CN101786007A - 用于乙烯氧氯化为1.2-二氯乙烷的催化剂 - Google Patents
用于乙烯氧氯化为1.2-二氯乙烷的催化剂 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000005977 Ethylene Substances 0.000 title claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 46
- 239000011148 porous material Substances 0.000 claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
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- 238000000034 method Methods 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
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- 229910052751 metal Inorganic materials 0.000 claims description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
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- 229910001593 boehmite Inorganic materials 0.000 description 13
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 13
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- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
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Abstract
一种用于乙烯氧氯化为1.2-二氯乙烷的催化剂,该催化剂为具有一定几何构型和孔体积分布的中空颗粒,其中颗粒中大孔占总孔体积的至少20%,大孔分布曲线最大值处的孔径为高于800且至多1500nm。
Description
技术领域
本发明涉及一种用于固定床中乙烯氧氯化(oxychlorination of ethylene)为1.2-二氯乙烷(DCE)的颗粒形式的催化剂,该颗粒为具有特定孔体积分布的中空几何构型,并且本发明涉及用于所述催化剂的中空载体。
背景技术
众所周知,乙烯氧氯化为二氯乙烷可以在流化床或固定床中进行。前种情况下,反应器中温度分布更均一,而在固定床中,虽然反应参数比较容易控制,但由于催化剂颗粒之间以及颗粒与反应气体之间热交换效率低,局部的热点温度会对产物选择性和催化剂寿命产生不利的影响。
催化剂通常采用中空圆柱状颗粒,由于它的S/V比(几何表面积和体积的比例)高于球体和实心圆柱,可以通过催化反应床获得更有效的热交换和较低的压降,所以比较容易控制沿着反应床的温度,增加工业反应器生产能力。
尽管具有以上优点,但是应仔细设计中空圆柱状颗粒,否则其他的缺点便会凸显出来。
例如,如果中空圆柱状颗粒的外径和内径的比例(De/Di)大于一定值,颗粒容易破碎,催化剂堆密度降低,由于催化剂活性相的总含量较低从而导致催化床单位体积的转化率降低。
圆柱体的De或者长度增加过多且保持De/Di不变会引起反应器管内催化剂装载的不均一,可能使颗粒破碎而导致压降增加。
EP1 053 789 A1公开了一种圆柱形催化剂,其De为4-7mm,Di为2.0-2.8mm,高度为6.1-6.9mm。
该催化剂优于US P 4740644所述的长度比外径短的圆柱体催化剂和长度大于外径的圆柱体催化剂(US P 5166120)。
后一个所引用的US专利中催化剂的总孔体积为0.6-1.0ml/g,所有的孔径都大于4nm,孔径为8-20nm的孔占孔体积的至少80%,其他孔的孔径为大于20且至多200nm。该催化剂与孔体积中主要孔的孔径小于8nm的催化剂相比,具有较高的活性。
依照EP 1 053 789的考虑,US P 5166120公开的催化剂,缺点在于床层空隙率太高,这意味着床层中催化材料的含量较低,导致较低的DCE比生产率(specific productivity)(g DCE/g催化剂.h)并伴随着装载步骤中催化剂颗粒的破裂所引起高的压降。
发明内容
本发明的目的在于提供一种固定床乙烯氧氯化为DCE的中空颗粒形式的催化剂,包括负载在中空圆柱形γ氧化铝颗粒上的氯化铜和选自碱金属、碱土金属和稀土金属的金属氯化物,该催化剂在选择性和转化率上具有令人满意的性能,并且与其他具有相同几何参数(形状和大小)和组成的催化剂相比,该催化剂具有较高的DCE(g DCE/g催化剂.h)比生产率。
具体实施方式
从本发明下面的描述中可以明显的看到达到了其他目的。
本发明的催化剂是具有一定几何构型的中空颗粒,包括负载在中空圆柱形氧化铝颗粒上的氯化铜和至少一种或多种选自碱金属、碱土金属和稀土金属的金属氯化物,其特征在于颗粒中大孔体积(macropore volume)分数为总孔体积的至少20%且至多40%,大孔体积分布曲线最大值处的孔径为从800nm到至多1500nm,堆密度(bulk density)优选为0.80g/ml-0.65g/ml,更优选为从0.7g/ml到小于0.78g/ml。
与已知的具有相似几何构型(形状和大小)和组成的颗粒状催化剂相比,本发明的催化剂具有单位时间内单位质量催化剂上较高的DCE产率,且其大孔分布曲线最大值处的大孔孔径高于已知催化剂相应的孔径。这意味着本发明的催化剂的活性(转化率和活性)高于已知催化剂。
用于制备本发明催化剂的勃姆石的d50为至少100μm且至多170μm,且小于100μm的颗粒分数低于50wt%。
例如,SASOLAG(德国)生产的Pural SCC 150商业勃姆石可用于本发明。
由相对质量筛分法测定的该勃姆石的颗粒大小分布(wt%)如下:
>250μm 0.7%
250-100μm 56.3%
100-63μm 27.3%
<63μm 15.7%
d50(平均值)为130μm,d90(平均值)为209μm。粒径小于100μm的颗粒体积占30%,粒径小于250μm的颗粒体积占98%。
上述勃姆石经压制成型后制得的中空圆柱形颗粒在650℃,700℃和800℃焙烧后转化为γ氧化铝,并具有以下性质:
-经上述温度焙烧后的表面积(BET)分别为239,208和183m2/g;
-孔体积(BET)为0.41-0.43ml/g;
-总孔体积=0.48-0.52ml/g(由颗粒密度(PD)和真密度(RD)的倒数之差计算得出,=1/PD-1/RD);
-大孔体积=0.1ml/g(压汞法(Hg porosimetry));
-大孔体积分布曲线最大值处孔径(MPS)=1068nm。
当勃姆石的d50大于150μm时可以得到高达1600nm的大孔孔径,由该勃姆石制得的催化剂具有优良的性能和足够的机械性能(轴向和径向抗冲击性)。
用于制备本发明催化剂的勃姆石可以通过已知的方法获得,将铝溶于经由齐格勒醇改性的己醇中:将得到的勃姆石浆料喷雾干燥。
表1列出了由勃姆石Pural SCC 150中空颗粒制得的中空圆柱形γ氧化铝颗粒的性质,该氧化铝颗粒外径(De)约为5mm,内径(De)为2.5mm,高约为5mm;此外还列出了与勃姆石Pural SCC 150制得的γ氧化铝颗粒具有相同的大小和形状的、由SASOL Pural SB1制得的γ氧化铝颗粒,其d50(平均值)为43μm,d90(平均值)为119μm,粒径小于100μm的颗粒体积占83.9%,粒径小于250μm颗粒体积占100%。
表1
性质 | 源自Pural SCC 150的氧化铝载体 | 源自Pural SB 1的氧化铝载体 |
焙烧温度℃ | 700 | 600 |
比表面积m2/g | 208 | 207 |
孔体积(BET)ml/g | 0.41 | 0.46 |
总孔体积ml/g | 0.51 | 0.50 |
大孔孔体积m/g | 0.1 | 0.06 |
大孔孔体积%占总孔体积 | 20 | 12 |
M.P.S孔径nm | 1068 | 401 |
轴向抗压率Kg/prt | 86±18 | 73±11 |
径向抗压率Kg/prt. | 1.9±0.4 | 2.0±0.4 |
将勃姆石粉末与润滑剂,如含量为3-6wt%硬脂酸铝,混合后压制成型得颗粒。
成型颗粒在大约600-800℃下焙烧,由勃姆石转化为γ氧化铝后,然后浸渍金属氯化物水溶液-催化剂成分。优选在溶液体积等于或小于氧化铝颗粒的总孔体积下浸渍。
催化剂中氯化物的含量,以金属计为3-12wt%Cu,1-4wt%碱金属,0.05-2wt%碱土金属,0.1-3wt%稀土金属。
优选Cu含量为4-10wt%,碱金属是钾和/或铯,含量为0.5-3wt%,碱土金属是镁,含量为0.05-2wt%,稀土金属是铈,含量为0.5-3wt%。
中空颗粒中至少有一个与颗粒轴向相平行的贯通孔。当颗粒形状为圆柱形时,De直径4-6mm,Di直径1-3mm,高度为4-7mm。
通常采用横截面为三叶草形的丸粒,每片叶具有平行于颗粒轴向的贯通孔。
表2列出本发明催化剂颗粒的主要性质,表3是实施例催化剂的催化性能测试的数据。
图1和2分别为本发明涉及的催化剂(图1,实施例1中的催化剂)和现有技术中的催化剂(图2,对比例1中的催化剂)的大孔体积分布图(压汞法)。纵坐标中,左边表示的是累计孔体积,右边表示的是孔体积增加量(对数值)与孔径的变化量的比值(log.d PV/d PD,PV代表孔体积,PD代表孔径)。
可根据已知方法在固定床中采用本发明的催化剂由乙烯氧氯化制1.2-二氯乙烷,以空气或氧气作为氧化剂,反应温度200-300℃,空气为氧化剂时,总的进料摩尔比C2H4/HCl/O2是1∶1.99∶0.51,氧气做氧化剂时,C2H4/HCl/O2摩尔比是1∶0.71∶0.18。
当以氧气作为氧化剂时,反应在串联的三个反应器中进行时优选的HCl/C2H4,O2/C2H4,和HCl/O2摩尔比分别是0.15-0.50,0.04-0.1和3.20-5.8,其中第三个反应器装载有由本发明所述的催化剂颗粒形成的或者包括所述催化剂的固定床。
测试
大孔孔体积由压汞法测量:微孔和中孔的孔体积由BET氮气吸附-脱附法测量。
堆密度(也称为表观堆密度)由ASTM方法D 4164-82测量。
以下实施例用来阐述本发明,但本发明不止局限于这些范围。
实施例1
由勃姆石Pural SCC 150粉末和6wt%三硬酯酸铝混合后的压制成型的圆柱体经700℃焙烧得到400gDe=5mm,Di=2.5mm和高=5mm的氧化铝中空圆柱体,其(BET)比表面积为208m2/g,总孔体积为0.51ml/g。将上述氧化铝置于可旋转的5升反应罐中,室温至50℃下,用200ml含有以下物质的水溶液进行浸渍:
CuCl2*2H2O=110.8g
KCl =7.9g
MgCl2*6H2O=2.1g
HCl 37wt%=8.0ml
余量=溶液加至200ml的去离子水
浸渍后的颗粒按下述程序于烘箱中干燥=60℃1小时,80℃2小时,100℃3小时,150℃16小时。
表2列出了实施例1催化剂颗粒的性质,以及对比例1和2的催化剂颗粒的性质。
催化剂性能结果在表3列出。
对比例1
由勃姆石Pural SB1粉末和4wt%三硬酯酸铝混合后压缩成型制得的粗圆柱形颗粒经煅烧得到300g与实施例1具有相同尺寸和形状的氧化铝中空圆柱体,然后置于可旋转的5升反应罐中,室温下,用150ml含有以下物质的水溶液浸渍:
CuCl2*2H2O=83.1g
KCl =5.9g
MgCl2*6H2O=1.5g
HCl 37wt%=6.0ml
余量=溶液加至150ml的去离子水
浸渍后的颗粒干燥条件如实施例1。
表3列出了和实施例1相同的反应条件下的催化测试结果。
对比例2
使用两种与实施例1的催化剂尺寸和形状相似、组成相近的商业催化剂,反应条件与实施例1相同。
表3列出测试结果。
表2
催化剂 | 源自Pural SCC150的催化剂 | 源自Pural SB 1的催化剂 | 商业催化剂1 | 商业催化剂2 |
Cu wt% | 7.98 | 7.95 | 7.92 | 7.68 |
Mg wt% | 0.05 | 0.05 | 0.22 | 0.12 |
K wt% | 0.78 | 0.8 | 0.86 | 0.84 |
(BET)比表面积m2/g | 115 | 129 | 135 | 102 |
孔体积(BET)ml/g | 0.27 | 0.29 | 0.30 | 0.21 |
颗粒密度g/ml | 1.55 | 1.55 | 1.47 | 1.78 |
真密度g/ml | 3.19 | 3.21 | 3.23 | 3.14 |
总孔体积ml/g | 0.33 | 0.33 | 0.37 | 0.24 |
大孔孔体积ml/g | 0.07 | 0.06 | 0.07 | 0.05 |
大孔孔体积%占总孔体积百分比 | 21 | 18 | 19 | 20 |
M.P.S直径(*) | 1050 | 310 | 660 | 480 |
重量(100prt) | 10.42 | 10.60 | 9.60 | 13.12 |
直径mm | 4.89 | 4.91 | 4.69 | 5.01 |
高度mm | 4.74 | 4.81 | 4.67 | 4.95 |
表观堆密度g/ml | 0.72 | 0.78 | 0.78 | 0.86 |
床层空隙分数(**) | 0.54 | 0.50 | 0.47 | 0.52 |
(*)M.P.S=大孔体积分布曲线最大值处孔径
大孔=孔径为大于50nm且至多10.000nm的孔。
(**)床层空隙分数=1-表观堆密度/颗粒密度。
表3
催化剂性能
催化剂 | 实施例1 | 对比例1 | 商业催化剂1 | 商业催化剂2 |
催化床层高度 cm体积 ml | 80420 | 80420 | 80420 | 80420 |
催化剂装载量 g催化剂堆密度 g/ml | 303.90.72 | 327.50.78 | 360.60.86 | 325.60.78 |
进料 总的进料 Nl/h(*)HCl Nl/h | 761.370.3 | 756.769.8 | 772.973.5 | 765.972.9 |
进料摩尔比 HCl/C2H4O2/C2H4 | 0.300.09 | 0.300.09 | 0.310.09 | 0.310.09 |
热量 T10cm ℃剖面 T20cm ℃催化床层 T30cm ℃T70cm ℃ | 269287272220 | 269291275223 | 304317283218 | 256279268228 |
转化率 HCl %molC2H4 %molO2 %mol | 99.015.396.5 | 98.715.695.6 | 96.415.697.9 | 95.015.292.5 |
纯度 EDC %mol | 99.58 | 99.53 | 99.57 | 99.51 |
C2H4 摩尔选择性CO%CO2%氯乙烷EDC% | 1.181.460.0496.96 | 1.401.880.0496.27 | 1.971.680.0795.93 | 1.211.400.0596.92 |
C2H4制EDC的比生产率gEDC/ml催化剂.h参考催化床层体积 | 0.37 | 0.36 | 0.37 | 0.36 |
比生产率gEDC/g催化剂.h参考催化剂重量 | 0.51 | 0.46 | 0.43 | 0.47 |
(*)总的进料:C2H4=30.4体积%,O2=2.7体积%,HCl=9.5体积%,N2=57.4体积%。
Claims (12)
1.用于乙烯氧氯化为1,2-二氯乙烷的催化剂,该催化剂为具有几何构型的中空颗粒形式,并且其包括氯化铜和至少一种或多种选自碱金属、碱土金属和稀土金属的金属氯化物,以金属计的含量为3-12wt%的铜,1-4wt%的碱金属,0.05-2wt%的碱土金属,和0.1-3wt%的稀土金属,所述的氯化物负载在氧化铝颗粒上,其特征在于该催化剂颗粒中大孔体积分数为总孔体积的20%-40%,且大孔体积分布曲线最大值处的孔径为至少800nm且至多1500nm。
2.根据权利要求1所述的催化剂,其中大孔体积分数为总孔体积的20%-30%,且大孔体积分布曲线最大值处的孔径为1000-1300nm。
3.根据权利要求1或2所述的催化剂,催化剂的堆密度为0.65-0.80g/ml。
4.根据权利要求1-3任一项所述的催化剂,其中铜的含量为4-10wt%,碱金属是钾和/或铯,碱土金属是镁,并且稀土金属是铈。
5.根据权利要求14任一项所述的催化剂,其中钾和/或铯的含量为0.5-3wt%,镁含量为0.1-2wt%,并且铈含量为0.5-2wt%。
6.根据权利要求1-5任一项所述的催化剂,其中催化剂为外径4-6mm,内径1-3mm和高度为4-7mm的中空圆柱体形式。
7.根据权利要求1-5任一项所述的催化剂,其具有三叶草形的圆柱横截面,每片叶具有平行于颗粒轴向的贯通孔,并且每片叶到其它叶的轴线是等距的。
8.由γ氧化铝形成的中空圆柱颗粒,其孔体积(BET)为0.35-0.58ml/g,大孔体积占总孔体积的20%-40%,其中大孔体积分布曲线最大值处的孔径为800-1600nm。
9.根据权利要求8所述的中空圆柱颗粒,其具有一个或多个平行于颗粒轴向的贯通孔。
10.根据权利要求8或9所述的中空圆柱颗粒,其为外径4-6mm,内径1-3mm和高度4-7mm的圆柱体形式。
11.用于将乙烯氧氯化为1,2-二氯乙烷的方法,其在由权利要求1-7所述的催化剂颗粒形成或包含所述催化剂颗粒的固定床中,以空气或氧气作为氧化剂在200-300℃温度下进行,当以空气为氧化剂时,HCl/C2H4/O2摩尔比是1∶1.99∶0.51,以氧气为氧化剂时,HCl/C2H4/O2摩尔比是1∶0.70∶1.79。
12.根据权利要求11所述的方法,其以氧气作为氧化剂,并在串联的三个反应器中进行,其中第三个反应器装载有由权利要求1-7所述的催化剂颗粒所形成或包含所述催化剂颗粒的固定床,并且其中HCl/C2H4,O2/C2H4和HCl/O2的摩尔比分别是0.15-0.50,0.04-0.10和3.20-5.8。
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US5861353A (en) * | 1992-10-06 | 1999-01-19 | Montecatini Tecnologie S.R.L. | Catalyst in granular form for 1,2-dichloroethane synthesis |
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CN1446627A (zh) * | 2002-03-21 | 2003-10-08 | 中国石油化工股份有限公司 | 一种氧氯化反应催化剂及其制备方法和应用 |
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