CN1902144A - 低级烯烃选择性齐聚复合材料催化剂和高辛烷产物的生产 - Google Patents
低级烯烃选择性齐聚复合材料催化剂和高辛烷产物的生产 Download PDFInfo
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- CN1902144A CN1902144A CNA2004800401177A CN200480040117A CN1902144A CN 1902144 A CN1902144 A CN 1902144A CN A2004800401177 A CNA2004800401177 A CN A2004800401177A CN 200480040117 A CN200480040117 A CN 200480040117A CN 1902144 A CN1902144 A CN 1902144A
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- Prior art keywords
- composite materials
- catalytic
- catalytic composite
- alkene
- distillation
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- Granted
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- 239000002131 composite material Substances 0.000 title claims abstract description 187
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 53
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 title claims description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 281
- 238000004821 distillation Methods 0.000 claims abstract description 102
- 238000000034 method Methods 0.000 claims abstract description 81
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims description 134
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 62
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 60
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 57
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 48
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 40
- 238000005984 hydrogenation reaction Methods 0.000 claims description 39
- 239000000945 filler Substances 0.000 claims description 35
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 31
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000013543 active substance Substances 0.000 claims description 19
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 16
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
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- 238000004231 fluid catalytic cracking Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 206010000269 abscess Diseases 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- -1 octane compound Chemical class 0.000 claims description 7
- WEPNJTDVIIKRIK-UHFFFAOYSA-N 2-methylhept-2-ene Chemical compound CCCCC=C(C)C WEPNJTDVIIKRIK-UHFFFAOYSA-N 0.000 claims description 6
- 241000264877 Hippospongia communis Species 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052697 platinum Inorganic materials 0.000 claims description 5
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims description 4
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- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
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- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
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- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
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- 239000004408 titanium dioxide Substances 0.000 claims description 3
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
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- 238000007254 oxidation reaction Methods 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 230000001020 rhythmical effect Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
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- 150000002431 hydrogen Chemical class 0.000 claims 2
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- 239000011707 mineral Substances 0.000 claims 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910001463 metal phosphate Inorganic materials 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
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- 229910052698 phosphorus Inorganic materials 0.000 claims 1
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- 238000006471 dimerization reaction Methods 0.000 description 27
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
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- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/10—Catalytic processes with metal oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
- B01J19/2485—Monolithic reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/30—Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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Abstract
本发明涉及a)包括载体结构和在载体结构上沉积催化物质的催化复合材料,b)低级烯烃和烯烃混合物的选择性齐聚方法,该方法包括在催化蒸馏设备中和在催化蒸馏条件下低级烯烃与催化复合材料接触,和c)生产高辛烷产物的方法,该方法包括在一个或多个催化蒸馏设备中和在催化蒸馏条件下氢化。
Description
技术领域
本发明涉及由催化蒸馏的低级烯烃和烯烃混合物的齐聚。更具体地,本发明涉及在低级烯烃的选择性齐聚的催化蒸馏塔中作为催化剂和填料介质的催化复合材料。此外,本发明也涉及烯烃或来自选择性齐聚的产物的氢化以生产高辛烷产物。
背景技术
催化蒸馏(CD)在单一蒸馏单元中催化反应和分离结合。此主意在1920年代早期首先实施用于生产酯(Backhaus,1921)和已经应用于基于均相催化剂的许多化学工艺。当Smith使用多相催化剂申请了新催化蒸馏技术的专利时(Smith,1980),直到1980才完全认识到反应和分离结合的优点。
采用蒸馏工艺的常规化学工艺(非催化的)主要由两个单独的单元操作组成。这些包括容纳化学反应的单元和从获得的反应混合物分离不同产物的另一个单元。在这样的状况下,难以循环由化学反应产生的热量,和通常需要冷却以控制反应区中的温度,因此导致工艺中无效率的能量利用。此外,优选化合物的生产率通常由于平衡限制受化学工艺中的转化率和选择性限制。由于质量和热量传递阻力是这样的反应单元中的共同问题,差的催化性能可与较短的催化剂寿命一起出现。
为避免化学平衡限制和完全使用反应热,化学反应单元与分离单元在传统蒸馏塔中的简单结合对于许多催化反应工艺提供成功的方案。此结合首先用于均相反应体系。由于这些体系包括反应和蒸馏两者,对于这些工艺例行名称反应蒸馏(RD)。传统的RD工艺主要是基于均相反应体系;因此,RD也称为均相催化蒸馏。尽管RD工艺通常导致高反应速率和对于某些所需产物的高选择性两者,几个缺点仍然经常发生。这些包括催化剂从反应产物的分离,催化剂的回收,塔结垢和腐蚀。此外,如果关于催化剂组合物的产物纯度是严格必须的,产物必须在反应蒸馏之后彻底处理以保证令人满意的催化剂脱除水平,这样会增加操作成本。
对于在固体催化剂(多相体系)的表面上发生的气体和/或液体反应,反应产物可以容易地从催化剂体系分离。如果多相反应可以在蒸馏单元中维持,可以克服在均相催化蒸馏中遇到的分离难度。然而,必须考虑的另一个因素是保证将足够的催化剂放入塔中而不显著增加压降。直到1980年才由Smith(1980)申请了在蒸馏塔内部使用玻璃纤维容纳袋悬挂催化剂粒料的方法,它称为Texas茶袋。这些袋的使用允许使用多相催化剂而不引起压降的较大增加。与均相催化蒸馏形成对照,多相催化蒸馏优先称为催化蒸馏(CD)。
在CD工艺中,固体催化剂必须采用合适的方式在蒸馏塔内部装填,使在蒸气和液相之间的接触最大化,而使塔液泛最小化。实际上已经报导了负载或包含催化剂的各种方法[Crossland等人,US专利5,431,890;Hearn,US专利5,266,546;Shelden,US专利5,417,938]。应当注意到采用所有这些方法,在设备中封装催化剂,该设备可增加塔中液相和气相的传质阻力。
由于催化蒸馏在单一蒸馏塔中多相反应和分离结合,可以获得相对于常规固定床反应器的如下优点:
i)由于在单一单元中结合两个操作降低资金和生产成本。
ii)由于反应热用于反应物的原位汽化可以最小化能量消耗。
iii)可以通过内部循环提高反应物的转化率。
iv)由于反应产物当它们形成时可从反应部位或催化剂表面连续脱除,正常化学平衡限制不适用,因此能够达到更高的转化率。
v)当形成产物时也可以通过从反应部位或催化剂表面连续脱除而改进所需产物的选择性。
vi)由反应产生的热量可以由液体和蒸汽有效地带走,因此消除或避免催化部位之上或之中热点的形成。冲洗液体或蒸汽具有的冲洗效果在于它从反应区脱除更高分子量齐聚产物,和因此释放出催化部位用于下一次反应。极大地降低催化剂的可能结垢和毒害。
vii)由于催化剂床层由在催化剂部位上恒定施加冲洗的热或沸腾液体和蒸汽围绕,也改进催化剂寿命。这样的冲洗效果脱除可经历进一步反应的产物和副产物,它们可导致催化剂的可能结垢和毒害。
尽管相对于以上提及的常规工艺CD技术具有许多优点,但催化蒸馏不适用于所有的化学反应工艺。为达到来自CD工艺的益处,化学反应体系应当优选满足如下要求:
i)反应应当在液相中进行。
ii)催化剂应当是多相的和热稳定的以及化学和物理稳定的以保持它的结构整体性以维持长的寿命。
iii)反应应当是放热的和在反应受平衡限制的状况下,CD工艺呈现选择性使平衡向右更多的移动,以更有效地达到更高的转化率和更高生产率。
满足这些要求的一种化学反应是低级烯烃(含有2-6个碳原子的烯烃分子)的齐聚。低级烯烃的烷基化和齐聚首先由Huss和Kennedy(1990)和Smith等人(1991)公开。低级烯烃的齐聚是重要的工业反应和呈现生产中间体的途径,该中间体用于生产发动机燃料,增塑剂,药物,染料,树脂,洗涤剂,润滑剂和添加剂(O′Connor和Kojima,1990)。关于丁烯齐聚,较少支化的二聚体产物,辛烯特别适用于增塑剂的制造。如果是高度支化的,混合物可以用作汽油掺合剂。
历史上,缺乏由烃流化催化裂化和蒸汽裂化生产高值产物(高辛烷值产物)作为副产物获得的C4馏分的开发。丁二烯,副产物的组分用于橡胶生产和从副产物萃取,留下剩余的C4馏分称为抽余液I的混合物。在抽余液I中包含的异丁烯用作甲基叔丁基醚(MTBE)生产的来源。在脱除异丁烯之后C4馏分的剩余组分,主要由线性C4烃(丁烯)组成,主要用作汽油掺合剂,尽管是差的掺合剂。在某些情况下,此产物由燃烧而简单地处理。在抽余液II中,正丁烯在70%-80%的平均含量下存在和在一些情况下可以为90%范围中。使用此来源,更小的齐聚物,特别是C8和C12齐聚物由目前的催化齐聚工艺生产。
已经提出了基于均相和多相反应的各种丁烯齐聚工艺(Keim等人,1979;Mathys,1984;Beltrame等人,1994)。这些工艺仅集中于催化剂选择和工艺优化,使得可以获得对所需产物具有高选择性的高齐聚速率,主要是短和较少支化的齐聚物的高选择性。
为增强烯烃齐聚的催化蒸馏的使用首先公开于1991年Smith的US专利No.5,003,124。此工艺采用在玻璃纤维袋内部放置的酸性离子交换树脂。
在烯烃齐聚领域中进行进一步的研究,但在大多数情况下,齐聚催化剂包含在第二结构如布或网袋中,和反应物必须通过此结构以接触催化剂。同样,产物必须通过该结构以从催化剂中脱除掉。在一个这样的例子中,Podrebarac(1992)研究了在CD塔中使用镍交换的沸石催化剂的丁烯二聚,其中将沸石直接放入玻璃纤维袋。在此情况下的沸石催化剂由不需要的长链齐聚物的产生而很快失活,该齐聚物阻断催化剂上的活性部位。由于由玻璃纤维袋引起的传质阻力,系统也显示对辛烷的选择性差。
进行另外的工作,发现直接在蒸馏塔的反应区中放置催化剂,而不需要在第二结构如布或网袋中包含催化剂的替代方法。
Gao等人的US专利6,291,719 B1公开了具有非常特定形状的双官能催化剂结构。这些催化剂结构,它们从树脂催化剂、金属氧化物过酸催化剂或分子筛催化剂形成,显示为适于醚化反应、烷基化反应、氢化反应和适于MTBE的分解反应。US 6,291,719 B1公开了限于两种非常具体形状的催化剂结构,和使用的材料也具有显著低的表面积数值。
Gottlieb等人的US专利No.5,244,929也公开了由强酸或碱离子交换树脂制成的模塑有机催化剂体。
发明内容
一方面,本发明提供一种用于催化蒸馏设备的催化复合材料,该催化复合材料包括:
a)一种载体结构,由无机氧化物制成,空隙分率为0.30-0.95,表面积为40m2/g-500m2/g和抗碎强度为2.4-9.9kg每结构单元,载体结构的形状选自环、中空圆筒体、具有2、3或4个泡孔分隔的交叉或多分隔环或圆筒体、鞍状物、实心环、实心圆筒体、球和蜂窝体;和
b)0.01-10wt%催化活性物质,基于催化复合材料的重量,它沉积在载体结构上。
另一方面,本发明提供用作催化蒸馏设备中氢化催化剂的催化复合材料,该催化复合材料包括:
a)一种载体结构,由无机氧化物制成,空隙分率为0.30-0.95和抗碎强度为2.4-9.9kg每结构单元,载体结构的形状选自环、中空圆筒体、具有2、3或4个泡孔分隔的交叉或多分隔环或圆筒体、鞍状物、实心环、实心圆筒体、球、和蜂窝体;和
b)0.01-10wt%钯、铂或铑,基于催化复合材料的重量,它沉积在载体结构上。
再一方面,本发明提供低级烯烃到C6-C18烯烃的选择性齐聚方法,该方法包括在催化蒸馏条件下低级烯烃与在此所述的催化复合材料接触。
还有再一方面,本发明提供烯烃到烷烃的氢化方法,该方法包括在催化蒸馏条件下烯烃与在此所述的催化复合材料和氢气接触。
还有再一方面,本发明提供制备高辛烷化合物的方法,该方法包括:
a)在催化蒸馏条件下C2-C6烯烃与在此所述的催化复合材料接触,以获得C6-C18烯烃;和
b)在催化蒸馏条件下来自步骤a)的C6-C18烯烃与适于氢化在此所述的催化复合材料和氢气接触以获得C6-C18烷烃。
还有再一方面,本发明提供制备高辛烷化合物的方法,该方法包括:
a)在催化蒸馏条件下异丁烯与在此所述的催化复合材料,以获得三甲基戊烯接触;和
b)在间歇反应条件下或在氢化反应条件下三甲基戊烯与氢化催化剂和氢气接触以获得三甲基戊烷。
还有再一方面,本发明提供C6-C18烯烃的生产方法,该方法包括在催化蒸馏条件下接触C2-C6烯烃的混合物与在此所述的催化复合材料。
还有再一方面,本发明提供从低级烯烃到C6-C18烯烃的选择性齐聚方法,该方法包括在催化蒸馏条件下C2-C6烯烃和C1-C6烷烃的混合物与在此所述的催化复合材料接触。
还有再一方面,本发明提供丁二烯的氢化方法,方法包括在催化蒸馏条件下丁二烯与在此所述的催化复合材料和氢气接触。
还有再一方面,本发明提供C3馏分中甲基乙炔和丙二烯的选择性氢化以提供丙烯的方法,该方法包括在在催化蒸馏条件下C3馏分与适于氢化在此所述的催化复合材料接触。
还有再一方面,本发明提供流化催化裂化(FCC)物流中丙二烯和丙炔的选择性氢化方法,方法包括在催化蒸馏条件下FCC物流与适于氢化在此所述的催化复合材料和氢气接触。
还有再一方面,本发明提供抽余液I或抽余液II物流中丁二烯的选择性氢化以提供丁烯的方法,该方法包括在催化蒸馏条件下抽余液I或抽余液II物流与适于氢化在此所述的催化复合材料和氢气接触。
当考虑包括实施例和其中给出的数据表的下述说明时,将更好地理解本
发明的具体实施方案。
具体实施方式
载体结构的基础材料
催化剂载体材料(载体结构)可以选自,例如无机氧化物。合适无机氧化物的例子包括氧化铝、氧化锆、二氧化硅、二氧化钛及其任何化学和物理组合,如二氧化硅/氧化铝。结构设计的材料如分子筛和沸石与选择的无机氧化物的混合物也是用作催化剂载体的合适组合。在这些物质中,优选是氧化铝,和更优选是γ-氧化铝。包括结构设计材料的无机氧化物以粉状材料购得,它们用作载体结构的基础材料。
载体结构
可以将粉状基础材料成型、模塑或其它方法成形为具体结构(在此称为载体结构)而不危害材料的整体性(如不改变材料的结晶态或元素组成和物理性能)。载体结构优选采用具体的形状或形式,该形状或形式选自各种形状,如环或圆筒体、具有2个泡孔、3个泡孔,或4个泡孔分隔的交叉或多分隔环或圆筒体、鞍状物(如槽鞍或弧鞍填料)、实心环或圆筒体、球、和蜂窝体(单或双)。
载体结构的尺寸可变化,不同的尺寸可用于具有不同尺寸的塔。例如,圆筒形载体结构的直径可以大至5cm和小至6mm。这些圆筒体的长度对直径的优选比例为1∶1,但此比例可以为1∶3-3∶1。
当催化载体选择用于形成载体结构时,除形状或形式以外,催化载体的表面积是重要的和是考虑的因素。具有大表面积的催化剂载体是非常所需的。依赖于工艺,进料和反应,载体结构的BET表面积可以选自40-600m2/g。优选表面积为60-450m2/g和最优选为80-350m2/g。
载体结构应当是牢固或坚固的。载体结构的抗碎强度提供当经受压力和温度变化时它承受磨损的强度和能力的相对量度。载体结构优选的抗碎强度为2.4kg-9.9kg每单元(即每单个结构)或每个催化复合材料单元。在催化活性物质,如金属化合物或酸性盐在它表面上的沉积之后,从载体结构获得催化复合材料。
当这样的结构在反应塔(如催化蒸馏塔)中散堆时,塔空隙体积分率是直接涉及载体结构的特征。载体结构的形状或形式确定塔空隙体积分率,它表示未由载体结构的固体部分占据的塔中空间的分率。载体结构的形状或形式以两种方式影响空隙体积。首先,在载体结构的中空部分中形成或包围的空间(完全或部分包围的体积)。其次,当在反应器塔中散装时,由载体结构的非均匀取向(假定的相对角度)和单个载体结构之间的相互作用产生空间。载体结构的非均匀取向不显著阻碍塔中液体或蒸汽的总体流动,该流动对于实际目的是单向的,但它提供气体或液体流过填装结构的随机分布。这样的流动模式增强气体或液体与载体结构的接触,它使塔的空隙空间中蒸汽到液体的更好转化,且也降低通过蒸馏塔反应区的传质阻力。
空隙分率1.0表示完全空的塔,而0.30和0.95的空隙分率分别表示塔中30和95%的空空间。容纳催化复合材料或催化复合材料加惰性载体结构的组合混合物的塔中的空隙分率可以为0.30-0.95。优选空隙分率为0.40-0.85,和更优选空隙分率为0.55-0.70。例如,形状为6mm长和6mm外径的圆筒体的催化复合材料得到0.50的塔空隙分率。
由结构引起的不规则流动模式、塔中催化剂数量的稀释和产物的同时分级和分离一起对催化蒸馏塔中进行的反应选择性起作用,该催化蒸馏塔装填在此所述的催化复合材料。当在塔中散装时,这些特征可因此看成或定义成催化复合材料的性能或催化复合材料和催化剂载体结构的均相混合物的性能。或者,这些特征可以称为催化复合材料的散装填料特性。
载体结构的表面特征影响可以在这样结构上加载的催化剂数量。通过成形工艺或其它工艺使表面变平滑或非多孔或光滑,对于沉积宽百分比变化的催化剂加载量不是所需的。在平滑或低孔隙率结构上仅发现痕量催化剂(小于.01%)。由于如下事实这是最可能的:容纳催化剂的部位由成形工艺堵塞。某些表面的不均匀性或粗糙度有助于催化剂的加载。一定范围的可能孔度是所需的以允许宽范围的催化剂加载量。在此使用的衍生自氧化铝环的载体结构和催化复合材料的BET吸附研究显示中孔和微孔两者。孔直径为从70埃到小于20埃。吸附研究表明催化剂大多在结构的中孔中发现。
催化复合材料
催化复合材料主要由两种单独的组分,即载体结构和作为催化剂的活性金属或金属离子物质组成。这些物质通过一种方法结合或合成以生产复合材料,而不损失包括两种组分的特征和性能,以构成或形成催化复合材料。
各种催化活性物质可以沉积在上述载体结构上以得到催化复合材料。活性物质的例子包括VI,VII和VIII族的金属和金属离子。这些金属或金属离子可以从相应的金属盐或金属配合物加载。在这些金属和金属离子中,从镍盐加载的镍离子优选作为齐聚的活性物质,它对于低级烯烃的齐聚是特别有效的。更优选,从硫酸镍水溶液或氯化镍和硫酸铵的水溶液加载的镍离子用作活性催化物质。用作齐聚的催化物质的金属也优选处于+1或+2氧化态。由于齐聚是酸催化的,酸和酸性盐可以沉积在载体上并用作催化剂。此外,包括镍离子的齐聚催化剂可以进一步通过曝露于硫酸盐如硫酸铵,磷酸盐如磷酸铵和酸如硫酸、磷酸或甲苯硫酸的溶液而得到进一步增强。这样的溶液在此称为催化剂增强剂。
由于可以使用某些盐,如硫酸铵,催化活性物质不必须是金属的。例如,在氢气存在下硫酸铵是用于异丁烯二聚的合适催化活性物质。
由钯、铂、铑和镍的金属配合物加载的金属有效用于烯烃的氢化,包括辛烯和甲基取代戊烯的氢化,甲基取代戊烯用在此所述的镍催化剂由丁烯的齐聚生产。如果可以还原衍生自盐的金属离子以得到活性的金属物物质,金属盐也可以用作氢化工艺中的催化物质。
载体结构上催化剂物质的数量依赖于溶液中金属盐或金属配合物的浓度,和更小程度依赖于载体结构在溶液中的曝露时间。催化物质的数量可以为0.01-10wt%,例如0.05-10%或0.1-8wt%。
用作齐聚催化剂的催化复合材料可,包含例如数量为0.1-8wt%的镍,相对于复合材料的重量。优选,镍的数量为0.2-6.0wt%和更优选,0.5%-5wt%。
用作氢化催化剂的催化复合材料可,包含例如数量为0.05-8wt%的钯,相对于复合材料的重量。优选,钯的数量可以为,例如0.1-8%,0.2-6%,0.2-5%,0.5-5%或0.3-2wt%。
金属离子在载体结构上的沉积可以由本领域已知的方法进行。这些方法的例子包括湿和干燥浸渍方法,蒸发方法,吸收技术,离子交换技术,溶胶-凝胶技术和气相沉积技术。这样技术的描述在实施例1a和1b中给出。
催化蒸馏填料
由于复合材料的大表面积和当在塔中散装复合材料时获得的空隙空间,当用于催化蒸馏塔时催化复合材料作为催化蒸馏填料应用的材料或介质是有效的。催化复合材料的催化剂组分进行所需的化学反应,同时表面积和空隙体积有效用于反应产物的分级和分离。复合材料可因此用作催化剂以及分级介质。根据反应的类型,催化剂的活性,或所需的分离水平,催化复合材料可以与惰性载体结构(即不包含催化剂和对反应是惰性的载体结构)混合,并用于催化蒸馏塔作为催化蒸馏填料。作为催化蒸馏塔中催化蒸馏填料材料的催化复合材料与载体结构的结合可导致催化蒸馏工艺选择性的增加。选择性的增加是由于:i)蒸馏塔中空隙空间的增加,和ii)对蒸馏塔中转化速率的更好控制。例如,在本发明中从6mm的拉西环制备的复合材料催化剂可以与槽鞍形填料(惰性载体结构)采用1∶1比例结合以形成混合物和用作催化蒸馏填料。塔中的这样散装混合物得到0.55的空隙体积分率,它在环(0.49)和鞍状物(0.62)的空隙体积分率之间。作为惰性填料材料的这样载体结构在反应区中的存在也可导致蒸馏塔中转化速率的更好控制。对于放热催化反应,存在如下可能性:由于反应产生的热量以指数方式增加反应速率,温度不受控地提高。这通常在工业中称为″温度失控″。由于更高的温度导致不希望产物的形成,如聚合物而不是齐聚物如二聚体的形成,温度失控对某些反应,如齐聚反应的选择性是特别有害的。因此在反应区中使用载体结构作为惰性填料材料可能是有益的,这是由于通过在反应区中细分催化复合材料它们可用于控制或降低蒸馏塔中的总体转化速率。惰性载体结构用作催化复合材料的稀释介质和同时提供发生分级的附加表面。这样对于不同的催化活性物质惰性填料材料对催化复合材料的比例可变化。惰性填料材料对催化复合材料的比例可以为,例如10∶1-1∶10。
要用作惰性填料材料的载体结构可以选自适用于催化蒸馏的任何已知填料材料。此填料材料可具有各种形状,如拉西环,鲍尔环,penta环,车轮填料,蜂窝环,弧鞍填料,槽鞍形填料,超槽鞍形填料,Hy-Pak填料,Tellerette填料,Maspac填料,串极微环,和Nutter环。使用的散装填料材料的尺寸依赖于蒸馏塔直径的大小,和通常相似于催化复合材料的尺寸。惰性填料材料可以用于用于载体结构的相似的那些材料制造,诸如氧化铝、氧化锆、二氧化硅、和二氧化钛,但它也可以用较少多孔的材料如碳化硅、金属、陶瓷、和塑料制造。
反应物和产物
在说明书中,表述“低级烯烃”表示含有2-6个碳原子的烯烃分子。主要感兴趣的是含有4个碳原子的那些烯烃(1-丁烯,2-丁烯,和异丁烯)。
本发明的选择性齐聚工艺的产物主要是C2-C6烯烃的二聚体和三聚体。这些产物包括含有6-18个碳原子的烯烃,尽管最感兴趣的产物是C4烯烃的二聚体。这些物质具有通式C8H16,和它们广泛用于石油工业作为汽油添加剂。C4的可能二聚体包括三甲基戊烯、正辛烯、二甲基己烯和甲基庚烯,其中更感兴趣的是二甲基己烯和三甲基戊烯,这是由于更多支化的辛烯具有更高辛烷值。特别地,2,4,4-三甲基戊烯-1和2,4,4-三甲基戊烯-2的氢化可生产辛烷值为100的2,2,4三甲基戊烷。令人惊奇地,与从间歇和流动反应器获得的辛烯产物相比,通过本发明的催化蒸馏工艺生产的1-丁烯的二聚获得的辛烯产物富含二甲基己烯。由于二甲基己烯的辛烷值高于甲基庚烯,在催化蒸馏塔中1-丁烯的二聚以来自1-丁烯的二聚的更高价值辛烷产物的形式提供增加的益处。
工艺设置和优化
本发明的方法称为″选择性的″,这是由于使用复合材料催化剂,或在使用惰性载体结构的混合物中的复合材料催化剂的催化蒸馏工艺,允许由反应物流产生和脱除辛烯的反应是选择性的。在常规齐聚反应中,形成许多产物和必须精制获得的产物混合物以分离所需的产物。混合物的生产也限制反应的总体选择性。然而采用催化蒸馏,可以选择工艺变量以增高主要为单一产物或产物组的生产。也可以选择工艺变量以控制反应和防止中间体产物,该中间体产物在常规反应条件下通常继续反应。
当进行CD工艺时可以改变许多工艺变量,和对于具体的反应或产物可以优化大多数变量。这样的变量包括进料入口的位置、反应区的位置、操作压力和进料速率。
·进料入口的位置
进料入口的位置是重要的,这是由于它确定在反应器CD塔中哪里引入低级烯烃原料和在CD塔中哪里开始反应。对于1-丁烯的二聚,优选在CD中引入1-丁烯的进料口位于塔的催化剂区或反应区以下,与进料口位于催化剂区或反应区以上时相比,以获得更高的选择性和生产率(参见表8中的数据)。
在催化剂区以上或以下引入原料之后的反应沿催化剂区产生不同的温度分布,和此依次影响转化率和选择性。对于异丁烯状况是相同的并示于实施例7。
在塔中也可以改变反应区,并因此改变催化复合材料的位置以优化反应。对于丁烯的选择性二聚,优选保持反应区在塔中相当高的位置,这是由于更低的区段通常具有高液相温度。此高温度可导致更快的反应,它有利于大齐聚物而不是二聚体的形成。
·操作压力的影响
塔中的操作压力也可以变化以优化CD工艺。塔中压力的变化会改变温度,和因此选择压力使得反应区中的温度适于发生化学反应和使得在反应区中保持液相。对于丁烯的二聚,操作压力可以为,例如90-115psi,及更高的压力增加丁烯转化率。然而,由于增加压力超过某些值会损害辛烯选择性,必须采取仔细的措施。
·进料速率的影响
也可以改变反应物的进料速率以优化反应。高进料速率导致更高的生产速率,但它们也可对反应的选择性具有负面影响。在C4的齐聚中,由于反应具有生成更高分子量产物如C12的较大倾向,当进料速率增加时C8产物的选择性降低。在本发明中,将原料在加入反应器之前优选与惰性溶剂混合。惰性溶剂的存在降低塔中反应物的浓度,因此使反应的选择性更高。可以使用的合适溶剂包括C4-C8烷烃、高级烷烃、环烷烃和烷基取代环烷烃。优选,异戊烷用作惰性溶剂。此外,惰性溶剂均匀地耗散由反应产生的热量和它有助于任何高级齐聚物或焦炭前体的萃取和脱除,该焦炭前体可失活催化剂。只要保持传质阻力相当低,它可以通过使用本发明的催化复合材料达到,由蒸馏塔生产的产物的分离提供良好的选择性,甚至在更高进料速率下。
多个催化剂或反应区
催化蒸馏塔也可以在相同的反应区中装配多于一种催化剂或多于一种复合材料催化剂,以同时进行多于一种反应。或者,可以设置塔以含有两个反应区,其中每个区可包含不同的催化剂或不同的催化复合材料,其中塔中每个区经历不同温度分布。用不同的催化剂或不同的催化复合材料填充和在单一塔中不同温度下操作的这些反应区,可因此进行多于一种反应,结果是使塔进行多于一种工艺。例如当需要二聚和氢化如丁烯的二聚和生产的辛烯的氢化时可以使用该工艺。在这样的情况下,一个反应区可包括复合材料催化剂,如在实施例1a中给出的用于齐聚的催化剂,和其它反应区可包括复合材料催化剂与氢化催化剂物质如铂或钯。在一个或多个反应区中的多种催化剂和催化复合材料,可用于不同烯烃如衍生自烃的蒸汽裂化、热和催化裂化的那些不同烯烃的同时或连续二聚。这样的混合物的例子包括来自石脑油的蒸汽裂化的抽余液物流和从流化催化裂化(FCC)工艺获得的轻质气体。抽余液物流通常包括异丁烯,1-丁烯,2-丁烯,丁二烯和丁烷。称为抽余液II的进一步抽余液物流主要包括正丁烯,丁烷和痕量丁二烯。FCC气体包括C3,C4和C5烯烃或烷烃的混合物,在一些情况下,它们也可包括C4或C5二烯烃。
多个催化蒸馏塔也可以结合以进行平行、同时或连续反应工艺。这可用于,例如1-丁烯,2-丁烯和异丁烯的两种或多种的混合物的同时或连续二聚。此工艺可以在2个或多个单独的塔中使用相同或不同的催化剂或催化复合材料在相同或不同的催化剂加载量下进行。与1-丁烯相比,异丁烯反应性更高和在更低的温度下二聚,1-丁烯依次比2-丁烯更具有反应性。第一反应区可位于塔的低温区以二聚异丁烯,和然后可以将主要包含1-丁烯和2-丁烯的塔顶产物送到第二或第三塔,该第二或第三塔包含催化剂或催化复合材料在足够温度的反应区中以进行1-丁烯和2-丁烯的二聚。两个或多个塔的使用提供在蒸馏塔的不同高度或区段放置催化复合材料的灵活性,以提供不同温度的反应区和避免另外的不需要的齐聚反应。多个塔的组合也可用于采用按顺序方式进行不同的反应如异丁烯的二聚和上述的为生产异辛烷(例如2,4,4-三甲基戊烷)的氢化反应。
单一或多个催化蒸馏塔也可以与防护床结合使用。防护床用于在将这些物流引入CD塔之前从反应物流分离不希望的反应物。例如,采用防护床的这样操作用于由丁烯和丁二烯组成的丁烯欲被二聚的进料物流。在这样的情况下,丁二烯需要在将进料流引入蒸馏塔之前脱除,这是由于已知丁二烯可毒害二聚催化剂。由选择性吸附脱除丁二烯,或选择性氢化丁二烯为丁烯的防护床可因此用于在将它引入CD塔之前预处理进料流。
实施例
提供如下实施例以说明本发明而不是对本发明的限制。
实施例1a:从金属盐制备催化复合材料
典型的催化复合材料由硫酸镍到载体结构上的湿浸渍制备,该载体结构衍生自一定长度和直径为6mm的γ-氧化铝环。将13.5g硫酸镍六水合物溶于70ml去离子水。然后将此溶液转移到包含100g载体结构(γ-氧化铝环)的容器(烧杯)。将容器轻微转动约3mins以达到在溶液和环之间的均匀接触。在台架上另外30mins平衡之后,使环在空气中干燥。接着在110℃下干燥12hrs。然后煅烧干燥的材料。将环放入预设定在110℃的加热炉。温度然后在5℃/min的速率下上升到最终温度500℃。煅烧在500℃下进行12hrs,在该时间之后温度逐渐降低到室温。将这样获得的催化复合材料脱除和在小瓶中贮存待用。重复浸渍过程以获得平均镍含量为3wt%的催化复合材料。
实施例1b:从金属配合物制备催化复合材料
Pd催化复合材料由湿浸渍技术制备,其中将0.34g Pd(乙酸)2溶于50mL丙酮和50mL水的混合物。将此溶液加入到在200℃下干燥的16gγ-氧化铝环(表面积为204m2/g)。将包含γ-氧化铝环的溶液放入旋转蒸发器和在减压下蒸发溶液。将包含Pd的γ-氧化铝环在烘箱中在90℃下干燥1天,随后在空气中在350℃下煅烧3小时和在氢气中在350℃下还原3小时。保护包含Pd的催化复合材料免受空气的影响。催化复合材料中Pd的重量是0.7wt%。
实施例2:塔的操作设置和优化
实施例的催化蒸馏工艺在总高度为24英尺,及内径为1英寸和总填料高度为16英尺的CD塔中进行。塔主要由三个区段组成总填料高度的冷凝器构成。上部非反应区段、反应区和具有再沸器的下部非反应区段。非反应区段由作为惰性填料材料的催化剂载体结构填充,如用1/4″槽鞍形填料,或上述任何其它已知和合适的载体结构填充。槽鞍形填料在非反应区中的使用产生0.62的空隙体积分率。反应区由以上实施例1中所述衍生自氧化铝环的催化复合材料组成,它的散装产生0.49的空隙体积分率。或者,总填料高度可由催化复合材料和催化剂载体结构的混合物组成。例如实施例1的衍生自氧化铝环的催化复合材料和槽鞍形填料,它们的1∶1混合物产生0.55的空隙体积分率。
总填料的高度依赖于在复合材料上催化剂和原料的数量,原料确定反应的本质。催化蒸馏塔通常在总回流下操作。将原料,例如1-丁烯或异丁烯与惰性溶剂混合和送入塔。惰性溶剂不参与反应但用于耗散从反应部位由反应产生的热量。溶剂也促进任何高级齐聚物或焦炭前体的萃取/溶解和脱除,该焦炭前体可潜在失活催化剂。根据对于特定操作的反应物、产物和工艺条件,溶剂可包括丁烷、戊烷、己烷、高级烷烃和环烷烃和烷基取代环烷烃。例如,在丁烯的二聚中,发现异戊烷是有效的溶剂。或者,塔中的填料材料可以是连续的,即不分成3个“区”。在这样情况下的填料材料沿整个塔包括本发明的催化复合材料,它包括催化复合材料与惰性填料材料的基本均相混合物。
以下是各种工艺参数对丁烯齐聚的影响的实施例。
实施例3:再沸器负荷对丁烯齐聚的影响
本实施例研究再沸器负荷对用于1-丁烯的二聚和齐聚的CD工艺的影响,在总压力140psig下,通过将再沸器负荷从200W改变到300W,采用1-丁烯进料速率48.17g/h,异戊烷进料速率13.27g/h,和79.45g包含3.0wt%Ni的催化复合材料。将催化复合材料与同体积的1/4in槽鞍形填料混合。结果见表1。
表1:再沸器负荷对1-丁烯齐聚的影响
CD6-V | CD6-IV | CD6-I | |
反应条件: | |||
操作压力,psig反应温度,℃再沸器负荷,W催化复合材料量,g镍浓度,wt%催化剂位置,ft1-丁烯进料速率,g/h异戊烷进料速率,g/h进料位置 | 140 | 140 | 140 |
93-111 | 96-114 | 97-117 | |
200 | 240 | 300 | |
79.45 | 79.45 | 79.45 | |
3.0 | 3.0 | 3.0 | |
12.5-14.5 | 12.5-14.5 | 12.5-14.5 | |
48.17 | 48.17 | 48.17 | |
13.27 | 13.27 | 13.27 | |
以下 | 以下 | 以下 | |
结果: | |||
转化率,wt%选择性,wt%生产率,g/g·h | 85.83 | 89.80 | 95.92 |
85.25 | 86.96 | 87.06 | |
0.52 | 0.54 | 0.58 |
·选择性表示辛烯在总齐聚物中的重量分率。
·生产率表示由单位重量催化复合材料每小时生产的齐聚物重量。
可以看出当再沸器负荷增加时,反应区温度增加几度,对应地转化率从85%以上增加到95%以上。令人惊奇地尽管转化率增加,对辛烯二聚体的选择性也增加。当连续反应如本发明中所述的丁烯齐聚在常规反应器中进行时,当转化率增加时通常二聚体的选择性降低。然而,实施例显示当齐聚在催化蒸馏填料中进行时,该填料含有本发明所述具有良好传质特性的此催化复合材料,辛烯二聚体的选择性不可预料地也随转化率增加。
也通过再沸器负荷从250W增加到380W,采用异丁烯进料速率58.30g/h,异戊烷进料速率63.25g/h,和75g包含1.5wt%Ni与同体积1/4in槽鞍形填料混合的催化复合材料,在总压力60psig下,检验再沸器负荷对异丁烯齐聚的影响。结果见表2。
表2:再沸器负荷对异丁烯齐聚的影响
S1CD3 | S1CD4 | S1CD5 | S1CD6 | |
反应条件: | ||||
反应压力,psig反应温度,℃再沸器负荷,W催化复合材料量,g镍浓度,wt%催化剂位置,ft异丁烯进料速率,g/h异戊烷进料速率,g/h进料位置 | 60 | 60 | 60 | 60 |
64-88 | 62-88 | 60-87 | 57-86 | |
250 | 300 | 350 | 380 | |
75 | 75 | 75 | 75 | |
1.5 | 1.5 | 1.5 | 1.5 | |
10.7-12.7 | 10.7-12.7 | 10.7-12.7 | 10.7-12.7 | |
58.30 | 58.30 | 58.30 | 58.30 | |
63.25 | 63.25 | 63.25 | 63.25 | |
以下 | 以下 | 以下 | 以下 | |
结果: | ||||
转化率,wt%选择性,wt%生产率,g/g·h | 92.14 | 93.45 | 91.64 | 91.35 |
65.14 | 68.82 | 73.94 | 76.20 | |
0.72 | 0.73 | 0.71 | 0.71 |
·选择性表示辛烯在总齐聚物中的重量分率。
·生产率表示由单位重量催化复合材料每小时生产的齐聚物重量。
当再沸器负荷增加时,对辛烯的选择性从65%以上增加到约76%,尽管转化率保持基本相同。此行为显示对于75g催化复合材料进料速率较低,这是由于所有的异丁烯基本上被转化。此实施例显示增加的再沸器负荷导致回流流量的增加和辛烯二聚体的更好选择性。
对于1-丁烯或异丁烯的齐聚,展示当再沸器负荷增加时,对辛烯的选择性增加,它显示催化复合材料对于反应和分离两者是有效的。由于异丁烯的反应性大于1-丁烯,发现在蒸馏塔中导致更低温度的较低系统压力,和在催化填料上更低的Ni加载量更适于异丁烯的齐聚。
实施例4:操作压力对1-丁烯齐聚的影响
本实施例研究操作压力对1-丁烯齐聚的影响,通过改变操作压力从90psig到140psig,采用1-丁烯进料速率48.17g/h,异戊烷进料速率13.27g/h,和142g包含3.0wt%Ni和与1.2倍体积1/4″陶瓷槽鞍形填料混合的催化复合材料。1-丁烯齐聚获得的结果见表3。
表3:操作压力对1-丁烯齐聚的影响
CD-7-I | CD-7-III | CD-7-IV | |
反应条件: | |||
操作压力,psig反应温度,℃再沸器负荷,W催化复合材料量,g镍浓度,wt%催化剂位置,ft1-丁烯的进料速率,g/h异戊烷的进料速率,g/h进料位置 | 90 | 115 | 140 |
83-104 | 94-115 | 106-122 | |
300 | 300 | 300 | |
142 | 142 | 142 | |
3 | 3 | 3 | |
10.5-14.5 | 10.5-14.5 | 10.5-14.5 | |
48.17 | 48.17 | 48.17 | |
13.27 | 13.27 | 13.27 | |
以下 | 以下 | 以下 | |
结果: | |||
转化率,wt%选择性,wt%生产率,g/g·h | 90.91 | 95.32 | 95.61 |
88.38 | 87.91 | 86.66 | |
0.31 | 0.32 | 0.32 |
·选择性表示辛烯在总齐聚物中的重量分率。
·生产率表示由单位重量催化复合材料每小时生产的齐聚物重量。
在增加催化蒸馏塔中的操作压力时,反应区中的温度对应增加。这使1-丁烯的转化率从90%以上增加到约96%。然而,对辛烯的选择性轻微降低。
实施例5:进料速率对1-丁烯的齐聚的影响
本实施例研究进料速率对1-丁烯齐聚的影响,通过首先将1-丁烯进料速率从35.31g/h增加到66.37g/h,采用79.45g包含3.0wt%Ni的催化复合材料在140psig总压力下与等体积1/4in槽鞍形填料混合(表4)。
表4:进料速率对1-丁烯齐聚的影响
CD6-VIII | CD6-V | CD6-VII | |
反应条件: | |||
操作压力,psig反应温度,℃再沸器负荷,W催化复合材料的数量,g镍浓度,wt%催化剂位置,ft1-丁烯的进料速率,g/h异戊烷的进料速率,g/h进料位置 | 140 | 140 | 140 |
99-118 | 97-117 | 91-107 | |
300 | 300 | 300 | |
79.45 | 79.45 | 79.45 | |
3.0 | 3.0 | 3.0 | |
12.5-14.5 | 12.5-14.5 | 12.5-14.5 | |
35.31 | 48.17 | 66.37 | |
9.96 | 13.27 | 17.69 | |
以下 | 以下 | 以下 | |
结果: | |||
转化率,wt%选择性,wt%生产率,g/g·h | 96.71 | 95.92 | 88.03 |
87.27 | 87.06 | 87.51 | |
0.43 | 0.58 | 0.74 |
·选择性表示辛烯在总齐聚物中的重量分率。
·生产率表示由单位重量催化复合材料每小时生产的齐聚物重量。
通过将1-丁烯进料速率从48.17g/h增加到85.63g/h,采用142g包含3.0wt%Ni和1.2倍体积1/4in槽鞍形填料的催化复合材料在140psig下进一步研究其影响(表5)。
表5:进料速率对1-丁烯齐聚的影响
CD7-IV | CD7-V | CD7-VI | |
反应条件: | |||
操作压力,psig反应温度,℃再沸器负荷,W催化复合材料的数量,g镍浓度,wt%催化剂位置,ft1-丁烯的进料速率,g/h异戊烷的进料速率,g/h进料位置 | 140 | 140 | 140 |
106-122 | 101-122 | 96-122 | |
300 | 300 | 300 | |
142 | 142 | 142 | |
3 | 3 | 3 | |
10.5-14.5 | 10.5-14.5 | 10.5-14.5 | |
48.17 | 66.37 | 85.63 | |
13.27 | 17.69 | 23.23 | |
以下 | 以下 | 以下 | |
结果: | |||
转化率,wt%选择性,wt%生产率,g/g·h | 95.61 | 95.40 | 93.39 |
86.66 | 86.53 | 87.76 | |
0.32 | 0.45 | 0.56 |
·选择性表示辛烯在总齐聚物中的重量分率。
·生产率表示由单位重量催化复合材料每小时生产的齐聚物重量。
增加进料速率增加生产率。在较低进料速率下,生产率较低,因此通过改变进料速率使每g催化剂生产率最大化是有利地。将异丁烯进料速率从58.30g/h增加到77.38g/h,采用75g包含1.5wt%Ni和同体积1/4in槽鞍形填料的催化复合材料,在60psig下,对异丁烯齐聚的影响见表6。
表6:进料速率对异丁烯齐聚的影响
S1CD4 | S1CD7 | |
反应条件: | ||
操作压力,psig反应温度,℃再沸器负荷,W催化复合材料的数量,g镍浓度,wt%催化剂位置,ft异丁烯的进料速率,g/h异戊烷的进料速率,g/h进料位置 | 60 | 60 |
62-88 | 48-56 | |
300 | 300 | |
75 | 75 | |
1.5 | 1.5 | |
10.7-12.7 | 10.7-12.7 | |
58.30 | 77.38 | |
63.25 | 40.25 | |
以下 | 以下 | |
结果: | ||
异丁烯转化率,wt%异辛烯选择性,wt%生产率,g/g·h | 93.45 | 90.71 |
68.82 | 77.94 | |
0.73 | 0.94 |
·选择性表示辛烯在总齐聚物中的重量分率。
·生产率表示由单位重量催化复合材料每小时生产的齐聚物重量。
可以看出当增加进料速率时生产率也增加,指示可以通过改变进料速率优化生产率。对于CD工艺中的最大生产率存在催化剂数量和进料速率的最优比例。
实施例6:1-丁烯齐聚的催化剂稳定性
1-丁烯齐聚的催化剂稳定性可以在表7中看出。
表7:1-丁烯齐聚的催化剂稳定性
CD6-I | CD6-III | CD6-VI | CD6-IX | |
反应条件: | ||||
时间间隔,h操作压力,psig反应温度,℃再沸器负荷,W催化复合材料的数量,g镍浓度,wt%催化剂位置,ft1-丁烯的进料速率,g/h异戊烷的进料速率,g/h进料位置 | 0-41 | 48-58 | 84-92 | 114-122 |
140 | 140 | 140 | 140 | |
97-117 | 96-115 | 5-114 | 95-114 | |
300 | 300 | 300 | 300 | |
79.45 | 79.45 | 79.45 | 79.45 | |
3.0 | 3.0 | 3.0 | 3.0 | |
12.5-14.5 | 12.5-14.5 | 12.5-14.5 | 12.5-14.5 | |
48.17 | 48.17 | 48.17 | 48.17 | |
13.27 | 13.27 | 13.27 | 13.27 | |
以下 | 以下 | 以下 | 以下 | |
结果: | ||||
转化率,wt%选择性,wt%生产率,g/g·h | 95.92 | 96.12 | 95.63 | 95.30 |
87.06 | 86.48 | 86.49 | 88.29 | |
0.58 | 0.58 | 0.58 | 0.58 |
·选择性表示辛烯在总齐聚物中的重量分率。
·生产率表示由单位重量催化复合材料每小时生产的齐聚物重量。
在122小时内,在再沸器负荷300W,1-丁烯进料速率48.17g/h,异戊烷进料速率13.27g/h,和79.45g包含3.0wt%Ni和同体积1/4in槽鞍形填料的催化复合材料在140psig下,转化率、选择性和生产率在122h时间内基本相同。这些数据显示催化复合材料在丁烯齐聚的CD工艺中非常稳定。在终止反应之后,从塔脱除催化复合材料。观察到催化复合材料保持完整,表明复合材料的机械强度适用于CD塔。催化复合材料的表面积测量值在齐聚之前和之后分别是183.7m2/g和182m2/g,指示催化复合材料的稳定性和抗失活性。
实施例7:进料位置对1-丁烯和异丁烯的齐聚的影响
尽管所有其它工艺条件如压力、催化复合材料、再沸器负荷和进料速率保持相同,进料入口对蒸馏塔的位置,即进料在催化剂区以上或以下,也可导致生产率和选择性的变化。对于1-丁烯和异丁烯获得的实施例见表8和9。结果显示进料入口位置的改变对生产率和选择性具有影响。
表8:进料位置对1-丁烯齐聚的影响
CD5-I | CD5-II | |
反应条件: | ||
操作压力,psig反应温度,℃再沸器负荷,W催化复合材料的数量,g镍浓度,wt%催化剂位置,ft1-丁烯的进料速率,g/h异戊烷的进料速率,g/h进料位置 | 130 | 130 |
118-125 | 114-119 | |
300 | 300 | |
84.64 | 84.64 | |
3.0 | 3.0 | |
10.5-12.5 | 10.5-12.5 | |
51.60 | 51.60 | |
14.26 | 14.26 | |
以下 | 以上 | |
结果: | ||
转化率,wt%选择性,wt%生产率,g/g·hC8生产率,g/g·h | 94.39 | 86.89 |
70.10 | 65.46 | |
0.58 | 0.53 | |
0.41 | 0.35 |
·选择性表示辛烯在总齐聚物中的重量分率。
·生产率表示由单位重量催化复合材料每小时生产的齐聚物重量。
然而对于异丁烯的齐聚,更有利地在催化区以上进料(表9)。
表8:进料位置对异丁烯齐聚的影响
S1CD4 | S1CD9 | |
反应条件: | ||
反应压力,psig反应温度,℃再沸器负荷,W催化复合材料的数量,g镍浓度,wt%催化剂位置,ft异丁烯的进料速率,g/h异戊烷的进料速率,g/h进料位置 | 60 | 60 |
62-88 | 55-84 | |
300 | 300 | |
75 | 75 | |
1.5 | 1.5 | |
10.7-12.7 | 10.7-12.7 | |
58.30 | 58.30 | |
63.25 | 63.25 | |
以下 | 以上 | |
结果: | ||
转化率,wt%选择性,wt%生产率,g/g·hC8生产率,g/g·h | 93.45 | 91.47 |
68.82 | 74.97 | |
0.73 | 0.71 | |
0.50 | 0.53 |
·选择性表示辛烯在总齐聚物中的重量分率。
·生产率表示由单位重量催化复合材料每小时生产的齐聚物重量。
实施例8:CD和间歇反应器的比较,-1-丁烯和异丁烯的齐聚用于异丁烯二聚的CD反应器的优点可以在表10中看出。
表10:在用于1-丁烯齐聚的不同类型反应器中
催化复合材料性能的比较
间歇反应器 | 流动反应器 | CD反应器 | |
反应条件: | |||
反应温度,℃1-丁烯流量(g/h)或其数量(g)催化剂,g催化复合材料类型镍浓度,wt%催化剂尺寸,mm反应时间或停留时间(min) | 110 | 110 | 101-122 |
40 | 13.37 | 66.37 | |
3.0 | 10 | 79.45 | |
Ni/γ氧化铝 | Ni/γ氧化铝 | Ni/γ氧化铝 | |
3.0 | 3.0 | 3.0 | |
15 | 2.0 | 15 | |
60 | 44.88 | 71.82 | |
结果: | |||
转化率,wt%选择性,wt%生产率,g/g·h | 29.83 | 71.61 | 88.03 |
78.91 | 64.81 | 87.51 | |
3.89 | 1.15 | 0.74 |
·停留时间表示催化复合材料的重量/1-丁烯的质量流量
·选择性表示辛烯在总齐聚物中的重量分率。
·生产率表示由单位重量催化复合材料每小时生产的齐聚物重量。
在相似反应条件如温度和反应时间下,在CD塔中进行的齐聚反应的转化率和选择性比间歇反应器或流动反应器高得多。这显示与间歇或流动反应器系统相比,包含Ni的催化复合材料在CD条件下对辛烯二聚体得到高转化率和选择性。
实施例9:用于低级烯烃齐聚的其它催化活性物质
除在多孔载体如γ氧化铝上作为催化组分的NiSO4以外,其它催化材料如(NH4)Fe(SO4)2、FeSO4和(NH4)2SO4对于异丁烯的二聚和齐聚也是活性的(表11)。
表11:不同金属硫酸盐对异丁烯齐聚的影响
反应条件: | |||||
反应温度,℃异丁烯数量,g催化剂数量,g催化相载体Ni浓度,wt%SO4 2-浓度,wt%反应时间,min | 65 | 65 | 65 | 65 | 65 |
45 | 45 | 45 | 45 | 45 | |
3 | 3 | 3 | 3 | 3 | |
(NH4)Fe(SO4)2 | FeSO4 | (NH4)2SO4 | NiSO4 | NiSO4 | |
γ-Al2O3 | γ-Al2O3 | γ-Al2O3 | γ-Al2O3 | γ-Al2O3 | |
0 | 0 | 0 | 1.5 | 3.0 | |
10.3 | 5.2 | 4.9 | 2.5 | 4.9 | |
75 | 60 | 60 | 60 | 60 | |
结果: | |||||
转化率,wt%选择性,wt% | 3.7 | 50.6 | 33.9 | 14.20 | 53.1 |
61.6 | 17.3 | 46.3 | 38.0 | 25.0 |
·选择性表示辛烯在总齐聚物中的重量分率。
实施例10:Ni盐对1-丁烯齐聚的影响
表12显示在基于γ氧化铝的多孔载体结构上的不同Ni化合物对1-丁烯齐聚的活性。硫酸Ni比氯化Ni活性大。NH4Cl加入到NiCl2可提高NiCl2的活性。新的和使用过的催化剂的表面积不是非常不同,这表明催化复合材料是相当稳定的。表13显示对于1-丁烯齐聚,多孔γ氧化铝比用于负载NiSO4或NiCl2的NaY沸石或BaNaY沸石更稳定,这可以从使用过的催化剂的表面积的降低看出。
表12:在间歇反应器中由在多孔γ氧化铝上负载的
不同催化相制备的催化复合材料性能的比较
催化剂 | 载体 | 镍加载量(wt%) | 反应条件 | 转化率(wt%) | 选择性(wt%) | 表面积m2/g |
NiCl2 | γ-Al2O3 | 5.53 | 100℃600psi2hrs | 12.53 | 93.28 | 新的=183.2使用过的=188.5 |
NiCl2+NH4Cl | γ-Al2O3 | 5.53 | 100℃600psi2hrs | 28.85 | 87.89 | 新的=185.7使用过的=190.1 |
NiSO4 | γ-Al2O3 | 4.04 | 110℃ | 36.71 | 72.15 | 新的=186.5 |
600psi2hrs | 使用过的=187.0 | |||||
NiSO4 | γ-Al2O3 | 4.04 | 60℃600psi2hrs | 19.15 | 77.35 | 新的=186.5使用过的=188.3 |
NiMo | γ-Al2O3 | >10 | 110℃600psi2hrs | 19.85 | 38.11 | 新的=148.1使用过的=144.1 |
·选择性表示辛烯在总齐聚物中的重量分率。
表13:在间歇反应器中使用不同载体制备的催化复合材料性能的比较
催化剂 | 载体 | 镍加载量(wt%) | 反应条件 | 转化率(wt%) | 选择性(wt%) | 表面积m2/g |
NiCl2 | γ-Al2O3 | 5.53 | 110℃600psi2hrs | 12.53 | 93.28 | 新的=183.2使用过的=188.5 |
NiCl2 | NaY | 4.85 | 110℃600psi2hrs | 52.15 | 69.51 | 新的=622.9使用过的=182.4 |
NiCl2 | BaNaY | 0.87 | 110℃600psi2hrs | 39.18 | 81.58 | 新的=581.5使用过的=363.2 |
NiSO4 | γ-Al2O3 | 4.04 | 110℃600psi2hrs | 36.71 | 72.15 | 新的=186.5使用过的=187.0 |
NiSO4 | NaY | 5.20 | 110℃600psi2hrs | 41.82 | 73.26 | 新的=635.8使用过的=211.9 |
·选择性表示辛烯在总齐聚物中的重量分率。
实施例11:在CD塔中由异丁烯齐聚和氢化一步生产异辛烷
此实施例显示在同一蒸馏塔中使用两个单独的催化蒸馏区,能达到从异丁烯一步生产异辛烷的高选择性,上部催化剂区包含二聚/齐聚催化剂和下部催化剂区包含氢化催化复合材料。在二聚区中,将Ni催化复合材料与大约等体积的槽鞍形填料混合。异丁烯可以在二聚区以上任何位置或就在二聚区以下加入。氢气应当在氢化区以下加入。在二聚区中,催化复合材料包含1wt%镍。在氢化区中,催化复合材料包含0.7wt%Pd。表14显示以步反应的结果。当不将氢气加入塔时(参见试验号2-3),齐聚物由84.9wt%辛烯,13.5wt%十二碳烯和1.6wt%十六碳烯组成,和对辛烯的选择性是84.9wt%。辛烯由77.8wt%2,4,4三甲基戊烯-1和22.2wt%2,4,4三甲基戊烯-2组成。当将氢气在包含Pd催化复合材料的反应区以下引入催化蒸馏塔时(试验号2-2),辛烯超过98%氢化成2,2,4-三甲基戊烷(辛烷等级100)。也发生十二碳烯和十六碳烯的一些氢化。氢气的存在不降低异丁烯到辛烯的二聚的生产率和在给定的试验中观察到齐聚的轻微增加。应当控制氢气流量使得氢气进料的数量足以氢化齐聚物。再沸器负荷从350W下降到300W不显著影响辛烯的生产率或2,2,4三甲基戊烷的生产(比较试验号2-5和试验号2-2)。表14中试验号2-5和试验号2-8的比较显示增加异丁烯进料速率增加齐聚活性和也增加2,2,4三甲基戊烷的生产率。
由于塔中的压力控制催化蒸馏塔中的温度,塔中的压力应当使得CD塔中的温度分布适于在CD塔的顶部区段生产齐聚物和在CD塔的底部区段发生氢化。压力对工艺的影响的实施例见表15。可以看出在不增加压力时,齐聚区和氢化区中的温度增加,齐聚活性和2,2,4-三甲基戊烷的生产率增加,但对辛烯的选择性降低。
催化复合材料用于二聚/齐聚和氢化的活性在20天内在运转中是稳定的。
表14:工艺参数对由异丁烯齐聚和氢化生产2,2,4三甲基戊烷的影响
试验号 | 2-3 | 2-5 | 2-2 | 2-8 |
反应条件: | ----- | H2 | H2 | H2 |
在Ni催化复合材料区的温度在Pd催化复合材料区的温度再沸器负荷,WNi催化复合材料的数量,gPd催化复合材料的数量,g从再沸器的Ni催化复合材料的位置,以英尺计的距离从再沸器的Pd催化复合材料的位置,以英尺计的距离异丁烯的进料速率,g/h异戊烷的进料速率,g/hH2进料速率(L/hr@STP) | 75℃ | 75℃ | 75℃ | 75℃ |
121℃ | 121℃ | 121℃ | 121℃ | |
350 | 300 | 350 | 300 | |
81.5 | 81.5 | 81.5 | 81.5 | |
224.6 | 224.6 | 224.6 | 224.6 | |
11.5-13.5 | 11.5-13.5 | 11.5-13.5 | 11.5-13.5 | |
0.3-4.3 | 0.3-4.3 | 0.3-4.3 | 0.3-4.3 | |
49.95 | 49.95 | 49.95 | 62.85 | |
69.74 | 69.74 | 69.74 | 44.64 | |
----- | 8.77 | 8.77 | 13.21 | |
结果: |
齐聚活性,g/g·h对辛烯的选择性,wt%2,2,4三甲基戊烷的生产率,g/g·h | 0.51 | 0.51 | 0.54 | 0.85 |
84.9 | 86.37 | 87.32 | 84.37 | |
----- | 0.16 | 0.17 | 0.25 |
·选择性表示辛烯在总齐聚物中的重量分率。
·齐聚活性表示由单位重量催化剂每小时生产的辛烯,十二碳烯和十六碳烯的重量。
表15:压力对由异丁烯齐聚和氢化生产异辛烷的影响
试验号 | 4-17 | 4-15 | 4-18 |
反应条件: | H2 | H2 | H2 |
在Ni催化复合材料区的温度在Pd催化复合材料区的温度压力,psigNi催化复合材料的数量,gPd催化复合材料的数量,g从再沸器的Ni催化复合材料的位置,以英尺计的距离从再沸器的Pd催化复合材料的位置,以英尺计的距离异丁烯的进料速率,g/h异戊烷的进料速率,g/hH2进料速率(L/hr@STP) | 76℃ | 78℃ | 85℃ |
124℃ | 125℃ | 130℃ | |
100 | 125 | 150 | |
81.5 | 81.5 | 81.5 | |
224.6 | 224.6 | 224.6 | |
11.5-13.5 | 11.5-13.5 | 11.5-13.5 | |
0.3-4.3 | 0.3-4.3 | 0.3-4.3 | |
68.37 | 68.37 | 79.83 | |
78.46 | 78.46 | 66.83 | |
8.77 | 8.77 | 15.01 | |
结果: | |||
齐聚活性,g/g·h对辛烯的选择性,wt%2,2,4三甲基戊烷的生产率,g/g·h | 0.79 | 0.83 | 0.92 |
85.24 | 83.07 | 58.73 | |
0.20 | 0.20 | 0.28 |
·选择性表示辛烯在总齐聚物中的重量分率。
·齐聚活性表示由单位重量催化剂每小时生产的辛烯,十二碳烯和十六碳烯的重量。
实施例12:丁二烯的氢化
将3.7g乙酰丙酮Pd溶于100g二氯甲烷,和将获得的溶液加入50g直径和长度为8mm在200℃下干燥的α-氧化铝环(表面积0.22m2/g)。将包含α-氧化铝环的溶液在室温下振动24小时。将包含Pd的α-氧化铝环从溶液取出和在烘箱中在90℃下干燥24小时。在350℃下进行煅烧3小时,随后采用氢气在350℃下还原3小时。保护催化复合材料免受空气的影响。Pd在催化复合材料中的重量是0.31wt%。
使用以上催化复合材料在间歇高压釜中在丁二烯和异丁烯的混合物中进行丁二烯的氢化。对于在异丁烯中包含5.4wt%丁二烯的混合物,丁二烯到1-丁烯和2-丁烯和正丁烷的选择性氢化在50-90℃的温度和160-300psig的压力下在间歇高压釜中达到。催化复合材料重量是1.63-2.45g及Pd加载量是0.31wt%。在约2-4小时内,获得丁二烯的100%氢化。
说明书中引用的所有出版物、专利和专利申请在此引入作为参考,如同每篇单个出版物、专利或专利申请具体地和单个地引入作为参考。引用的任何出版物是在申请日之前公开的内容,且不应当解释为由于在先发明,本发明不给予这样出版物占先公开的权利。
尽管为了理解清楚的目的,通过说明和实施例一定程度上详细地描述了上述本发明,按照本发明的教导,显然本领域普通技术人员容易地对其进行某些改变和改进,而不背离所附权利要求的精神或范围。
必须注意到用于此说明书和所附权利要求的单数形式″a″,″an″,和″the″包括复数形式,除非上下文清楚地另外指示。除非另外定义在此使用的所有技术科学术语具有与本发明所属领域技术人员通常理解的意义。
Claims (55)
1.一种用于催化蒸馏设备的催化复合材料,该催化复合材料包括:
a)一种载体结构,由无机氧化物制成,空隙分率范围为0.30-0.95,表面积为40m2/g-500m2/g和抗碎强度为2.4-9.9kg每结构单元的载体结构,载体结构的形状选自环、中空圆筒体、具有2、3或4个泡孔分隔的交叉或多分隔环或圆筒体、鞍状物、实心环、实心圆筒体、球、和蜂窝体;和
b)基于催化复合材料的重量,0.01-10wt%催化活性物质,它沉积在载体结构上。
2.根据权利要求1的催化复合材料,其中空隙分率为0.30-0.95,表面积为50m2/g-500m2/g和抗碎强度为2.4-9.9kg每结构单元。
3.根据权利要求1或2的催化复合材料,其中无机氧化物选自氧化铝、二氧化硅、二氧化钛、氧化锆及其混合物。
4.根据权利要求1或2的催化复合材料,其中无机氧化物是γ-氧化铝。
5.根据权利要求的催化复合材料,其中无机氧化物是α-氧化铝。
6.根据权利要求1-5任意一项的催化复合材料,其中载体结构的形状为拉西环。
7.根据权利要求1-6任意一项的催化复合材料,其中催化活性物质包括IV、V、VI、VII族或VIII族金属。
8.根据权利要求1-6任意一项的催化复合材料,其中催化活性物质包括VI族、VII族或VIII族金属。
9.根据权利要求8的催化复合材料,其中催化活性物质包括镍。
10.根据权利要求7-9任意一项的催化复合材料,其中金属的形式为金属盐或金属配合物。
11.根据权利要求10的催化复合材料,其中金属盐为离子状态。
12.根据权利要求10的催化复合材料,其中金属盐是金属硫酸盐、金属磷酸盐、金属草酸盐或金属乙酸盐。
13.根据权利要求1-6任意一项的催化复合材料,其中催化活性物质是硫酸镍。
14.根据权利要求1-6任意一项的催化复合材料,其中催化活性物质是氯化镍。
15.根据权利要求1-14任意一项的催化复合材料,其中催化活性物质在与硫酸铵或磷酸铵的混合物中。
16.根据权利要求1-6任意一项的催化复合材料,其中催化活性物质是有机酸、无机酸或从其衍生的盐。
17.根据权利要求16的催化复合材料,其中有机酸是甲磺酸、甲苯磺酸或三氟乙酸。
18.根据权利要求16的催化复合材料,其中无机酸是硫酸或磷酸。
19.根据权利要求16的催化复合材料,其中盐是硫酸铵或磷酸铵。
20.根据权利要求1-6任意一项的催化复合材料,其中催化活性物质包括VIII族金属和配体,其中配体包括一个或多个选自碳、氢、氧、氮和磷的原子。
21.根据权利要求20的催化复合材料,其中VIII族金属处于零氧化态。
22.根据权利要求1-6任意一项的催化复合材料,其中催化活性物质是钯、铂或铑。
23.权利要求1-22任意一项的催化复合材料作为催化蒸馏塔中填料材料的用途。
24.权利要求1-22任意一项的催化复合材料作为催化蒸馏塔中催化剂的用途。
25.一种低级烯烃到C6-C18烯烃的选择性齐聚方法,该方法包括在催化蒸馏条件下低级烯烃与权利要求1-22任意一项的催化复合材料接触。
26.根据权利要求25的方法,其中低级烯烃选自1-丁烯、2-丁烯和异丁烯,C6-C12烯烃选自三甲基戊烯、正辛烯、二甲基己烯和甲基庚烯。
27.根据权利要求25或26的方法,其中催化复合材料与惰性蒸馏填料混合。
28.根据权利要求27的方法,其中催化复合材料与惰性蒸馏填料的比例为10∶1-1∶10。
29.根据权利要求27的方法,其中催化复合材料和惰性蒸馏填料用于催化蒸馏塔的单独区域。
30.根据权利要求25的方法,其中低级烯烃是C4烯烃和C6-C18烯烃主要是C8烯烃。
31.根据权利要求30的方法,其中C8烯烃是三甲基戊烯。
32.一种烯烃到烷烃的氢化方法,该方法包括在催化蒸馏条件下烯烃与权利要求19-21任意一项的催化复合材料和氢气接触。
33.根据权利要求32的方法,其中烯烃选自三甲基戊烯、正辛烯、二甲基己烯和甲基庚烯。
34.根据权利要求31的方法,其中催化复合材料与惰性蒸馏填料混合。
35.根据权利要求34的方法,其中催化复合材料对惰性蒸馏填料的比例为10∶1-1∶10。
36.根据权利要求34的方法,其中催化复合材料和惰性蒸馏填料用于催化蒸馏塔的单独区域。
37.根据权利要求32-35任意一项的方法,其中烯烃是三甲基戊烯,烷烃是三甲基戊烷。
38.一种制备高辛烷化合物的方法,该方法包括:
a)在催化蒸馏条件下C2-C6烯烃与权利要求1-22任意一项的催化复合材料接触,以获得C6-C18烯烃;和
b)在催化蒸馏条件下来自步骤a)的C6-C18烯烃与权利要求19-21任意一项的催化复合材料和氢气接触,以获得C6-C18烷烃。
39.根据权利要求38的方法,其中工艺步骤a)和b)在单一催化蒸馏塔中进行。
40.根据权利要求38的方法,其中工艺步骤a)和b)在单独的催化蒸馏塔中进行。
41.根据权利要求38-39任意一项的方法,其中C2-C6烯烃是C4烯烃,C6-C18烯烃是C8烯烃。
42.根据权利要求41的方法,其中C8烯烃是三甲基戊烯。
43.一种制备高辛烷化合物的方法,该方法包括:
a)在催化蒸馏条件下异丁烯与权利要求1-22任意一项的催化复合材料接触,以获得三甲基戊烯;和
b)在间歇反应条件下或在氢化反应条件下三甲基戊烯与氢化催化剂和氢气接触以获得三甲基戊烷。
44.一种C6-C18烯烃的生产方法,该方法包括在催化蒸馏条件下接触C2-C6烯烃的混合物与权利要求1-22任意一项的催化复合材料。
45.根据权利要求44的方法,其中混合物中的每种C2-C6烯烃在单一催化蒸馏塔中的不同反应区中齐聚。
46.根据权利要求44的方法,其中每种C2-C6烯烃在两个或多个连接的催化蒸馏塔中的不同反应区中齐聚。
47.根据权利要求44-46任意一项的方法,其中C2-C6烯烃的混合物包括一种或多种C4烯烃。
48.一种低级烯烃到C6-C18烯烃的选择性齐聚方法,该方法包括在催化蒸馏条件下C2-C6烯烃和C1-C6烷烃的混合物与权利要求1-22任意一项的催化复合材料接触。
49.一种用作催化蒸馏设备中氢化催化剂的催化复合材料,该催化复合材料包括:
a)一种载体结构,由无机氧化物制成,空隙分率为0.30-0.95和抗碎强度为2.4-9.9kg每结构单元的载体结构,载体结构的形状选自环、中空圆筒体、具有2,3,或4个泡孔分隔的交叉或多分隔环或圆筒体、鞍状物、实心环、实心圆筒体、球、和蜂窝体;和
b)基于催化复合材料的重量,0.01-10wt%钯、铂或铑,它沉积在载体结构上。
50.根据权利要求49的催化复合材料,其中无机氧化物是α-氧化铝。
51.根据权利要求50的催化复合材料,其中α-氧化铝的表面积为0.1-1.0m2/g。
52.一种丁二烯的氢化方法,该方法包括在催化蒸馏条件下丁二烯与权利要求49-51任意一项的催化复合材料和氢气接触。
53.一种C3馏分中甲基乙炔和丙二烯的选择性氢化以提供丙烯的方法,该方法包括在在催化蒸馏条件下C3馏分与权利要求49-51任意一项的催化复合材料和氢气接触。
54.一种流化催化裂化(FCC)物流中丙二烯和丙炔的选择性氢化方法,该方法包括在催化蒸馏条件下FCC物流与权利要求49-51任意一项的催化复合材料和氢气接触。
55.一种抽余液I或抽余液II物流中丁二烯的选择性氢化以提供丁烯的方法,该方法包括在催化蒸馏条件下抽余液I或抽余液II物流与权利要求49-51任意一项的催化复合材料和氢气接触。
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- 2004-12-10 EP EP04802288A patent/EP1697282A1/en not_active Withdrawn
- 2004-12-10 JP JP2006543337A patent/JP2007513753A/ja active Pending
- 2004-12-10 CA CA2548429A patent/CA2548429C/en not_active Expired - Fee Related
- 2004-12-10 RU RU2006124865/04A patent/RU2006124865A/ru not_active Application Discontinuation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111217661A (zh) * | 2018-11-27 | 2020-06-02 | 中国石油化工股份有限公司 | 一种异丁烯叠合-加氢制备异辛烷的方法 |
CN111217662A (zh) * | 2018-11-27 | 2020-06-02 | 中国石油化工股份有限公司 | 一种异丁烯叠合-加氢制备异辛烷的方法 |
CN111217661B (zh) * | 2018-11-27 | 2022-11-18 | 中国石油化工股份有限公司 | 一种异丁烯叠合-加氢制备异辛烷的方法 |
CN111217662B (zh) * | 2018-11-27 | 2022-11-18 | 中国石油化工股份有限公司 | 一种异丁烯叠合-加氢制备异辛烷的方法 |
CN110776952A (zh) * | 2019-10-31 | 2020-02-11 | 中国石油天然气集团有限公司 | 可生产异辛烷的叠合油加氢装置及方法 |
Also Published As
Publication number | Publication date |
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US20070123743A1 (en) | 2007-05-31 |
CA2548429A1 (en) | 2005-06-23 |
ZA200605251B (en) | 2007-11-28 |
BRPI0416855A (pt) | 2007-02-27 |
RU2006124865A (ru) | 2008-01-20 |
CN1902144B (zh) | 2010-06-09 |
JP2007513753A (ja) | 2007-05-31 |
WO2005056503A1 (en) | 2005-06-23 |
US7718569B2 (en) | 2010-05-18 |
CA2548429C (en) | 2012-12-04 |
EP1697282A1 (en) | 2006-09-06 |
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