CN1205244A - 加氢催化剂 - Google Patents
加氢催化剂 Download PDFInfo
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- CN1205244A CN1205244A CN98109754A CN98109754A CN1205244A CN 1205244 A CN1205244 A CN 1205244A CN 98109754 A CN98109754 A CN 98109754A CN 98109754 A CN98109754 A CN 98109754A CN 1205244 A CN1205244 A CN 1205244A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 10
- 239000003610 charcoal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
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- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229940005654 nitrite ion Drugs 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 11
- 150000002941 palladium compounds Chemical class 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
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- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- VCZNNAKNUVJVGX-UHFFFAOYSA-N 4-methylbenzonitrile Chemical compound CC1=CC=C(C#N)C=C1 VCZNNAKNUVJVGX-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
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- 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 description 5
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- MGMNPSAERQZUIM-UHFFFAOYSA-N 2-(hydroxymethyl)benzoic acid Chemical compound OCC1=CC=CC=C1C(O)=O MGMNPSAERQZUIM-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
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- 238000007654 immersion Methods 0.000 description 2
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- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WWYFPDXEIFBNKE-UHFFFAOYSA-N 4-(hydroxymethyl)benzoic acid Chemical compound OCC1=CC=C(C(O)=O)C=C1 WWYFPDXEIFBNKE-UHFFFAOYSA-N 0.000 description 1
- -1 4-carboxyl benzylidene aldehyde Chemical class 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- 230000008676 import Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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Abstract
加氢催化剂包括载持在活性炭上的金属钯,其中小于50%Pd(wt)位于达50μm深度的表面层内,而其余的Pd位于50—400μm深的一层内。催化剂可特别用于通过对二甲苯的氧化反应制备的粗对苯二甲酸的纯化。
Description
本发明涉及加氢催化剂,所述催化剂包括载在活性炭上的金属钯,本发明涉及及催化剂的制备方法和在加氢反应中的应用。
具体地说,本发明涉及催化剂在从包括4-羧基亚苄基醛(4-CBA)的杂质中纯化对苯二甲酸的应用。
包括载在活性炭上的金属钯的加氢催化剂在文献中是已知的。它们是通过将一钯化合物吸附在活性炭上,然后还原吸附的化合物成金属钯来制备。
由美国专利3138560号已知,如果从四氯钯酸钠或氯化钯的溶液中吸附钯,那么许多钯立即被还原并以生成钯金属薄膜沉积在表面上。
这样制备的催化剂几乎没有活性。钯还原成金属钯是因为存在在活性炭的表面上的官能团例如醛基的缘故。
为了避免这种还原反应,已经使用含氧化剂例如过氧化氢的钯化合物溶液。
为了使沉积在活性炭表面上的钯结晶有较小的粒径(如果可能小于35_),已经使用钯化合物有机溶剂的溶液(美国专利4476242)。在这种情况下,所有的钯都集中在厚度小于70-80μm处的一层。
如果是从四硝基钯酸钠的水溶液中沉积钯,得到了与上述相似的结果(美国专利4421676)。
根据传统的方法,催化剂是通过用水洗涤活性炭除去其粉末来制备;因此所处理的炭被分散在水中,可为相应于水的碱度,然后钯盐的水溶液逐滴加入活性炭。
对二甲苯氧化制备的对苯二甲酸中的杂质主要是由对甲苯甲酸和4-CBA构成。
当通过含对甲苯甲酸的对苯二甲酸溶液的冷却和结晶可除去对甲苯甲酸时,而除去4-CBA要求通过还原转化成通过结晶可被分离的化合物。
这种转换是通过在活性炭载体上的在钯催化剂上加氢来进行。
为了把4-CBA的浓度降低到对苯二甲酸用户可接受的值和将上述4-CBA转换成通过结晶可分离的化合物,催化剂要有高的活性和选择性。
人们已经意外地发现,如果钯化合物是干浸在活性炭载体上,包括载持在活性炭上的钯催化剂的活性和选择性都可以明显地提高,优选从所使用的量等于或小于活性孔体积的浓的水溶液中吸附钯化合物。
载持优选通过把钯化合物液喷洒在活性炭上浸渍,所使用的溶液量优选等于活性炭孔体积的1/2-1/5(孔体积是通过用于载持的活性炭的重量乘以炭的孔隙率测定)。
按照这种方法操作,小于50%的钯金属包括在直到50μm的深度的一层;其余的钯金属包括在50-400μm深度的一层。
钯的分布用X-射线电子微探针分析(EMPA)测定。
可以使用的钯化合物是各种钯化合物。实例是卤化物、双乙酸盐,硝酸盐、氯铂酸的碱式盐、Pd氨的配合物和盐类如四硝基钯酸钠(Na2Pd(NO2)4)。
优选使用的化合物是易溶于水的化合物,例如四氯钯酸钠。在这种情况下,所使用的钯盐的浓度等于1-10%(wt)。
在其它的情况下,钯化合物的浓度优选等于在室温下测量的它的饱和浓度的50-100%。
使用已知类型的装置,每100g载体以0.1-1ml溶液/分的速率喷洒钯化合物溶液。
喷洒优选在室温下进行。如果温度升高,干燥速率加快,可以生成细的分散相;但是钯自发的还原速率也增加,在载体表面上可能形成钯金属不希望的薄膜。
在喷洒后,钯化合物溶液浸渍的载体,其中载持的钯可以已经部分为钯金属态,用已知种类的还原剂处理,通常将钯还原成金属钯,以便钯完全还原。
可以使用甲醛、次磷酸钠、葡萄糖和其它的化合物。还可以使用氢气,只要还原反应是在室温或稍高的温度(使用高温导致结晶不希望粒晶的增加)下进行。
使用8-10%浓度的次磷酸盐溶液便利,使用的溶液体积小于孔体积。然后催化剂从溶液中排出,洗涤和干燥。
制备催化剂所使用的活性炭可以是源自动物或植物。优选椰子炭。炭的表面积优选大于600m2/g(BET),可达1000m2/g或更高。孔隙率(BET)为0.3-0.9cm3/g。优选使用粒状的炭,粒径一般为2-15目之间;但是可以使用小片状、丸状或其它粒状的活性炭。
用于空气流和/或筛分排除粉末状的炭(细粉)。
在喷洒Pd化合物溶液前,活性炭优选用含1-5重量%的浓HCL的酸性水溶液进行预处理。喷洒在活性炭上的溶液量等于或小于孔体积。
用酸溶液处理提高了催化剂的酸性。
固定在活性炭上的Pd量一般为0.1-5%(wt);在催化剂用于纯化对苯二甲酸的情况下,优选为0.2-0.6%(wt),更优选为0.3-0.5%(wt)。除Pd外,其它的金属例如Rh或Cu可以存在。使用本发明的催化剂纯化粗对苯二甲酸是通过将上述酸悬浮在水中加热来进行,在100℃和300℃度温度间操作,并且氢气压力为约15-100巴。
催化剂也可用于纯化除去饮水中的硝酸盐和/或亚硝酸盐离子及有机氯化物(例如三氯乙烷)。在这种情况下,除Pd外,催化剂也优选包括Cu,而Pd/Cu为2∶1-20∶1。
在硝酸盐的情况下,方法是室温下进行,使水和氢气流流过催化剂的固定床、而在氯化物的情况下,方法是在15℃和150℃间的温度下进行。
根据本发明方法得到的催化剂的特征是Pd金属结晶分布在活性炭颗粒的表面上,结果50%以下的Pd包含在50μm的层内,而其余的Pd是分布在50-400μm深度。
称为Pd金属的Pd结晶的表面积大于150m2/gPd,并且可以高到300m2/g或更高;关于催化剂,表面积大于0.8m2/g,可以达到1.5-2m2/g。
Pd的表面积是由CO的化学吸附数据得到的;而催化剂的表面积是用BET法测定的。
结晶纵向尺寸的平均值一般小于100_:在某些情况下(特别是通过喷洒制备的催化剂)可以减少到小于50_或甚至小于35_(35_是通过X-射线测量结晶尺寸不能够测定的下限)。结晶的平均尺寸是由X-射线衍射数据测定。平均尺寸小于35_的结晶的百分数是通过催化剂上的Pd浓度(用化学方法测定)和尺寸大于35_的结晶百分数的浓度间的差来计算。
本发明催化剂的进一步特征是催化剂的CO的化学吸附值为0.2ml CO/g催化剂,并且可达到0.5ml CO/g催化剂;Pd的化学吸附值大于50ml/gPd,可以达到100ml/gPd。
CO的化学吸附值是通过把已知体积的CO加到样品来测量。
加入的CO直到样品被其饱和为止,不能再化学吸附,和释放出相应加入CO体积的CO的恒定的体积。
测量是室温下进行;约6g的干催化剂加入-U型的设置进、出口阀的样品容器。
分析前,样品用氢气在室温下处理,以便还原在干燥期间被氧化的Pd,和排除任何痕量的氧,痕量的氧会使CO转化成CO2。
然后样品用氢气清洗,排除任何痕量的氢。
然后在惰气流(He)下加入已知体积的CO(用已知体积的回路装置测量):用热导池测量吸附的体积。
有关化学吸附的色谱有各种不同的峰:每一峰值与加入样品的CO有关。
催化活性(按标准的4-CBA加氢试验测量,以4-CBA的浓度的对数与反应时间(分)的函数关系绘图得到的直线的斜率表示)大于0.05,可达到0.08。以斜率与Pd重量(g)之间的比表示大于10,可达到20。在反应45分钟后的4-CBA的转化率大于90%,可达到99%。
加氢反应是在设置螺旋浆搅拌器和线网催化剂贮留器的反应釜中进行。
当反应条件达到时(200℃),自动阀使催化剂贮留器浸入反应溶液。反应釜有一提升器,通过提升器,样品按有规则的间隔取出。
在一个上升的位置,将含500ppm的4-CBA的1.5l的水溶液加入反应釜,并将0.750g催化剂输入贮留器。
反应釜关闭后,首先用氩气洗涤,排除所有痕量的氧,然后用氮气清洗。在开始和加热前,充入18巴的氢气。
一旦已经达到操作温度(200℃),但是在贮留器浸入溶液前,取出样品,作为反应时间为零的样品。
然后,按5、10、15、20、30、45、60和90分钟时间,相继的取出样品。为测定4-CBA的残留量,和生成的羟甲基苯甲酸和对甲苯甲酸,所有样品都通过HPLC分析。
除了高的活性外,本发明的催化剂的特征是在4-CBA还原成对甲苯甲酸和羟甲基苯甲酸方面有相当高的选择性(举例来说,按上述的试验操作45分钟后,上述的酸生成为200-300ppm)。
例如,使用美国专利4476242号的已知类型的催化剂,和上述的试验条件,用4-CBA浓度的对数与反应时间(分)的函数关系绘制的线得到的斜率小于0.04。对甲苯甲酸和p-羟甲基苯甲酸的浓度小于100ppm。
下述的实施例是用于说明本发明,而不是限制本发明。实施例1
薄片状的椰子炭500g,表面积(BET)为1100m2/g,孔隙率(BET)为0.68cm3/g和粒径4-8目,通过适度的筛分和氮气吹洗除出细粉末,装入设置无级变速马达的一容器,使所述容器以24转/分旋转。
含7.1gNa2PdCL4的水溶液40ml,用HD调PH值为0-1,并加入35%(wt)的H2O26ml,在20分钟内,喷洒在活性炭上,容器继续旋转。
浸渍在室温下进行,和上述容器转动。
在喷洒过程结束后,保持其原有外观的活性炭用含25g的Na2H2PO2H2O的水溶液300ml处理。
排出催化剂,洗涤并在120℃干燥。
钯载持量为0.413%(wt)。
催化剂的其它特征和按上述标准测定的还原4-CBA的活性列如表中。实施例2
重复实施例1的制备方法,不同的只是通过活性炭浸渍在加入300ml氯钯酸钠溶液的容器中进行。
成品催化剂中Pd的载持量为0.464%(wt)。
催化剂的特征和活性示于表中。对比例1
重复实施例2的试验,不同的只是活性炭用水冲洗除粉末后用600ml的Pd盐溶液浸渍。在加入5分钟后,溶液无色载体有金属外观。
通过加入含25g次磷酸钠的溶液50ml完成还原反应。
成品催化剂的Pd载持量为0.474%(wt)。
催化的其它特征和按上述试验标准的活性示于表中。实施例3
重复实施例1的制备方法,不同的只是已经排除活性炭粉末的活性炭与实施例1不同,本例的活性炭在用Pd盐溶液浸渍前,用HD水溶液进行预处理。用HD溶液进行预处理的方法与浸渍使用的方法相同,也就是说,将HD溶液(含3.5%HD(wt)100ml)喷洒在连续转动的容器中的活性炭上。
催化剂的特征列于表中。
在催化剂一些颗粒上进行X-射线电子微探针分析。这种方法(EMPA)在于是检测初级的X-射线照射,通常是检测一种元素,在样品中用电子进行轰击。
利用EDX(或EDS,能量分散光谱仪)方法,可以快速地评价构成所检测样品的元素,得到组成图。但是,这种系统的分辨力太低(150ev)所颁布的元素浓度的信息不可靠。
为了得到定量的信息,必须有更高的分辨力,通过使用WDX(或WDS,波长分散光谱仪)方法可达到此目的。在这种情况下,用这种系统,人们得到非常高的分辨力(10ev)和Pd的百分数与所得到的部分表面上的光束的位置的关系绘制的定量图。
在这种情况下,在每一测量后,通过电子束的调整移动,借助计算机,逐点得到沿扫描区域的轴的所有的定量分析数据。
沿粒子的整个厚度的线的Pd的L2射线的剖面图表明Pd位于约350μm深的一层内,而小于50%Pd,位于50μm的一层深处。实施例4和5
重复实施例3,不同的只是实施例4中喷洒7%CL(wt)的溶液100ml,而在实施例5中喷洒1.75%CL(wt)溶液200ml。
催化剂中的特征列于表中。对比例2
按美国专利4476241号实例C制备催化剂。
实施例1中所使用的薄片状的活性炭12g用甲醇冲洗除去粉末。倾析出甲醇,活性炭转移到300ml三颈烧瓶中,然后悬浮在40ml甲醇中。用浸没在液体上层(没有与固体接触)的搅拌器浆叶搅拌分散体系。
进行冷却到5℃逐滴加入含0.072g Pd(NO3)2的甲醇溶液50ml,继续搅拌21小时。
然后加入水,洗涤催化剂,在60℃干燥。
在催化剂上载持的Pd量为0.17%(wt)。催化剂有金属外观(表明Pd的分散度差)。
催化剂的特征列于表。
如上述实施例3的电子微探针分析表明所有的Pd都位于在60-70μm深的一层内。表
催化剂实施例 | pdwt% | CO化学吸附值(mL CO/g催化剂) | 结晶_ | pd结晶表面积 | 活性斜率 | 斜率/pd | 45分钟时的4-CBA转化率% |
实施例1 | 0.413 | 0.34 | 53 | 339 | 0.065 | 15.74 | 94.4 |
实施例2 | 0.464 | 0.275 | 105 | 244 | -------- | --------- | --------- |
实施例3 | 0.498 | 0.36 | 34 | 296 | 0.073 | 4.66 | 96.7 |
实施例4 | 0.486 | 0.2 | 68 | 168 | 0.0572 | 11.77 | 92.9 |
实施例5 | 0.485 | 0.31 | 44 | 264 | 0.0678 | 13.98 | 95.2 |
对比例1 | 0.474 | 0.17 | 87 | 148 | 0.0409 | 8.63 | 84.9 |
对比例2 | 0.17 | 0.04 | 76 | 97 | 0.0395 | 23.24 | 83.2 |
Claims (16)
1.加氢催化剂,包括载在活性炭上的钯金属,其中小于50%Pd(wt)包括在达50μm深的一表面层内,其余的位于在50-400μm深度的一层内。
2.按权利要求1的催化剂,能够化学吸附CO的量大于0.2mlCO/g催化剂。
3.按权利要求1和2的催化剂,其中固定在活性炭上的CO的化学吸附值大于50ml CO/gPd。
4.按权利要求1的催化剂,其中Pd载持量为0.1和5%(wt)之间。
5.按权利要求2和3的催化剂,其中Pd载持量为0.2-0.6%(wt)。
6.按权利要求2和3的催化剂,其中Pd的表面积为150-300m2/g之间。
7.按权利要求1的催化剂,除Pd之外,还包括选自Rh和Cu中的金属。
8.按权利要求2和3的催化剂,其中Pd结晶的平均粒径为小于100A°。
9.按权利要求2和3的催化剂,其中Pd结晶的平均粒径小于50A°。
10.按前述权利要求的催化剂,其中活性炭是植物炭,表面积小于600m2/g。
11.制备前述权利要求催化剂的方法,其中把Pd化合物的一种水溶液干浸在活性炭上,所利用的溶液量等于或小于活性炭的孔体积。
12.按权利要求11的方法,其中浸渍是通过喷洒来进行。
13.按权利要求11和12的方法,其中吸附是在与室温下的50-100%的饱和浓度相等的浓度的Pd化合物溶液中进行。
14.按权利要求11-13的方法,其中活性炭用PH值为0和1的酸溶液预处理,所使用的溶液的量等于或小于活性炭的孔体积。
15.权利要求1-10的催化剂在纯化粗对苯二甲酸中的应用,所述的对苯二甲酸是对二甲苯氧化反应中产生的,含4-CBA杂质。
16.权利要求1-10的催化剂在纯化含硝酸盐和/或亚硝酸盐离子的水中的应用。
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CN101347730B (zh) * | 2007-07-18 | 2011-07-13 | 中国石油化工股份有限公司 | 用于粗对苯二甲酸精制的加氢催化剂 |
CN102070441B (zh) * | 2009-11-25 | 2014-02-12 | 中国石油化工股份有限公司 | 一种催化加氢精制对苯二甲酸的方法 |
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