CN109833904B - A kind of acid-base bifunctional catalyst, its preparation method and application in ethanol conversion reaction - Google Patents

A kind of acid-base bifunctional catalyst, its preparation method and application in ethanol conversion reaction Download PDF

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CN109833904B
CN109833904B CN201711227079.1A CN201711227079A CN109833904B CN 109833904 B CN109833904 B CN 109833904B CN 201711227079 A CN201711227079 A CN 201711227079A CN 109833904 B CN109833904 B CN 109833904B
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molecular sieve
tin
acid
bifunctional catalyst
base bifunctional
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CN109833904A (en
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金长子
黄声骏
张大治
邹明明
焦雨桐
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Dalian Institute of Chemical Physics of CAS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production

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Abstract

本申请公开了一种酸碱双功能催化剂、其制备方法及在乙烯转化制备烯烃反应中的应用。所述酸碱双功能催化剂,其特征在于,包括锡掺杂β分子筛和氧化镁;其中,所述锡掺杂β分子筛在酸碱双功能催化剂中的质量含量为10%~90%;所述氧化镁在酸碱双功能催化剂中的质量含量为10%~90%。该催化剂是采用沉积沉淀法,以锡掺杂β分子筛与氧化镁按照一定的比例复合制备而成。该酸碱双功能催化剂通过组分调变,能够实现酸碱协同作用,克服了现有技术中该领域催化剂酸碱性难以调控的问题,高效地催化乙醇转化,选择性生成1,3‑丁二烯、乙烯、1‑丁烯等化学品,其制备工艺简单,可操作性强,可进行大规模工业生产。The present application discloses an acid-base bifunctional catalyst, its preparation method and its application in the reaction of converting ethylene to olefin. The acid-base bifunctional catalyst is characterized in that it comprises tin-doped beta molecular sieve and magnesium oxide; wherein, the mass content of the tin-doped beta molecular sieve in the acid-base bifunctional catalyst is 10% to 90%; The mass content of magnesium oxide in the acid-base bifunctional catalyst is 10% to 90%. The catalyst is prepared by a deposition precipitation method, and is prepared by compounding tin-doped beta molecular sieve and magnesium oxide in a certain proportion. The acid-base bifunctional catalyst can realize the synergistic effect of acid-base through component modulation, overcomes the problem that the acidity and alkalinity of catalysts in this field are difficult to control in the prior art, catalyzes the conversion of ethanol efficiently, and selectively generates 1,3-butylene Chemicals such as diene, ethylene and 1-butene have simple preparation process and strong operability, and can be used for large-scale industrial production.

Description

一种酸碱双功能催化剂、其制备方法及在乙醇转化反应中的 应用A kind of acid-base bifunctional catalyst, its preparation method and its use in ethanol conversion reaction application

技术领域technical field

本申请涉及一种酸碱双功能催化剂及其制备方法,可用于催化乙醇脱水、脱氢、缩合反应选择性生成1,3-丁二烯、1-丁烯、乙烯等化学品,属于催化合成领域。The present application relates to an acid-base bifunctional catalyst and a preparation method thereof, which can be used to catalyze the dehydration, dehydrogenation, and condensation reactions of ethanol to selectively generate 1,3-butadiene, 1-butene, ethylene and other chemicals, belonging to catalytic synthesis field.

背景技术Background technique

1,3-丁二烯、1-丁烯以及乙烯都是重要的有机化工原料,有着非常广泛的用途,它们的生产主要依靠石油炼化工艺。随着石油资源的日益枯竭以及碳排放压力的增加,寻找其它的原料资源或者开发新的生产路径具有十分重要的意义。1,3-butadiene, 1-butene and ethylene are all important organic chemical raw materials, which have a very wide range of uses, and their production mainly depends on the petroleum refining process. With the depletion of petroleum resources and the increasing pressure of carbon emissions, it is of great significance to find other raw material resources or develop new production paths.

乙醇在适当的催化剂作用下可以转化为这些烯烃产品(Chem.Soc.Rev.,2014,43,7917;ACS Catal.2017,7,3703)。然而,传统的乙醇工业生产方式主要基于生物发酵工艺,使得乙醇转化制备烯烃受到成本、粮食产量等多方面限制。近来,随着煤制乙醇技术的研发成功,乙醇的生产成本将会进一步大幅降低。因此,利用乙醇转化代替传统路线生产高值烯烃,将更具有现实意义。Ethanol can be converted to these olefin products with appropriate catalysts (Chem. Soc. Rev., 2014, 43, 7917; ACS Catal. 2017, 7, 3703). However, the traditional ethanol industrial production method is mainly based on biological fermentation process, which makes the conversion of ethanol to produce olefins limited by cost and grain yield. Recently, with the successful research and development of coal-to-ethanol technology, the production cost of ethanol will be further greatly reduced. Therefore, it will be more practical to use ethanol conversion to replace the traditional route to produce high-value olefins.

用于乙醇转化制烯烃的传统催化剂主要有复合金属氧化物、氧化镁/氧化硅以及海泡石等(J.Appl.Chem.,1962,105;Catal.Sci.Technol.,2017,7,168;Catal.Lett.,1995,34,359),其中氧化镁/氧化硅催化剂的活性和选择性较好,曾被用于早期的工业化生产,但是对于该催化剂的酸碱性调控一直是一个难点。乙醇转化制烯烃的反应过程需要酸碱协同催化,因此,能否对催化剂的酸碱性进行优化调控将是研制该反应过程的新催化剂的关键考量因素。The traditional catalysts used for ethanol conversion to olefins mainly include composite metal oxides, magnesium oxide/silica and sepiolite (J.Appl.Chem., 1962, 105; Catal. Sci. Technol., 2017, 7, 168; Catal. .Lett., 1995, 34, 359), among which the magnesium oxide/silica catalyst has better activity and selectivity, and has been used in early industrial production, but the acid-base control of the catalyst has always been a difficulty. The reaction process of converting ethanol to olefins requires the synergistic catalysis of acid and alkali. Therefore, whether the acidity and alkalinity of the catalyst can be optimized and controlled will be a key consideration in the development of new catalysts for this reaction process.

发明内容SUMMARY OF THE INVENTION

根据本申请的一个方面,提供一种酸碱双功能催化剂,通过组分调变,能够实现酸碱协同作用,克服了现有技术中该领域催化剂酸碱性难以调控的问题,高效地催化乙醇转化,选择性生成1,3-丁二烯、乙烯、1-丁烯等高价值烯烃,其制备工艺简单,可操作性强,可进行大规模工业生产。According to one aspect of the present application, an acid-base bifunctional catalyst is provided, which can realize the synergistic effect of acid-base through component modulation, overcomes the problem that the acidity and alkalinity of catalysts in this field are difficult to control in the prior art, and efficiently catalyzes ethanol It can be converted to selectively generate high-value olefins such as 1,3-butadiene, ethylene, and 1-butene. The preparation process is simple, the operability is strong, and large-scale industrial production can be carried out.

所述酸碱双功能催化剂,其特征在于,包括锡掺杂β分子筛和氧化镁;其中锡掺杂β分子筛在酸碱双功能催化剂中的质量含量为10%~90%;所述氧化镁在酸碱双功能催化剂中的质量含量为10%~90%。The acid-base bifunctional catalyst is characterized in that it comprises tin-doped beta molecular sieve and magnesium oxide; wherein the mass content of the tin-doped beta molecular sieve in the acid-base bifunctional catalyst is 10% to 90%; The mass content of the acid-base bifunctional catalyst is 10% to 90%.

优选地,其中锡掺杂β分子筛在酸碱双功能催化剂中的质量含量为30%~90%。Preferably, the mass content of the tin-doped beta molecular sieve in the acid-base bifunctional catalyst is 30% to 90%.

优选地,所述酸碱双功能催化剂由锡掺杂β分子筛与氧化镁复合而成。Preferably, the acid-base bifunctional catalyst is composed of tin-doped beta molecular sieve and magnesium oxide.

优选地,所述锡掺杂β分子筛中,硅元素与锡元素的摩尔比为40~200:1。Preferably, in the tin-doped beta molecular sieve, the molar ratio of silicon element to tin element is 40-200:1.

根据本申请的另一个方面,提供了上述酸碱双功能催化剂的制备方法。该方法工艺简单,制备得到的催化剂产品性能稳定,能够实现大规模工业化生产。According to another aspect of the present application, a method for preparing the above acid-base bifunctional catalyst is provided. The method is simple in process, the prepared catalyst product has stable performance, and can realize large-scale industrial production.

所述制备酸碱双功能催化剂的方法至少包含以下步骤:The method for preparing an acid-base bifunctional catalyst at least comprises the following steps:

a)获得锡掺杂β分子筛;a) obtaining tin-doped beta molecular sieve;

b)将所述锡掺杂β分子筛置于含有镁离子的溶液中,加入碱溶液调节pH值;b) placing the tin-doped beta molecular sieve in a solution containing magnesium ions, and adding an alkaline solution to adjust the pH value;

c)分离、洗涤所得到的固体经干燥、焙烧后,即得所述酸碱双功能催化剂。c) After separating and washing the obtained solid, drying and calcining, the acid-base bifunctional catalyst is obtained.

所述锡掺杂β分子筛可以来自商业购买、根据现有技术中的记载制备得到,或者根据本申请中记载的方法制备得到。The tin-doped beta molecular sieve can be purchased commercially, prepared according to the description in the prior art, or prepared according to the method described in this application.

作为一种优选的方式,所述锡掺杂β分子筛通过至少包括以下步骤的制备方法制备得到:As a preferred way, the tin-doped beta molecular sieve is prepared by a preparation method comprising at least the following steps:

(1)将H-β分子筛进行脱铝处理;(1) carry out dealumination treatment to H-β molecular sieve;

(2)将脱铝处理后的H-β分子筛与锡前驱体混合研磨,再经过焙烧,得到所述锡掺杂β分子筛。(2) Mixing and grinding the dealuminated H-β molecular sieve with a tin precursor, and then calcining to obtain the tin-doped β molecular sieve.

本领域技术人员可根据具体情况选择H-β分子筛的来源,可以通过商业购买获得,也可以根据现有技术中的记载制备得到。Those skilled in the art can select the source of H-β molecular sieve according to the specific situation, which can be obtained through commercial purchase, or can be prepared according to the records in the prior art.

优选地,所述H-β分子筛的硅铝摩尔比SiO2/Al2O3=12.5~50。进一步优选地,所述H-β分子筛的硅铝摩尔比SiO2/Al2O3=20~30。Preferably, the molar ratio of Si to Al of the H-β molecular sieve is SiO 2 /Al 2 O 3 =12.5-50. Further preferably, the molar ratio of silicon to aluminum of the H-β molecular sieve is SiO 2 /Al 2 O 3 =20-30.

作为一种实施方式,所述脱铝处理是将H-β分子筛置于浓度为10~14mol/L的硝酸溶液中,于不低于50~90℃的温度下保持不少于7~30小时。As an embodiment, in the dealumination treatment, the H-β molecular sieve is placed in a nitric acid solution with a concentration of 10-14 mol/L, and kept at a temperature of not less than 50-90° C. for not less than 7-30 hours .

优选地,所述脱铝处理是将H-β分子筛置于质量浓度为65%~68%的硝酸溶液中,于不低于75℃~85℃的温度下保持不少于8~20小时。Preferably, in the dealumination treatment, the H-β molecular sieve is placed in a nitric acid solution with a mass concentration of 65% to 68%, and kept at a temperature not lower than 75°C to 85°C for not less than 8 to 20 hours.

作为一种实施方式,所述脱铝处理中,H-β分子筛与硝酸溶液的固液比为1g:15~100mL。优选地,所述脱铝处理中,H-β分子筛与硝酸溶液的固液比为1g:20~40mL。As an embodiment, in the dealumination treatment, the solid-to-liquid ratio of the H-beta molecular sieve and the nitric acid solution is 1 g: 15-100 mL. Preferably, in the dealumination treatment, the solid-to-liquid ratio of the H-beta molecular sieve to the nitric acid solution is 1 g: 20-40 mL.

作为一种实施方式,所述含有镁离子的溶液由镁盐溶于水得到。优选地,所述镁盐为硝酸镁和/或醋酸镁。As an embodiment, the solution containing magnesium ions is obtained by dissolving magnesium salts in water. Preferably, the magnesium salt is magnesium nitrate and/or magnesium acetate.

本领域技术人员可根据具体需要,选择含有镁离子溶液的浓度以及含有镁离子溶液与锡掺杂β分子筛的比例。作为一种具体的实施方式,所述步骤b)中,所述含有镁离子的溶液中镁元素的摩尔数与锡掺杂β分子筛的质量比为0.25~6mmol:1g。Those skilled in the art can select the concentration of the magnesium ion-containing solution and the ratio of the magnesium ion-containing solution to the tin-doped beta molecular sieve according to specific needs. As a specific embodiment, in the step b), the molar ratio of the magnesium element in the solution containing magnesium ions to the mass ratio of the tin-doped beta molecular sieve is 0.25-6 mmol:1 g.

本领域技术人员可根据实际需要,选择锡前驱体的种类。优选地,所述锡前驱体为结晶四氯化锡、二甲基二氯化锡、氯化亚锡或者草酸亚锡中的至少一种。Those skilled in the art can select the type of tin precursor according to actual needs. Preferably, the tin precursor is at least one of crystalline tin tetrachloride, dimethyltin dichloride, stannous chloride or stannous oxalate.

作为一种实施方式,所述脱铝处理后的H-β分子筛中硅元素的摩尔数与锡前驱体中锡元素的摩尔比为:As an embodiment, the mole ratio of the silicon element in the H-β molecular sieve after the dealumination treatment and the tin element in the tin precursor is:

Si:Sn=40~200:1;Si:Sn=40~200:1;

作为一种实施方式,所述脱铝处理后的H-β分子筛与锡前驱体的质量比为2:0.05~0.3。优选地,所述脱铝处理后的H-β分子筛与锡前驱体的质量比为2:0.058~0.29。As an embodiment, the mass ratio of the dealuminated H-β molecular sieve to the tin precursor is 2:0.05-0.3. Preferably, the mass ratio of the dealuminated H-β molecular sieve to the tin precursor is 2:0.058-0.29.

优选地,所述加入碱溶液调节pH值是加入碱溶液将体系pH值调至10~12。Preferably, the addition of the alkali solution to adjust the pH value is to add the alkali solution to adjust the pH value of the system to 10-12.

优选地,所述碱溶液选自氨水和/或氢氧化钠溶液。进一步优选地,所述氨水和/或氢氧化钠溶液的浓度为1mol/L。Preferably, the alkaline solution is selected from ammonia water and/or sodium hydroxide solution. Further preferably, the concentration of the ammonia water and/or sodium hydroxide solution is 1 mol/L.

作为一种具体的实施方式,所述制备酸碱双功能催化剂的方法为:将锡掺杂β分子筛置于镁前驱体的水溶液中,加入碱溶液调节pH值为10~12,所得固体产物经过过滤、洗涤、干燥后,于空气中500℃焙烧4h制得。As a specific embodiment, the method for preparing an acid-base bifunctional catalyst is as follows: placing tin-doped beta molecular sieve in an aqueous solution of magnesium precursor, adding an alkaline solution to adjust the pH to 10-12, and the obtained solid product is subjected to After filtering, washing and drying, it was prepared by calcining at 500℃ for 4h in the air.

作为一种具体的实施方式,所述的锡掺杂β分子筛的制备方法为:As a specific embodiment, the preparation method of the tin-doped beta molecular sieve is:

(1)将H-β分子筛(硅铝摩尔比12.5-50)用10-14mol/L的硝酸进行脱铝,所得产品进行洗涤、干燥;(1) H-β molecular sieve (silicon-aluminum molar ratio 12.5-50) is dealuminated with the nitric acid of 10-14mol/L, and the obtained product is washed and dried;

(2)将脱铝的β分子筛与锡前驱体混合研磨,再经过550℃焙烧,得到锡掺杂β分子筛。(2) Mixing and grinding the dealuminated beta molecular sieve with a tin precursor, and then calcining at 550° C. to obtain a tin-doped beta molecular sieve.

根据本申请的又一个方面,提供上述酸碱双功能催化剂、根据上述任一方法制备得到的酸碱双功能催化剂作为乙醇转化制烯烃反应过程的催化剂的应用。According to yet another aspect of the present application, the application of the above acid-base bifunctional catalyst and the acid-base bifunctional catalyst prepared according to any of the above methods as catalysts in the reaction process of ethanol conversion to olefins is provided.

所述乙醇转化包括乙醇脱水、乙醇脱氢、乙醇缩合中的一种。The ethanol conversion includes one of ethanol dehydration, ethanol dehydrogenation, and ethanol condensation.

优选地,乙醇转化制烯烃反应为乙醇转化制1,3-丁二烯、乙醇转化制乙烯、乙醇转化制1-丁烯中的至少一种。Preferably, the reaction of converting ethanol to olefins is at least one of converting ethanol to 1,3-butadiene, converting ethanol to ethylene, and converting ethanol to 1-butene.

本申请的有益效果包括但不限于:The beneficial effects of this application include but are not limited to:

(1)本申请提供了一种酸碱双功能催化剂,通过组分调变,能够实现酸碱协同作用,高效地催化乙醇转化选择性生成1,3-丁二烯、乙烯、1-丁烯等高价值烯烃。(1) The present application provides an acid-base bifunctional catalyst, which can achieve acid-base synergy through component modulation, and efficiently catalyze the conversion of ethanol to selectively generate 1,3-butadiene, ethylene, and 1-butene and other high-value olefins.

(2)本申请提供了上述酸碱双功能催化剂的制备方法,制备工艺简单,可操作性强,可进行大规模工业生产。(2) The present application provides a method for preparing the above acid-base bifunctional catalyst, the preparation process is simple, the operability is strong, and large-scale industrial production is possible.

具体实施方式Detailed ways

下面结合实施例详述本申请,但本申请并不局限于这些实施例。The present application will be described in detail below with reference to the examples, but the present application is not limited to these examples.

未经特殊说明,本申请所采用的原料均通过商业购买,未经特殊处理直接使用。Unless otherwise specified, the raw materials used in this application were purchased commercially and used directly without special treatment.

本申请中,所采用的H-β分子筛购自南开大学催化剂厂。In this application, the used H-β molecular sieve was purchased from Nankai University Catalyst Factory.

实施例1催化剂的制备The preparation of embodiment 1 catalyst

取5g H-β分子筛(SiO2/Al2O3=25)分散到100mL浓度为14mol/L的硝酸溶液中,在80℃下搅拌8h,过滤、洗涤、干燥后得到脱铝β分子筛;取2g脱铝β分子筛,与0.29g结晶四氯化锡混合研磨10min,所得粉末在550℃空气气氛中焙烧4h,得到锡掺杂β分子筛。Disperse 5g of H-β molecular sieve (SiO 2 /Al 2 O 3 =25) into 100 mL of nitric acid solution with a concentration of 14 mol/L, stir at 80° C. for 8 h, filter, wash and dry to obtain dealuminated β molecular sieve; take 2g of dealuminated beta molecular sieve was mixed with 0.29g of crystalline tin tetrachloride and ground for 10 minutes, and the obtained powder was calcined in an air atmosphere at 550°C for 4 hours to obtain tin-doped beta molecular sieve.

取1.42g六水合硝酸镁溶于80mL去离子水中,加入2g锡掺杂β分子筛,用1mol/L的氢氧化钠水溶液滴加至上述溶液中,至体系的pH值等于12,室温下继续搅拌6h,过滤,洗涤至滤液呈中性,产物经过100℃干燥,500℃焙烧4h,得到Sn-β/MgO催化剂,记为样品1#Dissolve 1.42 g of magnesium nitrate hexahydrate in 80 mL of deionized water, add 2 g of tin-doped beta molecular sieve, and add 1 mol/L aqueous sodium hydroxide solution dropwise to the above solution until the pH of the system is equal to 12, and continue stirring at room temperature 6h, filtered, washed until the filtrate was neutral, the product was dried at 100°C, and calcined at 500°C for 4h to obtain a Sn-β/MgO catalyst, denoted as sample 1 # .

实施例2催化剂的制备The preparation of embodiment 2 catalyst

取5g H-β分子筛(SiO2/Al2O3=25)分散到100mL浓度14mol/L的硝酸溶液中,在80℃下搅拌8h,过滤、洗涤、干燥后得到脱铝β分子筛;取2g脱铝β分子筛,与0.29g结晶四氯化锡混合研磨10min,所得粉末在550℃空气气氛中焙烧4h,得到锡掺杂β分子筛。Disperse 5 g of H-β molecular sieve (SiO 2 /Al 2 O 3 =25) into 100 mL of nitric acid solution with a concentration of 14 mol/L, stir at 80°C for 8 h, filter, wash and dry to obtain dealuminated β molecular sieve; take 2 g The dealuminated β molecular sieve was mixed with 0.29 g of crystalline tin tetrachloride and ground for 10 minutes, and the obtained powder was calcined in an air atmosphere at 550° C. for 4 hours to obtain a tin-doped β molecular sieve.

取2.88g六水合硝酸镁溶于80mL去离子水中,加入0.5g锡掺杂β分子筛,用1mol/L的氨水溶液滴加至上述溶液中,至体系的pH值等于12,室温下继续搅拌6h,过滤,洗涤至滤液呈中性,产物经过100℃干燥,500℃焙烧4h,得到Sn-β/MgO催化剂,记为样品2#Dissolve 2.88g of magnesium nitrate hexahydrate in 80mL of deionized water, add 0.5g of tin-doped beta molecular sieve, and dropwise add 1mol/L ammonia solution to the above solution until the pH of the system is equal to 12, and continue to stir at room temperature for 6h , filtered and washed until the filtrate was neutral. The product was dried at 100°C and calcined at 500°C for 4 h to obtain a Sn-β/MgO catalyst, which was designated as sample 2 # .

实施例3催化剂的制备The preparation of embodiment 3 catalyst

取5g H-β分子筛(SiO2/Al2O3=6.25)分散到100mL浓度为10mol/L的硝酸溶液中,在80℃下搅拌8h,过滤、洗涤、干燥后得到脱铝β分子筛;取2g脱铝β分子筛,与0.058g结晶四氯化锡混合研磨10min,所得粉末在550℃空气气氛中焙烧4h,得到锡掺杂β分子筛。Disperse 5 g of H-β molecular sieve (SiO 2 /Al 2 O 3 =6.25) into 100 mL of nitric acid solution with a concentration of 10 mol/L, stir at 80° C. for 8 h, filter, wash and dry to obtain dealuminated β molecular sieve; take 2g of dealuminated beta molecular sieve was mixed with 0.058g of crystalline tin tetrachloride and ground for 10 minutes, and the obtained powder was calcined in an air atmosphere at 550°C for 4 hours to obtain tin-doped beta molecular sieve.

取1.42g六水合硝酸镁溶于80mL去离子水中,加入2g锡掺杂β分子筛,用1mol/L的氢氧化钠水溶液滴加至上述溶液中,至体系的pH值等于10,室温下继续搅拌6h,过滤,洗涤至滤液呈中性,产物经过100℃干燥,500℃焙烧4h,得到Sn-β/MgO催化剂,记为样品3#Dissolve 1.42 g of magnesium nitrate hexahydrate in 80 mL of deionized water, add 2 g of tin-doped beta molecular sieve, and add 1 mol/L aqueous sodium hydroxide solution dropwise to the above solution until the pH value of the system is equal to 10, and continue to stir at room temperature 6h, filtered, washed until the filtrate was neutral, the product was dried at 100°C, and calcined at 500°C for 4h to obtain a Sn-β/MgO catalyst, denoted as sample 3 # .

实施例4催化剂的制备The preparation of embodiment 4 catalyst

取5g H-β分子筛(SiO2/Al2O3=15)分散到100mL浓度为12mol/L的硝酸溶液中,在80℃搅拌8h,过滤、洗涤、干燥后得到脱铝β分子筛;取2g脱铝β分子筛,与0.29g结晶四氯化锡混合研磨10min,所得粉末在550℃空气气氛中焙烧4h,得到锡掺杂β分子筛。Disperse 5g of H-β molecular sieve (SiO 2 /Al 2 O 3 =15) into 100mL of nitric acid solution with a concentration of 12mol/L, stir at 80°C for 8h, filter, wash and dry to obtain dealuminated β molecular sieve; take 2g The dealuminated β molecular sieve was mixed with 0.29 g of crystalline tin tetrachloride and ground for 10 minutes, and the obtained powder was calcined in an air atmosphere at 550° C. for 4 hours to obtain a tin-doped β molecular sieve.

取0.22g六水合硝酸镁溶于80mL去离子水中,加入2g锡掺杂β分子筛,用1mol/L的氨水溶液滴加至上述溶液中,至体系的pH值等于10,室温下继续搅拌6h,过滤,洗涤至滤液呈中性,产物经过100℃干燥,500℃焙烧4h,得到Sn-β/MgO催化剂,记为样品4#Dissolve 0.22 g of magnesium nitrate hexahydrate in 80 mL of deionized water, add 2 g of tin-doped beta molecular sieve, and dropwise add 1 mol/L ammonia solution to the above solution until the pH of the system is equal to 10, and continue to stir at room temperature for 6 h. Filter and wash until the filtrate is neutral. The product is dried at 100°C and calcined at 500°C for 4 hours to obtain a Sn-β/MgO catalyst, which is designated as sample 4 # .

实施例5催化剂的制备The preparation of embodiment 5 catalyst

取5g H-β分子筛(SiO2/Al2O3=20)分散到100mL浓度14mol/L的硝酸溶液中,在80℃下搅拌8h,过滤、洗涤、干燥后得到脱铝β分子筛;取2g脱铝β分子筛,与0.29g结晶四氯化锡混合研磨10min,所得粉末在550℃空气气氛中焙烧4h,得到锡掺杂β分子筛。Disperse 5g H-β molecular sieve (SiO 2 /Al 2 O 3 =20) into 100mL of nitric acid solution with a concentration of 14mol/L, stir at 80°C for 8h, filter, wash and dry to obtain dealuminated β molecular sieve; take 2g The dealuminated β molecular sieve was mixed with 0.29 g of crystalline tin tetrachloride and ground for 10 minutes, and the obtained powder was calcined in an air atmosphere at 550° C. for 4 hours to obtain a tin-doped β molecular sieve.

取5.36g四水合醋酸镁溶于80mL去离子水中,加入2g锡掺杂β分子筛,用1mol/L的氢氧化钠水溶液滴加至上述溶液中,至体系的pH值等于12,室温下继续搅拌6h,过滤,洗涤至滤液呈中性,产物经过100℃干燥,500℃焙烧4h,得到Sn-β/MgO催化剂,记为样品5#Dissolve 5.36g of magnesium acetate tetrahydrate in 80mL of deionized water, add 2g of tin-doped beta molecular sieve, and dropwise add 1mol/L sodium hydroxide aqueous solution to the above solution until the pH value of the system is equal to 12, and continue to stir at room temperature 6h, filter, wash until the filtrate becomes neutral, the product is dried at 100°C and calcined at 500°C for 4h to obtain Sn-β/MgO catalyst, which is designated as sample 5 # .

实施例6催化剂的制备The preparation of embodiment 6 catalyst

取5g H-β分子筛(SiO2/Al2O3=25)分散到100mL浓度14mol/L的硝酸溶液中,在80℃下搅拌8h,过滤、洗涤、干燥后得到脱铝β分子筛;取2g脱铝β分子筛,与0.18g二甲基二氯化锡混合研磨10min,所得粉末在550℃空气气氛中焙烧4h,得到锡掺杂β分子筛。Disperse 5 g of H-β molecular sieve (SiO 2 /Al 2 O 3 =25) into 100 mL of nitric acid solution with a concentration of 14 mol/L, stir at 80°C for 8 h, filter, wash and dry to obtain dealuminated β molecular sieve; take 2 g The dealuminated beta molecular sieve was mixed with 0.18 g of dimethyltin dichloride and ground for 10 minutes, and the obtained powder was calcined in an air atmosphere at 550° C. for 4 hours to obtain a tin-doped beta molecular sieve.

取1.42g六水合硝酸镁溶于80mL去离子水中,加入2g锡掺杂β分子筛,用1mol/L的氢氧化钠水溶液滴加至上述溶液中,至体系的pH值等于12,室温下继续搅拌6h,过滤,洗涤至滤液呈中性,产物经过100℃干燥,500℃焙烧4h,得到Sn-β/MgO催化剂,记为样品6#Dissolve 1.42 g of magnesium nitrate hexahydrate in 80 mL of deionized water, add 2 g of tin-doped beta molecular sieve, and add 1 mol/L aqueous sodium hydroxide solution dropwise to the above solution until the pH of the system is equal to 12, and continue stirring at room temperature 6h, filtered, washed until the filtrate was neutral, the product was dried at 100°C, and calcined at 500°C for 4h to obtain a Sn-β/MgO catalyst, denoted as sample 6 # .

实施例7催化剂的制备The preparation of embodiment 7 catalyst

取5g H-β分子筛(SiO2/Al2O3=25)分散到100mL浓度14mol/L的硝酸溶液中,在80℃下搅拌8h,过滤、洗涤、干燥后得到脱铝β分子筛;取2g脱铝β分子筛,与0.18g二甲基二氯化锡混合研磨10min,所得粉末在550℃空气气氛中焙烧4h,得到锡掺杂β分子筛。Disperse 5 g of H-β molecular sieve (SiO 2 /Al 2 O 3 =25) into 100 mL of nitric acid solution with a concentration of 14 mol/L, stir at 80°C for 8 h, filter, wash and dry to obtain dealuminated β molecular sieve; take 2 g The dealuminated beta molecular sieve was mixed with 0.18 g of dimethyltin dichloride and ground for 10 minutes, and the obtained powder was calcined in an air atmosphere at 550° C. for 4 hours to obtain a tin-doped beta molecular sieve.

取1.42g六水合硝酸镁溶于80mL去离子水中,加入2g锡掺杂β分子筛,用1mol/L的氨水溶液滴加至上述溶液中,至体系的pH值等于11,室温下继续搅拌6h,过滤,洗涤至滤液呈中性,产物经过100℃干燥,500℃焙烧4h,得到Sn-β/MgO催化剂,记为样品7#Dissolve 1.42 g of magnesium nitrate hexahydrate in 80 mL of deionized water, add 2 g of tin-doped beta molecular sieve, and dropwise add 1 mol/L ammonia solution to the above solution until the pH of the system is equal to 11, and continue to stir at room temperature for 6 h. Filter and wash until the filtrate is neutral. The product is dried at 100°C and calcined at 500°C for 4 hours to obtain a Sn-β/MgO catalyst, which is designated as sample 7 # .

实施例8催化剂的制备The preparation of embodiment 8 catalyst

取5g H-β分子筛(SiO2/Al2O3=25)分散到100mL浓度14mol/L的硝酸溶液中,在80℃下搅拌8h,过滤、洗涤、干燥后得到脱铝β分子筛;取2g脱铝β分子筛,与0.16g氯化亚锡混合研磨10min,所得粉末在550℃空气气氛中焙烧4h,得到锡掺杂β分子筛。Disperse 5 g of H-β molecular sieve (SiO 2 /Al 2 O 3 =25) into 100 mL of nitric acid solution with a concentration of 14 mol/L, stir at 80°C for 8 h, filter, wash and dry to obtain dealuminated β molecular sieve; take 2 g The dealuminated beta molecular sieve was mixed with 0.16 g of stannous chloride and ground for 10 minutes, and the obtained powder was calcined in an air atmosphere at 550°C for 4 hours to obtain a tin-doped beta molecular sieve.

取1.42g六水合硝酸镁溶于80mL去离子水中,加入2g锡掺杂β分子筛,用1mol/L的氢氧化钠水溶液滴加至上述溶液中,至体系的pH值等于12,室温下继续搅拌6h,过滤,洗涤至滤液呈中性,产物经过100℃干燥,500℃焙烧4h,得到Sn-β/MgO催化剂,记为样品8#Dissolve 1.42 g of magnesium nitrate hexahydrate in 80 mL of deionized water, add 2 g of tin-doped beta molecular sieve, and add 1 mol/L aqueous sodium hydroxide solution dropwise to the above solution until the pH of the system is equal to 12, and continue stirring at room temperature 6h, filtered, washed until the filtrate was neutral, the product was dried at 100°C, and calcined at 500°C for 4h to obtain a Sn-β/MgO catalyst, denoted as sample 8 # .

实施例9催化剂的制备The preparation of embodiment 9 catalyst

取5g H-β分子筛(SiO2/Al2O3=25)分散到100mL浓度14mol/L的硝酸溶液中,在80℃下搅拌8h,过滤、洗涤、干燥后得到脱铝β分子筛;取2g脱铝β分子筛,与0.17g草酸亚锡混合研磨10min,所得粉末在550℃空气气氛中焙烧4h,得到锡掺杂β分子筛。Disperse 5 g of H-β molecular sieve (SiO 2 /Al 2 O 3 =25) into 100 mL of nitric acid solution with a concentration of 14 mol/L, stir at 80°C for 8 h, filter, wash and dry to obtain dealuminated β molecular sieve; take 2 g The dealuminated β molecular sieve was mixed with 0.17 g of stannous oxalate and ground for 10 minutes, and the obtained powder was calcined in an air atmosphere at 550° C. for 4 hours to obtain a tin-doped β molecular sieve.

取1.42g六水合硝酸镁溶于80mL去离子水中,加入2g锡掺杂β分子筛,用1mol/L的氢氧化钠水溶液滴加至上述溶液中,至体系的pH值等于12,室温下继续搅拌6h,过滤,洗涤至滤液呈中性,产物经过100℃干燥,500℃焙烧4h,得到Sn-β/MgO催化剂,记为样品9#Dissolve 1.42 g of magnesium nitrate hexahydrate in 80 mL of deionized water, add 2 g of tin-doped beta molecular sieve, and add 1 mol/L aqueous sodium hydroxide solution dropwise to the above solution until the pH of the system is equal to 12, and continue stirring at room temperature 6h, filtered, washed until the filtrate was neutral, the product was dried at 100°C, and calcined at 500°C for 4h to obtain a Sn-β/MgO catalyst, denoted as sample 9 # .

实施例10催化剂的应用Example 10 Application of Catalyst

分别取0.5g经过压片、40~60目过筛的Sn-β/MgO催化剂样品1#、样品2#、样品3#、样品6#、样品7#、样品8#、样品9#(分子筛质量含量50%),装入固定床反应器中,先在氮气气氛中450℃预处理30min,然后温度降至425℃,通入原料乙醇开始反应,乙醇流速0.017mL/min,氮气流速50mL/min,反应30min后进行分析。Take 0.5g of Sn-β/MgO catalyst sample 1 # , sample 2 # , sample 3 # , sample 6 # , sample 7 # , sample 8 # , sample 9 # (molecular sieve mass content 50%), loaded into a fixed-bed reactor, first pretreated at 450°C for 30min in a nitrogen atmosphere, then the temperature was reduced to 425°C, and the raw material ethanol was introduced to start the reaction, the ethanol flow rate was 0.017mL/min, and the nitrogen flow rate was 50mL/min. min, and analysis was performed after 30 min of reaction.

产物分析利用天美气相色谱7900在线分析,FID检测器,HP-PLOT Q毛细管柱。The products were analyzed using Tianmei gas chromatography 7900 online analysis, FID detector, HP-PLOT Q capillary column.

结果显示,样品1#、样品2#、样品3#、样品6#、样品7#、样品8#、样品9#的结果类似,均具有较高的1,3-丁二烯选择性和乙烯选择性。The results show that the results of sample 1 # , sample 2 # , sample 3 # , sample 6 # , sample 7 # , sample 8 # , and sample 9 # are similar, with higher 1,3-butadiene selectivity and higher ethylene Optional.

以样品1#为典型代表,反应结果:乙醇转化率77%,1,3-丁二烯选择性50%,乙烯选择性34%。Taking sample 1 # as a typical representative, the reaction results: the conversion rate of ethanol is 77%, the selectivity of 1,3-butadiene is 50%, and the selectivity of ethylene is 34%.

实施例11催化剂的应用Example 11 Application of catalyst

取0.5g经过压片、40-60目过筛的Sn-β/MgO催化剂样品4#(分子筛质量含量90%),装入固定床反应器中,先在氮气气氛中450℃预处理30min,然后温度降至425℃,通入原料乙醇开始反应,乙醇流速0.017mL/min,氮气流速50mL/min,反应30min后进行分析。Take 0.5 g of Sn-β/MgO catalyst sample 4 # (the mass content of molecular sieves is 90%) that has been compressed and sieved with 40-60 meshes, and put it into a fixed-bed reactor. Then the temperature was lowered to 425° C., the raw material ethanol was introduced to start the reaction, the flow rate of ethanol was 0.017mL/min, the flow rate of nitrogen was 50mL/min, and the analysis was carried out after the reaction for 30min.

产物分析利用天美气相色谱7900在线分析,FID检测器,HP-PLOT Q毛细管柱。The products were analyzed using Tianmei gas chromatography 7900 online analysis, FID detector, HP-PLOT Q capillary column.

反应结果:乙醇转化率90%,1,3-丁二烯选择性5%,乙烯选择性90%。The reaction results: the conversion rate of ethanol is 90%, the selectivity of 1,3-butadiene is 5%, and the selectivity of ethylene is 90%.

实施例12催化剂的应用Example 12 Application of catalyst

取0.5g经过压片、40-60目过筛的Sn-β/MgO催化剂样品5#(分子筛质量含量30%),装入固定床反应器中,先在氮气气氛中450℃预处理30min,然后温度降至425℃,通入原料乙醇开始反应,乙醇流速0.017mL/min,氮气流速50mL/min,反应30min后进行分析。Take 0.5g of the Sn-β/MgO catalyst sample 5 # (molecular sieve mass content 30%) that has been compressed and sieved with 40-60 meshes, loaded into a fixed-bed reactor, pretreated at 450° C. for 30min in a nitrogen atmosphere, Then the temperature was lowered to 425° C., the raw material ethanol was introduced to start the reaction, the flow rate of ethanol was 0.017mL/min, the flow rate of nitrogen was 50mL/min, and the analysis was carried out after the reaction for 30min.

产物分析利用天美气相色谱7900在线分析,FID检测器,HP-PLOT Q毛细管柱。The products were analyzed using Tianmei gas chromatography 7900 online analysis, FID detector, HP-PLOT Q capillary column.

反应结果:乙醇转化率80%,1,3-丁二烯选择性60%,乙烯选择性8%。The reaction results: the conversion rate of ethanol is 80%, the selectivity of 1,3-butadiene is 60%, and the selectivity of ethylene is 8%.

以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。The above are only a few embodiments of the present application, and are not intended to limit the present application in any form. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Without departing from the scope of the technical solution of the present application, any changes or modifications made by using the technical content disclosed above are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims (11)

1.一种用于乙醇转化制烯烃反应的酸碱双功能催化剂,其特征在于,由锡掺杂β分子筛和氧化镁组成;1. an acid-base bifunctional catalyst for ethanol conversion to olefin reaction, is characterized in that, is made up of tin-doped beta molecular sieve and magnesium oxide; 其中,所述锡掺杂β分子筛在酸碱双功能催化剂中的质量含量为10%~90%;Wherein, the mass content of the tin-doped beta molecular sieve in the acid-base bifunctional catalyst is 10% to 90%; 所述氧化镁在酸碱双功能催化剂中的质量含量为10%~90%;The mass content of the magnesium oxide in the acid-base bifunctional catalyst is 10% to 90%; 所述锡掺杂β分子筛中,硅元素与锡元素的摩尔比为40~200:1;In the tin-doped beta molecular sieve, the molar ratio of silicon element to tin element is 40-200:1; 所述用于乙醇转化制烯烃反应的酸碱双功能催化剂的制备方法至少包含以下步骤:The preparation method of the acid-base bifunctional catalyst for ethanol conversion to olefin reaction at least comprises the following steps: a)获得锡掺杂β分子筛;a) obtaining tin-doped beta molecular sieve; b)将锡掺杂β分子筛置于含有镁离子的溶液中,加入碱溶液调节pH值;b) placing the tin-doped beta molecular sieve in a solution containing magnesium ions, and adding an alkaline solution to adjust the pH value; c)分离、洗涤所得到的固体,经干燥、焙烧后,即得所述酸碱双功能催化剂。c) separating and washing the obtained solid, and after drying and calcining, the acid-base bifunctional catalyst is obtained. 2.一种如权利要求1所述的用于乙醇转化制烯烃反应的酸碱双功能催化剂的制备方法,其特征在于,至少包含以下步骤:2. a preparation method of the acid-base bifunctional catalyst for ethanol conversion to olefin reaction as claimed in claim 1, is characterized in that, comprises the following steps at least: a)获得锡掺杂β分子筛;a) obtaining tin-doped beta molecular sieve; b)将锡掺杂β分子筛置于含有镁离子的溶液中,加入碱溶液调节pH值;b) placing the tin-doped beta molecular sieve in a solution containing magnesium ions, and adding an alkaline solution to adjust the pH value; c)分离、洗涤所得到的固体,经干燥、焙烧后,即得所述酸碱双功能催化剂。c) separating and washing the obtained solid, and after drying and calcining, the acid-base bifunctional catalyst is obtained. 3.根据权利要求2所述的方法,其特征在于,所述锡掺杂β分子筛通过至少包括以下步骤的制备方法制备得到:3. The method according to claim 2, wherein the tin-doped beta molecular sieve is prepared by a preparation method comprising at least the following steps: (1)将H-β分子筛进行脱铝处理;(1) carry out dealumination treatment to H-β molecular sieve; (2)将脱铝处理后的H-β分子筛与锡前驱体混合研磨,再经过焙烧,得到所述锡掺杂β分子筛。(2) Mixing and grinding the dealuminated H-β molecular sieve with a tin precursor, and then calcining to obtain the tin-doped β molecular sieve. 4.根据权利要求3所述的方法,其特征在于,所述H-β分子筛的硅铝摩尔比SiO2/Al2O3=12.5~50。The method according to claim 3, characterized in that, the molar ratio of silicon to aluminum of the H-β molecular sieve is SiO 2 /Al 2 O 3 =12.5-50. 5.根据权利要求3所述的方法,其特征在于,所述脱铝处理是将H-β分子筛置于浓度为10~14mol/L的硝酸溶液中,于不低于50℃的温度下保持不少于7小时。5. The method according to claim 3, wherein the dealumination treatment is to place the H-β molecular sieve in a nitric acid solution with a concentration of 10-14 mol/L, and keep it at a temperature not lower than 50°C Not less than 7 hours. 6.根据权利要求3所述的方法,其特征在于,所述脱铝处理是将H-β分子筛置于质量浓度为65%~68%的硝酸溶液中,于不低于75℃的温度下保持不少于8小时。6 . The method according to claim 3 , wherein the dealumination treatment is to place the H-β molecular sieve in a nitric acid solution with a mass concentration of 65% to 68% at a temperature not lower than 75° C. 7 . Keep for no less than 8 hours. 7.根据权利要求3所述的方法,其特征在于,所述锡前驱体为结晶四氯化锡、二甲基二氯化锡、氯化亚锡或者草酸亚锡中的至少一种。7. The method according to claim 3, wherein the tin precursor is at least one of crystalline tin tetrachloride, dimethyltin dichloride, stannous chloride or stannous oxalate. 8.根据权利要求3所述的方法,其特征在于,所述脱铝处理后的H-β分子筛中硅元素的摩尔数与锡前驱体中锡元素的摩尔比为Si:Sn=40~200:1。8 . The method according to claim 3 , wherein the mole ratio of silicon element in the H-β molecular sieve after the dealumination treatment to the mole ratio of tin element in the tin precursor is Si:Sn=40~200 8 . :1. 9.根据权利要求3所述的方法,其特征在于,所述脱铝处理后的H-β分子筛与锡前驱体的质量比为2:0.05~0.3。9 . The method according to claim 3 , wherein the mass ratio of the dealuminated H-β molecular sieve to the tin precursor is 2:0.05-0.3. 10 . 10.根据权利要求2所述的方法,其特征在于,所述加入碱溶液调节pH值是加入碱溶液将体系pH值调至10~12。10 . The method according to claim 2 , wherein the pH value adjustment by adding an alkaline solution is to adjust the pH value of the system to 10-12 by adding an alkaline solution. 11 . 11.权利要求1所述的用于乙醇转化制烯烃反应的酸碱双功能催化剂或一种如权利要求2至10任意一项所述方法制备的酸碱双功能催化剂作为乙醇转化制烯烃反应催化剂的应用。11. The acid-base bifunctional catalyst for ethanol conversion to olefin reaction according to claim 1 or a kind of acid-base bifunctional catalyst prepared by the method according to any one of claims 2 to 10 as ethanol conversion to olefin reaction catalyst Applications.
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