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CN101879444A - Preparation and application of a kind of stannate solid superbase catalyst - Google Patents

Preparation and application of a kind of stannate solid superbase catalyst Download PDF

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CN101879444A
CN101879444A CN2010101931159A CN201010193115A CN101879444A CN 101879444 A CN101879444 A CN 101879444A CN 2010101931159 A CN2010101931159 A CN 2010101931159A CN 201010193115 A CN201010193115 A CN 201010193115A CN 101879444 A CN101879444 A CN 101879444A
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stannate
catalyst
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solid superbase
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CN101879444B (en
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尹双凤
张树国
罗胜联
韦玉丹
陈浪
邱仁华
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Hunan University
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Abstract

本发明提供了一种锡酸盐固体超强碱催化剂的制备方法:取一种或两种以上的锡酸盐或锡酸盐水合物,在氮气气氛下,置于焙烧炉中并逐步升温至400~1200℃,焙烧2~12小时,即得。本发明所提供的锡酸盐固体超强碱催化剂制备简便易行,催化剂组成简单、催化活性高,可应用于多种类型的催化反应中。The invention provides a preparation method of a stannate solid superbase catalyst: take one or more than two stannates or stannate hydrates, place them in a roasting furnace under a nitrogen atmosphere, and gradually heat up to 400 ~ 1200 ℃, roasting for 2 ~ 12 hours, that is. The stannate solid superbase catalyst provided by the invention is easy to prepare, has simple catalyst composition and high catalytic activity, and can be applied to various types of catalytic reactions.

Description

一种锡酸盐固体超强碱催化剂的制备与应用 Preparation and application of a kind of stannate solid superbase catalyst

【技术领域】【Technical field】

本发明涉及催化和有机化学合成技术领域,具体地说涉及一种锡酸盐固体超强碱催化剂的制备与应用。The invention relates to the technical field of catalysis and organic chemical synthesis, in particular to the preparation and application of a stannate solid superbase catalyst.

【背景技术】【Background technique】

固体碱就是能够化学吸附酸性物质的固体或能使酸性指示剂变色的固体。固体超强碱的碱强度(哈莫特函数H-)大于26,也可认为强度比中性物质(H-=7)高出19个单位的碱性物质。目前已有报道发现了H->37的固体超强碱催化剂。固体超强碱作为催化剂在多种反应中表现出优异的性能:(1)催化活性极高,可使反应条件温和,而作为固体又耐高温;(2)选择性极高,产物纯度高,易与产物分离,工艺简单;(3)催化剂可重复使用,也可连续使用;(4)对反应设备腐蚀性小,废水少。此外,固体超强碱催化剂在多种有机反应中不像固体强酸性催化剂因结焦而易失活。A solid base is a solid that can chemisorb acidic substances or that can discolor an acid indicator. The base strength (Hammert's function H - ) of solid superbase is greater than 26, and it can also be considered as an alkaline substance whose strength is 19 units higher than that of neutral substances (H - = 7). So far, it has been reported that solid superbase catalysts with H - >37 have been found. As a catalyst, the solid superbase shows excellent performance in various reactions: (1) the catalytic activity is extremely high, which can make the reaction conditions mild, and as a solid, it can withstand high temperature; (2) the selectivity is extremely high, the product purity is high, It is easy to separate from the product, and the process is simple; (3) the catalyst can be used repeatedly and continuously; (4) it is less corrosive to reaction equipment and less waste water. In addition, solid superbase catalysts are not as easily deactivated by coking as solid strong acid catalysts in various organic reactions.

常用的碱性固体催化剂主要有碱土金属氧化物及氢氧化物、碱金属氧化物,负载型碱金属和碱金属氧化物等。它们虽然具有高活性,但其活性组分遇水易流失而失活,这是这类催化剂难以在工业上大规模应用的主要原因之一。稀土氧化物不溶于水,且具有与碱土金属氧化物类似的碱性,稀土与其它元素组成的复合氧化物更是有可能成为性能优良的超强碱催化剂。因此,采用复合氧化物固体碱催化剂不仅能大大丰富固体碱的种类,而且碱中心结构和形成机理的研究成果对于设计开发新型固体碱催化剂具有科学价值和现实意义。Commonly used basic solid catalysts mainly include alkaline earth metal oxides and hydroxides, alkali metal oxides, supported alkali metals and alkali metal oxides, etc. Although they have high activity, their active components are easily lost and deactivated when they meet with water, which is one of the main reasons why this type of catalyst is difficult to apply on a large scale in industry. Rare earth oxides are insoluble in water, and have similar alkalinity to alkaline earth metal oxides, and composite oxides composed of rare earth and other elements are more likely to become super-strong base catalysts with excellent performance. Therefore, the use of composite oxide solid base catalysts can not only greatly enrich the types of solid bases, but also the research results on the base center structure and formation mechanism have scientific value and practical significance for the design and development of new solid base catalysts.

碳酸二甲酯(DMC)作为一种环境友好的新型化学试剂,因其独特的理化性质,其合成和应用近年来受到了国内外的广泛关注.合成碳酸二甲酯的工业方法主要有甲醇氧化碳基化法和酯交换法,其中酯交换法应用最为广泛。Dimethyl carbonate (DMC), as a new environment-friendly chemical reagent, has received extensive attention at home and abroad in recent years for its synthesis and application due to its unique physical and chemical properties. The industrial methods for synthesizing dimethyl carbonate mainly include methanol oxidation Carbonylation and transesterification, among which transesterification is the most widely used.

酯交换法合成碳酸二甲酯主要是由二氧化碳和环氧乙烷(EO)或环氧丙烷(PO)反应生成乙烯酯(EC)或碳酸丙烯酯(PC)后,再由EC或PC与甲醇(MeOH)反应制的DMC,同时副产物乙二醇(EG)或丙二醇(PG)。在该反应中,一般多以碱金属氢氧化物、碱金属碳酸盐、碱金属醇盐等作为催化剂。但因其为均相反应,给催化剂的分离与重复使用造成困难。目前也有很多文献报道使用无机非均相催化剂:碱性树脂、金属氧化物、水滑石等。然而,这些催化剂需要比较高的温度和压强,而且DMC收率比较低。例如Raquel Jua′rez(Green Chem.,2009,11,949-952)等人以Au/CeO2为催化剂,PC∶MeOH为1∶10,在140℃下回流6小时,碳酸丙烯酯的转化率为63%,DMC收率仅为35%;B.M.Bhanagea,(Appl.Catal.A:Gen.,2001,219,259.)等人以固体氧化物为催化剂,PC∶MeOH为2∶25,压力8Mpa,反应温度150℃,反应时间为4小时,DMC的最高收率仅为32.4%。The synthesis of dimethyl carbonate by transesterification is mainly by the reaction of carbon dioxide and ethylene oxide (EO) or propylene oxide (PO) to generate vinyl ester (EC) or propylene carbonate (PC), and then by EC or PC and methanol (MeOH) DMC produced by reaction, while by-product ethylene glycol (EG) or propylene glycol (PG). In this reaction, alkali metal hydroxides, alkali metal carbonates, alkali metal alkoxides, etc. are generally used as catalysts. However, because of its homogeneous reaction, it is difficult to separate and reuse the catalyst. At present, there are also many reports on the use of inorganic heterogeneous catalysts: basic resins, metal oxides, hydrotalcites, etc. However, these catalysts require relatively high temperature and pressure, and the DMC yield is relatively low. For example, Raquel Jua'rez (Green Chem., 2009, 11 , 949-952) and others use Au/CeO as a catalyst, PC: MeOH is 1: 10, reflux at 140°C for 6 hours, the conversion rate of propylene carbonate is 63%, and the DMC yield is only 35%; BMBhanagea, (Appl.Catal.A: Gen., 2001,219,259.) et al. take solid oxide as catalyst, PC: MeOH is 2: 25, pressure 8Mpa , the reaction temperature was 150°C, the reaction time was 4 hours, and the highest yield of DMC was only 32.4%.

寻求一种固体超强碱催化剂并将其应用催化反应,尤其是应用于催化酯交换法合成碳酸二甲酯中,一直是催化和有机化学合成领域技术人员的不懈追求。Seek a kind of solid superbasic catalyst and apply it to catalytic reaction, especially in the synthesis of dimethyl carbonate by catalytic transesterification, has been the relentless pursuit of those skilled in the field of catalysis and organic chemical synthesis.

【发明内容】【Content of invention】

本发明的目的是提供一种锡酸盐固体超强碱催化剂的制备方法,其制备简便易行,催化剂用量小且可重复使用,催化稳定性好且活性高。The purpose of this invention is to provide a kind of preparation method of stannate solid superbase catalyst, and its preparation is simple and easy, and catalyst consumption is little and reusable, and catalytic stability is good and activity is high.

实现本发明目的的具体方案是:提供一种锡酸盐固体超强碱催化剂的制备方法,包含的步骤为:取一种或两种以上的锡酸盐或锡酸盐水合物,在氮气气氛下,置于焙烧炉中并逐步升温至400~1200℃,焙烧,即得。The specific scheme of realizing the object of the present invention is: provide a kind of preparation method of stannate solid superbase catalyst, the step that comprises is: get one or more than two kinds of stannate or stannate hydrate, in nitrogen atmosphere , put it in a roasting furnace and gradually raise the temperature to 400-1200°C, and roast it to get it.

上述锡酸盐固体超强碱催化剂的制备方法中,所述锡酸盐是选自锡酸钠、锡酸钾、锡酸锂、锡酸镁、锡酸钙、锡酸锶、锡酸钡、锡酸铕或锡酸镱。In the preparation method of above-mentioned stannate solid superbase catalyst, described stannate is selected from sodium stannate, potassium stannate, lithium stannate, magnesium stannate, calcium stannate, strontium stannate, barium stannate, Europium stannate or ytterbium stannate.

上述锡酸盐固体超强碱催化剂的制备方法中,所述两种以上的锡酸盐是以任意比例相混合的。In the preparation method of the above-mentioned stannate solid superbase catalyst, the two or more stannates are mixed in any proportion.

上述锡酸盐固体超强碱催化剂的制备方法中,所述焙烧炉中的升温速率为2~12℃/分钟。In the preparation method of the above-mentioned stannate solid superbase catalyst, the heating rate in the roasting furnace is 2-12° C./minute.

本发明的再一目的在于提供上述锡酸盐固体超强碱催化剂在酯交换法合成碳酸二甲酯中的应用。在该应用中,催化剂的用量占反应物总量的0.5~9wt%。Another object of the present invention is to provide the application of the above-mentioned stannate solid superbase catalyst in the synthesis of dimethyl carbonate by transesterification. In this application, the catalyst is used in an amount of 0.5-9 wt% of the total amount of reactants.

本发明的更一目的在于提供上述锡酸盐固体超强碱催化剂在烯烃的异构化反应、醇醚合成反应、酯交换反应、醛酮缩合反应、酯缩合反应、羟醛缩合反应、烷基化反应、酰基化反应、双键转移反应、Michael反应、Henry反应、Konevenagel反应、Perkin反应、Claisen-Schmidt反应、Tishchenko反应、Hantzsch反应等反应中的应用。在该应用中,催化剂的用量占反应物总量的0.5~9wt%。Another object of the present invention is to provide the above-mentioned stannate solid superbase catalyst in the isomerization reaction of olefins, alcohol ether synthesis reaction, transesterification reaction, aldehyde and ketone condensation reaction, ester condensation reaction, aldol condensation reaction, alkyl Chemical reaction, acylation reaction, double bond transfer reaction, Michael reaction, Henry reaction, Konevenagel reaction, Perkin reaction, Claisen-Schmidt reaction, Tishchenko reaction, Hantzsch reaction and other reactions. In this application, the catalyst is used in an amount of 0.5-9 wt% of the total amount of reactants.

本发明的有益效果在于,本发明所提供的锡酸盐固体超强碱催化剂不同于传统的以碱土金属氧化物及氢氧化物、碱金属氧化物、负载型碱金属和碱金属氧化物为主的固体超强碱催化剂,该催化剂组成简单、催化活性高,制备简便易行,当其应用于各种催化反应中时,催化剂用量小,对反应器无腐蚀,属于环境友好催化剂,反应结束后,催化剂可通过离心得到分离,得以重复使用。The beneficial effects of the present invention are that the stannate solid superbase catalyst provided by the present invention is different from the traditional ones based on alkaline earth metal oxides and hydroxides, alkali metal oxides, loaded alkali metals and alkali metal oxides. The solid super-strong base catalyst, the catalyst has simple composition, high catalytic activity, and is easy to prepare. When it is applied to various catalytic reactions, the amount of catalyst is small, and there is no corrosion to the reactor. It is an environmentally friendly catalyst. After the reaction , the catalyst can be separated by centrifugation and reused.

【具体实施方式】【Detailed ways】

实施例1Example 1

取锡酸钠在氮气氛围下置入焙烧炉中,逐步升温,升温速率为5℃/min,直至焙烧炉温度为500℃,过程中氮气的流速为60ml/min,然后焙烧4小时,得到本反应催化剂。Take sodium stannate and place it in a roasting furnace under a nitrogen atmosphere, gradually increase the temperature at a rate of 5°C/min, until the temperature of the roasting furnace is 500°C, the flow rate of nitrogen in the process is 60ml/min, and then roast for 4 hours to obtain this reaction catalyst.

按15∶1的摩尔配比取甲醇和碳酸丙烯酯,加入反应容器内,以反应物总量的2.67wt%取前面制得的锡酸钠固体超强碱催化剂加入到反应体系内;在搅拌条件下,反应体系升温至80℃,持续反应6小时,冷却,过滤,将催化剂与反应液分离,反应液用气相色谱分析,PC的转化率为91.8%。Get methyl alcohol and propylene carbonate by the molar ratio of 15:1, add in the reaction vessel, get the sodium stannate solid superbase catalyst that makes in front and join in the reaction system with 2.67wt% of reactant total amount; Under the conditions, the temperature of the reaction system was raised to 80° C., and the reaction was continued for 6 hours, cooled, filtered, and the catalyst was separated from the reaction solution. The reaction solution was analyzed by gas chromatography, and the conversion rate of PC was 91.8%.

产物分析方法与条件:Product analysis methods and conditions:

产物样品采用南京科捷分析仪器有限公司生产的GC9890F气相色谱仪,氢火焰离子化检测器进行分析检测。色谱分析条件为:毛细管柱AT·SE30m×0.32mm×0.33μm,进样口温度:250℃;检测器温度:250℃;柱温初始温度50℃,保持1min,然后以20℃/min升至210℃,在210℃保持3min,进样量为0.5μL。The product samples were analyzed and detected by GC9890F gas chromatograph and hydrogen flame ionization detector produced by Nanjing Kejie Analytical Instrument Co., Ltd. The chromatographic analysis conditions are: capillary column AT·SE30m×0.32mm×0.33μm, inlet temperature: 250°C; detector temperature: 250°C; initial column temperature 50°C, keep it for 1min, then increase to 20°C/min 210°C, keep at 210°C for 3min, and the injection volume is 0.5μL.

实施例2Example 2

锡酸钠在氢气氛围下以5℃/min升温至600℃后焙烧3小时,过程中氢气流速80ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为92.1%。Sodium stannate was heated up to 600°C at a rate of 5°C/min in a hydrogen atmosphere and then calcined for 3 hours with a hydrogen flow rate of 80ml/min to obtain the reaction catalyst. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 92.1%.

实施例3Example 3

锡酸纳在氩气氛围下以5℃/min升温至450℃后焙烧6小时,过程中氩气流速50ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为90.5%。Sodium stannate was heated to 450°C at 5°C/min under an argon atmosphere and then calcined for 6 hours with an argon flow rate of 50ml/min to obtain the reaction catalyst. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 90.5%.

实施例4Example 4

锡酸钾在氦气氛围下下以5℃/min升温至500℃后焙烧8小时,过程中氦气流速80ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为92.1%。Potassium stannate was heated to 500°C at 5°C/min under a helium atmosphere and then calcined for 8 hours with a helium flow rate of 80ml/min to obtain the reaction catalyst. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 92.1%.

实施例5Example 5

先将锡酸钾在110℃烘箱中烘干,再将锡酸钾置入氮气氛围下以3℃/min升温至800℃后焙烧2小时,过程中氮气流速60ml/min,得到本反应催化剂。其余同实施例1。反应用气相色谱分析,PC的转化率为95.6%。Potassium stannate was first dried in an oven at 110°C, and then potassium stannate was placed in a nitrogen atmosphere at a rate of 3°C/min to 800°C and then roasted for 2 hours with a nitrogen flow rate of 60ml/min to obtain the reaction catalyst. All the other are with embodiment 1. The reaction was analyzed by gas chromatography, and the conversion rate of PC was 95.6%.

实施例6Example 6

锡酸钠在氮气氛围下以8℃/min升温至500℃后焙烧4小时,过程中氮气流速70ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为93.4%。Sodium stannate was heated at 8°C/min to 500°C under a nitrogen atmosphere and then calcined for 4 hours with a nitrogen flow rate of 70ml/min to obtain the reaction catalyst. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 93.4%.

实施例7Example 7

回收的锡酸钾在氮气氛围下以10℃/min升温至550℃后焙烧2小时,过程中氮气流速80ml/min,得到本反应催化剂。其余同实施例1。反应用气相色谱分析,PC的转化率为90.2%。The recovered potassium stannate was heated up to 550° C. at a rate of 10° C./min under a nitrogen atmosphere and then calcined for 2 hours with a nitrogen flow rate of 80 ml/min to obtain the reaction catalyst. All the other are with embodiment 1. The reaction was analyzed by gas chromatography, and the conversion rate of PC was 90.2%.

实施例8Example 8

锡酸钠在氮气氛围下以12℃/min升温至700℃焙烧4小时,氮气流速70ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为95.8%。Sodium stannate was roasted at 12°C/min to 700°C for 4 hours under a nitrogen atmosphere with a nitrogen flow rate of 70ml/min to obtain the reaction catalyst. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 95.8%.

实施例9Example 9

取等摩尔的锡酸钠和锡酸钾混合均匀后在氮气氛围下以升温速率为5℃/min升到550℃后焙烧5小时,过程中氮气流速90ml/min,得到本反应催化剂。Take equimolar sodium stannate and potassium stannate, mix them evenly, raise the temperature to 550°C at a rate of 5°C/min under a nitrogen atmosphere, and then roast for 5 hours with a nitrogen flow rate of 90ml/min to obtain the catalyst for this reaction.

取3.9mmol的苯甲醛、7.8mmol的乙酰乙酸乙酯和3.9mmol的醋酸铵加入到反应器中,加入56mg上述制得的催化剂,再加入10ml乙腈作为溶剂。在室温下反应6.5小时,得到的目标产物二氢吡啶,分离收率为56.3%。3.9 mmol of benzaldehyde, 7.8 mmol of ethyl acetoacetate and 3.9 mmol of ammonium acetate were added to the reactor, 56 mg of the catalyst prepared above was added, and 10 ml of acetonitrile was added as a solvent. After reacting at room temperature for 6.5 hours, the target product dihydropyridine was obtained with an isolated yield of 56.3%.

实施例10Example 10

取等摩尔的锡酸钠和锡酸钙(自制)混合均匀后在氢气氛围下以升温速率为5℃/min升到500℃后焙烧4小时,过程中氢气流速80ml/min,得到本反应催化剂。Take equimolar sodium stannate and calcium stannate (self-produced) and mix them evenly, then raise the temperature to 500°C at a rate of 5°C/min under a hydrogen atmosphere, and then roast for 4 hours, with a hydrogen flow rate of 80ml/min during the process, to obtain the catalyst for this reaction .

取1.061g的苯甲醛和3ml硝基甲烷于反应器中,加入100mg上述制得的催化剂,在40度下反应6小时,反应液用气相色谱分析,苯甲醛的转化率为62.7%。Get 1.061g of benzaldehyde and 3ml of nitromethane in a reactor, add 100mg of the catalyst prepared above, react at 40°C for 6 hours, and analyze the reaction solution by gas chromatography, the conversion rate of benzaldehyde is 62.7%.

实施例11Example 11

取3.245g苯甲醛于反应器中,加入1.007g由实施例6制得的催化剂,在50度下反应4小时,反应液用气相色谱分析,苯甲醛的转化率为42.0%。Get 3.245g benzaldehyde in the reactor, add 1.007g by the catalyst that embodiment 6 makes, react at 50 degree for 4 hours, reaction liquid is analyzed by gas chromatography, and the conversion ratio of benzaldehyde is 42.0%.

实施例12Example 12

取2mmol的苯胺、1mmol的碳酸二甲酯(DMC)于反应器中,加入83mg由实施例6制得的催化剂,130度反应5小时。反应液用气相色谱分析,苯胺的转化率为53.9%。Take 2 mmol of aniline and 1 mmol of dimethyl carbonate (DMC) in a reactor, add 83 mg of the catalyst prepared in Example 6, and react at 130 degrees for 5 hours. The reaction liquid was analyzed by gas chromatography, and the conversion rate of aniline was 53.9%.

实施例13Example 13

先将锡酸钠置于110度的烘箱中烘干,研磨后再在氮气氛围下以升温速率为5℃/min升到500℃后焙烧4小时,氮气流速100ml/min,得到本反应催化剂。Sodium stannate was dried in an oven at 110°C, ground, then heated to 500°C at a rate of 5°C/min under nitrogen atmosphere, and then roasted for 4 hours at a nitrogen flow rate of 100ml/min to obtain the catalyst for this reaction.

取12mmol的甲醇、4mmol的丙烯腈于反应器中,加入50mg上述催化剂,在50度下反应2小时,气相色谱分析结果丙烯腈的转化率为100%。Take 12mmol of methanol and 4mmol of acrylonitrile in a reactor, add 50mg of the above catalyst, and react at 50°C for 2 hours. The conversion rate of acrylonitrile is 100% as a result of gas chromatography analysis.

实施例14Example 14

取1mmol的苯甲醛、1.2mmol的丙二酸二乙酯和10ml的乙腈作为溶剂于反应器中,加入0.105g由实施例13制得的催化剂,50度反应4小时。反应液用气相色谱分析,苯甲醛的转化率为71.6%。Take 1 mmol of benzaldehyde, 1.2 mmol of diethyl malonate and 10 ml of acetonitrile as a solvent in a reactor, add 0.105 g of the catalyst prepared in Example 13, and react at 50 degrees for 4 hours. The reaction liquid was analyzed by gas chromatography, and the conversion rate of benzaldehyde was 71.6%.

实施例15Example 15

取1mmol的乙酰丙酮、1mmol的丙烯腈于反应器中,加入0.066g由实施例13制得的催化剂,50度反应4小时。反应液用气相色谱分析,丙烯腈的转化率为57.3%。Take 1 mmol of acetylacetone and 1 mmol of acrylonitrile in a reactor, add 0.066 g of the catalyst prepared in Example 13, and react at 50°C for 4 hours. The reaction liquid was analyzed by gas chromatography, and the conversion rate of acrylonitrile was 57.3%.

实施例16Example 16

取2mmol的乙酰丙酮、2mmol的丁醛于反应器中,加入0.336g由实施例13制得的催化剂,60度反应4小时。反应液用气相色谱分析,苯甲醛的转化率为43.6%。Take 2mmol of acetylacetone and 2mmol of butyraldehyde in a reactor, add 0.336g of the catalyst prepared in Example 13, and react at 60°C for 4 hours. The reaction liquid was analyzed by gas chromatography, and the conversion rate of benzaldehyde was 43.6%.

实施例17Example 17

锡酸钠在氩气氛围下以5℃/min升温至500℃焙烧4小时,过程中氮气流速70ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为92.5%。Sodium stannate was roasted at 5 °C/min to 500 °C for 4 hours under an argon atmosphere, and the nitrogen flow rate was 70 ml/min during the process to obtain the reaction catalyst. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 92.5%.

实施例18Example 18

取等摩尔的锡酸钠、锡酸钾、锡酸钙(自制)和锡酸镁(自制)研磨后在氩气氛围下以5℃/min升温至550℃焙烧4小时,过程中氩气流速90ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为93.7%。Take equimolar sodium stannate, potassium stannate, calcium stannate (self-made) and magnesium stannate (self-made) and grind them in an argon atmosphere at 5°C/min to 550°C for 4 hours. During the process, the argon flow rate 90ml/min, obtains this reaction catalyst. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 93.7%.

实施例19Example 19

取锡酸铕(自制)在氮气氛围下以5℃/min升温至800℃焙烧4小时,过程中氮气流速90ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为94.2%。Take europium stannate (self-made) and heat it up to 800°C at 5°C/min for 4 hours in a nitrogen atmosphere and roast it for 4 hours with a nitrogen flow rate of 90ml/min to obtain the catalyst for this reaction. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 94.2%.

实施例20Example 20

取锡酸镱(自制)在氮气氛围下以5℃/min升温至800℃焙烧6小时,过程中氮气流速90ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为91.0%。Take ytterbium stannate (self-made) and heat it up to 800°C at 5°C/min for 6 hours under a nitrogen atmosphere and roast it for 6 hours with a nitrogen flow rate of 90ml/min to obtain the catalyst for this reaction. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 91.0%.

实施例21Example 21

取锡酸锶(自制)在氮气氛围下以5℃/min升温至800℃焙烧6小时,过程中氮气流速90ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为94.4%。Take strontium stannate (self-produced) and heat it up to 800°C at 5°C/min under nitrogen atmosphere for 6 hours and roast at a nitrogen flow rate of 90ml/min to obtain the catalyst for this reaction. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 94.4%.

实施例22Example 22

取锡酸镁(自制)在氮气氛围下以5℃/min升温至800℃焙烧8小时,过程中氮气流速90ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为91.7%。Take magnesium stannate (self-made) and heat it up to 800°C at 5°C/min for 8 hours under a nitrogen atmosphere, and roast it for 8 hours with a nitrogen flow rate of 90ml/min to obtain the catalyst for this reaction. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 91.7%.

实施例23Example 23

取锡酸钙(自制)在氮气氛围下以5℃/min升温至900℃焙烧8小时,过程中氮气流速90ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为92.3%。Take calcium stannate (self-made) and heat up to 900° C. for 8 hours at 5° C./min under a nitrogen atmosphere and roast at a nitrogen flow rate of 90 ml/min to obtain the catalyst for this reaction. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 92.3%.

实施例24Example 24

取锡酸钡(自制)在氮气氛围下以5℃/min升温至800℃焙烧8小时,过程中氮气流速90ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为90.5%。Take barium stannate (self-made) and heat it up to 800°C at 5°C/min for 8 hours under a nitrogen atmosphere and roast it for 8 hours with a nitrogen flow rate of 90ml/min to obtain the catalyst for this reaction. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 90.5%.

实施例25Example 25

取等摩尔的锡酸钠、锡酸钾、锡酸钙(自制)、锡酸镁(自制)、锡酸铕(自制)、锡酸镱(自制)、锡酸锶(自制)、锡酸钡(自制)研磨后在氮气氛围下以5℃/min升温至800℃焙烧10小时,过程中氮气流速90ml/min,得到本反应催化剂。其余同实施例1,反应液用气相色谱分析,PC的转化率为91.5%。Take equimolar sodium stannate, potassium stannate, calcium stannate (self-made), magnesium stannate (self-made), europium stannate (self-made), ytterbium stannate (self-made), strontium stannate (self-made), barium stannate (self-made) After grinding, heat up to 800°C at 5°C/min and roast for 10 hours under a nitrogen atmosphere with a nitrogen flow rate of 90ml/min to obtain the catalyst for this reaction. All the other are the same as in Example 1, the reaction solution is analyzed by gas chromatography, and the conversion rate of PC is 91.5%.

实施例26Example 26

取原料三水合锡酸钠直接用于实施例1的反应,反应液用气相色谱分析,PC的转化率为70.4%。The raw material sodium stannate trihydrate was directly used in the reaction of Example 1, and the reaction liquid was analyzed by gas chromatography, and the conversion rate of PC was 70.4%.

实施例27Example 27

由实施例6分离后回收的锡酸钠不经过干燥直接用于实施例1的反应,反应液用气相色谱分析,PC的转化率为74.3%。The sodium stannate recovered after separation in Example 6 was directly used in the reaction of Example 1 without drying, and the reaction liquid was analyzed by gas chromatography, and the conversion rate of PC was 74.3%.

Claims (8)

1.一种锡酸盐固体超强碱催化剂的制备方法,其特征在于,包含以下步骤:取至少一种或两种以上的锡酸盐或锡酸盐水合物,在氮气、氢气或惰性气体氛围下,置于焙烧炉中并逐步升温至400~1200℃,焙烧,即得。1. a preparation method of stannate solid superbase catalyst, is characterized in that, comprises the following steps: get at least one or more than two stannates or stannate hydrates, in nitrogen, hydrogen or inert gas Under the atmosphere, put it in a roasting furnace and gradually raise the temperature to 400-1200°C, and roast it to get it. 2.根据权利要求1所述的锡酸盐固体超强碱催化剂的制备方法,其特征在于,所述锡酸盐是选自锡酸钠、锡酸钾、锡酸锂、锡酸镁、锡酸钙、锡酸锶、锡酸钡、锡酸铕或锡酸镱。2. the preparation method of stannate solid superbase catalyst according to claim 1, is characterized in that, described stannate is selected from sodium stannate, potassium stannate, lithium stannate, magnesium stannate, tin calcium stannate, strontium stannate, barium stannate, europium stannate or ytterbium stannate. 3.根据权利要求1所述的锡酸盐固体超强碱催化剂的制备方法,其特征在于,所述两种以上的锡酸盐是以任意比例相混合的。3. the preparation method of stannate solid superbase catalyst according to claim 1, is characterized in that, described two or more stannates are mixed in any proportion. 4.根据权利要求1-3任意一项所述的锡酸盐固体超强碱催化剂的制备方法,其特征在于,所述焙烧炉中的升温速率为2~12℃/分钟。4. The preparation method of the stannate solid superbase catalyst according to any one of claims 1-3, characterized in that, the heating rate in the roasting furnace is 2 to 12° C./min. 5.权利要求1所述的锡酸盐固体超强碱催化剂在酯交换法合成碳酸二甲酯中的应用。5. the application of the stannate solid superbase catalyst claimed in claim 1 in the synthesis of dimethyl carbonate by transesterification. 6.根据权利要求5所述的锡酸盐固体超强碱催化剂在酯交换法合成碳酸二甲酯中的应用,其特征在于,催化剂的用量占反应物总量的0.5~9wt%。6. the application of stannate solid superbase catalyst according to claim 5 in the synthesis of dimethyl carbonate by transesterification, is characterized in that, the consumption of catalyzer accounts for 0.5~9wt% of reactant total amount. 7.权利要求1所述的锡酸盐固体超强碱催化剂在烯烃的异构化反应、醇醚合成反应、酯交换反应、醛酮缩合反应、酯缩合反应、羟醛缩合反应、烷基化反应、酰基化反应、双键转移反应、Michael反应、Henry反应、Konevenagel反应、Perkin反应、Claisen-Schmidt反应、Tishchenko反应或Hantzsch反应中的应用。7. stannate solid superbase catalyst described in claim 1 is in the isomerization reaction of olefin, alcohol ether synthetic reaction, transesterification, aldehyde and ketone condensation reaction, ester condensation reaction, aldol condensation reaction, alkylation reaction, acylation reaction, double bond transfer reaction, Michael reaction, Henry reaction, Konevenagel reaction, Perkin reaction, Claisen-Schmidt reaction, Tishchenko reaction or Hantzsch reaction. 8.根据权利要求7所述的锡酸盐固体超强碱催化剂在烯烃的异构化反应、醇醚合成反应、酯交换反应、醛酮缩合反应、酯缩合反应、羟醛缩合反应、烷基化反应、酰基化反应、双键转移反应、Michael反应、Henry反应、Konevenagel反应、Perkin反应、Claisen-Schmidt反应、Tishchenko反应或Hantzsch反应中的应用,其特征在于,催化剂的用量占反应物总量的0.5~9wt%。8. stannate solid superbase catalyst according to claim 7 is in the isomerization reaction of olefin, alcohol ether synthesis reaction, transesterification reaction, aldehyde and ketone condensation reaction, ester condensation reaction, aldol condensation reaction, alkyl Application in chemical reaction, acylation reaction, double bond transfer reaction, Michael reaction, Henry reaction, Konevenagel reaction, Perkin reaction, Claisen-Schmidt reaction, Tishchenko reaction or Hantzsch reaction, it is characterized in that, the consumption of catalyst accounts for the total amount of reactants 0.5~9wt%.
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CN106975475A (en) * 2017-04-26 2017-07-25 中国石油化工股份有限公司 It is a kind of for catalyst of synthesizing trimethylol propane ester and preparation method thereof and application
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CN110586079A (en) * 2019-09-23 2019-12-20 湘潭大学 Preparation and application of layered CaMnAl hydrotalcite solid base catalyst
CN113181894A (en) * 2021-04-10 2021-07-30 张威 Catalytic system for catalyzing decarbonylation of dimethyl oxalate to directly generate dimethyl carbonate
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CN103265425A (en) * 2013-05-30 2013-08-28 福建农林大学 Method for preparing conjugated linoleic acid through stannate catalysis
CN104945261B (en) * 2014-03-31 2017-07-25 中国石油化工股份有限公司 A method of co-producing dimethyl carbonate and propylene glycol
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CN109331876A (en) * 2018-11-14 2019-02-15 山西大学 A kind of sodium-magnesium bimetallic catalyst and its preparation method and application
CN110586079A (en) * 2019-09-23 2019-12-20 湘潭大学 Preparation and application of layered CaMnAl hydrotalcite solid base catalyst
CN113181894A (en) * 2021-04-10 2021-07-30 张威 Catalytic system for catalyzing decarbonylation of dimethyl oxalate to directly generate dimethyl carbonate
CN113181894B (en) * 2021-04-10 2023-08-18 张威 Catalytic system for catalyzing decarbonylation of dimethyl oxalate to directly generate dimethyl carbonate
CN115974136A (en) * 2023-01-17 2023-04-18 湖北亿纬动力有限公司 A magnesium-doped calcium stannate composite material for negative electrode active material and preparation method thereof

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