CN101678321B - 钯-金催化剂的制备 - Google Patents
钯-金催化剂的制备 Download PDFInfo
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- CN101678321B CN101678321B CN2008800156597A CN200880015659A CN101678321B CN 101678321 B CN101678321 B CN 101678321B CN 2008800156597 A CN2008800156597 A CN 2008800156597A CN 200880015659 A CN200880015659 A CN 200880015659A CN 101678321 B CN101678321 B CN 101678321B
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- palladium
- gold
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- titanium dioxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 48
- 239000010931 gold Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 97
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 23
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 17
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 16
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims abstract description 16
- 150000002940 palladium Chemical class 0.000 claims abstract description 14
- 150000003868 ammonium compounds Chemical class 0.000 claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 34
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 16
- 229910052753 mercury Inorganic materials 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 13
- 238000007598 dipping method Methods 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
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- 239000007789 gas Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
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- 235000011056 potassium acetate Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 239000011148 porous material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 238000009825 accumulation Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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- BHJJZKMIOQKFJK-UHFFFAOYSA-N carbonic acid gold Chemical compound [Au].OC(O)=O BHJJZKMIOQKFJK-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
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Abstract
公开了一种制备负载型钯-金催化剂的方法。所述方法包括：增大二氧化钛载体的孔隙率；用钯盐、金盐和任选的碱金属或铵化合物来浸渍所述载体；和还原所述经煅烧的载体。所制得的负载型钯-金催化剂在乙酰氧基化作用中活性增大。
Description
技术领域
本发明涉及负载型钯-金催化剂。更具体地，本发明涉及在乙酰氧基化作用中具有提高的催化活性和活性稳定性的负载型钯-金催化剂。
发明背景
钯-金催化剂是已知的。将其用于乙酰氧基化作用中。例如，在钯-金催化剂和乙酸的存在下对乙烯进行氧化来制造乙酸乙烯酯，乙酸乙烯酯为聚合物工业的有用单体。
通常使用负载型钯-金催化剂通过气相反应器来进行乙酰氧基化。钯-金催化剂的负载方法也是已知的。通常，所述方法涉及在载体上沉积钯盐和金盐的混合物，然后将钯和金还原成金属。
钯和金两者都是昂贵的贵金属。因此，进行了许多尝试来提高催化活性并降低催化剂的需要量。例如，美国专利号6022823教导了在还原所述金属之前，对浸渍了钯盐和金盐的载体进行煅烧。催化剂显示了提高的活性。
因此，对于化学工业而言，发现更好的方法来提高负载型钯-金催化剂的催化活性仍是非常重要的。理想地，所述催化剂将具有提高的活性并需要更少的贵金属。
发明概述
本发明为制备负载型钯-金催化剂的方法。所述方法包括增大二氧化钛(氧化钛)载体的总孔隙率。例如通过将具有不同粒度的两种二氧化钛载体混合，能够增大二氧化钛载体的孔隙率。然后，用钯盐、金盐和任选地利用碱金属或铵化合物浸渍所述二氧化钛载体。然后还原所述经浸渍的载体，以形成负载型钯-金催化剂。或者，首先对所述经浸溃的载体进行煅烧，然后进行还原，以形成负载型钯-金催化剂。
本发明包括根据本发明方法制备的钯-金催化剂及其在制备乙酸乙烯酯和乙酸烯丙酯的乙酰氧基化中的用途。与本领域中已知的钯-金催化剂相比，根据本发明的方法制备的催化剂在乙酰氧基化作用中显示了提高的催化活性。
发明详述
本发明的方法包括增大二氧化钛(氧化钛)载体的孔隙率。通过总汞压入量能够测量载体的孔隙率。例如，利用三重蒸馏的汞使用Micromeretics AutoPore IV 9500能够测量载体的孔隙率。将试样减压至0.05托并持续5分钟，使用30秒平衡时间在0.5～30000psia下测量压入量。能够使用任何增大二氧化钛孔隙率的方法。在一种方法中，通过混合两种具有不同粒度的二氧化钛来增大二氧化钛载体的孔隙率。在另一种方法中，通过将烧结的二氧化钛与未烧结的二氧化钛进行混合来增大二氧化钛载体的孔隙率。在又一种方法中，通过将喷雾干燥的二氧化钛与未喷雾干燥的二氧化钛进行混合来增大二氧化钛载体的孔隙率。
优选地，通过本发明的方法制造的二氧化钛载体的孔隙率大于或等于0.31mL Hg/g。更优选地，该二氧化钛载体的孔隙率大于或等于0.35mL Hg/g。最优选地，该二氧化钛载体的孔隙率大于或等于0.40mL Hg/g。
任选地，对二氧化钛载体进行煅烧。优选在500℃～900℃、更优选在600℃～800℃、最优选在650℃～750℃的温度下，通过对二氧化钛进行加热来实施煅烧。
用钯盐、金盐和任选的碱金属或铵化合物来浸渍煅烧的或未煅烧的载体。能够使用任意适合的浸渍方法。例如，美国专利号6022823教导了如何浸渍载体。例如，能够用钯盐、金盐和碱金属或铵化合物同时地或相继地处理载体。优选地，在水溶液中实施所述浸渍。通过最终催化剂产品中所期望的钯和金的浓度来控制所使用的溶液浓度和各种溶液的量。
适合的钯盐包括氯化钯、氯亚钯酸钠、硝酸钯、硫酸钯等，和它们的混合物。适合的金盐包括氯化金、四氯金酸、四氯金酸钠等，和它们的混合物。最经常使用四氯金酸钠和氯化钯或氯亚钯酸钠。
适合的碱金属或铵化合物包括碱金属或铵的氢氧化物、碱金属或铵的碳酸盐、碱金属或铵的碳酸氢盐、碱金属或铵的硅酸盐等，和它们的混合物。
用于浸渍载体的一种方法涉及首先用碱金属或铵化合物的水溶液对载体进行处理。然后，将处理过的载体与含钯盐和金盐的水溶液进行接触。
在另一种方法中，在用碱金属或铵化合物的水溶液处理之前，用钯和金的溶液进行浸渍。在这种程序中，载体的吸收性空间基本上完全充满了钯盐和金盐的水溶液。典型地，这通过将溶液滴加到载体上直至达到初始润湿来完成。然后，将浸渍了钯盐和金盐的载体与碱金属或铵化合物接触。
第三种方法涉及在与载体接触之前，将碱金属或铵化合物与贵金属化合物混合。通过将该混合物滴加或喷施到载体上直至初始润湿或通过在溶液中制备粉末状载体的浆料来完成与载体的接触。
优选用水对浸渍的催化剂进行洗涤以除去在浸渍期间形成的碱金属盐如氯化物，并在煅烧之前进行干燥。
对经浸渍的载体进行还原。任选地，在还原之前，对浸渍的载体进行煅烧，即在非还原性气氛中在高温下进行加热。优选地，在使得钯盐和金盐部分分解的条件下进行煅烧。更优选地，在煅烧期间，分解至少10％的钯盐和金盐。
优选地，在约100℃～约600℃的温度下对经浸渍的载体进行煅烧。更优选地，所述温度为100℃～300℃。最优选地，所述温度为150℃～250℃。
用于煅烧的适合的非还原性气体包括惰性气体或氧化性气体，例如氦气、氮气、氩气、氖气、氮氧化物、氧气、空气、二氧化碳等，和它们的混合物。优选地，在氮气、氧气、空气或它们的混合物的气氛中进行煅烧。
钯盐和金盐的分解程度取决于煅烧温度、沉积的盐、以及对经浸渍的载体进行煅烧的时间长短；随后对挥发性分解产物进行监测。例如，当用碳酸钯和碳酸金对载体进行浸渍时，能够测量放出的二氧化碳(CO2)的量。
在任选的煅烧步骤之后，将制得的产物还原以将钯盐和金盐转化成相应的金属。通过在还原剂的存在下进行加热来进行还原。适合的还原剂包括氨、一氧化碳、氢气、烃、烯烃、醛、醇、肼、伯胺、羧酸、羧酸盐、羧酸酯等，和它们的混合物。氢气、乙烯、丙烯、碱性肼和碱性甲醛为优选还原剂，尤其优选乙烯和氢气。
还原所使用的温度为从环境温度至高达约600℃。优选地，还原温度为300℃～600℃。最优选地，还原温度为450℃～550℃。所述还原制得负载型钯-金催化剂。
本发明包括根据本发明的方法制造的负载型钯-金催化剂。优选地，所述负载型钯-金催化剂包含0.1wt％～3wt％的钯、0.1wt％～3wt％的金，且钯与金的重量比为5/1～1/3。更优选地，所述负载型钯-金催化剂包含0.5wt％～1.5wt％的钯和0.25wt％～0.75wt％的金；钯与金的重量比为2.5/1～1/1.5。
根据本发明制造的负载型钯-金催化剂具有许多用途。例如，能够将它们用于部分氧化、加氢、羰基化、氨合成、选择性加氢、乙酰氧基化(acetyloxylation)、催化燃烧或完全氧化、三元催化、NOX的去除、甲醇合成、过氧化氢的合成、加氢甲酰化、烷基化和烷基转移、氧化性羰基化、烯烃与芳烃的偶合，以及用于从丙酮制备甲基异丁基酮。
根据本发明制备的负载型钯-金催化剂对生产乙酸乙烯酯和乙酸烯丙酯特别有用。已知多种生产乙酸乙烯酯和乙酸烯丙酯的方法。例如，美国专利号3743607和3775342教导了如何使用钯-金催化剂来制备乙酸乙烯酯。
对于在生产乙酸乙烯酯和乙酸烯丙酯中的用途，优选用钾化合物如乙酸钾对负载型钯-金催化剂进行处理。通过将该催化剂与乙酸钾溶液混合、过滤、以及对处理过的催化剂进行干燥来完成所述钾处理。
通常，通过在乙酸和所述负载型钯-金催化剂的存在下对乙烯进行氧化来制备乙酸乙烯酯。通过类似方式但使用丙烯而不是乙烯来制备乙酸烯丙酯。
令人惊奇地发现，根据本发明制备的催化剂不仅给出高催化活性，而且还给出高活性稳定性。在现有技术的钯-金催化剂中存在的一个问题是催化剂随时间而丧失活性。本发明提供了解决上述问题的方案。例如通过乙酸乙烯酯的氧得率能够测量催化活性。根据本发明制备的催化剂对乙酸乙烯酯的氧得率在开工100小时时测量优选大于或等于35％，更优选大于或等于37％，最优选大于或等于40％。
下列实施例仅用于说明本发明。本领域中的技术人员应承认，在本发明主旨和权利要求书的范围内具有许多变体。
挤出物制备
通过将400g二氧化钛粉末(Millennium Chemicals DT51)与8.2g粘合剂(所述粘合剂在下列实施例中指明)混合来制备干燥的混合物，然后，在温和搅拌下添加5.5g的增塑剂(聚环氧乙烷)、217g的水和16g的浓氢氧化铵，形成松散、干燥的混合物。将所使用组分的重量和相对值都列于表1中。然后，将该混合物添加至Thermo HaakeRheomix 3000混合器(内容积为625ml)中并使用∑形桨叶进行混合。所述桨叶通过Thermo Haake Rheocord 300p驱动装置以逆时针旋转的方式在50转/分钟(rpm)下旋转超过30分钟时间，以由原始组分生产混合良好的糊剂。
表1浆料组成
| 组分 | 质量，g | 相对量，wt％ |
| 二氧化钛粉末 | 400 | 61.9 |
| 水 | 217 | 33.6 |
| 增塑剂 | 5.5 | 0.9 |
| 粘合剂 | 8.2 | 1.3 |
| 浓氢氧化铵 | 16 | 2.5 |
从混料碗中移出糊剂并在密封塑料袋中老化24小时，以使得糊剂均匀化且粘合剂完全水合。然后，使用具有Rheocord 300p驱动装置的Thermo Haake Rheomex 202p将所述糊剂挤成1/8″的圆柱体。在室温下，对所述挤出物干燥至少24小时，然后在105℃下干燥至少16小时。在700℃下煅烧所述挤出物，使用的升温速率为：从室温至500℃为1℃/分钟，在500℃下保持1小时，然后在10℃/分钟下从500℃升至700℃，并在700℃下保持6小时。
压汞法
用三重蒸馏的汞使用Micromeretics AutoPore IV 9500来测量载体的孔隙率。将试样减压至0.05托并持续5分钟，并使用30秒的平衡时间从0.5至30000psia测量压入量。总的累积压入量报告于表2中。
催化剂制备
将NaAuCl4(0.987克)、Na2PdCl4(2.645克)和NaHCO3(2.760克)溶于水(33ml)中。使用一次性移液管将所述溶液施加至二氧化钛挤出物(100克)上，同时在旋转盘上滚动所述挤出物直至所有可利用的挤出物孔容积被填满。然后，使所述挤出物滚动30分钟，然后使用热空***在80～85℃下干燥表面1小时。在烘箱中于105℃下干燥该混合物至少16小时，然后用去离子水进行充分洗涤以除去氯化物。
在反应器中，在70psig的流动空气中于200℃下煅烧上述经浸渍的二氧化钛3小时，以使得沉积的贵金属盐部分分解，分解量超过10％。
在上述煅烧之后，用氮气吹扫反应器，然后向容器中导入70psig下的20％氢气在氮气中的混合物。以10℃/分钟的速度将温度升至500℃。温度在500℃下保持三小时。用氮气吹扫反应器，并在流动的氮气中将制得的催化剂冷却至室温。
在室温下，将25g制得的催化剂与5w％乙酸钾和0.5％氢氧化钾的过量(＞50ml)水溶液接触10分钟。倾析所述混合物，在烘箱中于105℃下干燥该经钾处理的催化剂至少4小时。
催化剂测试
使用填充床活塞流管式(标称外径为1英寸，不锈钢)反应器针对乙酸乙烯酯的生产来评价催化剂。所述床的体积为30ml，并用惰性氧化铝对催化剂进行稀释，氧化铝与催化剂挤出物的比例为2.5∶1。反应器压力为80psig，相对于所使用的催化剂的空速在0℃和1atm压力下为3800/小时，组成为84.7％的乙烯、9.9％的乙酸、3.8％的氧气和1.6％的氮气。反应器冷却剂的温度为130℃。乙酸乙烯酯的氧得率报告于表2中。
对比例1～3
对比例1～3使用制备负载型钯-金催化剂的常规方法。用于这些对比例中的二氧化钛载体具有相对小的孔隙率，所述孔隙率通过压汞体积测量。
对比例1
使用羧甲基纤维素钠作为粘合剂。按如上所述制备挤出物和催化剂。将通过压汞法测量而得到的孔隙率和通过开工100小时时乙酸乙烯酯的氧得率而测量的催化剂性能列于表2中。
对比例2
使用羧甲基纤维素作为粘合剂。按如上所述制备挤出物和催化剂。将通过压汞法测量而得到的孔隙率和通过开工100小时时乙酸乙烯酯的氧得率而测量的催化剂性能列于表2中。
对比例3
使用甲基纤维素作为粘合剂。按如上所述制备挤出物和催化剂。将通过压汞法测量而得到的孔隙率和通过开工100小时时乙酸乙烯酯的氧得率而测量的催化剂性能列于表2中。
实施例4～8
实施例4～8用于说明本发明。在这些实施例中，使用多种方式来提高载体的孔隙率。制备的负载型钯-金催化剂孔隙率增大，且通过乙酸乙烯酯的氧得率而测量的性能提升。
实施例4
使用羧甲基纤维素作为粘合剂。按如上所述制备挤出物和催化剂，不同之处在于用400g颜料级二氧化钛(源自Millennium Chemicals的AT1)代替300g的DT51超细二氧化钛。所使用水的总量也从217g减至166g。实施例4与对比例2的比较表明，颜料级二氧化钛的使用增大了通过总汞压入量测量的总的孔容积。负载在该载体上的钯-金催化剂显示了提高的性能，所述性能通过开工100小时时乙酸乙烯酯的氧得率测量。
实施例5
使用甲基纤维素作为粘合剂。按如上所述制备挤出物和催化剂，不同之处在于将400g总的二氧化钛粉末中的100g替换成已经在850℃下烧结了6小时的二氧化钛粉末。所使用水的总量也从217g减至160g。表2显示，使用预烧结的二氧化钛增大了通过总汞压入量测量的总孔容积。负载在该载体上的钯-金催化剂显示了提高的性能，所述性能通过开工100小时时乙酸乙烯酯的氧得率测量。
实施例6
按如上所述制备挤出物和催化剂，不同之处在于将400g总的二氧化钛粉末中的100g替换成已经在900℃下烧结了6小时的二氧化钛粉末。表2显示，使用预烧结的二氧化钛增大了通过总汞压入量测量的总孔容积。负载在该载体上的钯-金催化剂显示了提高的性能，所述性能通过开工100小时时乙酸乙烯酯的氧得率测量。
实施例7
使用羧甲基纤维素作为粘合剂。按如上所述制备挤出物和催化剂，不同之处在于将400g总的二氧化钛粉末中的100g替换成喷雾干燥的二氧化钛粉末。在3英尺直径的喷雾干燥器中对二氧化钛在水的浆料进行喷雾干燥。进口温度为220℃，出口温度为90℃，旋转速度为27000rpm。使用在旋风分离器处收集的粒度为10～20微米的那部分。所使用水的总量也从217g减至183g。表2显示，使用喷雾干燥的二氧化钛增大了通过总汞压入量测量的总孔容积。负载在该载体上的钯-金催化剂显示了提高的性能，所述性能通过开工100小时时乙酸乙烯酯的氧得率测量。
实施例8
按如上所述制备挤出物和催化剂，不同之处在于将400g总的二氧化钛粉末中的100g替换成已经在825℃下烧结了6小时的二氧化钛粉末。表2显示，使用预烧结的二氧化钛增大了通过总汞压入量测量的总孔容积。负载在该载体上的钯-金催化剂显示了提高的性能，所述性能通过开工100小时时乙酸乙烯酯的氧得率测量。
表2汞压入量和催化剂性能
| 实施例编号 | 总的汞压入体积ml/g | 在VAM生产中在100小时时的催化剂性能，乙酸乙烯酯的氧得率，％ |
| C1 | 0.264 | 31.8 |
| C2 | 0.304 | 28.3 |
| C3 | 0.304 | 34.2 |
| 4 | 0.311 | 37.4 |
| 5 | 0.370 | 37.1 |
| 6 | 0.385 | 39.5 |
| 7 | 0.387 | 41.4 |
| 8 | 0.427 | 43.5 |
Claims (14)
1.制备负载型钯-金催化剂的方法，所述方法包括
(a)用钯盐、金盐和任选的碱金属或铵化合物浸渍二氧化钛载体，其中所述二氧化钛载体是喷雾干燥的二氧化钛和非喷雾干燥的二氧化钛的混合物或烧结的二氧化钛和非烧结的二氧化钛的混合物和总压入体积大于或等于0.40ml汞/g；和
(b)还原所述经浸渍的载体，以形成所述负载型钯-金催化剂，所述负载型钯-金催化剂包含0.5-1.5wt％的钯和0.25-0.75wt％的金，和钯与金的重量比为2.5/1-1/1.5。
2.权利要求1的方法，其中所述碱金属或铵化合物选自氢氧化物、碳酸盐、碳酸氢盐、硅酸盐和它们的混合物。
3.权利要求1的方法，其中所述碱金属或铵化合物为碳酸盐或碳酸氢盐。
4.权利要求1的方法，其中所述钯盐选自氯化钯、氯亚钯酸钠、硝酸钯和硫酸钯；且所述金盐选自氯化金、四氯金酸、四氯金酸钠和它们的混合物。
5.权利要求1的方法，其中所述经浸渍的二氧化钛在它被还原之前被煅烧。
6.权利要求5的方法，其中所述煅烧在100℃至600℃范围内的温度下在非还原性气氛中进行。
7.权利要求6的方法，其中所述非还原性气氛选自氦气、氮气、氩气、氖气、氮氧化物、氧气、空气、二氧化碳和它们的混合物。
8.权利要求7的方法，其中所述煅烧温度在100℃至300℃的范围内。
9.权利要求5的方法，其中所述还原在氢气的存在下进行。
10.权利要求9的方法，其中所述还原在300℃至600℃的范围内的温度下进行。
11.权利要求9的方法，其中所述还原在450℃至550℃的范围内的温度下进行。
12.权利要求5的方法，还包括用钾盐处理所述负载型钯-金催化剂。
13.通过权利要求1的方法制备的负载型钯-金催化剂。
14.制备乙酸乙烯酯的方法，包括在乙酸和权利要求13的负载型钯-金催化剂的存在下对乙烯进行氧化。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/801,935 US7811968B2 (en) | 2007-05-11 | 2007-05-11 | Preparation of palladium-gold catalysts |
| US11/801,935 | 2007-05-11 | ||
| PCT/US2008/004381 WO2008140658A1 (en) | 2007-05-11 | 2008-04-04 | Preparation of palladium-gold catalysts |
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| Publication Number | Publication Date |
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| CN101678321A CN101678321A (zh) | 2010-03-24 |
| CN101678321B true CN101678321B (zh) | 2012-09-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008800156597A Expired - Fee Related CN101678321B (zh) | 2007-05-11 | 2008-04-04 | 钯-金催化剂的制备 |
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| Country | Link |
|---|---|
| US (1) | US7811968B2 (zh) |
| EP (1) | EP2152407A1 (zh) |
| CN (1) | CN101678321B (zh) |
| BR (1) | BRPI0811132A2 (zh) |
| CA (1) | CA2683952A1 (zh) |
| RU (1) | RU2457903C2 (zh) |
| WO (1) | WO2008140658A1 (zh) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100121100A1 (en) * | 2008-11-12 | 2010-05-13 | Daniel Travis Shay | Supported palladium-gold catalysts and preparation of vinyl acetate therewith |
| US8507720B2 (en) * | 2010-01-29 | 2013-08-13 | Lyondell Chemical Technology, L.P. | Titania-alumina supported palladium catalyst |
| JP2013514174A (ja) | 2009-12-16 | 2013-04-25 | ライオンデル ケミカル テクノロジー、 エル．ピー． | チタニア含有押出し品 |
| US8329611B2 (en) | 2009-12-16 | 2012-12-11 | Lyondell Chemical Technology, L,P. | Titania-containing extrudate |
| SG183159A1 (en) | 2009-12-16 | 2012-09-27 | Lyondell Chemical Tech Lp | Titania-alumina supported palladium catalyst |
| US8273682B2 (en) * | 2009-12-16 | 2012-09-25 | Lyondell Chemical Technology, L.P. | Preparation of palladium-gold catalyst |
| US20110306748A1 (en) | 2010-06-11 | 2011-12-15 | Daniel Travis Shay | Titania-alumina-tungsta extrudate and its use |
| US8822717B2 (en) * | 2010-11-24 | 2014-09-02 | LyondellBassell Acetyls, LLC | Vinyl acetate production process |
| GB201908844D0 (en) * | 2019-06-20 | 2019-08-07 | Johnson Matthey Plc | Gold containing catalyst, method of preparation and use |
| CN111569874B (zh) * | 2020-05-28 | 2023-02-17 | 台州学院 | 一种活性炭-钯金镓液态合金复合催化剂及其制备方法和应用 |
| CN111530449B (zh) | 2020-06-09 | 2021-08-10 | 江苏龙净科杰环保技术有限公司 | 一种烟气壁流式除尘低温脱硝蜂窝式催化剂及其制备工艺 |
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| CN1345256A (zh) * | 1999-03-27 | 2002-04-17 | 人造丝化学欧洲有限公司 | 乙烯和乙酸气相氧化为乙酸乙烯酯所用催化剂及其制法和用途 |
| US6821922B1 (en) * | 1998-09-24 | 2004-11-23 | Degussa - Huls Ag | Supported catalyst for the production of vinyl acetate monomer |
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| US3380934A (en) * | 1966-10-20 | 1968-04-30 | Exxon Research Engineering Co | Noble metal catalysts and their production |
| CH534005A (de) | 1968-02-01 | 1973-02-28 | Bayer Ag | Verfahren zur Herstellung eines Palladium und Gold enthaltenden Katalysators |
| SA97180048B1 (ar) * | 1996-05-24 | 2005-12-21 | هوكست سيلانس كوربوريشن | محفز بلاديوم - ذهب palladium gold ثنائي المعدن متغاير الخواص heterogeneous bimetallic vinyl acetate لإنتاج أسيتات فينيل |
| DE69708880T2 (de) * | 1996-07-01 | 2002-04-11 | Dow Chemical Co | Verfahren zur direkten oxidation von olefinen zu olefinoxiden |
| US6207128B1 (en) * | 1997-05-05 | 2001-03-27 | Akzo Nobel N.V. | Method of producing a catalyst |
| DK1017477T3 (da) * | 1997-09-09 | 2001-08-06 | Aea Technology Plc | Behandling af afgasser |
| GB9810928D0 (en) * | 1998-05-22 | 1998-07-22 | Bp Chem Int Ltd | Catalyst and process |
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| US6358882B1 (en) * | 1998-12-08 | 2002-03-19 | The Standard Oil Company | Fluid bed vinyl acetate catalyst |
| US6797669B2 (en) * | 2000-12-29 | 2004-09-28 | China Petroleum & Chemical Corporation | Catalyst for selective hydrogenation, its preparation process and application |
| US7541012B2 (en) * | 2004-07-07 | 2009-06-02 | The Hong Kong University Of Science And Technology | Catalytic material and method of production thereof |
| US7521393B2 (en) * | 2004-07-27 | 2009-04-21 | Süd-Chemie Inc | Selective hydrogenation catalyst designed for raw gas feed streams |
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2007
- 2007-05-11 US US11/801,935 patent/US7811968B2/en not_active Expired - Fee Related
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2008
- 2008-04-04 RU RU2009141301/04A patent/RU2457903C2/ru not_active IP Right Cessation
- 2008-04-04 EP EP08727280A patent/EP2152407A1/en not_active Withdrawn
- 2008-04-04 WO PCT/US2008/004381 patent/WO2008140658A1/en active Application Filing
- 2008-04-04 CA CA002683952A patent/CA2683952A1/en not_active Abandoned
- 2008-04-04 BR BRPI0811132-4A2A patent/BRPI0811132A2/pt not_active IP Right Cessation
- 2008-04-04 CN CN2008800156597A patent/CN101678321B/zh not_active Expired - Fee Related
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| US6022823A (en) * | 1995-11-07 | 2000-02-08 | Millennium Petrochemicals, Inc. | Process for the production of supported palladium-gold catalysts |
| US6821922B1 (en) * | 1998-09-24 | 2004-11-23 | Degussa - Huls Ag | Supported catalyst for the production of vinyl acetate monomer |
| CN1345256A (zh) * | 1999-03-27 | 2002-04-17 | 人造丝化学欧洲有限公司 | 乙烯和乙酸气相氧化为乙酸乙烯酯所用催化剂及其制法和用途 |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20080281122A1 (en) | 2008-11-13 |
| CA2683952A1 (en) | 2008-11-20 |
| WO2008140658A1 (en) | 2008-11-20 |
| EP2152407A1 (en) | 2010-02-17 |
| BRPI0811132A2 (pt) | 2014-12-23 |
| RU2457903C2 (ru) | 2012-08-10 |
| RU2009141301A (ru) | 2011-06-20 |
| US7811968B2 (en) | 2010-10-12 |
| CN101678321A (zh) | 2010-03-24 |
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