CN110882716A - Preparation method of novel solid acid catalyst for one-pot multi-step catalytic conversion of biomass-derived furfural to γ-valerolactone - Google Patents

Preparation method of novel solid acid catalyst for one-pot multi-step catalytic conversion of biomass-derived furfural to γ-valerolactone Download PDF

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CN110882716A
CN110882716A CN201910982463.5A CN201910982463A CN110882716A CN 110882716 A CN110882716 A CN 110882716A CN 201910982463 A CN201910982463 A CN 201910982463A CN 110882716 A CN110882716 A CN 110882716A
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吕学斌
韩怡雯
柏慧
叶磊
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    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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    • C07D307/30Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

The invention discloses a preparation method for converting biomass derived furfural into gamma-valerolactone by a novel solid acid catalyst through one-pot multi-step catalysis, which comprises the following steps: uniformly mixing a precursor generated by 0.3g-0.7g of zirconium nitrate with distilled water; adding a ZSM-5 carrier into the solution prepared in the last step; adding 6g-10g of urea for regulating the PH; heating the mixed solution to 95 ℃ and stirring vigorously for 5 hours; the solution was filtered, washed with distilled water and then dried at 90 ℃ for 14 hours; calcining the mixture in an oven at 550 ℃ for 4 hours; before the reaction, introducing nitrogen into the reaction kettle for discharging air in the kettle to keep the reaction environment in a nitrogen atmosphere; adding 20mL of solution formed by mixing isopropanol and water into a stainless steel high-pressure reaction kettle, adding furfural, a solid acid catalyst and a magnetic stirring rotor, and setting experimental conditions for reaction; after the reaction was completed, the reactor was placed in cold water to be rapidly cooled to room temperature, and the catalyst was recovered.

Description

新型固体酸催化剂一锅多步催化生物质衍生糠醛转化为γ- 戊内酯的制备方法One-pot multi-step catalytic conversion of biomass-derived furfural to γ- The preparation method of valerolactone

技术领域technical field

本发明属于酸催化剂制备领域,涉及新型多功能固体酸催化剂HZSM-5-ZrO2,特别是催化糠醛催化转化为γ-戊内酯的制备方法。The invention belongs to the field of acid catalyst preparation, and relates to a novel multifunctional solid acid catalyst HZSM-5-ZrO 2 , in particular to a preparation method for catalyzing the catalytic conversion of furfural into γ-valerolactone.

背景技术Background technique

大规模利用化石资源极大地促进了人类社会和经济的发展,同时也引发了许多不可避免的衍生问题,包括全球变暖,空气污染和能源短缺,以改善环境恶化污染和全球能源危机,研究人员近年来逐渐寻求开发新的绿色可再生资源利用策略。作为一种天然清洁的可再生能源,具有广泛的来源,丰富的储备和低廉的价格,生物质能可以转化为各种重要的高附加值燃料和化学品,具有巨大的潜力取代传统的化石能源,对更有效的生物质资源利用方法的探索正引起学术界和工业界的广泛关注。γ-戊内酯因其优异的物理性质而备受研究人员的关注。γ-戊内酯的基本性质主要包括高沸点,高闪点,低熔点,低毒性等。γ-戊内酯可参与多种反应,广泛应用于燃料添加剂,医药中间体,高级烯烃燃料,绿色再生溶剂,尼龙中间体等的生产中。糠醛制备γ-戊内酯的反应涉及到两个水解反应和一个加氢反应。目前由生物质平台化合物糠醛制备γ-戊内酯,供氢体多使用氢气,催化剂多使用液体酸、复合催化剂、引入贵金属等,导致安全性差、催化剂难回收、制造成本高等问题。本发明使用分子筛ZSM-5负载ZrO2,制备一种单一双功能固体酸催化剂,用于糠醛催化转化为γ-戊内酯的反应中。The large-scale utilization of fossil resources has greatly promoted the development of human society and economy, but also caused many inevitable derived problems, including global warming, air pollution and energy shortages, to improve environmental degradation, pollution and global energy crisis, researchers In recent years, it has gradually sought to develop new green and renewable resource utilization strategies. As a natural and clean renewable energy with extensive sources, abundant reserves and low prices, biomass energy can be converted into various important high value-added fuels and chemicals, and has great potential to replace traditional fossil energy , the exploration of more efficient biomass resource utilization methods is attracting extensive attention from academia and industry. γ-Valerolactone has attracted much attention of researchers due to its excellent physical properties. The basic properties of γ-valerolactone mainly include high boiling point, high flash point, low melting point, and low toxicity. γ-Valerolactone can participate in various reactions and is widely used in the production of fuel additives, pharmaceutical intermediates, advanced olefin fuels, green regeneration solvents, nylon intermediates, etc. The preparation of γ-valerolactone from furfural involves two hydrolysis reactions and one hydrogenation reaction. At present, γ-valerolactone is prepared from the biomass platform compound furfural. The hydrogen donor mostly uses hydrogen, and the catalyst mostly uses liquid acid, composite catalyst, introduction of precious metals, etc., resulting in poor safety, difficult catalyst recovery, and high manufacturing costs. The invention uses molecular sieve ZSM-5 to support ZrO 2 to prepare a single bifunctional solid acid catalyst, which is used in the reaction of furfural catalytically converting into γ-valerolactone.

发明内容SUMMARY OF THE INVENTION

为了解决现有催化剂的问题。本发明着重于一种新型单一双功能固体酸催化剂,使用分子筛负载非贵金属氧化物ZrO2,使用共沉淀法合成催化剂,烘干备用的催化剂呈现白色粉末状。In order to solve the problem of existing catalysts. The invention focuses on a novel single dual-function solid acid catalyst, uses molecular sieves to support non-precious metal oxide ZrO 2 , uses a co-precipitation method to synthesize the catalyst, and the catalyst after drying is in the form of white powder.

本发明采用如下技术方案,新型固体酸催化剂一锅多步催化生物质衍生糠醛转化为γ-戊内酯的制备方法,包括如下步骤:The present invention adopts the following technical scheme, and the preparation method of the novel solid acid catalyst one-pot multi-step catalyzing biomass-derived furfural into γ-valerolactone comprises the following steps:

1)将0.3g-0.7g硝酸锆生成的前驱物与蒸馏水均匀混合;1) Evenly mix the precursor generated by 0.3g-0.7g of zirconium nitrate with distilled water;

2)将ZSM-5载体加入上一步配置的溶液中;2) adding the ZSM-5 carrier to the solution configured in the previous step;

3)加入6g-10g尿素用于调节PH;3) add 6g-10g urea for adjusting pH;

4)将混合溶液加热至95℃并剧烈搅拌5小时;4) The mixed solution was heated to 95°C and vigorously stirred for 5 hours;

5)将溶液过滤,用蒸馏水洗涤,然后在90℃下干燥14小时;5) The solution was filtered, washed with distilled water, and then dried at 90°C for 14 hours;

6)在烘箱中以550℃条件煅烧4小时;6) calcined in an oven at 550°C for 4 hours;

7)反应前向反应釜中通入氮气,用以排出釜内的空气,使反应环境保持在氮气氛围下;7) feed nitrogen into the reaction kettle before the reaction, in order to discharge the air in the kettle, so that the reaction environment is kept under the nitrogen atmosphere;

8)将异丙醇和水混合组成的20mL溶液加入不锈钢高压反应釜中,加入糠醛,固体酸催化剂和磁力搅拌转子,设置实验条件进行反应;8) adding the 20mL solution of isopropanol and water to the stainless steel autoclave, adding furfural, solid acid catalyst and magnetic stirring rotor, and setting experimental conditions to react;

9)反应完成后,将反应器置于冷水中以迅速冷却至室温,将催化剂回收,得到含有γ-戊内酯的溶液。9) After the reaction is completed, the reactor is placed in cold water to rapidly cool to room temperature, and the catalyst is recovered to obtain a solution containing γ-valerolactone.

所述步骤2)中硅铝比为27。In the step 2), the ratio of silicon to aluminum is 27.

所述步骤3)中尿素与ZSM-5分子筛质量比例为5-10g分子筛:1g尿素,PH的调节是通过尿素加热分解形成氨水,从而控制Ph在9-11.6之间。In described step 3), the mass ratio of urea and ZSM-5 molecular sieve is 5-10g molecular sieve: 1g urea, and the regulation of pH is to form ammoniacal liquor by thermal decomposition of urea, thereby controlling Ph to be between 9-11.6.

所述步骤2)中硝酸锆生成的含有等摩尔Zr离子的前驱物。The precursor containing equimolar Zr ions generated by zirconium nitrate in the step 2).

所述步骤8)中异丙醇与水以任意比例互溶。In described step 8), isopropanol and water are mutually soluble in any proportion.

所述步骤8)中催化剂用量控制在0.15g-0.6g之间。In the step 8), the amount of catalyst is controlled between 0.15g-0.6g.

所述步骤2)金属负载量控制在5wt%-20wt%。The step 2) metal loading is controlled at 5wt%-20wt%.

所述步骤8)反应温度控制在125-200℃。The step 8) reaction temperature is controlled at 125-200°C.

所述步骤8)反应时间控制在16-22h。The step 8) reaction time is controlled at 16-22h.

所述步骤8)固体酸催化剂HZSM-5-ZrO2回收后可以循环使用。The step 8) the solid acid catalyst HZSM-5-ZrO2 can be recycled after being recovered.

实验方法:experimental method:

1.将异丙醇和水混合组成的20mL溶液加入不锈钢高压反应釜中,加入糠醛,固体酸催化剂催化剂和磁力搅拌转子,设置五因素(金属负载,催化剂用量,反应温度,反应时间,异丙醇投加量)四水平的正交实验。1. Add the 20mL solution of isopropanol and water into the stainless steel autoclave, add furfural, solid acid catalyst catalyst and magnetic stirring rotor, set five factors (metal load, catalyst dosage, reaction temperature, reaction time, isopropanol) Dosing amount) four-level orthogonal experiment.

2.反应前向反应釜中通入氮气,用以排出釜内的空气,使反应环境保持在氮气氛围下。将反应釜螺丝拧紧使釜内保持密闭环境,并连入电源,连接温度传感器,之后设置反应釜温度和反应时间,磁子搅拌转速保持在500转/分钟,开始反应。2. Pour nitrogen into the reaction kettle before the reaction to discharge the air in the kettle and keep the reaction environment under nitrogen atmosphere. Tighten the screws of the reaction kettle to maintain a closed environment in the kettle, connect the power supply, connect the temperature sensor, then set the temperature and reaction time of the reaction kettle, and keep the magnetic stirring speed at 500 rpm to start the reaction.

3.反应完成后,将反应器置于冷水中以迅速冷却至室温。将催化剂回收,得到含有γ-戊内酯的溶液,等待测试。3. After the reaction was completed, the reactor was placed in cold water to rapidly cool to room temperature. The catalyst was recovered to obtain a solution containing γ-valerolactone, waiting for testing.

产物检测办法:Product testing method:

1.使用Bio-Rad Aminex HPX-87H柱在65℃下用高效液相色谱和折射率检测器测定滤液的糠醛和γ-戊内酯浓度。1. The furfural and γ-valerolactone concentrations of the filtrate were determined using a Bio-Rad Aminex HPX-87H column at 65°C with high performance liquid chromatography and a refractive index detector.

2.使用5mM硫酸水溶液作为流动相,流速为0.6mL/min。2. Use 5mM aqueous sulfuric acid as the mobile phase at a flow rate of 0.6mL/min.

3.配置不同浓度梯度的标准样,用于糠醛和γ-戊内酯标准曲线的拟合。3. Configure standard samples with different concentration gradients for the fitting of the standard curves of furfural and γ-valerolactone.

4.产物检测,根据峰面积计算浓度和γ-戊内酯产率。4. Product detection, calculate the concentration and γ-valerolactone yield according to the peak area.

附图说明Description of drawings

图1为基于表中的实验条件九的结果。Figure 1 shows the results based on experimental condition nine in the table.

图中:0.2ml糠醛,15wt%的Zr,0.4g的催化剂,17.4mL的异丙醇,175℃,16小时;仅一个变量改变以获得新的反应条件和产率。In the figure: 0.2 ml furfural, 15 wt% Zr, 0.4 g catalyst, 17.4 mL isopropanol, 175°C, 16 hours; only one variable was changed to obtain new reaction conditions and yields.

具体实施方式Detailed ways

以下结合附图和具体实施例来对本发明作进一步的说明。The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

将糠醛和异丙醇混合溶液组成的20mL溶液与催化剂一同加入高压反应釜中,加入固体酸催化剂催化剂和磁力搅拌转子,设置五因素(金属负载,催化剂用量,反应温度,反应时间,异丙醇投加量)四水平的正交实验,如下表1。反应前向反应釜中通入氮气,用以排出釜内的空气,使反应环境保持在氮气氛围下。将反应釜螺丝拧紧使釜内保持密闭环境,并连入电源,连接温度传感器,之后设置反应釜温度和反应时间,磁子搅拌转速保持在500转/分钟,开始反应。反应完成后,将反应器置于冷水中以迅速冷却至室温。将催化剂回收,得到含有γ-戊内酯的溶液,等待测试。使用Bio-Rad Aminex HPX-87H柱在65℃下用高效液相色谱和折射率检测器测定滤液的糠醛和γ-戊内酯浓度。使用高效液相色谱测试产物,首先配置0.05mol/L的稀硫酸溶液作为流动相,将配好的稀硫酸溶液放入容量瓶;将稀硫酸倒入烧杯中并放入超声震荡器中震荡30分钟,震荡完成的溶液使用滤膜过滤,以去除流动相中的气泡;按照操作程序打开高效液相色谱走基线;流动相流速控制为0.6mL/min;基线趋于平稳时,使用进样针进样,根据峰面积计算浓度和γ-戊内酯产率。The 20mL solution that furfural and isopropanol mixed solution is formed is added in autoclave together with catalyst, add solid acid catalyst catalyst and magnetic stirring rotor, set five factors (metal load, catalyst consumption, reaction temperature, reaction time, isopropanol Dosing amount) four-level orthogonal experiment, as shown in Table 1 below. Nitrogen was introduced into the reaction kettle before the reaction to discharge the air in the kettle, so that the reaction environment was kept under a nitrogen atmosphere. Tighten the screws of the reaction kettle to maintain a closed environment in the kettle, connect the power supply, connect the temperature sensor, then set the temperature and reaction time of the reaction kettle, and keep the magnetic stirring speed at 500 rpm to start the reaction. After the reaction was completed, the reactor was placed in cold water to rapidly cool to room temperature. The catalyst was recovered to obtain a solution containing γ-valerolactone, waiting for testing. The furfural and γ-valerolactone concentrations of the filtrate were determined using a Bio-Rad Aminex HPX-87H column at 65°C with high performance liquid chromatography and a refractive index detector. Using high performance liquid chromatography to test the product, firstly configure 0.05mol/L dilute sulfuric acid solution as the mobile phase, put the prepared dilute sulfuric acid solution into the volumetric flask; pour the dilute sulfuric acid into the beaker and put it into the ultrasonic oscillator to shake for 30 The solution after shaking is filtered with a filter membrane to remove air bubbles in the mobile phase; open the high performance liquid chromatography according to the operation procedure to take the baseline; the flow rate of the mobile phase is controlled to 0.6mL/min; when the baseline becomes stable, use the injection needle Samples were injected, and concentrations and γ-valerolactone yields were calculated from the peak areas.

Zr可以作为具有促进氢供体脱氢功能的金属,分子筛负载的ZrO2与CuO或SnO2相比,具有明显的催化效果,认为Zr/ZSM-5催化剂具有催化糠醛生产γ-戊内酯的效果,其可完成该过程中串联的MPV反应和酸水解反应。表1结果显示,不同反应条件对γ-戊内酯产率具有较大的影响,当金属负载量达到15%时,催化性能最佳。在表中第九组(金属负载量15wt%、催化剂投加量0.4、反应温度175℃、反应时间16小时、异丙醇用量17.4ml)的条件下,γ-戊内酯产率达到49.71%。可能的原因是Zr/ZSM-5催化剂具有较合适的Bronsted酸性位点和Lewis酸性位点,B酸位点与L酸位点的比例和数量均适宜,且催化条件较适宜该反应进行,这确保了反应可以较为充分的进行。Zr can be used as a metal with the function of promoting the dehydrogenation of hydrogen donors. Compared with CuO or SnO2 , ZrO2 supported by molecular sieves has obvious catalytic effect. It is believed that Zr/ZSM-5 catalyst has the effect of catalyzing furfural to produce γ-valerolactone , which can complete the MPV reaction and acid hydrolysis reaction in series in the process. The results in Table 1 show that different reaction conditions have a greater impact on the yield of γ-valerolactone, and when the metal loading reaches 15%, the catalytic performance is the best. Under the conditions of the ninth group in the table (metal loading 15wt%, catalyst dosage 0.4, reaction temperature 175°C, reaction time 16 hours, isopropanol consumption 17.4ml), the yield of γ-valerolactone reached 49.71% . The possible reason is that the Zr/ZSM-5 catalyst has more suitable Bronsted acid sites and Lewis acid sites, the ratio and number of B acid sites and L acid sites are suitable, and the catalytic conditions are more suitable for the reaction, which is It is ensured that the reaction can be carried out sufficiently.

表1:Zr/ZSM-5的反应条件Table 1: Reaction conditions of Zr/ZSM-5

Figure BDA0002235640690000041
Figure BDA0002235640690000041

(a:在20毫升溶液中的IPA体积)(a: volume of IPA in 20 mL solution)

之后,对于新型多功能固体酸催化剂HZSM-5-ZrO2的催化效果进行详细优化。After that, the catalytic effect of the novel multifunctional solid acid catalyst HZSM-5-ZrO2 was optimized in detail.

通过使用Zr/ZSM-5催化剂进一步研究适合γ-戊内酯生产的反应条件,以得到更高的γ-戊内酯产率,在表1中第9组实验条件(金属负载量15%wt、催化剂投加量0.4g、反应温度175℃、反应时间16小时、异丙醇用量17.4ml)的基础上继续进行10组单变量反应。例如,第一个单变量的两组反应对应的反应条件为:0.2ml糠醛,10wt%的Zr或20wt%的Zr,0.4g的催化剂,17.4mL的异丙醇,175℃,16h,改变的条件仅仅是金属负载量的变化,后续实验条件变化规律同第一组。此时,γ-戊内酯产量得到显着改善,大部分GVL产量达到40%以上。从图中可以明显看出,分子筛上Zr的金属负载量对FAL转化和GVL产生起着至关重要的作用,高金属负载量的催化剂,效果显著下降。可能的原因是,金属在分子筛载体的负载量已经达到了饱和,此时若持续增加,会堵塞分子筛孔道,使分子筛的酸性显著下降,且降低了催化剂整体的比表面积,因此催化性能下降。此外,反应温度和反应时间的变化对GVL产率具有中等影响,将温度控制在165℃和185℃,γ-戊内酯产率发生较小的变动。将时间由14小时延长至18小时,γ-戊内酯产率增加,因此,随着反应时间的增长,推动反应朝正向发展。而催化剂用量和IPA量对其影响不大,说明0.3g催化剂投加量和18.5ml异丙醇使用量,已经满足该条件下反应所需条件。通过优化Zr/ZSM-5催化条件,使用0.4g15wt%Zr/ZSM-5作为催化剂和17.4mL异丙醇作为氢供体,在175℃,18小时的条件下GVL的产率达到最高值52.43%。The reaction conditions suitable for γ-valerolactone production were further investigated by using Zr/ZSM-5 catalyst to obtain higher γ-valerolactone yield, in Table 1, the 9th set of experimental conditions (metal loading 15% wt , catalyst dosage 0.4g, reaction temperature 175°C, reaction time 16 hours, isopropanol consumption 17.4ml), 10 groups of univariate reactions were continued. For example, the reaction conditions corresponding to the two sets of reactions for the first univariate are: 0.2ml furfural, 10wt% Zr or 20wt% Zr, 0.4g catalyst, 17.4mL isopropanol, 175°C, 16h, modified The condition is only the change of the metal loading, and the change rule of the subsequent experimental conditions is the same as that of the first group. At this time, the γ-valerolactone yield was significantly improved, and most of the GVL yields reached more than 40%. It is obvious from the figure that the metal loading of Zr on the molecular sieve plays a crucial role in FAL conversion and GVL generation, and the effect of catalysts with high metal loading is significantly reduced. The possible reason is that the metal loading on the molecular sieve carrier has reached saturation, and if it continues to increase at this time, it will block the molecular sieve pores, significantly reduce the acidity of the molecular sieve, and reduce the overall specific surface area of the catalyst, so the catalytic performance will decline. In addition, the variation of reaction temperature and reaction time had a moderate effect on the GVL yield, with the temperature controlled at 165°C and 185°C, the γ-valerolactone yield changed slightly. Extending the time from 14 hours to 18 hours increases the yield of γ-valerolactone, thus pushing the reaction forward as the reaction time increases. However, the amount of catalyst and IPA has little effect on it, indicating that the dosage of 0.3g of catalyst and the amount of 18.5ml of isopropanol have met the conditions required for the reaction under this condition. By optimizing the catalytic conditions of Zr/ZSM-5, using 0.4 g of 15 wt% Zr/ZSM-5 as catalyst and 17.4 mL of isopropanol as hydrogen donor, the yield of GVL reached the highest value of 52.43% at 175 °C for 18 h. .

Claims (10)

1. The preparation method for converting biomass derived furfural into gamma-valerolactone by using the novel solid acid catalyst through one-pot multi-step catalysis is characterized by comprising the following steps of:
1) uniformly mixing a precursor generated by 0.3g-0.7g of zirconium nitrate with distilled water;
2) adding a ZSM-5 carrier into the solution prepared in the last step;
3) adding 6g-10g of urea for regulating the PH;
4) heating the mixed solution to 95 ℃ and stirring vigorously for 5 hours;
5) the solution was filtered, washed with distilled water and then dried at 90 ℃ for 14 hours;
6) calcining the mixture in an oven at 550 ℃ for 4 hours;
7) before the reaction, introducing nitrogen into the reaction kettle for discharging air in the kettle to keep the reaction environment in a nitrogen atmosphere;
8) adding 20mL of solution formed by mixing isopropanol and water into a stainless steel high-pressure reaction kettle, adding furfural, a solid acid catalyst and a magnetic stirring rotor, and setting experimental conditions for reaction;
9) after the reaction was completed, the reactor was placed in cold water to be rapidly cooled to room temperature, and the catalyst was recovered to obtain a solution containing γ -valerolactone.
2. The method according to claim 1, wherein the ratio of Si to Al in step 2) is 27.
3. The preparation method of claim 1, wherein the mass ratio of urea to ZSM-5 molecular sieve in the step 3) is 5-10g of molecular sieve to 1g of urea, and the pH is adjusted by heating urea to decompose into ammonia water, so that the pH is controlled to be 9-11.6.
4. The method according to claim 1, wherein the zirconium nitrate is generated as a precursor containing Zr ions in an equimolar amount in the step 2).
5. The method of claim 1, wherein the isopropanol in step 8) is miscible with water in any ratio.
6. The method as claimed in claim 1, wherein the amount of the catalyst used in the step 8) is controlled to be 0.15g to 0.6 g.
7. The method of claim 1, wherein the metal loading of step 2) is controlled to be in the range of 5 wt% to 20 wt%.
8. The method as set forth in claim 1, wherein the reaction temperature in the step 8) is controlled to be 125-200 ℃.
9. The preparation method according to claim 1, wherein the reaction time of the step 8) is controlled to 16 to 22 hours.
10. The preparation method according to claim 1, wherein the solid acid catalyst HZSM-5-ZrO2 in step 8) is recovered and recycled.
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