Phosphate catalyst for preparing sandalwood 803 as well as preparation method, application and continuous production process of phosphate catalyst

Abstract

The invention relates to a phosphate catalyst for preparing sandalwood 803 as well as a preparation method, application and a continuous production process of the phosphate catalyst. The preparation method of the phosphate catalyst comprises the following steps: adding Zr (NO3) 4. 5H2O and Ce (NO3) 3. 6H2O into water, and dissolving to prepare a Zr-Ce nitrate mixed solution; adding phosphoric acid and / or acid salt thereof into water for dissolving to obtain a phosphoric acid and / or acid salt solution thereof; and adding the phosphoric acid and / or the acidic salt solution thereof into the Zr-Ce nitrate mixed solution, adjusting the pH value, stirring, standing, precipitating, carrying out suction filtration, washing, drying and calcining to obtain the phosphate catalyst, and completing the reaction. Compared with the prior art, the phosphate catalyst with high safety, high activity, high stability and strong acidity is obtained, high-yield conversion of phenol camphene is realized, the content of meta-terpenyl phenol is improved, the content of terpenyl cyclohexanol in sandalwood 803 is further improved, and long-term and stable use in a fixed bed gas phase reaction process can be realized.

Description

Technical Field

[0001] The invention relates to the technical field of sandalwood 803 preparation, and in particular to a phosphate catalyst for preparing sandalwood 803, a preparation method and application thereof, and a continuous production process. Background Art

[0002] Sandalwood 803 is a colorless to slightly yellow viscous liquid with a lasting sandalwood-type fragrance. Sandalwood 803 is an important monomeric fragrance, and its usage is relatively large in a variety of flavors, and its usage is particularly large in the field of incense. In the mixture of sandalwood 803, its terpene cyclohexanol is a product with a strong sandalwood smell. With the development of the cosmetics industry in recent years, demand has increased sharply. The traditional production method is to use amphene and guaiacol to condense and then hydrogenate and reduce to make it. But in hydrogenation, the -OCH3 on the guaiacol molecule will be removed by hydrogenolysis, and the guaiacol cost is higher. And directly using phenol and amphene to carry out condensation can greatly reduce costs, and in the hydrogenation process, Raney nickel is often used as a hydrogenation catalyst, and Raney nickel is more active, which can cause the hydroxyl on phenol to be removed by hydrogenolysis during the reaction.

[0003] The traditional production process of preparing sandalwood 803 by condensation of phenol and camphene adopts reactor kettle intermittent production, with phenol and camphene as raw materials into reactor, adding carclazyte as catalyst for liquid phase reaction, and then the terpene phenol generated by alkylation is put into 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 occupied space, high labor cost, and liquid phase alkylation reaction, and the reaction temperature is low, resulting in less terpene phenol meta content in the alkylated product. This is because the catalyst used for intermittent production is carclazyte, which has poor stability and low lifespan, and cannot be applied to fixed bed gas phase reaction continuous production process. Therefore, developing a catalyst with high safety, high activity, high stability and strong acidity to be applied to fixed bed gas phase continuous reaction production process can effectively improve the output and quality of sandalwood 803, and has important industrial application value. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the above-mentioned prior art in the fixed-bed gas-phase alkylation synthesis of terpene phenols in low yield and short catalyst life, and to provide a phosphate catalyst for the preparation of sandalwood 803 and its preparation method and application, and a continuous production process, so as to obtain a phosphate catalyst with high safety, high activity, high stability and strong acidity, realize high-yield conversion of phenol camphene, increase the content of meta-terpene phenol, and further increase the content of terpene cyclohexanol in sandalwood 803, and realize long-term and stable use in the fixed-bed gas-phase reaction process.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] One of the technical solutions of the present invention is to provide a method for preparing a phosphate catalyst for preparing sandalwood 803, comprising the following steps:

[0007] Add Zr(NO3)4·5H2O and Ce(NO3)3·6H2O into water and dissolve them to prepare a Zr-Ce nitrate mixed solution;

[0008] Add phosphoric acid and / or its acid salt into water and dissolve them to obtain a phosphoric acid and / or its acid salt solution;

[0009] The phosphoric acid and / or its acid salt solution is added to the Zr-Ce nitrate mixed solution, the pH is adjusted, the mixture is stirred and then allowed to stand for precipitation, filtered, washed, dried, and calcined to obtain a phosphate catalyst, and the reaction is completed.

[0010] Further, the molar ratio of Zr(NO3)4·5H2O and Ce(NO3)3·6H2O is 0.1-8:1, preferably 0.1-4:1, such as 4:1, 2:1, 1:1, 0.5:1, 0.25:1, 0.1:1;

[0011] The concentration of Zr(NO3)4·5H2O in the Zr-Ce nitrate mixed solution is 0.01-1 mol / L.

[0012] Further, the phosphoric acid and / or its acid salts include one or more of H3PO4, NH4H2PO4, (NH4)2HPO4;

[0013] The concentration of the phosphoric acid and / or its acid salt solution is 0.01-1 mol / L.

[0014] Furthermore, the actual amount of phosphoric acid and / or its acid salt added is 0.75 to 1.25 times the molar amount of the theoretical phosphoric acid and / or its acid salt required to completely form a precipitate of Zr(NO3)4·5H2O and Ce(NO3)3·6H2O.

[0015] Furthermore, during the pH adjustment process, ammonia water is used to adjust the pH to 6 to 8;

[0016] The calcination temperature is 350-650° C., preferably 500-600° C.; the calcination time is 4-8 hours; and the calcination is carried out in an air atmosphere.

[0017] Furthermore, the phosphoric acid and / or its acid salt solution is added dropwise into the Zr-Ce nitrate mixed solution at a flow rate of 1% to 5% solution volume / min.

[0018] Furthermore, the stirring speed is 200 to 800 rpm, preferably 400 to 600 rpm, and the stirring time is 0.5 to 2 h.

[0019] Furthermore, the static sedimentation time is 1 to 5 hours.

[0020] Furthermore, water is used as the washing liquid during washing.

[0021] Furthermore, the drying temperature is 100-120°C.

[0022] Furthermore, the temperature during stirring and static precipitation is 5 to 30°C, preferably 5 to 15°C.

[0023] The second technical solution of the present invention is to provide a phosphate catalyst for the preparation of sandalwood 803, which is prepared by the preparation method.

[0024] The third technical solution of the present invention is to provide an application of a phosphate catalyst for the preparation of sandalwood 803, wherein the phosphate catalyst is used for the preparation of sandalwood 803.

[0025] The fourth technical solution of the present invention is to provide a continuous production process for preparing sandalwood 803, which is produced using the phosphate catalyst. The continuous production process comprises the following steps:

[0026] The phosphate catalyst is fixed and formed into a fixed bed reactor, and the phosphate catalyst is preheated;

[0027] Passing phenol and camphene into the fixed bed reactor to carry out gas phase reaction, and obtaining a crude terpene phenol product after cooling;

[0028] The crude terpene phenol product is distilled and separated to obtain a terpene phenol concentrate, which is placed in a high-pressure reactor, and Raney nickel is used as a hydrogenation catalyst. Hydrogen is introduced to carry out a hydrogenation reaction to obtain sandalwood 803.

[0029] Further, the phosphate catalyst is preheated using a reaction gas at 300-400°C;

[0030] The loading amount of the phosphate catalyst is 50% to 80% of the volume of the constant temperature section of the fixed bed reactor;

[0031] Before the phenol and camphene are introduced into the fixed bed reactor, the pressure in the fixed bed reactor is 1-4 MPa;

[0032] The molar ratio of phenol to camphene is 1 to 4:1, and the mass space velocity is adjusted to 1 to 5 h -1 , adjust the reaction temperature to 300-400°C.

[0033] Furthermore, the reaction gas is nitrogen.

[0034] Furthermore, the preheating time is 0.5 to 2 hours.

[0035] Furthermore, nitrogen is introduced into the fixed bed reactor to make the pressure in the fixed bed reactor be 1-4 MPa.

[0036] Furthermore, the mass of the Raney nickel is 1wt% to 6wt% of the terpene phenol concentrate;

[0037] The hydrogenation reaction is carried out under a pressure of 3 to 6 MPa, a temperature of 120 to 200° C. and a time of 4 to 10 hours.

[0038] Furthermore, the phosphate catalyst is fixed and formed by a mold.

[0039] Furthermore, the hydrogen introduced is 1-3 MPa.

[0040] Furthermore, the initial pressure in the high-pressure reactor can be 1-3 MPa.

[0041] Furthermore, the stirring rate in the high-pressure reactor is 300-600 rpm.

[0042] Compared with the prior art, the present invention has the following advantages:

[0043] (1) The present invention prepares a phosphate catalyst, which has strong acidity and high catalytic activity. Zirconium phosphate has better selectivity for CC alkylation in the phenol-camphene alkylation reaction. Cerium phosphate has a larger specific surface area. By adding cerium phosphate, the conversion rate of the reaction is enhanced, the selectivity of the meta-alkylation product is improved, and the molecular flow in the catalyst is reduced to reduce reaction coking, and the life of the catalyst is also improved. The prepared phosphate has the advantages of high activity, good stability, and fast reaction speed in the preparation process (alkylation reaction) of sandalwood 803, and the effect is much higher than that of using conventional kaolin as a reaction catalyst.

[0044] (2) The continuous production process for preparing sandalwood 803 provided by the present invention makes full use of the advantages of high reaction temperature, continuous reaction and high pressure reaction of fixed bed reactor, changes the phenol-camphene alkylation reaction from kettle liquid phase reaction to fixed bed high temperature gas phase reaction, and provides a new sandalwood 803 gas phase alkylation synthesis route. In the alkylation reaction process, the meta-position reaction product is difficult to prepare, mostly ortho-position or para-position products, and the yield of the meta-position product can be improved by increasing the reaction temperature, and the conversion rate and CC alkylation selectivity of the reaction under gas phase reaction conditions are higher, and high pressure reaction also promotes the reaction. It overcomes the intermittent nature of the traditional kettle reactor and the shortcomings of low meta-terpene phenol content at low liquid phase reaction temperature, is safer and more environmentally friendly, and is simple to amplify, and is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1The reaction mechanism of the preparation process of sandalwood 803;

[0046] Figure 2 The structural isomerization of camphene group occurs during the alkylation of phenol and camphene under the action of acidic catalyst. DETAILED DESCRIPTION

[0047] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and a detailed implementation method and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments. Based on the given embodiments, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0048] Unless otherwise specified, the reagents, methods, instruments and equipment used in the present invention are conventional reagents, methods, instruments and equipment in the art. The experimental reagents and instruments used in the following examples are shown in Tables 1 and 2.

[0049] Table 1 Experimental reagents

[0050]

[0051] Table 2 Instruments used in the experiment

[0052]

[0053] Example 1

[0054] A method for preparing a phosphate catalyst for preparing sandalwood 803 comprises the following steps:

[0055] (1) Add Zr(NO3)4·5H2O and Ce(NO3)3·6H2O into a beaker at a molar ratio of 4:1, and add deionized water to prepare a 0.1 mol / L Zr-Ce nitrate mixed solution;

[0056] (2) Dissolve H3PO4 in deionized water and stir to completely dissolve it to prepare a 0.1 mol / L H3PO4 solution;

[0057] (3) The H3PO4 solution was introduced into the Zr-Ce nitrate mixture at a rate of 20 mL / min using a peristaltic pump, and ammonia water was added to adjust the solution pH to 7, and the solution was stirred at 500 rpm / min for 1 hour. After the stirring, the solution was allowed to stand for 2 hours. During the stirring and standing process, the temperature was controlled at 10°C using a constant temperature water bath. The molar ratio of the H3PO4 required for the precipitation of Zr(NO3)4·5H2O and Ce(NO3)3·6H2O to the actual added H3PO4 was 1:1.2.

[0058] (4) After the precipitated product is filtered, the filter cake is repeatedly washed with deionized water and filtered, and this process is repeated three times. The obtained filter cake is dried in an oven at 110° C. and then calcined in a muffle furnace at 550° C. for 4 h to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0059] A continuous production process for preparing sandalwood 803, using the Ce-Zr(HPO4)2 phosphate catalyst for production, the continuous production process comprising the following steps:

[0060] (1) The Ce-Zr(HPO4)2 phosphate catalyst described in this example was fixed into a shape, 6 g was taken and loaded into a fixed bed reactor, and nitrogen (20 mL / min) was continuously introduced for 30 minutes to remove excess air in the fixed bed. The temperature was raised to a reaction temperature of 380°C at a rate of 10°C / min and maintained for 1 hour to preheat and activate the Ce-Zr(HPO4)2 phosphate catalyst.

[0061] (2) The nitrogen temperature was maintained, and nitrogen was continuously introduced until the pressure in the fixed bed was maintained at 2 MPa. Camphene and phenol were melted and mixed in a ratio of 1:4, and the solution was heated with a heat-insulating high-pressure pump at a mass space velocity of 1 h -1 The gas phase alkylation reaction was carried out in a fixed bed. The catalyst and reaction conditions were evaluated for 48 hours, and samples were taken at intervals of 12 hours to detect the content of the reaction product.

[0062] (3) The gas phase alkylation reaction was carried out for 48 hours, and the collected reaction liquid was distilled to separate the raw materials to obtain a terpene phenol concentrate. A 3 wt% Raney nickel and terpene phenol mixture was placed in a high-pressure reactor, and 2 MPa hydrogen was introduced twice repeatedly to remove excess air. Hydrogen was continuously introduced to maintain a reaction pressure of 4 MPa in the reactor, and the reaction temperature was adjusted to 150° C. and the stirring speed of the reactor was adjusted to 400 rpm / min to hydrogenate terpene phenol to prepare sandalwood 803. The reaction process is as follows: Figure 1 and Figure 2 . Figure 1 The present invention is a reaction process flow chart of the preparation process of sandalwood 803, which includes an alkylation reaction of phenol and camphene under the catalysis of an acidic catalyst and a reaction of preparing sandalwood 803 product by hydrogenation of the alkylation product through Raney nickel catalysis. Figure 2 In the alkylation process, camphene is alkylated with phenol under the catalysis of an acidic catalyst, and the camphene group is isomerizes to form different isomeric groups.

[0063] The present invention prepares a phosphate catalyst, which has strong acidity and high catalytic activity. Zirconium phosphate has better selectivity for CC alkylation in the phenol-camphene alkylation reaction, and cerium phosphate has a large specific surface area. By adding cerium phosphate, the conversion rate of the reaction is enhanced, the selectivity of the meta-alkylation product is improved, and the molecular flow in the catalyst reduces the reaction coking. In the alkylation reaction process, the meta-position reaction product is difficult to prepare, and most of them are ortho-position or para-position products. The yield of the meta-position product can be improved by increasing the reaction temperature, and the conversion rate and CC alkylation selectivity of the reaction under gas phase reaction conditions are higher, and the high-pressure reaction also promotes the reaction. The conventional kettle reactor overcomes the intermittent and liquid phase reaction temperature and the disadvantages of low meta-terpene phenol content, which are safer and more environmentally friendly, simple to scale up, and suitable for industrial production.

[0064] Example 2

[0065] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that the molar ratio of Zr(NO3)4·5H2O and Ce(NO3)3·6H2O is changed from 4:1 to 2:1 to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0066] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0067] Example 3

[0068] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that the molar ratio of Zr(NO3)4·5H2O and Ce(NO3)3·6H2O is changed from 4:1 to 1:1 to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0069] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0070] Example 4

[0071] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that the molar ratio of Zr(NO3)4·5H2O and Ce(NO3)3·6H2O is changed from 4:1 to 0.5:1 to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0072] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0073] Example 5

[0074] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that the molar ratio of Zr(NO3)4·5H2O and Ce(NO3)3·6H2O is changed from 4:1 to 0.25:1 to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0075] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0076] Example 6

[0077] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that the molar ratio of Zr(NO3)4·5H2O and Ce(NO3)3·6H2O is changed from 4:1 to 0.1:1 to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0078] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0079] Example 7

[0080] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that H3PO4 is adjusted to NH4H2PO4 to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0081] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0082] Example 8

[0083] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that H3PO4 is adjusted to (NH4)2HPO4 to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0084] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0085] Example 9

[0086] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that ammonia water is added to adjust the solution pH from 7 to 6 to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0087] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0088] Example 10

[0089] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that ammonia water is added to adjust the solution pH from 7 to 8 to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0090] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0091] Embodiment 11

[0092] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that the temperature during stirring and standing is controlled at 10°C instead of 5°C to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0093] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0094] Example 12

[0095] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that the temperature during stirring and standing is controlled at 10°C and changed to 20°C to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0096] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0097] Embodiment 13

[0098] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that the temperature during stirring and standing is controlled at 10°C instead of 30°C to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0099] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0100] Embodiment 14

[0101] A preparation method for a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that the muffle furnace calcination temperature of 550°C is changed to 350°C to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0102] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0103] Embodiment 15

[0104] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that the muffle furnace calcination temperature is changed from 550°C to 650°C to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0105] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this example.

[0106] Example 16

[0107] A method for preparing a phosphate catalyst for preparing sandalwood 803 is the same as that in Example 1, and a Ce-Zr(HPO4)2 phosphate catalyst is obtained.

[0108] A continuous production process for preparing sandalwood 803 is mostly the same as Example 1, except that the reaction temperature is changed from 380°C to 300°C.

[0109] Embodiment 17

[0110] A method for preparing a phosphate catalyst for preparing sandalwood 803 is the same as that in Example 1, and a Ce-Zr(HPO4)2 phosphate catalyst is obtained.

[0111] A continuous production process for preparing sandalwood 803 is mostly the same as Example 1, except that the reaction temperature is changed from 380°C to 350°C.

[0112] Embodiment 18

[0113] A method for preparing a phosphate catalyst for preparing sandalwood 803 is the same as that in Example 1, and a Ce-Zr(HPO4)2 phosphate catalyst is obtained.

[0114] A continuous production process for preparing sandalwood 803 is mostly the same as Example 1, except that the reaction temperature of 380°C is changed to 400°C.

[0115] Embodiment 19

[0116] A method for preparing a phosphate catalyst for preparing sandalwood 803 is the same as that in Example 1, and a Ce-Zr(HPO4)2 phosphate catalyst is obtained.

[0117] A continuous production process for preparing sandalwood 803 is mostly the same as Example 1, except that the pressure in the fixed bed reactor is changed from 2 MPa to 1 MPa.

[0118] Embodiment 20

[0119] A method for preparing a phosphate catalyst for preparing sandalwood 803 is the same as that in Example 1, and a Ce-Zr(HPO4)2 phosphate catalyst is obtained.

[0120] A continuous production process for preparing sandalwood 803 is mostly the same as Example 1, except that the pressure in the fixed bed reactor is changed from 2 MPa to 3 MPa.

[0121] Embodiment 21

[0122] A method for preparing a phosphate catalyst for preparing sandalwood 803 is the same as that in Example 1, and a Ce-Zr(HPO4)2 phosphate catalyst is obtained.

[0123] A continuous production process for preparing sandalwood 803 is mostly the same as Example 1, except that the ratio of camphene to phenol is changed from 1:4 to 1:1.

[0124] Embodiment 22

[0125] A method for preparing a phosphate catalyst for preparing sandalwood 803 is the same as that in Example 1, and a Ce-Zr(HPO4)2 phosphate catalyst is obtained.

[0126] A continuous production process for preparing sandalwood 803 is mostly the same as Example 1, except that the ratio of camphene to phenol is changed from 1:4 to 1:2.

[0127] Embodiment 23

[0128] A method for preparing a phosphate catalyst for preparing sandalwood 803 is the same as that in Example 1, and a Ce-Zr(HPO4)2 phosphate catalyst is obtained.

[0129] A continuous production process for preparing sandalwood 803 is mostly the same as Example 1, except that the ratio of camphene to phenol is changed from 1:4 to 1:3.

[0130] Embodiment 24

[0131] A method for preparing a phosphate catalyst for preparing sandalwood 803 is the same as that in Example 1, and a Ce-Zr(HPO4)2 phosphate catalyst is obtained.

[0132] A continuous production process for preparing sandalwood 803, which is mostly the same as Example 1, except that the mass space velocity is 1h -1 Change to 2h -1 .

[0133] Embodiment 25

[0134] A method for preparing a phosphate catalyst for preparing sandalwood 803 is the same as that in Example 1, and a Ce-Zr(HPO4)2 phosphate catalyst is obtained.

[0135] A continuous production process for preparing sandalwood 803, which is mostly the same as Example 1, except that the mass space velocity is 1h -1 Change to 3h -1 .

[0136] Embodiment 26

[0137] A method for preparing a phosphate catalyst for preparing sandalwood 803 is the same as that in Example 1, and a Ce-Zr(HPO4)2 phosphate catalyst is obtained.

[0138] A continuous production process for preparing sandalwood 803 is substantially the same as Example 1, except that the gas phase alkylation reaction time is changed from 48 h to 300 h.

[0139] Comparative Example 1

[0140] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that the molar ratio of Zr(NO3)4·5H2O and Ce(NO3)3·6H2O is changed from 4:1 to 10:1 to obtain a Ce-Zr(HPO4)2 phosphate catalyst.

[0141] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Ce-Zr(HPO4)2 phosphate catalyst prepared in this comparative example.

[0142] Comparative Example 2

[0143] A preparation method for a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that Zr(NO3)4·5H2O and Ce(NO3)3·6H2O are both replaced by Al(NO3)3·9H2O, that is, the amount of H3PO4 added is 1.2 times the theoretical amount, to obtain an AlPO4 phosphate catalyst.

[0144] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the AlPO4 phosphate catalyst prepared in this comparative example.

[0145] Comparative Example 3

[0146] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that Zr(NO3)4·5H2O and Ce(NO3)3·6H2O are both replaced by Zr(NO3)4·6H2O, that is, the amount of H3PO4 added is 1.2 times the theoretical amount, to obtain a Zr(HPO4)2 phosphate catalyst.

[0147] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Zr(HPO4)2 phosphate catalyst prepared in this comparative example.

[0148] Comparative Example 4

[0149] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that Zr(NO3)4·5H2O and Ce(NO3)3·6H2O are both replaced by Zn(NO3)2·6H2O, that is, the amount of H3PO4 added is 1.2 times the theoretical amount, and a Zn3(PO4)2 phosphate catalyst is obtained.

[0150] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Zn3(PO4)2 phosphate catalyst prepared in this comparative example.

[0151] Comparative Example 5

[0152] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that Zr(NO3)4·5H2O and Ce(NO3)3·6H2O are both replaced by La(NO3)3·6H2O, that is, the amount of H3PO4 added is 1.2 times the theoretical amount, to obtain a LaPO4 phosphate catalyst.

[0153] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the LaPO4 phosphate catalyst prepared in this comparative example.

[0154] Comparative Example 6

[0155] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that Zr(NO3)4·5H2O and Ce(NO3)3·6H2O are both replaced by Mg(NO3)2·6H2O, that is, the amount of H3PO4 added is 1.2 times the theoretical amount, and a Mg3(PO4)2 phosphate catalyst is obtained.

[0156] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Mg3(PO4)2 phosphate catalyst prepared in this comparative example.

[0157] Comparative Example 7

[0158] A method for preparing a phosphate catalyst for preparing sandalwood 803 is mostly the same as Example 1, except that Zr(NO3)4·5H2O and Ce(NO3)3·6H2O are both replaced by Ce(NO3)3·6H2O, that is, the amount of H3PO4 added is 1.2 times the theoretical amount, to obtain a CePO4 phosphate catalyst.

[0159] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the CePO4 phosphate catalyst prepared in this comparative example.

[0160] Comparative Example 8

[0161] A method for preparing a phosphate catalyst for preparing sandalwood 803, which is mostly the same as Example 1, except that Ce(NO3)3·6H2O is replaced by Al(NO3)3·9H2O, and the amount of H3PO4 added is 1.2 times the theoretical amount, to obtain Al-Zr(HPO4)2 phosphate catalyst

[0162] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Al-Zr(HPO4)2 phosphate catalyst prepared in this comparative example.

[0163] Comparative Example 9

[0164] A method for preparing a phosphate catalyst for preparing sandalwood 803, which is mostly the same as Example 1, except that Ce(NO3)3·6H2O is replaced by Zn(NO3)2·6H2O, and the amount of H3PO4 added is 1.2 times the theoretical amount, to obtain a Zn-Zr(HPO4)2 phosphate catalyst

[0165] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Zn-Zr(HPO4)2 phosphate catalyst prepared in this comparative example.

[0166] Comparative Example 10

[0167] A method for preparing a phosphate catalyst for preparing sandalwood 803, which is mostly the same as Example 1, except that Ce(NO3)3·6H2O is replaced by Mg(NO3)2·6H2O, that is, the amount of H3PO4 added is 1.2 times the theoretical amount, to obtain a Mg-Zr(HPO4)2 phosphate catalyst

[0168] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the Mg-Zr(HPO4)2 phosphate catalyst prepared in this comparative example.

[0169] Comparative Example 11

[0170] A method for preparing a phosphate catalyst for preparing sandalwood 803, which is mostly the same as Example 1, except that Ce(NO3)3·6H2O is replaced by La(NO3)3·6H2O, that is, the amount of H3PO4 added is 1.2 times the theoretical amount, to obtain La-Zr(HPO4)2 phosphate catalyst

[0171] A continuous production process for preparing sandalwood 803 is the same as Example 1, except that the Ce-Zr(HPO4)2 phosphate catalyst is replaced by the La-Zr(HPO4)2 phosphate catalyst prepared in this comparative example.

[0172] The product results obtained by the gas phase alkylation reaction of Examples 1 to 26 and Comparative Examples 1 to 11 were averaged, and the content, conversion rate and selectivity of each component are shown in Table 3 below:

[0173] Table 3 Contents, conversion rates and selectivities of various components in gas phase alkylation reactions of Examples 1 to 26 and Comparative Examples 1 to 11

[0174]

[0175]

[0176] The camphene conversion rate, CO alkylation selectivity, CC alkylation selectivity and selectivity of meta-terpene phenol in the fixed-bed gas phase alkylation of phenol camphene carried out by embodiments 1 to 26 and comparative examples 1 to 11 are as shown in Table 1. The camphene conversion rate, CC alkylation selectivity and selectivity of meta-terpene phenol obtained under the prepared Ce-Zr(HPO4)2 phosphate catalyst and fixed-bed reaction conditions of embodiments 1 to 26 are better than comparative examples 1 to 11, wherein the camphene conversion rate, CC alkylation selectivity and selectivity of meta-terpene phenol obtained under the prepared Ce-Zr(HPO4)2 phosphate catalyst and fixed-bed reaction conditions of embodiment 1 are the highest, and the prepared catalyst has good stability. And it can be known from embodiment 26 that the Ce-Zr(HPO4)2 phosphate catalyst after reaction for 300h still remains active, and the camphene conversion rate, CC alkylation selectivity and meta-terpene phenol are not reduced.

[0177] Although the present invention has been described in detail above by means of general description, specific implementation methods and tests, it is obvious to those skilled in the art that some modifications or improvements may be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a phosphate catalyst for preparing sandalwood 803, characterized in that: The following steps are involved: Add Zr(NO3)4·5H2O and Ce(NO3)3·6H2O into water and dissolve them to prepare a Zr-Ce nitrate mixed solution; Add phosphoric acid and / or its acid salt into water and dissolve them to obtain a phosphoric acid and / or its acid salt solution; The phosphoric acid and / or its acid salt solution is added to the Zr-Ce nitrate mixed solution, the pH is adjusted, the mixture is stirred and then allowed to stand for precipitation, filtered, washed, dried, and calcined to obtain a phosphate catalyst, and the reaction is completed.

2. The method for preparing a phosphate catalyst for preparing sandalwood 803 according to claim 1, characterized in that: The molar ratio of Zr(NO3)4·5H2O and Ce(NO3)3·6H2O is 0.1-8:1; The concentration of Zr(NO3)4·5H2O in the Zr-Ce nitrate mixed solution is 0.01-1 mol / L.

3. The method for preparing a phosphate catalyst for preparing sandalwood 803 according to claim 1, characterized in that: The phosphoric acid and / or its acid salts include one or more of H3PO4, NH4H2PO4, (NH4)2HPO4; The concentration of the phosphoric acid and / or its acid salt solution is 0.01-1 mol / L.

4. The method for preparing a phosphate catalyst for preparing sandalwood 803 according to claim 1, characterized in that: The actual amount of phosphoric acid and / or its acid salt added is 0.75 to 1.25 times the molar amount of phosphoric acid and / or its acid salt required for the complete formation of precipitation of Zr(NO3)4·5H2O and Ce(NO3)3·6H2O.

5. The method for preparing a phosphate catalyst for preparing sandalwood 803 according to claim 1, characterized in that: During the pH adjustment process, ammonia water was used to adjust the pH to 6-8; The calcination temperature is 350-650°C.

6. A phosphate catalyst for the preparation of sandalwood 803, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 5.

7. The use of a phosphate catalyst for preparing sandalwood 803 as claimed in claim 6, characterized in that: The phosphate catalyst is used to prepare sandalwood 803.

8. A continuous production process for preparing sandalwood 803, characterized in that: The phosphate catalyst according to claim 6 is used for production, and the continuous production process comprises the following steps: The phosphate catalyst is fixed and formed into a fixed bed reactor, and the phosphate catalyst is preheated; Passing phenol and camphene into the fixed bed reactor to carry out gas phase reaction, and obtaining a crude terpene phenol product after cooling; The crude terpene phenol product is distilled and separated to obtain a terpene phenol concentrate, which is placed in a high-pressure reactor, and Raney nickel is used as a hydrogenation catalyst. Hydrogen is introduced to carry out a hydrogenation reaction to obtain sandalwood 803.

9. A continuous production process for preparing sandalwood 803 according to claim 8, characterized in that: Preheating the phosphate catalyst using a reaction gas at 300-400° C.; The loading amount of the phosphate catalyst is 50% to 80% of the volume of the constant temperature section of the fixed bed reactor; Before the phenol and camphene are introduced into the fixed bed reactor, the pressure in the fixed bed reactor is 1-4 MPa; The molar ratio of phenol to camphene is 1 to 4:1, and the mass space velocity is adjusted to 1 to 5 h -1 ; Adjust the reaction temperature to 300-400°C.

10. The continuous production process for preparing sandalwood 803 according to claim 8, characterized in that: The mass of the Raney nickel is 1wt% to 6wt% of the terpene phenol concentrate; The pressure of the hydrogenation reaction is 3-6 MPa and the temperature is 120-200°C.

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