技术领域Technical field
本发明属于绿色/低能耗催化技术、高分子塑料单体合成领域，尤其涉及一种H-Beta分子筛/γ-氧化铝共混颗粒催化剂及其制备方法、与其作为催化剂在催化乳酸液相一步法合成丙交酯中的应用。The invention belongs to the field of green/low energy consumption catalytic technology and polymer plastic monomer synthesis. In particular, it relates to an H-Beta molecular sieve/γ-alumina blend particle catalyst and its preparation method, and its use as a catalyst in a one-step method of catalyzing lactic acid liquid phase. Application in the synthesis of lactide.
背景技术Background technique
聚乳酸(PLA)是一种生物可降解、具有良好生物相容性的环境友好型塑料，具有优良的热稳定性和机械性能，广泛应用于一次性餐具、塑料袋、农用地膜、生物医药、3D打印材料等领域。2022年我国聚乳酸市场需求量为40万吨，预计2025年将达到208万吨，聚乳酸产品需求仍在快速增长中，这使得聚乳酸的工业化生产进程需要不断优化和突破。Polylactic acid (PLA) is a biodegradable, environmentally friendly plastic with good biocompatibility and excellent thermal stability and mechanical properties. It is widely used in disposable tableware, plastic bags, agricultural mulch films, biomedicine, 3D printing materials and other fields. my country's polylactic acid market demand is 400,000 tons in 2022, and is expected to reach 2.08 million tons in 2025. The demand for polylactic acid products is still growing rapidly, which requires continuous optimization and breakthroughs in the industrial production process of polylactic acid.
丙交酯(LT)是合成聚乳酸的关键中间体，通过高纯度丙交酯的开环聚合可以制备高分子量的优质聚乳酸。目前丙交酯的生产主要有两种方法，一是传统的工业两步法，由乳酸直接缩聚得到低聚乳酸，再通过热裂解得到丙交酯，这种方法产量稳定，但流程较为复杂，能耗高；二是发展的一步法，由乳酸直接环化生成丙交酯，这种方法流程简单，但对催化剂和催化机理还需要进一步探究。Lactide (LT) is a key intermediate for the synthesis of polylactic acid. High-molecular-weight, high-quality polylactic acid can be prepared through ring-opening polymerization of high-purity lactide. There are currently two main methods for the production of lactide. One is the traditional industrial two-step method, which involves direct polycondensation of lactic acid to obtain oligomeric lactic acid, and then thermal cracking to obtain lactide. This method has stable output, but the process is complicated. The energy consumption is high; the second is the developed one-step method, which directly cyclizes lactic acid to produce lactide. This method has a simple process, but further exploration of the catalyst and catalytic mechanism is needed.
目前液相一步法合成丙交酯常见的催化剂有微孔分子筛、负载型多孔SiO2材料和一些MOFs材料。其中H-Beta分子筛作为微孔分子筛的一种，其特有的Bronsted酸性活性位点在催化合成丙交酯中发挥着重要作用。在最新的研究中，通过调节H-Beta分子筛的Si/Al比或改造晶体尺寸可以提高其催化选择性和产率。但是，这种催化剂在实验室中通常以粉末形式进行催化反应，不利于工业化应用，需要制备较大颗粒的分子筛催化剂，然而大颗粒的催化剂难免会导致其催化活性下降，如何提高其催化效果已成为新的研究方向。At present, common catalysts for the one-step liquid phase synthesis of lactide include microporous molecular sieves, supported porous SiO2 materials and some MOFs materials. Among them, H-Beta molecular sieve is a type of microporous molecular sieve, and its unique Bronsted acidic active sites play an important role in the catalytic synthesis of lactide. In the latest research, the catalytic selectivity and yield of H-Beta molecular sieve can be improved by adjusting the Si/Al ratio or modifying the crystal size. However, this kind of catalyst is usually used for catalytic reactions in the form of powder in the laboratory, which is not conducive to industrial application. It is necessary to prepare larger particle molecular sieve catalysts. However, large particle catalysts will inevitably lead to a decrease in its catalytic activity. How to improve its catalytic effect has been become a new research direction.
发明内容Contents of the invention
本发明所要解决的技术问题是针对现有技术中H-Beta分子筛颗粒与H-Beta粉末对比催化效果下降、产率低、反应速率低、不利于工业化实施等问题，提供一种新型复合高效的H-Beta分子筛/γ-氧化铝共混颗粒催化剂，以提高丙交酯的产率和一步法合成丙交酯的反应速率。The technical problem to be solved by the present invention is to provide a new type of composite high-efficiency catalytic effect compared with the H-Beta powder in the existing technology, such as reduced yield, low reaction rate, and unfavorable industrial implementation. H-Beta molecular sieve/γ-alumina blended particle catalyst to increase the yield of lactide and the reaction rate of one-step synthesis of lactide.
为了解决上述技术问题，本发明采用的技术方案如下：In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows:
本发明公开了一种H-Beta分子筛/γ-氧化铝共混颗粒催化剂的制备方法，包括如下步骤：The invention discloses a preparation method of H-Beta molecular sieve/γ-alumina blend particle catalyst, which includes the following steps:
(1)将H-Beta分子筛与拟薄水铝石混合压实，研磨过筛，得到共混颗粒；(1) Mix and compact H-Beta molecular sieve and pseudo-boehmite, grind and sieve to obtain blended particles;
(2)将步骤(1)得到的共混颗粒置于马弗炉中进行煅烧，即得H-Beta分子筛/γ-氧化铝共混颗粒催化剂。(2) Place the blended particles obtained in step (1) for calcination in a muffle furnace to obtain the H-Beta molecular sieve/γ-alumina blended particle catalyst.
在一些实施例中，步骤(1)中，所述H-Beta分子筛为H-Beta分子筛粉末；所述拟薄水铝石为拟薄水铝石粉末。In some embodiments, in step (1), the H-Beta molecular sieve is H-Beta molecular sieve powder; the pseudo-boehmite is pseudo-boehmite powder.
其中，所述H-Beta分子筛为H-Beta分子筛粉末的目数为80～100目；所述拟薄水铝石为拟薄水铝石粉末的目数为80～100目。Wherein, the H-Beta molecular sieve is an H-Beta molecular sieve powder with a mesh number of 80 to 100 mesh; the pseudo-boehmite is a pseudo-boehmite powder with a mesh number of 80 to 100 mesh.
在一些实施例中，步骤(1)中，所述H-Beta分子筛与拟薄水铝石的质量比为2～4：1。In some embodiments, in step (1), the mass ratio of the H-Beta molecular sieve to pseudo-boehmite is 2 to 4:1.
在一些实施例中，步骤(1)中，所述研磨过筛，过筛所用的筛网所能通过的颗粒大小为20～50目。In some embodiments, in step (1), the grinding and sieving are performed, and the particle size that can pass through the sieve used for sieving is 20 to 50 mesh.
在一些实施例中，步骤(1)中，所述的压实，优选为液压，液压压力为10～15MPa，液压时间为2～3min；进一步优选地，液压压力为10MPa，液压时间为3min。In some embodiments, in step (1), the compaction is preferably hydraulic, with a hydraulic pressure of 10 to 15 MPa and a hydraulic time of 2 to 3 minutes; further preferably, the hydraulic pressure is 10 MPa and the hydraulic time is 3 minutes.
在一些实施例中，步骤(2)中，所述煅烧，煅烧温度为550～650℃，煅烧时间为6～10h。In some embodiments, in step (2), the calcination temperature is 550-650°C, and the calcination time is 6-10 hours.
在一些实施例中，优选地，步骤(2)中，所述煅烧，煅烧温度为550℃，煅烧时间为6h。In some embodiments, preferably, in step (2), the calcination temperature is 550°C and the calcination time is 6 hours.
其中，上述制备得到的H-Beta分子筛/γ-氧化铝共混颗粒催化剂在制备过程中不添加额外的酸、扩孔剂和水；例如不添加盐酸、硝酸、醋酸等酸，不添加聚乙烯醇、田菁粉等扩孔剂。Among them, the H-Beta molecular sieve/γ-alumina blend particle catalyst prepared above does not add additional acid, pore expander and water during the preparation process; for example, no hydrochloric acid, nitric acid, acetic acid and other acids are added, and no polyethylene is added. Alcohol, sesbania powder and other pore expanders.
上述的制备方法制备得到的H-Beta分子筛/γ-氧化铝共混颗粒催化剂也在本发明的保护范围之内。The H-Beta molecular sieve/γ-alumina blend particle catalyst prepared by the above preparation method is also within the protection scope of the present invention.
进一步地，本发明公开了上述的H-Beta分子筛/γ-氧化铝共混颗粒催化剂在催化乳酸液相一步法合成丙交酯中的应用。Further, the present invention discloses the application of the above-mentioned H-Beta molecular sieve/γ-alumina blend particle catalyst in the one-step synthesis of lactide from lactic acid liquid phase.
具体地，以甲苯为溶剂，使用H-Beta分子筛/γ-氧化铝共混颗粒催化剂与乳酸通过液相一步法反应合成丙交酯单体。Specifically, using toluene as the solvent, H-Beta molecular sieve/γ-alumina blend particle catalyst and lactic acid were used to synthesize lactide monomer through a liquid phase one-step reaction.
其中，使用H-Beta分子筛/γ-氧化铝共混颗粒催化剂与乳酸通过液相一步法反应合成丙交酯单体的化学方程式如下：Among them, the chemical equation for synthesizing lactide monomer through a liquid phase one-step reaction using H-Beta molecular sieve/γ-alumina blended particle catalyst and lactic acid is as follows:
具体地，所述乳酸的纯度大于等于96.7wt％，其余为水或杂质。Specifically, the purity of the lactic acid is greater than or equal to 96.7wt%, and the rest is water or impurities.
具体地，所述H-Beta分子筛/γ-氧化铝共混颗粒催化剂与乳酸的质量比为2～3：5；所述H-Beta分子筛/γ-氧化铝共混颗粒催化剂与甲苯的质量体积比为0.2～0.3g：12mL。Specifically, the mass ratio of the H-Beta molecular sieve/γ-alumina blended particle catalyst and lactic acid is 2 to 3:5; the mass volume of the H-Beta molecular sieve/γ-alumina blended particle catalyst and toluene The ratio is 0.2~0.3g:12mL.
具体地，所述液相一步法反应，反应温度为135℃～140℃，反应时间为90min～120min。Specifically, the liquid phase one-step reaction has a reaction temperature of 135°C to 140°C and a reaction time of 90min to 120min.
具体地，在液相一步法反应过程中同步去除反应体系中的水；优选地，在液相一步法反应所使用的反应装置上连接有水分分离装置以除去反应中产生的水分；进一步优选地，在液相一步法反应所使用的反应装置上连接相沉降器保证溶剂回流以脱除反应中产生的水分。Specifically, water in the reaction system is removed simultaneously during the one-step liquid phase reaction; preferably, a moisture separation device is connected to the reaction device used in the one-step liquid phase reaction to remove moisture generated during the reaction; further preferably , connect a phase settler to the reaction device used in the liquid phase one-step reaction to ensure that the solvent refluxes to remove the moisture generated during the reaction.
上述的H-Beta分子筛/γ-氧化铝共混颗粒催化剂在催化乳酸液相一步法合成丙交酯中的应用也在本发明的保护范围之内。The application of the above-mentioned H-Beta molecular sieve/γ-alumina blend particle catalyst in catalyzing the one-step lactic acid liquid phase synthesis of lactide is also within the protection scope of the present invention.
有益效果：Beneficial effects:
(1)本发明以H-Beta分子筛/γ-氧化铝共混颗粒为催化剂，用来催化乳酸液相一步法合成丙交酯，与纯的H-Beta分子筛颗粒催化剂相比，H-Beta分子筛/γ-氧化铝共混颗粒催化剂在2h内提升了催化合成丙交酯的产率，且在20min内反应速率得到明显提升。H-Beta分子筛混合了γ-氧化铝后2h催化产率由47.5％提升到66.4％，20min内平均反应速率由9.4mg min-1gcat-1提升到11.1mg min-1gcat-1，产率由9.7％提升到11.5％，基本接近实验室中纯H-Beta粉末催化剂的平均反应速率11.3mg min-1gcat-1，产率11.7％。(1) The present invention uses H-Beta molecular sieve/γ-alumina blend particles as catalysts to catalyze the one-step synthesis of lactide in the liquid phase of lactic acid. Compared with pure H-Beta molecular sieve particle catalysts, H-Beta molecular sieve /γ-alumina blended particle catalyst increased the yield of catalytic synthesis of lactide within 2 hours, and the reaction rate was significantly improved within 20 minutes. After H-Beta molecular sieve is mixed with γ-alumina, the catalytic yield increases from 47.5% to 66.4% in 2 hours, and the average reaction rate within 20 minutes increases from 9.4mg min-1 gcat-1 to 11.1mg min-1 gcat-1 . The yield increased from 9.7% to 11.5%, which is basically close to the average reaction rate of pure H-Beta powder catalyst in the laboratory of 11.3 mg min-1 gcat-1 , with a yield of 11.7%.
(2)本发明H-Beta分子筛/γ-氧化铝共混颗粒催化剂效果稳定，丙交酯产率提升且反应速率快，且H-Beta分子筛/γ-氧化铝共混颗粒催化剂反应后收集煅烧后可重复使用减小了成本，有利于工业化和连续化应用。(2) The H-Beta molecular sieve/γ-alumina blended particle catalyst of the present invention has a stable effect, the lactide yield is increased and the reaction rate is fast, and the H-Beta molecular sieve/γ-alumina blended particle catalyst is collected and calcined after the reaction. It can be reused to reduce costs and is conducive to industrialization and continuous application.
(3)与现有技术相比，本发明制备H-Beta分子筛/γ-氧化铝共混颗粒催化剂的过程中避免使用酸，绿色环保。(3) Compared with the existing technology, the present invention avoids the use of acid in the process of preparing H-Beta molecular sieve/γ-alumina blend particle catalyst, which is green and environmentally friendly.
(4)本发明制备得到的H-Beta分子筛/γ-氧化铝共混颗粒催化剂催化效果好，避免了H-Beta分子筛粉末在工业化生产中堵塞固定床反应器、装置压力损失大无法大量生产使用等问题。(4) The H-Beta molecular sieve/γ-alumina blend particle catalyst prepared by the present invention has good catalytic effect and avoids the H-Beta molecular sieve powder from clogging the fixed-bed reactor in industrial production and causing large pressure loss in the device, making it impossible to use in mass production. And other issues.
(5)本发明中使用甲苯为回流溶剂，液相一步法合成反应温度低，能耗小。(5) Toluene is used as the reflux solvent in the present invention, and the one-step liquid phase synthesis reaction temperature is low and the energy consumption is small.
附图说明Description of drawings
下面结合附图和具体实施方式对本发明做更进一步的具体说明，本发明的上述和/或其他方面的优点将会变得更加清楚。The above and/or other advantages of the present invention will become more clear when the present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments.
图1为不同催化剂颗粒催化乳酸反应20min合成丙交酯的产率和平均反应速率的对比图。Figure 1 is a comparison chart of the yield and average reaction rate of lactide synthesized by lactic acid reaction catalyzed by different catalyst particles for 20 minutes.
图2为液相反应的装置图示。Figure 2 is a diagram of the device for liquid phase reaction.
图3为H-Beta分子筛/γ-氧化铝共混颗粒催化剂实物图，由实施例1制备。Figure 3 is a physical diagram of the H-Beta molecular sieve/γ-alumina blend particle catalyst, prepared in Example 1.
图4为H-Beta分子筛/γ-氧化铝共混颗粒催化剂扫描电镜图，由实施例1制备。Figure 4 is a scanning electron microscope image of the H-Beta molecular sieve/γ-alumina blend particle catalyst prepared in Example 1.
具体实施方式Detailed ways
下面结合具体实施例对本发明作出详细说明。The present invention will be described in detail below with reference to specific embodiments.
本发明实施例中所用的H-Beta分子筛粉末，Si/Al＝12.5，80～100目，天津南化催化剂有限公司。H-Beta molecular sieve powder used in the examples of the present invention, Si/Al=12.5, 80-100 mesh, Tianjin Nanhua Catalyst Co., Ltd.
本发明实施例中所用的拟薄水铝石粉末，纯度为GR(≥99.8％)，80～100目，上海麦克林生化科技有限公司。The pseudo-boehmite powder used in the embodiments of the present invention has a purity of GR (≥99.8%), 80-100 mesh, and is from Shanghai McLean Biochemical Technology Co., Ltd.
本发明实施例中液相一步法合成丙交酯的反应装置如图2所示。The reaction device for the liquid phase one-step synthesis of lactide in the embodiment of the present invention is shown in Figure 2.
对比例1Comparative example 1
H-Beta分子筛颗粒催化剂制备：取H-Beta分子筛粉末1.2g，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用30～50目的筛网过筛收集，再将所得颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛颗粒催化剂。Preparation of H-Beta molecular sieve particle catalyst: Take 1.2g of H-Beta molecular sieve powder, further mix it in a mortar and grind it into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse it into fine particles, and sieve and collect them with a 30-50 mesh mesh. The resulting particles are then placed in a muffle furnace and calcined at 550°C for 6 hours to obtain H- Beta molecular sieve particle catalyst.
H-Beta分子筛颗粒催化剂催化乳酸合成丙交酯：在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.2g H-Beta分子筛颗粒催化剂(本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，依次反应10min、30min、60min、90min、120min后取样液相检测。在此条件下，丙交酯的产率依次为4.22％、12.3％、24.0％、35.5％、47.5％。H-Beta molecular sieve particle catalyst catalyzes the synthesis of lactide from lactic acid: add 0.5g 96.7wt% lactic acid aqueous solution, 0.2g H-Beta molecular sieve particle catalyst (prepared in this example), 12 mL of toluene was connected to a phase settler to ensure that the solvent refluxed to remove the moisture produced during the reaction. The reaction temperature was 135°C. The reaction was performed for 10 min, 30 min, 60 min, 90 min, and 120 min. After the reaction, samples were taken for liquid phase detection. Under these conditions, the yields of lactide were 4.22%, 12.3%, 24.0%, 35.5%, and 47.5%.
对比例2Comparative example 2
H-Beta分子筛/γ-氧化铝共混颗粒催化剂制备：Preparation of H-Beta molecular sieve/γ-alumina blend particle catalyst:
(1)取H-Beta分子筛粉末1.2g和拟薄水铝石粉末0.4g，按照质量比3：1混合，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用30～50目的筛网过筛收集，得到共混颗粒。(1) Take 1.2g of H-Beta molecular sieve powder and 0.4g of pseudo-boehmite powder, mix them according to the mass ratio of 3:1, further mix in a mortar and grind them into fine powder (100-200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse into fine particles, and sieve and collect them with a 30-50 mesh screen to obtain blended particles.
(2)再将步骤(1)所得的共混颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛/γ-氧化铝共混颗粒催化剂。(2) The blended particles obtained in step (1) are then calcined in a muffle furnace at a temperature of 550°C for 6 hours to obtain the H-Beta molecular sieve/γ-alumina blended particle catalyst.
H-Beta分子筛/γ-氧化铝共混颗粒催化剂催化乳酸合成丙交酯：H-Beta molecular sieve/γ-alumina blend particle catalyst catalyzes the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.2g H-Beta分子筛/γ-氧化铝共混颗粒催化剂(本实施例制备得到)、12mL甲苯，上接冷凝管(不分离反应过程中产生的水)，反应温度为135℃，依次反应10min、30min、60min、90min、120min后取样液相检测。在此条件下，丙交酯的产率依次为4.16％、13.2％、24.7％、37.0％、45.6％。Add 0.5g 96.7wt% lactic acid aqueous solution, 0.2g H-Beta molecular sieve/γ-alumina blended particle catalyst (prepared in this example), and 12mL toluene into a 25mL round-bottomed flask with a magnetic rotor, followed by condensation tube (water produced during the reaction is not separated), the reaction temperature is 135°C, and liquid phase detection is taken after reacting for 10 minutes, 30 minutes, 60 minutes, 90 minutes, and 120 minutes. Under these conditions, the yields of lactide were 4.16%, 13.2%, 24.7%, 37.0%, and 45.6%.
对比例3Comparative example 3
γ-氧化铝颗粒催化剂制备：取拟薄水铝石粉末1.0g，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用30～50目的筛网过筛收集，再将所得颗粒置于马弗炉中在550℃的温度下煅烧6h，得到γ-氧化铝颗粒催化剂。Preparation of γ-alumina particle catalyst: Take 1.0g of pseudo-boehmite powder, further mix it in a mortar and grind it into fine powder (100-200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse it into fine particles, and sieve and collect them with a 30-50 mesh mesh. The resulting particles are then placed in a muffle furnace and calcined at 550°C for 6 hours to obtain γ- Alumina particle catalyst.
γ-氧化铝颗粒催化剂催化乳酸合成丙交酯：在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.2gγ-氧化铝颗粒催化剂(本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，依次反应10min、30min、60min、90min、120min后取样液相检测。在此条件下，丙交酯的产率依次为1.0％、3.7％、5.6％、7.5％、9.3％。γ-alumina particle catalyst catalyzes the synthesis of lactide from lactic acid: Add 0.5g 96.7wt% lactic acid aqueous solution, 0.2g γ-alumina particle catalyst (prepared in this example), 12 mL into a 25 mL round-bottomed flask with a magnetic rotor. Toluene was connected to a phase settler to ensure solvent reflux to remove the moisture produced during the reaction. The reaction temperature was 135°C. The reaction was performed for 10 min, 30 min, 60 min, 90 min, and 120 min in sequence, and liquid phase detection was taken after the reaction. Under these conditions, the yields of lactide were 1.0%, 3.7%, 5.6%, 7.5%, and 9.3%.
实施例1Example 1
H-Beta分子筛/γ-氧化铝共混颗粒催化剂制备：Preparation of H-Beta molecular sieve/γ-alumina blend particle catalyst:
(1)取H-Beta分子筛粉末1.2g和拟薄水铝石粉末0.4g，按照质量比3：1混合，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用30～50目的筛网过筛收集，得到共混颗粒。(1) Take 1.2g of H-Beta molecular sieve powder and 0.4g of pseudo-boehmite powder, mix them according to the mass ratio of 3:1, further mix in a mortar and grind them into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse into fine particles, and sieve and collect them with a 30-50 mesh screen to obtain blended particles.
(2)再将步骤(1)所得的共混颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛/γ-氧化铝共混颗粒催化剂。(2) The blended particles obtained in step (1) are then calcined in a muffle furnace at a temperature of 550°C for 6 hours to obtain the H-Beta molecular sieve/γ-alumina blended particle catalyst.
本实施例制备的H-Beta分子筛/γ-氧化铝共混颗粒催化剂的实物图见图3，催化剂为纯白色颗粒，扫描电镜图见图4，SEM图像显示催化剂晶格规整，孔隙多，具备优良的催化潜力。The physical picture of the H-Beta molecular sieve/γ-alumina blend particle catalyst prepared in this example is shown in Figure 3. The catalyst is pure white particles. The scanning electron microscope picture is shown in Figure 4. The SEM image shows that the catalyst has a regular crystal lattice, many pores, and has Excellent catalytic potential.
H-Beta分子筛/γ-氧化铝共混颗粒催化剂催化乳酸合成丙交酯：H-Beta molecular sieve/γ-alumina blend particle catalyst catalyzes the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.2g H-Beta分子筛/γ-氧化铝共混颗粒催化剂(本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，依次反应10min、30min、60min、90min、120min后取样液相检测。在此条件下，丙交酯的产率依次为4.41％、14.5％、28.2％、43.2％、66.4％。In a 25mL round-bottomed flask with a magnetic rotor, add 0.5g 96.7wt% lactic acid aqueous solution, 0.2g H-Beta molecular sieve/γ-alumina blended particle catalyst (prepared in this example), 12mL toluene, and connect the phase The settler ensures that the solvent refluxes to remove the moisture produced during the reaction. The reaction temperature is 135°C. Samples are taken for liquid phase detection after the reaction for 10 minutes, 30 minutes, 60 minutes, 90 minutes, and 120 minutes. Under these conditions, the yields of lactide were 4.41%, 14.5%, 28.2%, 43.2%, and 66.4%.
实施例2Example 2
H-Beta分子筛/γ-氧化铝共混颗粒催化剂制备：Preparation of H-Beta molecular sieve/γ-alumina blend particle catalyst:
(1)取H-Beta分子筛粉末1.2g和拟薄水铝石粉末0.3g，按照质量比4：1混合，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用30～50目的筛网过筛收集，得到共混颗粒。(1) Take 1.2g of H-Beta molecular sieve powder and 0.3g of pseudo-boehmite powder, mix them according to the mass ratio of 4:1, further mix in a mortar and grind them into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse into fine particles, and sieve and collect them with a 30-50 mesh screen to obtain blended particles.
(2)再将步骤(1)所得的共混颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛/γ-氧化铝共混颗粒催化剂。(2) The blended particles obtained in step (1) are then calcined in a muffle furnace at a temperature of 550°C for 6 hours to obtain the H-Beta molecular sieve/γ-alumina blended particle catalyst.
H-Beta分子筛/γ-氧化铝共混颗粒催化剂催化乳酸合成丙交酯：H-Beta molecular sieve/γ-alumina blend particle catalyst catalyzes the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.2g H-Beta分子筛/γ-氧化铝共混颗粒催化剂(本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，反应120min后取样液相检测。在此条件下，丙交酯的产率为48.4％。In a 25mL round-bottomed flask with a magnetic rotor, add 0.5g 96.7wt% lactic acid aqueous solution, 0.2g H-Beta molecular sieve/γ-alumina blended particle catalyst (prepared in this example), 12mL toluene, and connect the phase The settler ensures that the solvent refluxes to remove the moisture produced during the reaction. The reaction temperature is 135°C. After 120 minutes of reaction, a sample is taken for liquid phase detection. Under these conditions, the yield of lactide was 48.4%.
实施例3Example 3
H-Beta分子筛/γ-氧化铝共混颗粒催化剂制备：Preparation of H-Beta molecular sieve/γ-alumina blend particle catalyst:
(1)取H-Beta分子筛粉末1.2g和拟薄水铝石粉末0.6g，按照质量比2：1混合，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用30～50目的筛网过筛收集，得到共混颗粒。(1) Take 1.2g of H-Beta molecular sieve powder and 0.6g of pseudo-boehmite powder, mix them according to the mass ratio of 2:1, further mix in a mortar and grind them into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse into fine particles, and sieve and collect them with a 30-50 mesh screen to obtain blended particles.
(2)再将步骤(1)所得的共混颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛/γ-氧化铝共混颗粒催化剂。(2) The blended particles obtained in step (1) are then calcined in a muffle furnace at a temperature of 550°C for 6 hours to obtain the H-Beta molecular sieve/γ-alumina blended particle catalyst.
H-Beta分子筛/γ-氧化铝共混颗粒催化剂催化乳酸合成丙交酯：H-Beta molecular sieve/γ-alumina blend particle catalyst catalyzes the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.2g H-Beta分子筛/γ-氧化铝共混颗粒催化剂(本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，反应120min后取样液相检测。在此条件下，丙交酯的产率为65.1％。In a 25mL round-bottomed flask with a magnetic rotor, add 0.5g 96.7wt% lactic acid aqueous solution, 0.2g H-Beta molecular sieve/γ-alumina blended particle catalyst (prepared in this example), 12mL toluene, and connect the phase The settler ensures that the solvent refluxes to remove the moisture produced during the reaction. The reaction temperature is 135°C. After 120 minutes of reaction, a sample is taken for liquid phase detection. Under these conditions, the yield of lactide was 65.1%.
对比例4Comparative example 4
H-Beta分子筛颗粒催化剂制备：取H-Beta分子筛粉末1.2g，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用30～50目的筛网过筛收集，再将所得颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛颗粒催化剂。Preparation of H-Beta molecular sieve particle catalyst: Take 1.2g of H-Beta molecular sieve powder, further mix it in a mortar and grind it into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse it into fine particles, and sieve and collect them with a 30-50 mesh mesh. The resulting particles are then placed in a muffle furnace and calcined at 550°C for 6 hours to obtain H- Beta molecular sieve particle catalyst.
H-Beta分子筛颗粒催化剂催化乳酸合成丙交酯：H-Beta molecular sieve particle catalyst catalyzes the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.2g H-Beta分子筛颗粒催化剂(本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，反应20min后取样液相检测。在此条件下，丙交酯的产率为9.7％，20min内平均反应速率为9.4mg min-1gcat-1。Add 0.5g 96.7wt% lactic acid aqueous solution, 0.2g H-Beta molecular sieve particle catalyst (prepared in this example), and 12mL toluene into a 25mL round-bottomed flask with a magnetic rotor, and connect it to a phase settler to ensure that the solvent refluxes to remove the In addition to the moisture produced during the reaction, the reaction temperature was 135°C, and liquid phase detection was taken after 20 minutes of reaction. Under these conditions, the yield of lactide was 9.7%, and the average reaction rate within 20 minutes was 9.4 mg min-1 gcat-1 .
实施例4Example 4
H-Beta分子筛/γ-氧化铝共混颗粒催化剂制备：Preparation of H-Beta molecular sieve/γ-alumina blend particle catalyst:
(1)取H-Beta分子筛粉末1.2g和拟薄水铝石粉末0.6g，按照质量比2：1混合，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用30～50目的筛网过筛收集，得到共混颗粒。(1) Take 1.2g of H-Beta molecular sieve powder and 0.6g of pseudo-boehmite powder, mix them according to the mass ratio of 2:1, further mix in a mortar and grind them into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse into fine particles, and sieve and collect them with a 30-50 mesh screen to obtain blended particles.
(2)再将步骤(1)所得的共混颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛/γ-氧化铝共混颗粒催化剂。(2) The blended particles obtained in step (1) are then calcined in a muffle furnace at a temperature of 550°C for 6 hours to obtain the H-Beta molecular sieve/γ-alumina blended particle catalyst.
H-Beta分子筛/γ-氧化铝共混颗粒催化剂催化乳酸合成丙交酯：H-Beta molecular sieve/γ-alumina blend particle catalyst catalyzes the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.3g H-Beta分子筛/γ-氧化铝共混颗粒催化剂(0.2g H-Beta分子筛活性组分+0.1gγ-氧化铝组分，本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，反应20min后取样液相检测。在此条件下，丙交酯的产率为11.0％，20min内平均反应速率为10.7mg min-1gcat-1。In a 25mL round bottom flask with a magnetic rotor, add 0.5g 96.7wt% lactic acid aqueous solution and 0.3g H-Beta molecular sieve/γ-alumina blended particle catalyst (0.2g H-Beta molecular sieve active component + 0.1gγ- The alumina component (prepared in this example) and 12 mL of toluene were connected to a phase settler to ensure solvent reflux to remove the moisture generated during the reaction. The reaction temperature was 135°C. After 20 minutes of reaction, a sample was taken for liquid phase detection. Under these conditions, the yield of lactide was 11.0%, and the average reaction rate within 20 minutes was 10.7 mg min-1 gcat-1 .
实施例5Example 5
H-Beta分子筛/γ-氧化铝共混颗粒催化剂制备：Preparation of H-Beta molecular sieve/γ-alumina blend particle catalyst:
(1)取H-Beta分子筛粉末1.2g和拟薄水铝石粉末0.4g，按照质量比3：1混合，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用30～50目的筛网过筛收集，得到共混颗粒。(1) Take 1.2g of H-Beta molecular sieve powder and 0.4g of pseudo-boehmite powder, mix them according to the mass ratio of 3:1, further mix in a mortar and grind them into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse into fine particles, and sieve and collect them with a 30-50 mesh screen to obtain blended particles.
(2)再将步骤(1)所得的共混颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛/γ-氧化铝共混颗粒催化剂。(2) The blended particles obtained in step (1) are then calcined in a muffle furnace at a temperature of 550°C for 6 hours to obtain the H-Beta molecular sieve/γ-alumina blended particle catalyst.
H-Beta分子筛/γ-氧化铝共混颗粒催化剂催化乳酸合成丙交酯：H-Beta molecular sieve/γ-alumina blend particle catalyst catalyzes the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.267g H-Beta分子筛/γ-氧化铝共混颗粒催化剂(0.2g H-Beta分子筛活性组分+0.067gγ-氧化铝组分，本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，反应20min后取样液相检测。在此条件下，丙交酯的产率为11.5％，20min内平均反应速率为11.1mg min-1gcat-1。In a 25mL round bottom flask with a magnetic rotor, add 0.5g 96.7wt% lactic acid aqueous solution and 0.267g H-Beta molecular sieve/γ-alumina blended particle catalyst (0.2g H-Beta molecular sieve active component + 0.067gγ- The alumina component (prepared in this example) and 12 mL of toluene were connected to a phase settler to ensure solvent reflux to remove the moisture generated during the reaction. The reaction temperature was 135°C. After 20 minutes of reaction, a sample was taken for liquid phase detection. Under these conditions, the yield of lactide was 11.5%, and the average reaction rate within 20 minutes was 11.1 mg min-1 gcat-1 .
实施例6Example 6
H-Beta分子筛/γ-氧化铝共混颗粒催化剂制备：Preparation of H-Beta molecular sieve/γ-alumina blend particle catalyst:
(1)取H-Beta分子筛粉末1.2g和拟薄水铝石粉末0.3g，按照质量比4：1混合，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用30～50目的筛网过筛收集，得到共混颗粒。(1) Take 1.2g of H-Beta molecular sieve powder and 0.3g of pseudo-boehmite powder, mix them according to the mass ratio of 4:1, further mix in a mortar and grind them into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse into fine particles, and sieve and collect them with a 30-50 mesh screen to obtain blended particles.
(2)再将步骤(1)所得的共混颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛/γ-氧化铝共混颗粒催化剂。(2) The blended particles obtained in step (1) are then calcined in a muffle furnace at a temperature of 550°C for 6 hours to obtain the H-Beta molecular sieve/γ-alumina blended particle catalyst.
H-Beta分子筛/γ-氧化铝共混颗粒催化剂催化乳酸合成丙交酯：H-Beta molecular sieve/γ-alumina blend particle catalyst catalyzes the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.25g H-Beta分子筛/γ-氧化铝共混颗粒催化剂(0.2g H-Beta分子筛活性组分+0.05gγ-氧化铝组分，本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，反应20min后取样液相检测。在此条件下，丙交酯的产率为8.9％，20min内平均反应速率为8.6mg min-1gcat-1。In a 25mL round bottom flask with a magnetic rotor, add 0.5g 96.7wt% lactic acid aqueous solution and 0.25g H-Beta molecular sieve/γ-alumina blended particle catalyst (0.2g H-Beta molecular sieve active component + 0.05gγ- The alumina component (prepared in this example) and 12 mL of toluene were connected to a phase settler to ensure solvent reflux to remove the moisture generated during the reaction. The reaction temperature was 135°C. After 20 minutes of reaction, a sample was taken for liquid phase detection. Under these conditions, the yield of lactide was 8.9%, and the average reaction rate within 20 minutes was 8.6 mg min-1 gcat-1 .
对比例5Comparative example 5
H-Beta分子筛颗粒催化剂制备：取H-Beta分子筛粉末1.2g，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用20～30目的筛网过筛收集，再将所得颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛颗粒催化剂。Preparation of H-Beta molecular sieve particle catalyst: Take 1.2g of H-Beta molecular sieve powder, further mix it in a mortar and grind it into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse it into fine particles, and sieve them with a 20-30 mesh mesh to collect them. The resulting particles are then placed in a muffle furnace and calcined at 550°C for 6 hours to obtain H- Beta molecular sieve particle catalyst.
H-Beta分子筛颗粒催化剂催化乳酸合成丙交酯：在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.2g H-Beta分子筛颗粒催化剂(本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，反应20min后取样液相检测。在此条件下，丙交酯的产率为8.1％，20min内平均反应速率为7.8mg min-1gcat-1。H-Beta molecular sieve particle catalyst catalyzes the synthesis of lactide from lactic acid: add 0.5g 96.7wt% lactic acid aqueous solution, 0.2g H-Beta molecular sieve particle catalyst (prepared in this example), 12 mL of toluene was connected to a phase settler to ensure solvent reflux to remove the moisture produced during the reaction. The reaction temperature was 135°C. After 20 minutes of reaction, a sample was taken for liquid phase detection. Under these conditions, the yield of lactide was 8.1%, and the average reaction rate within 20 minutes was 7.8 mg min-1 gcat-1 .
实施例7Example 7
H-Beta分子筛/γ-氧化铝共混颗粒催化剂制备：Preparation of H-Beta molecular sieve/γ-alumina blend particle catalyst:
(1)取H-Beta分子筛粉末1.2g和拟薄水铝石粉末0.6g，按照质量比2：1混合，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用20～30目的筛网过筛收集，得到共混颗粒。(1) Take 1.2g of H-Beta molecular sieve powder and 0.6g of pseudo-boehmite powder, mix them according to the mass ratio of 2:1, further mix in a mortar and grind them into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse into fine particles, and sieve and collect them with a 20-30 mesh screen to obtain blended particles.
(2)再将步骤(1)所得的共混颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛/γ-氧化铝共混颗粒催化剂。(2) The blended particles obtained in step (1) are then calcined in a muffle furnace at a temperature of 550°C for 6 hours to obtain the H-Beta molecular sieve/γ-alumina blended particle catalyst.
H-Beta分子筛/γ-氧化铝共混颗粒催化剂催化乳酸合成丙交酯：H-Beta molecular sieve/γ-alumina blend particle catalyst catalyzes the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.3g H-Beta分子筛/γ-氧化铝共混颗粒催化剂(0.2g H-Beta分子筛活性组分+0.1gγ-氧化铝组分，本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，反应20min后取样液相检测。在此条件下，丙交酯的产率为9.7％，20min内平均反应速率为9.4mg min-1gcat-1。In a 25mL round bottom flask with a magnetic rotor, add 0.5g 96.7wt% lactic acid aqueous solution and 0.3g H-Beta molecular sieve/γ-alumina blended particle catalyst (0.2g H-Beta molecular sieve active component + 0.1gγ- The alumina component (prepared in this example) and 12 mL of toluene were connected to a phase settler to ensure solvent reflux to remove the moisture generated during the reaction. The reaction temperature was 135°C. After 20 minutes of reaction, a sample was taken for liquid phase detection. Under these conditions, the yield of lactide was 9.7%, and the average reaction rate within 20 minutes was 9.4 mg min-1 gcat-1 .
实施例8Example 8
H-Beta分子筛/γ-氧化铝共混颗粒催化剂制备：Preparation of H-Beta molecular sieve/γ-alumina blend particle catalyst:
(1)取H-Beta分子筛粉末1.2g和拟薄水铝石粉末0.4g，按照质量比3：1混合，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用20～30目的筛网过筛收集，得到共混颗粒。(1) Take 1.2g of H-Beta molecular sieve powder and 0.4g of pseudo-boehmite powder, mix them according to the mass ratio of 3:1, further mix in a mortar and grind them into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse into fine particles, and sieve and collect them with a 20-30 mesh screen to obtain blended particles.
(2)再将步骤(1)所得的共混颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛/γ-氧化铝共混颗粒催化剂。(2) The blended particles obtained in step (1) are then calcined in a muffle furnace at a temperature of 550°C for 6 hours to obtain the H-Beta molecular sieve/γ-alumina blended particle catalyst.
H-Beta分子筛/γ-氧化铝共混颗粒催化剂催化乳酸合成丙交酯：H-Beta molecular sieve/γ-alumina blend particle catalyst catalyzes the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.267g H-Beta分子筛/γ-氧化铝共混颗粒催化剂(0.2g H-Beta分子筛活性组分+0.067gγ-氧化铝组分，本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，反应20min后取样液相检测。在此条件下，丙交酯的产率为9.3％，20min内平均反应速率为9.0mg min-1gcat-1。In a 25mL round bottom flask with a magnetic rotor, add 0.5g 96.7wt% lactic acid aqueous solution and 0.267g H-Beta molecular sieve/γ-alumina blended particle catalyst (0.2g H-Beta molecular sieve active component + 0.067gγ- The alumina component (prepared in this example) and 12 mL of toluene were connected to a phase settler to ensure solvent reflux to remove the moisture generated during the reaction. The reaction temperature was 135°C. After 20 minutes of reaction, a sample was taken for liquid phase detection. Under these conditions, the yield of lactide was 9.3%, and the average reaction rate within 20 minutes was 9.0 mg min-1 gcat-1 .
实施例9Example 9
H-Beta分子筛/γ-氧化铝共混颗粒催化剂制备：Preparation of H-Beta molecular sieve/γ-alumina blend particle catalyst:
(1)取H-Beta分子筛粉末1.2g和拟薄水铝石粉末0.3g，按照质量比4：1混合，在研钵中进一步混合并研磨成细小的粉末(100～200目)。随后转移粉末至模具中，用摇杆液压机在10MPa的压力下液压3min将粉末挤压成片。对压成片的粉末再次研磨，使之分散成细小的颗粒，并用20～30目的筛网过筛收集，得到共混颗粒。(1) Take 1.2g of H-Beta molecular sieve powder and 0.3g of pseudo-boehmite powder, mix them according to the mass ratio of 4:1, further mix in a mortar and grind them into fine powder (100~200 mesh). The powder was then transferred to the mold, and the powder was extruded into tablets using a rocker hydraulic press at a pressure of 10 MPa for 3 minutes. Grind the powder pressed into tablets again to disperse into fine particles, and sieve and collect them with a 20-30 mesh screen to obtain blended particles.
(2)再将步骤(1)所得的共混颗粒置于马弗炉中在550℃的温度下煅烧6h，得到H-Beta分子筛/γ-氧化铝共混颗粒催化剂。(2) The blended particles obtained in step (1) are then calcined in a muffle furnace at a temperature of 550°C for 6 hours to obtain the H-Beta molecular sieve/γ-alumina blended particle catalyst.
H-Beta分子筛/γ-氧化铝共混颗粒催化剂催化乳酸合成丙交酯：H-Beta molecular sieve/γ-alumina blend particle catalyst catalyzes the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、0.25g H-Beta分子筛/γ-氧化铝共混颗粒催化剂(0.2g H-Beta分子筛活性组分+0.05gγ-氧化铝组分，本实施例制备得到)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，反应20min后取样液相检测。在此条件下，丙交酯的产率为9.7％，20min内平均反应速率为9.4mg min-1gcat-1。In a 25mL round bottom flask with a magnetic rotor, add 0.5g 96.7wt% lactic acid aqueous solution and 0.25g H-Beta molecular sieve/γ-alumina blended particle catalyst (0.2g H-Beta molecular sieve active component + 0.05gγ- The alumina component (prepared in this example) and 12 mL of toluene were connected to a phase settler to ensure solvent reflux to remove the moisture generated during the reaction. The reaction temperature was 135°C. After 20 minutes of reaction, a sample was taken for liquid phase detection. Under these conditions, the yield of lactide was 9.7%, and the average reaction rate within 20 minutes was 9.4 mg min-1 gcat-1 .
实施例10Example 10
本实施例所用的催化剂如下：The catalysts used in this example are as follows:
本实施例所用的H-Beta分子筛颗粒由对比例1制备得到。The H-Beta molecular sieve particles used in this example were prepared from Comparative Example 1.
本实施例所用的H-Beta分子筛/γ-氧化铝共混颗粒由实施例1制备得到，其中，H-Beta分子筛粉末与拟薄水铝石粉末的质量比为3：1。The H-Beta molecular sieve/γ-alumina blend particles used in this example were prepared from Example 1, in which the mass ratio of H-Beta molecular sieve powder and pseudo-boehmite powder was 3:1.
本实施例所用的H-Beta分子筛/二氧化锡颗粒制备方法同实施例1，不同的是：将拟薄水铝石粉末替换为二氧化锡。The preparation method of H-Beta molecular sieve/tin dioxide particles used in this embodiment is the same as that in Example 1, except that the pseudo-boehmite powder is replaced with tin dioxide.
本实施例所用的H-Beta分子筛/氧化钙颗粒制备方法同实施例1，不同的是：将拟薄水铝石粉末替换为氧化钙。The preparation method of H-Beta molecular sieve/calcium oxide particles used in this embodiment is the same as that in Example 1, except that the pseudo-boehmite powder is replaced with calcium oxide.
本实施例所用的H-Beta分子筛/氧化锌颗粒制备方法同实施例1，不同的是：将拟薄水铝石粉末替换为氧化锌。The preparation method of H-Beta molecular sieve/zinc oxide particles used in this embodiment is the same as that in Example 1, except that the pseudo-boehmite powder is replaced with zinc oxide.
本实施例所用的H-Beta分子筛/二氧化硅颗粒制备方法同实施例1，不同的是：将拟薄水铝石粉末替换为二氧化硅。The preparation method of H-Beta molecular sieve/silica particles used in this embodiment is the same as that in Example 1, except that the pseudo-boehmite powder is replaced with silica.
不同的催化剂催化乳酸合成丙交酯：Different catalysts catalyze the synthesis of lactide from lactic acid:
在25mL带有磁力转子的圆底烧瓶中加入0.5g 96.7wt％的乳酸水溶液、不加催化剂或加0.2～0.3g催化剂(所有催化剂中H-Beta分子筛组分均为0.2g，分别为H-Beta分子筛颗粒、H-Beta分子筛/γ-氧化铝共混颗粒、H-Beta分子筛/二氧化锡颗粒、H-Beta分子筛/氧化钙颗粒、H-Beta分子筛/氧化锌颗粒、H-Beta分子筛/二氧化硅颗粒)、12mL甲苯，上接相沉降器保证溶剂回流以脱除反应中产生的水分，反应温度为135℃，反应20min后取样检测。In a 25mL round-bottomed flask with a magnetic rotor, add 0.5g of 96.7wt% lactic acid aqueous solution without adding a catalyst or adding 0.2 to 0.3g of catalyst (the H-Beta molecular sieve component in all catalysts is 0.2g, respectively H- Beta molecular sieve particles, H-Beta molecular sieve/γ-alumina blend particles, H-Beta molecular sieve/tin dioxide particles, H-Beta molecular sieve/calcium oxide particles, H-Beta molecular sieve/zinc oxide particles, H-Beta molecular sieve/ Silica particles) and 12 mL of toluene were connected to a phase settler to ensure solvent reflux to remove the moisture produced during the reaction. The reaction temperature was 135°C, and samples were taken for detection after 20 minutes of reaction.
在此条件下，H-Beta分子筛颗粒催化合成丙交酯产率为9.7％，20min内平均反应速率为9.4mg min-1gcat-1；H-Beta分子筛/γ-氧化铝颗粒催化合成丙交酯产率为11.5％，20min内平均反应速率为11.1mg min-1gcat-1；H-Beta分子筛/二氧化锡颗粒催化合成丙交酯产率为8.7％，20min内平均反应速率为8.5mg min-1gcat-1；H-Beta分子筛/二氧化硅颗粒催化合成丙交酯产率为4.4％，20min内平均反应速率为4.2mg min-1gcat-1；H-Beta分子筛/氧化钙颗粒催化合成丙交酯产率为2.0％，20min内平均反应速率为1.9mg min-1gcat-1；H-Beta分子筛/氧化锌颗粒催化合成丙交酯产率为2.6％，20min内平均反应速率为2.5mg min-1gcat-1；没有添加催化剂颗粒时催化合成丙交酯产率为1.6％，20min内平均反应速率为1.5mg min-1gcat-1。具体的不同催化剂催化乳酸合成丙交酯的丙交酯产率和平均反应速率见图1所示。Under these conditions, the H-Beta molecular sieve particles catalytically synthesized lactide with a yield of 9.7%, and the average reaction rate within 20 minutes was 9.4 mg min-1 gcat-1 ; H-Beta molecular sieve/γ-alumina particles catalytically synthesized propyl lactide. The yield of lactide is 11.5%, and the average reaction rate within 20 minutes is 11.1mg min-1 gcat-1 ; the yield of lactide synthesized by H-Beta molecular sieve/tin dioxide particles catalytically is 8.7%, and the average reaction rate within 20 minutes is 8.5mg min-1 gcat-1 ; H-Beta molecular sieve/silica particle catalytic synthesis of lactide yield is 4.4%, and the average reaction rate within 20 minutes is 4.2mg min-1 gcat-1 ; H-Beta molecular sieve /Calcium oxide particles catalyzed the synthesis of lactide with a yield of 2.0%, and the average reaction rate within 20 minutes was 1.9 mg min-1 gcat-1 ; H-Beta molecular sieve/zinc oxide particles catalyzed the synthesis of lactide with a yield of 2.6%, The average reaction rate within 20 minutes is 2.5 mg min-1 gcat-1 ; when no catalyst particles are added, the yield of catalytically synthesized lactide is 1.6%, and the average reaction rate within 20 minutes is 1.5 mg min-1 gcat-1 . The specific lactide yield and average reaction rate for the synthesis of lactide from lactic acid catalyzed by different catalysts are shown in Figure 1.
由图中可以得出，H-Beta分子筛/γ-氧化铝共混颗粒催化剂较其它金属氧化物能更好的催化乳酸合成丙交酯。It can be concluded from the figure that the H-Beta molecular sieve/γ-alumina blend particle catalyst can catalyze the synthesis of lactide from lactic acid better than other metal oxides.
本发明提供了一种H-Beta分子筛/γ-氧化铝共混颗粒催化剂及其制备方法与应用的思路及方法，具体实现该技术方案的方法和途径很多，以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。The present invention provides an H-Beta molecular sieve/γ-alumina blended particle catalyst and its preparation method and application ideas and methods. There are many methods and ways to implement the technical solution, and the above are only the preferred ones of the present invention. embodiment, it should be pointed out that those of ordinary skill in the art can make several improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention. All components not specified in this embodiment can be implemented using existing technologies.
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| CN114437017A (en)* | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing lactide from lactic acid |
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| CN114805284A (en)* | 2022-05-11 | 2022-07-29 | 南京大学 | A kind of method for synthesizing lactide by one-step method of high-concentration lactic acid |
| CN115417851A (en)* | 2022-08-30 | 2022-12-02 | 中国科学院长春应用化学研究所 | A kind of method for directly preparing lactide from lactic acid |
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