CN106179403B - 一种合成2,3,3,3-四氟丙烯的方法 - Google Patents
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
本发明公开了一种合成2,3,3,3‑四氟丙烯的方法,在催化剂作用下,将一溴甲烷与四氟乙烯进行连续反应制备2,3,3,3‑四氟丙烯,所述一溴甲烷与四氟乙烯摩尔比为1~5∶1,反应物停留时间为5~50s,反应压力为0.1~0.5Mpa,反应温度为300~500℃,所述催化剂为用P或S元素掺杂改性的γ‑Al2O3,所述P或S元素的质量百分含量为1‑10%。优点是目标产物选择性好,收率高。
Description
技术领域
本发明涉及HFO-1234yf制备领域,特别涉及一种合成2,3,3,3-四氟丙烯的方法。
背景技术
2,3,3,3-四氟丙烯,分子式为CF3CF=CH2,沸点-28.3℃,CAS号:754-12-1,其ODP为0,GWP为4,具有良好的寿命期气候性能,大气寿命仅11天;具有优良的物化性能,其分子量和HFC-134a相近,具有较低的沸点和常温时较高的饱和蒸汽压,且与HFC-134a有相近的密度和临界点,因此被认为是HFC-134a的“直接替代物”,成为最具有潜力的第四代低碳制冷剂之一。
根据文献及专利,目前2,3,3,3-四氟丙烯合成路线按起始原料分主要有:四氟乙烯法、三氟丙炔法、三氟丙烯法、四氟丙醇法、六氟丙烯法(HFP)、四氯丙烯法、HCFC-242法、二氟氯甲烷法、CF3COCH2COCF3法、HFO-1234ze异构化法等。其中六氟丙烯法是研究最多的路线之一。如US20070179324A、CN102267869A、CN102026947A等公开由六氟丙烯为起始原料,经过加氢、脱氟化氢,再加氢、脱氟化氢等四步反应得到CF3CF=CH2。尽管如此,这些专利提供的方法工艺仍然存在步骤多且复杂、设备投资大,分离成本高、能耗大、三废排放多等缺点。
CN104169246A公开了一种2,3,3,3-四氟丙烯的制造方法,它是一种由含一氯二氟甲烷和氯甲烷的原料组合物,通过伴随着热分解的合成反应制造2,3,3,3-四氟丙烯。CN102675038A同样公开了一种2,3,3,3-四氟丙烯的制备方法,是以二氟一氯甲烷和一氯甲烷为原料,采用在N2气体存在下,于600~1000℃高温条件下热裂解反应制得2,3,3,3-四氟丙烯。但这两篇专利公开的制备方法中,一氯二氟甲烷和氯甲烷虽然可以一步反应制备2,3,3,3-四氟丙烯,大大缩短了工艺流程,但两种反应原料二氟一氯甲烷和一氯甲烷在较高温度下均易发生热裂解反应,导致反应生成的产物成分复杂,导致制备2,3,3,3-四氟丙烯选择性差。
CN102442880A报道采用CHXYZ与四氟乙烯为原料催化制备2,3,3,3-四氟丙烯。所述通式CHXYZ中X为Cl、Br或I中的一种,Y、Z同时或分别选自H或卤素。反应温度为400~700℃,反应压力为0.3~0.5Mpa,物料停留时间为2~150s。尽管采用了催化剂,一氯甲烷裂解成卡宾所需反应温度仍然较高,致使四氟乙烯在此温度下同样会发生裂解导致副产物种类较多,且在较高温度下发生催化热裂解反应,催化剂极易积碳,导致催化剂寿命短,且易堵塞管道,无工业化前景。
发明内容
针对现有技术的不足,本发明的目的在于提供一种催化活性好、使用寿命长、安全环保、易于工业化的合成2,3,3,3-四氟丙烯的方法。
本发明的上述目的是通过以下技术方案实现的:一种合成2,3,3,3-四氟丙烯的方法,在催化剂作用下,将一溴甲烷与四氟乙烯进行连续反应制备2,3,3,3-四氟丙烯,所述一溴甲烷与四氟乙烯摩尔比为1~5∶1,反应物停留时间为5~50s,反应压力为0.1~0.5Mpa,反应温度为300~500℃,所述催化剂为用P或S元素掺杂改性的γ-Al2O3,所述P或S元素的质量百分含量为1-10%。
所述活性γ-Al2O3粒径为1~5mm,比表面积为300~380m2/g。
催化剂的制备方法,包括以下步骤:
(1)将含P或S元素的改性前躯物的水溶液分别等体积浸渍到γ-Al2O3载体上,得到浸渍产物;
(2)将浸渍产物干燥,得到干燥后的产物;
(3)将干燥后的产物在于空气氛中焙烧,得到催化剂。
所述含P元素的改性前躯物优选为H3PO4、(NH3)3PO4、(NH3)2HPO4、NH3H2PO4中一种。
所述含S元素的改性前躯物优选为(NH4)2SO4或NH4HSO4。
所述浸渍时间优选为6-24h,所述干燥温度优选为100-150℃,干燥时间优选为10-15h,所述焙烧温度优选为350-450℃,焙烧时间优选为2-6h。
本发明中催化剂载体采用容易商业采购的球形或其它形状的成型活性γ-Al2O3(粒径1-5mm,比表面积300-380m2/g),具有成本低的优点。
本发明的催化剂制备方法采用传统的浸渍法,方法简单,省去催化剂成型步骤,催化剂不需要再进行活化,空气氛焙烧后即可使用,具有工艺简单、安全环保的优点。
与现有技术相比,本发明具有以下优点:
1、催化活性好、使用寿命长,HFO-1234选择性在80.6%以上,最高可达94.3%;
2、催化剂制备工艺简单,成本低、安全环保,催化剂制备方法采用传统的浸渍法,采用已经成型的高表面积活性γ-Al2O3担载的非金属氟化催化剂,省去了催化剂成型步骤,方法简单,催化剂不需要再进行活化,空气氛焙烧后即可使用,具有工艺简单、安全环保的优点;
3、本发明制备的催化剂用于一溴甲烷与四氟乙烯为原料合成2,3,3,3-四氟丙烯,催化反应能在较低的温度下进行,原料TFE转化率在81.1%以上,最高可达92.9%,效率高,减少了大量的物料循环,降低了能耗,具有原料易得,能耗低,易于工业化的优点。
具体实施方式
以下通过实施例对本发明进行更具体的说明,但本发明并不限于所述的实施例。
实施例1
(1)P2O5/γ-Al2O3催化剂制备
将H3PO4按P负载量2wt%的量溶于水,配成30ml的水溶液,取50克粒径3mm,比表面积300m2/g的球形γ-Al2O3为载体,将上述H3PO4水溶液等体积浸渍到载体上,浸渍时间为12h。浸渍完成后,100℃干燥12h,400℃空气氛中焙烧4h。制备得到P含量为2wt%的P2O5/γ-Al2O3催化剂。焙烧后的催化剂填装至内径26mm,长60mm的316L不锈钢管式反应器中。
(2)2,3,3,3-四氟丙烯制备
将催化剂用氮气室温下吹扫12h除氧,停氮气,通入一溴甲烷和四氟乙烯混合气体,混合气体中一溴甲烷与四氟乙烯摩尔流量比为1.5:1,设定反应温度300℃,压力0.1Mpa,物料在反应器恒温区有效停留时间5s,出口混合气经碱洗、干燥,反应2h后取样气相色谱分析,结果见表1。
实施例2
(1)P2O5/γ-Al2O3催化剂制备
将(NH3)3PO4按P负载量5wt%的量溶于水,配成30ml的水溶液,取50克粒径1mm,比表面积380m2/g的球形γ-Al2O3为载体,将上述(NH3)3PO4水溶液等体积浸渍到载体上,浸渍时间为6h。浸渍完成后,120℃干燥10h,350℃空气氛中焙烧6h。制备得到P含量为5wt%的P2O5/γ-Al2O3催化剂。焙烧后的催化剂填装至内径26mm,长60mm的316L不锈钢管式反应器中。
(2)2,3,3,3-四氟丙烯制备
将催化剂用氮气室温下吹扫12h除氧,停氮气,通入一溴甲烷和四氟乙烯混合气体,混合气体中一溴甲烷与四氟乙烯摩尔流量比为5:1,设定反应温度400℃,压力0.5Mpa,物料在反应器恒温区有效停留时间50s,出口混合气经碱洗、干燥,反应2h后取样气相色谱分析,结果见表1。
实施例3
(1)P2O5/γ-Al2O3催化剂制备
将(NH3)2HPO4按P负载量10wt%的量溶于水,配成30ml的水溶液,取50克粒径5mm,比表面积320m2/g的球形γ-Al2O3为载体,将上述(NH3)2HPO4水溶液等体积浸渍到载体上,浸渍时间为24h。浸渍完成后,150℃干燥24h,450℃空气氛中焙烧2h。制备得到P含量为10wt%的P2O5/γ-Al2O3催化剂。焙烧后的催化剂填装至内径26mm,长60mm的316L不锈钢管式反应器中。
(2)2,3,3,3-四氟丙烯制备
将催化剂用氮气室温下吹扫12h除氧,停氮气,通入一溴甲烷和四氟乙烯混合气体,混合气体中一溴甲烷与四氟乙烯摩尔流量比为1.5:1,设定反应温度300℃,压力0.1Mpa,物料在反应器恒温区有效停留时间10s,出口混合气经碱洗、干燥,反应2h后取样气相色谱分析,结果见表1。
表1:实施例1-3反应条件及结果
实施例4
(1)S/γ-Al2O3催化剂制备
将(NH4)2SO4按S负载量1wt%的量溶于水,配成30ml的水溶液,取50克粒径2mm,比表面积360m2/g的球形γ-Al2O3为载体,将上述(NH4)2SO4水溶液等体积浸渍到载体上,浸渍时间为12h。浸渍完成后,100℃干燥12h,400℃空气氛中焙烧4h。制备得到S含量为1wt%的S/γ-Al2O3催化剂。焙烧后的催化剂填装至内径26mm,长60mm的316L不锈钢管式反应器中。
(2)2,3,3,3-四氟丙烯制备
将催化剂用氮气吹扫12h除氧,停氮气,通入一溴甲烷和四氟乙烯混合气体,混合气体中一溴甲烷与四氟乙烯摩尔流量比为1.5:1,设定反应温度300℃,压力0.1Mpa,物料在反应器恒温区有效停留时间5s,出口混合气经碱洗、干燥,反应2h后取样气相色谱分析,结果见表2。
实施例5
(1)S/γ-Al2O3催化剂制备
将NH4HSO4按S负载量3wt%的量溶于水,配成30ml的水溶液,取50克粒径4mm,比表面积340m2/g的球形γ-Al2O3为载体,将上述NH4HSO4水溶液等体积浸渍到载体上,浸渍时间为12h。浸渍完成后,100℃干燥12h,400℃空气氛中焙烧4h。制备得到S含量为3wt%的S/γ-Al2O3催化剂。焙烧后的催化剂填装至内径26mm,长60mm的316L不锈钢管式反应器中。
(2)2,3,3,3-四氟丙烯制备
将催化剂用氮气吹扫12h除氧,停氮气,通入一溴甲烷和四氟乙烯混合气体,混合气体中一溴甲烷与四氟乙烯摩尔流量比为1.5:1,设定反应温度500℃,压力0.3Mpa,物料在反应器恒温区有效停留时间10s,出口混合气经碱洗、干燥,反应2h后取样气相色谱分析,结果见表2。
表2:实施例4-5反应条件及结果
Claims (6)
1.一种合成2,3,3,3-四氟丙烯的方法,在催化剂作用下,将一溴甲烷与四氟乙烯进行连续反应制备2,3,3,3-四氟丙烯,所述一溴甲烷与四氟乙烯摩尔比为1~5∶1,反应物停留时间为5~50s,反应压力为0.1~0.5Mpa,反应温度为300~500℃,其特征在于所述催化剂为用P或S元素掺杂改性的γ-Al2O3,所述P或S元素的质量百分含量为1-10%。
2.根据权利要求1所述的合成2,3,3,3-四氟丙烯的催化剂,其特征在于所述γ-Al2O3粒径为1~5mm,比表面积为300~380m2/g。
3.根据权利要求1所述的合成2,3,3,3-四氟丙烯的方法,其特征在于催化剂的制备包括以下步骤:
(1)将含P或S元素的改性前躯物的水溶液分别等体积浸渍到γ-Al2O3载体上,得到浸渍产物;
(2)将浸渍产物干燥,得到干燥后的产物;
(3)将干燥后的产物在于空气氛中焙烧,得到催化剂。
4.根据权利要求3所述的合成2,3,3,3-四氟丙烯的方法,其特征在于所述含P元素的改性前躯物为H3PO4、(NH4)3PO4、(NH4)2HPO4、NH4H2PO4中一种。
5.根据权利要求3所述的合成2,3,3,3-四氟丙烯的方法,其特征在于所述含S元素的改性前躯物为(NH4)2SO4或NH4HSO4。
6.根据权利要求3所述的合成2,3,3,3-四氟丙烯的方法,其特征在于所述浸渍时间为6-24h,所述干燥温度为100-150℃,干燥时间为10-15h,所述焙烧温度为350-450℃,焙烧时间为2-6h。
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