nm，更优选100～150nm。
所述催化剂的制备过程为:
①在均匀搅拌条件下，将0.001-0.015mol/L的聚异丁烯马来酸三乙醇胺酯和0.05～0.25mol/L的润滑油基础油按(5-8):1的体积比充分混合，缓慢升温至90～100℃，得到混合物料A；同时在均匀搅拌条件下将1～5.5mol/L尿素水溶液和0.5～1.5mol/L九水硝酸铝水溶液按1：(3-5)的体积比充分混合，加热至90～100℃，得到混合物料B；
②将混合物料A、B按1:1的质量比缓慢混和，形成超增溶胶团，得到一次超增溶胶团自组装体；将该一次超增溶胶团自组装体在100～110℃反应2～4h，产物经水洗、150-200℃ 下干燥1-2h，得到二次纳米自组装体；将该二次纳米自组装体于550～600℃焙烧6～8h，粉碎，得到粒径10～30μm的大孔Al2O3载体；
③将0.01～0.1mol/L的Ni(NO3)2水溶液和0.01～0.05mol/L的Cu(NO3)2水溶液混合，得到浸渍液；将步骤②得到的大孔Al2O3载体粉末加入浸渍液中搅拌混合均匀，形成流动性浆料；
④将步骤③得到的流动性浆料于110℃～130℃烘干8～10h，300℃～500℃焙烧3～5h，优选将所述流动性浆料注入前述反应系统中的微反应通道中进行。
一种制备β-苯乙醇的工艺方法，包括如下步骤：(1)通入经预热的氢气将装载有催化剂的反应器升温；(2)通入氧化苯乙烯，进行加氢反应，得到β-苯乙醇；所述催化剂为前述以Al2O3为载体、Ni元素和Cu元素为活性组分的纳米自组装催化剂或所述催化剂为由前述催化剂制备方法得到的催化剂，所用的反应器为前述的反应系统。
在所述步骤(1)前还包括对反应器中的催化剂进行还原的步骤。
所述还原步骤为：先将微反应通道升温至120～130℃，停留2～2.5h，然后升温至200～220℃，停留18～24h，还原完成，其中，还原过程中氢气空速为300～500h-1，压力为0.5～1.5Mpa(表压)，然后在氢气气氛下降至室温。其中，表压指超过大气压的部分。
步骤(1)所述经预热的氢气的温度为25～60℃，优选30～50℃，更优选35～45℃。
步骤(2)中氧化苯乙烯的通入方式为用泵打入。步骤(2)中氢气的流量为0.5～13Nm3/h，优选1.5～10Nm3/h，更优选2.5～7Nm3/h；氧化苯乙烯进料速率为1～35Kg/h，优选3～20Kg/h，更优选5～10Kg/h；氢气与氧化苯乙烯的摩尔比为2-69，优选2.6-17，更优选3.7-14。
步骤(2)中反应温度为30～120℃，优选40～100℃，更优选50～70℃；反应压力(表压)为0.3～10Mpa，优选0.5～3Mpa，更优选1～1.5Mpa。
本发明的具体实施方式的有益效果在于：
所述β-苯乙醇制备技术，在具有超声场的所述反应系统中进行，所述微反应通道的比表面积大，传质充分，比表面积大的另一优势就是传热能力强，可使氧化苯乙烯加氢反应热 快速的移除，可使反应在无溶剂条件下进行，减少了产品精制过程中脱溶剂的工序，简化产品分离流程，降低生产成本，同时保障产品香气纯正；同时外加超声场作用，进一步加强传质，这使得β-苯乙醇制备过程中不需要添加助剂也可保证高选择性高收率，β-苯乙醇的选择性可以达到99％以上。减少了脱助剂工序，使产品分离过程简单，成本低。所述微反应通道的极大的比表面积，加上超声场的传质增强作用，使得反应得以在温和条件下进行，减小了设备投入及安全风险。采用所述反应系统，设备占地面积小，无放大效应，可多台反应器并联，灵活配置产能产量。
本发明的具体实施方式中采用了大孔Ni-Cu/Al2O3纳米自组装催化剂，催化剂孔径大、均匀，可有效防止反应过程中生成的缩醛等高沸物阻塞催化剂孔道，同时超声场提供的扰动也可进一步阻止高沸物在催化剂表面的沉积，这使得催化剂寿命大幅度延长，催化剂单耗降低；另外，Ni-Cu/Al2O3纳米自组装催化剂中，Cu的加入将有效促进苯乙醛的加氢，减少苯乙醛与β-苯乙醇反应生成高沸物的几率，降低反应液中高沸物含量，减小焦油量，并延长催化剂寿命。
本发明选择的超声场功率范围既能保证强化传质效果，又不会致使反应器剧烈震动。Y型通道数量、直径及微反应通道直径的合理搭配，保障了传质传热效果，使反应可以在无溶剂、无助剂条件下进行。优选的催化剂孔径范围，可保障催化剂寿命，同时不会影响催化剂强度及选择性。合理的Cu添加量，有效促进苯乙醛加氢，减少高沸物生成，延长了催化剂寿命，同时不会影响氧化苯乙烯开环主反应反应速率。
附图说明
图1为实施例5的反应结果。
图2为对比例4的反应结果。
图3为对比例5的反应结果。
图4为对比例6的反应结果。
图5是本发明超声场微填充床反应器的俯视示意图，其中1表示：Y型通道，2表示：微反应通道，3表示：超声场发生器，4表示：出口过滤单元，5表示：气液分离系统，6 表示：微反应通道加热器，7表示：气体、液体原料预热器。
图6是微反应通道的结构示意图。
图7是Y型通道的结构示意图及气体通道和液体通道的截面图。
具体实施方式
现结合具体实施方式对本发明作如下说明。这里需要说明的是实施例只是用于对本发明作进一步的说明，而不能理解为对本发明保护范围的限定，凡根据本发明的内容对其做出非实质性的改进和调整均属于本发明保护之列。
以下为实施例中所用的主要原料及仪器的来源：
聚异丁烯马来酸三乙醇胺酯：中国石油化工股份有限公司抚顺石油化工研究院；润滑油基础油：韩国SK润滑油公司；尿素：盘锦中润化工有限公司；九水硝酸铝：淮南市科迪化工科技有限公司；三水硝酸铜：上海阿拉丁生化科技股份有限公司；六水硝酸镍：上海阿拉丁生化科技股份有限公司；氧化苯乙烯：阿拉丁工业公司(Aladdin Industrial Corporation)；氢气：烟台万华华胜气体有限公司；氢氧化钠：西陇化工股份有限公司；经刻蚀的硅柱：苏州华林科纳半导体设备技术有限公司；超声场发生器：南京翰洲科技有限公司。
平均孔径可采用氮气吸脱附法(BET)测定，催化剂中的金属组分含量可采用ICP(离子耦合广谱法)测定。
样品采用色谱乙醇稀释后在SHIMADZU AOC-20i上进行GC分析，使用HP-88(88％-氰丙基-芳基-聚硅氧烷，100m×0.25mm×0.20μm)毛细管色谱柱，FID检测器。进样口温度280℃，检测器温度300℃，柱温采用程序升温控制：初始柱温50℃保持0.5分钟，以3℃/min升温至120℃，保持5分钟，再以20℃/min升温至220℃。柱压力77.3kpa，柱流量1.1ml/min，分流比1：50，进样量：0.2μL。转化率和选择性采用面积归一法进行计算。
气体反应原料、液体反应原料分别通过Y型通道1的两端被分成若干流股后汇集进入装载有催化剂的微反应通道2，出口过滤单元4装填经刻蚀的硅柱，用于过滤催化剂，超声场发生器3对所述微反应通道施加超声场。
如图5所示，以下实施例中制备β-苯乙醇所用的反应系统包括：微反应通道2，所述微反应通道2为直径为微米级的盘管，作反应场所用；与所述微反应通道的一端连通的Y型通道1，其中所述Y型通道1的两个通道分别为用于通入气体反应原料的气体通道和用于通入液体反应原料的液体通道；与所述微反应通道的另一端连通的出口过滤单元4，所述出口过滤单元4用于阻止所述微反应通道2中的催化剂穿过而允许液体产物和气体流出；与所述出口过滤单元4连通的气液分离系统5，所述气液分离系统5用于分离所述液体产物和气体；用于给所述微反应通道2施加超声场的超声场发生器3；用于给气体反应原料和液体反应原料预热的预热器7以及用于给所述微反应通道加热的加热器6。
其中，所述超声场发生器3为一个箱体，所述微反应通道2水平固定于箱体中；所述Y型通道1和所述出口过滤单元4分别位于所述箱体外，且分别位于所述箱体的后侧中部和前侧中部位置；所述Y型通道的气体通道和液体通道位于同一高度且与所述箱体的底面平行设置；所述加热器6为夹套型加热器，共有3组，通过分别夹持在所述箱体的左侧和右侧而使加热元件套在所述箱体的外部，所述预热器7为2个，分别夹持在所述Y型通道的气体通道和液体通道上。
如图6所示，所述微反应通道2为盘管状；如图7所示，所述Y型通道的气体通道和液体通道均由若干均匀分布的细管组成，且所述气体通道的细管与所述液体通道的细管数量及分布完全相同。
所述反应系统的一些具体参数，例如超声功率、Y型通道及微反应通道的直径等将在具体实施例中给出。
实施例1
催化剂制备：
Ni-Cu/Al2O3纳米自组装催化剂CAT-1：以催化剂质量计，Ni含量9.06wt％，Cu含量1.64wt％，催化剂的平均孔径为33.27nm。
催化剂制备过程为:
①在均匀搅拌条件下，将0.008mol/L的聚异丁烯马来酸三乙醇胺酯和0.15mol/L的润滑 油基础油按5:1的体积比充分混合，缓慢升温至100℃，得到混合物料A；同时将2.5mol/L尿素水溶液和0.7mol/L九水硝酸铝水溶液按1:5的体积比充分混合，加热至95℃，在此过程中要均匀的搅拌，得到混合物料B；然后将混合物料A、B按1:1的质量比缓慢混合，形成超增溶胶团，得到一次超增溶胶团自组装体；将该一次超增溶胶团自组装体105℃反应3.5h，产物经水洗、200℃干燥2h，得到二次纳米自组装体，然后将二次纳米自组装体于580℃焙烧6h，粉碎，得到平均粒径为13.58μm的大孔Al2O3载体。
②将0.02mol/L的Ni(NO3)2水溶液和0.03mol/L的Cu(NO3)2水溶液按照9：1(体积比)的比例混合，得到浸渍液；将步骤①得到的大孔Al2O3载体粉末加入浸渍液中，搅拌混合均匀，形成流动性浆料。
③将步骤②得到的流动性浆料注入前述反应系统的微反应通道2内，然后在所述反应系统的加热器6的作用下于125℃烘干8h，350℃焙烧5h，得到Ni-Cu/Al2O3纳米自组装催化剂。
β-苯乙醇制备：
(1)预先对所述反应系统(Y型通道1的每个通道流股数为8，通道直径17.35μm，微反应通道2的直径228.86μm，所述出口过滤单元4的硅柱的平均孔径为3.52μm)中的Ni-Cu/Al2O3纳米自组装催化剂进行还原：先通过所述Y型通道的气体通道向所述微反应通道中通入氢气，然后通过加热器6将所述微反应通道升温至125℃，停留2h，然后升温至220℃，停留18h，还原完成，在氢气气氛下降至室温，还原过程中氢气空速为320h-1，压力为1.5Mpa(表压)。
(2)催化剂还原完成后，打开超声发生器，将超声功率设定为300W，从所述Y型通道的气体通道通入经所述预热器7预热的氢气对所述微反应通道进行升温，氢气预热温度35℃。
(3)将所述微反应通道温度升至35℃后，以10Kg/h的速度打入原料氧化苯乙烯进行加氢反应，氢气流量6.5Nm3/h，控制反应温度为70℃，反应压力1.5Mpa。待反应进行8h后，取样分析反应液组成，结果如表1所示。
实施例2
催化剂制备：
Ni-Cu/Al2O3纳米自组装催化剂CAT-2，以催化剂质量计，Ni含量17.82wt％，Cu含量3.17wt％，催化剂的平均孔径为208.69nm。
催化剂制备过程为:
①在均匀搅拌条件下，将0.003mol/L的聚异丁烯马来酸三乙醇胺酯和0.24mol/L的润滑油基础油按7:1的体积比充分混合，缓慢升温至100℃，得到混合物料A；同时将5.2mol/L尿素水溶液和1.1mol/L九水硝酸铝水溶液按1:3.3的体积比充分混合，加热至90℃，在此过程中要均匀的搅拌，得到混合物料B；然后将混合物料A、B按1:1的质量比缓慢混合，形成超增溶胶团，得到一次超增溶胶团自组装体；将该一次超增溶胶团自组装体在105℃反应3h，产物经水洗、185℃干燥1.5h，得到二次纳米自组装体，然后将二次纳米自组装体于550℃焙烧8h，粉碎，得到平均粒径为19.36μm的大孔Al2O3载体。
②将0.034mol/L的Ni(NO3)2水溶液和0.05mol/L的Cu(NO3)2水溶液按照9：1(体积比)的比例混合，得到浸渍液；将步骤①得到的大孔Al2O3载体粉末加入浸渍液中，搅拌混合均匀，形成流动性浆料。
③将步骤②得到的流动性浆料注入前述反应系统的微反应通道2内，然后在所述反应系统的加热器6的作用下于110℃烘干8h，500℃焙烧5h，得到Ni-Cu/Al2O3纳米自组装催化剂。
β-苯乙醇制备：
(1)预先对所述反应系统(Y型通道1的每个通道流股数为14，通道直径25.56μm，微反应通道2直径342.87μm，所述出口过滤单元4的硅柱的平均孔径为1.63μm)中的Ni-Cu/Al2O3纳米自组装催化剂进行还原：先通过所述Y型通道的气体通道向所述微反应通道中通入氢气，然后通过加热器6将所述微反应通道升温至120℃，停留2.5h，然后升温至200℃，停留18h，还原完成，在氢气气氛下降至室温，还原过程中氢气空速为500h-1，压力为0.5Mpa(表压)。
(2)催化剂还原完成后，打开超声发生器，将超声功率设定为200W，从所述Y型通道的气体通道通入经所述预热器7预热的氢气对所述微反应通道进行升温，氢气预热温度40℃。
(3)将所述微反应通道温度升至40℃后，以5Kg/h的速度打入原料氧化苯乙烯进行加氢反应，氢气流量2Nm3/h，控制反应温度为50℃，反应压力0.5Mpa。待反应进行8h后，取样分析反应液组成，结果如表1所示。
实施例3
催化剂制备：
Ni-Cu/Al2O3纳米自组装催化剂CAT-3，以催化剂质量计，Ni含量24.88wt％，Cu含量1.36wt％，催化剂的平均孔径为146.21nm。
催化剂制备过程为:
①在均匀搅拌条件下，将0.015mol/L的聚异丁烯马来酸三乙醇胺酯和0.06mol/L的润滑油基础油按7:1的体积比充分混合，缓慢升温至95℃，得到混合物料A；同时将2.6mol/L尿素水溶液和0.75mol/L九水硝酸铝水溶液按1:4.7的体积比充分混合，加热至100℃，在此过程中要均匀的搅拌，得到混合物料B；然后将混合物料A、B按1:1的质量比缓慢混合，形成超增溶胶团，得到一次超增溶胶团自组装体；将该一次超增溶胶团自组装体110℃反应2h，产物经水洗、150℃下干燥2h，得到二次纳米自组装体，然后将二次纳米自组装体于600℃焙烧6h，粉碎，得到平均粒径为28.36μm的大孔Al2O3载体。
②将0.044mol/L的Ni(NO3)2水溶液和0.02mol/L的Cu(NO3)2水溶液按照9：1(体积比)的比例混合，得到浸渍液；将步骤①得到的大孔Al2O3载体粉末加入浸渍液中，形成流动性浆料。
③将步骤②得到的流动性浆料注入前述反应系统的微反应通道2内，然后在所述反应系统的加热器6的作用下于130℃烘干9h，450℃焙烧5h，得到Ni-Cu/Al2O3纳米自组装催化剂。
β-苯乙醇的制备：
(1)预先对所述反应系统(Y型通道1的每个通道流股数为17，通道直径7.32μm，微反应通道2直径48.62μm，所述出口过滤单元4的硅柱的平均孔径为11.33μm)中的Ni-Cu/Al2O3纳米自组装催化剂进行还原：先通过所述Y型通道的气体通道向所述微反应通道中通入氢气，然后通过加热器6将所述微反应通道升温至125℃，停留2.5h，然后升温至210℃，停留22h，还原完成，在氢气气氛下降至室温，还原过程中氢气空速为450h-1，压力为1.0Mpa(表压)。
(2)催化剂还原完成后，打开超声发生器，将超声功率设定为250W，从所述Y型通道的气体通道通入经所述预热器7预热的氢气对反应器进行升温，氢气预热温度25℃。
(3)将所述微反应通道温度升至25℃后，以7.5Kg/h的速度打入原料氧化苯乙烯进行加氢反应，氢气流量4.5Nm3/h，控制反应温度为35℃，反应压力7Mpa。待反应进行8h后，取样分析反应液组成，结果如表1所示。
实施例4
催化剂制备：
Ni-Cu/Al2O3纳米自组装催化剂CAT-4，以催化剂质量计，Ni含量22.37wt％，Cu含量1.71wt％，催化剂的平均孔径为311.58nm。
催化剂制备过程为:
①在均匀搅拌条件下，将0.002mol/L的聚异丁烯马来酸三乙醇胺酯和0.22mol/L的润滑油基础油按8:1的体积比充分混合，缓慢升温至95℃，得到混合物料A；同时将1.1mol/L尿素水溶液和1.35mol/L九水硝酸铝水溶液按1:3.5的体积比充分混合，加热至100℃，在此过程中要均匀的搅拌，得到混合物料B；然后将混合物料A、B按1:1的质量比缓慢混合，形成超增溶胶团，得到一次超增溶胶团自组装体；将该一次超增溶胶团自组装体110℃反应4h，产物经水洗、200℃下干燥1.5h，得到二次纳米自组装体，然后将二次纳米自组装体于560℃焙烧7.5h，粉碎，得到平均粒径为19.64μm的大孔Al2O3载体。
②将0.047mol/L的Ni(NO3)2水溶液和0.03mol/L的Cu(NO3)2水溶液按照9：1(体积比)的比例混合，得到浸渍液；将步骤①得到的大孔Al2O3载体粉末加入浸渍液中，形成 流动性浆料。
③将步骤②得到的流动性浆料注入前述反应系统的微反应通道2内，然后在所述反应系统的加热器6的作用下于118℃烘干10h，500℃焙烧5h，得到Ni-Cu/Al2O3纳米自组装催化剂。
β-苯乙醇制备：
(1)预先对所述反应系统(Y型通道1的每个通道流股数为8，通道直径15.98μm，微反应通道2直径256.76μm，所述出口过滤单元4的硅柱的平均孔径8.52μm)中的Ni-Cu/Al2O3纳米自组装催化剂进行还原：先通过所述Y型通道的气体通道向所述微反应通道中通入氢气，然后通过加热器6将所述微反应通道升温至120℃，停留2.5h，然后升温至220℃，停留20h，还原完成，在氢气气氛下降至室温，还原过程中氢气空速为400h-1，压力为0.8Mpa(表压)。
(2)催化剂还原完成后，打开超声发生器，将超声功率设定为400W，从所述Y型通道的气体通道通入经所述预热器7预热的氢气对所述微反应通道进行升温，氢气预热温度40℃。
(3)将所述微反应通道温度升至40℃后，以5Kg/h的速度打入原料氧化苯乙烯进行加氢反应，氢气流量3Nm3/h，控制反应温度为65℃，反应压力0.8Mpa。待反应进行8h后，取样分析反应液组成，结果如表1所示。
实施例5
催化剂制备：
Ni-Cu/Al2O3纳米自组装催化剂CAT-5，以催化剂质量计，Ni含量23.09wt％，Cu含量1.82wt％，催化剂的平均孔径为136.59nm。
催化剂制备过程为:
①在均匀搅拌条件下，将0.003mol/L的聚异丁烯马来酸三乙醇胺酯和0.24mol/L的润滑油基础油按8:1的体积比充分混合，缓慢升温至95℃，得到混合物料A；同时将3.5mol/L 尿素水溶液和1.35mol/L九水硝酸铝水溶液按1:4的体积比充分混合，加热至100℃，在此过程中要均匀的搅拌，得到混合物料B；然后将混合物料A、B按1:1的质量比缓慢混合，形成超增溶胶团，得到一次超增溶胶团自组装体；将该一次超增溶胶团自组装体110℃反应3h，产物经水洗、180℃下干燥2h，得到二次纳米自组装体，然后将二次纳米自组装体于600℃焙烧7h，粉碎，得到平均粒径为25.71μm的大孔Al2O3载体。
②将0.054mol/L的Ni(NO3)2水溶液和0.035mol/L的Cu(NO3)2水溶液按照9：1(体积比)的比例混合，得到浸渍液；将步骤①得到的大孔Al2O3载体粉末加入浸渍液中，形成流动性浆料。
③将步骤②得到的流动性浆料注入前述反应系统的微反应通道2内，然后在所述反应系统的加热器6的作用下于125℃烘干9h，500℃焙烧4h，得到Ni-Cu/Al2O3纳米自组装催化剂。
β-苯乙醇的制备：
(1)预先对所述反应系统(Y型通道1的每个通道流股数为10，通道直径45.85μm，微反应通道2直径208.61μm，所述出口过滤单元4的硅柱平均孔径为1.53μm)中的Ni-Cu/Al2O3纳米自组装催化剂进行还原：先通过所述Y型通道的气体通道向所述微反应通道中通入氢气，然后通过加热器6将所述微反应通道升温至130℃，停留2.5h，然后升温至220℃，停留24h，还原完成，在氢气气氛下降至室温，还原过程中氢气空速为450h-1，压力为1.5Mpa(表压)。
(2)催化剂还原完成后，打开超声发生器，将超声功率设定为350W，从所述Y型通道的气体通道通入经所述预热器7预热的氢气对所述微反应通道进行升温，氢气预热温度45℃。
(3)将所述微反应通道温度升至45℃后，以7.5Kg/h的速度打入原料氧化苯乙烯进行加氢反应，氢气流量6Nm3/h，控制反应温度为110℃，反应压力1.0Mpa。待反应进行8h后，每间隔一段时间取样分析反应液组成，考察长周期运行过程中催化剂性能变化，总共运行4500h，结果如图1所示。
从图中可知，在本发明所述工艺条件下，催化剂性能稳定，寿命长，且产物选择性高。
对比例1
将10g Raney6800催化剂(格雷斯公司)、50g氧化苯乙烯、450g乙醇加入反应釜(型号GSH-1，材质316L，厂家为威海化工机械有限公司)中，关闭反应釜，保压置换后，通入氢气进行反应，反应温度80℃，反应压力6Mpa，搅拌转速700rpm，反应时间3h，反应结束后取样对反应液进行分析，结果如表1所示。
对比例2
将10g Raney6800催化剂(格雷斯公司)、50g氧化苯乙烯、450g乙醇、0.2gNaOH加入反应釜(型号GSH-1，材质316L，厂家为威海化工机械有限公司)中，关闭反应釜，保压置换后，通入氢气进行反应，反应温度60℃，反应压力1Mpa，搅拌转速700rpm，反应时间3h，反应结束后取样对反应液进行分析，结果如表1所示。从表中可知，即使是添加助剂NaOH条件下，β-苯乙醇的选择性仍不甚理想，且助剂的加入将会导致分离过程中精馏塔塔底阻塞，同时会对产品品质产生影响。
对比例3
将30g Raney6800催化剂(格雷斯公司)、500g氧化苯乙烯加入反应釜(型号GSH-1，材质316L，厂家为威海化工机械有限公司)中，关闭反应釜，保压置换后，通入氢气进行反应，反应温度80℃，反应压力6Mpa，搅拌转速700rpm，反应时间4.5h，反应结束后取样对反应液进行分析，结果如表1所示。
对比例4
在直径20mm的普通固定床(型号TORCH，材质316SS，厂家为北京拓川石化评价装置技术开发有限公司，反应管长度1400mm)中进行氧化苯乙烯的加氢反应，采用的催化剂、催化剂还原程序、反应温度、压力、空速均与实施例5相同，运行4500h，反应结果如图2所示。
从图中可知，采用普通的固定床反应器，反应效果明显差于超声微填充床反应器，产物β-苯乙醇选择性呈明显下降趋势。
对比例5
将实施例5中的Ni-Cu/Al2O3纳米自组装催化剂更换为Raney6800(格雷斯公司)，其余工艺参数均同实施例5，运行4500h，反应结果如图3所示。
从图中可知，催化剂Raney6800的性能明显不如本专利所述Ni-Cu/Al2O3纳米自组装催化剂性能优异。
对比例6
无超声场条件下进行氧化苯乙烯加氢，其余工艺参数均同实施例5，运行4500h，反应结果如图4所示。
从图中可知，去除超声场后，反应效果明显变差，催化剂稳定性降低。
表1
编号 氧化苯乙烯转化率/％ β‐苯乙醇选择性/％ 乙苯选择性/％
实施例1 100 99.34 0.51
实施例2 100 99.07 0.73
实施例3 100 99.52 0.36
实施例4 100 99.35 0.48
对比例1 100 91.42 8.05
对比例2 100 98.57 1.26
对比例3 100 79.67 20.15

Claims (13)

  1. 一种制备β-苯乙醇所用的反应系统，其特征在于：所述反应系统包括，
    用于装载催化剂的微反应通道，所述微反应通道为直径为微米级的盘管，作为反应场所；
    与所述微反应通道的一端连通的Y型通道，其中所述Y型通道的两个通道分别为用于通入气体反应原料的气体通道和用于通入液体反应原料的液体通道；
    与所述微反应通道的另一端连通的出口过滤单元，所述出口过滤单元用于阻止所述微反应通道中的催化剂穿过而允许液体产物和气体流出；
    与所述出口过滤单元连通的气液分离系统，所述气液分离系统用于分离所述液体产物和气体；以及
    用于给所述微反应通道施加超声场的超声场发生器。
  2. 根据权利要求1所述的反应系统，其特征在于：所述超声场发生器的超声功率为50～600W，优选150～400W，更优选200～300W。
  3. 根据权利要求1或2所述的反应系统，其特征在于：所述Y型通道的通道直径为5～50μm，优选10～35μm，更优选20～30μm；所述Y型通道的气体通道和液体通道均由若干均匀分布的细管组成；每个通道的所述细管数为1～20，优选3～15，更优选5～10；优选所述气体通道的细管与所述液体通道的细管数量及分布完全相同；所述微反应通道的直径为5～500μm，优选50～350μm，更优选200～300μm；所述出口过滤单元为经刻蚀的硅柱，所述硅柱的平均孔径为0.1～15μm，优选0.5～10μm，更优选1～2μm。
  4. 一种制备β-苯乙醇所用的催化剂，其特征在于：所述催化剂为以Al2O3为载体、Ni元素和Cu元素为活性组分的纳米自组装催化剂；其中，以催化剂质量计，Ni元素含量为5～30wt％，优选10～27wt％，更优选20～25wt％；Cu元素含量为0.5～3.5wt％，优选1～3wt％，更优选1.5～2wt％；余量为Al2O3载体。
  5. 根据权利要求4所述的催化剂，其特征在于：所述催化剂的平均孔径为10～350nm，优选50～300nm，更优选100～150nm。
  6. 一种制备权利要求4或5所述的催化剂的方法，其特征在于：
    ①在搅拌条件下，将0.001-0.015mol/L的聚异丁烯马来酸三乙醇胺酯和0.05～ 0.25mol/L的润滑油基础油按(5-8):1的体积比充分混合，缓慢升温至90～100℃，得到混合物料A；在搅拌条件下，将1～5.5mol/L尿素水溶液和0.5～1.5mol/L九水硝酸铝水溶液按1：(3-5)的体积比充分混合，加热至90～100℃，得到混合物料B；
    ②将混合物料A、B按1:1的质量比混和，形成超增溶胶团，得到一次超增溶胶团自组装体；将所述一次超增溶胶团自组装体在100～110℃下反应，产物经水洗、干燥，得到二次纳米自组装体；将所述二次纳米自组装体焙烧，粉碎，得到所述Al2O3载体；
    ③将0.01～0.1mol/L的Ni(NO3)2水溶液和0.01～0.05mol/L的Cu(NO3)2水溶液混合，得到浸渍液；将步骤②得到的Al2O3载体粉末加入浸渍液中搅拌混合均匀，形成流动性浆料；
    ④将步骤③得到的流动性浆料烘干，焙烧，得到所述催化剂。
  7. 根据权利要求6所述的制备催化剂的方法，其特征在于：在所述步骤②中，所述一次超增溶胶团自组装体的反应时间为2-4小时，干燥温度为150-200℃，所述二次纳米自组装体的焙烧温度为550-600℃，焙烧时间为6-8小时，粉碎后Al2O3载体的粒径为10-30μm；在所述步骤④中，烘干温度为110-130℃，烘干时间为8-10小时，焙烧温度为300℃～500℃，焙烧时间为3-5小时；在所述步骤④中，所述焙烧为将步骤③得到的流动性浆料注入权利要求1-3任意一项所述的反应系统中的微反应通道中进行。
  8. 一种制备β-苯乙醇的工艺方法，包括如下步骤：
    (1)通入经预热的氢气将装载有催化剂的反应器升温；
    (2)通入氧化苯乙烯，进行加氢反应，得到β-苯乙醇；
    其特征在于：所述催化剂为权利要求4或5所述的催化剂或使用由权利要求6或7的方法制备得到的催化剂，所用的反应器为权利要求1或2或3所述的反应系统。
  9. 根据权利要求8所述的方法，其特征在于，在所述步骤(1)前还包括对反应器中的催化剂进行还原的步骤。
  10. 根据权利要求8或9所述的方法，其特征在于：所述还原步骤为：先将微反应通道升温至120～130℃，停留2～2.5h，然后升温至200～220℃，停留18～24h，还原完成，其中，还原过程中氢气空速为300～500h-1，压力为0.5～1.5Mpa，然后在氢气气氛下降至室温。
  11. 根据权利要求8-10中任意一项所述的方法，其特征在于：步骤(1)所述经预热的氢气的温度为25～60℃，优选30～50℃，更优选35～45℃。
  12. 根据权利要求8-11中任意一项所述的方法，其特征在于：步骤(2)中氢气的流量为0.5～13Nm3/h，优选1.5～10Nm3/h，更优选2.5～7Nm3/h；氧化苯乙烯进料速率为1～35Kg/h，优选3～20Kg/h，更优选5～10Kg/h；氢气与氧化苯乙烯的摩尔比为2-69，优选2.6-17，更优选3.7-14。
  13. 根据权利要求8-12中任意一项所述的方法，其特征在于：步骤(2)中反应温度为30～120℃，优选40～100℃，更优选50～70℃；反应压力为0.3～10Mpa，优选0.5～3Mpa，更优选1～1.5Mpa。
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