CN1533835A - 用于将乙烯氧氯化为1,2-二氯乙烷的催化剂 - Google Patents
用于将乙烯氧氯化为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 51
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000005977 Ethylene Substances 0.000 title claims abstract description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 title abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract 2
- 239000002184 metal Substances 0.000 claims abstract 2
- 239000011148 porous material Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 150000002681 magnesium compounds Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000005749 Copper compound Substances 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims description 3
- 150000001880 copper compounds Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims 2
- 150000001339 alkali metal compounds Chemical class 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 230000007423 decrease Effects 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000007598 dipping method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- -1 rare earth metal salt Chemical class 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
将乙烯氧氯化为1,2-二氯乙烷的催化剂,其含有载在氧化铝上的铜和镁化合物,其中以金属计铜为7-12%(重量),Mg/Cu比为0.05-1,并且其中由表面Al/Cu比提供的铜浓度和催化剂全部颗粒中Al/Cu所提供的铜浓度之间的比例是0.8-1.3。
Description
技术领域
本发明涉及用于将乙烯氧氯化为1,2-二氯乙烷(1,2-DCE)的催化剂,其制备方法以及其在氧氯化方法中的用途。
背景技术
含有铜化合物,通常为氯化铜,并含有基于碱和/或碱土金属盐和稀土金属盐助催化剂的将乙烯氧氯化为1,2-DCE的催化剂,在文献中是众所周知的。
这些催化剂中的铜含量通常不高于6-8%(重量)。
铜含量达到12-14%(重量)的催化剂也是已知的。在专利GB1189815中公开了这些催化剂的例子。
催化剂的制备是通过:将氧化铝和铜的水凝胶共沉淀,然后在10-40℃下老化沉淀物至少10小时,干燥,洗涤以及最后在300-600℃之间的温度下煅烧足够长的时间,使氧化铝水凝胶转化为γ-氧化铝。
催化剂优选在流化床中使用。
根据上面引用的专利,采用铜盐溶液浸渍氧化铝制得高铜含量(12重量%)的催化剂可提供低的盐酸转化率且相当多的乙烯燃烧成CO和CO2,而与之不同的是,采用共沉淀制备的催化剂,在专利引用的操作条件下,可以在流化床中,获得良好的转化率,选择性和稳定性。
然而,这些催化剂的缺陷应归于其需要在高的空速下操作,即短的接触时间,并因此有相当多的未转化的乙烯的再循环。
已知市售的高铜含量(12-13重量%)的催化剂可能通过共沉淀法制得,甚至在相对低的温度下(210℃)操作也会引起大量的乙烯燃烧。
发明内容
现在出人意料地发现,可以得到通过浸渍氧化铝制备具有高铜含量的用于将乙烯氧氯化为1,2-二氯乙烷的催化剂,其没有用共沉淀法制得的现有催化剂的缺陷,反而却能提供对1,2-DCE摩尔选择性和产率(1,2-DCE kg/催化剂/小时)的良好性能。
本发明中催化剂的铜含量为7-12%(重量);这样的催化剂除铜化合物外还含有镁化合物,其中Mg/Cu比为0.05-1。
这些催化剂中铜分布为使得X/Y比在0.8-1.3的范围内,其中X是用XPS(X-射线光衍分光镜)测得的Al/Cu比,Y是催化剂全部颗粒中的Al/Cu比。
所用的铜和镁化合物优选氯化物。
催化剂中除铜和镁化合物外,还含有选自碱金属,碱土金属和稀土金属化合物或其混合物的助催化剂。优选氯化钾,氯化铷和氯化铯,及其混合物。
氧化铝的表面积为90-260m2/g,孔体积是0.4-0.6cm3/g。催化剂表面积为60-150m2/g。优选地,采用孔体积为0.15-0.35m2/g的γ-氧化铝。
优选地,氧化铝的粒径分布由至少60%粒径在60和125微米之间的颗粒组成。
催化剂通过以两个或者多个步骤浸渍氧化铝来制备,其中所使用的铜盐和镁盐溶液的体积,在第一次浸渍中,等于,优选小于氧化铝的孔体积,在第二次浸渍中,小于第一次浸渍使用的体积,如60%孔体积,在第三次浸渍中,甚至更低,如40%孔体积。
当负载的化合物的铜含量高于9-10%(重量)时优选使用三次浸渍。
第一次浸渍的粉末在100-130℃炉中干燥足够长时间,如16小时;然后进行第二次浸渍,并在炉中干燥生成的粉末,以同样的方式继续接下来的浸渍。
将上述的盐溶解于蒸馏水中制得盐溶液,并温和加热以利于溶解。然后将溶液喷淋到放置在旋转容器中的氧化铝上。其也可以在流化床中进行。
该溶液优选酸,例如盐酸或其它强酸,其用量是0.1-1当量/g铜原子。尤其是当固定的铜大于9-10%时使用这些溶液。
铜分布用XPS法确定,其可用于测量2-3nm表面层中铜原子的浓度(即,Al/Cu比)。
为进一步说明XPS法,参见US专利4587230和4871707。
氧氯化方法优选根据现有方法在流化床中进行,操作温度为190-235℃,并且随催化剂中镁含量提高,温度也随之升高。
催化剂中高活性铜含量使得甚至在上述相对低的温度下操作就DCE收率和产率而言也有良好性能。
该方法优选在Cl/C反应比为0.60-0.65,O2/乙烯摩尔反应比为0.4-0.5,线性速率为20-22cm/s以及接触时间为5-6秒下进行。
具体实施方式
下述实施例用于阐述而不是限制本发明的范围。
实施例1
在室温下,5升旋转瓶中用720ml水溶液对1600gγ-氧化铝进行第一次喷淋浸渍,水溶液总体积是1200ml,其中含有:
CuCl22H2O:481.5g
MgCl26H2O:187.7g
剩余物:加软化水使体积至1200ml。
将720ml体积逐步加到瓶中。
在达到选定的温度前,浸渍的粉末在110℃炉中干燥16小时。
接着用剩下的溶液(480ml)进行第二次浸渍,最后在110℃下干燥16小时。
使用的氧化铝有如下的性质:
表面积:218m2/g;
孔体积:0.50cm3/g;
具有如下直径的颗粒的粒径分布:
-大于125微米=4.8%
-90-125微米=35.2%
-63-90微米=44.4%
-40-63微米=13.9%
-小于40微米=1.7%
催化剂表面积为119m2/g,孔体积为0.22cm3/g,平均孔半径3.7nm,表观密度为1.77g/cm3,堆密度为1.16g/cm3,78%粒径为63-125微米,8%为40-63微米,2.2%大于125微米,以及1.9%小于40微米。
铜含量为7.82%(重量);镁含量为1.02%。
Al/Cu比(Y)为12.7,且XPS Al/Cu比(2-3nm层)为11.6;X/Y比为0.91。
催化剂在玻璃反应器中测试,该反应器配有控制加料和反应剂剂量的系统和冷凝和回收可冷凝产物的冷却体系。
不能冷凝的部分用气相色谱法测定。
测试中,收集的冷凝物质为两相,水相和有机相。两相被分离并称重;用气相色谱法分析盐酸以测定DCE纯度并测得氯化副产物的量。
反应器的尺寸为:内径,20.6mm;高度,3200mm。
测试在压力1.6个大气压,线性速率21-22cm/s,操作温度210-230℃的条件下进行。氧气做为氧化剂,Cl/C比为0.60-0.65,O2/C2H4比为0.41-0.44。
催化剂产率以纯DCE(kg)/催化剂(升)/小时表达。
获得的结果在表中列出。
实施例2
在室温下,5升旋转瓶中用6750ml水溶液对1500g具有与实施例1同样性质的γ-氧化铝进行第一次浸渍,水溶液总体积是1500ml,其中含有:
CuCl22H2O:777.9g
MgCl26H2O:303.9g
HCl37%(重量)=65.0ml
剩余物:加软化水使体积至1500ml。
在达到选定的温度前,粉末在110℃炉中干燥16小时。接着用450ml剩余的溶液进行第二次浸渍,接着在110℃炉中干燥。
接下来用375ml剩余的溶液进行第三次浸渍并在110℃炉中干燥16小时。
催化剂含有11.49%(重量)铜和1.47%(重量)镁;Y比是7.6以及X比是9;X/Y是1.18。表面积为90.6m2/g,孔体积为0.19cm3/g,平均半径4.2nm,表观密度为1.89g/cm3,体积密度为1.21g/cm3。
具有如下直径(微米)颗粒的粒径分布:77%直径为63-125微米;15.8%直径为40-63微米;6.2%直径小于40微米。
催化剂在实施例1条件下进行氧氯化测试。
催化剂产率以纯DCE(kg)/催化剂(升)/小时表达。
结果在表中给出。
对比实施例1
在5升旋转瓶中用540ml溶液对1200g具有与实施例1同样性质的氧化铝进行浸渍,其中溶液含有:
CuCl22H2O:282.1g
MgCl26H2O:135.3g
HCl 37%(重量)=48.0ml
粉末在实施例1的条件下干燥。
催化剂含有6.31%(重量)铜和1.00%(重量)镁。X/Y是1.8,表面积为93m2/g,孔体积为0.26cm3/g,平均半径5.6nm。粒径分布与实施例1相似。
催化剂在实施例1条件下进行氧氯化测试。
结果见下表。
该实施例的催化剂的产率,以及与实施例2的比较,以纯DCE(kg)/催化剂(升)/小时表述。
对比实施例2
市售载于γ-氧化铝上的催化剂,含有12.50%(重量)铜和5.58%(重量)氯,其中X/Y是3,表面积为237m2/g,孔体积为0.34cm3/g,平均孔半径2.9nm,表观密度为1.56g/cm3,58%的颗粒尺寸为63-125微米;20.5%为40-63微米;15.9%小于40微米,在实施例1的条件下测试。结果见下表。
表
平均反应温度=210℃ | ||||||
催化剂 | HCl转化率% | C2H4选择性mol% | DCE纯度mol% | 产率kgDCE/升催化剂/小时 | ||
DCE | COx | 不同氯化物 | ||||
实施例1 | 99.92 | 98.01 | 1.60 | 0.39 | 99.60 | 0.51 |
对比实施例1 | 99.91 | 97.87 | 1.77 | 0.53 | 99.63 | 0.50 |
对比实施例2 | 99.93 | 94.61 | 5.00 | 0.39 | 99.60 | 0.50 |
平均反应温度=220℃ | ||||||
HCl转化率% | C2H4选择性mol% | DCE纯度mol% | ||||
DCE | COx | 不同氯化物 | ||||
实施例1 | 99.94 | 97.26 | 2.35 | 0.39 | 99.59 | 0.50 |
对比实施例1 | 99.96 | 97.76 | 1.82 | 0.42 | 99.57 | 0.51 |
对比实施例2 | 99.92 | 96.98 | 2.58 | 0.44 | 99.55 | 0.50 |
平均反应温度=230℃ | ||||||
HCl转化率% | C2H4选择性mol% | DCE纯度mol% | ||||
DCE | COx | 不同氯化物 | ||||
实施例1 | 99.92 | 96.00 | 3.53 | 0.47 | 99.52 | 0.50 |
对比实施例1 | 99.95 | 96.83 | 2.70 | 0.43 | 99.52 | 0.51 |
对比实施例2 | 99.92 | 95.67 | 3.89 | 0.44 | 99.54 | 0.50 |
Claims (9)
1、用于将乙烯氧氯化为1,2-二氯乙烷的催化剂,其含有载在氧化铝上的铜和镁化合物,其中以金属计的铜为7-12重量%,Mg/Cu比为0.05-1,其特征在于,催化剂颗粒内的铜分布为:在表面(20-30A层)Al/Cu比(X)提供的表面铜原子浓度和在全部颗粒中Al/Cu比(Y)给定的浓度之间的X/Y比为0.8-1.3。
2、根据权利要求1的催化剂,其中铜化合物是氯化铜,镁化合物是氯化镁。
3、根据权利要求1或2的催化剂,其中铜含量为9-12重量%并且Mg/Cu比为0.1-0.5。
4、根据权利要求1-3任一项的催化剂,其表面积是60-150m2/g。
5、根据权利要求1-4任一项的催化剂,包括做为助催化剂的碱金属化合物。
6、根据权利要求1-5任一项的催化剂,其负载在γ-氧化铝上。
7、制备权利要求1-6任一项催化剂的方法,包括进行以多个步骤浸渍氧化铝,其中第一个步骤使用的Cu和Mg化合物水溶液的体积等于或小于氧化铝的孔体积,并且随后的步骤使用比第一个步骤中使用的体积逐步递减的体积。
8、根据权利要求7的方法,其中浸渍的粉末在每一个浸渍步骤前进行干燥。
9、一种乙烯氧氯化为1,2-二氯乙烷的方法,其使用权利要求1-6任一项的催化剂,在温度为190-235℃的流化床中操作,使用氧气做为氧化剂,并且反应的Cl/C摩尔比为0.6-0.7,反应的O2/C2H4摩尔比为0.4-0.5。
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TWI341218B (en) * | 2005-11-14 | 2011-05-01 | Oxy Vinyls Lp | Catalyst compositions and process for oxychlorination |
EP2208528A1 (en) * | 2008-12-23 | 2010-07-21 | Süd Chemie - Catalysts Italia S.R.L. | Catalysts for fixed bed oxychlorination of ethylene to 1.2-dichloroethane |
WO2014071423A1 (en) * | 2012-11-05 | 2014-05-08 | Basf Corporation | Catalyst for the oxychlorination of ethylene to 1, 2-dichloroethane |
US9248434B2 (en) | 2012-11-06 | 2016-02-02 | Basf Corporation | Catalyst for the oxychlorination of ethylene to 1, 2-dichloroethane |
RU2664116C2 (ru) | 2013-03-15 | 2018-08-15 | ОКСИ ВАЙНИЛЗ, ЭлПи | Катализатор и процесс оксихлорирования этилена до дихлорэтана |
HUE046713T2 (hu) | 2014-06-23 | 2020-03-30 | Oxy Vinyls Lp | Katalizátor és eljárás etilén oxiklórozására diklóretánná |
WO2023141486A1 (en) | 2022-01-19 | 2023-07-27 | Oxy Vinyls, Lp | Oxychlorination process |
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FR2141452B1 (zh) | 1971-06-03 | 1973-06-29 | Pechiney Saint Gobain | |
US4115323A (en) * | 1977-10-19 | 1978-09-19 | Diamond Shamrock Corporation | Catalyst and process for production of VCM |
IT1163160B (it) * | 1983-03-22 | 1987-04-08 | Montepolimeri Spa | Catalizzatori supportati per la sintesi di 1-2 dicloroetano per ossiclorurazione di etilene in letto fluidizzato |
IT1176719B (it) * | 1984-09-19 | 1987-08-18 | Ausind | Metodo per la preparazione di un catalizzatore per la sintesi di 1,2-dicloroetano |
IT1202538B (it) * | 1987-02-13 | 1989-02-09 | Enichem Sintesi | Catalizzatore di ossiclorurazione e procedimento per la sua preparazione |
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ES2026073A6 (es) * | 1991-01-03 | 1992-04-01 | Aiscondel Sa | Procedimiento para la preparacion de un catalizador para la oxicloracion del etileno. |
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BE1007818A3 (fr) * | 1993-12-08 | 1995-10-31 | Solvay | Composition catalytique et procede d'oxychloration de l'ethylene utilisant une telle composition. |
EP0931587A1 (en) * | 1998-01-08 | 1999-07-28 | Evc Technology Ag | Catalyst, process for its preparation, and its use in the synthesis of 1,2-dichloroethane |
PT1002576E (pt) * | 1998-11-10 | 2004-06-30 | Sued Chemie Mt Srl | Catalisador a base de cobre para oxicloracao de etileno a 1,2-dicloroetano |
DE10003510A1 (de) * | 2000-01-27 | 2001-08-02 | Basf Ag | Verfahren zur Herstellung von 1,2-Dichlorethan |
DE10024928A1 (de) * | 2000-05-19 | 2001-11-22 | Basf Ag | Katalysatoren für heterogen katalysierte Reaktionen |
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CN108654587B (zh) * | 2017-03-28 | 2021-09-07 | 中国石油化工股份有限公司 | 制备卤代烃的方法 |
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