CN101481290A - 一种将丙烷转化为丙烯的方法 - Google Patents
一种将丙烷转化为丙烯的方法 Download PDFInfo
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- CN101481290A CN101481290A CNA2009100029600A CN200910002960A CN101481290A CN 101481290 A CN101481290 A CN 101481290A CN A2009100029600 A CNA2009100029600 A CN A2009100029600A CN 200910002960 A CN200910002960 A CN 200910002960A CN 101481290 A CN101481290 A CN 101481290A
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- Prior art keywords
- propane
- propylene
- weight
- silicon
- component
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000001294 propane Substances 0.000 title claims abstract description 85
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 title abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 32
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 61
- WNOHDFYRLUENNX-UHFFFAOYSA-N chromium dioxosilane Chemical compound [Cr].[Si](=O)=O WNOHDFYRLUENNX-UHFFFAOYSA-N 0.000 claims description 30
- 235000011089 carbon dioxide Nutrition 0.000 claims description 19
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 10
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 239000011651 chromium Substances 0.000 abstract description 22
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- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
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- 238000006356 dehydrogenation reaction Methods 0.000 description 36
- 238000001354 calcination Methods 0.000 description 14
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- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 6
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- 239000007864 aqueous solution Substances 0.000 description 4
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
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- 229910052684 Cerium Inorganic materials 0.000 description 1
- 206010019332 Heat exhaustion Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- JTXAHXNXKFGXIT-UHFFFAOYSA-N propane;prop-1-ene Chemical group CCC.CC=C JTXAHXNXKFGXIT-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
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Abstract
描述了一种将丙烷转化为丙烯的方法,该方法包括使二氧化硅铬催化剂组合物与丙烷进料物流和二氧化碳相接触。进一步描述了所述二氧化硅铬催化剂组合物,所述组合物任选地还包含促进剂组分。
Description
政府权益
本发明是在美国能源部第DE-FC36-O4GO14272号经费的资助下进行的。政府享有本发明的某些权利。
技术领域
本发明涉及丙烷到丙烯的催化转化以及适用于该过程的催化剂。
背景技术
众所周知的制备丙烯酸和丙烯腈之类的单体的商业方法通常通过催化气相氧化将丙烯转化为所需的单体产物。由于工业竞争产生的压力,以及丙烷和丙烯之间的价格差异,人们正在致力于开发一种新方法,该方法采用丙烷作为起始物质,最终以较低的总成本得到所需的单体。
Takehira等人测试了负载在含硅的负载材料(包括介孔MCM-41,Cab-O-Sil和二氧化硅)上的各种金属氧化物催化剂(Cr,Ga,Ni,V,Fe,Mn和Co)的活性,发现负载在MCM-41上的基于Cr的催化剂对于丙烷在存在二氧化碳的条件下脱氢形成丙烯的反应提供最好的结果。(参见Takehira,K.;Oishi,Y.;Shishido,T.;Kawabata,T.;Takaki,K.;Zhang,Q.和Wang,Y.,“在Cr-MCM-41催化剂上的丙烷的CO2脱氢(CO2 Dehydrogenation of Propane over Cr-MCM-41 Catalyst),”Studies in SurfaceScience and Catalysis,2004,153,323-328)。虽然已显示许多这些金属氧化物/载体组合具有在将丙烷转化成丙烯的反应中用作催化体系的前景,但仍然需要鉴别出能够由丙烷高产率制备丙烯的体系。还希望鉴别出能够通过吸热脱水过程高产率制备丙烯的催化体系。这种吸热过程可提供与丙烷放热脱水偶联的选项,所得组合过程的能量消耗总体为零或非常低。
发明内容
我们已发现了一种在二氧化碳的存在下将丙烷催化转化成丙烯的方法,该方法的丙烯产率出乎意料地高。吸热脱氢过程可采用二氧化硅铬催化剂组合物来实现,其中氧化铬负载在多孔二氧化硅上,多孔二氧化硅的表面积至少为400到不超过1,200平方米/克,多孔二氧化硅中孔的平均孔径至少为20到小于100埃。
本发明的一方面涉及将丙烷转化成丙烯的方法,该方法包括以下步骤:
(A)使丙烷进料物流和二氧化碳与二氧化硅铬催化剂组合物相接触;
所述丙烷进料物流包含丙烷,和
所述二氧化硅铬催化剂组合物包含:
a)催化组分,基于多孔二氧化硅的重量以铬金属当量计,包含含量至少为2重量%且不超过15重量%的氧化铬;和
b)载体组分,其包含具有以下性质的多孔二氧化硅:
i)多个孔的平均孔径至少20埃且小于100埃;和
ii)表面积至少400平方米/克且不超过1200平方米/克;和
(B)在二氧化碳和二氧化硅铬催化剂组合物的存在下,将丙烷转化成丙烯。
具体实施方式
本文所用术语具有以下涵义:
除非另有具体说明,本说明书中使用的词“一”和“一个”表示“至少一个”。
“范围”。本文描述的范围采用上限和下限的形式。可存在一个或多个下限以及独立地一个或多个上限。通过选择一个下限和一个上限来限定给定范围。然后由选择的上限和下限来限定具体范围的边界。这样,所有范围可限定为包括端值并且是可组合的,即任意下限可与任意上限组合以确定范围。例如,如果某特定参数的范围为60-120和80-110,则60-110和80-120也是可以的。此外,如果最小量程值为1和2,最大量程值为3、4和5,则考虑了以下范围:1-3,1-4,1-5,2-3,2-4以及2-5。
本领域技术人员应理解,可对本文具体描述的适当方法和组合物进行改动而不背离本发明的广泛概念。因此,应理解,本发明并不限于所述具体适当的方法和组合物,这些方法和组合物的描述旨在额外地覆盖本文所述且由所附权利要求书所限定的本发明精神和范围内的改进形式。
二氧化碳(与“二氧化碳气体”可互换)能够作为氧化剂参与丙烷的催化脱氢,与从丙烷去除的氢原子结合,产生含有至少一个从丙烷去除的氢原子和至少一个早先包含在二氧化碳中的原子的副产物化合物。
“二氧化硅铬催化剂组合物”是包含“催化组分”、“载体组分”以及任选的“促进剂组分”的组合物。
“催化组分”是包含氧化铬的组分,所述催化组分能够催化丙烷的吸热脱氢而形成丙烯。将丙烷转化成丙烯的吸热脱氢过程中,铬通常以Cr(III)的形式存在,但也可以其他氧化态形式存在,例如Cr(IV)。
“载体组分”是包括“多孔二氧化硅”的组分,所述多孔二氧化硅包括以下性质:多孔的平均孔径至少为20埃到小于100埃,表面积至少为400m2/g且不超过1,200m2/g。
“促进剂组分”是包含“催化促进剂”的组分。
“催化促进剂”是当包含在本发明的二氧化硅铬催化剂组合物中时能够改变二氧化硅铬催化剂组合物,通常增强其将丙烷转化成丙烯的催化效率或催化寿命的物质。
“稀释剂”是任何基本上惰性的材料,即其不会参与相关特定反应、不会受到该反应的影响,和/或在该反应中没有活性。例如,在由丙烷制备丙烯的氧化脱氢反应中,氮气是惰性的。
术语“丙烷重量分数转化率”(“丙烷w.f.转化率”)的定义是脱氢过程中未转化的丙烷摩尔数除以用于吸热脱氢的原料中包含的丙烷摩尔数得到的商与1之间的差值。“丙烷百分转化率”(“丙烷%转化率”)的定义是丙烷重量分数转化率乘以100%。原料中包含的丙烷的摩尔数和化学反应之后产物物流中包含的丙烷的摩尔数可通过分析测定。
丙烷%转化率=(丙烷重量分数转化率)X100%
术语“丙烯重量分数选择性”(“丙烯w.f.选择性”)的定义是化学反应期间形成的丙烯的摩尔数除以原料中丙烷的摩尔数与化学反应后仍然未转化的丙烷的摩尔数之间的差值。“丙烯百分选择性”(“丙烯%选择性”)的定义是丙烯重量分数选择性乘以100%。化学反应后的产物物流中包含的丙烯的摩尔数可通过分析测定。
丙烯%选择性=(丙烯重量分数选择性)X 100%
术语“丙烯重量分数产率”(“丙烯w.f.产率”)的定义是丙烷重量分数转化率乘以丙烯重量分数选择性。“丙烯百分产率”(“丙烯%产率”)的定义是丙烯重量分数产率乘以100%。
丙烯重量分数产率=(丙烷w.f.转化率)X(丙烯w.f.选择性)
丙烯%产率=(丙烯重量分数产率)X100%
术语“含二氧化碳的气体”表示包含0.01%到最高达100%二氧化碳的任何气体。含二氧化碳的气体的非限制性例子包括:富含二氧化碳的空气、纯二氧化碳、以及二氧化碳与惰性气体如氮气和氩气的混合物。
“氧化脱氢”表示一种化学反应,烃和氧反应导致从烃除去一个或多个氢原子而制得氧化产物。因此,氧化脱氢需要含氧气体或者气态含氧化合物以提供所需的氧。
“脱氢”是一种化学反应,从化学部分去除一个或多个氢原子而形成含有原始化学部分中不存在的不饱和基团的产物部分。在本文中,“脱氢”表示从丙烷去除两个氢原子以形成在脱氢之前不存在的双键的丙烯。
“吸热脱氢”是一种伴有热量消耗的脱氢反应,该反应需要由反应外部热源来提供热量。
“放热脱氢”是一种伴有放热的脱氢反应,该反应需要由冷却装置带走热量。
本发明的“催化促进剂”包括选自以下的金属的氧化物:钒(V);银(Ag);铈(Ce)和其他镧系元素如La、Pr、Nd;Gd;Ti;Zr;V;Nb;Mo;W;Zn;以及它们的组合。
“丙烷进料物流”(“进料物流”)是包含丙烷的气态物流。丙烷进料物流可以是纯或基本上纯的丙烷。或者,丙烷进料物流可还包含一种或多种再循环丙烯产物物流的组分,例如稀释剂、丙烯、丙烷脱氢副产物、蒸汽、一氧化碳(CO)以及它们的组合。
“丙烷脱氢副产物”是丙烷转化成丙烯反应(“丙烷脱氢反应”)期间形成的副产物,其中至少一部分被消耗的丙烷没有转化成丙烯。典型的丙烷脱氢副产物包括但不限于:甲烷、乙烯、乙烷、乙炔以及它们的组合。
“吸热反应区域”是实现吸热脱氢的反应区域。本发明的“脱氢反应器”包括吸热反应区域。
本发明的“载体组分”包括具有多个孔的“多孔二氧化硅”。本发明多孔二氧化硅的多个孔的平均孔径为:至少20,至少25或至少30埃();并且小于100,不超过80,不超过70或不超过60。本发明多孔二氧化硅的多个孔的表面积为:以多孔二氧化硅的重量计,至少为400或至少450平方米/克(m2/g),并且不超过1,200,不超过1,000,不超过800或不超过700平方米/克。载体组分可以是例如小珠、丸料、团粒、圆柱体、挤出物(例如三裂片状)、管状、球形颗粒、不规则形状的颗粒、规则形状的整体料及不规则形状整体料的形式。
本发明的“催化组分”包括氧化铬形式的铬。氧化铬在“二氧化硅铬催化剂组合物”中的含量为:基于载体组分的重量以铬金属当量计,至少为2、至少3、或至少4重量%;并且不超过15,不超过12,或不超过10重量%。
选择本发明催化促进剂的含量以优化催化组分的效率和寿命。如果存在,催化促进剂在二氧化硅铬催化剂组合物中的含量为:基于载体组分的重量,以金属当量计,等于或大于0.01,至少0.05,至少0.5,至少1或至少2重量%;并且不超过10,不超过8,不超过5,不超过2.5重量%。氧化钒在二氧化硅铬催化剂组合物中的含量为:基于载体组分的重量,以钒金属当量计,等于或大于0,至少0.5,至少1或至少2重量%;不超过10,不超过8,或不超过5重量%。氧化银在二氧化硅铬催化剂组合物中的含量为:基于载体组分的重量,以银金属当量计,大于或等于0,至少0.01,至少0.05,或至少0.1重量%;并且不超过2,不超过1或不超过0.5重量%。
二氧化硅负载的铬基催化剂的制备通常包括煅烧步骤。技术人员将理解煅烧是在已负载含催化剂前体的溶液的载体组分上进行的步骤。在煅烧步骤中,将负载有催化剂前体溶液的载体组分加热以蒸发溶剂。例如,当溶剂是水中,宜首先在接近但低于水沸点的温度下进行加热,然后在接近但高于水沸点的温度下长时间干燥。在氧的存在下,进一步升高温度至催化剂前体(例如金属盐)转化成相应的金属氧化物的温度,以完成煅烧步骤。通常,煅烧温度为450-750℃。本发明的煅烧步骤可用于将铬催化剂前体(通常是金属盐)转化成含铬氧化物的催化剂组分。煅烧步骤可以在单一温度下保持一段时间实现,或者在多种温度下和/或保持不同时间而实现。二氧化硅铬催化剂组合物的制备可还包括多个催化剂组分/促进剂组分负载步骤和/或多个煅烧步骤。
技术人员将理解,还可以在溶剂蒸发和煅烧之前对载体组分负载含促进剂前体的溶液。含催化剂前体的溶液可与含促进剂前体的溶液相同。或者,含催化剂前体的溶液与含促进剂前体的溶液是两种不同的溶液。在另一种合适的替代形式中,促进剂前体的一部分可在溶液中与所有或一部分的催化剂前体组合;或者催化剂前体的一部分可在溶液中与所有或一部分促进剂前体组合。
在本发明的方法中,提供本发明二氧化硅铬催化剂组合物的吸热反应区域。可将丙烷进料物流、二氧化碳气体及任意稀释剂分别引入吸热反应区域,或者各组分的一部分或所有组分进行混合。丙烷进料物流和二氧化碳气体在反应温度下与二氧化硅铬催化剂组合物接触,反应一段时间后实现丙烷到丙烯的有效转化。产生的“丙烯产物物流”包含丙烯,可还包含未反应的丙烷、甲烷、乙烯、未反应的二氧化碳、一氧化碳、水蒸气、分子氢、以及副反应产物如甲烷、乙烯和乙烷。
丙烯产物物流的后续处置可根据具体应用而改变。例如,丙烯产物物流可无需改良用于其他步骤,例如丙烯衍生物的制备,例子包括丙烯酸、丙烯酸酯、丙烯腈或其组合;或者所有或一部分的丙烷进料物流再循环,用于吸热反应区域中丙烷的另一氧化脱氢。本领域技术人员将理解,丙烯产物物流可经历“选择性分配”步骤,该步骤中所有或一部分的一种或多种非丙烯组分被选择性地去除。选择性分配步骤可用于制备纯化的丙烯,适用于后续转化成丙烯衍生物,包括上文列出的那些。选择性分配的步骤还可用于浓缩未反应的丙烷,然后作为丙烷进料物流或作为丙烷进料物流的一部分再循环进行氧化脱氢。
合适的“稀释剂”包括但不限于:氮气;稀有气体如氦气和氩气;以及蒸汽。
本发明的“脱氢进料组合物”包含丙烷,其含量为:以脱氢进料组合物的总体积计,至少5,至少10,或至少15体积%;并且不超过70,不超过40,不超过30体积%。本发明的脱氢进料组合物还包含二氧化碳,其含量为:以脱氢进料组合物的总体积计,至少10或至少20体积%;并且不超过80或60体积%。脱氢进料组合物还可包含稀释剂,其含量为:以脱氢进料组合物的总体积计,等于或大于0,至少1,或至少5体积%;并且不超过50,不超过40或不超过20体积%。合适的脱氢进料组合物可还可包含丙烷脱氢副产物,其含量为:以脱氢进料组合物的总体积计,等于或大于0,至少1,或至少2体积%;并且不超过20,不超过10或不超过5体积%。当所有或一部分的丙烯产物物流再循环时,脱氢进料组合物中通常存在丙烷脱氢副产物。
本发明的“载体组分”包括具有多个孔的“多孔二氧化硅”。本发明多孔二氧化硅的多个孔的平均孔径为:至少20,至少25或至少30埃();并且小于100,或不超过80,或不超过70或不超过60。本发明多孔二氧化硅的多个孔的表面积为:以多孔二氧化硅的重量计,至少400或至少450平方米/克(m2/g),并且不超过1,200,不超过1,000,不超过800,或不超过700平方米/克。载体组分可以是例如颗粒形状(例如片剂或挤出物),规则形状的整体料以及不规则形状的整体料。
二氧化硅铬催化剂组合物可通过本领域已知的任何合适的方法进行制备。可以对载体组分进行改性、稳定化或预处理,以得到能够耐受使用催化剂的操作条件的合适的结构稳定性。所述载体组分可以是片剂、挤出物、整体料、颗粒、蜂窝体、环和其它形状。当所述载体为颗粒形式的时候,颗粒的形状没有特别的限制,可以包括小粒、珠粒、丸剂、团粒、圆柱体、三裂片形、球形、不规则形状等。可通过本领域已知的任何方法将催化剂组分施加到载体组分上,所述方法包括例如:初始湿浸渍、化学气相沉积、水热合成、盐熔法或共沉淀法。当二氧化硅铬催化剂组合物中包含促进剂组分时,该促进剂组分也可通过本领域已知的任何方法施加到载体组分上,所述方法包括例如:初始湿浸渍、化学气相沉积、水热合成、盐熔法或共沉淀法。催化剂组分以及任选的促进剂组分可以在任何时间施加到载体组分上,包括但不限于煅烧步骤之前或之后。如果使用促进剂组分,则可以在施加到载体组分上之前或施加期间将所有或一部分的促进剂组分与所有或一部分的催化剂组分进行混合。
将催化剂组分以及任选的促进剂组分负载到载体组分上的一种方法是“初始潮湿法”。初始潮湿法是将催化剂组分或催化剂组分的前体(以及任选的促进剂组分、或促进剂组分的前体)的溶液逐渐负载到载体组分上直到载体组分被该溶液饱和并开始在其表面出现潮湿。这种首先出现的潮湿被称为“初始潮湿”。
当载体组分是整体料时,该整体料包括多孔二氧化硅,是任意连续制造的整体型件,例如多孔硅氧化物、二氧化硅泡沫体或二氧化硅蜂窝体结构。整体料可进一步被制造成硅氧化物“蜂窝体”直通道挤出物或者具有能够以最小压降得到高空速的纵向通道或路径的其他整体料。例如,整体料可进一步负载在“整体型下部结构”上,例如由堇青石或莫来石构成的耐火氧化物“蜂窝体”直通道挤出物或整体料,或者具有能够以最小压降得到高空速的纵向通道或路径的其它结构。本领域已知,在需要的时候,反应区可以包含两个或更多个互相叠置的整体料。
而且,催化剂组分可以通过本领域技术人员已知的方法以一个或多个外涂层(wash coat)的形式沉积在整体型载体组分上。此外,通过将载体组分以一个或多个外涂层的形式沉积在整体型下部结构上,然后用催化剂组分以及任选的促进剂组分浸渍所述载体组分外涂层,以实现催化剂组分与整体型载体组分的组合。
整体型载体可以包含稳定化的氧化锆(PSZ)泡沫体(用Mg,Ca或Y稳定化),或以下物质的泡沫体:α-氧化铝、堇青石、陶瓷、氧化钛、富铝红柱石、锆稳定化的α-氧化铝、或者它们的混合物。整体型载体还可以由金属和金属合金制造,例如使用铝、钢、菲萨合金(fecralloy)、赫斯特合金(hastalloy)和本领域技术人员已知的其它合金。另外,其他的耐火泡沫体和非泡沫整体料可以用作令人满意的载体。可以对促进剂金属前体和任意基础金属前体(包含或不含陶瓷氧化物载体形成组分)进行挤出,以制备三维形式或结构,例如蜂窝体、泡沫体、或者其它合适的弯曲路径或直路径结构。
本发明的脱氢反应器可以是任何本领域已知的合适的反应器,包括但不限于间歇反应器、搅拌釜式反应器、连续搅拌釜式反应器(CSTR)、管式反应器、管壳式热交换器反应器、多程反应器、具有微通道的反应器、短接触时间反应器、催化固定床反应器、以及具有上述特征的组合的反应器。脱氢反应器可包括单个吸热脱氢区或多个吸热脱氢区。并且,每个反应区可任选地包括一个或多个亚区,每个亚区可以在操作温度、二氧化硅铬催化剂组成或催化剂组分浓度上存在不同。另外,所述二氧化硅铬催化剂组合物可以任意合适的设置形式设置在各自的反应区内,包括但不限于固定床、流化床和喷射床。所有这些结构都是本领域熟知的。
合适的丙烷吸热脱氢操作条件是本领域普通技术人员所熟知的,可用于吸热脱氢反应器的操作。例如,可以单一物流或以独立成分物流的形式向吸热脱氢反应器供应脱氢进料组合物。例如,丙烷进料物流、二氧化碳和稀释剂可以独立物流的形式分别输送;所有或一部分的丙烷进料物流和稀释剂可在输送到反应器之前进行混合;所有或一部分的丙烷进料物流和二氧化碳可以在输送到反应器之前进行混合;所有或一部分的二氧化硅和稀释剂可以是输送到反应器之前进行混合;或者所有或一部分的丙烷进料物流、二氧化碳和稀释剂可以在输送到反应器之前进行混合。脱氢进料组合物通常以总“气时空速”(“GHSV”)至少500,至少1,000,或至少5,000hr-1;并且不超过100,000,不超过50,000,或不超过20,000hr-1进行输送。反应压力通常为:至少0.1,至少0.5,或至少1大气压;并且不超过20,不超过10,或不超过5大气压。反应温度通常为:至少300,至少450,至少600,至少620℃;并且不超过900℃,不超过700,或不超过660℃。脱氢进料组合物和二氧化硅铬催化剂组合物之间的接触时间通常为:至少0.03,至少0.05,或至少0.1秒;并且不超过10,不超过8,不超过5,或不超过1秒。向反应器供应的丙烷与二氧化碳的摩尔比为:至少0.1,至少0.2,或至少0.5;并且不超过10,不超过5,或不超过2。
本领域技术人员将理解,本发明丙烷吸热脱氢反应的产率可能受到以下因素的影响而变化,例如脱氢反应器的设计、脱氢反应器的组成、反应组分的比例、停留时间、以及二氧化碳-铬组合物随时间对物流催化效率的变化。然而,“新鲜丙烯百分产率”(即操作10分钟后测定的丙烯百分产率)通常为:至少25,或至少30%;并且不超过60,或不超过50%,其中丙烯百分产率是产生的丙烯的摩尔数除以输送到反应器的丙烷摩尔数再乘以100%。
实验实施例
现在将在实施例中详细描述本发明的一些实施方式。实施例中采用表1所示的多孔二氧化硅材料。
表1:实施例中用作载体的多孔二氧化硅
a)压汞法(Hg)孔体积
测试方法
孔隙率的测定
在实验区用作载体组分的多孔二氧化硅的孔径、孔体积和表面积由供应商提供(见表1)。通常,关于孔隙率的信息根据Brunauer等,J.Am.Chem Soc.60,309(1938)所示的方法通过氮吸附来分析确定。
实施例1 通过负载在二氧化硅载体上基于铬的催化剂进行催化由丙烷制备丙烯
负载硝酸铬前体的二氧化硅的制备
用Cr(NO3)3水溶液将多孔二氧化硅浸渍到初始潮湿中,然后在80℃干燥8小时,在120℃干燥8小时。
单阶段煅烧过程
在静态马弗炉中,将干燥的负载硝酸铬前体的二氧化硅在空气中650℃煅烧2小时。
分析经煅烧的负载铬基催化剂的二氧化硅中氧化铬的量
通过ASTM方法测定经煅烧的二氧化硅铬催化剂组合物中包含的氧化铬的量,该方法用酸浸出铬并通过ICP测定含量。根据浸渍步骤中加入的Cr-硝酸盐溶液的量计算经煅烧的二氧化硅铬催化剂组合物中的Cr2O3负载,并记录为[(Cr2O3重量)/(催化剂重量)]×100)。
两阶段煅烧过程
用Cr(NO3)3水溶液第一次浸渍之后,将负载硝酸铬前体的二氧化硅在500℃进行煅烧。制备一定量的第二等分试样的Cr(NO3)3水溶液。计算该溶液中包含的Cr(NO3)3的量,使得以经煅烧的二氧化硅铬催化剂组合物的重量计,最终经煅烧的负载铬基催化剂的二氧化硅中的铬含量为10重量%。然后将第二等分试样的Cr(NO3)3水溶液加入经煅烧的二氧化硅铬催化剂中间体组合物中并浸渍该中间体组合物。然后将浸渍的中间体组合物在80℃干燥8小时,再在120℃干燥8小时,然后在650℃煅烧2小时,以形成最终的经煅烧的二氧化硅铬催化剂组合物。经煅烧的二氧化硅铬催化剂组合物是粉末。
从丙烷制备丙烯
在内径10毫米的烧结石英管中装入2.1克经煅烧的二氧化硅铬催化剂组合物粉末,在氮气流中加热至630℃。然后将气体含量调节至:10体积%丙烷,50体积% CO2,40体积%氮气,气流速率设定在225毫升/分钟。开始操作10分钟后记录“新鲜产率”。表2列出了实施例1-1至1-5的催化剂特征、由其构成的二氧化硅载体及“新鲜产率”。
表2:实施例1的载体、催化剂及丙烷转化为丙烯的结果。
a)“新鲜产率”是操作10分钟后记录的产率
实施例C:在二氧化硅铬催化剂组合物的催化下,由丙烷制备丙烯的对比例采用实施例1所述相同的方法制备实施例C。即,用于制备实施例1-1至1-5的二氧化硅铬催化剂组合物的方法和用于制备实施例C-1至C-5的方法是相同的。而且,用于在实施例1-1至1-5中由丙烷制备丙烯的的方法和实施例C-1至C-5中的方法也是相同的。表3列出了实施例C-1至C-5的二氧化硅铬催化剂组分的特征、由其构成的载体组分的特征及“新鲜产率”。
表3:对比例的载体、催化剂及丙烷转化为丙烯的结果。
a)“新鲜产率”是操作10分钟后记录的产率
b)压汞法(Hg)孔体积
Claims (6)
1.一种将丙烷转化为丙烯的方法,所述方法包括以下步骤:
(A)使丙烷进料物流和二氧化碳与二氧化硅铬催化剂组合物相接触;
所述丙烷进料物流包含丙烷;和
所述二氧化硅铬催化剂组合物包含:
a)载体组分,其包含具有以下性质的多孔二氧化硅:
i)多个孔的平均孔径至少20埃且小于100埃;和
ii)表面积至少400平方米/克且不超过1200平方米/克;和
b)催化组分,基于多孔二氧化硅的重量以铬金属当量计,包含含量至少为2重量%且不超过15重量%的氧化铬;和
(B)在二氧化碳和二氧化硅铬催化剂组合物的存在下,将丙烷转化成丙烯。
2.如权利要求1所述的方法,其特征在于,所述平均孔径至少为25埃且不超过70埃。
3.如权利要求1所述的方法,其特征在于,所述表面积至少为450平方米/克且不超过800平方米/克。
4.如权利要求1所述的方法,其特征在于,所述二氧化硅铬催化剂组合物还包含促进剂组分,所述促进剂组分包含催化促进剂,所述催化促进剂选自氧化钒、氧化银、氧化铈、氧化钼、氧化锌、氧化锆以及它们的组合。
5.如权利要求4所述的方法,其特征在于,基于载体组分的重量,以金属当量计,所述催化促进剂的含量至少为0.1重量%且不超过5重量%。
6.如权利要求1所述的方法,其特征在于,所述将丙烷转化为丙烯是吸热的。
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CN107537461A (zh) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | 低碳烷烃脱氢的催化剂及其应用 |
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- 2009-01-09 CN CNA2009100029600A patent/CN101481290A/zh active Pending
- 2009-01-09 KR KR1020090001897A patent/KR20090077720A/ko not_active Application Discontinuation
- 2009-01-12 US US12/319,765 patent/US20090182186A1/en not_active Abandoned
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108025999A (zh) * | 2015-08-28 | 2018-05-11 | 加的夫大学学院咨询有限公司 | 包含烯基的化合物的制造方法 |
CN107537509A (zh) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | 低碳烷烃脱氢的催化剂及其用途 |
CN107537461A (zh) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | 低碳烷烃脱氢的催化剂及其应用 |
CN107537461B (zh) * | 2016-06-29 | 2020-08-07 | 中国石油化工股份有限公司 | 低碳烷烃脱氢的催化剂及其应用 |
CN107537509B (zh) * | 2016-06-29 | 2020-10-30 | 中国石油化工股份有限公司 | 低碳烷烃脱氢的催化剂及其用途 |
CN112495422A (zh) * | 2020-12-03 | 2021-03-16 | 昆明理工大学 | 一种原位焙烧制备硅基铬催化剂的方法及其产品和应用 |
CN112495422B (zh) * | 2020-12-03 | 2022-02-22 | 昆明理工大学 | 一种原位焙烧制备硅基铬催化剂的方法及其产品和应用 |
Also Published As
Publication number | Publication date |
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MX2009000282A (es) | 2009-08-19 |
JP2009167171A (ja) | 2009-07-30 |
EP2080747A1 (en) | 2009-07-22 |
US20090182186A1 (en) | 2009-07-16 |
SG154386A1 (en) | 2009-08-28 |
BRPI0900504A2 (pt) | 2012-05-08 |
KR20090077720A (ko) | 2009-07-15 |
TW200932716A (en) | 2009-08-01 |
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