CN104350032A - 在负载型双金属金-钯催化剂存在下环烷烃的氧化 - Google Patents
在负载型双金属金-钯催化剂存在下环烷烃的氧化 Download PDFInfo
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- CN104350032A CN104350032A CN201380017704.3A CN201380017704A CN104350032A CN 104350032 A CN104350032 A CN 104350032A CN 201380017704 A CN201380017704 A CN 201380017704A CN 104350032 A CN104350032 A CN 104350032A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 230000003647 oxidation Effects 0.000 title claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 38
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- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 title claims description 15
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000010931 gold Substances 0.000 claims abstract description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 25
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 27
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims description 25
- 229930195733 hydrocarbon Natural products 0.000 claims description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 24
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- 150000001875 compounds Chemical class 0.000 claims description 21
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- 239000000395 magnesium oxide Substances 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 17
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- 239000012298 atmosphere Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- 239000010941 cobalt Substances 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- 229910015900 BF3 Inorganic materials 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
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- 239000000284 extract Substances 0.000 description 1
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- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
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- 238000005502 peroxidation Methods 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- 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
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Abstract
本发明涉及使用负载型金和钯催化剂氧化环烷烃的方法和所述负载型金和钯催化剂用于氧化环烷烃的用途。本发明还描述了制备所述负载型催化剂的方法。
Description
本发明涉及使用负载型金和钯催化剂氧化环烷烃的方法和所述负载型金和钯催化剂用于氧化环烷烃的用途。本发明还描述了制备所述催化剂的方法。
环己烷的氧化特别是在温和反应条件下的氧化对于工业至关重要,原因是产物,尤其是环己醇和环己酮,是制造己二酸的前体,己二酸为聚酰胺、聚氨酯、聚酯和增塑剂的制造中的关键中间体。通常,己二酸通过用硝酸氧化环己醇和环己酮的混合物(KA油)来制备。KA油为环己烷氧化的初级产物。环己酮还用作己内酰胺的起始材料。
目前,商业环己烷氧化通过在高于423K的温度下使用均相的钴和锰盐来进行。该方法以85%的选择性提供作为产物的环己醇和环己酮。还生成了显著量的环己基过氧化氢(CHHP)和痕量的羧酸副产物。然而,环己醇和环己酮产物的高选择性仅在低转化率水平、通常小于10%且最通常小于5%转化率下获得。虽然操控反应条件可提供更大的转化率,但这通常伴随着环己醇和环己酮的选择性的劣化。
已经发现,在使用过氧化氢或叔丁基过氧化氢(TBHP)氧化环己烷中可实现转化率高于5%的催化性能。然而,在商业上具有吸引力的是在任何工业方法中采用氧气或空气,这归因于在大规模操作中的价格低廉和可实行性。出于类似的原因且从环境观点来看,还希望采用不使用溶剂的方法。
在考虑催化剂对于大规模生产的适合性时,环境问题也是相关的。较高的转换频率(turn-over frequency)可通过使用低浓度的均相催化剂获得。然而,均相催化剂的再循环和废液的处置成问题且对环境具有显著的影响。大多数常规非均相催化剂由于晶格氧的相对较低活动性而在温和反应条件下通常为非活性的。
本发明的催化剂和方法解决了与用于环烷烃氧化的当前市售催化剂和方法相关的上述问题。因此,本发明的一个目的在于提供环烷烃(特别是环己烷)氧化的方法,其以高选择性(至少85%且优选至少90%)和5%以上的转化率水平(特别是高于10%)产生环烷醇和环烷酮(特别是环己醇和环己酮),这将是当前工业方法的显著发展。本发明的另一目的在于提供非均相催化剂,其可再循环且其可用于氧化环烷烃的方法中,其适合工业规模且其以有利的选择性和转化率产生环烷醇和/或环烷酮。本发明的一个特定目的在于提供非均相催化剂,其可在单一装置操作中选择性地分解CHHP,以在环己烷的氧化中提高转化率并维持或改善转化为环己醇和环己酮的反应选择性。本发明的另一特定目的在于提供由环己烷的氧化生成己二酸的更有效且经济的方法。己二酸的当前工业生产的总成本的关键因素为蒸汽用量且由本发明提供的供选催化剂体系显著降低该因素。
第一方面,本发明提供氧化环烷烃的方法,其包括使一种或多种环烷烃与氧化剂在负载型催化剂存在下接触,其中所述负载型催化剂包含含有金-钯粒子的催化剂和选自碳化物、氮化物和氧化物的载体,其中所述氧化物选自氧化镁、氧化铝和氧化锌。
还描述了制备负载型催化剂的方法,其包括以下步骤:
(a) 制备金和钯盐的水溶液;和
(b) 将载体加入其中,其中所述载体选自碳化物、氮化物和氧化物,其中所述氧化物选自氧化镁、氧化铝和氧化锌,
且其中所述方法还包括还原所述金和钯离子的步骤。
所述还原步骤通常包括在加入所述载体之前或之后加入合适的还原剂,且在一个优选的实施方案中,所述还原剂在加入所述载体之前加入。或者,所述还原步骤可通过煅烧进行。所述还原步骤将所述金和钯离子还原成本发明催化剂的金-钯合金。
第二方面,本发明提供制备环烷醇和/或环烷酮的氧化方法,其包括使一种或多种环烷烃与氧化剂在负载型催化剂存在下接触,其中所述负载型催化剂包含含有金-钯粒子的催化剂和选自碳化物、氮化物和氧化物的载体,其中所述氧化物选自氧化镁、氧化铝和氧化锌。
第三方面,本发明提供负载型催化剂作为环烷烃氧化的催化剂的用途,其中所述负载型催化剂包含含有金-钯粒子的催化剂和选自碳化物、氮化物和氧化物的载体,其中所述氧化物选自氧化镁、氧化铝和氧化锌。
催化剂
所述催化剂的金-钯粒子为金-钯(AuPd)合金,且优选以纳米粒子的形式。纳米粒子的平均最长直径优选为至多约200nm,更优选为至多约50nm,更优选为至多约30nm,且更优选为至多约20nm,且最优选在约5nm-约15nm范围内。所述纳米粒子的平均尺寸和尺寸分布合适地通过STEM (扫描透射电子显微术)测量,其中所述负载型催化剂样品的典型截面的目测检查用以计数在给定横截面积内的不同尺寸的粒子。
所述金-钯合金的组成影响催化活性且本发明人已经发现在环烷烃氧化中的最佳转化率和选择性在所述合金中的金与钯的摩尔比在约1:18-约18:1范围内、更优选为约1:15-约15:1、更优选为约1:12-约12:1、更优选为约1:10-约10:1且最优选为约1:9-约9:1时获得。
载体对环烷烃氧化中的金-钯粒子的催化性能具有非常显著的影响。例如,发现负载在二氧化硅上的AuPd催化剂在环己烷氧化反应中没有活性,而用氮化硅(Si3N4)代替二氧化硅作为载体对于环己烷氧化中的AuPd催化剂提供良好的催化活性。因此,载体(特别是表面氧物质)与活性物质之间的相互作用为催化活性的关键因素。本发明人意外地发现,使用某些载体时,另外量的催化剂并不改善催化性能,而是中止整个反应。该现象将与常规催化剂性能似乎相反,因为通常预期更大量的催化剂将提高活性氧物质的浓度,促进反应物的氧化。然而,该现象是不为人知的。所谓的催化剂-抑制剂转变由J. F. Black (JACS, 1978, 100, 527-535)确定,Black发现催化性能方面的突变取决于金属催化的自动氧化中钴/锰盐的浓度。
所述催化剂-抑制剂转变在工业方法中具有特别的重要性。对催化剂量非常敏感的与催化剂-抑制剂转变相关的催化剂体系需要存在精确量的催化剂用于工业生产。所类催化剂体系不具有灵活性(inflexible)且会对生产率具有不利影响,且因此对于工业方法没有吸引力。
本发明的催化剂体系使用选自碳化物、氮化物和某些氧化物的载体。优选所述碳化物载体选自B4C3、Mo2C、ZrC、WC、SiC和TiC,更优选选自B4C3和SiC,且更优选所述碳化物为SiC。优选所述氮化物选自BN、C3N4、AlN和Si3N4,且优选选自BN和Si3N4。镁、锌和铝的氧化物可为单一金属氧化物或混合金属氧化物,例如选自MgO、Al2O3、ZnO和MgAl2O4。优选本发明的催化剂体系使用碳化物或氮化物载体,更优选碳化物载体。所述碳化物载体在环烷烃氧化中、即使在较高温度下,也表现出高稳定性和化学惰性,且发现其在这些方面比例如氮化物载体优越。因此,所述碳化物载体对于环烷烃氧化有效地具有惰性,且既不是催化剂,也不是抑制剂。本发明的一个特别优势在于优选的载体(最值得注意的是碳化物载体)以大大改善催化剂体系对催化剂量的耐受性(resistance)的方式对催化剂性能进行改性,且因此特别适合工业方法。
所述AuPd催化剂的装载量基于载体和催化剂的总重量计优选在约0.1-约10重量%范围内,优选为约0.5-约5重量%,优选为约0.5-约2重量%。
本发明人还发现,通过掺杂对AuPd催化剂改性进一步改善了催化性能。这种改性兼具催化剂体系对催化剂量的改善的耐受性与增加的转化率和/或选择性。另外,掺杂改性抑制了开环羧酸物质的生成,诸如在环己烷氧化中己二酸的生成。这是有利的,因为己二酸及其他副产物将另外必须从反应混合物中分离。
所述掺杂剂的引入通常通过使用如本文所述的方法,例如通过涂布负载型AuPd催化剂的表面将负载型AuPd催化剂表面改性来实现。优选的掺杂剂为碱性金属氧化物和氢氧化物,且特别是MgO、Al2O3、ZnO、CaO、Mg(OH)2、Al(OH)3、Zn(OH)2和Ca(OH)2。特别有效的掺杂剂选自Mg(OH)2和Al(OH)3,优选为Al(OH)3。本文使用的术语“掺杂剂”是指与载体和催化剂的材料不同的材料。因此,将在上文列表中的碱性金属氧化物或氢氧化物用作负载型催化剂中的“掺杂剂”,所述负载型催化剂不含该物质作为载体。在上文列表中的碱性金属氧化物和氢氧化物在负载型AuPd催化剂中具有特别的效用,其中所述载体选自本文所述的碳化物和氮化物。
引入所述负载型AuPd催化剂中的掺杂剂的量优选量化为催化剂制备期间使用的掺杂剂的量的函数,且定义为掺杂剂相对于在该制备中使用的金和钯盐的初始水溶液的总重量的重量%。因此,相对于制备中使用的金和钯盐的初始水溶液的总重量,在所述催化剂制备期间使用的掺杂剂的量优选在约1.25 x 10-3重量%-约2 x 10-2重量%范围内,优选为约1.5 x 10-3重量%-约2 x 10-2重量%,且在一个实施方案中,为约5 x 10-3重量%。
所述负载型催化剂适合在氧化环烷烃的方法中作为非均相催化剂使用。所述催化剂的非均相性质为有利的,这使得催化剂更容易地从反应产物中分离并再循环。例如,当所述环烷烃为环己烷时,产物处于液相且催化剂为固体,由此使得通过过滤从反应混合物中提取催化剂。
因此,第四方面,本发明提供本文定义的负载型催化剂在氧化环烷烃、特别用于制备环烷醇和/或环烷酮的方法中作为催化剂、合适地作为非均相催化剂的用途。
制备负载型AuPd催化剂
所述催化剂的金-钯粒子优选根据下文定义的溶胶-固定方法(sol-immobilisation)制备,其中将水溶性聚合物加到金和钯盐的溶液中,随后加入还原剂。所得金-钯粒子作为溶胶获得且随后将其负载在载体上。通常在剧烈搅拌条件下将所述载体作为固体加到所述溶胶中历时高达约3小时。所述负载型催化剂可通过过滤提取,用水洗涤且随后干燥。典型的干燥温度为约120℃,且干燥可进行8-12小时。因此,用于制备本发明催化剂的所述溶胶-固定方法优选包括以下步骤:
(a) 制备金和钯盐的水溶液;
(b) 将水溶性聚合物加到在步骤(a)中获得的溶液中;
(c) 将还原剂加到在步骤(b)中获得的溶液中以形成溶胶;和
(d) 将载体加到在步骤(c)中获得的溶胶溶液中以形成浆料。
制备本发明的负载型催化剂的方法除了上述步骤(a)-(d)外还可包括以下步骤:
(e) 过滤在步骤(d)中获得的所得浆料;
(f) 用水洗涤步骤(e)的产物;和
(e) 干燥步骤(f)的洗涤产物。
可使用任何合适的钯盐,且优选所述钯盐为钯(II)盐,例如PdCl2,其通常用于生产钯催化剂。可使用任何合适的金盐,且优选所述金盐为金(III)盐,例如氯化金(III)、KAuCl4或氯金酸(HAuCl4),氯金酸在本文中以其三水合物HAuCl4.3H2O形式使用。
可使用任何合适的还原剂,且在一个优选的实施方案中,所述还原剂为NaBH4。相对于金的量,所述还原剂优选以摩尔过量提供,且在一个实施方案中,以至少约2:1的摩尔比提供,且在另一实施方案中,以5:1的摩尔比提供。所述还原剂通常以水溶液形式提供,且在一个实施方案中,其作为0.1M水溶液提供。
所述水溶性聚合物优选为聚乙烯醇(PVA)。所述PVA可以部分或完全水解的形式提供,且在一个实施方案中,所述PVA为部分水解的。所述PVA合适地表现出至少约70%的水解度,且在一个实施方案中,在约70-约90%范围内的水解度。在一个优选的实施方案中,所述水溶性聚合物具有约5000-约20,000的分子量,且优选约8,000-约12,000的分子量。所述水溶性聚合物通常以水溶液形式提供,且在一个实施方案中,其作为1重量%水溶液提供。相对于金的量,所述水溶性聚合物优选以重量过量提供,且在一个实施方案中,相对于金的量,其以1.2:1的重量比提供。PVA与所述催化剂(AuPd)的金属物质的比率优选为约0.01:1-约0.1:1。
本发明的掺杂的负载型金-钯催化剂优选使用本文所述的溶胶-固定方法制备,所述方法包括通常在制备溶胶(步骤(c))之后且在加入载体(步骤(d))之前将包含所述掺杂剂的金属离子的盐的溶液(通常为水性溶液)引入所述方法中的另外步骤。金属硝酸盐特别合适,在本文中使用硝酸镁和硝酸铝以分别产生氢氧化镁和氢氧化铝掺杂剂。随后,如本文所述加入所述载体且使用例如氨的任何合适的碱将所述溶液的pH值调节到8-12的值。在剧烈搅拌之后,如上所述,将所述负载型催化剂过滤,洗涤并干燥。
在一个实施方案中,可在干燥之后将所述负载型催化剂煅烧。煅烧可在空气、氮气、氢气、氦气等气氛下进行,且通常在空气气氛下进行。煅烧温度可为200-1000℃,通常为200-700℃。煅烧时间可为约1-约40小时,更通常为约2-约15小时。然而,在一个优选的实施方案中,不将本发明的负载型催化剂(特别是掺杂的负载型催化剂)煅烧,因为虽然选择性可增加,但转化率会减小。
制备所述负载型催化剂的供选方法包括浸渍法、沉淀法和晶种介导的生长,且这些方法可使用上文描述的反应物。
在浸渍法中,制备金和钯盐的水溶液,且将所述载体以所要的重量比加入其中。随后将悬浮液搅拌,过滤并洗涤。如上文对于溶胶-固定方法所述,随后将负载型催化剂干燥,且如上所述随后煅烧。需氧煅烧方法将浸渍的金和钯盐前体还原以提供金-钯粒子。
在沉淀法中,制备金和钯盐的水溶液,在搅拌下向其中加入合适的碱(例如,碳酸钠),直至获得约9-约11的pH。在连续搅拌下加入载体历时高达约3小时,维持pH为9-11。将混合物从室温加热到约70℃,且随后加入合适的还原剂(例如,甲醛)。如上所述,将固体过滤,洗涤并干燥。
氧化环烷烃
本文所述的负载型催化剂特别适合将环烷烃氧化成相应的环烷醇和/或环烷酮。
作为原料的环烷烃的实例包括在环上没有取代基的单环环烷烃,诸如环丙烷、环丁烷、环戊烷、环己烷、环庚烷、环辛烷、环壬烷、环十二烷和环十八烷;多环环烷烃,诸如十氢化萘和金刚烷;和在环上具有取代基的环烷烃,诸如甲基环戊烷和甲基环己烷。可使用环烷烃的混合物,虽然只要可能的话,优选将反应限于单一反应物,从而避免交叉反应并便于目标化合物的分离。本发明对于氧化环己烷或环十二烷,特别是环己烷,具有特别的商业效用。
通常将含氧气体用作氧源。该含氧气体例如可为空气、纯氧或用诸如氮气、氩气或氦气的惰性气体稀释的空气或纯氧。还可使用富氧空气。
基于100重量份环烷烃计,所述负载型催化剂的使用量通常在约0.01-约50重量份范围内,且优选为约0.1-约10重量份。
反应温度通常为至多约200℃,优选为至多180℃,且通常为约50℃-约150℃,且优选为约100℃-约150℃。反应压力通常为约0.01-约10MPa,且优选为约0.1-约2MPa。反应的持续时间通常为至多24小时,且通常在约1-约20小时范围内,优选为1-5小时。可将溶剂用于所述反应,且合适的溶剂包括腈溶剂,诸如乙腈和苄腈,和羧酸溶剂,诸如乙酸和丙酸。在一个优选的实施方案中,所述反应在不存在溶剂的情况下进行。
在所述负载型AuPd催化剂存在下的氧化反应也可在自由基引发剂存在下操作。所述自由基引发剂的实例包括偶氮腈化合物,诸如2,2'-偶氮二(异丁腈)、2,2'-偶氮二(2,4-二甲基戊腈)和2,2'-偶氮二(4-甲氧基-2,4-二甲基戊腈);和过氧化物,诸如TBHP、过氧化二苯甲酰、过氧化二月桂酰、过氧化2-乙基己酸叔丁酯和过氧化二碳酸双(2-乙基己基)酯。引发剂的其他实例包括环己酮、N-羟基邻苯二甲酰亚胺和2-丁酮。这些自由基引发剂中的两种或更多种可组合使用,或者可使用单一自由基引发剂。当使用自由基引发剂时,每摩尔环烷烃中的用量通常为0.1摩尔或更少。然而,商业方法(特别是连续方法)优选不使用这种自由基引发剂,例外之处在于使用对应于目标环烷酮的引发剂。因此,在一个实施方案中,本发明的氧化方法在引发剂存在下操作,所述引发剂为氧化环烷烃原料的目标环烷酮,例如,在原料为环己烷的情况下,可将环己酮作为自由基引发剂加到反应混合物中。作为引发剂的目标环烷酮的加入通常通过使一部分目标环烷酮产物再循环回到反应器中来实现。
氧化反应一旦完成,则可进行常规后处理步骤。因此,通常将反应混合物过滤以分离催化剂,接着用水洗涤并进一步蒸馏。
在连续商业方法中,该氧化反应可使用本领域已知的常规氧化反应器进行。例如,在US-3,957,876、US-3,510,526和US-3,530,185中描述的那些。
通过以下实施例进一步说明本发明。这些实施例并非想要限制如上所述的发明。可以在不偏离本发明的范围的情况下进行细节的改进。
实施例
使用以下通用方法来合成在表1中所列的各催化剂。
制备负载型Au/Pd催化剂(溶胶-固定方法)
制备所要浓度的PdCl2 (Johnson Matthey)和/或HAuCl4-3H2O的水溶液。加入聚乙烯醇(PVA) (1重量%溶液;Aldrich;MW = 10 000;80%水解)(PVA/Au (重量) = 1.2),且随后加入NaBH4(Aldrich,NaBH4/Au (摩尔/摩尔) = 5)的0.1M新鲜制备的溶液以形成深褐色溶胶。在溶胶产生之后30分钟,通过在剧烈搅拌条件下加入所要量的载体而固定胶体。在过滤浆料2小时之后,将催化剂用蒸馏水(中性母液)充分洗涤,且在120℃下干燥过夜。
通过掺杂Mg(OH)
2
或Al(OH)
3
将负载型Au/Pd催化剂表面改性
改性的催化剂通过使用改进的溶胶-固定方法制备。在溶胶中形成Au-Pd纳米粒子之后,将所要量(在本文中,10、40、80或160mg)的硝酸镁或硝酸铝加到溶液中。然后,加入所要量的载体且通过加入氨将溶液的pH值调节到11。在搅拌2小时之后,洗涤滤液并在120℃下干燥过夜。
表1
氧化环己烷
在试验室规模上通过如下所述的方法研究所制备的催化剂在环己烷氧化的氧化中的催化活性。
催化氧化试验使用玻璃实验台反应器(glass bench reactor)进行,将该反应器连接到O2气体的气瓶。在加入环己烷(10mL)且已经将所要量的催化剂加到装置中之后,在140℃和3巴O2下将反应物磁力搅拌17小时。在反应完成之后,将所要量的氯苯作为外标物加到产物中。随后将液态产物注入用于酮、醇、过氧化物、醚和酯定量的具有CP-Wax 42管柱和FID检测器的气相色谱仪(Varian 3200)中。通过过滤收集最终混合物中存在的任何固态反应产物,用环己烷洗涤且随后溶解于已知重量的甲醇中。随后,将10mL产物溶液当中的300μL样品与2mL 14%三氟化硼(BF3)/甲醇混合,随后将其在70℃下加热并磁力搅拌半小时。在酸产物完全转化成相应的甲酯之后,通过加入2mL水终止反应。最后,所形成的酯通过使用已知体积的二氯甲烷从混合物中萃取并将其注入GC中以便定量。结果描述如下。
I:不同载体对AuPd催化剂的活性的影响
在不同载体上的Au基催化剂在环己烷氧化中的催化性能根据上述程序使用6mg催化剂进行测试。在下表2中提供的结果证明,AuPd纳米合金可显示显著的催化活性,但这非常依赖于载体。11%转化率和97%选择性的最佳性能通过使用MgO负载型AuPd获得,其甚至比市售催化剂环烷酸钴的性能好。一些载体如二氧化硅或沸石中止整个反应。在该系列实验中,将MgO负载型AuPd催化剂的性能与AuAg和AuPt纳米合金相比较,AuAg和AuPt纳米合金显示较差的催化性能。
表2
II:Au:Pd比率的影响
进行一系列实验以确定使用MgO作为载体时催化剂中金与钯的最佳摩尔比。结果示于图1中,且证明优选的Au:Pd摩尔比在约1:9-约9:1范围内。
III:催化剂量的影响
在设计成优化MgO负载型催化剂(1% AuPd/MgO)的反应条件的实验中,发现催化量从0增加到6mg产生高选择性且转化率水平增加。然而,令人意外地,进一步增加催化剂的量并不改善催化性能,而是相反地中止整个反应。
因此,当表2中的1号实验使用8mg催化剂再次进行时,未观察到环己烷氧化(0%转化率)。
IV:不同载体对于AuPd催化剂对催化剂剂量的耐受性的影响
使用氧化物、氮化物和碳化物载体研究载体对于AuPd催化剂对催化剂量的耐受性的影响。氧化反应根据上述程序进行,但使用变化量的负载型催化剂。在下表3中提供的结果证明碳化物负载型催化剂对大剂量催化剂表现出优异的耐受性。
表3
V:掺杂Mg(OH)
2
和Al(OH)
3
的碳化物负载型AuPd的催化性能
碳化物负载型AuPd催化剂的催化性能通过将氧化镁或氧化铝引入负载型催化剂中来改善。使用不同量的催化剂时如本文所示进行的环己烷氧化的结果提供在表4中。
表4
VI:掺杂Mg(OH)
2
和Al(OH)
3
的碳化物负载型AuPd催化剂的Au:Pd比率的影响
进行另外的氧化反应以确定Au:Pd比率对掺杂的碳化物负载型AuPd催化剂的影响。结果提供在下表5中。
表5
Claims (16)
1.制备环烷醇和/或环烷酮的氧化方法,其包括使一种或多种环烷烃与氧化剂在负载型催化剂存在下接触,其中所述负载型催化剂包含含有金-钯粒子的催化剂和选自碳化物、氮化物和氧化物的载体,其中所述氧化物选自氧化镁、氧化铝和氧化锌。
2.氧化环烷烃的方法,其包括使一种或多种环烷烃与氧化剂在负载型催化剂存在下接触,其中所述负载型催化剂包含含有金-钯粒子的催化剂和选自碳化物、氮化物和氧化物的载体,其中所述氧化物选自氧化镁、氧化铝和氧化锌。
3.负载型催化剂作为环烷烃氧化的催化剂的用途,其中所述负载型催化剂包含含有金-钯粒子的催化剂和选自碳化物、氮化物和氧化物的载体,其中所述氧化物选自氧化镁、氧化铝和氧化锌。
4.负载型催化剂在氧化环烷烃的方法中的用途,其中所述负载型催化剂包含含有金-钯粒子的催化剂和选自碳化物、氮化物和氧化物的载体,其中所述氧化物选自氧化镁、氧化铝和氧化锌。
5.权利要求1或2的方法或权利要求3或4的用途,其中所述金-钯粒子为表现出至多200nm且在一个实施方案中至多50nm且在另一实施方案中至多30nm的平均最长直径的纳米粒子。
6.权利要求1、2和5中任一项的方法或权利要求3-5中任一项的用途,其中金与钯的摩尔比在约1: 15-约15:1范围内,且在一个实施方案中,在约1:9-约9:1范围内。
7.权利要求1、2、5和6中任一项的方法或权利要求3-6中任一项的用途,其中所述载体选自碳化物和氮化物。
8.权利要求1、2和5-7中任一项的方法或权利要求3-7中任一项的用途,其中所述载体为选自B4C3、Mo2C、ZrC、WC、SiC和TiC的碳化物载体,且在一个实施方案中,为选自B4C3和SiC的碳化物载体,且在另一实施方案中,所述碳化物载体为SiC。
9.权利要求1、2和5-7中任一项的方法或权利要求2-7中任一项的用途,其中所述载体为选自BN、C3N4、AlN和Si3N4的氮化物载体,在一个实施方案中,为选自BN和Si3N4的氮化物载体。
10.权利要求1、2和5-6中任一项的方法或权利要求3-6中任一项的用途,其中所述载体为选自MgO、Al2O3、ZnO和MgAl2O4的氧化物载体。
11.权利要求1、2和5-10中任一项的方法或权利要求3-10中任一项的用途,其中所述AuPd催化剂的装载量基于所述载体和催化剂的总重量计在约0.1-约10重量%范围内。
12.权利要求1、2和5-11中任一项的方法或权利要求3-11中任一项的用途,其中所述负载型AuPd催化剂还包含选自碱性金属氧化物和氢氧化物的掺杂剂,且在一个实施方案中,选自MgO、Al2O3、ZnO、CaO、Mg(OH)2、Al(OH)3、Zn(OH)2和Ca(OH)2的掺杂剂,且在另一实施方案中,选自Mg(OH)2和Al(OH)3的掺杂剂。
13.权利要求1、2和5-12中任一项的方法或权利要求3-12中任一项的用途,其中所述环烷烃为环己烷或环十二烷。
14.权利要求1、2和5-13中任一项的方法,其中所述负载型催化剂的量基于100重量份环烷烃计在约0.01-约10重量份范围内。
15.权利要求1、2和5-14中任一项的方法,其中反应温度为至多200℃,和/或反应压力为0.01-10MPa,和/或反应的持续时间在1-20小时范围内。
16.权利要求1、2和5-15中任一项的方法,其中所述氧化方法在引发剂存在下操作,所述引发剂为所述氧化反应的目标环烷酮。
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CN104499055B (zh) * | 2014-12-19 | 2017-01-18 | 中国科学技术大学先进技术研究院 | 一种有孪晶界的Au75Pd25二十面体纳米晶体及其制备方法和应用 |
CN104525239A (zh) * | 2015-01-09 | 2015-04-22 | 江苏大学 | 一种金钯合金/氮化碳复合纳米材料及其制备方法和用途 |
CN104646046B (zh) * | 2015-03-11 | 2017-08-01 | 湖南大学 | 一种选择性氧化环己烷的方法 |
KR101964275B1 (ko) * | 2015-09-01 | 2019-04-01 | 주식회사 엘지화학 | 아크릴산 제조용 촉매 제조방법 및 이로부터 제조되는 촉매 |
CN108722466A (zh) * | 2018-06-05 | 2018-11-02 | 青岛科技大学 | 一种g-C3N4/ZnO复合空心微球的制备方法 |
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- 2013-02-01 CN CN201380017704.3A patent/CN104350032A/zh active Pending
- 2013-02-01 WO PCT/IB2013/050866 patent/WO2013114330A1/en active Application Filing
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CN108137464A (zh) * | 2016-04-12 | 2018-06-08 | Lg化学株式会社 | 制备丙烯酸的方法 |
CN108137464B (zh) * | 2016-04-12 | 2022-03-18 | Lg化学株式会社 | 制备丙烯酸的方法 |
CN114768801A (zh) * | 2022-04-26 | 2022-07-22 | 海南大学 | 一种负载型钯金合金纳米片催化剂的制备方法及应用 |
CN114768801B (zh) * | 2022-04-26 | 2023-12-01 | 海南大学 | 一种负载型钯金合金纳米片催化剂的制备方法及应用 |
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GB201201866D0 (en) | 2012-03-21 |
WO2013114330A1 (en) | 2013-08-08 |
US20150011797A1 (en) | 2015-01-08 |
EP2852567A1 (en) | 2015-04-01 |
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