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CN109174084B - A catalytic hydrogenation catalyst and its preparation and application in the selective hydrogenation of tetrahydrofarnesyl acetone - Google Patents

A catalytic hydrogenation catalyst and its preparation and application in the selective hydrogenation of tetrahydrofarnesyl acetone Download PDF

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CN109174084B
CN109174084B CN201810976629.8A CN201810976629A CN109174084B CN 109174084 B CN109174084 B CN 109174084B CN 201810976629 A CN201810976629 A CN 201810976629A CN 109174084 B CN109174084 B CN 109174084B
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catalytic hydrogenation
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CN109174084A (en
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卢春山
王昊
朱倩文
周烨彬
张雪洁
季豪克
张群峰
赵佳
丰枫
马磊
许孝良
李小年
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Zhejiang University of Technology ZJUT
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Abstract

本发明公开了一种催化加氢催化剂及其制备和在四氢法呢基丙酮选择性加氢反应中的应用。所述催化剂由涂覆有改性涂层的活性炭载体及负载在所述载体上的金属量子点组成；所述金属为钯，金属量子点的粒径范围在3～6nm之间；所述活性炭为无规则或成型的颗粒活性炭，尺寸不大于1cm；所述的涂覆有改性涂层的活性炭的孔结构以中孔为主，微孔比例下降至10％以下且所述改性涂层的组成物质为二氧化钛、二氧化硅和硅酸钛。本发明公开了所述的催化加氢催化剂在四氢法呢基丙酮选择性催化加氢合成六氢法呢基丙酮的反应中的应用，具有无需添加剂、转化率高、选择性好、加氢反应速率快、稳定性好、催化剂寿命长用且氢气可循环使用的特点。The invention discloses a catalytic hydrogenation catalyst and its preparation and application in the selective hydrogenation reaction of tetrahydrofarnesylacetone. The catalyst is composed of an activated carbon carrier coated with a modified coating and metal quantum dots supported on the carrier; the metal is palladium, and the particle size of the metal quantum dots ranges from 3 to 6 nm; the activated carbon It is a random or shaped granular activated carbon with a size of not more than 1 cm; the pore structure of the activated carbon coated with the modified coating is mainly mesopores, the proportion of micropores is reduced to below 10%, and the modified coating is The constituent substances are titanium dioxide, silicon dioxide and titanium silicate. The invention discloses the application of the catalytic hydrogenation catalyst in the selective catalytic hydrogenation of tetrahydrofarnesyl acetone to synthesize hexahydrofarnesyl acetone, and has the advantages of no additive, high conversion rate, good selectivity, and hydrogenation The reaction rate is fast, the stability is good, the catalyst life is long, and the hydrogen can be recycled.

Description

Catalytic hydrogenation catalyst, preparation thereof and application thereof in selective hydrogenation reaction of tetrahydrofarnesyl acetone
(I) technical field
The invention relates to a fixed bed catalytic hydrogenation catalyst, and preparation and application thereof, in particular to application of the catalyst in a fixed bed catalytic selective hydrogenation reaction of tetrahydrofarnesyl acetone.
(II) technical background
6,10, 14-trimethyl-2-pentadecanone (hexahydrofarnesyl acetone, PA) is an important chemical intermediate for preparing vitamin E, and the VE demand is greatly increased along with the enhancement of the demand of people on health. Currently, PA is prepared industrially mainly from 6, 7-dihydrolinalool or 1, 2-dehydrolinalool. However, in these existing PA synthesis routes, the PA is finally obtained by catalytic hydrogenation of 6,10, 14-trimethyl-13-ene-2-pentadecanone (tetrahydrofarnesylacetone, FA-4H), so that the production of tetrahydrofarnesylacetone is increased year by year. Therefore, the development of a green catalytic hydrogenation process aiming at the industrial production requirement is of great significance.
Tetrahydrofarnesylacetone is a class of unsaturated ketone compounds containing a C ═ C bond in which the carbon-carbon double bond has a lower activation energy than the carbonyl group, and therefore the former is more susceptible to hydrogenation than the latter. However, when C ═ C or C ═ O is present in the compound at the same time, the hydrogenation is different from the individual C ═ C or C ═ O hydrogenation reaction, so it is still very difficult to achieve PA selectivity of 100% (carbonyl-free hydrogenation), and it is important to control the selectivity of the reaction.
The properties of the catalyst metal and the choice of the support are of particular importance for this reaction. Firstly, the nature of the metal has great influence on the catalytic hydrogenation performance, the larger the d orbital bandwidth of the metal selected by the catalyst is, the stronger the repulsion action with four electrons of C ═ C bonds is, and the adsorption of the C ═ O bonds to form unsaturated alcohols is easy to occur. Furthermore, the carbon chain of the tetrahydrofarnesyl acetone molecule is longer, the long carbon chain cannot be adsorbed on a flat metal surface in parallel due to steric hindrance, a certain distance is kept, and in addition, the number of branched chains connected with vinyl is more than that of branched chains connected with carbonyl, so that the steric hindrance effect is obvious, the absorption of C-C bonds is not facilitated, and the carbonyl is more prone to adsorption hydrogenation reaction. When the metal particles are small, the influence of the stereoscopic effect is not obvious, the C-C, C-O bond can contact the metal surface, and the C-C bond is mainly hydrogenated; when the metal particles are large, C ═ O is more easily contacted with the metal surface than C ═ C due to the existence of steric hindrance, and the adsorption of C ═ O bonds is facilitated.
The larger the carrier particle size, the longer the pore channel is, the longer the time is spent for the PA generated by the reaction on the inner hole to diffuse out of the catalyst particles through the pore channel, and the product is not easy to desorb from the carrier surface to cause carbonyl hydrogenation. In addition, the catalyst with small particle size is easier to be uniformly dispersed in the reaction liquid, and the effective contact of reactants and the catalyst is increased, so that the reaction rate is accelerated.
The specific surface area of the carrier is an important parameter for measuring the activity of the reaction catalyst, and the carrier with high specific surface area is also favorable for dispersing active components on the surface of the carrier. However, the activity of the catalyst is also affected by the pore size. The carrier has smaller pore diameter, and the small pore diameter ensures that large reactant molecules are difficult to enter pores, namely, the steric hindrance effect (or the shape-selective and domain-limited effect of pore channels) can only generate catalytic reaction on the surface of the catalyst, and the inside is not fully utilized, namely, the effective active sites are reduced, thus leading to low activity.
Therefore, the fixed bed catalytic hydrogenation catalyst is prepared by a photo-deposition method to prepare the Pd/C catalyst with small and controllable metal particle size in one step, the preparation method is simple and convenient to operate, and the catalyst is easy to recover; the catalyst is applied to the reaction of preparing hexahydrofarnesyl acetone by catalytic hydrogenation under the fixed bed condition, does not need to add an auxiliary agent, has good catalytic performance, high selectivity and long service life, and hydrogen in the catalytic reaction can be recycled.
Disclosure of the invention
The invention aims to provide a catalytic hydrogenation catalyst, which is particularly suitable for the reaction of synthesizing hexahydrofarnesyl acetone by selective hydrogenation of tetrahydrofarnesyl acetone.
The invention also aims to provide a method for preparing the catalytic hydrogenation catalyst, which is simple to operate, can realize the one-step in-situ generation and growth of metal points on the surface of a carbon sphere, and has the advantages of precise and controllable particle size distribution range of the metal points.
The invention further aims to provide the application of the catalytic hydrogenation catalyst in the catalytic hydrogenation reaction of the tetrahydrofarnesyl acetone, and the catalyst has the characteristics of no need of additives, high conversion rate, good selectivity, high hydrogenation reaction rate, good stability, long service life of the catalyst and recycling of hydrogen.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a catalytic hydrogenation catalyst, which consists of an activated carbon carrier coated with a modified coating and metal quantum dots loaded on the carrier; the metal is palladium, and the particle size range of the metal quantum dots is 3-6 nm; the activated carbon is irregular or formed granular activated carbon, and the size of the activated carbon is not more than 1 cm; the pore structure of the active carbon coated with the modified coating is mainly mesopores, the proportion of micropores is reduced to below 10%, and the components of the modified coating are titanium dioxide, silicon dioxide and titanium silicate; in the catalyst, the mass fraction of the metal quantum dots is 1-2%, the total mass of the modified coating composition substances is not more than 15% of the mass of the active carbon, wherein the mass of the titanium silicate is not more than 1.5% of the mass of the active carbon, and the mass ratio of the silicon dioxide to the titanium dioxide is not less than 20.
Furthermore, in the catalyst, the mass fraction of the metal quantum dots is 1.5-2%.
Further, the total mass of the modified coating composition substances is 1-15% of the mass of the activated carbon.
Further, the quality of the titanium silicate is not higher than 0.5 percent of the quality of the active carbon.
Further, the mass ratio of the silicon dioxide to the titanium dioxide is 30-50.
In another aspect, the present invention provides a preparation method of the catalytic hydrogenation catalyst, including:
1) putting activated carbon, methyl orthosilicate and tetrabutyl titanate in a distillation device, adding a tetramethylammonium hydroxide aqueous solution, distilling alcohol generated by hydrolysis at 90-100 ℃, then putting the obtained activated carbon particles in a closed container, heating at 150-200 ℃ for 5-24 h, cooling to room temperature, and taking out the activated carbon to obtain the activated carbon coated with the modified coating; the mass ratio of the activated carbon to the total mass of the methyl orthosilicate and the tetrabutyl titanate is 20: 0.2-3.0, and the mass ratio of the methyl orthosilicate to the tetrabutyl titanate is 20-30: 1, the mass of the tetramethylammonium hydroxide is not more than 10 percent of the total mass of the methyl orthosilicate and the tetrabutyl titanate;
2) preparing the activated carbon coated with the modified coating obtained in the step 1), deionized water and methanol into mixed slurry, stirring for 10-20 min, adding a palladium salt aqueous solution into the prepared mixed slurry, placing the mixed slurry under an ultraviolet lamp, performing illumination stirring for 10-25 min under the conditions that the power is 250-300 w and the wavelength is 350-400 nm, then taking out the mixed slurry, and washing and drying to obtain the catalytic hydrogenation catalyst.
In step 1) of the present invention, the mass of the tetramethylammonium hydroxide is preferably 1 to 10% of the total mass of the methyl orthosilicate and the tetrabutyl titanate. The mass concentration of the tetramethylammonium hydroxide aqueous solution is preferably 15-25%.
The size of the metal point is controlled by controlling the ultraviolet irradiation condition in the step 2). The feeding mass ratio of the activated carbon coated with the modified coating to the deionized water is 1g: 10-25 ml, preferably 1g: 15 ml; the volume ratio of the methanol to the deionized water is 1: 2-8, and preferably 1: 5. The palladium salt may be a combination of one or more of the following: palladium nitrate, chloropalladic acid, ethylenediamine palladium chloride, ammonium tetrachloropalladate, sodium chloropalladate, tetraamminepalladium nitrate and tetraamminepalladium bicarbonate. The mass concentration of palladium in the palladium salt aqueous solution is preferably 0.001-0.05 g/mL, and the feeding ratio of the activated carbon coated with the modified coating to the palladium salt aqueous solution is preferably 1g: 4-20 mL. The drying conditions are preferably: and drying the water-washed sample at 40-80 ℃ for 12-48 hours.
In a third aspect, the invention provides an application of the catalytic hydrogenation catalyst in a reaction for synthesizing hexahydrofarnesyl acetone shown in a formula II by selective catalytic hydrogenation of tetrahydrofarnesyl acetone shown in a formula I;
the application method of the catalyst comprises the following steps:
loading a catalytic hydrogenation catalyst into the tubular reactor, the catalyst having a size less than 1/10 of the inside diameter of the tubular reactor; replacing air in the reaction tube with nitrogen, and replacing the nitrogen with hydrogen to ensure that the pressure of the hydrogen in the reaction tube is 0.5-1.5 MPa and the temperature is 25-150 ℃; dissolving tetrahydrofarnesyl acetone shown as formula I in an alcohol solvent (preferably methanol or ethanol) to obtain a reaction solution, pumping the reaction solution into a mixing tube in front of a reaction tube by a high-pressure liquid pump, mixing the reaction solution with hydrogen gas, then putting the mixture into the reaction tube filled with a catalyst, turning on a light source to irradiate for starting reaction, wherein the irradiation wavelength range of the light source is 280-350 nm, the power is 200-250W, and the radiation intensity is 3660-3980 muW/cm2After the reaction is finished, the unreacted hydrogen is recycled through a gas-liquid separation device, and the liquid product is separated and then treated to obtain hexahydrofarnesyl acetone shown in a formula II;
Figure BDA0001777597330000031
further, in the application, the ratio of the tetrahydrofarnesylacetone shown in the formula I to the alcohol solvent is not higher than 7g/10ml, the volume ratio of the reaction liquid to hydrogen (in a standard state) during gas-liquid mixing is not higher than 2:1, and the liquid space velocity is20～100min-1。
Further, the method for separating and post-treating the hydrogenation liquid comprises the following steps: the hydrogenation liquid is rectified under reduced pressure to obtain the product.
Compared with the prior art, the invention has the beneficial effects that:
1) the active carbon is used as a carrier of the catalyst, so that a larger specific surface area is provided, and meanwhile, the metal salt solution and the active carbon enable metal to be better dispersed on the carrier under the irradiation of ultraviolet light, so that the metal is not easy to agglomerate, and the metal utilization rate is improved; the electronic characteristics of metal points can be modified and the electronic characteristics of a carrier adsorbing active centers can be improved by coating a small amount of silicon dioxide, titanium silicate and titanium dioxide on the surface of the active carbon, and the existence of the modified coating enables the aperture to be in a mesopore range, so that the steric hindrance effect is effectively avoided, the surface and the interior of the catalyst can simultaneously generate catalytic reaction, and the activity is improved.
2) The method adopts the photo-deposition method to prepare the metal particle size controllable Pd/C catalyst in one step, and the preparation method is simple and convenient to operate;
3) the invention adopts metal Pd as an active component, the d-orbital bandwidth of the Pd is smaller, the rejection effect of the Pd and four electrons of a C-C bond is weak, the addition of carbon-carbon double bonds is facilitated, the influence of the stereoscopic effect of the Pd with small particle size is not obvious, the C-C, C-O bond can be in parallel contact with the metal surface, and the bond energy of the carbon-carbon double bond is lower than that of a carbonyl bond, so that the C-C bond is mainly hydrogenated, and the reaction selectivity of synthesizing hexahydrofarnesyl acetone by selective catalytic hydrogenation of the tetrahydrofarnesyl acetone is further improved. The catalyst is particularly suitable for the reaction of preparing hexahydrofarnesyl acetone by catalytic hydrogenation under the fixed bed condition.
(IV) description of the drawings
FIG. 1 is a transmission electron micrograph of the first example, wherein the black particles are Pd metal dots.
(V) detailed description of the preferred embodiments
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1
1.5g of water-soluble methyl orthosilicate and 0.05g of n-butyl titanate are weighed and added into a distillation flask, 20g of activated carbon is added after full stirring, then 20% of tetramethylammonium hydroxide aqueous solution (containing 0.075g of tetramethylammonium hydroxide) with the mass concentration of 20% is dripped, distillation is carried out at 95 ℃ to separate hydrolysis products, and then the solid matters in the flask are heated at 180 ℃ for 12 hours.
Taking 1g of the activated carbon prepared by the method (the detected mesopore proportion is 70 percent, the detected micropore proportion is 30 percent, and the size is not more than 1cm), 15mL of deionized water and 3mL of methanol to prepare mixed slurry, stirring for 15min, taking 10mL of chloropalladate solution with the palladium concentration of 0.002g/mL, dripping the chloropalladate solution into the mixed solution, placing the mixed solution under an ultraviolet lamp for illumination stirring at the power of 275w and 386nm for 20min, then taking out the mixed slurry, washing the mixed slurry to be neutral by water, and placing the mixed slurry into an oven to dry for 24 hours at the temperature of 60 ℃. Detected SiO27.5% of TiO20.15 percent of the titanium silicate, 0.1 percent of the titanium silicate, 97.5 percent of the mesopore, 2.5 percent of the micropore, 2 percent of the metal load and 4-5 nm of the metal particle size.
Examples two to thirteen are catalysts prepared according to the procedure of example one, with specific parameters as shown in table 1.
Comparative example 1
Weighing 1g of untreated activated carbon (the detected mesopore proportion is 70 percent, the detected micropore proportion is 30 percent, and the size is not more than 1cm), 15mL of deionized water and 3mL of methanol to prepare mixed slurry, stirring for 15min, dripping 10mL of palladium chloride solution with the palladium concentration of 0.002g/mL into the mixed solution, placing the mixed solution under an ultraviolet lamp for illumination and stirring for 20min under the power of 275w and 386nm, then taking out the mixed slurry, washing the mixed slurry to be neutral, and then placing the mixed slurry into an oven to dry for 24 hours at the temperature of 60 ℃. According to detection, the mesopore proportion is 70%, the micropore proportion is 30%, the metal loading is 2%, and the metal particle size is 4-5 nm.
Comparative example 2
1.5g of water-soluble methyl orthosilicate and 0.05g of n-butyl titanate are weighed and added into a distillation flask, 20g of activated carbon is added after full stirring, solid substances in the flask are taken out after 3 hours of impregnation, and the mixture is heated at 180 ℃ for 12 hours. Detected SiO20.5% of TiO20.01 percent, 0.0 percent of titanium silicate, 70.5 percent of mesopore and 29.5 percent of micropore.
Taking 1g of the activated carbon prepared by the method (the detected mesopore proportion is 70 percent, the detected micropore proportion is 30 percent, and the size is not more than 1cm), 15mL of deionized water and 3mL of methanol to prepare mixed slurry, stirring for 15min, taking 10mL of chloropalladate solution with the palladium concentration of 0.002g/mL, dripping the chloropalladate solution into the mixed solution, placing the mixed solution under an ultraviolet lamp for illumination stirring at the power of 275w and 386nm for 20min, then taking out the mixed slurry, washing the mixed slurry to be neutral by water, and placing the mixed slurry into an oven to dry for 24 hours at the temperature of 60 ℃. The metal loading is 2%, and the metal particle size is 4-5 nm.
Comparative example 3
1.5g of water-soluble methyl orthosilicate and 0.05g of n-butyl titanate were weighed out and charged into a distillation flask, then a 20% by mass aqueous tetramethylammonium hydroxide solution (containing 0.075g of tetramethylammonium hydroxide) was added dropwise thereto, and distillation was carried out at 95 ℃ to separate a hydrolyzate, and then the solid matter in the flask was heated at 180 ℃ for 12 hours.
Taking 1g of the silicon dioxide and titanium dioxide solid prepared by the method, 15mL of deionized water and 3mL of methanol to prepare mixed slurry, stirring for 15min, taking 10mL of chloropalladate solution with palladium concentration of 0.002g/mL, dripping the chloropalladate solution into the mixed solution, placing the mixed solution under an ultraviolet lamp for illumination and stirring for 20min under the power of 275w and 386nm, taking out the mixed slurry, washing the mixed slurry to be neutral by water, and placing the mixed slurry into an oven to dry for 24 hours at the temperature of 60 ℃. The metal loading is 2%, and the metal particle size is 4-5 nm.
Example 14
The catalyst of example 1 was charged into a tubular reactor having an inner diameter of 20cm, and air was replaced with nitrogen, and then nitrogen was replaced with hydrogen. Dissolving tetrahydrofarnesyl acetone into a methanol solvent according to the total volume of the tetrahydrofarnesyl acetone and the methanol and the volume ratio of hydrogen of 1:1 and the ratio of the tetrahydrofarnesyl acetone to the methanol of 2g:5ml, pumping the mixture into a mixing tube in front of a reaction tube by a high-pressure liquid pump, mixing the mixture with hydrogen in a gas-liquid manner, then feeding the mixture into a tubular reactor filled with a catalyst, setting the hydrogen pressure of 1MPa, the temperature of 50 ℃ and the liquid airspeed of 50min-1Turning on the illumination device, setting the illumination power at 325nm, the power at 225W, and the radiation intensity at 3820 μ W/cm2Starting reaction, passing through a gas-liquid separation device after the one-way reaction is finished, recycling unreacted hydrogen, and separating and post-treating a liquid product to obtain a product hexahydroFarnesyl acetone. The analysis result is as follows: the reaction conversion rate is 100 percent, and the selectivity is 98.99 percent.
Examples 15 to 27
Examples 15 to 27 were carried out according to the fixed bed catalytic evaluation procedure of example 14, using the fixed bed catalytic hydrogenation catalysts prepared in examples 1 to 13 and comparative examples 1 to 2, and the specific parameters are shown in table 2.
Comparative examples 4 to 15
Comparative examples 4 to 15 are the results of the application of the reaction conditions of examples 14 to 25 to the hydrogenation reaction catalyzed by tetrahydrofarnesylacetone under the non-light condition, and are shown in Table 3 below.
Example 28
In example 28, the catalyst prepared in example 1 was continuously reacted under the evaluation conditions of example 14, and the life of the catalyst was examined, as shown in table 4 below.
Figure BDA0001777597330000071
Figure BDA0001777597330000081
TABLE 3 comparative examples four to fifteen Single pass conversion and Selectivity without light
Examples Conversion rate% Selectivity%
Comparative example 4 96.7 92.29
Comparative example 5 97.4 92.36
Comparative example 6 96.6 89.98
Comparative example 7 97.2 92.25
Comparative example 8 96.4 89.34
Comparative example 9 95.1 91.58
Comparative example 10 96.2 91.85
Comparative example 11 97.2 92.47
Comparative example 12 96.8 91.15
Comparative example 13 96.5 92.47
Comparative example 14 97.4 93.13
Comparative example 15 96.4 90.97
Table 4 example 28 conversion and selectivity of catalyst for continuous reaction
Time/h Conversion rate/% Selectivity/%)
10 100 99.37
50 100 99.36
100 100 99.48
120 100 99.55
150 100 99.39
180 100 99.58
200 100 98.88
220 100 99.77
240 100 99.65
280 100 99.57
300 100 99.33
350 100 98.99

Claims (11)

1.一种催化加氢催化剂在式I所示的四氢法呢基丙酮选择性催化加氢合成式II所示的六氢法呢基丙酮的反应中的应用，所述催化加氢催化剂由涂覆有改性涂层的活性炭载体及负载在所述载体上的金属量子点组成；所述金属为钯，金属量子点的粒径范围在3~6 nm之间；所述活性炭为无规则或成型的颗粒活性炭，尺寸不大于1cm；所述的涂覆有改性涂层的活性炭的孔结构以中孔为主，微孔比例下降至10%以下且所述改性涂层的组成物质为二氧化钛、二氧化硅和硅酸钛；所述催化剂中，金属量子点的质量分数为1~2%，改性涂层组成物质的总质量不超过活性炭质量的15%，其中硅酸钛的质量不高于活性炭质量的1.5%，二氧化硅与二氧化钛的质量比不小于20；1. the application of a catalytic hydrogenation catalyst in the reaction of the tetrahydrofarnesyl acetone shown in the formula I selective catalytic hydrogenation to synthesize the hexahydrofarnesyl acetone shown in the formula II, the catalytic hydrogenation catalyst is composed of The activated carbon carrier coated with the modified coating and the metal quantum dots supported on the carrier are composed; the metal is palladium, and the particle size of the metal quantum dots is between 3 and 6 nm; the activated carbon is random Or shaped granular activated carbon, the size is not more than 1cm; the pore structure of the activated carbon coated with the modified coating is dominated by mesopores, the proportion of micropores is reduced to less than 10%, and the composition of the modified coating is It is titanium dioxide, silicon dioxide and titanium silicate; in the catalyst, the mass fraction of metal quantum dots is 1~2%, and the total mass of the modified coating composition material does not exceed 15% of the mass of activated carbon, of which the mass fraction of titanium silicate is 1~2%. The mass is not higher than 1.5% of the mass of activated carbon, and the mass ratio of silicon dioxide to titanium dioxide is not less than 20;
Figure DEST_PATH_IMAGE001
。
Figure DEST_PATH_IMAGE001
. 2.如权利要求1所述的应用，其特征在于：所述催化剂中，金属量子点的质量分数为1.5~2%。2. The application according to claim 1, characterized in that: in the catalyst, the mass fraction of metal quantum dots is 1.5-2%. 3.如权利要求1或2所述的应用，其特征在于：所述改性涂层组成物质的总质量为活性炭质量的1~15%，硅酸钛质量不高于活性炭质量的0.5%，二氧化硅与二氧化钛的质量比在30~50之间。3. The application according to claim 1 or 2, characterized in that: the total mass of the modified coating constituent substances is 1～15% of the activated carbon mass, and the titanium silicate mass is not higher than 0.5% of the activated carbon mass, The mass ratio of silicon dioxide to titanium dioxide is between 30 and 50. 4.如权利要求1所述的应用，其特征在于：所述催化加氢催化剂的制备方法包括：4. application as claimed in claim 1 is characterized in that: the preparation method of described catalytic hydrogenation catalyst comprises: 1）将活性炭、正硅酸甲酯和钛酸四丁酯置于蒸馏装置中，再加入四甲基铵氢氧化物水溶液，在90~100℃下将水解产生的醇蒸馏出，然后将所得活性炭颗粒置于密闭容器内于150~200℃加热5~24h，再降至室温后，取出活性炭，即得涂覆有改性涂层的活性炭；所述活性炭质量与正硅酸甲酯和钛酸四丁酯的总质量之比为20:0.2~3.0，正硅酸甲酯和钛酸四丁酯的质量比为20~30：1，所述四甲基铵氢氧化物的质量不超过正硅酸甲酯和钛酸四丁酯总质量的10%；1) Put activated carbon, methyl orthosilicate and tetrabutyl titanate in a distillation device, then add tetramethylammonium hydroxide aqueous solution, distill out the alcohol produced by hydrolysis at 90~100 °C, and then distill the obtained The activated carbon particles are placed in an airtight container and heated at 150-200 ° C for 5-24 hours, and then cooled to room temperature, and the activated carbon is taken out to obtain the activated carbon coated with the modified coating; the quality of the activated carbon is the same as that of methyl orthosilicate and titanium The total mass ratio of tetrabutyl acid is 20:0.2~3.0, the mass ratio of methyl orthosilicate and tetrabutyl titanate is 20~30:1, and the mass of the tetramethylammonium hydroxide does not exceed 10% of the total mass of methyl orthosilicate and tetrabutyl titanate; 2）将步骤1）得到的涂覆有改性涂层的活性炭与去离子水、甲醇制成混合浆液，搅拌10min~20min，将硝酸钯、或氯钯酸、或乙二胺氯化钯、或四氯钯酸铵、或氯钯酸钠、或硝酸四氨合钯的水溶液加入到配制的混合浆液中，将混合浆液置于紫外灯下在功率250w~300w和波长350~400nm下进行光照搅拌10~25min，随后取出混合浆液，经水洗干燥得到催化加氢催化剂。2) The activated carbon coated with the modified coating obtained in step 1) is made into a mixed slurry with deionized water and methanol, stirred for 10min-20min, and palladium nitrate, or chloropalladic acid, or ethylenediamine palladium chloride, Or the aqueous solution of ammonium tetrachloropalladate, or sodium chloropalladate, or tetraammine palladium nitrate is added to the mixed slurry of preparation, and the mixed slurry is placed under the ultraviolet lamp to illuminate under power 250w～300w and wavelength 350～400nm After stirring for 10-25 min, the mixed slurry was taken out, washed with water and dried to obtain a catalytic hydrogenation catalyst. 5.如权利要求4所述的应用，其特征在于：步骤1）中，所述四甲基铵氢氧化物的质量为正硅酸甲酯和钛酸四丁酯总质量的1~10%，所述四甲基铵氢氧化物水溶液的质量浓度为15~25%。5. application as claimed in claim 4 is characterized in that: in step 1), the quality of described tetramethylammonium hydroxide is 1～10% of the total mass of methyl orthosilicate and tetrabutyl titanate , the mass concentration of the tetramethylammonium hydroxide aqueous solution is 15~25%. 6.如权利要求4所述的应用，其特征在于：步骤2）中，涂覆有改性涂层的活性炭与去离子水的投料比为1g:10~25ml；甲醇和去离子水的体积比为1:2~8。6. The application according to claim 4, characterized in that: in step 2), the feeding ratio of the activated carbon coated with the modified coating and deionized water is 1g:10～25ml; the volume of methanol and deionized water The ratio is 1:2~8. 7.如权利要求4所述的应用，其特征在于：步骤2）中，涂覆有改性涂层的活性炭与去离子水的投料比为1g：15ml；甲醇和去离子水的体积比为1:5。7. The application according to claim 4, characterized in that: in step 2), the feed ratio of the activated carbon coated with the modified coating and deionized water is 1 g: 15ml; the volume ratio of methanol and deionized water is 1:5. 8.如权利要求4所述的应用，其特征在于：步骤2）中，所述的硝酸钯、或氯钯酸、或乙二胺氯化钯、或四氯钯酸铵、或氯钯酸钠、或硝酸四氨合钯的水溶液中钯质量浓度为0.001~0.05g/mL，涂覆有改性涂层的活性炭与硝酸钯、或氯钯酸、或乙二胺氯化钯、或四氯钯酸铵、或氯钯酸钠、或硝酸四氨合钯的水溶液的投料比为1g:4~20ml。8. application as claimed in claim 4 is characterized in that: in step 2), described palladium nitrate, or chloropalladium acid, or ethylenediamine palladium chloride, or ammonium tetrachloropalladate, or chloropalladium acid In the aqueous solution of sodium or tetraammine palladium nitrate, palladium mass concentration is 0.001～0.05g/mL, and the gac and palladium nitrate, or chloropalladium acid, or ethylenediamine palladium chloride, or four The charging ratio of the aqueous solution of ammonium chloropalladate, or sodium chloropalladate, or tetraammine palladium nitrate is 1g:4～20ml. 9.如权利要求4所述的应用，其特征在于：步骤2）中，所述的干燥条件为：将水洗样在40~80℃干燥12~48小时。9 . The application according to claim 4 , wherein in step 2), the drying conditions are: drying the washed sample at 40-80° C. for 12-48 hours. 10 . 10.如权利要求1所述的应用，其特征在于所述催化剂的应用方法为：10. application as claimed in claim 1 is characterized in that the application method of described catalyst is: 将催化加氢催化剂装入到管式反应器中，催化剂尺寸小于管式反应器内径的1/10；用氮气置换反应管中的空气，再用氢气置换氮气，使反应管中氢气压力为0.5~1.5MPa、温度为25~150℃；将式I所示的四氢法呢基丙酮溶解于醇溶剂中得到反应液，由高压液体泵泵入反应管前的混合管，与氢气进行气液混合，然后一起进入装入催化剂的反应管中，打开光源照射开始反应，光源的照射波长范围280 ~ 350nm，功率为200 ~ 250W，辐射强度为3660 ~3980μW/cm2，反应结束后经过气液分离装置，未反应的氢气循环使用，液态产物分离后处理得到式II所示的六氢法呢基丙酮；Put the catalytic hydrogenation catalyst into the tubular reactor, the size of the catalyst is less than 1/10 of the inner diameter of the tubular reactor; replace the air in the reaction tube with nitrogen, and then replace the nitrogen with hydrogen, so that the hydrogen pressure in the reaction tube is 0.5 ~1.5MPa, the temperature is 25 ~ 150 ℃; the tetrahydrofarnesyl acetone shown in formula I is dissolved in the alcohol solvent to obtain the reaction solution, which is pumped into the mixing tube before the reaction tube by the high-pressure liquid pump, and gas-liquid is carried out with hydrogen gas Mix, and then enter the reaction tube loaded with catalyst together, turn on the light source to irradiate to start the reaction, the irradiation wavelength range of the light source is 280 ~ 350nm, the power is 200 ~ 250W, and the radiation intensity is 3660 ~ 3980μW/cm 2 , after the reaction is completed, the gas-liquid Separation device, unreacted hydrogen is recycled, and the liquid product is separated and processed to obtain the hexahydrofarnesyl acetone shown in formula II;
Figure DEST_PATH_IMAGE002
。
Figure DEST_PATH_IMAGE002
. 11.如权利要求10所述的应用，其特征在于：所述应用中，所述式I所示的四氢法呢基丙酮与醇溶剂比例为不高于7g/10ml，气液混合时反应液与标准状态下的氢气的体积比不高于2:1，液体空速为20~100 min-1。11. application as claimed in claim 10, is characterized in that: in described application, the ratio of tetrahydrofarnesyl acetone shown in described formula I and alcohol solvent is not higher than 7g/10ml, reacts during gas-liquid mixing The volume ratio of liquid to hydrogen in standard state is not higher than 2:1, and the liquid space velocity is 20~100 min -1 .
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4240692A1 (en) * 1992-12-03 1994-06-09 Leuna Werke Ag Catalyst comprising titanium silicalite supported on active carbon - and use in oxidn. under mild conditions, obtd. by pptn. of titanium- and silicon di:oxide(s) onto active carbon and impregnating with titanium cpd. etc.
CN104525251A (en) * 2014-12-29 2015-04-22 河北美邦工程科技有限公司 In-situ supported forming preparation method of titanium silicon molecular sieve composite catalyst
CN107335418A (en) * 2017-06-20 2017-11-10 浙江工业大学 Novel hollow TiO2Preparation method of nano cup catalyst and application of nano cup catalyst after metal loading

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4240692A1 (en) * 1992-12-03 1994-06-09 Leuna Werke Ag Catalyst comprising titanium silicalite supported on active carbon - and use in oxidn. under mild conditions, obtd. by pptn. of titanium- and silicon di:oxide(s) onto active carbon and impregnating with titanium cpd. etc.
CN104525251A (en) * 2014-12-29 2015-04-22 河北美邦工程科技有限公司 In-situ supported forming preparation method of titanium silicon molecular sieve composite catalyst
CN107335418A (en) * 2017-06-20 2017-11-10 浙江工业大学 Novel hollow TiO2Preparation method of nano cup catalyst and application of nano cup catalyst after metal loading

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
New Route for the Preparation of Pd and PdAu Nanoparticles Using Photoexcited Ti-Containing Zeolite as an Efficient Support Material and Investigation of Their Catalytic Properties;Kohsuke Mori et al.;《LANGMUIR》;20090715;第25卷(第18期);摘要、第11181页左栏第2段及第2.2部分、图5a *
Parameters affecting the synthesis of titanium silicalite 1;van der Pol et al.;《Applied Catalysis A》;19921231;第92卷(第2期);第95页第1段 *
TS-1 zeolite as an effective diffusion barrier for highly stable Pd membrane supported on macroporous α-Al2O3 tube;Xiaobin Wang et al.;《RSC Advances》;20130201;第3卷(第14期);第4821页第1部分、第4822页第2.2部分 *
负载型金属催化剂的四氢法呢基丙酮选择性加氢性能研究;李杰;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20180615(第6期);第64页第五章5.2部分 *

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