CN108067211A - 一种甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法 - Google Patents
一种甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法 Download PDFInfo
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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Abstract
本发明涉及甘油加氢制备1,3‑丙二醇催化剂的制备方法。包括有以下步骤:将ZrO2粉体、粘结剂与水混合,捏合,然后老化,再挤出使成型,烘干,200‑800℃焙烧,获得条形ZrO2载体;在上述制备过程中,所述粘结剂选自无机酸、有机酸、溶胶中的一种或几种。本发明的特点是使用纳米级单斜晶型ZrO2粉体为原料,通过调整粘结剂种类与添加量、水与粉体比例、捏合时间、老化时间、焙烧温度和时间等条件控制成型强度,通过挤出成型法制得的条形ZrO2载体。使用成型的ZrO2载体通过浸渍法负载组分WO3和Pt,焙烧后制得甘油加氢制备1,3‑丙二醇催化剂,制成后催化剂的晶体结构为单斜晶型,不但具有良好的加氢性能,制备的二氧化锆基催化剂强度可以满足工业生产要求。
Description
技术领域
本发明涉及甘油加氢制备1,3-丙二醇催化剂的制备方法。
背景技术
1,3-丙二醇(1,3-PDO)是合成聚对苯二甲酸丙二醇酯(PTT)的基本原料。PTT是纺织工业中一种新型聚酯化学纤维,性能明显优于PET和PBT,克服了PET的刚性和PBT的柔性,特别是它有优异的回弹性、易染性、抗污性、耐磨性、低吸水性以及良好的色牢度,兼具涤纶、锦纶甚至氨纶的优点。PTT纤维将逐步替代涤纶和锦纶而成为21世纪重要的纤维种类之一。目前为止,全球1,3-丙二醇的生产主要掌控在壳牌、德固萨和杜邦三家公司手中,1,3-丙二醇主要生产工艺路线为环氧乙烷法、丙烯醛法和生物法。环氧乙烷法和丙烯醛法路线分别使用乙烯、丙烯等非可再生石油原料,工艺路线复杂,反应条件苛刻。虽然目前生物法制备1,3-丙二醇在技术上已经成熟,但是也存在菌种昂贵、产物分离复杂等缺点。而使用甘油选择性加氢制备1,3-丙二醇,生产工艺简单、反应条件温和,为1,3-丙二醇的合成提供了一条新途径。
二氧化锆基催化剂是目前甘油加氢制备1,3-丙二醇催化剂中研究较多的一种催化剂,二氧化锆基催化剂具有反应条件温和、产物选择性高等优点。中国发明专利CN200810195218.1公开了一种甘油直接加氢制备1,3-丙二醇的技术,以固定床反应器和Pt/WO3/ZrO2为催化剂进行甘油加氢制备1,3-丙二醇。文献Catalysis Communication,2008, 9(6): 1360- 1363以WO3/ZrO2载体负载贵金属Pt为催化剂,使用高压反应釜在温度为443 K,氢气压力8.0 MPa的条件下进行甘油催化加氢合成1,3-丙二醇。
上述甘油加氢制备1,3-丙二醇的二氧化锆基催化剂均为粉末催化剂,主要制备方法为:先采用共沉淀法或溶胶-凝胶法制备Zr(OH)4,高温焙烧后得ZrO2粉体,负载活性组分后将粉末催化剂压片供加氢使用,由于加氢反应过程中原料甘油粘度高、反应过程中产生水及多元醇等各种因素,用该方法制备的催化剂机械强度差,在使用过程中易破碎、活性组分易流失,仅可用于实验室小试评价。而制备满足工业加氢使用要求的高机械强度催化剂是甘油加氢制备1,3-丙二醇工艺实现产业化的重要前提。
目前二氧化锆的成型技术要集中在高温陶瓷材料领域,由于二氧化锆易受热发生表面积和孔体积损失,降低了二氧化锆的强度和耐久性,用途受到较大的局限,因此用于催化剂载体的二氧化锆成型技术的报道较少。中国发明专利CN201410002106.5公开了一种用于生产生物柴油的氧化锆催化剂及制备方法,将氧化锆与氧化铝、二氧化钛等混合,以酸性硅溶胶为粘结剂,使用造粒机造粒成型,焙烧后制得成型催化剂。中国发明专利CN201080010127.1公开了一种多元酸促进的氧化锆催化剂或催化剂载体的制备方法。
上述方法制备的二氧化锆载体或二氧化锆基催化剂在成型过程中掺杂或引入其他物质,这对甘油加氢催化剂的反应性能有着较大的影响,同时二氧化锆成型工艺和方法直接影响到用其制备催化剂的比表面积、孔径、晶型、机械强度等,进而影响催化剂的加氢性能。因此,二氧化锆的成型方法对Pt/WO3/ZrO2催化剂甘油加氢制备1,3-丙二醇的性能起着至关重要的作用。
发明内容
本发明的目的是提供一种用于甘油加氢制备1,3-丙二醇的二氧化锆基催化剂的制备方法。
本发明的用于甘油加氢制备1,3-丙二醇的二氧化锆基催化剂的成型方法,包括如下步骤:
(1)将单斜晶型的ZrO2粉体、粘结剂与水混合,捏合10-120 min,然后老化1-48 hr,再挤出使成型,在60-180 ℃烘1-12 hr,200-800 ℃焙烧1-12 hr,获得条状ZrO2载体;
所述的粘结剂选自硝酸、盐酸、硫酸、磷酸、硼酸、钛酸等无机酸、甲酸、乙酸、丙酸、草酸、柠檬酸、酒石酸、丙二酸等有机酸、甲基纤维素、聚乙烯醇、氧化铝溶胶、氧化硅溶胶、氧化锆溶胶、氧化钛溶胶等物质中的一种或几种。
以ZrO2粉体、粘结剂和水的总质量计,粘结剂用量为1-30%,水的用量为1-20%,余量为ZrO2粉体;
术语“老化”,指的是,在静置状态下放置一定的时间;
ZrO2粉体的粒径为5-20 nm;
(2)在制得的条状ZrO2载体上进一步浸渍负载组分WO3和Pt,即制得甘油加氢制备1,3-丙二醇成型Pt/WO3/ZrO2催化剂;
步骤(2)为公知的方法,如文献Catal Commun.,2008,9,1360报道的方法。
本发明的特点是使用纳米级单斜晶型ZrO2粉体为原料,通过调整粘结剂种类与添加量、水与粉体比例、捏合时间、老化时间、焙烧温度和时间等条件控制成型强度,通过挤出成型法制得的条形ZrO2载体。使用成型的ZrO2载体通过浸渍法负载组分WO3和Pt,焙烧后制得甘油加氢制备1,3-丙二醇催化剂,制成后催化剂的晶体结构为单斜晶型,不但具有良好的加氢性能,制备的二氧化锆基催化剂强度可以满足工业生产要求。
具体实施方式
实施例1
称取平均粒径为20 nm的单斜晶型ZrO2粉体80 g,加入质量浓度为0.13 g/ml的硝酸溶液18.8 g,混合均匀后使用捏合机捏合30 min,常温老化10 hr后,使用挤条机将ZrO2湿团挤成直径为3 mm的条状,120 ℃烘2 hr,500 ℃焙烧4 hr后制得条形ZrO2载体,载体平均侧向抗压碎力为18.1 N/颗。
侧向抗压碎力采用KQ-3 型颗粒强度测定仪(云南省化工研究院)测定载体颗粒(颗粒直径3 mm,颗粒长度3-4 mm)侧向抗压碎强度,每种载体测40个,取平均值。
实施例2
称取平均粒径为5 nm的单斜晶型ZrO2粉体80 g,加入2.4 g羟丙基纤维素,再加入质量浓度为0.13 g/ml的硝酸溶液18.8 g,混合均匀后使用捏合机捏合30 min,常温老化10 hr后使用挤条机将ZrO2湿团挤成直径为3 mm的条状,烘干后经500 ℃焙烧4 hr后制得条形ZrO2载体,载体平均侧向抗压碎力为26.1 N/颗。
实施例3
称取平均粒径为10 nm的单斜晶型ZrO2粉体80 g,加入2.4 g羟丙基纤维素和1.2 g乙酸,再加入质量浓度为0.13 g/ml的硝酸溶液18.8 g,混合均匀后使用捏合机捏合30 min,常温老化24 hr后使用挤条机将ZrO2湿团挤成直径为3 mm的条状,烘干后经600 ℃焙烧6hr后制得条形ZrO2载体,载体平均侧向抗压碎力为35.4 N/颗。
实施例4
称取平均粒径为10 nm的单斜晶型ZrO2粉体80 g,加入2.4 g聚乙烯醇和1.2 g酒石酸,再加入质量浓度为0.13 g/ml的硝酸溶液18.8 g,混合均匀后使用捏合机捏合30 min,常温老化24 hr后使用挤条机将ZrO2湿团挤成直径为3 mm的条状,烘干后经600 ℃焙烧6 hr后制得条形ZrO2载体,载体平均侧向抗压碎力为32.1 N/颗。
实施例5
称取平均粒径为15nm的单斜晶型ZrO2粉体80 g,加入2.4 g羟丙基纤维素和1.2 g酒石酸,再加入质量浓度为0.13 g/ml的磷酸溶液18.8 g,混合均匀后使用捏合机捏合30 min,常温老化24 hr后使用挤条机将ZrO2湿团挤成直径为3 mm的条状,烘干后经600 ℃焙烧6hr后制得条形ZrO2载体,载体平均侧向抗压碎力为29.8 N/颗。
实施例6
称取平均粒径为15 nm的四方晶型ZrO2粉体80 g,加入2.4 g羟丙基纤维素和1.2 g乙酸,再加入质量浓度为0.13 g/ml的硝酸溶液18.8 g,混合均匀后使用捏合机捏合30 min,常温老化24 hr后使用挤条机将ZrO2湿团挤成直径为3 mm的条状,烘干后经600 ℃焙烧6hr后制得条形ZrO2载体,载体平均侧向抗压碎力为30.1 N/颗。
实施例7
采用与实施例2相同方法制备的条形ZrO2载体制备甘油加氢制备1,3-丙二醇催化剂,催化剂的制备按如下步骤:
(1) 分别量取0.13 g/ml氯铂酸溶液2.5 g与1.52 g/ml钨酸铵溶液1.8 g进行混合,将所得混合溶液与5.0 g条形ZrO2载体混和,使混合溶液均匀浸渍在所述ZrO2载体上;
(2)将以上浸渍后的催化剂在120 ℃下烘干2 hr;
(3)将以上烘干后的催化剂固体在500 ℃下焙烧4 hr;
(4)将以上焙烧后的催化剂固体用氢气在250 ℃下还原活化2 hr,即得到甘油加氢制备1,3-丙二醇加氢催化剂。其中催化剂中Pt的含量为2%(wt%),WO3的含量为5%(wt%),ZrO2的含量为93%(wt%)。
将5 g采用浸渍法制备的二氧化锆基催化剂装入一个直径为12 mm的不锈钢反应器中,将甘油与水混合后用高压恒流泵打入反应器,与氢气共同进入不锈钢反应器进行反应,甘油溶液进料量为0.24 ml/hr,氢气进料流量为0.003 m3/hr,反应温度为135 ℃,反应压力2.5 MPa。甘油转化率为69.1%,1,3-丙二醇的选择性为74.8%。
实施例8
本例采用与实施例3相同方法制备的条形ZrO2载体,采用实施例5的方法制备甘油加氢制备1,3-丙二醇催化剂,相同的反应条件下甘油转化率为84.5%,1,3-丙二醇的选择性为79.9%。
实施例9
本例采用与实施例6相同方法制备的条形ZrO2载体,采用实施例5的方法制备甘油加氢制备1,3-丙二醇催化剂,相同的反应条件下甘油转化率为56.4%,1,3-丙二醇的选择性为61.0%。
尽管已结合优选实施例来描述本发明,但应了解,本发明不应受限于这些例示性实施例,而可由本领域技术人员在不背离本发明之实质和范围的情况下进行各种修改。
Claims (10)
1.甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法,其特征在于,包括有以下步骤:将ZrO2粉体、粘结剂与水混合,捏合,然后老化,再挤出使成型,烘干,200-800 ℃焙烧,获得条形ZrO2载体;
在上述制备过程中,所述粘结剂选自无机酸、有机酸、溶胶中的一种或几种。
2.根据权利要求1所述的甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法,其特征在于,采用单斜晶型的ZrO2粉体。
3.根据权利要求2所述的甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法,其特征在于,所述粘结剂采用无机酸和溶胶的混合物,或者有机酸和溶胶的混合物。
4.根据权利要求1所述的甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法,其特征在于,采用单斜晶型ZrO2粉体,所述粘结剂选用有机酸和溶胶的混合物。
5.根据权利要求1所述的甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法,其特征在于,所述粘结剂选用有机酸和溶胶的混合物。
6.根据权利要求1所述的甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法,其特征在于,所述粘结剂选自硝酸、盐酸、硫酸、磷酸、硼酸、钛酸无机酸;甲酸、乙酸、丙酸、草酸、柠檬酸、酒石酸、丙二酸有机酸;羟丙基纤维素、甲基纤维素、聚乙烯醇、氧化铝溶胶、氧化硅溶胶、氧化锆溶胶、氧化钛溶胶等物质中的一种或几种。
7.根据权利要求1所述的甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法,其特征在于,条形ZrO2载体获得后,分别浸渍负载组分WO3和Pt,即制得甘油加氢制备1,3-丙二醇成型Pt/WO3/ZrO2催化剂。
8.根据权利要求1所述的甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法,其特征在于,ZrO2粉体、粘结剂与水混合,捏合10-120 min,然后老化1-48 hr,再挤出使成型,接着在60-180 ℃烘1-12 hr,200-800 ℃焙烧1-12 hr。
9.根据权利要求1所述的甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法,其特征在于,以ZrO2粉体、粘结剂和水的总质量计,粘结剂用量为1-30%,水的用量为1-20%,余量为ZrO2粉体。
10.根据权利要求1所述的甘油加氢制备1,3-丙二醇的二氧化锆基催化剂制备方法,其特征在于,所述ZrO2粉体的粒径为5-20 nm。
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