CN101376629B - 一种氧化酯化生产不饱和脂肪酸酯的方法 - Google Patents
一种氧化酯化生产不饱和脂肪酸酯的方法 Download PDFInfo
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Abstract
本发明涉及一种氧化酯化生产不饱和脂肪酸酯的方法,以小分子醇类和不饱和脂肪醛为原料,在含有金属Pd活性成分催化剂的作用下,加入促进剂固体金属化合物MxNy的一种或多种,通入分子氧一步氧化酯化得到不饱和脂肪酸酯;促进剂用量在10-6-1.0g/ml;固体金属化合物成分中至少有一种催化剂所含活性组分的一种或几种保持一致;促进剂粒度在5nm-1000μm之间;形状是粉末、颗粒、球形、柱状;它与现有的技术相比,除了具有延缓催化剂组分的流失,提高催化剂稳定性和使用寿命的优点外,同时还具有提高转化率、选择性和降低成本的特点,醛转化率达到99.2%,酯选择性达到90.23%。
Description
技术领域
本发明涉及一种以不饱和脂肪醛为原料,加入固体金属化合物反应促进剂,在催化剂作用下氧化酯化生产不饱和脂肪酸酯的方法。
背景技术
不饱和脂肪酸酯是树脂塑料最主要的聚合单体,其合成方法以前主要经由初始原料,不饱和脂肪醛,不饱和脂肪酸,不饱和脂肪酸酯三步完成,由于该路线较长,中间产品不饱和脂肪酸会腐蚀设备等原因,现在研究的方向逐渐转移到不饱和脂肪醛一步氧化酯化生产不饱和脂肪酸酯。本发明涉及该反应,即以小分子醇类和不饱和脂肪醛为原料,在催化剂的作用下,被分子氧选择性氧化同时发生酯化反应得到不饱和脂肪酸酯。
分子氧、小分子醇类和不饱和脂肪醛发生氧化酯化反应生产不饱和脂肪酸酯通常以Pd为催化剂的主要组分,但单金属Pd催化剂转化率低、副产物多、选择性差。通过添加其它组分如Pb、Bi等来进行改进,催化剂性能逐步得到提高,但催化剂活性组分流失严重,失活很快,给工业应用带来极大困难。
专利USP4518796以甲基丙烯酸甲酯为例,报道了在体系中引入碱性溶液(一般是NaOH的甲醇溶液)的方法,保持反应在弱碱性环境下进行,pH=7-7.5。碱的加入加快了反应速度,在同样时间里转化率得到提高;同时减缓了由于反应中产生酸性副产物对催化剂活性组分的破坏,延长了寿命。但碱的中和作用使副反应平衡右移,使得目的产物MMA选择性受到较大 的影响。碱的加入仍无法从根本上改变催化剂组分流失这一现状,催化剂失活仍然严重,需要不断更换或再生催化剂,不仅操作复杂,而且增加了成本。
发明内容
本发明的目的是提供一种氧化酯化生产不饱和脂肪酸酯的方法;找到一种由不饱和脂肪醛被分子氧选择氧化同时和甲醇发生酯化反应生产不饱和脂肪酸酯的反应促进剂。
本发明所述的一种氧化酯化生产不饱和脂肪酸酯的方法,以小分子醇类和不饱和脂肪醛为原料,在含有金属Pd活性成分催化剂的作用下,加入促进剂固体金属化合物MxNy的一种或多种,通入分子氧一步氧化酯化得到不饱和脂肪酸酯;促进剂分子式MxNy:其中金属M是指镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、镓(Ga)、铟(In)、锡(Sn)、铊(Tl)、铅(Pb)、铋(Bi)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、钌(Ru)、铑(Rh)、银(Ag)、镉(Gd)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、金(Au)、汞(Hg)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)和镥(Lu)。N是指O2-、OH-、HCO3 -或者CO3 2-。x和y是符合实际组成的化学计量系数。这些金属氧化物、氢氧化物和碳酸盐以固体形式存在,通过自身的溶解,抑制该类元素从催化剂上流失,补充流失元素,延长催化剂的使用寿命。
促进剂可以和催化剂一同加入,也可以与反应物预先混合,通过搅拌分散于体系中。但它们既不是催化剂的活性组分,也不是载体。促进剂形状是粉末、颗粒、球形、柱状,加入浓度控制在10-6-1.0g/ml范围内,粒度 要求在5nm-1000μm之间,建议最好大于催化剂孔道,以免引起阻塞而影响反应。
反应中所用催化剂成分、载体和形状没有具体要求,但促进剂的成分中至少有一种必须与催化剂所含活性组分的一种或几种保持一致。反应温度、压力、氧气流量、MAL/MeOH比以等工艺条件及反应器型式根据要求调整。
促进剂是通过在体系中的溶解,抑制该类元素从催化剂上流失,补充流失元素,延长催化剂的使用寿命。它与现有的技术相比,除了具有延缓催化剂组分的流失,提高催化剂稳定性和使用寿命的优点外,同时还具有提高转化率、选择性和降低成本的特点,醛转化率达到99.2%,酯选择性达到90.23%。
具体实施方式
下面用实施例来具体说明本发明,其中涉及到的术语定义如下:
醛转化率C(%)=反应消耗不饱和脂肪醛摩尔数/投入反应总不饱和脂肪醛摩尔数×100%
酯选择性S(%)=反应生成不饱和脂肪酸酯摩尔数/理论不饱和脂肪酸酯生成摩尔数×100%
实施例1
在100ml烧瓶中加入2.0ml甲基丙烯醛和50.0ml甲醇,用0.3mol/L的NaOH-MeOH溶液调节pH值至10.0。然后再加入0.10g Fe2O3和1.0g催化剂Pd5Bi2PbFe/CaCO3,搅拌均匀。设定氧气流量15ml/min,在60℃下反应60min。重复反应3次,结果见附表。
实施例2
在100ml烧瓶中加入2.0ml甲基丙烯醛和50.0ml甲醇,然后加入0.10gMg(OH)2和1.0g催化剂Pd5Pb5Mg2/γ-Al2O3,搅拌均匀。设定氧气流量18ml/min,在60℃下反应60min。重复反应3次,结果见附表。
实施例3
在100ml烧瓶中加入2.0ml甲基丙烯醛和50.0ml甲醇,然后加入0.10gLa2O3和1.0g催化剂Pd5Pb5MgLa/γ-Al2O3,搅拌均匀。设定氧气流量18ml/min,在60℃下反应60min。重复反应3次,结果见附表。
实施例4
在100ml烧瓶中加入1.6ml丙烯醛和50.0ml甲醇,用0.3mol/L的NaOH-MeOH溶液调节pH值至8.0。然后再加入0.20g Fe2O3和1.0g催化剂Pd5Bi2PbFe/CaCO3,搅拌均匀。设定氧气流量15ml/min,在60℃下反应60min。重复反应3次,结果见附表。
实施例5
在100ml烧瓶中加入1.6ml丙烯醛和50.0ml甲醇,然后加入0.20gMg(OH)2和1.0g催化剂Pd5Pb5Mg2/γ-Al2O3,搅拌均匀。设定氧气流量18ml/min,在60℃下反应60min。重复反应3次,结果见附表。
实施例6
在100ml烧瓶中加入1.6ml丙烯醛和50.0ml甲醇,然后加入0.05g La2O3和1.0g催化剂Pd5Pb5MgLa/γ-Al2O3,搅拌均匀。设定氧气流量18ml/min,在60℃下反应60min。重复反应3次,结果见附表。
对比例1
在100ml烧瓶中加入2.0ml甲基丙烯醛和50.0ml甲醇,用0.3mol/L的NaOH-MeOH溶液调节pH值至10.0。然后加入1.0g催化剂Pd5Bi2PbFe/CaCO3,设定氧气流量15ml/min,在60℃下搅拌反应60min。重复反应3次,结果见附表。
对比例2
在100ml烧瓶加入2.0ml甲基丙烯醛和50.0ml甲醇,然后加入1.0g催化剂Pd5Pb5Mg2/γ-Al2O3,设定氧气流量18ml/min,在60℃下反应60min。重复反应3次,结果见附表。
对比例3
在100ml烧瓶加入2.0ml甲基丙烯醛和50.0ml甲醇,然后加入1.0g催化剂Pd5Pb5MgLa/γ-Al2O3,设定氧气流量18ml/min,在60℃下反应60min。重复反应3次,结果见附表。
对比例4
在100ml烧瓶中加入1.6ml丙烯醛和50.0ml甲醇,用0.3mol/L的NaOH-MeOH溶液调节pH值至8.0。然后加入1.0g催化剂Pd5Bi2PbFe/CaCO3,设定氧气流量18ml/min,在60℃下反应60min。重复反应3次,结果见附表。
对比例5
在100ml烧瓶中加入1.6ml丙烯醛和50.0ml甲醇,然后加入1.0g催化剂Pd5Pb5Mg2/γ-Al2O3,设定氧气流量18ml/min,在60℃下反应60min。重复反应3次,结果见附表。
对比例6
在100ml烧瓶加入1.6ml丙烯醛和50.0ml甲醇,然后加入1.0g催化剂Pd5Pb5MgLa/γ-Al2O3,设定氧气流量18ml/min,在60℃下反应60min。重复反应3次,结果见附表。
实施例及对比例中的结果如下:
Claims (1)
1.一种氧化酯化生产不饱和脂肪酸酯的方法,其特征在于:以甲醇和不饱和脂肪醛为原料,在含有金属Pd活性成分催化剂的作用下,加入促进剂固体金属化合物MxNy的一种或多种,通入分子氧一步氧化酯化得到不饱和脂肪酸酯;
促进剂分子式MxNy:
其中金属M是指镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、镓(Ga)、铟(In)、锡(Sn)、铊(Tl)、铅(Pb)、铋(Bi)、钪(Sc)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钇(Y)、锆(Zr)、铌(Nb)、钼(Mo)、钌(Ru)、铑(Rh)、银(Ag)、镉(Gd)、铪(Hf)、钽(Ta)、钨(W)、铼(Re)、锇(Os)、铱(Ir)、铂(Pt)、金(Au)、汞(Hg)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)和镥(Lu);N是指O2-、OH-、CO3 2-或HCO3 -;x和y是符合实际组成的化学计量系数;
促进剂用量在10-6-1.0g/ml;形状是粉末、颗粒、球形、柱状;粒度在5nm-1000μm之间;
促进剂固体金属化合物其成分中至少有一种必须与催化剂所含活性组分的一种或几种保持一致。
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