Preparation method of sandalwood 803

Abstract

The invention belongs to the field of sandalwood 803 preparation, and particularly relates to a preparation method of sandalwood 803. Sandalwood 803 is continuously produced in a fixed bed under the catalytic action of a solid acid catalyst and a hydrogenation catalyst, phenol and camphene are catalyzed by the solid acid catalyst to be subjected to an alkylation reaction, a terpene-phenol mixture in an alkylation reaction product is catalyzed by the hydrogenation catalyst to be subjected to a hydrogenation reaction, and the sandalwood 803 is prepared. The hydrogenation catalyst is a cobalt-based catalyst containing lanthanide oxides. Compared with the prior art, the continuous process for synthesizing the sandalwood 803 has the advantages that the sandalwood 803 can be continuously and uninterruptedly synthesized by selecting and preparing the solid acid catalyst and the hydrogenation catalyst which are high in activity and good in stability, so that the production efficiency of the sandalwood 803 is improved, the production cost is reduced, and large-scale production is facilitated.

Description

Technical Field

[0001] The invention belongs to the field of sandalwood 803 preparation, and particularly relates to a method for preparing sandalwood 803. Background Art

[0002] Sandalwood 803 is a trade name in my country. It was successfully developed by the former Light Industry Ministry’s Spice Research Institute in 1958, and then produced by Shanghai Xinhua Spice Factory and Dalian Oil Chemical Factory. The product is a colorless to slightly yellow viscous liquid with a lasting sandalwood-type aroma. Sandalwood 803 is an important monomer fragrance, which is used in a large amount in many flavors, especially in the field of incense. In recent years, with the development of the cosmetics industry, the demand for sandalwood 803 has increased dramatically. The traditional production method is to use camphene and guaiacol condensation followed by hydrogenation reduction. However, during the hydrogenation process, the -OCH 3 It will be removed by hydrogenation, and the cost of guaiacol is relatively high. Directly condensing phenol and camphene can greatly reduce the cost. Raney nickel is often used as a hydrogenation catalyst in the hydrogenation process, but Raney nickel has a high activity and will cause the hydroxyl group on phenol to be removed by hydrogenation during the reaction. Raney nickel is also very flammable when exposed to air, which is dangerous.

[0003] The preparation method reported at present does not have a fixed bed continuous preparation method. The traditional sandalwood 803 production process adopts a reactor-type intermittent production, with phenol and camphene as raw materials put into the reactor, adding kaolin as a catalyst for reaction, and then the alkylation product is placed in an autoclave and passed through high-pressure hydrogen for hydrogenation to prepare sandalwood 803. This process is intermittently produced according to a fixed formula, with low production efficiency, large space occupation, and high labor cost. The fixed bed production process can realize the continuous production of sandalwood 803, effectively improve production efficiency, save production space, and reduce production costs. The catalyst used in intermittent production is kaolin, which has poor stability and low life. The fixed bed production process requires a catalyst with high activity and high stability. The development of a catalyst with high safety and high stability for continuous production of new processes can effectively improve the output and quality of sandalwood 803, which has important industrial application value. Summary of the invention

[0004] The purpose of the present invention is to provide a method for preparing sandalwood 803 in order to solve at least one of the above problems, so as to solve the problem of low yield of sandalwood 803 synthesized by fixed bed in the prior art, as well as the problem of poor stability and low activity of the catalyst used in the production process of sandalwood 803, thereby realizing efficient and continuous fixed production of sandalwood 803 under the catalysis of a high-efficiency catalyst.

[0005] The present invention aims to propose a continuous process for the synthesis of sandalwood 803. A new catalyst is selected to solve the problems of low yield and short catalyst life in the synthesis of sandalwood 803 using a fixed bed, thereby solving the problems of low production efficiency, large space occupation and high labor cost in intermittent production.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] The technical solution of the present invention is to provide a preparation method of sandalwood 803. The sandalwood 803 is continuously produced in a fixed bed through the catalytic action of a solid acid catalyst and a hydrogenation catalyst, the solid acid catalyst catalyzes phenol and camphene to carry out an alkylation reaction, and a terpene-phenol mixture in the alkylation reaction product is hydrogenated by the hydrogenation catalyst to prepare sandalwood 803.

[0008] The reaction mechanism is as follows:

[0009]

[0010] Furthermore, the alkylation reaction uses zeolite molecular sieve as a solid acid catalyst.

[0011] Furthermore, the solid acid catalyst includes any one of mordenite, β molecular sieve, ZSM-5 molecular sieve, MCM-41 molecular sieve, MCM-48 molecular sieve and MCM-22 molecular sieve.

[0012] Furthermore, the silicon-aluminum ratio of the solid acid catalyst is (10-120):1, preferably 25:1.

[0013] Furthermore, the Si / Al atomic ratio of the MCM-22 molecular sieve is 20-200; the Si / Al atomic ratio of the ZSM-5 molecular sieve is 30-200; the Si / Al atomic ratio of the β molecular sieve is 20-200; the Si / Al atomic ratio of the MCM-41 molecular sieve is 20-200; and the Si / Al atomic ratio of the MCM-48 molecular sieve is 20-200.

[0014] Furthermore, in the alkylation reaction, the catalyst preheating temperature is 100-180°C, preferably 160°C.

[0015] Furthermore, the reaction temperature of the alkylation reaction is 100-180°C, preferably 160°C.

[0016] Furthermore, a mixed solution of phenol and camphene is introduced into the fixed bed through a peristaltic pump, wherein the molar ratio of phenol to camphene is (1-2):1, preferably 1.6:1; and the mass space velocity of the mixed solution is 1-4h -1 , preferably 2h -1 .

[0017] Furthermore, the alkylation reaction step includes: placing a solid acid catalyst in a fixed bed, first raising the reaction temperature to 160°C to preheat the solid acid catalyst for 1 hour, introducing phenol and camphene into the reactor at a molar ratio of 1.6:1 through a temperature-controlled peristaltic pump, and adjusting the mass space velocity to 2h -1 , the reaction temperature was 160°C, and samples were taken and analyzed every 12 hours.

[0018] Furthermore, the alkylation product is distilled to extract a terpene phenol mixture, which is then introduced into a fixed bed containing a hydrogenation catalyst for hydrogenation reaction to prepare sandalwood 803.

[0019] Furthermore, the hydrogenation reaction step includes: placing a hydrogenation catalyst in a fixed bed, continuously introducing hydrogen before the reaction and pretreating the hydrogenation catalyst under high temperature conditions, dissolving the terpene phenol mixture in cyclohexane and then introducing it into the fixed bed for hydrogenation reaction to prepare sandalwood 803.

[0020] Furthermore, the time for introducing hydrogen before the reaction is 0.5 to 1 h, preferably 0.5 h, in order to remove excess air in the fixed bed.

[0021] Furthermore, the temperature of the hydrogen pretreatment catalyst is 350°C to 550°C for 1 to 6 hours, preferably, hydrogen is introduced at 500°C and 0.1 MPa for 2 hours.

[0022] Furthermore, the temperature of the hydrogenation reaction is 120-240°C, preferably 200°C.

[0023] Furthermore, the flow rate of hydrogen introduced into the hydrogenation reaction is 20 to 160 mL / min, preferably 20 mL / min.

[0024] Furthermore, the fixed bed is maintained at a pressure of 3-6 MPa, preferably 4 MPa, during the hydrogenation reaction.

[0025] Furthermore, the mass fraction of the terpene phenol mixture in the cyclohexane solution is 10% to 50%, preferably 30%.

[0026] Furthermore, in the hydrogenation reaction, the terpene-phenol mixture solution is introduced into the fixed bed through a high-pressure pump, and the mass space velocity of the solution is 0.5 to 2 h -1 , preferably 1.5h -1 .

[0027] Furthermore, the hydrogenation reaction step includes: placing a hydrogenation catalyst in a fixed bed, continuously introducing hydrogen at 20 mL / min for 0.5 h, removing excess air in the fixed bed, introducing hydrogen at 20 mL / min for 2 h at 500 ° C and 0.1 MPa, and after the fixed bed temperature reaches 200 ° C, adjusting the fixed bed pressure to 4 MPa, dissolving the terpene phenol mixture in cyclohexane at a mass ratio of 30%, and pumping the solution with a high-pressure pump at a mass space velocity of 1.5 h -1 The product was passed into a fixed bed for hydrogenation reaction to prepare sandalwood 803.

[0028] Furthermore, the hydrogenation catalyst is a cobalt-based catalyst containing lanthanide oxides.

[0029] Furthermore, the lanthanide element includes any one of Ce, Sm, La, Y and Nd.

[0030] Furthermore, the preparation method of the hydrogenation catalyst comprises: 3 ) 2 6H 2 O and a lanthanide salt are dissolved in deionized water to obtain a bimetallic solution, a precipitant is added, the solution is stirred and allowed to stand for precipitation, and the precipitate is filtered, washed, and calcined to obtain the hydrogenation catalyst.

[0031] Furthermore, the concentration of the bimetallic solution is 1-3 mol / L, preferably 1 mol / L.

[0032] Furthermore, the atomic ratio of Co:lanthanide in the bimetallic solution is (0.0625-16):1, preferably 2:1.

[0033] Further, the lanthanide salt includes Ce(NO 3 ) 3 6H 2 O、Sm(NO 3 ) 3 6H 2 O、La(NO 3 ) 3 6H 2 O、Y(NO 3 ) 3 6H 2 O and Nd(NO 3 ) 3 6H 2 Any of O.

[0034] Further, the precipitant includes Na 2 CO 3 , NaOH and NH 3 ·H 2Any of O.

[0035] Furthermore, the precipitant is introduced into the bimetallic solution via a peristaltic pump, and the flow rate of the peristaltic pump is 5-20 mL / min, preferably 20 mL / min.

[0036] Furthermore, the amount of the precipitant added is 1.2 to 2.8 of the theoretical amount required for the precipitation of nitrate in the bimetallic solution.

[0037] Furthermore, the stirring speed is 400-600 rpm / min, preferably 500 rpm / min, and the mixture is stirred for 1 hour and then allowed to settle.

[0038] Furthermore, the static sedimentation time is 2 hours.

[0039] Furthermore, the temperature during the stirring and standing is controlled at 30-80°C, preferably 30°C.

[0040] Furthermore, after the precipitate is filtered, the filter cake is washed with deionized water and filtered again, and after repeating three times, the filter cake is placed in an oven at 110° C. to dry.

[0041] Furthermore, the calcination is carried out in an air atmosphere at a temperature of 300-550° C. for 4-6 hours, preferably at 400° C. for 4 hours.

[0042] On the basis of being in accordance with the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0043] Compared with the prior art, the present invention has the following advantages:

[0044] 1. The synthesis route of sandalwood 803 provided by the present invention is a brand-new synthesis route designed by making full use of a fixed bed reactor. By using it in combination with a catalyst, the synthesis route overcomes the shortcomings of intermittent production in a traditional kettle reactor and operator contact with reagents, and can continuously and uninterruptedly synthesize sandalwood 803, thereby improving production efficiency, saving production space, and effectively improving the yield and quality of sandalwood 803.

[0045] 2. The present invention selects a solid acid catalyst to continuously catalyze the alkylation reaction of phenol and camphene in a fixed bed. The selected solid acid catalyst zeolite molecular sieve has the advantages of high activity, good stability, fast reaction speed, etc., and the effect is much higher than using conventional kaolin as a reaction catalyst.

[0046] 3. The hydrogenation catalyst prepared by the present invention can significantly reduce the hydroxyl group falling after the hydrogenation of terpene phenols. The hydrogenation catalyst has high selectivity for sandalwood 803, the terpene phenol conversion rate can reach 99.7%, and the selectivity for sandalwood 803 can reach 99.2%. The by-product content of the catalytic terpene phenol hydrogenation is small, and the reduction of the aroma of sandalwood 803 after traditional terpene phenol hydrogenation is reduced. The formed catalyst still maintains activity after 200 hours of reaction, indicating that the hydrogenation catalyst prepared by the present invention has high activity, good stability, and can be used for a long time.

[0047] 4. The method for synthesizing sandalwood 803 provided by the present invention does not require operators to contact the reactor, is safer and more environmentally friendly, and has a simple principle, is conducive to scale-up production, and is suitable for industrial production. DETAILED DESCRIPTION

[0048] The present invention is described in detail below in conjunction with specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0049] Unless otherwise specified, the experimental reagents and raw materials used in the present invention are commercially available.

[0050] The experimental methods without specific conditions in the following implementations are all selected according to conventional methods and conditions, or according to the product instructions. Unless otherwise specified, the experimental instruments used in the present invention are all conventional experimental instruments in the laboratory.

[0051] A method for preparing sandalwood 803. The sandalwood 803 is continuously produced in a fixed bed through the catalytic action of a solid acid catalyst and a hydrogenation catalyst. The solid acid catalyst catalyzes phenol and camphene to carry out an alkylation reaction. A terpene-phenol mixture in the alkylation reaction product is hydrogenated through the catalysis of the hydrogenation catalyst to prepare sandalwood 803.

[0052] The reaction mechanism is as follows:

[0053]

[0054] The alkylation reaction selects zeolite molecular sieve as a solid acid catalyst, and the solid acid catalyst includes any one of mordenite, β molecular sieve, ZSM-5 molecular sieve, MCM-41 molecular sieve, MCM-48 molecular sieve and MCM-22 molecular sieve, and the silicon-aluminum ratio of the solid acid catalyst is (10-120):1, preferably 25:1.

[0055] The catalyst preheating temperature in the alkylation reaction is 100-180°C, preferably 160°C.

[0056] The reaction temperature of the alkylation reaction is 100-180° C., preferably 160° C.; the mixed solution of phenol and camphene is introduced into the fixed bed through a peristaltic pump, wherein the molar ratio of phenol to camphene is (1-2):1, preferably 1.6:1; the mass space velocity of the mixed solution is 1-4h -1 , preferably 2h -1 .

[0057] The alkylation reaction comprises the following steps: placing a solid acid catalyst in a fixed bed, first raising the reaction temperature to 100-180° C. to preheat the solid acid catalyst for 1 hour, introducing phenol and camphene into the reactor at a molar ratio of (1-2):1 through a temperature-controllable peristaltic pump, and adjusting the mass space velocity to 1-4 h -1 The reaction temperature was 100-180°C, and samples were taken and analyzed every 12 hours.

[0058] The alkylation reaction comprises the following steps: placing a solid acid catalyst in a fixed bed, first raising the reaction temperature to 160° C. to preheat the solid acid catalyst for 1 hour, introducing phenol and camphene into the reactor at a molar ratio of 1.6:1 through a temperature-controllable peristaltic pump, and adjusting the mass space velocity to 2 h -1 , the reaction temperature was 160°C, and samples were taken and analyzed every 12 hours.

[0059] The alkylation product is distilled to extract a terpene phenol mixture, which is then introduced into a fixed bed containing a hydrogenation catalyst for hydrogenation reaction to prepare sandalwood 803.

[0060] The hydrogenation reaction steps include: placing a hydrogenation catalyst in a fixed bed, continuously introducing hydrogen before the reaction and pretreating the hydrogenation catalyst under high temperature conditions, dissolving a terpene phenol mixture in cyclohexane and then introducing it into the fixed bed for hydrogenation reaction to prepare sandalwood 803.

[0061] The time for introducing hydrogen before the reaction is 0.5 to 1 h, preferably 0.5 h, in order to remove excess air in the fixed bed; the temperature for introducing hydrogen to pretreat the catalyst is 350°C to 550°C, and the time is 1 to 6 h, preferably 2 h of hydrogen reduction at 500°C and 0.1 MPa.

[0062] The temperature of the hydrogenation reaction is 120-240° C., preferably 200° C.; the flow rate of the hydrogen is 20-160 mL / min, preferably 20 mL / min; and the fixed bed is maintained at a pressure of 3-6 MPa, preferably 4 MPa.

[0063] The mass fraction of the terpene phenol mixture in the cyclohexane solution is 10% to 50%, preferably 30%.

[0064] In the hydrogenation reaction, the terpene-phenol mixture solution is introduced into the fixed bed through a high-pressure pump, and the mass space velocity of the solution is 0.5 to 2 h -1, preferably 1.5h -1 .

[0065] The hydrogenation reaction comprises the following steps: placing a hydrogenation catalyst in a fixed bed, continuously introducing hydrogen at 20 mL / min for 0.5 h, removing excess air in the fixed bed, introducing hydrogen at 20 mL / min for 2 h at 500° C. and 0.1 MPa, adjusting the fixed bed pressure to 4 MPa after the fixed bed temperature reaches 200° C., dissolving a terpene phenol mixture in cyclohexane at a mass ratio of 30%, and pumping the solution at a mass space velocity of 1.5 h -1 The product was passed into a fixed bed for hydrogenation reaction to prepare sandalwood 803.

[0066] The hydrogenation catalyst is a cobalt-based catalyst containing a lanthanide oxide; the lanthanide includes any one of Ce, Sm, La, Y and Nd.

[0067] The preparation method of the hydrogenation catalyst comprises: 3 ) 2 6H 2 O and a lanthanide salt are dissolved in deionized water to obtain a bimetallic solution, a precipitant is added, the solution is stirred and allowed to stand for precipitation, and the precipitate is filtered, washed, and calcined to obtain the hydrogenation catalyst.

[0068] The concentration of the bimetallic solution is 1-3 mol / L, preferably 1 mol / L; the atomic ratio of Co: lanthanide elements in the bimetallic solution is (0.0625-16):1, preferably 2:1.

[0069] The lanthanide salts include Ce(NO 3 ) 3 6H 2 O、Sm(NO 3 ) 3 6H 2 O、La(NO 3 ) 3 6H 2 O、Y(NO 3 ) 3 6H 2 O and Nd(NO 3 ) 3 6H 2 Any of O.

[0070] The precipitant includes Na 2 CO 3 , NaOH and NH 3 ·H 2 Any of O.

[0071] The precipitant is introduced into the bimetallic solution through a peristaltic pump, the flow rate of the peristaltic pump is 5-20 mL / min, the stirring speed is 400-600 rpm / min, the temperature during stirring and standing is controlled at 30-80° C., and the calcination is carried out in an air atmosphere at a temperature of 300-550° C. for 4-6 hours.

[0072] The amount of precipitant added is 1.2 to 2.8 of the theoretical amount required for nitrate precipitation in the bimetallic solution.

[0073] After stirring for 1 hour, the mixture was allowed to settle for 2 hours.

[0074] After the precipitate was filtered, the filter cake was washed with deionized water and filtered again. After repeating three times, the filter cake was placed in an oven at 110° C. to dry.

[0075] 1. Fixed bed continuous alkylation reaction of phenol and camphene

[0076] Example 1-1

[0077] This embodiment provides a method for continuously catalyzing alkylation of phenol and camphene in a fixed bed in the production of sandalwood 803 by a fixed bed, and the specific steps are as follows:

[0078] Take 4g of fixed-bed MCM-22 (silicon-aluminum ratio of 25:1) catalyst and load it into the fixed bed reactor. First, raise the reaction temperature to 160℃ to pretreat the solid acid catalyst for 1h. Then, introduce phenol and camphene into the reactor at a molar ratio of 1.6:1 through a temperature-controlled peristaltic pump. Adjust the mass space velocity to 2h. -1 , control the fixed bed reaction temperature to 160°C, and take samples for analysis every 12 hours.

[0079] Example 1-2

[0080] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that MCM-22 is replaced by mordenite.

[0081] Examples 1-3

[0082] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that MCM-22 is replaced by β molecular sieve.

[0083] Examples 1-4

[0084] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that MCM-22 is replaced by ZSM-5 molecular sieve.

[0085] Examples 1-5

[0086] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that MCM-22 is replaced by MCM-41 molecular sieve.

[0087] Examples 1-6

[0088] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that MCM-22 is replaced by MCM-48 molecular sieve.

[0089] Examples 1-7

[0090] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the silicon-aluminum ratio is changed to 10:1.

[0091] Examples 1-8

[0092] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the silicon-aluminum ratio is changed to 50:1.

[0093] Examples 1-9

[0094] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the silicon-aluminum ratio is changed to 100:1.

[0095] Examples 1-10

[0096] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the temperature of the fixed bed is changed to 120°C.

[0097] Examples 1-11

[0098] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the temperature of the fixed bed is changed to 140°C.

[0099] Examples 1-12

[0100] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the temperature of the fixed bed is changed to 180°C.

[0101] Examples 1-13

[0102] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the molar ratio of phenol / camphene is changed to 1.

[0103] Examples 1-14

[0104] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the molar ratio of phenol / camphene is changed to 1.2.

[0105] Examples 1-15

[0106] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the molar ratio of phenol / camphene is changed to 2.

[0107] Examples 1-16

[0108] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the mass space velocity is changed to 1h -1 .

[0109] Examples 1-17

[0110] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the mass space velocity is changed to 3h -1 .

[0111] Examples 1-18

[0112] This embodiment provides a method for continuously catalyzing the alkylation reaction of phenol and camphene in a fixed bed, referring to Example 1-1, except that the mass space velocity is changed to 4h -1 .

[0113] Alkylation reaction was carried out using Examples 1-1 to 1-18, and each reaction was evaluated for 200 h. The results of the camphene conversion, CO selectivity, and CC selectivity obtained at 24 h and 200 h are shown in Tables 1 and 2:

[0114] Table 1 Results of 24h catalytic alkylation reaction of phenol and camphene by Examples 1-1 to 1-18

[0115] Camphene conversion rate (%) CC selectivity (%) CO selectivity (%) Example 1-1 99.2 80.2 6.8 Example 1-2 84.4 14.2 10 Examples 1-3 97.23 86.3 7.65 Examples 1-4 96.26 55.36 32.05 Examples 1-5 92.85 46.26 37.21 Examples 1-6 73.54 20.56 12.77 Examples 1-7 93.71 76.91 10.86 Examples 1-8 98.56 78.64 10.21 Examples 1-9 96.55 69.23 15.66 Examples 1-10 93.21 60.35 26.35 Embodiment 1-11 99.31 76.16 18.31 Examples 1-12 98.25 76.33 5.66 Examples 1-13 99.12 76.86 10.09 Examples 1-14 99.09 78.22 9.69 Examples 1-15 99.11 80.16 7.23 Examples 1-16 98.76 80.16 7.01 Examples 1-17 99.12 79.89 6.91 Examples 1-18 98.67 78.65 7.79

[0116] Table 2 Results of catalytic alkylation reaction of phenol and camphene for 200 h in Examples 1-1 to 1-18

[0117] Camphene conversion rate (%) CC selectivity (%) CO selectivity (%) Example 1-1 98.5 79.23 6.1 Example 1-2 76.1 9.23 8.26 Examples 1-3 80.3 61.89 14.53 Examples 1-4 96.78 54.23 33.19 Examples 1-5 91.26 45.32 30.66 Examples 1-6 63.5 16.77 15.28 Examples 1-7 93.23 70.61 12.27 Examples 1-8 95.74 73.95 11.55 Examples 1-9 94.91 65.78 14.65 Examples 1-10 93.11 60.05 25.96 Examples 1-11 97.23 75.93 18.92 Examples 1-12 93.89 74.65 5.89 Examples 1-13 98.79 75.99 8.94 Examples 1-14 98.65 76.99 10.13 Examples 1-15 98.09 79.89 6.13 Examples 1-16 98.11 78.92 6.99 Examples 1-17 98.77 78.96 6.89 Examples 1-18 97.56 78.09 8.18

[0118] As shown in Table 1, Example 1-1 has the highest camphene conversion of 99.2% and stable CC alkylation selectivity, and the catalyst has high catalytic stability. As shown in Table 2, Example 1-1 is continuously reacted for 200h without obvious deactivation; the reaction results of Example 1-13 and Example 1-1 are similar, and from the perspective of product yield, Example 1-1 is preferred; Examples 1-1 to 1-18 illustrate that the catalyst selected by the present invention is applicable to a variety of fixed-bed production environments; the remaining camphene and phenol in the reaction product can be separated from the terpene phenol product and the unreacted raw material by distillation, and the unreacted raw material can continue to enter the fixed-bed reaction, and the terpene phenol product is used for hydrogenation to prepare sandalwood 803.

[0119] 2. Fixed-bed continuous method for preparing sandalwood 803 by hydrogenation of terpene phenols

[0120] Example 2-1

[0121] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene-phenol mixture in the continuous production of sandalwood 803 by a fixed bed, and continuously catalyzing the hydrogenation of the terpene-phenol mixture in a fixed bed to produce sandalwood 803. The specific steps are as follows:

[0122] S1: 11.64 g Co(NO 3 ) 2 6H 2 O and 34.7376 g Ce(NO 3 ) 3 6H 2 O and deionized water were added to the beaker and stirred to dissolve to prepare a 1 mol / L bimetallic solution;

[0123] S2: Dissolve the precipitant in deionized water and stir to completely dissolve the precipitant to prepare a 1 mol / L precipitant solution;

[0124] S3: The precipitant is introduced into the bimetallic solution at a rate of 20 mL / min using a peristaltic pump, and stirred at 500 rpm / min for 1 hour. After the stirring is completed, the solution is allowed to settle for 2 hours. The temperature is controlled at 30-80°C during the stirring and settling process;

[0125] S4: After the obtained product is filtered, the filter cake is repeatedly washed with deionized water and filtered again, and the process is repeated 3 times. The obtained filter cake is dried in an oven at 110° C. and then calcined in a muffle furnace at 400° C. for 4 h to obtain the hydrogenation catalyst of this embodiment;

[0126] S5: Fix the hydrogenation catalyst into shape, take 6 g of the catalyst and place it in a fixed bed, continuously introduce hydrogen at 20 mL / min for 0.5 h, remove excess air in the fixed bed, and introduce hydrogen at 20 mL / min for reduction at 500°C and 0.1 MPa for 2 h;

[0127] S6: After the fixed bed temperature drops to 200°C, the fixed bed pressure is adjusted to 4 MPa, and the terpene phenol mixture is dissolved in cyclohexane at a mass ratio of 30%. The solution is pumped at a mass space velocity of 1.5 h -1 It is passed into a fixed bed for hydrogenation reaction.

[0128] Example 2-2

[0129] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in step S1, 34.7376 g Ce(NO 3 ) 3 6H 2 O was changed to 35.5568g Sm(NO 3 ) 3 6H 2 O, and the corresponding Co / Sm metal oxide catalysts were prepared.

[0130] Embodiment 2-3:

[0131] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in step S1, 34.7376 g Ce(NO 3 ) 3 6H 2 O was changed to 34.6408 g La(NO 3 ) 3 6H 2 O, and the corresponding Co / La metal oxide catalyst was prepared.

[0132] Embodiment 2-4:

[0133] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in step S1, 34.7376 g Ce(NO 3 ) 3 6H 2 O is changed to 30.6408g Y(NO 3 ) 3 6H 2 O, and the corresponding Co / Y metal oxide catalyst was prepared.

[0134] Embodiment 2-5:

[0135] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in step S1, 34.7376 g Ce(NO 3 ) 3 6H 2 O was changed to 35.068 g Nd(NO 3 ) 3 6H 2 O. The corresponding Co / Nd metal oxide catalyst was prepared.

[0136] Embodiment 2-6:

[0137] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in steps S1 and S2, Co(NO 3 ) 2 6H 2 O and Ce(NO 3 ) 3 6H 2 The amount of O added was changed to 1.82g and 43.422g, and the amount of Na 2 CO 3 The amount added was changed to 36.352 g.

[0138] Embodiment 2-7:

[0139] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in steps S1 and S2, Co(NO 3 ) 2 6H 2 O and Ce(NO 3 ) 3 6H 2 The amount of O added was changed to 29.1g and 2.71g, and the amount of Na 2 CO 3 The added amount was changed to 25.44 g.

[0140] Embodiment 2-8:

[0141] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in step S2, Na 2 CO 3 Amount added: 20.352 g.

[0142] Embodiment 2-9:

[0143] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in step S2, Na 2 CO 3 Added amount: 47.488g.

[0144] Embodiment 2-10:

[0145] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in step S2, Na 2 CO 3 Add and replace with NaOH.

[0146] Embodiment 2-11:

[0147] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in step S2, Na 2 CO 3 Add NH 3 ·H 2 O.

[0148] Embodiment 2-12:

[0149] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene-phenol mixture and continuously catalyzing the hydrogenation of the terpene-phenol mixture in a fixed bed to produce sandalwood 803, with reference to Example 1, except that in step S3, the temperature is controlled to 50° C. during the stirring and standing process.

[0150] Embodiment 2-13:

[0151] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene-phenol mixture and continuously catalyzing the hydrogenation of the terpene-phenol mixture in a fixed bed to produce sandalwood 803, with reference to Example 1, except that in step S3, the temperature is controlled to 70° C. during the stirring and standing process.

[0152] Embodiment 2-14:

[0153] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene-phenol mixture and continuously catalyzing the hydrogenation of the terpene-phenol mixture in a fixed bed to produce sandalwood 803, with reference to Example 1, except that in step S4, the temperature of the muffle furnace is adjusted to 300°C.

[0154] Embodiment 2-15:

[0155] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene-phenol mixture and continuously catalyzing the hydrogenation of the terpene-phenol mixture in a fixed bed to produce sandalwood 803, with reference to Example 1, except that in step S3, the temperature of the muffle furnace is adjusted to 500°C.

[0156] Embodiment 2-16:

[0157] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene-phenol mixture and continuously catalyzing the hydrogenation of the terpene-phenol mixture in a fixed bed to produce sandalwood 803, with reference to Example 1, except that in step S5, the fixed bed reaction temperature is adjusted to 160°C.

[0158] Embodiment 2-17:

[0159] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene-phenol mixture and continuously catalyzing the hydrogenation of the terpene-phenol mixture in a fixed bed to produce sandalwood 803, with reference to Example 1, except that in step S5, the fixed bed reaction temperature is adjusted to 240°C.

[0160] Embodiment 2-18:

[0161] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in step S6, the mass space velocity is adjusted to 1h -1 .

[0162] Embodiment 2-19:

[0163] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene phenol mixture and continuously catalyzing the hydrogenation of the terpene phenol mixture in a fixed bed to produce sandalwood 803. Referring to Example 1, the difference is that in step S6, the mass space velocity is adjusted to 2h -1 .

[0164] Embodiment 2-20:

[0165] This embodiment provides a method for preparing a catalyst for hydrogenating a terpene-phenol mixture and continuously catalyzing the hydrogenation of the terpene-phenol mixture in a fixed bed to produce sandalwood 803, with reference to Example 1, except that in step S6, the reaction time is adjusted to 200 hours.

[0166] The different hydrogenation catalysts prepared in Examples 2-1 to 2-20 were applied to the hydrogenation of terpene phenols to produce sandalwood 803 and the activity was evaluated. The conversion rate and selectivity of the reaction are shown in Table 3:

[0167] Table 3 Performance of different hydrogenation catalysts prepared in Examples 2-1 to 2-20 in catalyzing terpene phenol hydrogenation

[0168] Example Terpene phenol conversion rate (%) Sandalwood 803 selectivity (%) Example 2-1 99.7 99.2 Example 2-2 80.6 99.36 Example 2-3 60.3 80.6 Embodiment 2-4 87.64 82.53 Embodiment 2-5 31.66 99.21 Embodiment 2-6 90.23 99.26 Embodiment 2-7 98.26 95.63 Embodiment 2-8 99.26 97.62 Embodiment 2-9 99.11 95.65 Embodiment 2-10 99.65 99.12 Example 2-11 99.84 98.62 Example 2-12 99.26 97.98 Example 2-13 99.38 96.35 Example 2-14 98.25 76.33 Example 2-15 99.12 76.78 Example 2-16 89.33 99.16 Example 2-17 99.89 90.36 Example 2-18 99.66 97.79 Example 2-19 95.36 99.13 Embodiment 2-20 99.59 99.26

[0169] As shown in Table 3, the terpene phenol conversion rate and the selectivity of sandalwood 803 obtained under the Co / Ce bimetallic hydrogenation catalyst prepared in Example 2-1 and the fixed bed reaction conditions are the highest, with a terpene phenol conversion rate of 99.7% and a sandalwood 803 selectivity of 99.2%; and the prepared catalyst has good stability. In Example 2-20, the catalyst still remains active after 200 hours of reaction, and the terpene phenol conversion rate and the selectivity of sandalwood 803 do not decrease; Examples 2-1 to 2-20 illustrate that the hydrogenation catalyst prepared by the present invention can be applied to a variety of fixed bed production environments and maintain good performance.

[0170] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A method for preparing sandalwood 803, characterized in that: The sandalwood 803 is continuously produced in a fixed bed by the catalytic action of a solid acid catalyst and a hydrogenation catalyst. The solid acid catalyst catalyzes an alkylation reaction of phenol and camphene, and a terpene-phenol mixture in the alkylation reaction product is hydrogenated by the hydrogenation catalyst to prepare sandalwood 803.

2. The method for preparing sandalwood 803 according to claim 1, characterized in that: The solid acid catalyst includes any one of mordenite, beta molecular sieve, ZSM-5 molecular sieve, MCM-41 molecular sieve, MCM-48 molecular sieve and MCM-22 molecular sieve.

3. The method for preparing sandalwood 803 according to claim 1, characterized in that: The silicon-aluminum ratio of the solid acid catalyst is (10-120):

1.

4. The method for preparing sandalwood 803 according to claim 1, characterized in that: The reaction temperature of the alkylation is 100-180° C. The mixed solution of phenol and camphene is introduced into a fixed bed through a peristaltic pump to prepare terpene phenol, wherein the molar ratio of phenol to camphene is (1-2):1, and the mass space velocity of the mixed solution is 1-4h -1 .

5. The method for preparing sandalwood 803 according to claim 1, characterized in that: The temperature of the hydrogenation reaction is 120-240°C, the flow rate of hydrogen is 20-160 mL / min, the fixed bed is maintained at a pressure of 3-6 MPa, and the terpene-phenol mixture solution is introduced into the fixed bed through a high-pressure pump, and the mass space velocity of the solution is 0.5-2 h -1 .

6. The method for preparing sandalwood 803 according to claim 1, characterized in that: The hydrogenation catalyst is a cobalt-based catalyst containing a lanthanide oxide.

7. The method for preparing sandalwood 803 according to claim 6, characterized in that: The lanthanoid element includes any one of Ce, Sm, La, Y and Nd.

8. The method for preparing sandalwood 803 according to claim 1, characterized in that: The preparation method of the hydrogenation catalyst comprises: dissolving Co(NO3)2·6H2O and a lanthanide salt in deionized water to obtain a bimetallic solution, adding a precipitant, stirring and then standing to precipitate, and filtering, washing and calcining the precipitate to obtain the hydrogenation catalyst.

9. The method for preparing sandalwood 803 according to claim 8, characterized in that: The atomic ratio of Co to lanthanide elements in the bimetallic solution is (0.0625-16):

1.

10. The method for preparing sandalwood 803 according to claim 8, characterized in that: The precipitant is introduced into the bimetallic solution through a peristaltic pump, the flow rate of the peristaltic pump is 5-20 mL / min, the stirring speed is 400-600 rpm / min, the temperature during stirring and standing is controlled at 30-80° C., and the calcination is carried out in an air atmosphere at a temperature of 300-550° C. for 4-6 hours.

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