CN1056596C - 大颗粒脱氢催化剂及脱氢方法 - Google Patents
大颗粒脱氢催化剂及脱氢方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002245 particle Substances 0.000 title claims abstract description 28
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 12
- 239000011591 potassium Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 37
- 239000006187 pill Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
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- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
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- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
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- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 239000008188 pellet Substances 0.000 abstract 2
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- 238000001354 calcination Methods 0.000 description 13
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- 238000006243 chemical reaction Methods 0.000 description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- -1 alum Chemical compound 0.000 description 2
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- 238000001125 extrusion Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- KAWSDELCDUMWJE-UHFFFAOYSA-N CCCC.CC1(CC(C(=O)O)=CC=C1)C(=O)O Chemical compound CCCC.CC1(CC(C(=O)O)=CC=C1)C(=O)O KAWSDELCDUMWJE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- 229910002588 FeOOH Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
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- 229910001882 dioxygen Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- B01J35/40—
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/515—Specific contaminant removal
- Y10S502/517—Sulfur or sulfur compound removal
Abstract
本发明提出一种改善氧化铁催化剂的催化活性的方法,但不会产生选择性相应的损失,该催化剂由含大颗粒氧化铁的含铁化合物制成。还提出一种制备氧化铁脱氢催化剂方法,其中,包括大颗粒氧化铁在内的含铁化合物是与含钾化合物及水相混后再制成丸粒,丸粒再经煅烧。该催化剂尤适用由乙苯制备苯乙烯。
Description
本发明涉及用于烃类脱氢的催化剂及脱氢方法。
氧化铁基混合物常用作烃类脱氢的催化剂。氧化铁的常见形态有多种,包括所谓的红色、黄色及黑色形态。黄色氧化铁通常为geothite,它是水合氧化铁(FeOOH)的常见形态。黑色氧化铁为磁铁矿(Fe3O4)。红色氧化铁是无水形态的氧化铁,称赤铁矿,系由黄色氧化铁经煅烧脱水制得,如此制得的红色氧化铁颗粒一般为针状或棒状。针状无水氧化铁也可经直接沉淀获得。美国专利第3364277号及3703593号介绍了氧化铁在制备烃类脱氢催化剂中的用途。
美国专利第4006090号介绍了赤铁矿颗粒,其长度为0.05~5μm,物理构成为松散的微晶束,化学组成是含2%~4wt%化合硫及0.003%~0.02wt%锂的α-氧化铁,据言,这种颗粒易于转化为具良好磁性的γ-氧化铁,而且可用作颜料和催化剂。
美国专利第4139497号介绍了脱氢催化剂丸粒,含铁、钾及铬的氧化物。
美国专利第4144197号介绍的脱氢催化剂含铁、钾、矾、钼和/或钨、铈,以及任选的钴和/或铬的氧化物。
氧化铁基混合物所具有的颗粒结构及其它物理性质影响所制催化剂的物理或化学性能,这些性能表现在催化剂的性能中的选择性及活性有所增加或降低。广义而言,催化剂的选择性是它从两种或多种可能产物中产生一种特定产物的能力;催化剂的活性为其将反应物转化为产物的总能力。一般,催化剂选择性的改善总是与催化剂活性的恶化直接相关,反之也然。
催化剂选择性与活性间这种关系所产生的困难是,由于化学组分数可能增加,故而欲提高催化剂的活性,一般均需进行多次、深入的分离。另一方面,欲改善催化剂的选择性,就常要面对较低的产率或较多数量的循环物流。故此,若能改变某个参数而消除催化剂选择性与活性间的这种矛盾,本技术当可获益良多。
本发明提出一种改善氧化铁催化剂活性的方法,但不会导致选择性相应的损失。
首先,本发明脱氢催化剂由大颗粒氧化铁组成,其平均最大尺寸为2~10μm,多为2~6μm。
其次,本发明提出制备氧化铁脱氢催化剂的方法,其中,包括大颗粒氧化铁在内的含铁化合物是与含钾化合物和水相混后再制成丸粒,丸粒再经煅烧。
再次,本发明提出一种由乙苯制备苯乙烯的方法。在该法中,乙苯与蒸汽及含大颗粒氧化铁的脱氢催化剂相接触。
此外,本发明氧化铁脱氢催化剂的活性系通过增大其中所用氧化铁颗粒的尺寸而得以改善。
本发明涉及如下通式I化合物的制备方法:式中的R1和R2各自表示一个烷基、链烯基、苯基或是氢原子,该化合物系由如下通式∏化合物经非氧化性脱氢制得:其中R1和R2含义同式I。该法中,含通式∏化合物及过热蒸汽的混合物在加热下与含氧化铁和氧化钾的催化剂相接触,后者系将含铁化合物与含钾化合物相混后制成丸粒再经煅烧制得,其间,使用含大颗粒氧化铁的含铁化合物,用量至少为约10%~100%(重量,以Fe2O3为基)。所述氧化铁可为针状、云母片状或其它结构的氧化铁颗粒。本发明还涉及改进后的催化剂。
式II中R1可为带一个或多个甲基取代基的苯基基团。作为优选,R1为未取代苯基,R2是一个氢原子或甲基。有结果表明,乙苯作为原料化合物效果甚佳。式II的链烷烃优选每分子含2~20个碳原子,但对诸如正-丁烷及2-甲基丁烷而言,每分子含3~8个碳原子更佳。式II的链烷烃优选每分子含4~20个碳原子,更优选为每分子含4~8个碳原子,举例而言包括可生成1,3-丁二烯的1-丁烷,以及均可生成异戊二烯的2-甲基丁烷和3-甲基-1-丁烷。采用本方法,可将正-丁烷经1-丁烯转化为1,3-丁二烯,也可将2-甲基丁烷转化为异戊二烯。
本发明方法宜用于异戊二烯、α-甲基苯乙烯及苯乙烯制备。本发明催化剂尤适用于将乙苯转化为苯乙烯,其优点在于活性高、选择性好。
非氧化性脱氢为无分子氧介入过程,此即本发明方法的脱氢类别。
此处,“选择性”意指由转化为通式I化合物的通式II化合物的量除以已转化的通式II化合物的总量再乘以100。本说明书中,选择性均以通式II化合物的标准转化率计得。例如,用S70表示乙苯摩尔转化率为70%时乙苯转化为苯乙烯的摩尔选择性。催化剂活性与温度成反比,活性越高则获得相同转化率所需温度越低。本说明书中活性均与给定的转化率有关。例如,T70表乙苯摩尔转化率为70%时所对应的温度。
所述脱氢方法适宜的实施条件是:蒸汽对通式II化合物的摩尔比介于2~20,优选值5~13;温度最好是介于400~700℃,优选值550~650℃;压力为常压、高压或负压均可,其中常压或负压为优选。另外,若采用诸如管式或径向流反应器时,则该方法优选液时空速介于0.1~5.0l/l/h间。
催化剂可为诸如粒、片、球、丸、鞍、三叶或四叶等形状。一般,催化剂的组成是:重量5%~20%的氧化钾;重量0~10%的选自一种或多种下列一组助催化剂剂金属的氧化物:Sc,Y,La,稀土,Mo,W,Ca,Mg,V,Cr,Co,Ni,Mn,Cu,Zn,Cd,Al,Sn,Bi,或其混合物;其余为Fe2O3。优选的助催化剂金属包括下列一组,即Ca,Mg,Mo,W,Ce,Cr以及其混合物。如此处所指,“氧化物”的含义不仅包括单一的氧化物(如三氧化二铁),而且也指氧化物的混合物,如尖晶石,铁素体,以及二元和其它种氧化物混合物。在反应条件下,这些氧化物部分地以氧化性化合物形式存在,如碳酸盐和碳酸氢盐。
本发明催化剂可以各种方法制成。但主要的方法是,将含铁化合物与含钾化合物相混,它们初为氧化物或经煅烧后成为氧化物,其后,使混合物形成催化剂大小的颗粒,再升温煅烧,形成稳定的颗粒。含助催化剂金属的化合物为氧化物或经煅烧后分解为氧化物,可与含铁化合物及含钾化合物相混。含铁、钾及助剂金属的化合物也称氧化物供体且可包括诸如氧化物、碳酸盐、碳酸氢盐及硝酸盐等。
催化剂的制备程序是本领域所周知的。一种方法是在研磨机-混合器中将诸如铁、钾的氧化物/氢氧化物/碳酸盐等混合在一起,再加入少量的水,再将所得的膏体挤出形成小丸粒,后者于约100~300℃下干燥,并在500℃以上(优选值为700~1000℃)煅烧。另一种方法是,将这些成份溶解在一起或配成浆体,然后用喷射干燥方法制成粉体,将该粉体煅烧成氧化物,其后再加入足量的水配成膏状物,然后挤压成丸粒,再经干燥和煅烧。还有一种方法是,将这些材料以可沉淀形态沉淀下来,如铁的氢氧化物,部分除去所生成沉淀物的水份后,再加入诸如钾及助催化剂金属(如钙和镁)的可溶解盐,随后挤压成形,煅烧挤出物。磨成粒及挤压粒均用于生成丸粒。优选方法是首先将粉状物料干混在一起,再将这些物料与水研磨并相混合,以生成可挤压物质。研混后,混合物再经挤压、干燥及煅烧。
一般,上述组分形成催化剂颗粒后,颗粒再经升温煅烧后形成稳定的颗粒。煅烧温度在500℃以上,优选值为约700~1000℃。煅烧气氛一般为中性(氮气),也可为氧化性,如氧气或优选空气。
用于制备本发明催化剂的氧化铁供体的特征是其颗粒尺寸较大。作为优选,应合成尺寸较大的氧化铁,以使其尺寸为常规所用的四倍。熟悉本领域的人知道,颗粒尺寸系与颗粒尺寸统计分布有关。
含所述氧化铁颗粒的尺寸较之具同样化学结构及配比但氧化物颗粒尺寸仅为其1/4的催化剂组合物而言,其活性高出约6℃。而且,活性增高并不伴随选择性的降低。故此,可通过增大所用氧化铁颗粒的尺寸增进氧化铁催化剂混合物的性能。
用于本发明的大颗粒氧化铁最容易由氧化铁配制而成,该氧化铁由碎屑铁经黄色α-FeOOH的中间体脱水后制得。如美国专利第1368748号所述,该法在本领域称Penniman法。熟悉本领域的人不难理解,本方法中氧化铁颗粒的大小系通过沉淀时间调整。
本发明催化剂也可含任何其它铁的化合物,包括黄色、黑色及红色氧化铁。作为优选,包括选自下列一组的一种氧化铁供体:geothite,磁铁矿、赤铁矿,lipidocrocite,及其混合物。
按照本发明混配的催化剂一般较未按本发明制备的催化剂具有较大的平均孔直径及较大的孔体积。。通常,平均孔直径(MPD)介于220~300纳米(nm),孔体积为0.160~0.221cm3/g,优选催化剂混合物的MPDs为250~295nm,更优选为大于260nm。本说明书中平均孔直径均按ASTM标准D-4284-92的方法测得,孔体积均按ASTM标准D-4284-92的方法测得。
以下通过下列非限定性实例进一步介绍本发明。实施例催化剂制备
在下述每一例中,Penniman红色氧化铁(得自Bayer AG,德国)用于催化剂配方。这种氧化铁为由碎屑金属经黄色α-FeOOH的中间体脱水后制得的α-FeOOH。氧化铁颗粒尺寸按美国专利第1368748号所述方法控制。
附表列出了催化剂的物理性质及其所用氧化铁颗粒的大致尺寸。对每一情形,均在研磨机-混合器中将氧化铁和助催化剂的盐及水相混。所得的混合物经挤出成形后再于170℃下干燥1h,并在825℃下煅烧1h。每kg.固体用水量105mL.助催化剂的盐包括K2CO3,CeCO3,CaCO3,(NH4)10W12O41·5H2O,加入时以保持下列量值为度(以毫mol助催化剂/mol Fe2O3表示):516K,66Ce,22W,36Ca。催化剂试验
在连续操作反应器中,等温条件下,以上述方法所制催化剂由乙苯制备苯乙烯。催化剂试验条件如下:催化剂100cm3;反应器温度600℃;LHSV为0.65,每小时每升催化剂乙苯的升数;蒸汽对乙苯摩尔比10∶1;反应器压力75kPa。
催化剂试验结果以T70和S70给出,其中,T70表乙苯加料的70%转化为产物时相应催化剂所需的温度,S70表示转化为产物苯乙烯的摩尔选择性。催化剂试验结果一并示于表中。
如表中所示,本实施例结果表明,由颗粒尺寸较大氧化铁所制催化剂的活性得以改善,但反应选择性并无明显降低。结果也表明,按照本发明所制较大催化剂的MPD较大,活性增高,但选择性并不损失。催化剂 大约颗 表观密度 表面积 孔体积 平均孔 活性T70 选择性组合物 粒尺寸 (g/cm3) (m2/g) (cm3/g) 直径 (℃)S70 (%)
(μm) ()I 0.5 1.33 2.31 0.1853 2267 602.4 95.0II 0.5 1.38 1.63 0.1665 2395 603.7 95.2III 0.5 1.38 1.39 0.1606 2815 606.3 95.3IV 1 1.25 2.39 0.2213 2761 602.7 94.2V 1 1.37 1.81 0.1796 2574 600.6 94.3VI 1 1.36 1.33 0.1660 2867 603.2 95.1VII 2 1.35 2.13 0.1780 2618 599.4 95.0VIII 2 1.35 1.86 0.1818 2929 598.2 95.0IX 2 1.39 1.67 0.1685 2955 597.4 95.3
由本例知,平均尺寸2μm氧化铁颗粒所制催化剂的活性较之小颗粒催化剂为高。
Claims (11)
1脱氢催化剂,含氧化铁及钾,其特征在于所述氧化铁颗粒的平均最大尺寸为2~10μm。
2权利要求1的催化剂,其中氧化铁颗粒的平均最大尺寸为2~6μm。
3权利要求1或2的催化剂,其中尚含一种或多种助催化剂。
4权利要求3的催化剂,其中所述助催化剂选自Ce,Sc,Y,La,稀土,Mo,W,Ca,Mg,V,Cr,Co,Ni,Mn,Cu,Zn,Cd,Al,Sn,Bi,或是上列的混合物。
5权利要求1,2或4的催化剂,其中所述氧化铁含赤铁矿。
6权利要求3的催化剂,其中所述氧化铁含赤铁矿。
7制备脱氢氧化铁催化剂的方法,包括:选定一种含平均最大尺寸为2~10μm颗粒氧化铁的含铁化合物,再将其与含钾化合物及水相混形成混合物,所得混合物制成丸粒并煅烧该丸粒。
8权利要求7的方法,其中含铁颗粒平均最大尺寸为2~6μm。
9权利要求8的方法,其中尚包括所述氧化铁与一种或多种助催化剂相混的步骤。
10权利要求9的方法,其中所述助催化剂选自Ce,Sc,Y,La,稀土,Mo,W,Ca,Mg,V,Cr,Co,Ni,Mn,Cu,Zn,Cd,Al,Sn,Bi,或是上列的混合物。
11由乙苯经非氧化性脱氢制备苯乙烯的方法,包括在升温下使乙苯及水蒸汽与权利要求1~6中任一脱氢催化剂相接触。
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Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07178340A (ja) * | 1993-11-11 | 1995-07-18 | Idemitsu Petrochem Co Ltd | アルキル芳香族炭化水素の脱水素反応用触媒及びこれを用いたビニル芳香族炭化水素の製造方法 |
DE19535416A1 (de) * | 1995-09-23 | 1997-03-27 | Basf Ag | Verfahren zur Herstellung von Katalysatoren für selektive Dehydrierungen |
KR100358222B1 (ko) * | 1997-09-30 | 2003-05-16 | 한국화학연구원 | 방향족탄화수소의탈수소화촉매및이촉매와이산화탄소를이용한탈수소화방법 |
DE19814080A1 (de) | 1998-03-30 | 1999-10-07 | Basf Ag | Katalysator zur Dehydrierung von Kohlenwasserstoffen, insbesondere zur Dehydrierung von Ethylbenzol zu Styrol, sowie Verfahren zu seiner Herstellung |
US6242379B1 (en) | 1998-04-01 | 2001-06-05 | United Catalysts Inc. | Dehydrogenation catalysts |
US6756339B1 (en) | 1998-04-01 | 2004-06-29 | Sud-Chemie Inc. | Dehydrogenation catalysts |
EP1027928B1 (de) * | 1999-02-10 | 2006-03-01 | Basf Aktiengesellschaft | Katalysator zur Dehydrierung von Ethylbenzol zu Styrol |
TWI267401B (en) * | 2002-01-30 | 2006-12-01 | Shell Int Research | A catalyst, its preparation and its use in a dehydrogenation process |
US7244868B2 (en) | 2002-06-25 | 2007-07-17 | Shell Oil Company | Process for the dehydrogenation of an unsaturated hydrocarbon |
US6936743B2 (en) * | 2002-09-05 | 2005-08-30 | Fina Technology, Inc. | Method for extending catalyst life in processes for preparing vinyl aromatic hydrocarbons |
US7282619B2 (en) | 2003-10-14 | 2007-10-16 | Shell Oil Company | Method of operating a dehydrogenation reactor system |
US7297402B2 (en) * | 2004-04-15 | 2007-11-20 | Shell Oil Company | Shaped particle having an asymmetrical cross sectional geometry |
RU2385313C2 (ru) * | 2004-11-18 | 2010-03-27 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Улучшенный способ получения алкенилароматического соединения при низком отношении пар/углеводород |
TW200624170A (en) * | 2004-11-18 | 2006-07-16 | Shell Int Research | A high activity and high stability iron oxide based dehydrogenation catalyst having a low concentration of titanium and the manufacture and use thereof |
AR052137A1 (es) * | 2004-11-18 | 2007-03-07 | Shell Int Research | Metodos para disenar y operar un sistema de un proceso de deshidrogenacion que utiliza un catalizador de deshidrogenacion |
US20060224029A1 (en) * | 2005-03-29 | 2006-10-05 | Fina Technology, Inc. | Method of extending catalyst life in vinyl aromatic hydrocarbon formation |
WO2007035349A2 (en) * | 2005-09-16 | 2007-03-29 | Shell Internationale Research Maatschappij B.V. | A method of making aromatic products |
RU2314870C1 (ru) * | 2006-09-06 | 2008-01-20 | Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук | Катализатор паровой конверсии моноксида углерода, способ его приготовления и способ его использования |
BRPI0806589A2 (pt) * | 2007-01-18 | 2014-05-13 | Shell Int Research | Catalisador, sua preparação e uso. |
AR064916A1 (es) * | 2007-01-18 | 2009-05-06 | Shell Int Research | Catalizador preparacion y uso |
CN101821000A (zh) * | 2007-08-10 | 2010-09-01 | 瑞恩泰克公司 | 用于一氧化碳氢化的沉淀铁催化剂 |
KR100888143B1 (ko) * | 2007-12-12 | 2009-03-13 | 에스케이에너지 주식회사 | 혼성 망간 페라이트 촉매, 이의 제조방법 및 이를 이용한1,3-부타디엔의 제조방법 |
WO2009126601A1 (en) * | 2008-04-09 | 2009-10-15 | Shell Oil Company | A method of improving a dehydrogenation process |
US9138706B2 (en) * | 2008-04-22 | 2015-09-22 | Fina Technology, Inc. | Method and apparatus for addition of an alkali metal promoter to a dehydrogenation catalyst |
US8648007B2 (en) * | 2008-04-22 | 2014-02-11 | Fina Technology, Inc. | Vaporization and transportation of alkali metal salts |
US20110105316A1 (en) * | 2009-10-31 | 2011-05-05 | Fina Technology, Inc. | Mixed Metal Oxide Ingredients for Bulk Metal Oxide Catalysts |
KR101713328B1 (ko) * | 2010-07-20 | 2017-03-08 | 에스케이이노베이션 주식회사 | 혼성 망간 페라이트가 코팅된 촉매, 이의 제조방법 및 이를 이용한 1,3-부타디엔의 제조방법 |
CN102343269B (zh) * | 2010-08-05 | 2013-07-31 | 中国石油天然气股份有限公司 | 一种以微米级氧化铁和碳酸钾为原料的乙苯脱氢催化剂 |
US20130165723A1 (en) * | 2011-12-22 | 2013-06-27 | Basf Se | Catalyst for the dehydrogenation of hydrocarbons |
CN106000413B (zh) * | 2016-06-15 | 2018-07-27 | 河南大学 | 一种钼掺杂正方针铁矿纳米微粒的制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4006090A (en) * | 1974-06-28 | 1977-02-01 | The Dow Chemical Company | Alpha iron (III) oxide crystals and derivatives |
US4144197A (en) * | 1977-04-14 | 1979-03-13 | Shell Oil Company | Dehydrogenation catalyst |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1368748A (en) * | 1920-01-05 | 1921-02-15 | Nat Ferrite Company | Process of manufacturing iron compounds and product |
US3904552A (en) * | 1973-03-08 | 1975-09-09 | Girdler Chemical | Dehyrogenation catalyst |
US4052338A (en) * | 1975-07-03 | 1977-10-04 | Shell Oil Company | Dehydrogenation catalyst |
US4098723A (en) * | 1977-01-27 | 1978-07-04 | Shell Oil Company | Catalyst for dehydrogenation |
US4139497A (en) * | 1977-04-04 | 1979-02-13 | The Dow Chemical Company | Dehydrogenation catalyst tablet and method for making same |
CA1108114A (en) * | 1977-04-14 | 1981-09-01 | Gregor H. Riesser | Dehydrogenation catalyst |
FR2592375B1 (fr) * | 1985-12-27 | 1988-04-08 | Shell Int Research | Procede de deshydrogenation sans oxydation |
FR2617060A1 (fr) * | 1987-06-29 | 1988-12-30 | Shell Int Research | Catalyseur de deshydrogenation, application a la preparation de styrene et styrene ainsi obtenu |
US4758543A (en) * | 1987-07-01 | 1988-07-19 | The Dow Chemical Company | Dehydrogenation catalyst |
FR2630662A1 (fr) * | 1988-04-29 | 1989-11-03 | Shell Int Research | Catalyseur pour la deshydrogenation de composes organiques, procede pour sa preparation et son utilisation |
US5047382A (en) * | 1988-12-12 | 1991-09-10 | United Technologies Corporation | Method for making iron oxide catalyst |
DE3922106A1 (de) * | 1989-07-05 | 1991-01-17 | Bayer Ag | Synthetisches grobteiliges eisenoxid, verfahren zu seiner herstellung sowie dessen verwendung |
US5023225A (en) * | 1989-07-21 | 1991-06-11 | United Catalysts Inc. | Dehydrogenation catalyst and process for its preparation |
DE3935073A1 (de) * | 1989-10-20 | 1991-04-25 | Sued Chemie Ag | Verfahren zur katalytischen dehydrierung von kohlenwasserstoffen, insbesondere von alkylaromaten |
US5106486A (en) * | 1990-02-09 | 1992-04-21 | Ashland Oil, Inc. | Addition of magnetically active moieties for magnetic beneficiation of particulates in fluid bed hydrocarbon processing |
US5171914A (en) * | 1991-08-30 | 1992-12-15 | Shell Oil Company | Dehydrogenation catalyst and process |
US5214015A (en) * | 1992-04-03 | 1993-05-25 | The United States Of America As Represented By The United States Department Of Energy | Synthesis of iron based hydrocracking catalysts |
US5580839A (en) * | 1994-09-30 | 1996-12-03 | University Of Kentucky Research Foundation | Binary ferrihydrite catalysts |
-
1995
- 1995-12-13 CA CA002207560A patent/CA2207560A1/en not_active Abandoned
- 1995-12-13 AU AU43460/96A patent/AU696088B2/en not_active Ceased
- 1995-12-13 CN CN95196771A patent/CN1056596C/zh not_active Expired - Fee Related
- 1995-12-13 WO PCT/EP1995/005036 patent/WO1996018594A1/en not_active Application Discontinuation
- 1995-12-13 JP JP8518285A patent/JPH10510524A/ja not_active Ceased
- 1995-12-13 DE DE69508276T patent/DE69508276T2/de not_active Revoked
- 1995-12-13 ES ES95942179T patent/ES2129239T3/es not_active Expired - Lifetime
- 1995-12-13 EP EP95942179A patent/EP0797560B1/en not_active Revoked
- 1995-12-13 KR KR1019970703989A patent/KR100361059B1/ko not_active IP Right Cessation
-
1996
- 1996-07-10 US US08/677,759 patent/US5689023A/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4006090A (en) * | 1974-06-28 | 1977-02-01 | The Dow Chemical Company | Alpha iron (III) oxide crystals and derivatives |
US4144197A (en) * | 1977-04-14 | 1979-03-13 | Shell Oil Company | Dehydrogenation catalyst |
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CA2207560A1 (en) | 1996-06-20 |
AU4346096A (en) | 1996-07-03 |
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