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CN1118324C - 乙苯脱氢制苯乙烯的催化剂 - Google Patents

乙苯脱氢制苯乙烯的催化剂 Download PDF

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CN1118324C
CN1118324C CN00106401A CN00106401A CN1118324C CN 1118324 C CN1118324 C CN 1118324C CN 00106401 A CN00106401 A CN 00106401A CN 00106401 A CN00106401 A CN 00106401A CN 1118324 C CN1118324 C CN 1118324C
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M·拜尔
H·彼得森
H·旺杰克
C·瓦尔斯多夫
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Abstract

一种含铁氧化物的催化剂，用于制备该催化剂的铁氧化物是通过喷射焙烧铁盐溶液得到的，制备这种催化剂的方法，以及在这种催化剂存在时使乙苯脱氢制苯乙烯的方法。

Description

乙苯脱氢制苯乙烯的催化剂
本发明涉及一种含铁氧化物的催化剂，制备这种催化剂的方法，以及在这种催化剂存在时使乙苯脱氢制苯乙烯的方法。
对于制备以Fe2O3和K2O为基础的苯乙烯催化剂，通常使用天然的或合成的铁氧化物如α-FeOOH、α-Fe2O3、γ-Fe2O3和Fe3O4。通常通过铁盐溶液沉淀和热分解来制备合成的铁氧化物。
作为制备脱氢催化剂中的铁组分，除了传统的铁氧化物，还公开了一些特殊的铁氧化物或改性的铁氧化物。
在EP-A 0,532,078中描述的用于制备脱氢催化剂的含铁化合物中含有10-100wt％的层状铁氧化物，该铁氧化物优选具有少于100μm的最大薄层尺寸。
US 5,023,225描述了使用铬改性的铁氧化物制备脱氢催化剂。将黄色的铁水合物与氧化铬或铬盐混合，并加热混合物，来制备红色的铁氧化物。
WO 96/18593描述了一种含铁的脱氢催化剂，其铁组分在催化剂中为双峰的孔尺寸分布。优选使用磁性铁氧化物，如磁铁矿。
在WO 96/18458中采用一种预处理(预先用浓剂处理(predoped))的铁氧化物。使用一种预先制成浓液的、选自含有Be，Mg，Ca，Sr，Ba，Sc，Ti，Zr，Hf，V，Ta，Mo，W，Mn，Tc，Re，Ru，Os，Co，Rh，Ir，Ni，Pd，Pt，Cu，Ag，Au，Zn，Cd，Hg，Al，Ga，In，Tl，Ge，Sn，Pb，Bi，Ce，Pr，Nd，Pm，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb和Lu等元素的物质进行预处理，并将铁氧化物混合物加热到至少600℃。然后形成催化剂。
WO 96/18594描述了一种铁氧化物催化剂，其中含有最大平均尺寸范围为2-10μm的铁氧化物颗粒。平均孔径为0.22-0.30μm，孔体积为0.16-0.22cm3/g。使用由铁屑制备的铁氧化物α-Fe(OOH)，通过黄色的α-Fe(OOH)中间产物(Penniman铁氧化物)的脱水作用进行制备。
WO96/18457描述了一种制备铁氧化物催化剂的方法，其中在与一种或多种促进剂混合之前，对铁氧化物进行重整，以形成表面积(BET)小于1.9m2/g、颗粒长度为0.3-3μm、颗粒宽度为0.2-2μm的铁氧化物颗粒。所使用的重整试剂为元素Mo，Cu，Ca，Zn，Mn，Sn，Ti，Bi，Co，Ce，W，Cr，Mg和V的化合物。
作为原料，所述的催化剂需要精制或改性的铁氧化物。
因此本发明的一个目的是克服上述缺点并发现一种用于乙苯脱氢制苯乙烯的催化剂，这种催化剂便宜并且容易合成。具体地，该催化剂应具有高的孔体积，同时具有高活性、高选择性和高的机械稳定性。
因此我们已经发现了一种含铁氧化物的催化剂，制备该催化剂采用的是一种通过喷射焙烧铁盐溶液得到的铁氧化物。
优选地，该铁氧化物是利用Ruthner方法，例如EP-A 0,850,881中所描述的通过喷射焙烧一种含氯化铁的盐酸溶液得到的。
通过喷射焙烧含氯化铁的盐酸溶液得到的铁氧化物通常含有残留量的氯，这一残留量的氯应低于3000ppm，优选低于2000ppm，进一步优选低于1500ppm。
对于本发明的催化剂的制备来说，一种通过喷射焙烧法制备的铁氧化物是适合的，该铁氧化物的压实密度范围为0.6-1，优选为0.6-0.8g/cm3，比表面积范围为1-10，优选为2-7，进一步优选为3-5m2/g。
本发明的催化剂的孔体积为至少0.2cm3/g，优选范围为0.25-0.5cm3/g。平均孔径(中位值)至少为0.3μm，优选范围为0.4-0.8μm。
除了铁氧化物以外，本发明的催化剂通常还含有至少一种钾化合物。所使用的钾化合物优选为碳酸钾、氢氧化钾或草酸钾。优选地，以K2O计算，该催化剂含有5-40wt％的钾。
另外，该催化剂可以按通常浓度含有一种或多种传统的促进剂，以增大选择性、活性或稳定性。适合的促进剂为选自Be，Mg，Ca，Sr，Ba，Sc，Ti，Zr，Hf，V，Ta，Mo，W，Mn，Tc，Re，Ru，Os，Co，Rh，Ir，Ni，Pd，Pt，Cu，Ag，Au，Zn，Cd，Hg，Al，Ga，In，Tl，Na，Cs，La，Li，Ge，Sn，Pb，Bi，Ce，Pr，Nd，Pm，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb和Lu等元素的化合物，这些化合物可以单独或混合使用。优选的促进剂为选自Mg，Ca，Ce，W，Cr，Mo，W，Ti，Mn，Co和Al等元素的化合物。特别优选的促进剂为Mg，Ca，Ce，V，Cr，Mo和W。该催化剂可以含有一种、优选为两种，并且进一步优选为三种或多种Mg，Ca，Ce，V，Cr，Mo，W的促进剂。按最稳定的氧化物计算，促进剂优选的加入量为0-15wt％，具体为1-10wt％。
如果需要的话，本发明中所采用的铁氧化物可以含有部分或全部钾化合物或所述的促进剂。为了这一目的，例如可以将部分钾化合物和/或部分促进剂加入到用于喷射焙烧过程的铁盐溶液中。
本发明的催化剂可以通过已知的单步或多步制造方法得到，例如在EP-A0,195,252或EP-A 0,866,731中所描述的。为了这一目的，通过喷射焙烧铁盐溶液制备的铁氧化物可以单独使用或者与传统的天然或合成的铁氧化物如α-FeOOH、γ-FeOOH、α-Fe2O3、γ-Fe2O3或Fe3O4一起使用。以所采作的全部铁化合物为基准，通过喷射焙烧铁盐溶液制备的铁氧化物的含量为10-100mol％，优选为50-100mol％。
最终的粉末状催化剂组分可以干燥混合，或悬浮在水中混合并且喷射干燥。然后将干燥的粉末造粒得到机械稳定的成型产品，或加入水转化成糊状组合物并挤出成型，然后将挤出物粉碎为特定的长度。针对这一目的，可以使用成型助剂如硬脂酸盐、Walocel、石墨或淀粉。优选地，将催化剂组合物进行处理，以形成直径为2.5-6mm、长度为5-50mm的实心或中空的挤出物。特别优选的是使挤出物具有图1所示星形截面，并且为3mm的实心挤出物。
然后通常在80-140℃的温度范围内，将挤出物连续或间歇干燥。然后按一步或多步过程，在200-1000℃的温度范围内，将干燥成型的产品回火和/或煅烧。
本发明的催化剂适合用于烃类的非氧化脱氢，特别适用于乙苯脱氢制苯乙烯。为了这一目的，通常在500-700℃内，将摩尔比为2-20、优选为5-15的蒸汽和乙苯的混合物通过催化剂。在绝热过程中，反应器入口温度通常为600-650℃，然后由于反应吸热降至530-570℃。该反应优选在大气压或低于大气压的压力下进行。
本发明的催化剂具有大的孔体积。作为结果，在不降低活性或选择性的条件下，针对3mm固体催化剂挤出物进行测量时，每升催化剂的重量降低到1.3kg/L以下。同时，大于20N的刀切硬度对工业应用来说是足够的。
实施例
实施例1
在搅拌条件下，向168gK2CO3、200gCe2(CO3)3、46gCaCO3、29gMoO3和61g碱式碳酸镁(4-MgCO3xMg(OH)3·4H2O)与4.3L水所形成的悬浮液中加入900g铁氧化物Hoogovens RIO-200(由Hoogovens Staal BV出售)。然后在固含量为25wt％时，将喷射颗粒进行喷雾干燥。将所得到的含有大约(ca)340ml水的喷射粉末处理30分钟，形成糊状组合物，然后在挤压机中成形，得到直径为3mm的圆柱形实心挤出物，将该挤出物粉碎成长度为大约(ca)10mm的颗粒。然后在120℃下，在强制通风(forced air)的烘箱中，将催化剂挤出物干燥1小时，然后在煅烧炉中，首先在300下干燥2小时，然后在875℃干燥1小时。
对比例C1到C3
重复实施例1，只是按照相同的用量，将其中的铁氧化物用下列合成铁氧化物代替：
C1：沉积α-Fe2O3：    Bayferrox 1360
C2：合成γ-Fe2O3：    BayferroxE AB21
C3：沉积α-Fe2O3：    Bayferrrox 720N
有关催化剂挤出物的数据列于表1中。
实施例2
在搅拌条件下，向168g钾碱、249gCe2(CO3)3、34g水合熟石灰、35g仲钼酸铵和26g菱镁矿与4.3L水所形成的悬浮液中加入900g铁氧化物HoogovensRio-250(由Hoogovens Staal BV出售)。用大约500mL水将所形成的喷射粉末处理大约30分钟，以形成糊状组合物，然后将该糊状组合物挤出成形，制得直径为3mm的实心圆柱，并将这些圆柱切成长度为大约1mm的小圆柱。然后将这些催化剂挤出物在120℃下干燥1h，并且在煅烧炉中在300℃下煅烧2小时，然后在875℃下煅烧1小时。
对比例C4
重复实施例2，只是使用铁氧化物Bayferrox 1360代替Rio-250。
利用催化剂磨料(grit)测试催化剂E1和C1-C3。为了这一目的，将粒径为0.5-0.7mm的磨料部分装入管式反应器中，利用熔盐等温加热，然后在标准压力下进行检测，操作时LHSV为1.46/h、D/EB为1.25kg/kg。相关的性能数据列于表2中。
对催化剂E2和C4也使用实心挤出物进行检测。在这类实心圆柱测试中，将各种催化剂均放置250mL在内径为30mm的等温管式反应器中。在0.4bar的压力下检测催化剂，操作时LHSV为0.45/h、一个D/EB为1.25kg/kg，另一个D/EB为1.45kg/kg。10天以后，在有关转化率和选择性方面，催化剂已经达到稳定状态，并且液体和气体流出物的组成达到平衡。
利用由Engelsmann(Ludwigshafen)出售的压实体积计JEL测量压实密度(每升的重量)。在挤出物被压实750次后测量压实密度。堆积密度是挤出物在压实之前的密度。应用如DIN标准66133所述来确定孔体积。
对于确定平均孔径所采用的汞的接触角为140°(DIN 66133)。
在增大负载的条件下，将0.3mm的刀刃用于挤出物，直到切断为止，来确定刀切硬度(仪器由Zwick，Ulm出售)。取25次读数的平均值。
表1：催化剂性能
催化剂堆密度 kg/L  E10.870  C11.126  C20.994  C30.900
压实密度 kg/L  0.978  1.26  1.107  1.008
表面积(BET) m2/g  3.4  2.6  6.8  6.9
孔体积 g/cm3  0.38  0.23  0.30  0.35
平均孔径(中位值) μm  0.65  0.38  0.20  0.30
CeO2晶体尺寸 nm  24  24  23  25
刀切硬度 N  27  75  30  34
表2：
温度560℃ 催化剂转化率(％) E127.9  C129.1  C225.3  C324.7
选择性(％) 97.7  97.7  97.4  97.7
苯乙烯含量(wt％) 26.9  28.1  24.3  23.8
580℃ 转化率(％) 40.7  40.1  37.2  35.6
选择性(％) 97.1  97.3  97.0  97.3
苯乙烯含量(mol％) 39.1  38.7  35.7  34.3
600℃ 转化率(％) 54.5  50.8  48.1  50.3
选择性(％) 96.2  96.4  96.5  96.4
苯乙烯含量(mol％) 52.1  49  46.0  48.1
630℃ 转化率(％) 71.5  68.7  66.7  67.5
选择性(％) 94.0  95.4  94.8  94.6
苯乙烯含量(mol％) 67.4  65.6  63.3  63.8
催化剂E2和C4的物性及性能数据列于表3中。
表3：催化剂E2和C4的物性及性能
E2 C3
刀切硬度 44N 57N
压实密度 1.142kg/L 1.304kg/L
表面积(BET) 2.9m2/g 2.5m2/g
孔体积 0.28ml/g 0.22mL/g
平均孔体积 0.48μm  0.40μm
                 实心挤出物的性能H2O/EB＝1.45kg/kg；0.4bar：C(600℃)/S(600℃)    80.4％/94.8％    79.7％/94.7％C(575℃)/S(575℃)    69.8％/96.4％    65.8％/96.8％C(550℃)/S(550℃)    50.8％/97.7％    44.5％/97.9％
                 H2O/EB＝1.45kg/kg；0.4bar：C(575℃)/S(575℃)    80.4％/94.8％    65.1％/96.6％C(590℃)/S(590℃)    75.5％/95.2％    73.3％/95.7％C(600℃)/S(600℃)    79.4％/94.6％    78.6％/95.0％
                 磨料性能H2O/EB＝1.25kg/kg；1bar：C(560℃)/S(560℃)    31.2％/97.4％    26.6％/97.7％C(580℃)/S(580℃)    44.6％/96.7％    38.0％/97.3％C(600℃)/S(600℃)    57.9％/95.9％    50.1％/96.7％C(610℃)/S(610℃)    65.2％/95.5％    54.2％/96.4％C(630℃)/S(630℃)    74.3％/93.5％    65.9％/95.3％
C＝转化率
S＝选择性

Claims (8)

1.一种催化剂，该催化剂含有其氯含量低于3000ppm的铁氧化物并包含至少一种钾化合物，该铁氧化物是通过喷射焙烧含有氯化铁的盐酸溶液的方法得到的。
2.权利要求1的催化剂，其中所使用的铁氧化物的压实密度范围为0.6-1g/cm3，比表面积范围为1-10m2/g。
3.权利要求1或2中的催化剂，其中该催化剂的孔体积至少为0.2cm3/g。
4.权利要求1或2中的催化剂，其中该催化剂的平均孔径的中位值至少为0.3μm。
5.权利要求1或2的催化剂，其中该催化剂另外含有至少一种选自Mg，Ca，Ce，V，Cr，Mo，W等的化合物的促进剂。
6.权利要求5的催化剂，其中在喷射焙烧之前将至少一部分促进剂加入到铁盐溶液中。
7.一种用于制备权利要求1-6中任意一项权利要求的催化剂的方法，其中使用了由喷射焙烧一种含氯化铁的盐酸溶液而制得的一种铁氧化物。
8.一种用于乙苯脱氢制苯乙烯的方法，其中脱氢过程是在权利要求1-6中任意一项权利要求的催化剂存在的条件下进行的。
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