CN1317992A - 环氧化催化剂载体、其制备和用途 - Google Patents
环氧化催化剂载体、其制备和用途 Download PDFInfo
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- CN1317992A CN1317992A CN99810903A CN99810903A CN1317992A CN 1317992 A CN1317992 A CN 1317992A CN 99810903 A CN99810903 A CN 99810903A CN 99810903 A CN99810903 A CN 99810903A CN 1317992 A CN1317992 A CN 1317992A
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- Prior art keywords
- carrier
- catalyst
- sodium
- washing
- gram
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- 238000006735 epoxidation reaction Methods 0.000 title claims description 16
- 239000011734 sodium Substances 0.000 claims abstract description 35
- 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 claims abstract description 33
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 10
- 150000001336 alkenes Chemical class 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 150000002739 metals Chemical class 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000007598 dipping method Methods 0.000 claims description 37
- 238000005406 washing Methods 0.000 claims description 30
- 230000000694 effects Effects 0.000 claims description 25
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 238000009835 boiling Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 10
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 239000011147 inorganic material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000007928 solubilization Effects 0.000 abstract 3
- 238000005063 solubilization Methods 0.000 abstract 3
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- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 23
- 241000894007 species Species 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000003513 alkali Substances 0.000 description 12
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 11
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 10
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
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- -1 alkali metal compound silver compound Chemical class 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 239000011575 calcium Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
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- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical group N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
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- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 3
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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 3
- 238000005470 impregnation Methods 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
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- 238000013019 agitation Methods 0.000 description 2
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- 239000007864 aqueous solution Substances 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
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- OZUCXGWYZVDFOU-UHFFFAOYSA-N 2-(diethylamino)ethyl 6-hydroxy-4,7-dimethoxy-1-benzofuran-5-carboxylate;hydrochloride Chemical compound [Cl-].CC[NH+](CC)CCOC(=O)C1=C(O)C(OC)=C2OC=CC2=C1OC OZUCXGWYZVDFOU-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical class [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
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- 238000010561 standard procedure Methods 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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Abstract
本发明提供了一种包含钠增溶速率不超过5ppmw/5分钟的耐火无机材料的催化剂载体。还提供了一种包含钠增溶速率不超过5ppmw/5分钟的耐火无机材料、以及一种或多种沉积在所述载体上的催化反应性金属的催化剂。还提供了一种适合由烯烃和氧进行烯烃气相生产的催化剂,包含钠增溶速率不超过5ppmw/5分钟的矾土基载体、以及沉积在所述载体上的催化反应性银。
Description
本发明的领域
本发明涉及一种具有改进催化性能的催化剂,尤其是一种适用于制备环氧化物的催化剂。
本发明的背景
已经描述了用于降低可溶性物质在催化剂载体本体中的总浓度的方法。这些方法一般包括一种利用其生产载体以便降低那些物质在整个载体本体中的浓度的工艺。这些途径限制了载体的配方,通常伴随非所需结果,如高载体密度。
美国专利4797270公开通过水洗来降低矾土粉末的钠离子含量。洗涤水的pH可能需要调节以萃取其它金属,而日本专利JP56164013则公开利用低pH(酸)从煅烧α-矾土原料中萃取铀和钍。
美国专利4361504和4366092建议,在将银或银/金沉降在载体上之后水洗氧化乙烯催化剂。EP-211521公开,用热水洗涤催化剂以去除来自银浸渍工艺或碱金属物理沉积的留在催化剂上的碱性物质。美国专利4367167公开了一种用于承载催化剂的工艺,其中将浸渍载体浸入包含溶解脂族胺的惰性水可混溶有机溶剂。美国专利4810689公开,将银化合物沉积,在碱金属化合物的存在下将银化合物分解成银,洗涤去除有机沉积物,然后通过在洗涤阶段时或之后进行浸渍而引入新鲜碱金属。美国专利4186106和4125480公开,在催化金属沉积之后和在促进剂物质沉积之前用惰性液体进行洗涤。
已有技术仍然关心杂质,即,整个本体中杂质的总量。遗憾的是,所介绍的杂质去除技术通常会进攻载体本身。现已发现,通过控制某些物质,尤其是钠在载体表面上的增溶速率,可以提高催化剂的催化性能。
本发明的综述
按照本发明,提供了一种钠增溶速率不超过基于载体总重的5ppmw/5分钟的催化剂载体,由通过浸渍在3∶1重量/重量沸水中而释放的量来度量。
本发明的另一实施方案提供了一种制备所述催化剂载体的方法,其中所述钠增溶速率通过一种能够赋予所述载体表面上的可离子化物质以离子性并去除至少部分的该物质,或赋予可离子化物质以不溶性,或赋予可离子化物质以固定性的有效方式而实现。
本发明的另一实施方案提供了一种催化剂,尤其是一种适用于烯烃的气相环氧化的催化剂,该催化剂包含所述载体和一种或多种催化反应性金属以及可有可无的一种或多种沉积在其上的促进物质。
本发明的详细描述
已经发现,具有受控增溶速率,尤其是受控钠和/或可溶性硅酸盐增溶速率的载体能够改进催化剂的催化性能,如活性、选择性以及随着时间的活性和/或选择性性能。据信增溶速率的控制能够提高大多数催化剂的性能,而无论该本体载体材料如何不纯。此外,增溶速率的控制可应用于有机或无机载体。
本发明的典型载体在沸水中的钠增溶速率要控制不超过5ppmw/5分钟。本文所用的“增溶速率”是指,在将载体放在溶剂中规定时间之后且在3∶1的沸腾溶剂与载体的比率下,钠在溶剂中的可测增溶速率。即,在沸水中的5ppmw钠/5分钟增溶速率是,在载体已处于沸水中5分钟之后在水中测得的钠的量。
载体通常是无机材料,例如矾土-、硅石-或二氧化钛-基化合物、或其混合物,如矾土-硅石载体。载体还可由碳基材料,例如焦炭、活性炭、或富勒烯(fullerenes)制成。
可离子化物质通常存在于无机型载体上,包括钠、钾、铝酸盐、可溶性硅酸盐、钙、镁、硅铝酸盐、及其混合物。特别重要的是存在于表面上的可离子化的阴离子物质,尤其是可离子化硅酸盐。硅酸盐的增溶速率可通过电感耦合等离子体(ICP)技术来测定且硅物质在表面上的量可通过X-射线光电子能谱(XPS)来测定。但由于钠在该硅酸盐可溶入的相同溶液中可溶,因此钠的增溶速率可以较简单地检测离子物质的去除,而且已选作用于定义本发明的指标。另一测量技术是测定处理溶液的电导率。
本文所用的载体“表面”是可通过Brunauer、Emmett和Teller(B.E.T.)标准方法测定的载体区域。具体地说,载体的表面是发生反应的部位。已经发现,通过降低可离子化物质在载体表面上的浓度,可以有效且低成本地获得所需的表面钠增溶速率。“可离子化”物质是一种能够产生离子性的物质,而术语“离子的”或“离子”是指带电的化学部分。
可通过任何方式来降低可离子化物质的表面增溶速率,只要它有效地:(ⅰ)赋予可离子化物质以离子性并去除至少部分的该物质,或(ⅱ)赋予可离子化物质以不溶性,或(ⅲ)赋予可离子化物质以固定性。但进攻性介质的应用受到阻碍,因为这些介质容易溶解该载体,从本体中萃取太多的物质,且在孔中产生酸性或碱性部位。被认为是进攻性介质的酸可去除载体上的阳离子,但在去除非所需阴离子,如硅酸根时相当无效。降低浓度的有效方式包括洗涤载体;离子交换;将杂质挥发、沉淀或螯合;产生反应以使表面上的可离子化物质不溶;及其组合方式。可以处理本体载体,或可以在制造载体之前处理用于形成该载体的原料。如果载体原料和成品载体都得到处理,可明显更好地改进增溶速率控制。
为了由载体制成催化剂,通常使用溶解在合适溶剂中的金属化合物、复合物和/或盐浸渍该载体,这样将催化有效量的金属沉积或浸渗到载体上。本文所用的“催化有效量”是指能够产生可测催化效果的金属的量。例如,在涉及烯烃环氧化催化剂时的金属的催化有效量是,能可测地将烯烃和氧转化成氧化烯的金属的量。此外,还可在催化反应性金属沉积之前、同时或之后,将一种或多种促进剂沉积在载体上。本文所用的术语“促进剂”是指,一种在与不含该组分的催化剂相比能够有效提高催化剂的一种或多种性能的组分。
如果金属沉积通过将载体接触其氢离子活度已降低的浸渍溶液而进行,可以进一步改进催化剂性能。本文所用的“氢离子活度”通过氢离子选择电极的电势来度量。本文所用的具有“降低的”氢离子活度的溶液是指,该溶液的活度已通过加入碱而改变,这样,比起处于未改变态的相同溶液的氢离子活度,该改变溶液的氢离子活度下降。选择用于改变溶液的碱可选自任何碱或pKb低于原始浸渍溶液的化合物。特别理想地是选择一种不会改变该浸渍溶液的配方的,即,不会改变该浸渍溶液中的所需金属浓度并沉积在所述载体上的碱。有机碱不会改变浸渍溶液金属浓度,其例子为四烷基氢氧化铵和1,8-二-(二甲基氨基)萘。如果浸渍溶液的金属浓度改变不成问题,可以使用金属氢氧化物。
如果该浸渍溶液至少部分水性,氢活度变化的指标可用pH计来测定,但要理解,所得测量值不是根据真正水性定义的pH。本文所用的“测得的pH”应该是指使用标准pH探头测得的这种非水体系的pH。由原始浸渍溶液至加入碱时的即使小的“测得的pH”变化也是有效的,而且随着“侧得的pH”变化因加碱而增加,催化性能继续提高。高碱加入量似乎不会对催化剂性能有不利影响;但已发现,高的氢氧化物加入量造成浸渍溶液的淤积,产生制造困难。如果碱加入太低,氢离子活度不受影响。氢离子活度降低步骤在自身使用时,即,没有在浸渍之前降低任何可离子化物质的浓度时也十分有效。
将也称作催化剂前体的浸渍载体在一种也能还原催化金属的气氛的存在下进行干燥。本领域已知的干燥方法包括蒸汽干燥、在具有受控氧浓度的气氛中干燥、在还原气氛中干燥、空气干燥、和使用合适的斜坡或分步温度曲线的分步干燥。
通过实施例本发明将更详细描述一种适用于气相生产环氧化物的催化剂,也称作环氧化催化剂。
环氧化催化剂通常包含一种无机载体,例如矾土-基载体如α-矾土,所述载体上沉积有一种或多种催化反应性金属。该载体通常包含某些可离子化物质,例如α-矾土载体通常包含各种物质,包括钠、钾、铝酸盐、可溶性硅酸盐、钙、镁、硅铝酸盐、及其混合物。已经发现,硅酸盐和某些其它的阴离子是环氧化催化剂中特别不期望的可离子化物质。
按照本发明,在3∶1重量/重量沸水中的钠增溶速率控制低于5ppmwNa/5分钟。增溶速率可如上所述通过降低可离子化物质在表面上的浓度来控制。
使用溶解在合适溶剂中的金属离子或化合物、复合物和/或盐浸渍具有受控增溶速率的载体,足以在载体上产生所需沉积。如果银是沉积物质,通常沉积基于总催化剂重量的1-40%重量,优选1-30%重量的银。随后将浸渍载体从溶液中分离出并将沉积金属化合物还原成金属银。
可以在金属沉积之前、同时或之后沉积一种或多种促进剂。用于环氧化催化剂的促进剂通常选自硫、磷、硼、氟、ⅠA族-Ⅷ族金属、稀土金属、及其混合物。促进剂物质通常是溶解在合适溶剂中的促进剂的化合物和/或盐。
对于烯烃环氧化氧化物催化剂,ⅠA族金属通常选自钾、铷、铯、锂、钠、及其混合物:其中优选钾和/或铯和/或铷。甚至更优选的是铯与至少一种附加ⅠA族金属的组合,如铯与钾、铯与铷、或铯与锂。ⅡA族金属通常选自镁、钙、锶、钡、及其混合物,Ⅷ族过渡金属通常选自钴、铁、镍、钌、铑、钯及其混合物;且稀土金属通常选自镧、铈、钕、钐、钆、镝、铒、镱、及其混合物。其它促进剂的非限定性例子包括高铼酸盐、硫酸盐、钼酸盐、钨酸盐、铬酸盐、磷酸盐、硼酸盐、硫酸盐阴离子、氟化物阴离子、ⅢB-ⅥB族的氧离子、选自Ⅲ-ⅧB族的元素的氧离子、与卤化物阴离子的碱金属盐、以及选自ⅢA-ⅦA和ⅢB-ⅦB族的氧离子。ⅠA族金属促进剂的量通常为总催化剂重量的10-1500ppm(以金属表示),且ⅦB族金属低于总催化剂重量的3600ppm(以金属表示)。
为了进一步提高催化性能,例如通过加入碱来降低浸渍溶液的氢离子活度。用于环氧化催化剂的典型浸渍溶液开始非常碱性,因此使用一种强碱进一步降低氢离子活度。强碱的例子包括烷基氢氧化铵如四乙基氢氧化铵、氢氧化锂和氢氧化铯。为了保持所需的浸渍溶液配方和金属载量,四乙基氢氧化铵之类的有机碱是优选的。碱在这些体系的加入通常导致“测得的pH”变化最高约3,但要理解,该“测得的pH”不是真正的pH,因为该浸渍体系不是水性。
最概括地说,用于这些催化剂的载体可以是任何的大量常规的多孔耐火催化剂载体或被认为较惰性的载体材料。这些常规材料是本领域熟练技术人员已知的且可以是天然或合成来源的。用于环氧化催化剂的载体优选具有大孔结构且表面积低于约10米2/克,优选低于约3米2/克。不同催化剂的载体的例子为氧化铝(包括以商品名“Alundum”售卖的材料)、焦炭、浮石、氧化镁、氧化锆、硅藻土、漂白土、碳化硅、包含硅石和/或碳化硅的多孔聚集体、硅石、氧化镁、选择粘土、人造和天然沸石、碱土碳酸盐、和陶瓷。特别适用于制备烯烃环氧化催化剂的耐火载体包括铝土材料,尤其是包含α-矾土的那些。在含α-矾土的载体的情况下,优选的是通过B.E.T.法测得的比表面积为0.03-10米2/克,优选0.05-5米2/克,更优选0.1-3米2/克,且通过常规水吸收技术测得的水孔体积为0.1-0.75毫升/克(体积)的那些。用于测定比表面积的B.E.T.法描述于Brunauer,S.、Emmett,P.Y.和Teller,E.的美国化学学会杂志,60,309-16(1938)。
某些种类的含α-矾土的载体是特别优选的。这些α-矾土载体具有较一致的孔径且详细表征如下:B.E.T.比表面积为0.1-3米2/克,优选0.1-2米2/克,且水孔体积为0.10-约0.55毫升/克。这些载体的制造商包括Norton Chemical Process Products Corporation和UnitedCatalysts,Inc.(UCI)。
刚描述的所得环氧化催化剂可用于环氧化物,尤其是的环氧乙烷的气相生产。典型的环氧化工艺包括将催化剂装入反应器。将待转化的原料,通常是乙烯、氧、二氧化碳、氮气和乙基氯的混合物在升高的温度和压力下经过催化剂床之上。催化剂将该原料转化成包含环氧乙烷的出口物流产物。另外可将氮氧化物(NOx)加入原料中以促进催化剂转化性能。
以下实施例用于说明本发明。
实施例
载体
表Ⅰ给出了用于这些实施例的载体。
表Ⅰ
载体 | A | B | C | D |
B.E.T.表面积(米2/克)(a) | 0.84 | 0.97 | 0.78 | 0.87 |
水吸收(%) | 39.7 | 46.2 | 37.6 | 43.4 |
粉碎强度(千克)(b) | 6.53 | 8.07 | 12.29 | 5.44 |
总孔体积(毫升/克)(c) | 0.408 | 0.460 | 0.390 | - |
中值孔径(微米)(c) | 1.8 | 2.7 | 1.3 | - |
SiO2(%重量) | 0.5 | 0.8 | 0.1 | 0.5 |
本体的酸可浸滤Na(ppmw) | 438 | 752 | 186 | 339 |
本体的酸可浸滤K(ppmw) | 85 | 438 | 109 | 37 |
本体的酸可浸滤Ca(ppmw) | 207 | 508 | 526 | 123 |
本体的酸可浸滤Al(ppmw) | 744 | 1553 | 657 | 499 |
本体的酸可浸滤SiO2(ppmw) | 808 | 1879 | 1560 | 600 |
α-矾土(%重量) | Bal. | Bal. | Bal. | Bal. |
aBrunauer、Emmett和Teller的方法,引述如上。
b平板粉碎强度,单个粒料。
c使用Micromeritics Autopore 9200或9210(130°接触角,0.473牛顿/米的Hg表面张力),通过汞侵入至3.8×108Pa来测定。
用于实施例1、2、3、4、6、7、12的载体水洗步骤
载体洗涤通过将100克载体浸渍在300克沸腾的去离子水中15分钟来进行。然后将载体取出并另外放在新鲜的300克沸水中15分钟。再一次重复该步骤,总共浸渍3次,这时将载体从水中取出并在150℃下在通风良好的炉中干燥18小时。然后利用在以下实施例中概述的工艺步骤,将干燥载体用于制备催化剂。
浸渍溶液
按照以下的工艺步骤,制备出银-胺-草酸盐储备溶液:
将415克试剂级氢氧化钠溶解在2340毫升去离子水中,然后将温度调节至50℃。
将1699克高纯度“光谱纯”硝酸银溶解在2100毫升去离子水中,然后将温度调节至50℃。
将氢氧化钠溶液在搅拌下慢慢加入硝酸银溶液,同时保持50℃的溶液温度。将该混合物搅拌15分钟,然后将温度降至40℃。
将水从产生于混合步骤的沉淀物中去除,然后测定包含钠和硝酸根离子的水的电导率。将等于去除量的量的新鲜去离子水加回到银溶液。将该溶液在40℃下搅拌15分钟。重复该工艺,直到去除水的电导率低于90μmho/cm。然后加入1500毫升新鲜去离子水。
以约100克的增量加入630克高纯度二水合草酸。温度保持在40℃且pH保持7.8以上。
从混合物中去除水,留下高度浓缩的含银淤浆。将该草酸银淤浆冷却至30℃。
加入699克92%重量乙二胺(8%去离子水),同时保持温度不超过30℃。所得溶液包含约27-33%重量的银。
将足够的45%重量CsOH水溶液加入该溶液,得到具有14.5%重量银和所需铯载量(参见实施例)的成品催化剂。
钠测量步骤
所选载体的钠增溶速率这样测定:使用连接到Orion 290A型电压计上的Orion №8611BN型钠选择电极,测量萃取介质的钠含量。在典型实验中,将300克载体在900克去离子水中煮沸总共15分钟。在此过程中,以预定间隔取出3毫升等分试样。使用确定用于离子选择电极的工艺步骤,在25℃下分析每个等分试样的钠含量。使用在5分钟时取样的溶液中的钠浓度来评估该载体在用于催化剂制备时是良好还是不好。结果在表Ⅱ中给出。
表Ⅱ.对于所选α-矾土载体,每5分钟的钠增溶速率
载体 | 本体钠未洗涤载体(ppmw)a | 萃取钠未洗涤载体(ppmw) | 萃取钠已洗载体(ppmw) |
A | 438 | 9.2 | 1.3 |
Ab | 438 | 9.2 | 1.2 |
B | 752 | 9.2 | 1.8 |
C | 186 | 10.2 | - |
a来自表Ⅰ。
b在乙酸铵交换之后,如实施例8所述。
pH测量步骤
使用Metrohm744型pH计来测定银溶液的pH,其中采用6.0220.100型组合电极和用于温度补偿的Pt 100 6.1110.100型电阻温度计。在每次使用之前,使用市售缓冲溶液校正该pH计。在典型测量中,将用于催化剂浸渍的掺杂银溶液的50毫升等分试样通过一个在线连接到塑料注射器上的2微米过滤器滤入100毫升玻烧杯。将pH探头降至磁力搅拌溶液中,然后将3分钟之后得到的读数记录为平衡pH。在每次测量之间用去离子水清洗探头,然后检查校正。要特别仔细以防AgCl固体在电极膜上的聚集。这种聚集可按照制造商的建议,通过将该探头浸渍在氢氧化铵溶液中而去除。
实施例1
由载体A通过首先将载体进行载体洗涤而制备出催化剂前体。洗涤之后,将约30克的洗涤载体A在环境温度下放在3.33kPa真空下1分钟。然后将约50克的浸渍溶液加入以浸没该载体,然后在3.33kPa下再保持真空3分钟。铯的目标值为450ppm/克成品催化剂。然后释放真空,并将过量浸渍溶液通过在500rpm下离心处理2分钟而从催化剂前体中去除。随后将该催化剂前体干燥,同时在240℃下在11.3米3/小时的空气流下振动4分钟。
实施例1a(对比)
将载体A按照实施例1所述进行浸渍;但该载体没有进行载体洗涤。铯的目标值为400ppm/克成品催化剂。
实施例2
将载体B按照实施例1所述进行洗涤和浸渍。铯的目标值为450ppm/克成品催化剂。
实施例2a(对比)
将载体B按照实施例1所述进行浸渍;但该载体没有进行载体洗涤。铯的目标值为400ppm/克成品催化剂。
实施例3
将载体C按照实施例1所述进行洗涤和浸渍。铯的目标值为300ppm/克成品催化剂。
实施例3a(对比)
将载体C按照实施例1所述进行浸渍;但该载体没有进行载体洗涤。铯的目标值为360ppm/克成品催化剂。
实施例4
将载体A按照实施例1所述进行洗涤和浸渍。铯的目标值为450ppm/克成品催化剂。此外,将35%四乙基氢氧化铵(TEAH)水溶液以117.8微摩尔OH-/毫升Ag溶液的目标值加入储备浸渍溶液,将氢离子活度降至13.2的测得的pH”。
实施例5
将100克载体A浸渍在300毫升沸腾的5%重量TEAH中15分钟,然后六次浸渍于300毫升沸腾的去离子水中,每次15分钟。然后取出载体并在150℃下在通风良好的炉中干燥18小时。然后将该催化剂浸渍成400ppm/克成品催化剂的铯目标值。此外,将35%重量TEAH以117.8微摩尔OH-/毫升Ag的目标值加入储备浸渍溶液,将氢离子活度降至13.6的“测得的pH”。
实施例6
将载体A按照实施例1所述进行载体洗涤和浸渍。铯的目标值为720ppm/克成品催化剂。此外,将TEAH溶解在水中并以117.8微摩尔OH-/毫升Ag的目标值加入储备溶液,将氢离子活度降至13.2的“测得的pH”,然后将NH4ReO4溶解在水中并加入储备溶液以达到1.5微摩尔Re/克成品催化剂。
实施例7
将载体A按照实施例1所述进行载体洗涤和浸渍。铯的目标值为450ppm/克成品催化剂。此外,将LiOH溶解在水中并加入储备浸渍溶液,以将氢离子活度降至13.2的测得的pH”。
实施例7a(对比)
将载体A按照实施例7所述进行浸渍,但该载体没有进行载体洗涤。铯的目标值为400ppm/克成品催化剂。
实施例8
将300克载体A浸渍在900毫升沸腾的0.1M乙酸铵溶液中15分钟,然后在25℃下浸渍在300毫升去离子水中15分钟,随后三次浸渍于300毫升沸腾的去离子水中,每次15分钟。然后取出载体并在150℃下在通风良好的炉中干燥18小时。然后按照实施例1所述浸渍该载体。铯的目标值为450ppm/克成品催化剂。此外,将LiOH溶解在水中并加入储备浸渍溶液,以将氢离子活度降至13.2的“测得的pH”。
实施例9
将用于载体A的α-矾土原料在25℃下用去离子水洗涤,然后用相同的所用成分匀化形成载体A,然后挤出、干燥、并在马弗炉中烧。所得载体称作载体D。按照实施例1所述的相同方式,使用载体D来制备催化剂。铯的目标值为510ppm/克成品催化剂。此外,将LiOH溶解在水中并加入储备浸渍溶液,以将氢离子活度降至13.2的“测得的pH”。
实施例10
按照实施例9给出的相同方式,由载体D制备出催化剂;但该载体没有进行载体洗涤。铯的目标值为360ppm/克成品催化剂。
实施例11
将100克载体A在25℃下浸渍在300毫升沸腾的0.1M乙酸钡溶液中15分钟,然后在25℃下浸渍在300毫升去离子水中15分钟,随后三次浸渍于300毫升沸腾的去离子水中,每次15分钟。然后取出载体并在150℃下在通风良好的炉中干燥18小时。然后按照实施例1所述浸渍该载体。铯的目标值为400ppm/克成品催化剂。此外,将LiOH溶解在水中并加入储备浸渍溶液,以将氢离子活度降至13.2的“测得的pH”。
实施例12
按照实施例1所述将载体A进行载体洗涤和浸渍。铯的目标值为650ppm/克成品催化剂。此外,将LiOH溶解在水中并加入储备浸渍溶液,将氢离子活度降至13.2的“测得的pH”。然后将NH4ReO4溶解在水中并加入储备浸渍溶液以达到1.5微摩尔Re/克成品催化剂。
使用实施例1-12的催化剂,由乙烯和氧生产出环氧乙烷。将3-5克的粉碎催化剂装入6.35毫米内径的不锈钢U-形管中。该U管浸渍在熔融金属浴(热介质)且端部连接到气体流动体系上。催化剂的重量和入口气体流速通过调节以获得每毫升催化剂每小时6800毫升气体的气体时空速率。入口气体压力为1450kPa。
在整个试验(包括启动)过程中经过催化剂床(在单程操作中)的气体混合物由25%乙烯、7.0%氧、5%二氧化碳、63%氮气、和2.0-6.0ppmv乙基氯组成。
起始反应器(热介质)温度为180℃。温度以10℃/小时的速率由180℃升至225℃,然后调节以获得在出口气流中1.5%体积的恒定环氧乙烷含量。如果催化剂已在气流中总共至少1-2天,通常得到在该转化水平下的性能数据。由于在进料气体组成、气体流速、以及用于确定进料和产品气体组成的分析仪器的校正上差别轻微,因此给定催化剂的测得选择性和活性在每次试验之间相差轻微。
测定在1.5%环氧乙烷选择性下的起始性能值并记录于表Ⅲ。
表Ⅲ.由未洗涤和洗涤α-矾土制成的催化剂的性能特性
实施例 | 载体 | 预浸渍条件 | 碱加入 | 浸渍溶液“测得的pH” | 选择性(%) | 温度(℃) |
1 | A | 水洗 | 无 | 11.2 | 82.7 | 229 |
1a | A | 没有洗涤 | 无 | 11.2 | 81.3 | 237 |
2 | B | 水洗 | 无 | 11.2 | 82.5 | 226 |
2a | B | 没有洗涤 | 无 | 11.2 | 82.0 | 232 |
3 | C | 水洗 | 无 | 11.2 | 82.0 | 229 |
3a | C | 没有洗涤 | 无 | 11.2 | 82.0 | 235 |
4 | A | 水洗 | TEAH | 13.2 | 82.7 | 226 |
5 | A | TEAH洗涤+水洗 | TEAH | 13.6 | 82.7 | 222 |
6 | A | 水洗 | TEAH | 13.2 | 89.4 | 245 |
7 | A | 水洗 | LiOH | 13.2 | 82.7 | 226 |
7a | A | 没有洗涤 | LiOH | 13.2 | 82.0 | 227 |
8 | A | 乙酸铵洗涤 | LiOH | 13.2 | 83.1 | 222 |
9 | D | 原料洗涤+水洗 | LiOH | 13.2 | 82.7 | 222 |
10 | D | 原料洗涤 | LiOH | 13.2 | 83.0 | 225 |
11 | A | 乙酸钡洗涤 | LiOH | 13.2 | 82.7 | 226 |
12 | A | 水洗 | LiOH | 13.2 | 86.2 | 232 |
可以看出,如果降低钠增溶速率,可明显提高催化剂性能。载体A和B在进行载体洗涤步骤之后具有明显较低的钠增溶速率(参见表Ⅱ)。注意,尽管载体C的本体Na较低,但它具有高的钠增溶速率。如果在形成载体之前(载体D)将用于制备载体的原料进行洗涤,甚至可进一步取得改进。
用于实施例4-12催化剂的沉积溶液的氢离子活度通过加入碱而降低。可以看出,通过降低沉积溶液的氢离子活度,可进一步提高催化性能。还显然看出,pH作用的现象并不局限于特定的催化剂配方,这在实施例6和12中得到最佳说明,其中将能促进选择性的掺杂剂,如铼加入浸渍溶液。
本领域普通技术人员显然看出,本发明可在不背离本文所述的其主旨或范围的情况下进行许多变化和改进。
Claims (9)
1.一种催化剂载体,其钠增溶速率不超过基于载体总重量的5ppmw/5分钟,由通过浸渍在3∶1重量/重量沸水中而释放的量来度量。
2.制备根据权利要求1的催化剂载体的方法,其中所述钠增溶速率通过能够赋予所述载体表面上的可离子化物质以离子性并去除至少部分的该物质,或赋予可离子化物质以不溶性,或赋予可离子化物质以固定性,的有效方式而实现。
3.根据权利要求2的方法,其中所述方式选自洗涤、离子交换、挥发、杂质控制、沉淀、螯合、及其组合方式。
4.一种催化剂,包含根据权利要求1的载体、和一种或多种催化反应性金属、以及可有可无的一种或多种沉积在所述载体上的促进物质。
5.根据权利要求4的催化剂,其特征在于,它适用于烯烃的气相环氧化。
6.根据权利要求5的催化剂,其特征在于,所述载体是矾土基载体且所述催化反应性金属是银。
7.一种制备根据权利要求4-6中任何一项的催化剂的方法,其特征在于,所述催化反应性金属通过将载体浸没在浸渍溶液中而沉积在所述载体上,所述浸渍溶液的氢离子活度已被降低。
8.一种使用含氧气体催化环氧化烯烃的方法,其中使用根据权利要求4-6中任何一项的催化剂或按照权利要求7制成的催化剂。
9.根据权利要求11的方法,其特征在于将至少一种氮氧化物加入所述含氧气体。
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EP2125202A2 (en) | 2006-11-20 | 2009-12-02 | Shell Internationale Research Maatschappij B.V. | A process for treating a carrier, a process for preparing a catalyst, the catalyst, and use of the catalyst |
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1999
- 1999-09-10 EP EP99969045A patent/EP1140354A1/en not_active Withdrawn
- 1999-09-10 WO PCT/EP1999/006725 patent/WO2000015335A1/en active IP Right Grant
- 1999-09-10 RU RU2001110089/04A patent/RU2225255C2/ru not_active IP Right Cessation
- 1999-09-10 AU AU59770/99A patent/AU757735B2/en not_active Ceased
- 1999-09-10 CN CNB998109037A patent/CN1154538C/zh not_active Expired - Lifetime
- 1999-09-10 CA CA002343836A patent/CA2343836C/en not_active Expired - Fee Related
- 1999-09-10 KR KR1020017003173A patent/KR100641542B1/ko not_active IP Right Cessation
- 1999-09-10 BR BR9913602-3A patent/BR9913602A/pt not_active Application Discontinuation
- 1999-09-10 JP JP2000569914A patent/JP4794042B2/ja not_active Expired - Lifetime
- 1999-09-10 ID IDW20010576A patent/ID28790A/id unknown
- 1999-09-10 TR TR2001/00749T patent/TR200100749T2/xx unknown
- 1999-09-13 GC GCP1999281 patent/GC0000068A/xx active
- 1999-09-14 MY MYPI99003961A patent/MY130360A/en unknown
- 1999-10-19 TW TW088118046A patent/TW442331B/zh not_active IP Right Cessation
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2001
- 2001-02-26 IN IN173DE2001 patent/IN2001DE00173A/en unknown
- 2001-03-07 ZA ZA200101902A patent/ZA200101902B/en unknown
- 2001-03-12 MX MXPA01002587 patent/MX257765B/es not_active IP Right Cessation
- 2001-11-06 US US09/992,787 patent/US6579825B2/en not_active Expired - Lifetime
- 2001-11-06 US US09/992,784 patent/US7247600B2/en not_active Expired - Lifetime
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2007
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105377429A (zh) * | 2013-05-16 | 2016-03-02 | 科学设计有限公司 | 提高环氧乙烷催化剂的催化性能的载体处理 |
US9758498B2 (en) | 2013-05-16 | 2017-09-12 | Scientific Design Company, Inc. | Carrier treatment to improve catalytic performance of an ethylene oxide catalyst |
US10669247B2 (en) | 2013-05-16 | 2020-06-02 | Scientific Design Company, Inc. | Carrier treatment to improve catalytic performance of an ethylene oxide catalyst |
CN104447676A (zh) * | 2014-11-20 | 2015-03-25 | 中山大学 | 一种环状碳酸酯的制备方法 |
CN104447676B (zh) * | 2014-11-20 | 2016-09-28 | 中山大学 | 一种环状碳酸酯的制备方法 |
CN109641199A (zh) * | 2016-09-02 | 2019-04-16 | 陶氏技术投资有限责任公司 | 用于制备环氧化催化剂的方法 |
Also Published As
Publication number | Publication date |
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TW442331B (en) | 2001-06-23 |
CA2343836C (en) | 2007-12-04 |
RU2225255C2 (ru) | 2004-03-10 |
IN2001DE00173A (zh) | 2005-12-23 |
WO2000015335A1 (en) | 2000-03-23 |
US7439375B2 (en) | 2008-10-21 |
KR100641542B1 (ko) | 2006-10-31 |
EP1140354A1 (en) | 2001-10-10 |
US20020143197A1 (en) | 2002-10-03 |
MX257765B (en) | 2008-06-09 |
ZA200101902B (en) | 2002-10-18 |
GC0000068A (en) | 2004-06-30 |
CA2343836A1 (en) | 2000-03-23 |
AU757735B2 (en) | 2003-03-06 |
BR9913602A (pt) | 2001-05-22 |
US7247600B2 (en) | 2007-07-24 |
MXPA01002587A (es) | 2001-08-01 |
AU5977099A (en) | 2000-04-03 |
CN1154538C (zh) | 2004-06-23 |
JP4794042B2 (ja) | 2011-10-12 |
JP2002524247A (ja) | 2002-08-06 |
ID28790A (id) | 2001-07-05 |
US20070191618A1 (en) | 2007-08-16 |
MY130360A (en) | 2007-06-29 |
KR20010079798A (ko) | 2001-08-22 |
US6579825B2 (en) | 2003-06-17 |
US20020137957A1 (en) | 2002-09-26 |
TR200100749T2 (tr) | 2001-10-22 |
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