CN108187682B - Solid base catalyst for synthesizing 4-hydroxybutyl vinyl ether and preparation method and application thereof - Google Patents

Abstract

Translated fromChinese

本发明公开了一种合成4‑羟丁基乙烯基醚的固体碱催化剂及其制备方法和应用。本发明催化剂以二氧化锆（ZrO₂）为载体，Cu、K双组分为活性中心，各组分的质量百分比为：活性组分氧化亚铜（Cu₂O）为1%~15%，氧化钾（K₂O）为10~35%，载体ZrO₂为50%~89%。制备方法为：将铜盐、钾盐与锆盐混合，充分研磨后，加入去离子水搅拌均匀，然后经干燥、焙烧和液相还原等步骤制得催化剂。该方法工艺简单，操作性强，易于工业化生产，且成本低廉。所制备的催化剂用于乙炔法合成4‑羟丁基乙烯基醚，目标产物收率可达67.39%，解决了现有固体碱催化剂催化活性低、选择性差的问题。The invention discloses a solid base catalyst for synthesizing 4-hydroxybutyl vinyl ether and a preparation method and application thereof. The catalyst of the invention uses zirconium dioxide (ZrO₂ ) as a carrier, Cu and K two components as active centers, and the mass percentage of each component is: the active component cuprous oxide (Cu₂ O) is 1% to 15%, Potassium oxide (K₂ O) is 10~35%, and carrier ZrO₂ is 50%~89%. The preparation method is as follows: mixing copper salt, potassium salt and zirconium salt, fully grinding, adding deionized water and stirring evenly, and then drying, roasting and liquid-phase reduction to prepare the catalyst. The method has the advantages of simple process, strong operability, easy industrial production and low cost. The prepared catalyst is used for synthesizing 4-hydroxybutyl vinyl ether by acetylene method, and the yield of the target product can reach 67.39%, which solves the problems of low catalytic activity and poor selectivity of the existing solid base catalyst.

Description

Translated fromChinese

一种合成4-羟丁基乙烯基醚的固体碱催化剂及其制备方法和应用A kind of solid base catalyst for synthesizing 4-hydroxybutyl vinyl ether and preparation method thereofapplication

技术领域technical field

本发明涉及一种合成4-羟丁基乙烯基醚的固体碱催化剂及其制备方法和应用，属于催化剂制备技术领域。The invention relates to a solid base catalyst for synthesizing 4-hydroxybutyl vinyl ether, a preparation method and application thereof, and belongs to the technical field of catalyst preparation.

背景技术Background technique

乙烯基醚是一类重要的高聚物单体及有机合成中间体，其均聚物和共聚物由于具有低毒性、无味、低收缩、高强度、高黏合性、可溶性、优良的柔韧性和易于合成等特点，可作为活性稀释剂用于环氧树脂、丙烯酸树脂和不饱和聚酯等体系，也用于制作粘合剂、涂料、油类粘度改性剂、增塑剂、润滑剂、喷发胶、弹性体、泡沫材料、杀虫剂和表面保护材料等。作为有机合成中间体，乙烯基醚可用于合成四甲氧基丙烷、γ-甲基吡啶、2-氨基嘧啶以及性能优良的杀菌剂戊二醛等。此外，乙烯基醚还广泛应用于香料、调味剂以及药物产品等领域。Vinyl ether is an important class of polymer monomers and organic synthesis intermediates. Its homopolymers and copolymers have low toxicity, odorless, low shrinkage, high strength, high adhesion, solubility, excellent flexibility and It is easy to synthesize and can be used as a reactive diluent in epoxy resin, acrylic resin and unsaturated polyester systems, and also used in the production of adhesives, coatings, oil viscosity modifiers, plasticizers, lubricants, Hair sprays, elastomers, foams, insecticides and surface protection materials, etc. As organic synthesis intermediates, vinyl ethers can be used to synthesize tetramethoxypropane, γ-picoline, 2-aminopyrimidine and the excellent fungicide glutaraldehyde. In addition, vinyl ethers are also widely used in the fields of spices, flavoring agents and pharmaceutical products.

4-羟丁基乙烯基醚是乙烯基醚类化合物中重要的一种。在氢氧化钾的存在下，1,4-丁二醇与乙炔反应，可生成4-羟丁基乙烯基醚(HBVE)。反应式如下：

4-Hydroxybutyl vinyl ether is an important one of vinyl ether compounds. In the presence of potassium hydroxide, 1,4-butanediol reacts with acetylene to produce 4-hydroxybutyl vinyl ether (HBVE). The reaction formula is as follows:

1,4-丁二醇含有两个羟基，在一个羟基与一分子乙炔反应生成HBVE后，理论上还可继续与另一分子乙炔反应生成1,4-丁二醇二乙烯基醚(DBVE)，但由于两个羟基距离较近，空间位阻使得另一个羟基不易与乙炔分子反应，因而二乙烯基醚收率较低。反应式如下：1,4-Butanediol contains two hydroxyl groups. After one hydroxyl group reacts with a molecule of acetylene to generate HBVE, it can theoretically continue to react with another molecule of acetylene to generate 1,4-butanediol divinyl ether (DBVE). However, due to the close distance between the two hydroxyl groups, steric hindrance makes the other hydroxyl group not easy to react with acetylene molecules, so the yield of divinyl ether is low. The reaction formula is as follows:

同时，以KOH为催化剂的均相反应过程中，不可避免的会产生诸多副反应，具体过程如下：At the same time, in the homogeneous reaction process using KOH as a catalyst, many side reactions will inevitably occur. The specific process is as follows:

1,4-丁二醇发生分子内闭环脱水，生成四氢呋喃，1,4-Butanediol undergoes intramolecular ring closure dehydration to generate tetrahydrofuran,

乙炔环三聚反应生成苯，Acetylene ring trimerization produces benzene,

羟丁基乙烯基醚发生自身缩合，生成环状缩醛副产物—2-甲基-1,3-二氧庚环(MDOP)，Hydroxybutyl vinyl ether undergoes self-condensation to generate a cyclic acetal by-product—2-methyl-1,3-dioxane (MDOP),

均相催化反应过程产生的众多副产物，不仅导致目标产物选择性降低，而且会造成分离困难。The numerous by-products generated in the homogeneous catalytic reaction process not only lead to a decrease in the selectivity of the target product, but also cause separation difficulties.

德国专利(GB773331)介绍了以KOH作为催化剂，乙炔法制备二元醇单乙烯基醚的方法。该专利通过在反应柱内填充陶瓷填料，增加乙炔与二元醇(乙二醇、丙二醇、丁二醇、己二醇等)接触的时间，以降低环状缩醛副产物产生，但反应产物中仍会含有5～20％的环状缩醛副产物。German patent (GB773331) introduces a method for preparing glycol monovinyl ether by acetylene method with KOH as a catalyst. This patent increases the contact time of acetylene and diols (ethylene glycol, propylene glycol, butanediol, hexanediol, etc.) by filling ceramic fillers in the reaction column to reduce the generation of cyclic acetal by-products, but the reaction products There will still be 5 to 20% of cyclic acetal by-products.

中国专利(CN101898939)同样以KOH作为催化剂，采用乙炔法制备4-羟丁基乙烯基醚。该专利具体在反应体系中加入了二甲基亚砜作为乙炔的溶剂，通过延长乙炔与1,4-丁二醇的接触时间，提高了4-羟丁基乙烯基醚的含量，降低了环状缩醛副产物的含量；进一步通过加入表面活性剂十八烷基三甲基氯化铵，也促进了1,4-丁二醇转化率的提高。Chinese patent (CN101898939) also uses KOH as a catalyst to prepare 4-hydroxybutyl vinyl ether by acetylene method. In this patent, dimethyl sulfoxide is added as a solvent for acetylene in the reaction system. By prolonging the contact time between acetylene and 1,4-butanediol, the content of 4-hydroxybutyl vinyl ether is increased, and the cyclic The content of the acetal by-products was further increased by adding the surfactant octadecyltrimethylammonium chloride, which also promoted the improvement of the conversion rate of 1,4-butanediol.

美国专利(US20060205984)报道了以醇钾为催化剂，通过甲醇与乙炔反应连续制备甲基乙烯基醚的方法。与KOH作为催化剂相比，采用醇钾作为催化剂促进了乙炔的转化。US Patent (US20060205984) reported a method for continuously preparing methyl vinyl ether by reacting methanol and acetylene with potassium alkoxide as a catalyst. The use of potassium alkoxides as catalysts promoted the conversion of acetylene compared to KOH as catalysts.

上述以KOH或醇钾为催化剂的均相催化反应体系，通过填充陶瓷填料，改变反应溶剂，额外添加表面活性剂，或改由醇钾代替KOH等措施，在一定程度上降低了环状缩醛副产物的生成，提高了4-羟丁基乙烯基醚的含量，但仍存在副产物多、催化剂分离困难、不可重复使用、设备腐蚀和环境污染等问题。The above-mentioned homogeneous catalytic reaction system using KOH or potassium alkoxide as the catalyst reduces the cyclic acetal to a certain extent by filling ceramic fillers, changing the reaction solvent, adding additional surfactants, or replacing KOH with potassium alkoxide. The formation of by-products increases the content of 4-hydroxybutyl vinyl ether, but there are still problems such as many by-products, difficult catalyst separation, non-reusability, equipment corrosion and environmental pollution.

彭春睿[彭春睿.羟丁基乙烯基醚的合成工艺研究[D].南京林业大学,2011.]采用等体积浸渍法制备了KOH/Al₂O₃，K₂CO₃/Al₂O₃和KOH/AC等固体碱催化剂，并用于乙炔法催化合成4-羟丁基乙烯基醚。其中，与K₂CO₃/Al₂O₃和KOH/AC等相比，KOH/Al₂O₃的催化活性最好，但其催化反应的产物中目标产物4-羟丁基乙烯基醚的含量也仅为10.8％。Peng Chunrui [Peng Chunrui. Study on the synthesis process of hydroxybutyl vinyl ether [D]. Nanjing Forestry University, 2011.] Preparation of KOH/Al₂ O₃ , K₂ CO₃ /Al₂ O₃ and KOH by equal volume impregnation method /AC and other solid base catalysts, and used in the acetylene process to catalyze the synthesis of 4-hydroxybutyl vinyl ether. Among them, compared with K₂ CO₃ /Al₂ O₃ and KOH/AC, the catalytic activity of KOH/Al₂ O₃ is the best, but the target product 4-hydroxybutyl vinyl ether in its catalytic reaction product has the highest catalytic activity. The content is also only 10.8%.

众所周知，化学工业带来的环境污染日益严重，发展绿色化学和环境友好催化工艺已刻不容缓。固体碱催化剂在环境友好新催化工艺中发挥了重要的作用，尤其在精细化学品催化合成中备受研究者的青睐。然而，就乙炔法合成羟丁基乙烯基醚而言，现有的固体碱催化剂主要存在催化活性低、无法循环使用等问题。因此，通过催化剂组成结构的合理设计、制备方法的优化创新，提高固体碱催化剂的催化活性、循环使用性能，是当前亟待解决的问题。As we all know, the environmental pollution caused by the chemical industry is becoming more and more serious, and it is imperative to develop green chemistry and environmentally friendly catalytic processes. Solid base catalysts play an important role in environmentally friendly new catalytic processes, especially in the catalytic synthesis of fine chemicals. However, for the synthesis of hydroxybutyl vinyl ether by the acetylene method, the existing solid base catalysts mainly have problems such as low catalytic activity and inability to be recycled. Therefore, it is an urgent problem to improve the catalytic activity and recycling performance of solid base catalysts through rational design of catalyst composition and optimization and innovation of preparation methods.

发明内容SUMMARY OF THE INVENTION

本发明旨在提供一种合成4-羟丁基乙烯基醚的固体碱催化剂及其制备方法，本发明还提供了所述催化剂在合成4-羟丁基乙烯基醚中的应用。The present invention aims to provide a solid base catalyst for synthesizing 4-hydroxybutyl vinyl ether and a preparation method thereof, and the present invention also provides the application of the catalyst in synthesizing 4-hydroxybutyl vinyl ether.

本发明提供了一种合成4-羟丁基乙烯基醚的固体碱催化剂，该催化剂为Cu₂O-K₂O/ZrO₂，以二氧化锆(ZrO₂)为载体，以氧化亚铜(Cu₂O)、氧化钾(K₂O)为活性组分，各组分的质量百分比为：The invention provides a solid base catalyst for synthesizing 4-hydroxybutyl vinyl ether. The catalyst is Cu₂ OK₂ O/ZrO₂ , uses zirconium dioxide (ZrO₂ ) as a carrier, and uses cuprous oxide (Cu₂ O), potassium oxide (K₂ O) are active components, and the mass percentage of each component is:

活性组分Cu₂O的质量百分含量为1％～15％，K₂O的质量百分含量为10～35％，载体ZrO₂的质量百分含量为50％～89％。The mass percentage content of active component Cu₂ O is 1%-15%, the mass percentage content of K₂ O is 10-35%, and the mass percentage content of carrier ZrO₂ is 50%-89%.

优选地，所述催化剂中，各组分的质量百分比为：Preferably, in the catalyst, the mass percentage of each component is:

活性组分Cu₂O：5％～10％，Active component Cu₂ O: 5% to 10%,

活性组分K₂O：15％～30％，Active component K₂ O: 15% to 30%,

载体ZrO₂：60％～80％。Carrier ZrO₂ : 60% to 80%.

本发明提供了一种合成4-羟丁基乙烯基醚的固体碱催化剂的制备方法，包括以下步骤：The invention provides a preparation method of a solid base catalyst for synthesizing 4-hydroxybutyl vinyl ether, comprising the following steps:

(1)称取铜盐、钾盐与锆盐混合，充分研磨后，加入去离子水搅拌均匀，其中锆盐浓度为0.541mol/L～2.705mol/L，所述的铜盐、钾盐与锆盐质量比为0.001～0.139:0.009～0.689:1；(1) Weigh copper salt, potassium salt and mix with zirconium salt, after fully grinding, add deionized water and stir evenly, wherein the zirconium salt concentration is 0.541mol/L～2.705mol/L, and the described copper salt, potassium salt and The mass ratio of zirconium salt is 0.001～0.139:0.009～0.689:1;

(2)将上述溶液在80～150℃干燥3～15h，然后在空气气氛中300～700℃焙烧1～12h，得到CuO-K₂O/ZrO₂；(2) drying the above solution at 80-150°C for 3-15h, and then calcining at 300-700°C for 1-12h in an air atmosphere to obtain CuO-K₂ O/ZrO₂ ;

(3)配制浓度为0.01～0.45mol/L的还原剂水溶液，磁力搅拌下滴入5～15％氨水，调节溶液pH为8～11，将步骤(2)所得的CuO-K₂O/ZrO₂加入到上述溶液中，在70～100℃下，搅拌回流0.5～1h；(3) preparing a reducing agent aqueous solution with a concentration of 0.01 to 0.45 mol/L, dripping 5 to 15% ammonia water under magnetic stirring, adjusting the pH of the solution to 8 to 11, and mixing the CuO-K₂ O/ZrO obtained in step (2)₂ is added to the above solution, at 70～100℃, stirring and refluxing for 0.5～1h;

所述的还原剂与CuO-K₂O/ZrO₂的质量比为0.001～0.154:1；The mass ratio of the reducing agent to CuO-K₂ O/ZrO₂ is 0.001-0.154:1;

(4)反应后经过滤，将滤饼在60～80℃下干燥6～10h，即得到Cu₂O-K₂O/ZrO₂固体碱催化剂。(4) Filtration after the reaction, and drying the filter cake at 60-80° C. for 6-10 hours to obtain Cu₂ OK₂ O/ZrO₂ solid base catalyst.

上述制备方法中，所述铜盐是氯化铜、硫酸铜、硝酸铜、醋酸铜中的一种或多种。In the above preparation method, the copper salt is one or more of copper chloride, copper sulfate, copper nitrate and copper acetate.

上述制备方法中，所述钾盐是硝酸钾、碳酸钾、氢氧化钾、氯化钾、碳酸氢钾、硫酸钾中的一种或多种。In the above preparation method, the potassium salt is one or more of potassium nitrate, potassium carbonate, potassium hydroxide, potassium chloride, potassium bicarbonate and potassium sulfate.

上述制备方法中，所述锆盐是硝酸锆、硝酸氧锆、氧氯化锆中的一种或多种。In the above preparation method, the zirconium salt is one or more of zirconium nitrate, zirconium oxynitrate and zirconium oxychloride.

上述制备方法中，步骤(2)中，所述溶液在100～130℃下干燥5～8h，在空气气氛中400～600℃下焙烧3～8h。In the above preparation method, in step (2), the solution is dried at 100-130° C. for 5-8 hours, and calcined at 400-600° C. for 3-8 hours in an air atmosphere.

上述制备方法中，所述还原剂为抗坏血酸、甲醛、乙醛、硼氢化钠、葡萄糖、不饱和醇、柠檬酸钠、水合肼中的一种或多种。In the above preparation method, the reducing agent is one or more of ascorbic acid, formaldehyde, acetaldehyde, sodium borohydride, glucose, unsaturated alcohol, sodium citrate, and hydrazine hydrate.

本发明提供了上述固体碱催化剂在乙炔法合成4-羟丁基乙烯基醚中的应用。具体地，将本发明所得催化剂用于乙炔法合成4-羟丁基乙烯基醚中：将1,4-丁二醇和Cu₂O-K₂O/ZrO₂催化剂加入到100ml的三口烧瓶中，Cu₂O-K₂O/ZrO₂和1,4-丁二醇的质量比为10～30：100，通入乙炔，并控制乙炔流量为0.03～0.07L/min，启动搅拌，油浴加热至140～160℃，反应5～12h。反应结束后，过滤反应液回收催化剂，经乙醇洗涤后晾干，用于循环使用。The present invention provides the application of the above-mentioned solid base catalyst in synthesizing 4-hydroxybutyl vinyl ether by acetylene method. Specifically, the catalyst obtained by the present invention is used in acetylene method to synthesize 4-hydroxybutyl vinyl ether: 1,4-butanediol and Cu₂ OK₂ O/ZrO₂ catalyst are added into a 100ml there-necked flask, Cu₂ The mass ratio of OK₂ O/ZrO₂ and 1,4-butanediol is 10～30:100, pass acetylene, and control the flow rate of acetylene to 0.03～0.07L/min, start stirring, heat the oil bath to 140～160 ℃, the reaction is 5～12h. After the reaction, the reaction solution was filtered to recover the catalyst, washed with ethanol and then air-dried for recycling.

将本发明制备的Cu₂O-K₂O/ZrO₂催化剂用于乙炔法合成4-羟丁基乙烯基醚，目标产物收率能达到67.39％。The Cu₂ OK₂ O/ZrO₂ catalyst prepared by the invention is used for synthesizing 4-hydroxybutyl vinyl ether by acetylene method, and the yield of the target product can reach 67.39%.

本发明的有益效果：Beneficial effects of the present invention:

(1)本发明所制备的催化剂为固体碱，避免了使用KOH或醇钾等均相催化体系中普遍存在的副产物多、催化剂分离困难、不可重复使用、设备腐蚀和环境污染等弊端。(1) The catalyst prepared by the present invention is a solid base, which avoids the disadvantages such as many by-products, difficult catalyst separation, non-reusable, equipment corrosion and environmental pollution that are commonly present in homogeneous catalytic systems such as KOH or potassium alkoxide.

(2)与现有固体碱催化剂相比，该催化剂具有催化活性高、目标产物收率高以及可循环使用等优点。(2) Compared with the existing solid base catalyst, the catalyst has the advantages of high catalytic activity, high yield of target product and recyclable use.

(3)该催化剂制备工艺简单，原料来源广泛，价格低廉，对人体和环境无害，易于实现工业化生产，具有良好的应用前景。(3) The catalyst has a simple preparation process, a wide range of raw material sources, a low price, is harmless to human body and the environment, is easy to realize industrial production, and has a good application prospect.

具体实施方式Detailed ways

下面通过实施例来进一步说明本发明，但不局限于以下实施例。The present invention is further illustrated by the following examples, but is not limited to the following examples.

实施例1：Example 1:

称取0.84g Cu(NO₃)₂·3H₂O、0.89g KOH与15.69g ZrOCl₂·8H₂O混合，充分研磨后，加入一定量的去离子水搅拌均匀，在120℃下干燥6h，在空气气氛中500℃下焙烧4h，配制40mL 0.18mol/L的葡萄糖溶液，磁力搅拌下滴加10％氨水，调节溶液pH为10，在90℃下，将CuO-K₂O/ZrO₂加入到上述溶液中，搅拌回流1h，反应后经过滤，将滤饼在60℃下干燥6h，即得到Cu₂O-K₂O/ZrO₂固体碱催化剂。Weigh 0.84g Cu(NO₃ )₂ ·3H₂ O, 0.89g KOH and 15.69g ZrOCl₂ ·8H₂ O and mix, after fully grinding, add a certain amount of deionized water, stir evenly, and dry at 120 ℃ for 6h, Bake at 500 °C for 4 h in an air atmosphere to prepare 40 mL of 0.18 mol/L glucose solution, add 10% ammonia water dropwise under magnetic stirring, adjust the pH of the solution to 10, at 90 °C, add CuO-K₂ O/ZrO₂ Add to the above solution, stir and reflux for 1 hour, filter after the reaction, and dry the filter cake at 60° C. for 6 hours to obtain Cu₂ OK₂ O/ZrO₂ solid base catalyst.

将30g 1,4-丁二醇和4.5g上述催化剂加入到100ml的三口烧瓶中，通入乙炔，并控制乙炔流量为0.04L/min，启动搅拌，油浴加热至150℃，反应9h后，使用气相色谱OV-1701分析反应液，4-羟丁基乙烯基醚收率为67.39％，副产物总收率低于0.17％。Add 30g of 1,4-butanediol and 4.5g of the above catalyst into a 100ml three-necked flask, pass in acetylene, and control the acetylene flow rate to 0.04L/min, start stirring, heat the oil bath to 150°C, react for 9h, use The reaction solution was analyzed by gas chromatography OV-1701, and the yield of 4-hydroxybutyl vinyl ether was 67.39%, and the total yield of by-products was less than 0.17%.

气相色谱的检测条件如下：The detection conditions of gas chromatography are as follows:

仪器：Agilent 7890B型气相色谱仪Instrument: Agilent 7890B gas chromatograph

柱型：OV-1701Column type: OV-1701

气化温度：240℃Gasification temperature: 240℃

检测温度：280℃Detection temperature: 280℃

柱室温度(程序升温)：初温80℃，恒温1～5min，升温速率20℃/min，终温160℃。Column room temperature (programmed temperature): initial temperature 80°C, constant temperature 1-5min, heating rate 20°C/min, final temperature 160°C.

气体表压：Gas gauge pressure:

氮气：0.08MPaNitrogen: 0.08MPa

氢气：0.05MPaHydrogen: 0.05MPa

空气：0.1MPaAir: 0.1MPa

进样量：0.02μL。Injection volume: 0.02 μL.

实施例2Example 2

将实施例1中Cu(NO₃)₂·3H₂O、KOH与ZrOCl₂·8H₂O的质量分别改为0.28g、0.4g和13.08g，葡萄糖溶液改为抗坏血酸溶液，采用同样的方法制得Cu₂O-K₂O/ZrO₂固体碱催化剂。In Example 1, the masses of Cu(NO₃ )₂ ·3H₂ O, KOH and ZrOCl₂ ·8H₂ O were changed to 0.28g, 0.4g and 13.08g respectively, the glucose solution was changed to ascorbic acid solution, and the same method was used to prepare Obtained Cu₂ OK₂ O/ZrO₂ solid base catalyst.

采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为60.52％，副产物总收率低于0.41％。Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 60.52%, and the total yield of by-products was lower than 0.41%.

实施例3Example 3

将实施例1中Cu(NO₃)₂·3H₂O、KOH和ZrOCl₂·8H₂O分别改为CuSO₄·5H₂O、K₂CO₃和Zr(NO₃)₄·5H₂O，干燥温度改为110℃，采用同样的方法制得Cu₂O-K₂O/ZrO₂固体碱催化剂。Change Cu(NO₃ )₂ ·3H₂ O, KOH and ZrOCl₂ ·8H₂ O in Example 1 to CuSO₄ ·5H₂ O, K₂ CO₃ and Zr(NO₃ )₄ ·5H₂ O, respectively, The drying temperature was changed to 110°C, and the Cu₂ OK₂ O/ZrO₂ solid base catalyst was prepared by the same method.

采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为62.18％，副产物总收率低于0.36％。Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 62.18%, and the total yield of by-products was lower than 0.36%.

实施例4Example 4

将实施例1中Cu(NO₃)₂·3H₂O、KOH和ZrOCl₂·8H₂O分别改为Cu(CH₃COO)₂·H₂O、KNO₃和ZrO(NO₃)₂·2H₂O，葡萄糖溶液改为乙醛溶液，采用同样的方法制得Cu₂O-K₂O/ZrO₂固体碱催化剂。Change Cu(NO₃ )₂ ·3H₂ O, KOH and ZrOCl₂ ·8H₂ O in Example 1 to Cu(CH₃ COO)₂ ·H₂ O, KNO₃ and ZrO(NO₃ )₂ ·2H, respectively₂ O, glucose solution was changed to acetaldehyde solution, and Cu₂ OK₂ O/ZrO₂ solid base catalyst was prepared by the same method.

采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为60.35％，副产物总收率低于0.42％。Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 60.35%, and the total yield of by-products was lower than 0.42%.

实施例5Example 5

将实施例1中Cu(NO₃)₂·3H₂O、KOH与ZrOCl₂·8H₂O分别改为CuCl₂、KHCO₃和Zr(NO₃)₄，葡萄糖溶液改为硼氢化钠溶液，焙烧温度改为450℃，采用同样的方法制得Cu₂O-K₂O/ZrO₂固体碱催化剂。In Example 1, Cu(NO₃ )₂ ·3H₂ O, KOH and ZrOCl₂ ·8H₂ O were changed to CuCl₂ , KHCO₃ and Zr(NO₃ )₄ respectively, the glucose solution was changed to sodium borohydride solution, and the calcination The temperature was changed to 450℃, and the Cu₂ OK₂ O/ZrO₂ solid base catalyst was prepared by the same method.

采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为63.47％，副产物总收率低于0.32％。Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 63.47%, and the total yield of by-products was lower than 0.32%.

实施例6Example 6

将实施例1中Cu(NO₃)₂·3H₂O、KOH与ZrOCl₂·8H₂O的质量分别改为0.79g、0.94g和13.58g，葡萄糖溶液改为抗坏血酸溶液，干燥温度改为100℃，采用同样的方法制得Cu₂O-K₂O/ZrO₂固体碱催化剂。The masses of Cu(NO₃ )₂ ·3H₂ O, KOH and ZrOCl₂ ·8H₂ O in Example 1 were changed to 0.79g, 0.94g and 13.58g respectively, the glucose solution was changed to ascorbic acid solution, and the drying temperature was changed to 100 ℃, using the same method to prepare Cu₂ OK₂ O/ZrO₂ solid base catalyst.

采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为56.81％，副产物总收率低于0.47％。Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 56.81%, and the total yield of by-products was lower than 0.47%.

实施例7Example 7

将实施例1中Cu(NO₃)₂·3H₂O、KOH与ZrOCl₂·8H₂O的质量分别改为0.79g、0.94g和13.58g，干燥温度改为100℃，焙烧温度改为400℃，采用同样的方法制得Cu₂O-K₂O/ZrO₂固体碱催化剂。In Example 1, the masses of Cu(NO₃ )₂ ·3H₂ O, KOH and ZrOCl₂ ·8H₂ O were changed to 0.79g, 0.94g and 13.58g respectively, the drying temperature was changed to 100°C, and the calcination temperature was changed to 400 ℃, using the same method to prepare Cu₂ OK₂ O/ZrO₂ solid base catalyst.

采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为60.75％，副产物总收率低于0.39％。Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 60.75%, and the total yield of by-products was lower than 0.39%.

实施例8Example 8

将实施例1中葡萄糖溶液改为柠檬酸钠溶液，氨水质量分数改为15％，调节溶液pH为9，采用同样的方法制得Cu₂O-K₂O/ZrO₂固体碱催化剂。The glucose solution in Example 1 was changed to sodium citrate solution, the mass fraction of ammonia water was changed to 15%, the pH of the solution was adjusted to 9, and the Cu₂ OK₂ O/ZrO₂ solid base catalyst was prepared by the same method.

采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为65.28％，副产物总收率低于0.22％。Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 65.28%, and the total yield of by-products was lower than 0.22%.

实施例9Example 9

将实施例1中干燥温度改为130℃，焙烧温度改为600℃，还原温度改为75℃，采用同样的方法制得Cu₂O-K₂O/ZrO₂固体碱催化剂。In Example 1, the drying temperature was changed to 130°C, the calcination temperature was changed to 600°C, and the reduction temperature was changed to 75°C, and the Cu₂ OK₂ O/ZrO₂ solid base catalyst was prepared by the same method.

采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为59.36％，副产物总收率低于0.43％。Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 59.36%, and the total yield of by-products was lower than 0.43%.

实施例10Example 10

将实施例1中葡萄糖溶液改为柠檬酸钠溶液，还原温度改为85℃，回流时间改为0.5h，采用同样的方法制得Cu₂O-K₂O/ZrO₂固体碱催化剂。The glucose solution in Example 1 was changed to sodium citrate solution, the reduction temperature was changed to 85°C, and the reflux time was changed to 0.5h, and the Cu₂ OK₂ O/ZrO₂ solid base catalyst was prepared by the same method.

采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为66.23％，副产物总收率低于0.21％。Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 66.23%, and the total yield of by-products was lower than 0.21%.

实施例11Example 11

将实施例1评价条件中Cu₂O-K₂O/ZrO₂和1,4-丁二醇的质量比改为10：100，乙炔流量改为0.06L/min，油浴温度改为145℃，其他条件不变，取实施例1制备的Cu₂O-K₂O/ZrO₂固体碱催化剂用于反应，4-羟丁基乙烯基醚收率达到62.73％，副产物总收率低于0.27％。In the evaluation conditions of Example 1, the mass ratio of Cu₂ OK₂ O/ZrO₂ and 1,4-butanediol was changed to 10:100, the flow rate of acetylene was changed to 0.06L/min, the temperature of the oil bath was changed to 145℃, and other The conditions remained unchanged, the Cu₂ OK₂ O/ZrO₂ solid base catalyst prepared in Example 1 was used for the reaction, the yield of 4-hydroxybutyl vinyl ether reached 62.73%, and the total yield of by-products was lower than 0.27%.

实施例12Example 12

将实施例1评价条件中Cu₂O-K₂O/ZrO₂和1,4-丁二醇的质量比改为20：100，乙炔流量改为0.03L/min，反应时间改为5h，其他条件不变，取实施例1制备的Cu₂O-K₂O/ZrO₂固体碱催化剂用于反应，4-羟丁基乙烯基醚收率为63.27％，副产物总收率低于0.26％。In the evaluation conditions of Example 1, the mass ratio of Cu₂ OK₂ O/ZrO₂ and 1,4-butanediol was changed to 20:100, the acetylene flow rate was changed to 0.03L/min, the reaction time was changed to 5h, and other conditions were not changed. Variation, taking the Cu₂ OK₂ O/ZrO₂ solid base catalyst prepared in Example 1 for the reaction, the yield of 4-hydroxybutyl vinyl ether was 63.27%, and the total yield of by-products was lower than 0.26%.

实施例13Example 13

将实施例1评价条件中乙炔流量改为0.07L/min，油浴温度改为140℃，反应时间改为11h，其他条件不变，取实施例1制备的Cu₂O-K₂O/ZrO₂固体碱催化剂用于反应，4-羟丁基乙烯基醚收率为63.51％，副产物总收率低于0.25％。In the evaluation conditions of Example 1, the acetylene flow rate was changed to 0.07L/min, the oil bath temperature was changed to 140°C, the reaction time was changed to 11h, and other conditions remained unchanged, and the Cu₂ OK₂ O/ZrO₂ solid prepared in Example 1 was taken. The base catalyst was used for the reaction, the yield of 4-hydroxybutyl vinyl ether was 63.51%, and the total yield of by-products was less than 0.25%.

实施例14Example 14

将实施例1评价条件中Cu₂O-K₂O/ZrO₂和1,4-丁二醇的质量比改为20:100，乙炔流量改为0.07L/min，油浴温度改为140℃，反应时间改为8h，其他条件不变，取实施例1制备的Cu₂O-K₂O/ZrO₂固体碱催化剂用于反应，4-羟丁基乙烯基醚收率为64.25％，副产物总收率低于0.24％。In the evaluation conditions of Example 1, the mass ratio of Cu₂ OK₂ O/ZrO₂ and 1,4-butanediol was changed to 20:100, the flow rate of acetylene was changed to 0.07L/min, and the temperature of the oil bath was changed to 140°C. The time was changed to 8h, and other conditions remained unchanged. The Cu₂ OK₂ O/ZrO₂ solid base catalyst prepared in Example 1 was used for the reaction. The yield of 4-hydroxybutyl vinyl ether was 64.25%, and the total yield of by-products was 64.25%. below 0.24%.

催化剂的循环性能测试：Cycle performance test of catalyst:

实施例15Example 15

回收实施例1中的催化剂，标记为Cu₂O-K₂O/ZrO₂-1。采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为60.74％，副产物总收率低于0.39％。The catalyst in Example 1 was recovered, labeled Cu₂ OK₂ O/ZrO₂ -1. Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 60.74%, and the total yield of by-products was lower than 0.39%.

实施例16Example 16

回收实施例15中的催化剂，标记为Cu₂O-K₂O/ZrO₂-2。采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为58.25％，副产物总收率低于0.44％。The catalyst in Example 15 was recovered, labeled Cu₂ OK₂ O/ZrO₂ -2. Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 58.25%, and the total yield of by-products was lower than 0.44%.

实施例17Example 17

回收实施例16中的催化剂，标记为Cu₂O-K₂O/ZrO₂-3。采用实施例1评价条件，在上述评价条件下，4-羟丁基乙烯基醚收率为57.18％，副产物总收率低于0.45％。The catalyst in Example₁₆ was recovered, labeled_Cu2OK2O /_ZrO2-3 . Using the evaluation conditions of Example 1, under the above evaluation conditions, the yield of 4-hydroxybutyl vinyl ether was 57.18%, and the total yield of by-products was lower than 0.45%.

本发明中的催化剂，使用后分离回收方便，实施例15～17说明，该催化剂的循环性能好，可重复使用。The catalyst in the present invention is easy to separate and recover after use. Examples 15 to 17 illustrate that the catalyst has good cycle performance and can be reused.

Claims (10)

Translated fromChinese

1.一种合成4-羟丁基乙烯基醚的固体碱催化剂，其特征在于：所述催化剂为Cu₂O-K₂O/ZrO₂，以二氧化锆为载体，以氧化亚铜、氧化钾为活性组分，各组分的质量百分比为：1. a solid base catalyst for synthesizing 4-hydroxybutyl vinyl ether, is characterized in that: described catalyzer is Cu₂ OK₂ O/ZrO₂ , takes zirconium dioxide as carrier, takes cuprous oxide and potassium oxide as Active components, the mass percentage of each component is:活性组分氧化亚铜：1%~15%，Active component cuprous oxide: 1%~15%,氧化钾：10~35%，Potassium oxide: 10~35%,载体：50%~89%。Carrier: 50%~89%.2.根据权利要求1所述的合成4-羟丁基乙烯基醚的固体碱催化剂，其特征在于：所述催化剂中，各组分的质量百分比为：2. the solid base catalyst of synthesizing 4-hydroxybutyl vinyl ether according to claim 1, is characterized in that: in the described catalyzer, the mass percent of each component is:活性组分Cu₂O：5%~10%，Active component Cu₂ O: 5%~10%,活性组分K₂O：15%~30%，Active component K₂ O: 15%~30%,载体ZrO₂：60%~80%。Carrier ZrO₂ : 60%~80%.3.一种权利要求1或2所述的合成4-羟丁基乙烯基醚的固体碱催化剂的制备方法，其特征在于：包括以下步骤：3. the preparation method of the solid base catalyst of the synthetic 4-hydroxybutyl vinyl ether described in claim 1 or 2, is characterized in that: may further comprise the steps:（1）称取铜盐、钾盐与锆盐混合，充分研磨后，加入去离子水搅拌均匀，其中锆盐浓度为0.541mol/L~2.705 mol/L；(1) Weigh copper salt, potassium salt and zirconium salt and mix, after fully grinding, add deionized water and stir evenly, wherein the concentration of zirconium salt is 0.541mol/L~2.705mol/L;（2）将上述溶液在80~150 ℃干燥3~15 h，然后在空气气氛中300~700 ℃焙烧1~12 h，得到CuO-K₂O/ZrO₂；(2) drying the above solution at 80-150 ℃ for 3-15 h, and then calcining at 300-700 ℃ for 1-12 h in an air atmosphere to obtain CuO-K₂ O/ZrO₂ ;（3）配制浓度为0.01~0.45 mol/L的还原剂水溶液，磁力搅拌下滴入5~15%氨水，调节溶液pH为8~11，将步骤（2）所得的CuO-K₂O/ZrO₂加入到上述溶液中，在70~100 ℃下，搅拌回流0.5~1 h；所述的还原剂与CuO-K₂O/ZrO₂的质量比为0.001~0.154:1；(3) Prepare a reducing agent aqueous solution with a concentration of 0.01~0.45 mol/L, add 5~15% ammonia water dropwise under magnetic stirring, adjust the pH of the solution to 8~11, and mix the CuO-K₂ O/ZrO obtained in step (2).₂ is added to the above solution, and at 70-100 ℃, stirring and refluxing for 0.5-1 h; the mass ratio of the reducing agent to CuO-K₂ O/ZrO₂ is 0.001-0.154:1;（4）反应后经过滤，将滤饼在60~80 ℃下干燥6~10 h，即得到Cu₂O-K₂O/ZrO₂固体碱催化剂。(4) After the reaction, filter and dry the filter cake at 60-80 ℃ for 6-10 h to obtain Cu₂ OK₂ O/ZrO₂ solid base catalyst.4.根据权利要求3所述的合成4-羟丁基乙烯基醚的固体碱催化剂的制备方法，其特征在于：所述铜盐是氯化铜、硫酸铜、硝酸铜、醋酸铜中的一种或多种，铜盐与锆盐质量比为0.001~0.139:1。4. the preparation method of the solid base catalyst of synthesizing 4-hydroxybutyl vinyl ether according to claim 3, is characterized in that: described copper salt is one of copper chloride, copper sulfate, copper nitrate, copper acetate One or more, the mass ratio of copper salt to zirconium salt is 0.001~0.139:1.5.根据权利要求3所述的合成4-羟丁基乙烯基醚的固体碱催化剂的制备方法，其特征在于：所述钾盐是硝酸钾、碳酸钾、氯化钾、碳酸氢钾、硫酸钾中的一种或多种，钾盐与锆盐质量比为0.009~0.689:1。5. the preparation method of the solid base catalyst of synthetic 4-hydroxybutyl vinyl ether according to claim 3, is characterized in that: described potassium salt is saltpetre, salt of wormwood, Repone K, potassium bicarbonate, sulfuric acid One or more of potassium, the mass ratio of potassium salt to zirconium salt is 0.009~0.689:1.6.根据权利要求3所述的合成4-羟丁基乙烯基醚的固体碱催化剂的制备方法，其特征在于：所述锆盐是硝酸锆、硝酸氧锆、氧氯化锆中的一种或多种。6. the preparation method of the solid base catalyst of synthesizing 4-hydroxybutyl vinyl ether according to claim 3, is characterized in that: described zirconium salt is a kind of in zirconium nitrate, zirconium oxynitrate, zirconium oxychloride or more.7.根据权利要求3所述的合成4-羟丁基乙烯基醚的固体碱催化剂的制备方法，其特征在于：步骤（2）中，所述溶液在100~130 ℃下干燥5~8 h，在空气气氛中400~600 ℃下焙烧3~8 h。7. The method for preparing a solid base catalyst for synthesizing 4-hydroxybutyl vinyl ether according to claim 3, wherein in step (2), the solution is dried at 100-130 °C for 5-8 h , calcined at 400-600 °C for 3-8 h in an air atmosphere.8.根据权利要求3所述的合成4-羟丁基乙烯基醚的固体碱催化剂的制备方法，其特征在于：所述还原剂为抗坏血酸、甲醛、乙醛、硼氢化钠、葡萄糖、不饱和醇、柠檬酸钠、水合肼中的一种或多种。8. the preparation method of the solid base catalyst of synthesizing 4-hydroxybutyl vinyl ether according to claim 3, is characterized in that: described reducing agent is ascorbic acid, formaldehyde, acetaldehyde, sodium borohydride, glucose, unsaturated One or more of alcohol, sodium citrate, and hydrazine hydrate.9.一种权利要求1或2所述的合成4-羟丁基乙烯基醚的固体碱催化剂的应用，其特征在于：9. the application of the solid base catalyst of the described synthetic 4-hydroxybutyl vinyl ether of claim 1 or 2, is characterized in that:将1,4-丁二醇和Cu₂O-K₂O/ZrO₂催化剂加入到烧瓶中，Cu₂O-K₂O/ZrO₂催化剂和1,4-丁二醇的质量比为10~30:100，通入乙炔，控制乙炔流量为0.03~0.07 L/min，启动搅拌，油浴加热至140~160 ℃，反应5~12 h。1,4-Butanediol and Cu₂ OK₂ O/ZrO₂ catalyst were added to the flask, and the mass ratio of Cu₂ OK₂ O/ZrO₂ catalyst and 1,4-butanediol was 10~30:100. Add acetylene, control the flow rate of acetylene to 0.03~0.07 L/min, start stirring, heat the oil bath to 140~160 °C, and react for 5~12 h.10.根据权利要求9所述的应用，其特征在于：目标产物4-羟丁基乙烯基醚收率能达到67.39%。10. application according to claim 9 is characterized in that: target product 4-hydroxybutyl vinyl ether yield can reach 67.39%.