CN100457258C - 制备银基环氧化催化剂的碳酸钙载体 - Google Patents
制备银基环氧化催化剂的碳酸钙载体 Download PDFInfo
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- CN100457258C CN100457258C CNB038233223A CN03823322A CN100457258C CN 100457258 C CN100457258 C CN 100457258C CN B038233223 A CNB038233223 A CN B038233223A CN 03823322 A CN03823322 A CN 03823322A CN 100457258 C CN100457258 C CN 100457258C
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- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
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- 229910000019 calcium carbonate Inorganic materials 0.000 title claims description 22
- 238000006735 epoxidation reaction Methods 0.000 title description 7
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 44
- -1 alkaline earth metal carbonate Chemical class 0.000 claims abstract description 38
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
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- GTGFQGURYZVPBV-UHFFFAOYSA-L [Ag+2].NCCN.[O-]C(=O)C([O-])=O Chemical group [Ag+2].NCCN.[O-]C(=O)C([O-])=O GTGFQGURYZVPBV-UHFFFAOYSA-L 0.000 claims description 10
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- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 claims description 8
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- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
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- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims 1
- 229960003750 ethyl chloride Drugs 0.000 claims 1
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- 238000004519 manufacturing process Methods 0.000 abstract description 4
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
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- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- 125000002947 alkylene group Chemical group 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
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- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
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- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229910001958 silver carbonate Inorganic materials 0.000 description 1
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- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
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Abstract
本发明涉及一种制备催化剂的方法,其包括:(a)制备一种糊状物,所述糊状物包含至少一种碱土金属碳酸盐、液体介质、结合银的添加剂和至少一种挤出助剂和/或任选的燃尽添加剂的均匀混合物;(b)由所述糊状物形成一种或多种成型颗粒;(c)干燥并煅烧所述颗粒;和(d)用含银化合物的溶液浸渍所述经干燥和煅烧的颗粒。本发明还涉及一种制备氧化烯烃的方法,其包括在本发明方法所获得的催化剂组合物存在下使包含具有至少两个碳原子的烯烃和氧的气体组合物反应。
Description
技术领域
本发明涉及一种可用于生产烯化氧的催化剂的制备方法,该催化剂包含沉积于碱土金属碳酸盐材料载体上的银。本发明还涉及一种制备氧化烯烃的方法,所述方法包括在一种包含沉积于碱土金属碳酸盐载体上的银的催化剂组合物存在下使烯烃与氧反应。
背景技术
在一个反应例如烯化氧的生产中,催化剂的活性、效率、稳定性和耐久性取决于催化剂前体(即载体材料与载体颗粒)的化学、物理和结构性质,以及载体上催化材料的属性和分布。期望载体颗粒保持载体材料的提高催化活性的性质。一般而言,载体和包含少量位于载体上的催化材料的催化剂具有基本相同的物理和结构性质,仅有细微差别。
需要一种催化剂载体,这种载体不仅具有用于负载合适的催化剂所必要的空隙率特性,也具备良好的结构特性,例如压碎强度和耐磨损性。此外,包括所述载体的材料优选在需要提供例如更高的表面接触面积或更低的反应器床层压降时,可以生料状态挤压成复杂形状。
催化剂载体需要同时具备至少一个可沉积银组分的最小表面积、充足的吸水性和适当的压碎强度。但优化这些特性的困难在于改进一个性质可能会导致另一个性质的减弱。因此例如优化压碎强度可能导致低孔隙率。
通常由碱土金属碳酸盐制备的载体材料具有相对差的机械性能,尤其是差的压碎强度。因此,需要一种碱土金属碳酸盐载体,其具有用于负载合适的催化剂所必要的空隙率特性,而又具备改进的机械性能,尤其是压碎强度。
发明内容
本发明提供了一种制备催化剂的方法,所述方法包括:
(a)制备一种糊状物,所述糊状物包含以下材料的均匀混合物:
(i)至少一种碱土金属碳酸盐;
(ii)液体介质;
(iii)结合银的添加剂;和,
(iv)至少一种挤出助剂;
(b)由所述糊状物形成一种或多种成型颗粒;
(c)干燥并煅烧所述颗粒;和,
(d)用含银化合物的溶液浸渍所述经干燥和煅烧的颗粒。
本发明进一步提供了一种制备氧化烯烃的方法,所述方法包括在本发明制备的催化剂组合物存在下使烯烃与氧反应。
附图说明
附图1给出了以工作速率(WR)表征的催化剂活性和在使用无结合银的添加剂的载体生产环氧丙烷时的出口环氧丙烷(PO)组成。
附图2给出了在使用无结合银的添加剂的载体时的氧转化率、环氧丙烷(PO)选择性、氯乙烷(EC)浓度和NOx浓度,其中NOx是一氧化氮、二氧化氮和四氧化二氮的混合物。
附图3给出了以工作速率(WR)表征的催化剂活性和在使用具有结合银的添加剂的载体生产环氧丙烷时的出口环氧丙烷(PO)组成。
附图4给出了在使用具有结合银的添加剂的载体时的氧转化率、环氧丙烷(PO)选择性、氯乙烷(EC)浓度和NOx浓度,其中NOx是一氧化氮、二氧化氮和四氧化二氮的混合物。
具体实施方式
已发现在载体制备过程中将银、尤其是通过草酸银乙二胺溶液添加至催化剂载体生坯,可显著提高载体机械性能,并使其适于工业应用于用于烯烃环氧化过程的催化剂。术语“载体(carrier)”与术语“载体(support)”通用。
本发明提供了一种碱土金属碳酸盐(优选碳酸钙)的催化剂载体的制备方法,其中为提高载体压碎强度而引入有效量的银。
用于制备这种具有提高的压碎强度的催化剂载体的组合物包括:(a)80-99wt%的碱土金属碳酸盐;和(b)1-20wt%的银,以金属银计。一种优选的碱土金属碳酸盐催化剂载体的特征是高比表面积和22N(51bs)的最小耐压强度,优选包括85-89wt%的碱土金属碳酸盐和11-15wt%的银,且更优选90-95%(重量)的碱土金属碳酸盐和5-10wt%的银。
具有高压碎强度的碱土金属碳酸盐载体可通过下述方法制备:(a)形成一种混合物,其包括碱土金属碳酸盐、结合银的添加剂、液体介质和有机挤出助剂以及任选的燃尽添加剂,从而形成糊状物;(b)使所述糊状物成形而产生成型颗粒;和(c)干燥并煅烧所得到的颗粒。术语“烧制”可与术语“煅烧”通用。并且关于载体或载体颗粒的术语“成形”可与术语“成型”通用。
碱土金属碳酸盐可以是碳酸盐,例如碳酸镁或优选碳酸钙。典型地,它们具有0.5-20m2/g的比表面积,优选1-18m2/g,且更特别是3-15m2/g,其通过B.E.T方法测量。典型地,它们具有0.05-2ml/g的表观吸水量,优选0.07-1.7ml/g,且更特别是0.1-1.5ml/g,其通过常规的吸水技术测量。所述碱土金属碳酸盐载体是特别重要的,因为它们提供了具有随时间改进的活性性能的催化剂。所述碱土金属碳酸盐是可商购获得的材料,并且为如J.M.Huber和Alfa inorganic这样的公司所销售,并被粉碎成不同平均粒度,典型的是0.5-15微米(中值孔径)。
液体介质典型是含水的,但也可含有其它液体如乙醇。
结合银的添加剂优选是草酸银胺的水溶液,其银浓度为15-33wt%,优选20-33wt%,最优选27-33wt%。优选的胺是乙二胺,尽管其它的二胺例如1,3-丙二胺、1,4-环己二胺和1,4-丁二胺都可使用。载体中最终银含量为1-20重量份,优选1-15重量份,并最优选1-10重量份,基于所得载体的100份总重量计。银/碳酸钙的最终重量比典型为1∶5至1∶100,特别是1∶7至1∶30,更特别为1∶8至1∶10,例如1∶9,其中银以银金属计。
优选通过混合90-100重量份(pbw)碱土金属碳酸盐与1-2pbw有机挤出助剂如淀粉或凡士林而制备载体。随后加入足够量的水使所述组合物可挤出(通常当35-45pbw银溶液存在时可获得此效果),并且混合所得组合物直至均匀。
当制备出糊状物后,例如通过研磨且使其老化(若需要的话),其可用于成形,例如通过挤出或喷雾。使用挤出机使所述糊状物形成挤出物。所述挤出物可以具有任何直径,例如0.5mm至5cm,但为了具有最佳催化活性和便于处理与适于加工,所述挤出物直径优选1mm至5cm。也可制备更大或更小直径的挤出物,这取决于所得挤出物所期望的用途。在挤出物通过挤出机模具之后,若需要的话,可将其切割为均一的长度。但并非总是需要均一的长度,因此允许所述挤出物随意破裂为任何长度。若允许所述挤出物任意破裂,其长度通常2-7倍于其直径宽度。通常,允许所述挤出物任意破裂是因为便于生产以及经济原因。载体可形成成型颗粒,例如块、片等。优选地,为用于管状固定床反应器,则形成圆形,例如球、丸、圆柱体、环、车轮状或片状,典型地具有1mm至5cm的尺寸。
可运用多种干燥和煅烧工序。本方法中的干燥和煅烧步骤通常在100-1000℃的温度下进行。通过初始的温和加热,例如在100-215℃的温度下,使得成形载体前驱体不含未结合的和松散结合的水。在所述干燥过程之后,可以在200-950℃温度下的干燥或潮湿气氛中实施煅烧过程,优选220-850℃,更优选230-700℃。煅烧过程可进行1-16小时,或1-12小时,或1-10小时。如一个非限制性的描述实施例,所述挤出物在100℃干燥过夜并按如下步骤煅烧:历时1小时升至110℃并保持1小时,而后历时4小时升至240℃并保持1小时,且最后历时4小时升至500℃并保持5小时。
在一个优选实施方案中,一种成型的结合了银的碱土金属碳酸盐催化剂载体可以如此制备:(a)制备包含如下材料的均匀混合物的糊状物:(i)碳酸钙;(ii)至少一种溶剂;(iii)草酸银乙二胺络合物;和(iv)至少一种挤出助剂;(b)由所述糊状物形成成型颗粒;和(c)干燥并煅烧所述成型颗粒,其中所述糊状物的银与碳酸钙的重量比为约1∶5至1∶100,特别地为1∶7至1∶30,更特别地为1∶8至1∶10,例如1∶9。
在另一优选实施方案中,载体组合物可通过如下步骤生产:(a)混合80-99重量份碳酸钙和35-55重量份草酸银乙二胺水溶液(包含浓度为27-33wt%的所述银络合物),从而形成一种均匀混合物;(b)挤出所述均匀混合物从而形成挤出物;和(c)在200-950℃的温度下将所述挤出物煅烧1-16小时,所述温度优选220-850℃,更优选230-700℃。
所述碱土金属碳酸盐载体相对于那些由不含结合银的添加剂制备的碱土金属碳酸盐载体而言具有改进的压碎强度。所述载体的平板压碎强度通常至少为22N(5lbs),特别地至少为40N(9lbs),更特别地至少为53N(12lbs)。它们尤其适用于通过银催化的烯烃环氧化来制备烯化氧如环氧乙烷和环氧丙烷。它们可用于制备用于生产环氧乙烷、环氧丙烷、丁二烯单环氧化物等的银环氧化催化剂。
可根据已有的方法由所述载体制备催化剂。制备所述催化剂的适当方法可由US-A-3962136和WO-00/15333得知。
在一个合适的催化剂制备方法中,用一种液体组合物浸渍所述载体,所述液体组合物包括银、钾、钠和/或锂的化合物以及需要的其它化合物如一种或多种铷和/或铯化合物或其它有用的添加剂,随后在150-500℃的温度下加热使其干燥,尤其是200-450℃。干燥过程可进行1分钟至24小时,典型地为2分钟至2小时,更典型地为2分钟至30分钟。干燥气氛可以是空气、惰性气体如氮气或氩气或蒸汽。可用于所述液体组合物的银化合物可选自此前所定义的结合银的添加剂。
通常存在还原剂来实现将银化合物还原为金属银。例如,可采用还原气氛如含氢或乙烯的气体,或在一种或多种浸渍液体中存在还原剂,例如草酸盐。若需要的话,可在一个以上浸渍和干燥步骤中实施微孔浸渍。例如,可在一个以上步骤中浸渍银,且可在银浸渍之前、在银浸渍之后或在分开的银浸渍步骤之间在一个或多个单独步骤中浸渍促进剂。液体组合物典型地是一种溶液,更典型地是水溶液。
浸渍过程中使用的化合物可独立地选自例如无机和有机盐、氢氧化物和络合物。所述化合物的用量使所得催化剂具有所需组成。
本发明的催化剂可用于任何具有至少两个碳原子的烯烃的环氧化。典型地,碳原子数至多为10,更典型地至多为5。最优选碳原子数为3。
除了具有烯键(即>C=C<部分)之外,所述烯烃可包括其它烯键或任何其它不饱和键,例如为芳基形式,如苯基。因此所述烯烃可以是共轭或非共轭二烯或共轭或非共轭乙烯基芳族化合物,例如1,3-丁二烯、1,7-辛二烯、苯乙烯或1,5-环辛二烯。
在一个优选的实施方案中,烯烃包括单个烯键而对于剩余部分而言为饱和烃。其可为直链的、支链的和环状的。可结合单个烷基于所述烯键,例如1-己烯,或结合两个烷基于所述烯键,例如2-甲基-辛烯-1或戊烯-2。也可结合三或四个烷基于所述烯键。两个烷基可以连在一起形成例如环乙烯的环结构。在这些优选实施方案中,氢原子与所述烯键在未被烷基所占据的位置相连。尤其优选单个烷基与所述烯键相连。
具有至少3个碳原子的烯烃最优选为1-戊烯、1-丁烯,尤其是丙烯。本领域技术人员将会认识到,根据分子几何形状,一种烯烃可产生氧化烯烃混合物,例如多种异构形式的氧化烯烃。
通常,本发明的方法作为气相方法进行,所述方法中气相反应物在固体催化剂存在下反应。反应物经常和进一步加入所述工艺的任何其它组分混合并随后与催化剂接触。对于本发明而言,反应物和其它组分(若有的话)的数量比以及进一步的反应条件并不重要,其可在很宽的范围内选择。因为与催化剂接触的混合物通常是气相的,反应物和其它组分(若有的话)的数量浓度以气态形式的混合物中的分率限定如下。
烯烃的浓度适当地至少为0.1v%,典型地至少为0.5v%,和适当地,至多为60v%,特别是至多为50v%。优选地,所述烯烃浓度为1-40v%。
若烯烃是丙烯、1-丁烯或1-戊烯,则优选其浓度为1-30v%,特别是2-15v%。
氧的浓度适当地至少为2v%,典型地至少为4v%,和在实践中所述浓度通常至多为20v%,特别是至多为15v%。若烯烃是丙烯、1-丁烯或1-戊烯,则优选氧浓度为6-15v%,特别是8-15v%。氧的来源可以是空气,但优选使用可通过分离空气获得的含氧气体。
可将作为催化剂缓和剂向温合物中加入有机氯化物,以改善选择性。这种有机氯化物的例子是烷基氯和烯基氯。优选的有机氯化物是氯甲烷、氯乙烯、1,2-二氯乙烷,特别是氯乙烷。所述有机氯化物可以至少0.1ppm(体积)浓度使用,典型为至少0.2ppm(体积),为乙烯时,优选至少1ppm(体积)和至多20ppm(体积)。为丙烯时,有机氯化物浓度至少20ppm(体积),更优选至少50ppm(体积),且该浓度至多2000ppm(体积),尤其是至多1500ppm(体积),其中ppm(体积)是根据反应混合物总量中氯原子的摩尔量计算而得。因此,1ppm对应于1,000,000个气体分子中的1个氯乙烷分子。
可通过将硝酸根或亚硝酸根形成化合物添加到反应混合物中而改进本发明催化剂的性能。所述硝酸根或亚硝酸根形成化合物是在与催化剂接触条件下能够将硝酸根或亚硝酸根离子引入到催化剂上的化合物。通常,硝酸根或亚硝酸根离子在所述工艺中容易从催化剂上消失,这种情况下则需要对其进行补充。因此,优选将所述硝酸根或亚硝酸根形成化合物连续添加到混合物中,或以一种至少在需要的时候添加的间隙模式加入。对于所述过程的初始阶段,在催化剂制备阶段将硝酸根或亚硝酸根形成化合物或硝酸根或亚硝酸根离子添加至催化剂中就足够了。优选的硝酸根或亚硝酸根形成化合物是一氧化氮、二氧化氮和/或四氧化二氮。代替地,可使用肼、羟胺、氨或其它含氮化合物。优选使用氮氧化物的混合物,其可由通式NOx表示,其中x是1-2的数,表示混合物中氮氧化物的氧和氮的平均摩尔原子比。
对于乙烯环氧化而言,所使用的硝酸根或亚硝酸根形成化合物的适当浓度至少为1ppm(体积),典型地至少5ppm(体积),所述浓度适当地至多为30ppm(体积),尤其是至多20ppm(体积),其中ppm体积以相对于反应物和其它组分的混合物总体积的单体硝酸根或亚硝酸根形成化合物体积计算。对于丙烯环氧化而言,硝酸根或亚硝酸根形成化合物的适当的使用浓度至少为10ppm(体积),典型地至少50ppm(体积),且所述浓度适当地至多为500ppm(体积),尤其是至多300ppm(体积)。若用于丙烯环氧化的催化剂中有铷和/或铯,则所述硝酸根或亚硝酸根形成化合物的优选使用浓度至少为10ppm(体积),尤其是至少20ppm(体积),且所述浓度典型地至多为200ppm(体积),更典型地至多为150ppm(体积),优选至多80ppm(重量),尤其是至多50ppm(体积),基于相同的基准计。
所述混合物中可能有或没有二氧化碳。优选没有二氧化碳,因为二氧化碳降低催化剂的活性和选择性,因此降低氧化烯烃的产率。二氧化碳的浓度典型地至多35v%的浓度,特别是至多20v%。
而且,混合物中可存在惰性化合物,例如氮、氩和/或甲烷。优选存在甲烷,因为甲烷改进反应热量的散发,而不会对选择性和转化率产生不利影响。
所述方法优选在至少150℃的温度下实施,尤其是至少200℃。优选所述温度至多为320℃,尤其是至多为300℃。所述方法优选在至少0.5barg(即巴表压)的压力下实施,尤其是至少1barg。优选所述压力至多为100barg,尤其是至多为50barg。
通常,优选在高氧浓度下操作。但在实际中,为保持在反应物与其中任何其它组分组成的混合物处于可燃极限之外,随着烯烃浓度的增加,氧浓度应降低。实际的安全操作条件还取决于各装置条件,例如温度、压力和管尺寸。因此,在各装置中,用所谓的可燃性方程来决定氧浓度,其用于估计与任意浓度的烯烃混合的允许氧浓度。
当使用填充床反应器以气相过程运行所述方法时,气时空速(GHSV)优选至少为100Nl/l·h,尤其是至少200Nl/l·h。所述GHSV优选至多30000Nl/l·h,尤其是至多15000Nl/l·h。气时空速是进料气体的体积流量除以催化剂床层体积,在此以标准条件(即0℃和1巴绝对压力)限定所述气体体积流量。
在上述碳酸钙/银载体上制备的催化剂与在纯碳酸钙载体上制备的催化剂相比,在活性、选择性和稳定性方面均显示出优异的性能。见附图1-4。
实施例
通过常规的汞浸入设备,将液体汞压入载体孔隙,从而测量孔体积和孔尺寸分布。由于需要较大的压力迫使汞进入较小的孔,因此,压力增量的测量值对应于渗入的孔体积增量,并因此对应增加体积的孔尺寸。下述孔体积使用Micromeritics Autopore 9200型(130°接触角且汞具有0.473N/m的表面张力)获得逐渐增加至3.0×108Pa的压力下用汞浸入法确定。
实施例1A
银-胺-草酸盐原料溶液的制备
通过以下过程制备银-胺-草酸盐原料溶液:将415g试剂级氢氧化钠溶解于2340ml去离子水中且将温度调节至50℃。将1699g高纯度“光谱纯”硝酸银溶解于2100ml去离子水且温度调节至50℃。在搅拌下向硝酸银溶液中缓慢加入氢氧化钠溶液,同时保持溶液温度为50℃。搅拌混合物15分钟,然后将温度降低至40℃。从混合步骤所产生的沉淀上除去水,水中包含钠和硝酸根离子,并测量所述水的电导率。向银溶液中加入等量于所除去的水的新鲜去离子水。在40℃搅拌溶液15分钟。重复所述过程直至所除去水的电导率小于90μmho/cm。然后加入1500ml新鲜去离子水。
以约100g的增量分批加入630g高纯度草酸二水合物。温度维持在40℃且pH维持在7.8以上的水平。为得到高度浓缩的含银浆料,从混合物中除去水。所述草酸银浆料冷却至30℃。然后向所述浆料中加入699g 92wt%的乙二胺(8%去离子水),同时保持温度不超过30℃。所得溶液包含约27-33wt%的银。
上述原料溶液用于制备表1和2所示的掺杂银的碳酸钙载体。
实施例1B-16
样品的制备
如表1和2所示的碳酸钙载体按如下方法制备:将100重量份(pbw)的碳酸钙(CaCO3)与2pbw的有机挤出助剂(如淀粉)混合。加入足量的水使所述混合物可挤出(45pbw银溶液),并混合所得组合物直至均匀且可挤出。迫使所得糊状物通过3mm的模具。所得挤出物在100℃干燥过夜并煅烧如下:历时1小时升至110℃并保持1小时,然后历时4小时升至240℃并保持1小时,最后历时4小时升至500℃并保持5小时。在表1和2的实施例中金属银与碳酸钙的重量比均为1∶9。
为了比较,不含银的碳酸钙载体制备如下:在Cuisinart混合器中使500克碳酸钙和20克有机挤出助剂如淀粉混合30秒,加入350克去离子水(20-26pbw),且将整个混合物另外混合3分钟。用活塞挤出机将所得糊状物挤出,并在实验室烘箱中于110℃干燥过夜。历时5小时使挤出物升至500℃并保持5小时。
在如下的讨论中,将从添加的“银”的角度来讨论本发明,因为在煅烧操作之后,针对本申请的目的,假定载体中的银以零氧化态金属的银颗粒(非阳离子)形式存在。
表1
实施例 | 材料 | 表面积(m<sup>2</sup>/g) | 中值孔径(埃) | 平板压碎强度(N(lbs)) | 孔隙率(%) |
1B | CaCO<sub>3</sub> | 5.1 | 5900 | 5.3(1.2) | 63 |
2 | CaCO<sub>3</sub> | 5.9 | 1818 | 35(7.8) | 33 |
3 | CaCO<sub>3</sub>/Ag | * | * | * | 25.3 |
4 | CaCO<sub>3</sub>/Ag | 3.35 | * | * | 25 |
5 | CaCO<sub>3</sub>/Ag | 4.3 | * | 19(4.3) | 47 |
6 | CaCO<sub>3</sub>/Ag | 3.5 | 3300 | 72.5(16.3) | 30 |
7 | CaCO<sub>3</sub>/Ag | 3.6 | 4401 | * | 42 |
8 | CaCO<sub>3</sub>/Ag | 3.6 | 3484 | * | 35 |
9 | CaCO<sub>3</sub>/Ag | 3.7 | 3395 | 59.6(13.4) | 30 |
*未测量
表2
实施例 | 材料 | 表面积(m<sup>2</sup>/g) | 中值孔径(埃) | 平板压碎强度(N(lbs)) | 水孔体积(cc/g) |
10 | CaCO<sup>3</sup> | 1.1 | 7200 | 8.9(2) | .22 |
11 | CaCO<sup>3</sup>/Ag | 1 | 9000 | 44.9(10.1) | .227 |
12 | CaCO<sup>3</sup> | 2 | 4000 | 28(6.2) | .23 |
13 | CaCO<sup>3</sup>/Ag | 1.8 | 4039 | 61.3(13.8) | .21 |
14 | CaCO<sup>3</sup> | 2.7 | 2600 | 36(8.2) | .24 |
15 | CaCO<sup>3</sup>/Ag | 2.4 | 2910 | 69.8(15.7) | .217 |
16 | CaCO<sup>3</sup>/Ag | 3.7 | 3400 | 59.6(13.4) | 0.3 |
实施例17
针对环氧丙烷(PO)的催化剂制备及测试
于实施例16(见表2)的载体上制备催化剂1。制备掺杂铯的草酸银乙二胺溶液,其中1.258g氢氧化铯溶于150g如实施例1A所制备的银溶液中。先在真空下用该掺杂铯的银溶液浸渍载体,在250℃空气中干燥5分钟,然后再用掺杂铯的银溶液浸渍并在250℃干燥5分钟。将所得材料在真空中用一种水溶液浸渍,所述水溶液包含溶解于225g水中的42.8g硝酸钾、14.4g硝酸钠和1.8g氢氧化锂。一旦完成这一最后的浸渍操作,则将所述催化剂在250℃空气中干燥5分钟。所得催化剂包含34%银、500μmol/g钾、200μmol/g钠、50μmol/g锂和45μmol/g铯。然后,粉碎催化剂并将其筛分为20-30目。随后,将15g经筛分的催化剂装入一个U形微反应器管。
在230℃、38磅/平方英寸(表压)的压力和150cc/min的流量条件下进行测试。气体组成如下:7%丙烯、12%氧、100ppmNOx(NOx对应于一氧化氮、二氧化氮和四氧化二氮的混合物)、150ppm氯乙烷,余量为氮。操作24小时后,流出物含0.5%的PO,且测得催化剂对PO的选择性基于丙烯为55%。
实施例18
针对环氧乙烷(EO)的催化剂制备及测试
于实施例11(见表2)的载体上制备催化剂2如下。先通过真空浸渍用草酸银乙二胺溶液浸渍载体,并在250℃下干燥5分钟,然后将所述载体用溶于50g水的2.32g硝酸钾溶液真空浸渍于,随后在250℃下干燥5分钟。所得催化剂包含19.6%银和100μmol/g钾。粉碎催化剂并将其筛分为20-30目。随后,将1.75g经筛分的催化剂装入一个U形微反应器管。
在210磅/平方英寸(表压)的压力和281cc/min的流量下进行测试。气体组成如下:30%乙烯、8%氧、0.4%二氧化碳、5ppmNOx(而NOx对应于一氧化氮、二氧化氮和四氧化二氮的混合物)、5ppm氯乙烷,余量为氮。维持温度使得环氧乙烷出口浓度为1.5%,操作10天之后,测得在250℃时催化剂的选择性为90.5%。
实施例19
针对对环氧乙烷(EO)的催化剂制备及测试
于实施例15(表2)的载体上制备催化剂3如下。通过真空浸渍首先用草酸银乙二胺溶液浸渍载体,并在250℃下干燥5分钟,然后用溶于50g水的7.28g硝酸钾溶液真空浸渍所述载体,接着在250℃下干燥5分钟。所得催化剂包含19.2%银和300μmol/g钾。粉碎催化剂并将其筛分为20-30目。随后,将1.75g经筛分的催化剂装入一个U形微反应器管。
在210磅/平方英寸(表压)的压力和281cc/min的流量下进行测试。气体组成如下:30%乙烯、8%氧、5ppmNOx(而NOx对应于一氧化氮、二氧化氮和四氧化二氮的混合物)、5ppm氯乙烷,余量为氮。维持温度使得环氧乙烷出口浓度为1.5%,操作8天之后,测得在233℃时催化剂的选择性为90.0%。
实施例20
本实施例证实了与在纯碳酸钙载体上制备的催化剂相比,在碳酸钙/银载体上制备的催化剂在活性、选择性和稳定性方面均显示出优异的性能。催化剂AA(测试号I)在实施例2的碳酸钙载体(比较的)上制备。在催化剂制备过程中,将载体两次用银溶液浸渍,且在第三次浸渍时引入结合添加剂。所述催化剂包含15.5wt%银、500mmol/g钾(作为硝酸钾引入)、200mmol/g钠(作为硝酸钠引入)和50mmol/g锂(作为氢氧化锂引入)。在标准微反应器测试(管中有15g催化剂,进料含有8%丙烯、12%氧、150ppm二氯乙烷、100ppmNOx,余量为N2,GHSV为600Nl/l·h,T=250℃)中所述催化剂性能示于图1和2(测试号I)。催化剂BB在实施例6(本发明的)碳酸钙/银载体上制备并类似地测试,除了在两次浸渍过程中引入的银量(除去载体中已有的银)为21wt.%且在第二次浸渍时与银同时引入结合添加剂。所得催化剂性能示于图3和4(测试号II)。可以看出,根据本发明制备的催化剂达到55%的PO选择性。
本发明的载体可用于多种催化应用,其中反应物流(气体或液体)在高温下与负载于载体上的催化剂接触。在化学工业中有多种这类方法,但已经证实本发明载体尤其适用于由包含乙烯和氧的气流催化形成烯化氧。且本发明的实用性并非局限于此。
Claims (10)
1、一种制备催化剂的方法,所述方法包括:
(a)制备一种糊状物,所述糊状物包含以下材料的均匀混合物:
(i)至少一种碱土金属碳酸盐;
(ii)液体介质;
(iii)结合银的添加剂;和
(iv)至少一种挤出助剂;
(b)由所述糊状物形成一种或多种成型颗粒;
(c)干燥和煅烧所述颗粒;和
(d)用含银化合物的溶液浸渍所述经干燥和煅烧的颗粒。
2、权利要求1的方法,其中所述液体介质是含水的,所述结合银的添加剂是草酸银乙二胺络合物,且其中步骤(d)包括如下过程:
(i)用含银化合物的溶液浸渍在步骤(c)中获得的颗粒;和
(ii)在100-1000℃的温度下干燥所述经浸渍的颗粒。
3、权利要求1或2的方法,其中所述糊状物的以金属计的银与碱土金属碳酸盐的重量比为1∶5至1∶100;所述含银化合物的溶液的银浓度为27-33wt%,干燥和煅烧温度为200-950℃。
4、权利要求2的方法,其中所述碱土金属碳酸盐包括碳酸钙;且所述糊状物包括0.90-99重量份的碳酸钙和35-45重量份的草酸银乙二胺络合物水溶液的混合物,所述水溶液的草酸银乙二胺络合物浓度为27-33wt%。
5、权利要求2的方法,其中所述草酸银乙二胺络合物处于水溶液中,其中所述溶液进一步含有氢氧化铯。
6、一种制备氧化烯烃的方法,其包括:
制备催化剂,包括:
(a)制备一种糊状物,所述糊状物包含以下材料的均匀混合物:
(i)至少一种碱土金属碳酸盐;
(ii)液体介质;
(iii)结合银的添加剂;和
(iv)至少一种挤出助剂;
(b)由所述糊状物形成一种或多种成型颗粒;
(c)干燥和煅烧所述颗粒;和
(d)用含银化合物的溶液浸渍所述经干燥和煅烧的颗粒;以及在所获得的催化剂存在下使包含烯烃和氧的气体组合物反应。
7、权利要求6的方法,其中所述烯烃为丙烯或乙烯。
8、权利要求6或7的方法,其中所述气体组合物进一步包含氯乙烷和/或NOx。
9、权利要求8的方法,其中所述烯烃的浓度至少为0.5v%,氧的浓度至少为2v%,氯乙烷浓度以体积计至少为0.1ppm。
10、权利要求6或7的方法,其中所述温度为150-320℃,压力为0.5-100barg,气时空速为100-30,000N1/(1·h)。
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CA (1) | CA2500238A1 (zh) |
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US20050192448A1 (en) * | 2002-10-28 | 2005-09-01 | Rubinstein Leonid I. | Process for preparing an olefin oxide, a method of using the olefin oxide, a method of using the olefin oxide and a catalyst composition |
US20050027133A1 (en) * | 2003-07-29 | 2005-02-03 | Saudi Basic Industries Corporation | Method of making a catalyst for direct oxidation of an alkene to an alkene oxide |
US20060036105A1 (en) * | 2004-08-12 | 2006-02-16 | Shell Oil Company | Method of preparing a shaped catalyst, the catalyst, and use of the catalyst |
RU2008109027A (ru) | 2005-08-11 | 2009-09-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL) | Способ изготовления формованного катализатора, катализатор и использование такого катализатора |
US20090270640A1 (en) * | 2006-04-21 | 2009-10-29 | Basf Aktiengesellschaft | Method for production of ethylene oxide in a microchannel reactor |
JP2008184456A (ja) * | 2007-01-31 | 2008-08-14 | Sumitomo Chemical Co Ltd | 酸化プロピレンの製造法 |
DE102008011767B4 (de) | 2008-02-28 | 2012-07-26 | Basf Se | Verfahren zur Herstellung von olefinisch ungesättigten Carbonylverbindungen durch oxidative Dehydrierung von Alkoholen |
DE102008014910A1 (de) | 2008-03-19 | 2009-09-24 | Basf Se | Verwendung eines geträgerten edelmetallhaltigen Katalysators zur oxidativen Dehydrierung |
WO2010007011A1 (en) * | 2008-07-14 | 2010-01-21 | Basf Se | Process for making ethylene oxide |
CN102099345A (zh) * | 2008-07-14 | 2011-06-15 | 万罗赛斯公司 | 使用微通道工艺技术制造环氧乙烷的方法 |
US8524927B2 (en) | 2009-07-13 | 2013-09-03 | Velocys, Inc. | Process for making ethylene oxide using microchannel process technology |
EP3275537A1 (en) | 2016-07-25 | 2018-01-31 | Omya International AG | Surface-modified calcium carbonate as carrier for transition metal-based catalysts |
US20230347325A1 (en) | 2019-09-26 | 2023-11-02 | Omya International Ag | Gncc and/or pcc as a catalytic carrier for metal species |
KR20220069988A (ko) | 2019-09-26 | 2022-05-27 | 옴야 인터내셔널 아게 | 금속 화학종을 위한 촉매 담체로서의 srcc |
EP4306210A1 (en) | 2022-07-12 | 2024-01-17 | Omya International AG | High surface area pcc as a catalyst carrier for platinum compounds |
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2003
- 2003-09-29 CN CNB038233223A patent/CN100457258C/zh not_active Expired - Fee Related
- 2003-09-29 JP JP2004541773A patent/JP2006501066A/ja active Pending
- 2003-09-29 WO PCT/US2003/030492 patent/WO2004030813A1/en active Application Filing
- 2003-09-29 AU AU2003278999A patent/AU2003278999A1/en not_active Abandoned
- 2003-09-29 CA CA002500238A patent/CA2500238A1/en not_active Abandoned
- 2003-09-29 EP EP03770510A patent/EP1545768A1/en not_active Withdrawn
- 2003-09-29 KR KR1020057005340A patent/KR100985671B1/ko not_active IP Right Cessation
- 2003-09-30 US US10/677,647 patent/US7153987B2/en not_active Expired - Fee Related
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US7153987B2 (en) | 2006-12-26 |
WO2004030813A1 (en) | 2004-04-15 |
AU2003278999A1 (en) | 2004-04-23 |
US20040110972A1 (en) | 2004-06-10 |
CN1684764A (zh) | 2005-10-19 |
EP1545768A1 (en) | 2005-06-29 |
CA2500238A1 (en) | 2004-04-15 |
KR20050065563A (ko) | 2005-06-29 |
KR100985671B1 (ko) | 2010-10-05 |
JP2006501066A (ja) | 2006-01-12 |
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