CN110773143A - 具有最佳孔隙率结构和酸度的氧化铝 - Google Patents
具有最佳孔隙率结构和酸度的氧化铝 Download PDFInfo
- Publication number
- CN110773143A CN110773143A CN201910674713.9A CN201910674713A CN110773143A CN 110773143 A CN110773143 A CN 110773143A CN 201910674713 A CN201910674713 A CN 201910674713A CN 110773143 A CN110773143 A CN 110773143A
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- China
- Prior art keywords
- alumina
- weight
- equal
- alcohol
- dehydration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000011148 porous material Substances 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001336 alkenes Chemical class 0.000 claims abstract description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 37
- 230000018044 dehydration Effects 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000012071 phase Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 12
- 150000003333 secondary alcohols Chemical class 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- -1 aluminium oxyhydroxide Chemical compound 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 150000001298 alcohols Chemical class 0.000 description 14
- 239000011324 bead Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 10
- 229910052753 mercury Inorganic materials 0.000 description 10
- 238000006317 isomerization reaction Methods 0.000 description 8
- 239000012736 aqueous medium Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003361 porogen Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 229910001679 gibbsite Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002459 porosimetry Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000000326 densiometry Methods 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- ALRXDIKPRCRYAU-UHFFFAOYSA-N 2-methylpropan-2-ol Chemical compound CC(C)(C)O.CC(C)(C)O ALRXDIKPRCRYAU-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01F7/00—Compounds of aluminium
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Abstract
本发明涉及一种氧化铝,其具有的孔隙率结构使得直径在70‑2000Å之间的孔隙的体积在0.15‑0.50ml/g之间,并且包含至少一种碱金属(M),使得以M2O表示的碱金属重量含量为相对于氧化铝的总重量的400‑1500ppm。本发明还涉及将包含至少一种醇的原料转化为烯烃流出物的方法,所述方法包括在具有最佳孔隙结构和酸度的根据本发明的氧化铝存在下使所述醇脱水的步骤。
Description
发明领域
本发明涉及通过具有最佳孔隙率结构(structure de porosité)和酸度的氧化铝催化醇脱水生成烯烃的领域。它更具体地涉及具有降低碱金属含量和具有特定孔隙率结构的氧化铝及其作为催化剂,特别地用于醇,特别地仲醇和叔醇的脱水反应的催化剂,或作为吸附剂的用途。
发明背景和现有技术
氧化铝用作许多化学反应的催化剂,特别是需要酸性操作条件的反应的催化剂。例如,醇的脱水反应就是这种情况。在这样的反应中,氧化铝越活泼,转化率越大。因此,存在对具有高酸性特征的氧化铝的需要。
氧化铝,特别是酸性氧化铝,也经常用作为吸收剂。
然而,过酸性的氧化铝可能证明是有害的,因为可能发生副反应,导致所希望反应的低产率。在醇的脱水反应中,可发生缩合和脱氢反应。这些寄生副反应导致产率下降,并且可通过降低尤其氧化铝的寿命而在氧化铝的稳定性方面起到有害作用。例如,可以形成焦炭,阻塞吸附剂的孔隙率并导致短寿命。
已经进行了大量研究以制备氧化铝,该氧化铝被优化用于作为催化剂,特别地醇的脱水反应的催化剂或作为吸附剂的应用目的。
专利FR2780392描述了一种活性氧化铝,其具有为500至8000ppm重量的以M2O表示的碱金属含量,和包含至少5重量%的η相氧化铝的结晶结构。该氧化铝用于催化醇的脱水反应和烯烃的异构化反应,其中它在高碱金属含量范围(大于2200ppm重量)内具有令人满意的性能,所述性能在低碱金属含量范围内(小于1500ppm重量)被更多限制。
专利US9145342描述了一种通过在气相中使叔丁醇脱水来制备异丁烯的方法,通过使用包含为0.1%-0.6%重量(即按重量计在1000-6000ppm之间)的Na含量(以Na2O表示)和小于或等于0.4%重量以SiO2表示的Si含量的铝催化剂进行,该铝催化剂的孔隙率结构使得总孔体积为0.1至0.5ml/g,半径大于70Å的孔隙的体积大于总孔体积的60%。更特别地,当叔丁醇的脱水在含二氧化硅的铝催化剂(至少0.06重量%的SiO2)存在下进行时,异丁烯以令人满意的产率生产,所述铝催化剂包含至少1300ppm重量的Na2O并具有相当于总孔体积(其本身约为0.2ml/g)的74%和78%的为至少70Å的半径的孔体积。
在吸附领域,专利EP1372808描述了通过吸附在氧化铝附聚物上来除去存在于液体或气体有机流出物中的含氧有机分子如醇和有机酸的方法,所述氧化铝附聚物可包含掺杂化合物,如碱金属,其以M2O表示的重量含量小于5000ppm,并且具有孔隙率结构,使得直径大于70Å的孔隙的体积大于或等于0.15毫升/克。该吸附剂通过在环境温度下吸附它们来捕获在待处理料流中存在的痕量的醇和有机酸。
本发明的目的是提供一种氧化铝,它可用作醇,特别地仲醇和叔醇的脱水反应的催化剂。特别到,本发明提供了一种氧化铝,它允许在醇的脱水中获得良好的性能,甚至比现有技术中已知的氧化铝更好的性能。
发明内容
本发明涉及一种氧化铝,其具有孔隙率结构,使得直径在70-2000Å之间的孔隙的体积在0.15-0.50ml/g之间,并且包含至少一种碱金属(M),使得以M2O表示的碱金属重量含量为相对于氧化铝的总重量的400-1500ppm。
令人惊奇的是,申请人已经发现,根据本发明的氧化铝具有降低的碱金属含量和特定的多孔结构,特别地对于直径在70-2000Å的孔隙为0.15-0.50ml/g的孔的特定体积,允许获得良好的醇的脱水性能,其优于在现有技术中已知的氧化铝的脱水性能。申请人已经证明,这种氧化铝允许获得非常好的醇转化为烯烃的转化率,更好的选择性和改进的稳定性,特别是在寿命方面,同时限制寄生副反应。
因此,本发明还涉及将包含至少一种醇的原料转化为烯烃流出物的方法,所述方法包括所述醇的脱水步骤,其中根据本发明的氧化铝用作催化剂。有利地,根据本发明的氧化铝可以用作任何类型醇的脱水反应的催化剂,优选包含3至9个碳原子。根据本发明的氧化铝显示特别适合于仲醇和叔醇的脱水,非常优选包含3至6个碳原子,以产生相应的烯烃。
具体实施方式
本发明涉及一种氧化铝,其具有孔隙率结构,使得其直径在70-2000Å之间的孔隙的体积在0.15-0.50ml/g之间,并且包含至少一种碱金属(M),使得以M2O表示的碱金属的重量含量为相对于氧化铝总重量的400-1500ppm。
根据本发明的氧化铝具有最佳孔隙率结构。后者使得其直径为70至2000埃(表示为V70Å-V2000Å)的孔隙的体积有利地大于或等于0.15ml/g,优选大于或等于0.20ml/g,并小于或等于0.50ml/g,优选小于或等于0.40ml/g。
其直径在70-2000Å之间的孔隙的体积(表示为V70Å-V2000Å,V2000Å表示由直径大于或等于2000Å的孔隙产生的体积,V70Å表示由直径大于或等于70Å的孔隙形成的体积)对应于在V70Å和V2000Å之间的差值。它代表由直径在70Å-2000Å之间的所有孔隙产生的体积。体积V70Å和V2000Å对氧化铝样品通过水银孔隙度测定法根据标准ASTM D4284-83在最大压力4000巴下,使用484达因/厘米的表面张力和为140°的无定形氧化铝载体的接触角进行测量。
根据本发明的氧化铝包含至少一种碱金属,其含量有利地降低。相对于氧化铝的总重量,根据本发明的氧化铝的碱金属的重量含量(以M2O表示)特别地在400-1500ppm重量之间,优选在400-950ppm重量之间。
根据本发明的氧化铝的所述碱金属选自钠,钾,锂和它们的混合物。优选的碱金属是钠。碱金属通常为氧化物形式。
因此,根据本发明的氧化铝具有降低的酸度和孔隙率结构,其特别地对于醇的脱水反应为最佳的。根据本发明的氧化铝还有利地具有高异构化能力。特别地,根据本发明的氧化铝在300℃下具有使1-丁烯链异构化的能力,相对于热力学平衡,有利地严格地大于60%。此外,相对于热力学平衡,在400℃下,通过根据本发明的氧化铝使1-丁烯链异构化的能力优选大于80%。
优选地,根据本发明的氧化铝另外具有大于或等于0.50ml/g的总孔体积(VPT)。
根据本发明,总孔体积VPT通过根据下式的计算进行确定:
其中(Dg)是颗粒密度,(Da)是绝对密度,分别通过水银比重计法和氦比重法进行测定。
有利地,氧化铝具有其直径大于或等于70Å的孔的体积(表示为V70Å),其优选大于或等于0.35毫升/克,优选大于或等于0.45毫升/克,优选大于或等于0.50ml/g,更优选大于或等于0.52ml/g。直径大于或等于70Å的孔隙的体积(表示为V70Å)有利地小于或等于0.8ml/g,优选小于或等于0.70ml/g。
有利地,根据本发明的氧化铝具有为至少65m2/g,优选至少150m2/g,更优选至少200m2/g的BET比表面积。同时,根据本发明的氧化铝有利地具有至多350m2/g,优选至多325m2/g的BET比表面积。
该比表面积是通过BET法测量的面积,即根据标准ASTM D 3663-78通过氮吸附测定的比表面积,该标准是由在期刊"The Journal of the American Chemical Society",6Q, 309 (1938)中描述的Brunauer-Emmett-Teller方法建立。
有利地,根据本发明的氧化铝优选地包含至多500ppm重量的二氧化硅(以SiO2表示),优选至多100ppm重量的二氧化硅,相对于所述氧化铝的总重量,并且更优选为没有二氧化硅。优选地,相对于所述氧化铝的总重量,根据本发明的氧化铝以优选的方式包含至多800ppm重量的硫,优选至多500ppm重量的硫。优选地,根据本发明的氧化铝不含与前面定义的元素不同(特别地不同于上面定义的碱金属)的活性相或另外的掺杂剂。
根据本发明的氧化铝的晶体结构有利地包含χ-氧化铝(chi-氧化铝)和无定形氧化铝。根据本发明的氧化铝的晶体结构通过X射线衍射进行确定。
根据本发明的氧化铝优选含有严格小于80重量%的γ-氧化铝,优选严格小于50重量%的γ-氧化铝,并且优选小于35重量%的γ-氧化铝。此外,根据本发明的氧化铝有利地含有严格小于35%重量的η-氧化铝,优选严格小于12%重量的η-氧化铝,优选严格小于8%重量的η-氧化铝,并且更优选地仍然严格地小于5重量%的η-氧化铝。
有利地,根据本发明的氧化铝可以通过氢氧化铝或铝羟基氧化物(例如水铝矿)的快速脱水获得。典型地,根据本发明的氧化铝可以通过在专利FR2527197中描述的制备方法,通过在pH低于9的水性介质中处理活性氧化铝粉末来获得,所述活性氧化铝粉末本身通过根据在专利EP0015196中描述的方法水铝矿在热气流中快速脱水,通过雾化干燥然后进行煅烧的获得。它还可以有利地通过在专利FR2449650中描述的制备方法通过在pH低于9的水性介质中处理具有结晶性差和/或无定形结构的粉末的活性氧化铝粉末获得,其中结晶性差的氧化铝表示这样的氧化铝,其使得X射线分析给出仅具有一条或几条漫射线(对应于低温转变氧化铝的晶相,即基本上对应于χ,ρ,η或γ相)的图像。根据本发明的氧化铝还可以通过混合至少两种氧化铝来获得,例如,根据在专利FR2449650中描述的方法获得的氧化铝和根据在专利FR2527197中描述方法获得的氧化铝的混合物。
氢氧化铝或铝羟基氧化物,特别是水铝矿在热气流中的快速脱水通常在使用热气流的任何适当的器具中进行,在器具中气体的入口温度通常在大约400至1200°之间变化,氢氧化物或羟基氧化物与热气体的接触时间通常在几分之一秒和4-5秒之间。这种方法在专利申请FR1108011中更详细地描述。
通过快速煅烧氢氧化铝或铝羟基氧化物得到的氧化铝产生具有高Na2O含量的氧化铝,约为3500ppm。在pH低于9的水性介质中处理后,Na2O含量显著降低。在pH低于9的水性介质中处理后,Na2O含量通常小于或等于2000ppm重量,通常小于或等于1500ppm重量。有利地,在pH低于9的水性介质中处理后,根据本发明的氧化铝的Na2O含量为400至1500ppm重量,优选400至950ppm重量。
根据本发明的氧化铝可以有利地以所有已知的常规形式,例如以粉末,珠粒,挤出和破碎材料的形式存在。珠粒和挤出物将是优选的。珠粒的尺寸这时有用地为0.5至10mm,优选0.7至8mm,优选0.8至5mm。挤出物可以是圆柱形或多叶形,并且是实心的或空心的;它们的尺寸有用地在0.5-5mm之间,优选在0.7-3mm之间。
在一种实施方案中,制备的氧化铝可以进行粒化,即成形的,优选呈珠粒的形式。随后珠粒优选在80至130℃的温度下熟化。最后将熟化的珠粒在400至1100℃的温度下煅烧。
举例来说,珠粒可以通过旋转技术,通过在造粒机或滚筒中使氧化铝粉末附聚来获得。已知地,这种类型的方法允许获得具有直径和受控的孔分布的珠粒,这些尺寸和这些分布通常在附聚步骤期间产生。孔隙率可以通过不同的方法产生,如选择氧化铝粉末的粒度或使具有不同粒度的多种氧化铝粉末附聚。另一种方法在于在附聚步骤之前或期间,在氧化铝粉末中混合称为致孔化合物的化合物,其通过加热而消失并因此在珠粒中产生孔隙。作为所使用的致孔化合物,可以提及例如木粉,木炭,硫,焦油,塑料或塑料乳液,例如聚氯乙烯,聚乙烯醇,萘等。加入的致孔化合物的量由所需的体积决定。一次或多次热处理这时将完成珠粒的成形。
在另一种实施方案中,制备的氧化铝可以是挤出物的形式,例如通过捏合然后挤出氧化铝凝胶,或氧化铝粉末,或不同起始材料的混合物而获得。
本发明还涉及将包含至少一种醇的原料转化为烯烃流出物的方法,所述方法包括在根据本发明的氧化铝存在下使所述醇脱水的步骤。
有利地,根据本发明的氧化铝使得可以实现醇,特别地仲醇和/或叔醇转化为烯烃的高转化率,特别地大于或等于30%,优选大于或等于50%,优选大于或等于65%,更优选大于或等于70%。
根据本发明,烯烃流出物是指包含超过25重量%的烯烃,优选超过50重量%的烯烃,优选至少60重量%的烯烃,更优选至少75重量%的烯烃,更优选至少90%重量的烯烃的流出物,相对于所述流出物的重量,优选相应的(或目标)烯烃,即具有与在原料中包含的醇相同碳原子数的烯烃。
待处理的原料有利地包含至少一种醇,特别地至少50重量%的醇,优选至少70重量%,优选至少80重量%,更优选至少85重量%,仍然至少90%重量的所述醇,相对于所述原料的重量。原料可包含醇或醇的混合物。包含原料的醇可以由石油产品或化学产品生产,或者可以来自生物质。
根据本发明的氧化铝用作为任何类型醇的脱水催化剂,以产生相应的烯烃,即具有相同碳原子数的烯烃。具有3至9个碳原子,优选4至6个碳原子,特别是4个碳原子的醇是优选的。
根据本发明的氧化铝有利地用作为使仲醇和/或叔醇,特别是叔醇脱水的催化剂。根据本发明的一种实施方案,原料包含选自以下的仲醇:异丙醇,2-丁醇,3-甲基丁-2-醇,戊-2-醇,戊-3-醇和它们的混合物。根据本发明的另一种实施方案,原料包含选自以下的叔醇:2-甲基丙-2-醇(叔丁醇或叔丁基醇,表示为TBA)和/或2-甲基丁-2-酮(叔戊醇或叔戊基醇,表示为TAA)。优选地,根据本发明的氧化铝用于催化2-甲基丙-2-醇(叔丁醇)的脱水,得到异丁烯和/或催化2-甲基丁-2-醇(或叔戊醇)的脱水,得到2-甲基丁-2-烯和/或2-甲基丁-1-烯。
脱水步骤包括反应段,该反应段包括一个或多个包含催化剂的反应器。所述一个或多个反应器可以是非连续反应器之一或连续固定床反应器之一(径向,等温,绝热等)。在优选的方案中,脱水在固定床反应器配置中连续进行,通过使用多个具有相同或不同尺寸的串联反应器和/或多个并联操作的“可切换”反应器。有利地,脱水反应在至少两个单独的反应器中进行,优选在2至6个单独的反应器中进行,特别是在4个单独的反应器中进行,优选在串联反应器中,在反应器出口处获得的流出物可有利地在送到下面的反应器中之前重新加热。
脱水反应在反应段中在本领域技术人员已知的条件下进行,通常在气相,液相或混合相(即气体和液体的混合物)中进行,优选在气相中,在200℃-450℃,优选225℃-410℃的温度下,在0.1-4MPa,优选0.5-2MPa的压力下,并使用在0.5h-1至10h-1之间,优选在2h-1至7h-1之间的时空速度(VVH)进行。
时空速度(VVH)是指在反应器入口处的原料的体积流速(m3/h,在15℃,1大气压下)除以在反应器中包含的催化剂的体积(m3)的比率。
根据本发明的一种优选实施方案,该方法是将包含至少一种仲醇,叔醇或其混合物的原料转化为烯烃流出物的方法,所述方法包括所述醇的脱水步骤,所述步骤包括在根据本发明的氧化铝存在下,在气相、液相或混合相中,优选在气相中,在200℃至450℃的温度下,在0.1-4MPa之间压力下,并使用在0.5h-1至10h-1的时空速度(VVH)进行的反应段。有利地选择反应段入口处的绝对压力,使得原料在反应器入口处为气相。
根据本发明的一种非常特别的实施方案,该方法是将包含至少一种有利地包含4个碳原子的仲醇的原料转化为烯烃流出物的方法,所述方法包括所述醇的脱水步骤,其包括在本发明的氧化铝存在下,优选在气相中,在350℃-450℃,更优选350℃-400℃的温度下,在优选0.5-1.2MPa之间的压力下,并使用为2h-1至7h-1的时空速度(VVH)进行的反应部分。有利地选择在反应段入口处的绝对压力,使得原料在反应器入口为气相。
根据本发明的另一种非常特别的实施方案,该方法是将包含至少一种叔醇,有利地包含4个碳原子的叔醇的原料转化为烯烃流出物的方法,所述方法包括所述醇的脱水步骤,其包括在本发明的氧化铝存在下,优选在气相中,在250℃-410℃,更优选在275℃-380℃的温度下,在0.5-1.7MPa的压力下,并使用2h-1至4h-1的时空速度(VVH)进行的反应段。有利地选择在反应段入口处的绝对压力,使得原料在反应器入口处为气相。
有利地,在本发明中用作催化剂的氧化铝可以进行再生,特别地多次,例如通过在反应期间对沉积在氧化铝上的焦炭进行受控焚烧。因此,根据本发明的转化方法可以有利地在多个平行的“可切换”反应器中连续进行,其中当一个或多个反应器运行时,另一个反应器则进行催化剂的再生。
根据本发明的方法可任选地包括在包含反应段的脱水步骤上游的原料纯化阶段。该任选的纯化步骤,其包括至少一个纯化段,使得可以除去能够影响所述反应段的催化剂的杂质,例如任选含氮或含硫的有机杂质。本领域技术人员已知的任何纯化方法可以在所述一个或多个纯化段中使用。
有利地,根据本发明的方法通常还可以包括一个或多个其它段,如用于在进入反应段之前加热待处理的原料的加热段,用于在反应段出口处分离流出物和回收所得的不同产物的分离部分,或用于回收纯化的烯烃流出物,特别地包含至少90%重量的目标烯烃的纯化段。
根据本发明的氧化铝也可用作为吸附剂。
根据以下实施例将更好理解本发明,这些实施例是以说明而非限制的方式给出的。
测量方法
水银孔隙度测定法
直径大于或等于70埃的孔体积(V70Å)和直径大于或等于2000埃的孔体积(V2000Å)通过水银孔隙度测定法根据标准ASTM D4284-83,在4000巴的最大压力下,使用484达因/厘米的表面张力和140°的对于无定形氧化铝载体的接触角对氧化铝样品进行测量。
开尔文定律根据以下式给出了在压力、水银在所述压力下在其中穿透的最小孔的直径,润湿角和表面张力之间的关系:Ø=(-4γcosθ)/P
其中:
•Ø代表孔隙的直径,
•γ代表水银的表面张力,
•θ代表水银与固体之间的接触角,
•P代表绝对压力。
在实践中,将氧化铝样品置于柱中,在压力P下将水银引入其中。由于水银不润湿氧化铝,其渗透或其不渗透到具有给定直径的样品的孔隙中是P值的函数。为了被填充,最细的孔需要建立比填充更大孔隙的更高的压力P。对于不同的P值,测量渗透到样品中的水银的量允许确定由直径大于该给定的直径值的孔所占的体积。
1-丁烯链的异构化能力的测量
将500mg研磨的根据本发明的氧化铝(颗粒的尺寸在400-500μm之间)引入玻璃反应器中。将该产物在具有3.9升/小时的流速的氦气吹扫下在300℃下原位调理2小时。随后使反应器的温度升高,通过在300℃然后400℃两个平台期。在每个温度平台期,在反应器中进行三次0.2ml丁烯注入,反应器始终保持在3.9升/小时的氦气吹扫下。
通过气相色谱分析出口气体。该分析使得可以测量未转化的1-丁烯的量以及形成的顺式-2-和反式-2-丁烯的量。
通过计算确定理论热力学平衡常数Kth(T),通过真实平衡常数K(T)由测量结果进行确定。
Kth(T)=([顺式-2-丁烯]e+[反式-2-丁烯]e) / ([1-丁烯]e+[顺式-2-丁烯]e+[反式-2-丁烯]e)
K(T)=([顺式-2-丁烯]+[反式-2-丁烯]) / ([1-丁烯]+[顺式-2-丁烯]+[反式-2-丁烯])
其中T是反应器出口处丁烯的温度。其它值表示在反应器出口处浓度或对于所述温度T的平衡浓度([ ]e)。异构化能力或异构化率A(T)由下式给出:
。
实施例
实施例1
氧化铝A至I(参见表1)中的每一种均以下列方式进行制备:
使用热气体流在1000℃下对水铝矿粉末进行快速脱水,以获得含有3200ppm重量Na2O的粉末1。将一部分粉末1在水性介质中处理,以得到粉末2,其Na2O含量为500ppm(重量)。将粉末1和2混合。随后任选地在致孔化合物的存在下,将混合物使用水进行制粒为珠粒形式,以获得珠粒形式的氧化铝,其具有取决于粉末1与粉末2比率的钠含量。
将珠粒熟化然后煅烧。
所制备的氧化铝A至I的特征在表1中给出。此外,所得的氧化铝A至I含有小于500ppm(重量)的二氧化硅。
实施例2
根据上述方法和操作条件,对根据实施例1制备的每种氧化铝A至I测定1-丁烯的异构化能力。
结果在表1中给出。它们对应于在300℃下进行的三次丁烯注入的平均值和在400℃下进行的三次注入的平均值。
表1
根据本发明的氧化铝A至D的异构化能力大于不是根据本发明的氧化铝E至I的异构化能力。
实施例3
在中试规模反应器中在氧化铝A至I存在下测试异丙醇的脱水。
氧化铝A至I中的每一种都以下列方式进行测试:
研磨氧化铝样品以获得粒度在0.8-1mm之间的粉末。在中试反应器中装入0.4g研磨的氧化铝。在反应器中,将研磨的氧化铝在400℃下加热2小时。在回到实验温度(T=225℃)后,对氧化铝样品进行12次连续注入由氮气组成的已穿过保持在30℃的异丙醇浴的料流,该料流的流速为4升/小时。通过气相色谱分析每次注入的进入和离开料流。
在表2中给出的结果对应于在第十二次注射之后进行的测量。
显示的是,反应的主要产物是丙烯,对应于异丙醇脱水反应的产物。色谱分析还表明,缩合副反应产物二异丙醚和脱氢副反应产物丙酮以少量存在。
表2:在氧化铝A至I存在下,在225℃下获得的异丙醇的转化率和丙烯的选择性
ns=不显著。
在根据本发明的氧化铝A至D的存在下,转化率是非常令人满意的并且丙烯的选择性是高的。在醇(如异丙醇)的脱水反应期间获得的根据本发明的氧化铝A至D获得的催化性能比使用非根据本发明的氧化铝E至I获得的催化性能更好。
Claims (16)
1.一种氧化铝,其具有的孔隙率结构使得直径为70-2000Å的孔隙的体积在0.15-0.50ml/g之间,并且包含至少一种碱金属(M),使得以M2O表示的碱金属重量含量为相对于氧化铝的总重量的400-1500ppm。
2.根据权利要求1的氧化铝,其中其直径为70-2000Å的孔隙的体积大于或等于0.15ml/g,优选大于或等于0.20ml/g,并小于或等于0.50ml/g,优选小于或等于0.40ml/g。
3.根据权利要求1或2的氧化铝,其中以M2O表示的碱金属的重量含量为400-950ppm,相对于氧化铝的总重量。
4.根据前述权利要求中任一项的氧化铝,其中总孔体积大于或等于0.50ml/g。
5.根据前述权利要求中任一项的氧化铝,其具有的以V70Å表示的直径大于或等于70Å的孔隙的体积大于或等于0.35ml/g,优选大于或等于0.45ml/g,优选地大于或等于0.50ml/g,更优选大于或等于0.52ml/g。
6.根据前述权利要求中任一项的氧化铝,其具有为至少65m2/g,优选至少150m2/g,更优选至少200m2/g,并且至多350m2/g,优选至多325m2/g的BET比表面积。
7.根据前述权利要求中任一项的氧化铝,其含有至多500ppm重量的二氧化硅,以SiO2表示,优选至多100ppm重量的二氧化硅,相对于所述氧化铝的总重量,更优选不含二氧化硅。
8.根据前述权利要求中任一项的氧化铝,其具有包含χ(chi)氧化铝和无定形氧化铝的结构。
9.根据前述权利要求中任一项的氧化铝,其含有严格小于80重量%的γ-氧化铝,优选严格小于50重量%的γ-氧化铝,并且优选小于35重量%的γ-氧化铝。
10.根据前述权利要求中任一项的氧化铝,其含有严格小于35%重量的η-氧化铝,优选严格小于12%重量的η-氧化铝,优选严格小于8%重量的η-氧化铝和更优选地严格小于5重量%的η-氧化铝。
11.根据前述权利要求中任一项的氧化铝,其通过氢氧化铝或铝羟基氧化物的快速脱水获得。
12.将包含至少一种醇的原料转化为烯烃流出物的方法,所述方法包括在权利要求1-11之一的氧化铝存在下使所述醇脱水的步骤。
13.根据前一项权利要求的方法,其中原料包含至少50重量%,优选至少70重量%,优选至少80重量%,更优选至少85重量%的醇,更优选至少90%重量的所述醇,相对于所述原料的重量。
14.根据权利要求12或13的方法,其中所述醇包含3至9个碳原子,优选4至6个碳原子,更优选4个碳原子。
15.根据权利要求12-14之一的方法,其中所述醇是仲醇和/或叔醇,优选叔醇。
16.根据权利要求12-15中任一项的方法,其中脱水步骤包括反应段,其中脱水反应在气相、液相或混合相中,在200℃-450℃的温度下,在0.1-4MPa的压力下,并且使用0.5h-1-10h-1的时空速度(VVH)进行实施。
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FR3084267A1 (fr) | 2020-01-31 |
DK3599020T3 (da) | 2021-06-28 |
FR3084267B1 (fr) | 2021-10-08 |
JP2020055739A (ja) | 2020-04-09 |
EP3599020A1 (fr) | 2020-01-29 |
CN110773143B (zh) | 2023-08-04 |
US20200030773A1 (en) | 2020-01-30 |
JP7360835B2 (ja) | 2023-10-13 |
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US11110431B2 (en) | 2021-09-07 |
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