CN109012646B - 用于制备生物柴油的钾霞石催化剂的低温合成方法 - Google Patents
用于制备生物柴油的钾霞石催化剂的低温合成方法 Download PDFInfo
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Abstract
本发明公开了一种用于制备生物柴油的钾霞石催化剂的低温合成方法及该钾霞石催化剂用于制备生物柴油中的应用。制备方法是将循环流化床粉煤灰、钾水玻璃和氢氧化钾以质量比为1:0.350~0.656:0.112拌和,经成型、养护以及水热晶化等工艺直接合成块体钾霞石,将所得块体钾霞石破碎,筛选粒径为0.150~0.315mm的块体钾霞石颗粒,得到生物柴油的催化剂;与传统的固相合成法相比,具有制备工艺简单,成本低廉,合成温度低,可大幅度降低合成钾霞石的能耗。将该方法合成的钾霞石催化剂用于制备生物柴油的催化剂,具有反应温度低、催化活性高,产物易分离,产率髙等优点,具有潜在的工业应用前景。
Description
技术领域
本发明属于催化剂制备及固体废弃物资源化利用领域,具体涉及一种应用于制备生物柴油的钾霞石催化剂的合成方法。
背景技术
循环流化床粉煤灰是新型洁净煤燃烧技术循环流化床锅炉产生的固体废弃物。据统计,我国循环流化床粉煤灰的年排放量高达0.9亿吨[1]。由于循环流化床锅炉相对低的炉内燃烧温度(约800℃~900℃),产生的循环流化床粉煤灰主要为无定型的硅铝酸盐,但其颗粒疏松、易吸水,限制了其在水泥等建筑材料领域的应用,致使其大量堆积并造成了严重的资源浪费、环境污染及经济损失。
目前,循环流化床粉煤灰的资源化利用途径主要包括:回填材料[2]、粘土砖[3]、絮凝剂[4]、沸石分子筛[5]等。钾霞石(KAlSiO4)是一种似长石,具有与沸石相类似的架状硅酸盐结构[6],因此以循环流化床粉煤灰为原料合成钾霞石具有可行性和优越性。钾霞石具有钾含量高、晶格中钾高温不易流失等特点,已被开发为合成氨、乙苯脱氢制苯乙烯以及烃类蒸汽转化制氢等石油化工工业中的催化剂助剂[7]。此外,高含量强碱性的钾性活位点使其可以作为一种制备生物柴油的固体碱催化剂[8]。工业上主要以焙烧焦宝石为原料,混合氢氧化钾或碳酸钾,并于1000℃焙烧制备钾霞石。叶瑛[9]等的中国专利申请(公开号:CN101602511A)公开了一种以粉煤灰为原料制备钾霞石的方法,该方法将粉煤灰与氢氧化钾混合,于850℃~1000℃恒温焙烧1~2h,随后经酸溶,水热,洗涤,干燥得到钾霞石粉体。郑骥[10]等报道了一种快速溶胶凝胶法制备钾霞石的方法,该方法在无有机溶剂的条件下,使用氨水调节pH值,正硅酸乙酯-硝酸钾-硝酸铝-水体系在5min~12min内即迅速胶凝。干凝胶在862℃下热处理生成的钾霞石物相单一、颗粒大小均匀、平均粒径为8μm。温家玮[11]等的中国专利申请(公开号:CN102989440A)公开了一种共沉淀法制备钾霞石粉体的方法,具体是将硅酸钾与氢氧化钾溶液混合,在磁力搅拌作用下滴入硝酸铝溶液,沉化0.5~5h,经水洗,干燥后在900℃~1200℃下焙烧0.5~4h得到均匀的钾霞石粉体。
生物柴油是以动植物油脂和醇类物质(甲醇或乙醇)为原料,通过酯交换反应得到的脂肪酸甲(乙)酯,是一种清洁的可再生能源,对环境保护和实现人类社会可持续发展具有重要意义。固体碱催化是提高生物柴油产率的有效方法,具有反应活性高、可循环使用、对反应设备腐蚀性小、油脂交换酯化率高等优点[12]。温广[8]等报道了固定床钾霞石固体碱催化豆油酯化反应制备生物柴油,采用共沉淀法,经1200℃煅烧制备了钾霞石粉体,并通过浸渍负载LiNO3得到催化剂,在反应温度120℃,醇油摩尔比12:1,反应时间为2min时生物柴油产率可达100%。
目前专利文献报导的粉体钾霞石的合成均需要高温煅烧,其制备能耗高;通过系统查阅了大量的国内专利以及文献资料,未发现利用循环流化床粉煤灰直接低温合成钾霞石的相关报导。
以下是发明人给出的相关参考文献:
[1]殷景阁,王栋民,李端乐,郑大鹏,崔勇,任才富,循环流化床粉煤灰的特性及其应用研究,中国硅酸盐学会固废分会成立大会固废处理与生态环境材料学术交流会(2015)。
[2]李登新,吕俊复,郭庆杰,岳光溪,循环流化床灰渣利用研究进展,热能动力工程,18(1)(2003)5-8。
[3]N.Koukouzas,C.Ketikidis,G.Itskos,X.Spiliotis,V.Karayannis,G.Papapolymerou,Synthesis of CFB-coal fly ash clay bricks and theircharacterization,Waste and Biomass Valorization,2(1)(2011)87-94。
[4]裴亚利,循环流化床粉煤灰的特征及其综合利用研究,吉林大学,(2006)。
[5]石泽华,王增长,王永红,利用流化床粉煤灰合成分子筛的研究,山西煤炭,27(2)(2007)14-16。
[6]鞠凤龙,天然矿物原料超临界水热法快速合成类沸石材料及其脱汞性能,太原理工大学,(2015)。
[7]车东晖,李振华,合成钾霞石焙烧工艺的改进,齐鲁石油化工,4(1997)235-237。
[8]温广,张占全,阎子峰,钾霞石固体碱催化豆油酯化反应制备生物柴油,分子催化,25(1)(2011)55-58。
[9]叶瑛,姚志通,张路,李海晏,夏枚生,戴凌青,一种以粉煤灰为原料制备钾霞石的方法,中国专利申请(公开号:CN101602511A)。
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[11]温家玮,温广,汤春雷,一种改性钾霞石生物柴油固体碱催化剂及其生产工艺,中国专利申请(公开号:CN102989440A)。
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发明内容
本发明的目的在于,提供一种用于制备生物柴油的钾霞石催化剂的低温合成方法。
为了实现上述任务,本发明采取如下的技术解决方案:
一种用于制备生物柴油的钾霞石催化剂的低温合成方法,其特征在于,将循环流化床粉煤灰、氢氧化钾、钾水玻璃放入搅拌装置中,经拌合、模具成型、养护、水热晶化得到块体钾霞石,将所得块体钾霞石破碎,筛选粒径为0.150~0.315mm的块体钾霞石颗粒,作为制备生物柴油的催化剂,其中,循环流化床粉煤灰、钾水玻璃及氢氧化钾的质量比为1:0.350~0.656:0.112。
具体按以下步骤实施:
(1)按配方量称取循环流化床粉煤灰;
(2)按配方量称取氢氧化钾,置入烧杯中;
(3)按配方量称取钾水玻璃,置入烧杯中;
(4)将步骤(2)称取的氢氧化钾溶解于步骤(3)称取的钾水玻璃中,搅拌并冷却至室温;
(5)将步骤(4)的混合溶液置于搅拌机中,将步骤(1)称取的循环流化床粉煤灰置入搅拌机中,搅拌得到均匀的浆体;
(6)将浆体盛入模具中成型,震动消除气泡,模具用塑料薄膜密封袋密封,置于恒温箱中30℃~80℃养护24h后脱模,得到块体钾霞石前驱体;
(7)将步骤(6)所得块体钾霞石前驱体置于200mL水热反应釜内,加入4~8mol/L的氢氧化钾溶液50mL,封釜,在150℃~180℃下水热晶化0~36h后取出,经洗涤、干燥,得到块体钾霞石;
(8)将步骤(7)所得块体钾霞石破碎,筛选粒径为0.150~0.315mm的块体钾霞石颗粒,作为制备生物柴油的催化剂。
根据申请人的试验表明,本发明制得的生物柴油的钾霞石催化剂能够用于合成生物柴油,具体实施步骤如下:
(1)将甲醇与植物油(大豆油或菜籽油)以12~18:1的摩尔比加入回流装置的三口烧瓶中,加入植物油总质量的1%~5%的块体钾霞石催化剂,在磁力搅拌下,反应温度65℃~95℃,反应1~24h,制备得到含有生物柴油的产物;
(2)将步骤(1)所得混合物过滤,滤液经蒸馏除去甲醇后静置分层,上层产物即为生物柴油。并采用以下公式计算生物柴油的收率Y:
Y=W生物柴油/W植物油×100%。
本发明的用于制备生物柴油的钾霞石催化剂的低温合成方法,其创新之处在于,以固体废弃物循环流化床粉煤灰为原料,成本低廉的合成出用于制备生物柴油的块体钾霞石催化剂,与传统钾霞石的合成工艺相比,具有工艺简单,合成温度低,大大降低了钾霞石合成过程中的能耗。此外,合成的块体钾霞石用于合成生物柴油,催化活性高,易分离,具有潜在的工业应用前景。
附图说明
图1是制备实施例所得到的块体钾霞石的XRD图谱;
图2是制备实施例得到块体钾霞石的电子显微镜扫描照片;
图3是应用实例2合成生物柴油的气相色谱图。
以下结合附图和实施例对本发明作进一步的详细说明。
具体实施方式
需要说明的是以下的实施例仅为了更好的诠释本发明,本发明不限于这些实施例。
在以下的实施例中,申请人给出用于制备生物柴油的钾霞石催化剂的低温合成方法及其制得的钾霞石催化剂用于制备生物柴油的应用实施例。
本实施例给出的用于制备生物柴油的钾霞石催化剂的低温合成方法,原料采用流化床粉煤灰、钾水玻璃和氢氧化钾,其中,循环流化床粉煤灰、钾水玻璃及氢氧化钾的质量比为1:0.350~0.656:0.112。
具体原料如下:
(1)循环流化床粉煤灰,购于神华准能集团有限责任公司,经烘干,振动磨粉磨30秒后备用。
(2)钾水玻璃,购于山东优索化工科技有限公司,模数3.3,其中K2O含量为13%,SiO2含量为26%。
(3)固体氢氧化钾,购于国药集团化学试剂有限公司,分析纯试剂,分子量:56.1g/mol。
(4)大豆油和菜籽油购于超市,其酸值分别为0.8mg/g和0.5mg/g,皂化值分别为193mg/g和175mg/g。
(5)甲醇购于国药集团化学试剂有限公司,分析纯试剂,分子量:32.04g/mol。
制备实施例1:
(1)称取100g循环流化床粉煤灰;
(2)称取11.2g氢氧化钾,置入烧杯中;
(3)称取65.6g钾水玻璃,置入烧杯中;
(4)将步骤(2)称取的氢氧化钾溶解于步骤(3)称取的钾水玻璃中,搅拌并冷却至室温;
(5)将步骤(4)的混合溶液置于搅拌机中,将步骤(1)称取的循环流化床粉煤灰置入搅拌机中,搅拌得到均匀的浆体;
(6)将浆体盛入模具中成型,震动消除气泡,模具用塑料薄膜密封袋密封,置于恒温箱中60℃养护24h后脱模,得到块体钾霞石前驱体;
(7)将步骤(6)所得块体钾霞石前驱体置于200mL水热反应釜内,加入4mol/L的氢氧化钾溶液50mL,封釜,于180℃反应温度下,水热晶化24h后取出,经洗涤、干燥,制备得到块体钾霞石,将所得块体钾霞石破碎,筛选粒径为0.150~0.315mm的块体钾霞石颗粒,作为制备生物柴油的催化剂。
块体钾霞石的XRD图谱如图1所示,块体钾霞石的电子显微镜扫描照片如图2所示。
制备实施例2:
(1)称取100g循环流化床粉煤灰;
(2)称取11.2g氢氧化钾,置入烧杯中;
(3)称取50.5g钾水玻璃,置入烧杯中;
(4)将步骤(2)称取的氢氧化钾溶解于步骤(3)称取的钾水玻璃中,搅拌并冷却至室温;
(5)将步骤(4)的混合溶液置于搅拌机中,将步骤(1)称取的循环流化床粉煤灰置入搅拌机中,搅拌得到均匀的浆体;
(6)将浆体盛入模具中成型,震动消除气泡,模具用塑料薄膜密封袋密封,置于恒温箱中80℃养护24h后脱模,得到块体钾霞石前驱体;
(7)将步骤(6)所得块体钾霞石前驱体置于200mL水热反应釜内,加入6mol/L的氢氧化钾溶液50mL,封釜,于180℃温度下,水热晶化24h后取出,经洗涤、干燥,即得到块体钾霞石,将所得块体钾霞石破碎,筛选粒径为0.150~0.315mm的块体钾霞石颗粒,作为制备生物柴油的催化剂。
块体钾霞石的XRD图谱如图1,块体钾霞石的电子显微镜扫描照片如图2所示。
制备实施例3:
(1)称取100g循环流化床粉煤灰;
(2)称取11.2g氢氧化钾,置入烧杯中;
(3)称取35.0g钾水玻璃,置入烧杯中;
(4)将步骤(2)称取的氢氧化钾溶解于步骤(3)称取的钾水玻璃中,搅拌并冷却至室温;
(5)将步骤(4)的混合溶液置于搅拌机中,将步骤(1)称取的循环流化床粉煤灰置入搅拌机中,搅拌得到均匀的浆体;
(6)将浆体盛入模具中成型,震动消除气泡,模具用塑料薄膜密封袋密封,置于恒温箱中80℃养护24h后脱模,得到块体钾霞石前驱体;
(7)将步骤(6)所得块体钾霞石前驱体置于200mL水热反应釜内,加入6mol/L的氢氧化钾溶液50mL,封釜,180℃温度下,水热晶化24h后取出,经洗涤、干燥,即得到块体钾霞石,将所得块体钾霞石破碎,筛选粒径为0.150~0.315mm的块体钾霞石颗粒,作为制备生物柴油的催化剂。
块体钾霞石的XRD图谱如图1所示,块体钾霞石的电子显微镜扫描照片如图2所示。
应用实施例1:
(1)称取大豆油80g;
(2)称取甲醇42g;
(3)称取块体钾霞石颗粒1.6g作为催化剂;
(4)将步骤(1)的大豆油置于带有回流装置的三口烧瓶中,放入恒温水浴锅中,65℃加热20min;
(5)将步骤(2)的甲醇置于带有回流装置的三口烧瓶中;加入步骤(3)的催化剂,回流冷凝,65℃下反应2h,反应得到含有生物柴油的产物;
(6)将步骤(5)所得的反应产物进行固-液分离,滤液经蒸馏除去甲醇后静置分层,上层产物即为生物柴油;
(7)采用以下公式计算生物柴油的收率Y:
Y=W生物柴油/W植物油×100%。
即生物柴油的产率Y为41.2%。
应用实施例2:
(1)称取菜籽油80g;
(2)称取甲醇50g;
(3)称取块体钾霞石颗粒4.0g作为催化剂;
(4)将步骤(1)的菜籽油置于带有回流装置三口烧瓶中,放入恒温水浴锅中,95℃加热20min;
(5)将步骤(2)的甲醇置于带有回流装置三口烧瓶中;加入步骤(3)的催化剂,回流冷凝,95℃下反应6h,即得含有生物柴油的产物;
(6)将步骤(5)所得产物进行过滤,滤液经蒸馏除去甲醇后静置分层,上层产物即为生物柴油;
(7)采用以下公式计算生物柴油的收率Y:
Y=W生物柴油/W植物油×100%。
即生物柴油的产率Y为93.8%。
合成生物柴油的气相色谱分析如图3所示;气相色谱-质谱联用分析结果表明,合成的生物柴油的主要成分为:棕榈酸甲酯,反油酸甲酯,硬脂酸甲酯,11-顺-二十碳一烯酸甲酯,以及13-二十二碳一烯酸甲酯。
应用实施例3:
(1)称取菜籽油80g;
(2)称取甲醇50g;
(3)称取块体钾霞石颗粒4.0g作为催化剂;
(4)将步骤(1)的菜籽油置于带有回流装置的三口烧瓶中,放入恒温水浴锅中,85℃加热20min;
(5)将步骤(2)的甲醇置于三口烧瓶;加入步骤(3)的催化剂,回流冷凝,85℃下反应24h,反应得到含有生物柴油的产物;
(6)将步骤(5)所得反应产物进行固-液分离,滤液经蒸馏除去甲醇后静置分层,上层产物即为生物柴油;
(7)采用以下公式计算生物柴油的收率Y:
Y=W生物柴油/W植物油×100%。
即生物柴油的产率Y为90.6%。
Claims (5)
1.一种用于制备生物柴油的钾霞石催化剂的低温合成方法,其特征在于,将循环流化床粉煤灰、氢氧化钾、钾水玻璃放入搅拌装置中,经拌合、模具成型、养护、水热晶化得到块体钾霞石,将所得块体钾霞石破碎,筛选粒径为0.150~0.315mm的块体钾霞石颗粒,得到生物柴油的催化剂;其中,循环流化床粉煤灰、钾水玻璃及氢氧化钾的质量比为1:0.350~0.656:0.112。
2.如权利要求1所述的方法,其特征在于,具体按以下步骤实施:
(1)按配方量称取循环流化床粉煤灰;
(2)按配方量称取氢氧化钾,置入烧杯中;
(3)按配方量称取钾水玻璃,置入烧杯中;
(4)将步骤(2)称取的氢氧化钾溶解于步骤(3)称取的钾水玻璃中,搅拌并冷却至室温;
(5)将步骤(4)的混合溶液置于搅拌机中,将步骤(1)称取的循环流化床粉煤灰置入搅拌机中,搅拌得到均匀的浆体;
(6)将浆体盛入模具中成型,震动消除气泡,模具用塑料薄膜密封袋密封,置于恒温箱中30~80℃养护24h后脱模,得到块体钾霞石前驱体;
(7)将步骤(6)所得块体钾霞石前驱体置于200mL水热反应釜内,加入4mol/L~8mol/L的氢氧化钾溶液50mL,封釜,150℃~180℃下水热晶化24h后取出,经洗涤、干燥,得到块体钾霞石;
(8)将步骤(7)所得块体钾霞石破碎,筛选粒径为0.150mm~0.315mm的块体钾霞石颗粒,作为制备生物柴油的催化剂。
3.权利要求1或2所述方法制得的生物柴油的催化剂用于合成生物柴油的应用。
4.如权利要求3所述的应用,其特征在于,具体步骤如下:
(1)将甲醇与植物油以12~18:1的摩尔比加入回流装置的三口烧瓶中,然后加入植物油总质量1%~5%的块体钾霞石催化剂,在磁力搅拌下,反应温度65℃~95℃,反应1~24h,制备得到含有生物柴油的产物;
(2)将步骤(1)所得产物过滤,滤液经蒸馏除去甲醇后静置分层,上层产物即为生物柴油,并用以下公式计算生物柴油的收率Y:
Y=W生物柴油/W植物油×100%。
5.如权利要求4所述的应用,其特征在于,所述的植物油为大豆油或菜籽油。
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