CN107915563B - 脂肪酸脱羧的方法 - Google Patents
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Abstract
本发明涉及一种脂肪酸脱羧的方法,主要解决现有技术存在能耗高,生产成本高的问题。本发明通过采用包括在非临氢条件下,脂肪酸在固定床反应器中与催化剂接触生成C12‑C18长链烷烃的步骤;所述催化剂包括a)0.1~5重量%的选自Pt、Pd和Ru中的至少一种活性组分;和b)95~99.9重量%的载体;所述载体为纳米氧化锆,其比表面积大于100厘米2/克的技术方案较好地解决了该问题,可用于脂肪酸脱羧制备C12‑C18长链烷烃的工业生产中。
Description
技术领域
本发明涉及一种脂肪酸脱羧的方法。
背景技术
当今世界的能源结构主要是由以煤、石油、天然气为代表的化石能源来构成的。这些化石能源需要通过数以百万年的时间才可以形成,基本属于不可再生能源。与此同时,化石能源的使用也带来了很多现实的问题。一方面,化石能源中不可避免地会含有少量的S、N等元素,燃烧后会生成对环境有害的硫氧化合物和氮氧化合物;另一方面,燃烧过程本身排放的大量二氧化碳也会给人类带来全球范围内的温室效应。因此,在2009年的哥本哈根会议上,各国代表承诺2012~2020年大幅度减少CO2排放。
生物能源为CO2减排提供了一条可能的途径,生物质以CO2为基本原料生长,经过处理后得到生物柴油,燃烧后产生的CO2又能供给生物质的生长,因此,使用生物柴油能大幅降低CO2排放。
第一代生物柴油的主要成分是以甘油酯为原料制备的脂肪酸甲酯。与传统柴油相比,具有S、N等有害元素含量低,生物兼容性好等优点。但是,由于其中含有大量的氧原子,造成在燃烧时热效率比较低,动力不够等缺点。在此基础上,国内外开发了第二代生物柴油技术,即加氢脱氧法。该方法是以动植物油脂中含有的大量甘油三酯(甘油三酯是由甘油及长链脂肪酸形成的酯类化合物)为原料,通过加氢脱氧技术路线除去甘油三酯分子中的氧而得到长链烷烃,再进一步得到生物柴油。第二代生物柴油克服了第一代生物柴油氧含量高的缺点,品质已经达到甚至超过了传统石化柴油,同时保留了第一代生物柴油S、N等有害元素含量低的优点,目前已经小规模工业化。
然而,该项技术也存在自身的缺陷。加氢脱氧的工艺需要消耗大量的氢气,生成1分子长链烷烃需消耗4分子H2,导致该工艺成本较高,经济性欠佳。同时,我国废弃的油脂中,除了甘油三酯等脂肪酸酯以外,也存在大量的游离脂肪酸,如不将废弃油脂加以提纯精炼,加氢脱氧工艺将难以直接应用到这些废弃油脂上。这又无形中提高了该工艺的生产成本。
脱羧法通过脱羧反应直接脱除油脂分子中的羧基,将其转变成烃类化合物。文献CN102876350A公开了一种在Ru系催化剂上由植物油或长链脂肪酸制备高十六烷值烷烃燃料的方法,该发明为间歇式釜式反应,需要临氢和反应溶剂,反应压力较高,能耗高,生产成本高。
发明内容
本发明所要解决的技术问题是现有技术存在能耗高,生产成本高的问题,提供一种新的脂肪酸脱羧的方法。该方法催化剂活性高,C12-C18长链烷烃选择性高,能耗低,生产成本低,过程简单、绿色。
为解决上述技术问题,本发明采用的技术方案如下:一种脂肪酸脱羧的方法,包括在非临氢条件下,脂肪酸在固定床反应器中与催化剂接触生成C12-C18长链烷烃的步骤;
所述催化剂包括a)0.1~5重量%的选自Pt、Pd和Ru中的至少一种活性组分;和b)95~99.9重量%的载体;
所述载体为纳米氧化锆,其比表面积大于100米2/克。
上述技术方案中,所述纳米氧化锆的比表面积为120~160米2/克。
上述技术方案中,所述纳米氧化锆的晶型为四方相。
上述技术方案中,脂肪酸为C12-C18直链脂肪酸;优选地,选自软酯酸、油酸、棕榈酸、月桂酸、硬脂酸、亚油酸和亚麻油酸中的至少一种;更优选地选自月桂酸。
上述技术方案中,脂肪酸与催化剂在惰性气体气氛下接触。优选地,所述惰性气体选自VIII族稀有气体和氮气中的至少一种。
上述技术方案中,所述惰性气体的体积空速为1000~30000小时-1。
上述技术方案中,接触温度为100~400℃,压力为常压,脂肪酸和/或脂肪酸酯的质量空速为0.1~50小时-1。
上述技术方案中,脂肪酸与催化剂接触时不需溶剂。
上述技术方案中,回流温度为0~150℃,优选80~100℃。
上述技术方案中,回流时间为1~60小时,优选24~48小时。
上述技术方案中,所述锆盐为锆的可溶性硝酸盐、碳酸盐、氯盐、草酸盐、甲酸盐、乙酸盐和铵盐中的至少一种;优选硝酸锆、硝酸氧锆、氧氯化锆和氯化锆中的至少一种。
上述技术方案中,所述碱为氢氧化钾、氢氧化钠和氨水中的至少一种。
本发明还提供一种根据所述脂肪酸脱羧的方法制备的C12-C18长链烷烃的用途。所述制备的C12-C18长链烷烃作为生物柴油燃料的应用。
本发明方法中所提供的催化剂,可使用任何适当的方法使活性金属组分分散到载体上。例如,作为活性金属组分的金属的可溶性盐溶解于溶剂,在溶液中加入载体,蒸去溶剂,然后将得到的固体经过烘干、焙烧、还原处理得到所述催化剂。
本发明方法以脂肪酸为原料,在常压固定床非临氢的条件下通过流动的惰性气体带出产物进行脱羧反应得到高碳直链烷烃,所用的催化剂以高比表面积的纳米氧化锆为载体,与现有技术相比,在保证C12-C18长链烷烃的选择性的前提下,具有不耗氢气,不用加压,能耗低的优点,降低了生物柴油的生产成本,为低品位油脂低成本转化制备生物柴油提供了重要的技术手段,取得了较好的技术效果。
附图说明
图1为实施例1~4制备的纳米氧化锆的XRD衍射图。
图1表明,根据氧化锆XRD标准谱,制备的纳米氧化锆为四方晶相,根据谢乐公式计算得到的氧化锆粒径大约为4~8纳米。
具体实施方式
本发明提供的纳米氧化锆制备方法,具体步骤如下:
a)将锆盐溶于水,配置成溶液,优选硝酸锆、硝酸氧锆、氧氯化锆和氯化锆中的至少一种;
b)在搅拌下加入碱溶液至达到指定的pH值,终点pH值的范围为7-12;
c)调节环境度到0~150℃,加上回流装置让沉淀在碱溶液中回流1~60小时,在整个回流过程中保持母液pH值不变;
d)对沉淀进行过滤、洗涤至无杂质离子,干燥,焙烧。干燥温度为60~150℃,干燥时间4~48小时,焙烧温度为200~800℃,焙烧时间为1~12小时。
下面通过实施例对本发明作进一步的阐述。
实施例1~4
将硝酸锆、氧氯化锆、硝酸氧和氯化锆溶于去离子水,配置成0.5mol L-1的溶液,打开搅拌,在300rpm的搅拌速度下逐滴加入浓氨水(质量分数37%)至pH=9,加上回流装置,升高溶液温度值100℃,回流48小时。将沉淀过滤、洗涤至无杂质离子,120℃烘干,500℃下焙烧4小时,得到纳米氧化锆。其结构表征如表1所示。
实施例5~6
将氧氯化锆溶于去离子水,配置成0.5mol L-1的溶液,打开搅拌,在300rpm的搅拌速度下分别逐滴加入NaOH(2mol L-1)和KOH(2mol L-1)溶液至pH=9,加上回流装置,升高溶液温度值100℃,回流48小时。将沉淀过滤、洗涤至无杂质离子,120℃烘干,500℃下焙烧4小时,得到纳米氧化锆。其结构表征如表1所示。
实施例7~9
将氧氯化锆溶于去离子水,配置成0.5mol L-1的溶液,打开搅拌,在300rpm的搅拌速度下分别逐滴加入浓氨水(质量分数37%)至pH=9,加上回流装置,升高溶液温度值100℃,回流48小时。将沉淀过滤、洗涤至无杂质离子,120℃烘干,分别在300℃、400℃和600℃下焙烧4小时,得到纳米氧化锆。其结构表征如表1所示。
比较例1~2
将硝酸锆溶于去离子水,配置成0.5mol L-1的溶液,打开搅拌,在300rpm的搅拌速度下分别逐滴加入NaOH(2mol L-1)溶液和浓氨水至pH=9,不回流。将沉淀过滤、洗涤至无杂质离子,120℃烘干,500℃下焙烧4小时。其结构表征如表1所示。
表1
样品 | 比表面积(m<sup>2</sup> g<sup>-1</sup>) |
实施例1 | 124 |
实施例2 | 145 |
实施例3 | 137 |
实施例4 | 152 |
实施例5 | 124 |
实施例6 | 112 |
实施例7 | 105 |
实施例8 | 135 |
实施例9 | 122 |
比较例1 | 78 |
比较例2 | 62 |
实施例10~18:Pt负载的氧化锆催化剂
称取0.5g实施例1~9制备的氧化锆粉末,加入氯铂酸溶液10mL,超声0.5h促进氧化锆的分散,随后在60℃水浴中蒸去溶剂,120℃干燥12h,空气中300℃焙烧4h,得到的催化剂前驱体在管式炉里用5%H2/Ar还原,还原温度300℃,保持时间4h,得到Pt负载的氧化锆催化剂。
比较例3~4:Pt负载的氧化锆催化剂
称取0.5g比较例1~2制备的氧化锆粉末,加入氯铂酸溶液10mL,超声0.5h促进ZrO2的分散,随后在60℃水浴中蒸去溶剂,120℃干燥12h,适当温度下焙烧4h,得到的催化剂前驱体在管式炉里用5%H2/Ar还原,还原温度300℃,保持时间4h,得到Pt负载的氧化锆催化剂。
将实施例10~18和比较例3~4用于月桂酸脱羧反应,结果如表2。
反应条件:通入气体为Ar,催化剂1g,气体流速50mL min-1,反应温度300℃,月桂酸的WHSV为0.5min-1。
表2
Claims (10)
1.一种脂肪酸脱羧的方法,包括在非临氢条件下,脂肪酸在固定床反应器中与催化剂接触生成C12-C18长链烷烃的步骤;
所述催化剂包括a)0.1~5重量%的选自Pt、Pd和Ru中的至少一种活性组分;和b)95~99.9重量%的载体;
所述载体为纳米氧化锆,其比表面积为120~160米2/克;
所述纳米氧化锆的晶型为四方相;
所述纳米氧化锆的粒径为4~8纳米;
所述纳米氧化锆是根据包括如下步骤的制备方法制得的:
a)将选自硝酸锆、硝酸氧锆、氧氯化锆和氯化锆中的至少一种的锆盐溶于水,配置成溶液;
b)在搅拌下加入碱溶液至达到指定的pH值,终点pH值的范围为7-12;
c)调节环境温度到0~150℃,加上回流装置让沉淀在碱溶液中回流1~60小时,在整个回流过程中保持母液pH值不变;
d)对沉淀进行过滤、洗涤至无杂质离子,干燥,焙烧;干燥温度为60~150℃,干燥时间4~48小时,焙烧温度为200~800℃,焙烧时间为1~12小时。
2.根据权利要求1所述脂肪酸脱羧的方法,其特征在于,脂肪酸为C12-C18直链脂肪酸。
3.根据权利要求2所述脂肪酸脱羧的方法,其特征在于,所述脂肪酸选自软酯酸、油酸、棕榈酸、月桂酸、硬脂酸、亚油酸和亚麻油酸中的至少一种。
4.根据权利要求3所述脂肪酸脱羧的方法,其特征在于,所述脂肪酸选自月桂酸。
5.根据权利要求1所述脂肪酸脱羧的方法,其特征在于,脂肪酸与催化剂在惰性气体气氛下接触。
6.根据权利要求5所述脂肪酸脱羧的方法,其特征在于,所述惰性气体选自VIII族稀有气体和氮气中的至少一种。
7.根据权利要求5所述脂肪酸脱羧的方法,其特征在于,所述惰性气体的体积空速为1000~30000小时-1。
8.根据权利要求1所述脂肪酸脱羧的方法,其特征在于,接触温度为100~400℃,压力为常压,脂肪酸的质量空速为0.1~50小时-1。
9.根据权利要求1所述脂肪酸脱羧的方法,其特征在于,脂肪酸与催化剂接触时不需溶剂。
10.根据权利要求1所述脂肪酸脱羧的方法,其特征在于,回流温度为80~100℃,回流时间为24~48小时。
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Publication number | Priority date | Publication date | Assignee | Title |
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CN1524795A (zh) * | 2003-02-28 | 2004-09-01 | 中国石油化工股份有限公司 | 一种氧化锆的制备方法 |
CN104403683A (zh) * | 2014-11-14 | 2015-03-11 | 浙江大学 | 以非贵金属催化剂催化饱和脂肪酸脱羧制备长链烷烃的方法 |
CN105237319A (zh) * | 2015-10-15 | 2016-01-13 | 浙江大学 | 一种以不饱和脂肪酸为原料零氢耗制备长链烷烃的方法 |
CN107915255A (zh) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | 纳米氧化锆的制备方法及其制备的纳米氧化锆 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN104403683A (zh) * | 2014-11-14 | 2015-03-11 | 浙江大学 | 以非贵金属催化剂催化饱和脂肪酸脱羧制备长链烷烃的方法 |
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CN107915255A (zh) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | 纳米氧化锆的制备方法及其制备的纳米氧化锆 |
Non-Patent Citations (1)
Title |
---|
Manipulating Catalytic Pathways: Deoxygenation of Palmitic Acid on Multifunctional Catalysts;Baoxiang Peng et al.;《Chem. Eur. J.》;20130320;第19卷(第15期);第4732-4741页 * |
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