CN108136378A - 使用含有借助至少两种前体并入的硅和钼的催化剂的烯烃复分解方法 - Google Patents
使用含有借助至少两种前体并入的硅和钼的催化剂的烯烃复分解方法 Download PDFInfo
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- CN108136378A CN108136378A CN201680044735.1A CN201680044735A CN108136378A CN 108136378 A CN108136378 A CN 108136378A CN 201680044735 A CN201680044735 A CN 201680044735A CN 108136378 A CN108136378 A CN 108136378A
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- molybdenum
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- 239000002243 precursor Substances 0.000 title claims abstract description 112
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 74
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000011733 molybdenum Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 28
- 239000010703 silicon Substances 0.000 title claims abstract description 27
- 238000005865 alkene metathesis reaction Methods 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- -1 chlorate anions Chemical class 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 34
- 150000003839 salts Chemical group 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 24
- 150000001336 alkenes Chemical class 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- 239000012686 silicon precursor Substances 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 238000007598 dipping method Methods 0.000 claims description 19
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
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- 239000010941 cobalt Substances 0.000 claims description 16
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 13
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- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
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- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical compound OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 claims description 6
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
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- 125000003342 alkenyl group Chemical group 0.000 claims description 5
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- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- 125000004427 diamine group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 125000000879 imine group Chemical group 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical group O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
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- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
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- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 2
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- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims 1
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Classifications
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明涉及用包含中孔基质和至少元素钼和硅的催化剂实施的烯烃复分解方法,所述元素借助至少两种前体并入所述基质中,其中至少一种前体含有钼且至少一种前体含有硅。
Description
本发明涉及使用由至少两种前体制备的催化剂的烯烃复分解方法,其中至少一种前体含有钼且至少一种前体含有硅。
现有技术
烯烃复分解是各种化学领域中的重要反应。在有机合成中,使用由有机金属配合物催化的这种反应以获得各种高附加值分子。在石油化学中,烯烃复分解特别对源自蒸汽裂化的轻质烯烃,如乙烯、丙烯和丁烯的再平衡具有重大实际意义。特别地,考虑到丙烯在市场上的应用不断增长,乙烯与2-丁烯交叉复分解以产生丙烯是受关注的反应。
不同类型的催化剂能够用于该复分解反应。可以使用均相催化剂(其组成元素都可溶于反应介质),或不溶于反应介质的多相催化剂。
轻质烯烃的复分解使用多相催化剂。一种已知解决方案是专利US 8,586,813中描述的技术,其使用基于沉积在二氧化硅载体上的氧化钨WO3/SiO2的催化剂。但是,基于钨的多相催化剂在相对较高温度下,通常在高于300℃的温度下工作并且仅为中等活性。
此外,已知基于氧化铼Re2O7的复分解催化剂,如由Chauvin等人在出版物Journalof Molecular Catalysis 1991, 65, 39中描述的那些在接近环境温度的温度下具有良好活性。还已经开发出其它基于氧化钼的催化剂,如D. P. Debecker等人的出版物J.Catal., 2011, 277, 2, 154和Shell公司拥有的专利GB 1,164,687和GB 1,117,968中描述的那些。Shell的方法使用例如如专利US 4,754,099中描述的基于沉积在铝载体上的钼和钴氧化物CoMoO4/Al2O3并用磷掺杂的催化剂。
钼(Mo)的一个益处在于其没有铼(Re)昂贵。此外,其稳定性和其活性介于铼(Re)和钨(W)之间。特别地,钼可从环境温度开始呈活性。
以标准方式通过用钼盐或含钼的杂多阴离子,例如同多阴离子(isopolyanion)七钼酸铵的水溶液在载体如二氧化硅、氧化铝或多孔铝硅酸盐上浸渍进行基于氧化钼(MoO3)的催化剂的制备。但是,由七钼酸铵型前体制备的催化剂缺乏活性和稳定性。已经制备基于其它杂多阴离子,如H3PMo12O40的催化剂并能够显著提高活性,但需要进一步改进。
因此仍然需要开发用于烯烃的复分解反应,更特别用于乙烯和2-丁烯之间的复分解以生产丙烯的在活性和选择性方面具有改进的性能的新型催化剂。
申请人在其对改进用于烯烃复分解的多相催化剂的性能的研究中已经开发出用于烯烃的复分解反应的新型催化剂。这些催化剂由中孔基质和至少两种前体制备,其中至少一种前体含有钼且至少一种前体含有硅。出乎意料地,已经发现,与使用现有技术的其它前体制备的催化剂相比,使用这些类型的前体制备根据本发明的催化剂改进所得多相催化剂对烯烃复分解反应的活性和稳定性。由此改进烯烃转化率。也改进该催化剂的稳定性。
本发明的一个目的是提供与使用现有技术的多相催化剂相比,使用在活性和选择性方面具有改进的性能的催化剂的烯烃复分解方法。
根据本发明的催化剂具有能在再生前运行更长时间周期的优点,这对根据本发明的方法的运行成本具有重大经济影响。
发明主题
本发明涉及通过使烯烃与包含中孔基质和至少元素钼和硅的催化剂接触进行的烯烃复分解方法,所述元素借助至少两种前体并入所述基质中,其中至少一种前体含有钼且至少一种前体含有硅。
含钼前体
有利地,根据本发明的含钼前体是基于钼的配位配合物类型和/或基于钼的多金属氧酸盐类型和/或(硫代)钼酸盐类型的前体。
当根据本发明的含钼前体是基于钼的配位配合物型前体时,其有利地对应于式(I)
Mom(=Y)n(≡N)n’(X)o(=CR2)r (I)
其中
- Y基团,彼此相同或不同,可选自O、S和NR’,
- X基团,彼此相同或不同,可选自卤素(halides),如F、Cl、Br、I,氯酸根、溴酸根、碘酸根、硝酸根、硫酸根或硫酸氢根、烷基硫酸根、硫代硫酸根、碳酸根或碳酸氢根、磷酸根或磷酸氢根或磷酸二氢根、取代或未取代的烷基、环烷基或芳基、取代或未取代的环戊二烯基、烷氧基、芳氧基、甲硅烷氧基、酰胺基团(amide)、氢负离子(hydrido)、硝基、羧酸根、乙酰丙酮基团(acetylacetonate)、磺酸根、β-二酮亚胺基团(diketiminate)、亚氨基吡咯烷基团(iminopyrrolide)、脒基(amidinate)、硼酸根、氰根(cyanide)、氰酸根、硫氰酸根或NR2-CS2 -基团,
- R和R’基团,彼此相同或不同,可选自烷基和芳基,其优选包含1至10个碳原子,烷氧基和芳氧基,
- m等于1或2,
- n为0至4,
- n’为0至2,
- o为0至10,
- r为0至2,
- n+n’+o+r大于或等于1,优选大于或等于2。
根据本发明,基于钼的配位配合物型前体还可在其配位层中含有一个或多个L型配体,任选多齿。该L型配体可选自含碳化合物,如一氧化碳、烯、炔,含磷化合物,如碳膦配体(phosphines)、氧膦配体(phosphinites)、亚膦酸酯(phosphonites)、亚磷酸酯,含氧化合物,如水、醚,含氮化合物,如胺,含氮芳族化合物,如吡啶和/或菲咯啉,和/或含硫化合物,如硫醚。
对应于式(I)的基于钼的配位配合物型前体由于其化学性质以中性形式并入。
基于钼的配位配合物型前体可以例如选自下列化合物:MoCl5、MoOCl4、MoSCl4、Mo(C5H5)Cl4、Mo(SO4)3、Mo2(C5H5)2(CO)6、Mo(=CH-C(Me)2Ph)(=N-Ph(iPr)2)(OSO2CF3)2(CH3O(CH2)2OCH3)、MoO2(乙酰丙酮)2、Mo(=O)(OSitBu3)4、Mo(≡N)(OSiPh3)3(C6H5N)、Mo[OOCCH(C2H5)C4H9]4、Mo[OOCC7H15]2、环烷酸钼、Mo(CO)6等。
当根据本发明的含钼前体是基于钼的多金属氧酸盐型前体时,其有利地对应于式(II)
(XxMomMbOyHh)q-.nH2O (II)
其中
·x大于或等于0,
·m大于或等于2,
·b大于或等于0,
·y大于或等于7,
·h为0至12,
·q为1至20,
·n为0至200,
·x、m、b、y、h、n和q是整数,X是选自磷、硅和硼的元素,M是选自铝、锌、镍、钴、钨、钒、铌、钽、铁和铜的金属元素,M优选是选自铝、钴和钨,更优选选自铝和钴的金属元素,金属元素M还更优选是钴。
对应于式(II)的基于钼的多金属氧酸盐型前体可以以盐形式或以酸形式并入中孔基质中。在对应于式(II)的基于钼的多金属氧酸盐型前体以酸形式并入的情况下,通过质子H+补偿电荷q-。当对应于式(II)的基于钼的多金属氧酸盐型前体以盐形式引入时,抗衡离子选自本领域技术人员已知的所有阳离子。抗衡离子的实例可提到质子、铵、鏻、碱金属、碱土金属、过渡元素等。基于钼的多金属氧酸盐可包含相同阳离子或不同阳离子的混合物。
多金属氧酸盐型前体优选选自基于钼的同多阴离子和基于钼的杂多阴离子。
根据本发明的基于钼的同多阴离子前体对应于根据式(II)的前体
(XxMomMbOyHh)q-.nH2O (II)
其中元素X的下标x等于0,在根据本发明的下标和元素的定义方面,所有其它事项等同。根据本发明的基于钼的同多阴离子型前体可以例如选自Mo2O7 -、Mo7O24 6-。
根据本发明的基于钼的多金属氧酸盐型前体可含有取代上述式的所述多金属氧酸盐前体中所含的一个或多个钼原子的选自铝、锌、镍、钴、钨、钒、铌、钽、铁和铜的一个或多个金属元素M。金属元素M优选选自铝、钴和钨,更优选选自铝和钴,金属元素M还更优选是钴。
当用于制备根据本发明的复分解法中所用的催化剂的多金属氧酸盐型前体不含非钼的金属元素M时,其有利地是选自以下的杂多阴离子:式X2Mo5O23Hh q-. nH2O的Strandberg杂多阴离子、式XMo6O24Hh q-. nH2O的Anderson杂多阴离子、式XMo12O40Hh q-. nH2O的Keggin杂多阴离子、式XMo11O39Hh q-. nH2O的缺位Keggin杂多阴离子、式XMo9O34Hh q-. nH2O的缺位Keggin杂多阴离子、式X2Mo18O62Hh q-. nH2O的Dawson杂多阴离子、式X5Mo30O110Hh q-.nH2O的Preyssler杂多阴离子,其中X、h和q具有上文提到的根据本发明的定义。
当用于制备根据本发明的复分解法中所用的催化剂的基于钼的多金属氧酸盐型前体含有非钼的金属元素M时,M优选是钴,其有利地是选自以下的杂多阴离子:式X2Mo4CoO23Hh q-. nH2O的Strandberg杂多阴离子、式XMo5CoO24Hh q-. nH2O的Anderson杂多阴离子、式XMo11CoO40Hh q - . nH2O的Keggin杂多阴离子、式XMo10CoO39Hh q-. nH2O的缺位Keggin杂多阴离子、式XMo8CoO34Hh q-. nH2O的缺位Keggin杂多阴离子、式X2Mo17CoO62Hh q-.nH2O的Dawson杂多阴离子、式X5Mo29CoO110Hh q-.nH2O的Preyssler杂多阴离子,其中X、h和q具有上文提到的根据本发明的定义,它们的制备准确描述在申请FR 2,764,211中。
当根据本发明的含钼前体是(硫代)钼酸盐型前体时,其有利地对应于式(III)
Cc(MoY4)z (III)
其中
- C代表有机或无机阳离子。例如质子、铵、鏻、碱金属、碱土金属、过渡元素,
- Y基团,彼此相同或不同,可选自O和S,
- c为1至4,
- z为1至10。
含钼的(硫代)钼酸盐型前体可以例如选自下列化合物:(NH4)2MoS4、(NEt4)2MoS4、Na2MoO4、(NH4)2MoO4、Fe2(MoO4)3。
一种或多种对应于式(I)、(II)和/或(III)的前体可用于根据本发明的方法。
含硅前体
有利地,根据本发明的含硅前体是选自任何硅源并有利地选自硅酸(silicic)和/或硅烷和/或硅氧烷和/或倍半硅氧烷型前体和/或含硅的多金属氧酸盐型前体的前体。
当根据本发明的基于硅的前体是硅酸型前体时,其选自硅酸Si(OH)4及其与碱金属或碱土金属的盐。
当根据本发明的基于硅的前体是硅烷型前体时,其有利地对应于式(IV)
R4Si (IV)
其中
R基团,彼此相同或不同,可选自氢、卤素,例如F、Cl、Br、I,取代或未取代的烷基、烯基、炔基、环烷基或芳基,取代或未取代的环戊二烯基、羟基、烷氧基、芳氧基、甲硅烷氧基、硅氮烷基团(silazane)、胺基团(amine)、二胺基团(diamine)、酰胺基团、甲硅烷基、硝基、羧酸酯基、磺酸酯基。
含硅的硅烷型前体可以例如选自下列化合物:SiCl4、Si(CH3)4、Si(OEt)4、H2N(CH2)3Si(OC2H5)3、(CH3)3SiSi(CH3)3、(C6H5)2Si(OH)2、CF3SO3Si(C2H5)3。
当根据本发明的基于硅的前体是直链硅氧烷型前体时,其有利地对应于式(Va)
R1[R2R3SiO]nR4 (Va)
其中
R1、R2、R3和R4,彼此相同或不同,可选自氢、卤素,例如F、Cl、Br、I,取代或未取代的烷基、烯基、炔基、环烷基或芳基,取代或未取代的环戊二烯基、羟基、烷氧基、芳氧基、甲硅烷氧基、硅氮烷基团、胺基团、二胺基团、酰胺基团、甲硅烷基、硝基、羧酸酯基、磺酸酯基,
n是大于或等于2的整数。
当根据本发明的基于硅的前体是环状硅氧烷型前体时,其有利地对应于式(Va')
[R2R3SiO]n (Va')
其中
n、R2和R3具有对式(Va)的上述定义。
含硅的硅氧烷型前体可以例如选自下列化合物:[(CH3)3Si]2O、[CH2=CH(CH3)2Si]2O、聚硅氧烷,例如商业聚硅氧烷,例如rhodorsil®,或二氧化硅的任何胶体溶液。
含硅的环状硅氧烷型前体可以例如是[(CH3)2SiO]3。
当根据本发明的基于硅的前体是倍半硅氧烷型前体时,其有利地对应于式(VI)
[RSiO3/2]n (VI)
其中
R可选自氢、卤素,例如F、Cl、Br、I,取代或未取代的烷基、烯基、炔基、环烷基或芳基,取代或未取代的环戊二烯基、羟基、烷氧基、芳氧基、甲硅烷氧基、硅氮烷基团、胺基团、二胺基团、酰胺基团、甲硅烷基、硝基、羧酸酯基、乙酰丙酮基团、磺酸酯基、β-二酮亚胺基团(diketiminate)、亚氨基吡咯烷基团(iminopyrrolide)、脒基(amidinate)或硫氰酸酯基,
n是大于或等于2的整数。
倍半硅氧烷型前体可以例如选自下列化合物:[(C2H5)SiO3/2]8、[(CH3)3SiO-SiO3/2]8。
当根据本发明的基于硅的前体是多金属氧酸盐型前体时,其有利地对应于式(VII)
(SixM1mM2m'OyHh)q-. nH2O (VII)
其中
·x大于或等于1,
·m大于或等于0,
·m'大于或等于0,
·m+m'大于或等于2,
·b大于或等于0,
·y大于或等于20,
·h为0至12,
·q为1至20,
·n为0至200,
·x、m、b、y、h、n和q是整数,X是选自磷、硅和硼的元素,M1和M2,彼此相同或不同,是选自铝、锌、镍、钴、钼、钨、钒、铌、钽、铁和铜的金属元素。
对应于式(VII)的多金属氧酸盐型前体可以以盐的形式或以酸的形式并入中孔基质中。在多金属氧酸盐型前体以酸形式并入的情况下,通过质子H+补偿电荷q-。当对应于式(VII)的多金属氧酸盐以盐形式引入时,该多金属氧酸盐的抗衡离子选自本领域技术人员已知的所有阳离子。阳离子的实例可提到铵、鏻、碱金属、碱土金属、过渡元素等。所述盐可包含相同阳离子或不同阳离子的混合物。
对应于式(VII)的多金属氧酸盐型前体可以例如选自下列化合物:SiMo12O40H4、SiW12O40H4、SiCoMo11O40H4。
在根据本发明的方法中可以使用对应于式(IV)、(Va)、(Va')、(VI)和/或(VII)的硅酸、硅烷、硅氧烷、倍半硅氧烷、多金属氧酸盐型的一种或多种前体。
根据本发明的中孔基质有利地是基于选自硅、铝、钛、锆、镁、镧、铈及其混合物的至少一种元素X的氧化物的基质。元素X优选是铝或铝和硅的混合物。元素X更优选是铝。
被描述为中孔的所述基于氧化物的基质根据本发明被理解为是指根据IUPAC分类(K. S. W. Sing, D. H. Everett, W. R.A. Haul, L. Moscou, J. Pierotti, J.Rouquerol, T. Siemieniewska, Pure Appl. Chem. 1985, 57, 603)包含尺寸在2至50纳米之间变化的孔隙的基质,和/或中孔结构化(mesostructured)中孔基质(即具有尺寸一致并周期性分布在所述基质中的中孔)和/或具有分级孔隙率,即除中孔外还包含微孔和/或大孔的基质。
该预成型中孔基质可以是商业的或根据本领域技术人员已知的方法合成,特别通过使用“传统”无机合成法:在温和温度和压力条件下由盐沉淀/胶凝;或“现代”金属-有机法:在温和温度和压力条件下由醇盐沉淀/胶凝合成。在下文中和为清楚起见,这些方法简称为“溶胶-凝胶”。也可以使用与特定合成法,如喷雾干燥、浸涂等组合使用的“溶胶-凝胶”法。
该预成型中孔基质可以是粉末形式或例如以成丸、压碎或筛分的粉末、颗粒、片剂、珠粒、轮(wheels)、球体或挤出物(中空或非中空圆柱体,具有例如2、3、4或5个叶的多叶圆柱体,扭曲圆柱体)或环等形式成型。优选使用具有根据BET法的10至500平方米/克,优选至少50平方米/克的比表面积和至少0.1毫升/克的孔隙体积,优选0.3至1.2毫升/克的孔隙体积的基于氧化铝的中孔基质。
根据本发明使用的催化剂包含1至40%,优选2至30%,优选2至20%的由根据本发明的式(I)和/或(II)和/或(III)的前体提供的钼元素的重量含量——表示为相对于中孔基质重量计的钼的重量百分比。
根据本发明使用的催化剂包含0.01至50%,优选0.02至35%,优选0.02至25%的由根据本发明的式(IV)、(Va)、(Va')和(VI)和(VII)的前体提供的硅元素的重量含量——表示为相对于中孔基质重量计的硅元素的重量百分比。
根据本发明的催化剂可根据本领域技术人员已知的方法制备。
至少一种含钼前体和至少一种含硅前体在中孔基质上的沉积可以在中孔基质的成型之前、之中或之后进行。有利地,根据本发明,含钼前体和含硅前体的沉积在基质中同时进行。不受任何理论束缚,与以不同方式制备并使用现有技术的其它前体的催化剂相比,前体的同时并入提供催化剂中Mo和Si之间的接近,这改进用于烯烃复分解反应的所得多相催化剂的活性和稳定性。
根据本发明的前体在中孔基质上的沉积可通过被称作干浸渍、过量浸渍、CVD(化学气相沉积)、CLD(化学液相沉积)等的方法进行,所述方法例如描述在“Catalysis bytransition metal sulphides, from molecular theory to industrial application,Hervé Toulhouat和Pascal Raybaud编辑,第137页”中。
对于根据本发明的前体沉积到预成型中孔基质的表面上,被称作干浸渍和过量浸渍的方法是优选的。
关于干浸渍,对所述干浸渍步骤的重复次数没有特定限制。可以不用溶剂或使用一种或多种溶剂或溶剂混合物(根据本发明的前体可溶于其中)进行不同步骤。这些溶剂可以是极性/质子的,如水、甲醇或乙醇,极性/非质子的,如甲苯或二甲苯,或非极性/非质子的,如己烷。也可调节该溶液的酸度-碱度以改进这些物质的溶解度。类似地,根据本发明的各前体可以独自浸渍或与至少一种其它前体共浸渍,唯一限制是在根据本发明的催化剂的制备法结束时至少一种含钼前体和至少一种含硅前体共同存在。
在一个优选变体中,该催化剂可通过根据包括下列步骤的方法的干浸渍制备:
a) 同时将式(I)、(II)和/或(III)的含钼前体和式(IV)、(Va)、(Va')、(VI)和/或(VII)的含硅前体溶解在对应于基于氧化物的预成型中孔基质的孔隙体积的体积的溶液,优选水溶液中,
b) 用步骤a)中获得的溶液浸渍基于氧化物的预成型中孔基质,将由此获得的固体任选熟化,
c) 将在步骤b)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在50℃至1000℃的温度范围内干燥、煅烧和/或蒸汽处理的任选步骤,
d) 将在步骤c)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在100℃至1000℃的温度范围内热活化的步骤。
在另一变体中,该催化剂也可通过根据包括下列步骤的方法的干浸渍制备:
a') 将式(I)、(II)和/或(III)的含钼前体溶解在对应于基于氧化物的预成型中孔基质的孔隙体积的体积的溶液,优选水溶液中,
b’) 用步骤a)中获得的溶液浸渍基于氧化物的预成型中孔基质,将由此获得的固体任选熟化,
c’) 旨在从溶液a)中除去浸渍溶剂的干燥步骤,
d’) 将式(IV)、(Va)、(Va')、(VI)、和/或(VII)的含硅前体溶解在对应于在步骤c)中获得的固体的孔隙体积的体积的溶液,优选水溶液中,
e’) 用在步骤d)中获得的溶液浸渍在步骤c)中获得的固体,将由此获得的固体任选熟化,
f’) 将在步骤e)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在50℃至1000℃的温度范围内干燥、煅烧和/或蒸汽处理的任选步骤,
g’) 将在步骤f)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在100℃至1000℃的温度范围内热活化的步骤。
步骤a’)和d’)可以反转,即可以先浸渍含Si前体,然后浸渍含Mo前体。
在步骤b)、b’)和e’)中任选实施的熟化在受控气氛中和在受控温度下进行以促进所述前体在基于氧化物的预成型中孔基质的整个表面上分散。有利地,该熟化在20至120℃的温度和0.01至1 MPa的压力下进行。
步骤c)和/或d)或步骤c’)和/或f’)和/或g’)可以在氧化、还原或中性气氛下进行。
优选地,任选干燥步骤c)和f’)在20℃至200℃,优选50℃至150℃,优选100℃至130℃的温度范围内进行小于72小时,优选小于24小时。
优选地,热活化步骤d)和g’)在中性气氛下在大气压力下在200℃至800℃,优选350℃至650℃的温度范围内进行。优选地,该中性气氛是在0.01至20 Nl/h/克在步骤c)和f’)结束时获得的固体,优选0.1至10 Nl/h/克在步骤c)和f’)结束时获得的固体的流量范围内的氮气。
在过量浸渍的情况下,该催化剂可通过根据包括下列步骤的方法的过量浸渍制备
a’’) 同时将式(I)、(II)、(III)的含钼前体和式(IV)、(Va)、(Va')、(VI)和/或(VII)的含硅前体溶解在对应于基于氧化物的预成型中孔基质的孔隙体积的1.5至20倍的体积的溶液,优选水溶液中,
b’’) 用步骤a’’)中获得的溶液浸渍基于氧化物的预成型中孔基质、过滤和回收固体、将由此获得的固体任选熟化,
c’’) 将在步骤b’’)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在50℃至1000℃的温度范围内干燥、煅烧和/或蒸汽处理的任选步骤,
d’’) 将在步骤c’’)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在100℃至1000℃的温度范围内热活化的步骤。
在步骤b’’)中任选实施的熟化在受控气氛中和在受控温度下进行以促进所述前体在基于氧化物的预成型中孔基质的整个表面上分散。有利地,该熟化在20至120℃的温度和0.01至1 MPa的压力下进行。
优选地,步骤a’’)中的式(I)、(II)、(III)和式(IV)、(Va)、(Va')、(VI)和/或(VII)的含钼前体和含硅前体的溶解,其优选同时进行,在对应于基于氧化物的预成型中孔基质的孔隙体积的2至10倍的体积的溶液中进行。
步骤c’’)和/或d’’)可以在氧化、还原或中性气氛下进行。
优选地,任选干燥步骤c’’)在20℃至200℃,优选50℃至150℃,优选100℃至130℃的温度范围内进行小于72小时,优选小于24小时。
优选地,热活化步骤d’’)在中性气氛下在大气压力下在200℃至800℃,优选350℃至650℃的温度范围内进行。优选地,该中性气氛是在0.01至10 Nl/h/克在步骤c’’)结束时获得的固体,优选0.1至5 Nl/h/克在步骤c’’)结束时获得的固体的流量范围内的氮气。
在根据本发明的催化剂的制备过程中也可以使用有机化合物,其被称作有机添加剂。可通过在用前体浸渍的步骤前浸渍到中孔基质上、通过与前体共浸渍或在用前体浸渍后的后浸渍引入至少一种有机添加剂。
所用有机化合物或添加剂选自螯合剂、非螯合剂、还原剂和本领域技术人员已知的添加剂。
所述有机化合物或添加剂有利地选自任选醚化的单-、二-或多元醇、羧酸(柠檬酸、乙酸等)、糖、非环状单糖、二糖或多糖,如葡萄糖、果糖、麦芽糖、乳糖或蔗糖、环状或非环状酯、环状或非环状醚、酮、兼具这些官能的几种(酮、羧酸、醚、酯、醇、胺等)的化合物、冠醚、环糊精和含有至少硫或磷或氮的化合物,如次氮基乙酸、乙二胺四乙酸或二亚乙基三胺,氨基酸和两性离子化合物,它们独自或混合使用。
该浸渍和/或溶解溶剂优选是水,但可以使用本领域技术人员已知的任何溶剂。
也可以将一种或多种其它金属元素引入根据本发明的方法中所用的催化剂的组成中。这种金属元素可选自锌、镍、钴、钨、钒、铌、钽、铁和铜。以0.01至10%,优选0.02至5%的含量引入该金属元素,表示为相对于基于氧化物的中孔基质的重量计的金属的重量%。
这种金属元素可以由选自锌、镍、钴、钨、钒、铌、钽、铁和铜的盐和/或氧化物,优选锌、镍、钴、钨的盐和/或氧化物的化合物提供。该化合物优选是钴盐、羧酸盐、醇盐或氧化物。该化合物优选是Co(NO3)2或CoO。该化合物非常优选是Co(NO3)2。
可通过在用式(I)、(II)、(III)的含钼前体和用式(IV)、(Va)、(Va')、(VI)和/或(VII)的含硅前体浸渍前浸渍到中孔基质上、通过与所述前体共浸渍或在用所述前体浸渍后的后浸渍引入所述化合物。
在根据本发明的方法中所用的催化剂在上文公开的不同制备方法结束时以粉末形式获得的情况下,该粉末可根据本领域技术人员公知的方法成型。因此,其可以是成丸、压碎或筛分的粉末、颗粒、片剂、珠粒、轮、球体或挤出物(中空或非中空圆柱体,具有例如2、3、4或5个叶的多叶圆柱体,扭曲圆柱体)或环等形式。所述催化剂优选作为挤出物成型。
在所述成型操作的过程中,根据本发明的方法中所用的催化剂可任选与至少一种充当粘合剂的多孔氧化物材料混合以产生适合根据本发明的方法的催化剂的物理性质(机械强度、耐磨性等)。
所述多孔氧化物材料优选是选自氧化铝、二氧化硅、二氧化硅-氧化铝、氧化镁、粘土、氧化钛、氧化锆、氧化镧、氧化铈、磷酸铝和至少两种上文提到的氧化物的混合物的多孔氧化物材料。所述多孔氧化物材料也可选自氧化铝-氧化硼、氧化铝-氧化钛、氧化铝-氧化锆和钛-锆氧化物混合物。有利地使用铝酸盐,例如铝酸镁、铝酸钙、铝酸钡、铝酸锰、铝酸铁、铝酸钴、铝酸镍、铝酸铜和铝酸锌以及混合铝酸盐,例如含有至少两种上文提到的金属的那些作为多孔氧化物材料。也可以使用钛酸盐,例如钛酸锌、钛酸镍、钛酸钴。也可以有利地使用氧化铝和二氧化硅的混合物和氧化铝与其它化合物如第VIB族元素、磷、氟或硼的混合物。也可以使用二八面体层状硅酸盐2:1类型或三八面体层状硅酸盐3:1类型的简单、合成或天然粘土,如高岭石、叶蛇纹石、温石棉、蒙脱石、贝得石、蛭石、滑石、锂蒙脱石、皂石、锂皂石。这些粘土可任选分层(delaminated)。也可以有利地使用氧化铝和粘土的混合物和二氧化硅-氧化铝和粘土的混合物。使用至少两种上文提到的化合物的各种混合物也适合充当粘合剂。
任选地,在所述成型步骤的过程中还混合至少一种有机辅助剂。所述有机辅助剂的存在促进通过挤出成型。所述有机辅助剂可以有利地选自聚乙烯基吡咯烷酮、纤维素聚合物及其衍生物,优选选自纤维素醚,例如Dow Chemical公司出售的Methocel,聚乙烯醇、聚乙二醇、聚丙烯酰胺(polyacrymalides)、多糖、天然聚合物及其衍生物,例如藻酸盐、聚酯、聚酰胺和芳族聚酰胺、聚醚、聚(芳基醚)、聚氨酯、聚砜,如聚砜醚,杂环聚合物,优选选自聚酰亚胺、聚酰亚胺醚、聚酰亚胺酯、聚酰亚胺酰胺和聚苯并咪唑。
所述有机辅助剂的比例有利地为相对于成型的中孔基质总重量的0至20重量%,优选0至10重量%,优选0至7重量%。
复分解反应
通过使烯烃与上文定义的催化剂接触进行的烯烃复分解法有利地在0至500℃,优选0至400℃,更优选20至350℃,再更优选30至350℃的温度下进行。
烯烃的复分解反应可以在气相中或在液相中进行。该反应可以以分批模式、在搅拌反应器中进行或以连续模式、通过使一种或多种烯烃反应物经过催化剂的固定床、移动床或流化床进行。
进行根据本发明的方法时的压力不重要。但是,对于在液相中的操作,有利地使压力保持至少等于反应混合物在反应温度下的蒸气压。
该反应优选在不存在溶剂的情况下进行。但是,该反应可以在溶剂,如烃,或卤代、脂族、cyclanic或芳族烃存在下进行。
能够通过根据本发明的方法的复分解反应的烯烃可以是符合通式R1R2C=CR3R4的直链烯烃,其中R1、R2、R3和R4,相同或不同,是氢或具有1至20个碳原子的烃基,或具有环状结构的烯烃,该环包含3至20个碳原子。
烯烃可独自反应,或几种烯烃可以在混合物中一起反应。根据本发明的方法特别是乙烯与2-丁烯的交叉复分解反应以产生丙烯,或将丙烯转化成乙烯和2-丁烯的混合物的逆反应。
能够通过复分解反应的其它烯烃是单烯烃或多烯烃、直链或环状的、带有官能团,例如卤素或酯基团。该方法也可以在共同复分解(co-metathesis)中使用上述烯烃的混合物。
在通过乙烯和2-丁烯之间的复分解生产丙烯的情况下,2-丁烯可优选源自乙烯在本领域技术人员已知的均相或多相催化剂存在下的二聚反应。例如,2-丁烯可源自乙烯在NiCl2(PBu3)2类型的镍配合物存在下的二聚,以通过均相催化产生1-丁烯和2-丁烯的混合物。例如,2-丁烯可源自乙烯在NiSO4/Al2O3类型的基于镍的多相催化剂存在下的二聚,以通过多相催化产生1-丁烯和2-丁烯的混合物。
在通过乙烯与2-丁烯和1-丁烯混合物之间的复分解生产丙烯的情况下,优选使用用于将1-丁烯异构化成2-丁烯的催化剂以使丙烯收率最大化。例如,MgO或K2O型氧化物催化剂可用于将1-丁烯异构化成2-丁烯。
可以有利地通过生物来源的(biosourced)乙醇通过本领域技术人员已知的任何脱水法脱水获得乙烯,以能够生产生物来源的丙烯。
实施例
在实施例中,配位配合物型含钼前体MoCl5、MoO2(acac)2,同多阴离子型含钼前体(NH4)6Mo7O24,杂多阴离子型含钼前体PMo12O40H3、SiMo12O40H4,硅酸型含硅前体Na2SiO3,硅烷型含硅前体Si(CH3)4和硅氧烷型含硅前体[(CH3)3Si]2O可购得。
实施例1A(不根据本发明): 通过用PMo12O40 3-.3H+.30H2O溶液干浸渍制备6.7%Mo/
Al2O3
将1.5克PMo12O40 3-.3H+.30H2O在60℃下溶解在7.3毫升蒸馏水中。在完全溶解后,用该溶液浸渍氧化铝(SBET = 198平方米/克,Vp = 0.47毫升/克)。将所得固体在空气下在25℃下熟化24小时。将所得固体在烘箱中在120℃下干燥24小时,然后在氮气下在550℃下活化2小时。
实施例1B(根据本发明): 通过用PMo12O40 3-.3H+.30H2O和Si(OEt)4(TEOS)的溶液干
浸渍制备6.7%Mo+1.7%Si/Al2O3
将1.83克TEOS在60℃下在pH=2下溶解在7.3毫升蒸馏水中。在TEOS完全溶解后添加1.5克PMo12O40 3-.3H+。在完全溶解后,用该溶液浸渍氧化铝(SBET = 198平方米/克,Vp = 0.47毫升/克)。将所得固体在空气下在25℃下熟化24小时。将所得固体在烘箱中在120℃下干燥24小时,然后在氮气下在550℃下活化2小时。
实施例2: 丙烯复分解成乙烯和2-丁烯
在双夹套固定床反应器中将2克实施例1A和1B中制备的催化剂以50重量%的比例与碳化硅(SiC)混合。将该双夹套的传热流体加热至70℃。借助Gilson泵将纯丙烯传送至该反应器并将压力设定在4.5 MPa。在图1中根据标作t的时间(以小时计,标作h)定量以每克催化剂每小时消耗的丙烯的毫摩尔数表示的催化剂的生产率。
通过用含钼前体和含硅前体浸渍制备的根据本发明的催化剂1B的活性高于不根据本发明并通过用单一含钼前体浸渍制备的催化剂1A的活性。
根据本发明的催化剂1B的稳定性好于不根据本发明的催化剂1A的稳定性。
Claims (22)
1.通过使烯烃与包含中孔基质和至少元素钼和硅的催化剂接触进行的烯烃复分解方法,所述元素使用至少两种前体并入所述基质中,其中至少一种前体含有钼且至少一种前体含有硅。
2.根据权利要求1的方法,其中所述含钼前体是基于钼的配位配合物类型和/或基于钼的多金属氧酸盐类型和/或(硫代)钼酸盐类型的前体。
3.根据权利要求1或2的方法,其中基于钼的配位配合物型含钼前体对应于式(I)
Mom(=Y)n(≡N)n’(X)o(=CR2)r (I)
其中
- Y基团,彼此相同或不同,选自O、S和NR’,
- X基团,彼此相同或不同,选自卤素,如F、Cl、Br、I,氯酸根、溴酸根、碘酸根、硝酸根、硫酸根或硫酸氢根、烷基硫酸根、硫代硫酸根、碳酸根或碳酸氢根、磷酸根或磷酸氢根或磷酸二氢根、取代或未取代的烷基、环烷基或芳基、取代或未取代的环戊二烯基、烷氧基、芳氧基、甲硅烷氧基、酰胺基团、氢负离子、硝基、羧酸根、乙酰丙酮基团、磺酸根、β-二酮亚胺基团、亚氨基吡咯烷基团、脒基、硼酸根、氰根、氰酸根、硫氰酸根或NR2-CS2 -基团,
- R和R’基团,彼此相同或不同,选自烷基和芳基,其优选包含1至10个碳原子,烷氧基和芳氧基,
- m等于1或2,
- n为0至4,
- n’为0至2,
- o为0至10,
- r为0至2,
- n+n’+o+r大于或等于1。
4.根据权利要求1或2的方法,其中基于钼的多金属氧酸盐型含钼前体对应于式(II)
(XxMomMbOyHh)q-.nH2O (II)
其中
·x大于或等于0,
·m大于或等于2,
·b大于或等于0,
·y大于或等于7,
·h为0至12,
·q为1至20,
·n为0至200,
·x、m、b、y、h、n和q是整数,X是选自磷、硅和硼的元素,M是选自铝、锌、镍、钴、钨、钒、铌、钽、铁和铜的金属元素。
5.根据权利要求4的方法,其中基于钼的多金属氧酸盐型前体是基于钼的同多阴离子,其中元素X的下标x等于0。
6.根据权利要求4的方法,其中基于钼的多金属氧酸盐型前体是选自式X2Mo5O23Hh q-.nH2O的Strandberg杂多阴离子、式XMo6O24Hh q-. nH2O的Anderson杂多阴离子、式XMo12O40Hh q-.nH2O的Keggin杂多阴离子、式XMo11O39Hh q-. nH2O的缺位Keggin杂多阴离子、式XMo9O34Hh q-.nH2O的缺位Keggin杂多阴离子、式X2Mo18O62Hh q-. nH2O的Dawson杂多阴离子、式X5Mo30O110Hh q-.nH2O的Preyssler杂多阴离子的杂多阴离子,其中X、h和q具有根据权利要求4的定义。
7.根据权利要求4的方法,其中基于钼的多金属氧酸盐型前体是选自式X2Mo4CoO23Hh q-.nH2O的Strandberg杂多阴离子、式XMo5CoO24Hh q-. nH2O的Anderson杂多阴离子、式XMo11CoO40Hh q-. nH2O的Keggin杂多阴离子、式XMo10CoO39Hh q-. nH2O的缺位Keggin杂多阴离子、式XMo8CoO34Hh q-. nH2O的缺位Keggin杂多阴离子、式X2Mo17CoO62Hh q-. nH2O的Dawson杂多阴离子、式X5Mo29CoO110Hh q-.nH2O的Preyssler杂多阴离子的杂多阴离子,其中X、h和q具有根据权利要求4的定义。
8.根据权利要求1或2的方法,其中(硫代)钼酸盐型含钼前体对应于式(III)
Cc(MoY4)z (III)
其中
- C代表有机或无机阳离子,如质子、铵、鏻、碱金属、碱土金属、过渡元素,
- Y基团,彼此相同或不同,可选自O和S,
- c为1至4,
- z为1至10。
9.根据权利要求1的方法,其中所述含硅前体是选自硅酸和/或硅烷和/或硅氧烷和/或倍半硅氧烷型前体和/或含硅的多金属氧酸盐型前体的前体。
10.根据权利要求1或9的方法,其中所述硅酸型含硅前体选自硅酸Si(OH)4及其碱金属或碱土金属盐。
11.根据权利要求1或9的方法,其中所述硅烷型含硅前体对应于式(IV)
R4Si (IV)
其中
R基团,彼此相同或不同,选自氢、卤素,例如F、Cl、Br、I,取代或未取代的烷基、烯基、炔基、环烷基或芳基,取代或未取代的环戊二烯基、羟基、烷氧基、芳氧基、甲硅烷氧基、硅氮烷基团、胺基团、二胺基团、酰胺基团、甲硅烷基、硝基、羧酸酯基、磺酸酯基。
12.根据权利要求1或9的方法,其中所述直链硅氧烷型含硅前体对应于式(Va)
R1[R2R3SiO]nR4 (Va)
其中
R1、R2、R3和R4,彼此相同或不同,选自氢、卤素,例如F、Cl、Br、I,取代或未取代的烷基、烯基、炔基、环烷基或芳基,取代或未取代的环戊二烯基、羟基、烷氧基、芳氧基、甲硅烷氧基、硅氮烷基团、胺基团、二胺基团、酰胺基团、甲硅烷基、硝基、羧酸酯基、磺酸酯基,
n是大于或等于2的整数。
13.根据权利要求1或9的方法,其中所述环状硅氧烷型含硅前体对应于式(Va')
[R2R3SiO]n (Va')
其中
n、R2和R3具有权利要求12中对式(Va)的上述定义。
14.根据权利要求1或9的方法,其中所述倍半硅氧烷型含硅前体对应于式(VI)
[RSiO3/2]n (VI)
其中
R选自氢、卤素,例如F、Cl、Br、I,取代或未取代的烷基、烯基、炔基、环烷基或芳基,取代或未取代的环戊二烯基、羟基、烷氧基、芳氧基、甲硅烷氧基、硅氮烷基团、胺基团、二胺基团、酰胺基团、甲硅烷基、硝基、羧酸酯基、乙酰丙酮基团、磺酸酯基、β-二酮亚胺基团、亚氨基吡咯烷基团、脒基或硫氰酸酯基,
n是大于或等于2的整数。
15.根据权利要求1或9的方法,其中所述多金属氧酸盐型含硅前体对应于式(VII)
(SixM1mM2m'OyHh)q-. nH2O (VII)
其中
·x大于或等于1,
·m大于或等于0,
·m'大于或等于0,
·m+m'大于或等于2,
·b大于或等于0,
·y大于或等于20,
·h为0至12,
·q为1至20,
·n为0至200,
·x、m、b、y、h、n和q是整数,X是选自磷、硅和硼的元素,M1和M2,彼此相同或不同,是选自铝、锌、镍、钴、钼、钨、钒、铌、钽、铁和铜的金属元素。
16.根据前述权利要求之一的方法,其中所述中孔基质是基于选自硅、铝、钛、锆、镁、镧、铈及其混合物的至少一种元素X的氧化物的基质。
17.根据前述权利要求之一的方法,其中所述催化剂通过根据包括下列步骤的方法的干浸渍制备:
a) 同时将含钼前体和含硅前体溶解在对应于基于氧化物的预成型中孔基质的孔隙体积的体积的溶液中,
b) 用步骤a)中获得的溶液浸渍基于氧化物的预成型中孔基质,将由此获得的固体任选熟化,
c) 将在步骤b)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在50℃至1000℃的温度范围内干燥、煅烧和/或蒸汽处理的任选步骤,
d) 将在步骤c)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在100℃至1000℃的温度范围内热活化的步骤。
18.根据权利要求1至16之一的方法,其中所述催化剂通过根据包括下列步骤的方法的干浸渍制备:
a’) 将含钼前体溶解在对应于基于氧化物的预成型中孔基质的孔隙体积的体积的溶液中,
b’) 用步骤a)中获得的溶液浸渍基于氧化物的预成型中孔基质,将由此获得的固体任选熟化,
c’) 旨在从溶液a)中除去浸渍溶剂的干燥步骤,
d’) 将含硅前体溶解在对应于在步骤c)中获得的固体的孔隙体积的体积的溶液,优选水溶液中,
e’) 用在步骤d)中获得的溶液浸渍在步骤c)中获得的固体,将由此获得的固体任选熟化,
f’) 将在步骤e)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在50℃至1000℃的温度范围内干燥、煅烧和/或蒸汽处理的任选步骤,
g’) 将在步骤f)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在100℃至1000℃的温度范围内热活化的步骤。
19.根据权利要求1至16之一的方法,其中所述催化剂通过根据包括下列步骤的方法的过量浸渍制备:
a’’) 同时将含钼前体和含硅前体溶解在对应于基于氧化物的预成型中孔基质的孔隙体积的1.5至20倍的体积的溶液中,
b’’) 用步骤a’’)中获得的溶液浸渍基于氧化物的预成型中孔基质、过滤和回收固体、将由此获得的固体任选熟化,
c’’) 将在步骤b’’)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在50℃至1000℃的温度范围内干燥、煅烧和/或蒸汽处理的任选步骤,
d’’) 将在步骤c’’)结束时获得的固体在大于或等于0.1 MPa或小于或等于0.1 MPa的压力下在100℃至1000℃的温度范围内热活化的步骤。
20.根据前述权利要求之一的方法,其中所述复分解反应在0至500℃的温度下进行。
21.根据权利要求20的方法,其中所述烯烃是符合通式R1R2C=CR3R4的直链烯烃,其中R1、R2、R3和R4,相同或不同,是氢或具有1至20个碳原子的烃基,或具有环状结构的烯烃,所述环包含3至20个碳原子。
22.根据前述权利要求之一的方法,其中所述复分解反应是乙烯与2-丁烯的交叉复分解反应,或将丙烯转化成乙烯和2-丁烯的混合物的逆反应。
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