CN102861575B - Shell catalyst and preparation method thereof - Google Patents

Shell catalyst and preparation method thereof Download PDF

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CN102861575B
CN102861575B CN201110189186.6A CN201110189186A CN102861575B CN 102861575 B CN102861575 B CN 102861575B CN 201110189186 A CN201110189186 A CN 201110189186A CN 102861575 B CN102861575 B CN 102861575B
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catalyst
fluorine
mass fraction
molded article
calculated
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CN102861575A (en
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李丁健一
杨清河
曾双亲
贾燕子
聂红
李大东
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Abstract

一种壳层催化剂及其制备方法,该催化剂含有载体和负载在该载体上的Pd和Au金属组分,以元素计并以所述催化剂为基准,Pd的质量分数为0.1-2%,Au的质量分数为0.1-1%,所述的载体为成型的含氟水合氧化铝。 One kind of shell catalyst and preparation method, the catalyst comprising a support and Pd and Au metal component on the support, calculated as element and the reference to the catalyst, Pd content is 0.1-2%, Au the mass fraction of 0.1%, the carrier is formed of a fluorine-containing hydrated alumina. 与现有技术相比,本发明提供催化剂性能好,制备方法简单、生产成本低。 Compared with the prior art, the present invention provides a good performance of the catalyst preparation method is simple, low production cost.

Description

一种壳层催化剂及其制备方法 One kind of shell catalyst and preparation method

技术领域 FIELD

[0001] 本发明涉及一种活性金属组分壳层分布的催化剂及其制备方法。 [0001] The present invention relates to a method for preparing an active catalyst and a metal shell component distribution.

背景技术 Background technique

[0002] 活性金属组分壳层分布的催化剂可以用于多种多相催化反应。 [0002] The catalytically active metal component may be used in a variety shell distributed heterogeneous catalysis. 例如,氢化反应,氧化反应,醋酸乙烯酯的合成反应,以及受扩散控制的化学反应(如FT合成)等。 For example, hydrogenation reaction, oxidation reaction, vinyl acetate synthesis, and chemical reaction (e.g., the FT synthesis) is controlled by diffusion, and the like.

[0003] 现有技术中,壳层催化剂主要是采用金属盐通过浸渍、喷涂、蒸气淀积、浸涂或沉淀而涂覆在载体上的方法制备。 [0003] In the prior art, the shell metal catalyst is essentially prepared by dipping, spraying, vapor deposition, dipping or precipitation using coated on a support.

[0004] 例如,CN1306459A公开了一种使用可蒸发Pd/Au前体以CVD (化学蒸气淀积)法制备含Pd/Au载体化催化剂的工艺。 [0004] For example, CN1306459A discloses a vaporizable Pd / Au precursors to CVD (chemical vapor deposition) process Containing Pd / Au catalyst carrier method. 该工艺将合适的贵金属前体以蒸气相沉积在多孔载体上,之后通过化学或热还原成金属而固定在载体上。 This process is a suitable noble metal precursor vapor phase deposition on a porous support, then reduced to metal by chemical or heat immobilized on a carrier. 该工艺生产的Pd/Au催化剂活性金属组分具有壳层分布的特征,可用于合成醋酸乙烯酯。 The process for producing a Pd / Au active metal catalyst component having the features of the shell profile, for the synthesis of vinyl acetate.

[0005] US4048096公开了一种制备壳层催化剂的方法,该方法将催化剂载体用水溶性Pd 和Au的化合物的水溶液浸渍,通过将浸渍过的催化剂载体与可与水溶性Pd和Au化合物反应形成不溶于水的Pd和Au化合物的化合物溶液接触(优选偏硅酸钠),将水不溶性的Pd 和Au化合物沉淀到催化剂载体表面上。 [0005] US4048096 discloses a method of preparing a shell catalyst, which catalyst support impregnated with an aqueous solution of a water-soluble compound of Pd and Au, forming an insoluble compound by reaction of the Pd and Au catalyst support impregnated with a water soluble contacting the aqueous solution of the compound to Pd and Au compounds (preferably sodium metasilicate), water-insoluble compounds of Pd and Au on the support surface of the catalyst to precipitate. 从而制备出Pd/Au壳层分布的催化剂。 Thereby preparing a catalyst Pd / Au shell distribution.

[0006] CNlO 1462079A公开一种壳层分布催化剂制备方法,包括用含有效量活性金属组分的溶液浸渍载体,其特征在于所用溶液中的溶剂为水、醇、醚、醛、酮中的一种或几种与至少一种表面活性剂组成的混合物,以溶液的总量为基准,所述表面活性剂的含量为0. 01-10. 00重量%,所述的浸渍满足:V。 [0006] CNlO 1462079A discloses a process for preparing a shell catalyst distribution, comprising impregnating the support with a solution containing an effective amount of the active metal component, characterized in that the solvent used is a solution of water, alcohol, ether, aldehyde, ketone mixtures with at least one or more surfactant, the total amount of the solution as a reference, the content of the surfactant is 0.05% by weight of 01-1000, the impregnated satisfies:. V. = 0. 01-0. 99,其中\^为浸渍液体积,V。 = 0. 01-0. 99, where \ ^ is the volume of immersion liquid, V. 为载体的孔体积。 Pore ​​volume of the support. 该方法采用喷淋干燥,制备的催化剂活性金属组分在载体中的分布呈现明显的壳层分布。 The spray drying method employed, active metal catalyst component prepared in the carrier shell distribution presents significant distribution.

[0007] CN101143325A公开了一种制备催化剂的方法,首先制备一种含有被负载组分的可溶性化合物,之后将配制好的溶液喷涂到滚动的载体或预先负载了活性金属组分的载体上,喷涂过程的同时载体被加热,制成的产物干燥或焙烧。 [0007] CN101143325A discloses a process for preparing a catalyst comprising first preparing a compound soluble component is supported, then the prepared solution was sprayed onto the rolling support or pre-loaded with the active metal component on a carrier, spray support is heated while the process, and the resulting product was dried or calcined. 采用该方法制备的催化剂,可以得到明显壳层分布的催化剂。 The catalyst prepared by the method employed, the catalyst can be significantly shell distribution.

发明内容 SUMMARY

[0008] 本发明要解决的技术问题是提供一种新的活性金属组分为壳层分布的催化剂及其制备方法。 [0008] The present invention is to solve the technical problem is to provide a new active metal component shell catalysts and preparation method of distribution.

[0009] 本发明涉及如下的发明: [0009] The present invention relates to the following inventions:

[0010] 1. -种壳层分布催化剂,含有载体和负载在该载体上的Pd和Au金属组分,以元素计并以所述催化剂为基准,Pd的质量分数为0. 1-2%,Au的质量分数为0. 1-1%,所述的载体为含氟的水合氧化铝成型物。 [0010] 1 - Species shell distribution of the catalyst, comprising a carrier and supported on the support Pd and Au metal components, calculated as element and based on the catalyst to the mass fraction of 0. 1-2% Pd , Au content of 0. 1-1%, of the fluorine-containing hydrated alumina carrier is molded.

[0011] 2.根据1所述的催化剂,其特征在于,以元素计并以所述催化剂为基准,Pd的质量分数为0. 2-1. 6%,Au的质量分数为0. 2-0. 8%。 [0011] 2. The catalyst of claim 1, wherein, calculated as element and to the reference catalyst, Pd content is 0.2-1.5. 6%, mass fraction of 0. 2- Au 0.8%.

[0012] 3.根据1所述的催化剂,其特征在于,所述成型物含有水合氧化铝、含氟化合物和纤维素醚,所述成型物的径向压碎强度大于等于12N/mm,吸水率为0.4-1. 5, δ值为小于等于10%;其中,δ = ((Q1-Q2)/Ql) X 100%,Ql为含氟水合氧化铝成型物径向压碎强度,Q2 为含氟水合氧化铝成型物经水浸泡30分钟、经120°C烘干4小时后的径向压碎强度。 [0012] The catalyst according to claim 1, wherein said molded product comprising hydrated alumina, a fluorine-containing compound and cellulose ethers, the product is shaped radial crushing strength not less than 12N / mm, water absorption . rate of 0.4-1 5, δ value of less than equal to 10%; wherein, δ = ((Q1-Q2) / Ql) X 100%, Ql fluorine radial crush strength of hydrated alumina molded article, Q2 is the fluorine-containing hydrated alumina was molded by the water soak for 30 minutes, 120 ° C after 4 hours of drying after the radial crush strength.

[0013] 4.根据3所述的催化剂,其特征在于,所述成型物的径向压碎强度为15N/mm-30N/ mm,吸水率为0.6-1,δ小于等于5%。 [0013] 4. The catalyst of claim 3, wherein said molded product of a radial crush strength of 15N / mm-30N / mm, a water absorption of 0.6-1, δ 5% or less.

[0014] 5.根据3或4所述的催化剂,其特征在于,以所述成型物为基准,所述纤维素醚的质量分数为〇. 5-8%,以元素计的含氟化合物的质量分数为0. 2-10%。 [0014] 5. The catalyst of claim 3 or 4, characterized in that, with reference to the molded article, the cellulose ether mass fraction billion. 5-8%, calculated as elemental fluorine-containing compound to the mass fraction of 0. 2-10%.

[0015] 6.根据5所述的催化剂,其特征在于,以所述成型物为基准,所述纤维素醚的质量分数为1-6%,以元素计的含氟化合物的质量分数为0. 5-9%。 [0015] The catalyst according to claim 5, characterized in that, with reference to the molded article, the mass fraction of the cellulose ether is 1 to 6%, calculated as element content of fluorine-containing compound is 0 5-9%.

[0016] 7.根据6所述的催化剂,其特征在于,以所述成型物为基准,所述纤维素醚的质量分数为2-5%,以元素计的含氟化合物的质量分数为1% -8%。 [0016] The catalyst according to claim 6, characterized in that, with reference to the molded article, the mass fraction of the cellulose ether is 2-5%, calculated as element content of fluorine-containing compound is a % -8%.

[0017] 8.根据3所述的催化剂,其特征在于,所述纤维素醚选自甲基纤维素、羟乙基甲基纤维素、羟丙基甲基纤维素中一种或几种;所述含氟化合物选自HF、NH 4F、C6H5F、十二氟庚醇、聚四氟乙烯粉末、全氟辛酸、氟乙酸中的一种或几种。 [0017] 8. The catalyst according to claim 3, wherein the cellulose ether is selected from methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose in one or several of; the fluorine-containing compound is selected from HF, NH 4F, C6H5F, dodecafluoroheptyl alcohol, polytetrafluoroethylene powder, perfluorooctanoic acid, fluoro acetic acid is one or more.

[0018] 9.根据8所述的催化剂,其特征在于,所述纤维素醚为甲基纤维素、羟乙基甲基纤维素及它们的混合物;所述含氟化合物为NH 4F、十二氟庚醇、全氟辛酸的一种或几种。 [0018] 9. The catalyst of claim 8, wherein the cellulose ether is methyl cellulose, hydroxyethyl methyl cellulose, and mixtures thereof; the fluorine-containing compound is NH 4F, twelve fluoro-heptanol, perfluoro-octanoic acid is one or more.

[0019] 10.根据1或3所述的催化剂,其特征在于,所述水合氧化铝选自拟薄水铝石、薄水铝石、氢氧化铝、三水氢氧化铝中的一种或几种。 [0019] 10. A catalyst according to claim 1 or 3, characterized in that said hydrated alumina is selected from boehmite Quasi A boehmite, aluminum hydroxide, aluminum hydroxide or trihydrate several.

[0020] 11.根据10所述的催化剂,其特征在于,所述水合氧化铝为拟薄水铝石。 [0020] 11. The catalyst of claim 10, wherein the pseudoboehmite alumina hydrate is boehmite.

[0021] 12.根据3所述的催化剂,其特征在于,所述成型物中含有淀粉,以所述成型物为基准,所述淀粉的质量分数不超过8%。 [0021] 12. The catalyst of claim 3, wherein said molded product contains the starch, as a reference to the molded product, the starch content does not exceed 8%.

[0022] 13.根据12所述的催化剂,其特征在于,所述淀粉为田菁粉,以所述成型物为基准,所述淀粉的质量分数不超过5 %。 [0022] 13. The catalyst of claim 12, wherein the starch is Sesbania powder, with reference to the molded product, the starch content of less than 5%.

[0023] 14.根据1所述的催化剂,其特征在于,所述催化剂含有选自K、La、Ce、Zr、Cr、V、 B、Mn、Re、Pt、Ru、Ba、Ca中的一种或几种金属助剂组分,以氧化物计并以所述催化剂为基准, 所述助剂组分的质量分数不超过5%。 [0023] 14. The catalyst of claim 1, wherein said catalyst is selected from the group comprising K, La, Ce, Zr, Cr, V, B, Mn, Re, Pt, Ru, Ba, Ca in a one or several auxiliary metal component, calculated as the oxide and based on the catalyst to the mass fraction of the adjuvant component is not more than 5%.

[0024] 15.根据14所述的催化剂,其特征在于,所述助剂组分选自K和/或Ba,以氧化物计并以所述催化剂为基准,所述助剂组分的质量分数为1-3%。 [0024] 15. The catalyst of claim 14, wherein said auxiliary component is selected from K and / or Ba, and in the terms of oxide based on the catalyst mass of the aid component a score of 1-3%.

[0025] 16. -种制备壳层催化剂的方法,包括制备成型的含氟水和氧化铝载体并在该载体上负载活性金属组分,其中,所述成型的含氟水和氧化铝载体的制备方法包括将水合氧化铝、含氟化合物、纤维素醚混合、成型并干燥;或者是将水合氧化铝、纤维素醚混合成型并干燥,之后以浸渍的方式向该成型物中引入含氟化合物并干燥;其中,所述成型物的径向压碎强度大于等于12^!11111,吸水率为0.4-1.5,6值为小于等于1〇%;其中,6=((〇1-〇2)/ Ql) X 100%,Ql为含氟水合氧化铝成型物径向压碎强度,Q2为含氟水合氧化铝成型物经水浸泡30分钟、经120°C烘干4小时后的径向压碎强度。 [0025] 16. - The method of preparation of the shell catalyst species, including fluorine-containing water and forming an alumina support was prepared and active metal component loaded on the carrier, water and fluorinated alumina support wherein the shaped the method comprises preparing a hydrated alumina, a fluorine-containing compound, cellulose mixed ethers, molded and dried; or hydrated alumina, cellulose ether and dried molded mixture, then impregnated in the manner of the introduction of this fluorochemical was molded and drying; wherein the shaped radial crush strength of greater than or equal to 12 ^ 11111, a water absorption value of less 1〇 0.4-1.5,6%;! where 6 = ((〇1-〇2) / Ql) X 100%, Ql is a fluorine-containing hydrated alumina molded radial crushing strength, Q2 is a fluorine-containing alumina hydrate formed was soaked in water for 30 minutes by 120 ° C for 4 hours after drying radial pressure crushing strength.

[0026] 17.根据16所述的方法,其特征在于,所述成型物的径向压碎强度为15N/mm-30N/ mm,吸水率为0.6-1,δ小于等于5%。 [0026] 17. The method of claim 16, characterized in that the radial crush strength of the molded article was 15N / mm-30N / mm, a water absorption of 0.6-1, δ 5% or less.

[0027] 18.根据16或17所述的方法,其特征在于,以所述成型物为基准,所述纤维素醚的质量分数为0. 5-8%,以元素计的含氟化合物的质量分数为0. 2-10%;所述成型后的干燥条件包括:温度60°C至小于350°C,干燥时间1-48小时。 [0027] 18. The method of claim 16 or 17, characterized in that, with reference to the molded article, the cellulose ether mass fraction of 0. 5-8%, calculated as elemental fluorine compound is mass fraction of 0.5 to 10%; the drying conditions after molding comprising: a temperature of 60 ° C to less than 350 ° C, drying time of 48 hours.

[0028] 19.根据18所述的方法,其特征在于,以所述成型物为基准,所述纤维素醚的质量分数为1% -6%,以元素计的含氟化合物的质量分数为0. 5% -9% ;所述干燥条件包括:温度为80-180°C,干燥时间为0. 5-24小时。 [0028] 19. The method of claim 18, wherein, with reference to the molded article, the mass fraction of the cellulose ether is 1% to 6%, mass fraction of fluorine-containing compound is calculated as element 0.5% -9%; the drying conditions comprising: a temperature of 80-180 ° C, the drying time is 0. 5-24 hours.

[0029] 20.根据19所述的方法,其特征在于,以所述成型物为基准,所述纤维素醚的质量分数为2% -5%,以元素计的含氟化合物的质量分数为1% -8% ;所述干燥条件包括:温度为100-150°C,干燥时间为1-5小时。 [0029] 20. The method of claim 19, wherein, with reference to the molded article, the mass fraction of the cellulose ether is from 2% to 5%, mass fraction of fluorine-containing compound is calculated as element 1-8%; the drying conditions comprising: a temperature of 100-150 ° C, the drying time is 1-5 hours.

[0030] 21.根据16所述的方法,其特征在于,所述纤维素醚选自甲基纤维素、羟乙基甲基纤维素、羟丙基甲基纤维素中一种或几种;所述含氟化合物选自HF、NH 4F、C6H5F、十二氟庚醇、聚四氟乙烯粉末、全氟辛酸、氟乙酸中的一种或几种。 [0030] 21. The method of claim 16, wherein the cellulose ether is selected from methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose in one or several of; the fluorine-containing compound is selected from HF, NH 4F, C6H5F, dodecafluoroheptyl alcohol, polytetrafluoroethylene powder, perfluorooctanoic acid, fluoro acetic acid is one or more.

[0031] 22.根据21所述的方法,其特征在于,所述纤维素醚为甲基纤维素、羟乙基甲基纤维素及它们的混合物;所述含氟化合物为NH 4F、十二氟庚醇、全氟辛酸的一种或几种。 [0031] 22. The method of claim 21, wherein the cellulose ether is methyl cellulose, hydroxyethyl methyl cellulose, and mixtures thereof; the fluorine-containing compound is NH 4F, twelve fluoro-heptanol, perfluoro-octanoic acid is one or more.

[0032] 23.根据16所述的方法,其特征在于,所述水合氧化铝选自拟薄水铝石、薄水铝石、氢氧化铝、三水氢氧化铝中的一种或几种。 [0032] 23. The method of claim 16, wherein said hydrated alumina is selected from boehmite intended, one or more boehmite, aluminum hydroxide, aluminum hydroxide trihydrate in .

[0033] 24.根据23所述的方法,其特征在于,所述水合氧化铝为拟薄水铝石。 [0033] 24. The method of claim 23, wherein the pseudoboehmite alumina hydrate is boehmite.

[0034] 25.根据16所述的方法,其特征在于,所述在载体上负载活性金属组分的方法为浸渍法,在所述浸渍之后包括干燥的步骤,所述干燥的条件包括:温度为100-200°C,时间为1-15小时;以元素计并以所述催化剂为基准,所述浸渍液的浓度和用量使所述催化剂中Pd的质量分数为0. 1-2 %,Au的质量分数为0. 1-1%。 [0034] 25. The method of claim 16, wherein the method of supporting the active metal component on the carrier is impregnation method, comprising the step of drying after the impregnation, the drying conditions include: temperature of 100-200 ° C, to 15 hours; calculated as element and with reference to the catalyst, the concentration and amount of immersion liquid so that the content of Pd in ​​the catalyst was 0. 1-2%, Au content of 0. 1-1%.

[0035] 26.根据25所述的方法,其特征在于,所述干燥的条件包括:温度为100-200°C,时间为1-15小时;以元素计并以所述催化剂为基准,所述浸渍液的浓度和用量使所述催化剂中Pd的质量分数为0. 1-1%,Au的质量分数为0. 2-0. 8%。 [0035] 26. The method of claim 25, wherein the drying conditions include: a temperature of 100-200 ° C, to 15 hours; calculated as element and to the catalyst as a reference, the the amount and concentration of said impregnating liquid so that the content of Pd in ​​the catalyst was 0. 1-1%, mass fraction of Au and 0. 2-0. 8%.

[0036] 27.根据16所述的方法,其特征在于,在所述成型过程中包括一个引入淀粉的步骤,以所述成型物为基准,所述淀粉引入的质量分数不超过8%。 [0036] 27. The method of claim 16, characterized in that it comprises the step of introducing a starch in the molding process to the molded article as a reference, the mass fraction of starch introduced does not exceed 8%.

[0037] 28.根据27所述的成型物,其特征在于,所述淀粉为田菁粉,以所述成型物为基准,所述淀粉的引入的质量分数不超过5%。 [0037] 28. The molded article of claim 27, wherein the starch is Sesbania powder, with reference to the molded product, the starch content of less than 5% is introduced.

[0038] 29.根据16所述的方法,其特征在于,包括在所述载体中引入一种或几种助剂组分的步骤。 [0038] 29. The method of claim 16, wherein, comprising introducing one or more auxiliary components in the carrier of step.

[0039] 30.根据29所述的方法,其特征在于,所述助剂组分选自K、La、Ce、Zr、Cr、V、B、 Μη、Re、Pt、Ru、Ba、Ca中的一种或几种,以氧化物计并以所述催化剂为基准,所述助剂组分的质量分数不超过5%。 [0039] 30. The method of claim 29, wherein said auxiliary component is selected from K, La, Ce, Zr, Cr, V, B, Μη, Re, Pt, Ru, Ba, Ca in one or more, calculated as the oxide and based on the catalyst to the mass fraction of the adjuvant component is not more than 5%.

[0040] 31.根据30所述的方法,其特征在于,所述助剂组分选自K和/或Ba,以氧化物计并以所述催化剂为基准,所述助剂组分的质量分数为1-3%。 [0040] 31. The method of claim 30, wherein said auxiliary component is selected from K and / or Ba, and in the terms of oxide based on the catalyst mass of the aid component a score of 1-3%.

[0041] 按照本发明提供的催化剂,其中,所述壳层催化剂是指:催化剂的壳层因子σ为0< 〇<0.95的一类催化剂。 [0041] The catalyst according to the present invention provides, wherein said shell catalyst means: the catalyst is a shell catalyst factor σ 0 <billion <0.95. 其中,壳层因子〇为金属组分在催化剂颗粒中心处的浓度与外表面处的浓度之比。 Wherein the shell is a square factor of the concentration of the metal component ratio of the outer surface of the catalyst particles at the center. 其中,外表面处浓度为SEM-EDX表征结果中沿载体径向的外表面附近20个数值点记数率的平均值;中心处浓度为SEM-EDX表征结果中沿载体径向的中心点左右20个数值点记数率的平均值(SEM-EDX表征结果中沿载体径向每一点的记数率与该点金属含量相互对应,记数率的大小反映该点金属含量高低,但不代表该点金属的真实含量。 σ值代表催化剂上活性组分的分布形式以及定量说明不均匀分布时的不均匀程度)。 Wherein the concentration of the outer surface adjacent the outer surface as mean SEM-EDX characterization results in the radial direction vector 20 points count rate value; concentration approximately at the center of SEM-EDX characterization results along radial center point of the carrier radial vector of each point count rate of the metal content of the point corresponding to the average of 20 data points each count ratio (SEM-EDX along characterization results, the size of the count rate reflects the low point of the metal content, does not mean the content of the real point metal. [sigma] value represents the profile form of the active catalyst components, and a quantitative statement when an uneven distribution of the degree of unevenness).

[0042] 所述成型的含氟水和氧化铝载体的径向压碎强度为15N/mm-30N/mm,吸水率为0. 6-1,δ小于等于5%。 The [0042] forming a radial crushing strength of the fluorine-containing water and alumina support was 15N / mm-30N / mm, a water absorption of 0. 6-1, δ 5% or less. 所述δ = ((Q1-Q2)/Q1)X100%,Q1为含氟水合氧化铝成型物径向压碎强度,Q2为含氟水合氧化铝成型物经水浸泡30分钟,经120°C烘干4小时后的径向压碎强度。 The δ = ((Q1-Q2) / Q1) X100%, Q1 is fluorine hydrated alumina molded radial crushing strength, Q2 is a fluorine-containing alumina hydrate formed was soaked in water for 30 minutes by 120 ° C after 4 hours drying radial crush strength. S值的大小代表着含氟水合氧化铝成型物经水浸泡前后径向压碎强度的变化(或称为强度损失率)。 S value represents the size of the change before and after water soaking through the radial crushing strength of the fluorine-containing hydrated alumina molded article (or the rate of loss of strength).

[0043] 这里,所述成型物径向压碎强度的测量方法按照RIPP 25-90催化剂耐压强度测定法进行,关于成型物径向压碎强度测定的具体步骤在RIPP 25-90有详细介绍,这里不赘述。 DETAILED Step [0043] Here, the measurement method of radial crushing strength was carried out according to assay RIPP 25-90 compressive strength of the catalyst shaped, molded on radial crushing strength was measured RIPP 25-90 are described in detail in not be listed here.

[0044] 所述吸水率是指干燥含氟水合氧化铝成型物用过量去离子水浸泡30min后的重量增加值。 [0044] The water absorption refers to a dried alumina hydrate fluorine molded soaked weight gain values ​​after 30min with an excess of deionized water. 本发明采用如下方法测定:先将待测样品120°C烘干4小时。 The method of the present invention was measured as follows: 120 ° C sample to be tested first dried for 4 hours. 取出样品,放置于干燥器中冷却至室温,用40目标准筛筛分,称取筛上物20g(编号:wl)待测样品,加入50g 去离子水,浸泡30min,过滤,固相沥干5min,称量固相重量(编号:w2)。 Samples were removed, placed in a desiccator to cool to room temperature, sieved through a 40 mesh standard sieve, sieve material weighed 20g (ID: wl) sample to be tested, was added 50g of deionized water, soaking 30min, filtered, the solid drained 5min, by weight of the solid phase was weighed (ID: w2). 吸水率=(w2-wl) / wl,无量纲。 Water absorption = (w2-wl) / wl, dimensionless. 实际操作中,水的密度以1计,吸水率也可以由吸水体积/载体重量求得,其量纲为体积/重量,例如ml/g。 In practice, the density of water at 1 meter, the water absorption can be determined from the volume of water absorption / weight of the carrier, its dimension volume / weight, e.g. ml / g.

[0045] 在足以使成型物的径向压碎强度、吸水率和强度损失率满足要求的前提下,本发明对纤维素醚的含量没有特别限制,在具体的实施方式中,以水合氧化铝成型物总量为基准,纤维素醚的质量分数优选为0. 5 % -8 %,进一步优选为1 % -6 %,更为优选为2 % -5 %。 [0045] In the molded product of sufficient radial crush strength and water absorption rate of loss of strength, to meet the requirements of the premise, the present invention is not particularly limited content of the cellulose ether, in the specific embodiment, the hydrated alumina to total molded as a reference, the mass fraction of the cellulose ether is preferably 0.5% to 8%, more preferably from 1% to 6%, more preferably from 2% to 5%. 所述纤维素醚优选自甲基纤维素、羟乙基甲基纤维素、羟丙基甲基纤维素中一种或几种,进一步优选其中的甲基纤维素、羟乙基甲基纤维素及它们的混合物。 Preferably the cellulose ether from methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose in one or several, more preferably wherein the methyl cellulose, hydroxyethyl methyl cellulose and mixtures thereof.

[0046] 按照本发明提供的催化剂,其中,以水合氧化铝成型物总量为基准,以元素计的含氟化合物的质量分数为0.2% -10%,进一步优选为0.5% -9%,更加优选为1% -8%。 [0046] The catalyst according to the present invention provides, wherein the total amount of hydrated alumina molded article as a reference, in terms of mass fraction of the element fluorine-containing compound is 0.2% to 10%, more preferably from 0.5% to 9%, more preferably from 1% to 8%. 所述含氟化合物优选自HF、NH4F、C6H5F、十二氟庚醇、聚四氟乙烯粉末、全氟辛酸、氟乙酸中的一种或几种,进一步优选自NH 4F、十二氟庚醇、全氟辛酸的一种或几种。 The fluorine-containing compound is preferably selected from HF, NH4F, C6H5F, dodecafluoroheptyl alcohol, polytetrafluoroethylene powder, perfluorooctanoic acid, one or more fluorine-acetic acid, more preferably from NH 4F, dodecafluoroheptyl alcohol, perfluoro octanoic acid one or several.

[0047] 按照本发明提供的催化剂,其中所述的含氟水合氧化铝成型物中可以含有不影响或者有益于改善所述成型物的径向压碎强度、吸水率和S值的助剂组分。 [0047] The catalyst according to the present invention provides a fluorine-containing molded article wherein the hydrated alumina may be contained in or does not affect the benefit of the molded article improved radial crush strength aid component, and water absorption values ​​S Minute. 例如,含有淀粉添加组分,所述淀粉可以是任意的由植物种子经粉碎得到的粉体,如田菁粉。 For example, the additive component comprising starch, the starch may be any comminuted powder obtained from the plant seeds, such as Sesbania powder.

[0048] 所述水合氧化铝选自任何一种可用作吸附剂和催化剂载体前身物的水合氧化铝, 例如,可以是拟薄水铝石、薄水铝石、氢氧化铝、三水氢氧化铝,优选拟薄水铝石。 [0048] The hydrated alumina is selected from any of a hydrated alumina useful as adsorbents and catalyst supports predecessor thereof, for example, may be a quasi-boehmite, boehmite, aluminum hydroxide, hydrogen trihydrate alumina, pseudoboehmite, boehmite is preferred.

[0049] 按照本发明提供的制备方法,其中,所述成型的含氟水和氧化铝载体的成型方法可以是任意的已知方法。 [0049] The production method according to the present invention provided, wherein the fluorine-containing water and method of forming the shaped alumina carrier may be any known method. 例如,挤条、喷雾、滚圆、压片以及它们的组合的成型方法。 For example, extruding, spraying, spheronisation, tabletting molding method, and a combination thereof. 所述含氟化合物可以是直接与水合氧化铝、纤维素醚混合后成型并干燥,也可以是首先将水合氧化铝、纤维素醚混合成型并干燥,之后以浸渍的方式向该成型物中引入含氟化合物并干燥。 The fluorine-containing compound may be directly hydrated alumina, molded and dried after mixing the cellulose ether, may be first formed by mixing alumina hydrate, cellulose ether and dried, then impregnated in the manner of this molding was introduced into The fluorine-containing compound and dried. 为保证成型的顺利进行,在成型时可以向前述的物料(水合氧化铝、含氟化合物和纤维素醚的混合物;或者是水合氧化铝与纤维素醚混合)中引入和水、含或不含助剂等,例如,当采用挤条方法成型时,包括将所述的水合氧化铝和纤维素醚与水、含或不含助挤剂混合,然后经挤出成型得到湿条,再经干燥得到本发明所述的成型物。 To ensure the smooth molding, the molding may be the material (hydrated alumina, cellulose ethers and fluorine-containing compound mixture; or a mixture of cellulose ether and alumina hydrate) and introduced into the water, with or without additives, e.g., when using the extruding molding method, comprising the alumina hydrate and the cellulose ether and water, with or without a co-agent extrusion mixed, then wet article obtained by the extrusion, and then dried to obtain a molded product of the present invention. 所述助剂选自淀粉,所述淀粉可以是任意的由植物种子经粉碎得到的粉体,如田菁粉。 The adjuvant is selected from starch, the starch may be any comminuted powder obtained from the plant seeds, such as Sesbania powder. 优选的成型方法为挤条成型的方法。 The preferred forming method is extrusion molded article of the method.

[0050] 所述在成型的水和氧化铝载体上负载活性金属组分的方法可以是任意的惯常方法。 [0050] The method of supporting the active metal components on an alumina support and the water formed may be any conventional method. 优选为浸渍的方法,所述的浸渍方法为常规方法。 Preferably impregnation method, the dipping method is a conventional method. 以制备含Pd和Au的催化剂为例,包括:配制含Pd和Au金属盐的浸渍溶液,之后通过浸泡或喷淋的方法用该浸渍液浸渍所述载体。 Preparation of the catalyst containing Pd and for example Au, comprising: a preparation containing metal Pd and Au impregnation solution, followed by dipping method or spraying the support with the impregnating liquid is impregnated. 以元素计并以催化剂的质量为基准,所述浸渍液的浓度和用量使所述催化剂中的Pd含量为0. 1-2 %,Au含量为0. 1-1 %,优选Pd含量为0. 2-1. 6 %,Au含量为0. 2-0. 8 %。 Calculated as element and is used as a reference mass of the catalyst, the concentration and amount of immersion liquid so that the Pd content of the catalyst is 0. 1-2%, Au content of 0. 1-1%, preferably Pd content is 0 . 2-1. 6%, Au content of 0. 2-0. 8%. 所述含PcU含Au的金属盐分别选自它们可溶性盐,例如所述含Pd的金属盐可以是选自氯化钯、 醋酸钯、硝酸钯或氯钯酸;所述含Au的金属盐可以是选择可溶性的氯化金或四氯金酸盐。 PcU containing Au-containing metal salt are selected from soluble salts thereof, such as the Pd-containing metal salt may be selected from palladium chloride, palladium acetate, palladium nitrate or palladium chloride acid; metal containing Au may selecting a soluble gold chloride or tetrachloroaurate.

[0051] 当所述催化剂中还含有选自含有选自K、La、Ce、Zr、Cr、V、B、Mn、Re、Pt、Ru、Ba、Ca 中的一种或几种金属助剂组分时,所述选自含有选自K、La、Ce、Zr、Cr、V、B、Mn、Re、Pt、Ru、 Ba、Ca中的一种或几种金属助剂组分的引入方法可以是任意的方法,如可以是将含所述助剂的化合物直接与所述水合氧化铝混合、成型并干燥;可以是将含有所述助剂的化合物单独或同时与含PcU含Au的金属盐配制成混合溶液后浸渍所述的载体。 [0051] When the catalyst further contains selected from a selected K, La, Ce, Zr, Cr, V, B, Mn, Re, Pt, Ru, Ba, and Ca, or several metal promoter when component selected from the group comprising the selected K, the introduction of La, Ce, Zr, Cr, V, B, Mn, Re, Pt, Ru, Ba, Ca metal in one or more adjunct components, the method may be any method, as may be the compound containing the adjuvant directly mixed with the hydrated alumina, shaping and drying; may be a compound containing the adjuvant alone or simultaneously with the Au-containing containing PcU after mixing the metal salt solution is formulated to support impregnating said.

[0052] 与现有的技术方法相比,本发明提供的催化剂在保持应有性能的同时,制备方法简单、生产成本明显低于现有方法制备的催化剂。 [0052] Compared with the prior art methods, the present invention provides a catalyst while maintaining proper performance, simple preparation method, production costs are significantly lower than the catalyst prepared by a conventional method.

具体实施方式 Detailed ways

[0053] 下面的实例将对本发明做进一步说明,但不因此限制本发明内容。 [0053] The following examples will further illustrate the present invention, without thereby limiting the present invention.

[0054] 实例中所用试剂,除特别说明的以外,均为化学纯试剂。 [0054] The reagents used in the examples, except where otherwise noted, and are chemically pure reagents.

[0055] 采用SEM-EDX测定加氢活性金属组分沿载体径向分布,并由表征结果计算金属组分在颗粒外表处与中心处浓度之比,即〇=中心处浓度/外表面浓度。 [0055] SEM-EDX measurement using a hydrogenation active metal component in the radial distribution of the support, characterized by the result of the calculation of the concentration ratio of the metal component and the particles at the center of the outer, i.e. the center of the surface concentration of square = concentration / outside. 其中,外表面浓度为:外表面处20个数值点记数率的平均值;中心处浓度:中心点处20个数值点记数率的平均值(注:SEM-EDX表征结果中沿载体径向每一点的记数率与该点金属含量相互对应,记数率的大小反映该点金属含量高低,但不代表该点金属的真实含量)。 Wherein the concentration of the outer surface: the outer surface 20 of the average count rate data points; concentration at the center: a center point average of 20 data points count rate (note: SEM-EDX characterization results along the carrier path corresponds to each point of the point count of the content of each metal, the size of the count rate reflects the low point of the metal content, it does not mean the content of the true point metal).

[0056] 实施例1 [0056] Example 1

[0057] 取催化剂长岭分公司生产的拟薄水铝石粉100g,加入4. Og甲基纤维素,3. Og田菁粉,4. 5g NH4F和95mL去离子水,充分搅拌混合均匀,通过挤条机混捏均匀后,挤条成型得到水合氧化铝的成型物湿条。 [0057] Branch taken Changling Catalyst pseudo-boehmite powder 100g, 4. Og added methyl cellulose, 3. Og sesbania powder, 4. 5g NH4F and 95mL deionized water, sufficiently stirred and mixed uniformly, by after uniformly kneading extrusion machine, extrusion molded article obtained wet hydrated alumina molded article. 将湿条置于烘箱中150°C干燥12小时。 The wet bar placed in an oven dried 150 ° C for 12 hours. 测定干燥后成型载体的径向压碎强度、吸水率和δ值,结果列于表1。 After drying the shaped support was measured radial crushing strength, water absorption and δ values ​​are shown in Table 1.

[0058] 实施例2 [0058] Example 2

[0059] 取催化剂长岭分公司生产的拟薄水铝石粉50g,自制无定型氢氧化铝粉50g,加入2. Og甲基纤维素,3. Og羟乙基甲基纤维素,8. 5g NH4F和95mL去离子水,充分搅拌混合均匀,通过挤条机混捏均匀后,挤条成型得到氢氧化铝的湿成型物。 [0059] Branch taken Changling Catalyst pseudo-boehmite powder 50g, made of amorphous aluminum hydroxide powder 50g, methyl cellulose was added 2. Og, 3. Og hydroxyethyl methyl cellulose, 8. 5g after NH4F and 95mL deionized water, sufficiently stirred and mixed uniformly by uniformly kneading extrusion machine, extruding the wet aluminum hydroxide obtained by molding the molding material. 将湿氢氧化铝成型物放置于烘箱中220°C干燥6小时。 The wet molded aluminum hydroxide was placed in an oven dried 220 ° C for 6 hours. 测定干燥后成型载体的径向压碎强度、吸水率和δ值,结果列于表1。 After drying the shaped support was measured radial crushing strength, water absorption and δ values ​​are shown in Table 1.

[0060] 实施例3 [0060] Example 3

[0061] 取催化剂长岭分公司生产的拟薄水铝石粉60g,三水氢氧化铝40g,加入1.0 g甲基纤维素,2. Og羟丙基甲基纤维素,3. Og田菁粉,40. 0 % HF溶液5mL和95mL去离子水,充分搅拌混合均匀,通过挤条机混捏均匀后,挤条成型得到氢氧化铝的湿成型物。 [0061] Branch taken Changling Catalyst pseudo-boehmite powder 60g, aluminum trihydrate 40g, was added 1.0 g methyl cellulose, 2. Og hydroxypropylmethylcellulose, 3. Og sesbania powder after, 40. 0% HF solution, 5mL and 95mL of deionized water, sufficiently stirred and mixed uniformly by uniformly kneading extrusion machine, extruding the wet aluminum hydroxide obtained by molding the molding material. 将湿氢氧化铝成型物放置于烘箱中80°C干燥12小时。 The wet molded aluminum hydroxide was placed in an oven dried 80 ° C for 12 hours. 测定干燥后成型载体的径向压碎强度、吸水率和δ值,结果列于表1。 After drying the shaped support was measured radial crushing strength, water absorption and δ values ​​are shown in Table 1.

[0062] 实施例4 [0062] Example 4

[0063] 取Sasol公司生产的拟薄水铝石SB粉100g,加入3. Og羟乙基甲基纤维素,40. 0% HF溶液IOmL和SOmL去离子水,充分搅拌混合均匀,通过挤条机混捏均匀后,挤条成型得到成型条。 [0063] company Sasol taken pseudo boehmite SB powder 100g, hydroxyethyl methyl cellulose was added 3. Og, 40. 0% HF solution IOmL SOmL and deionized water, sufficiently stirred and mixed uniformly, by extruding after uniformly kneading machines, extruding molding to obtain a molded article. 氢氧化铝成型条放置于烘箱中150°C干燥12小时。 Aluminum hydroxide formed article is placed in an oven dried 150 ° C for 12 hours. 测定干燥后成型载体的径向压碎强度、吸水率和S值,结果列于表1。 After drying the shaped support was measured radial crushing strength, water absorption, and S values ​​shown in Table 1.

[0064] 实施例5 [0064] Example 5

[0065] 取Sasol公司生产的拟薄水铝石SB粉100g,加入3. Og羟乙基甲基纤维素,2g羟丙基甲基纤维素,3. Og田菁粉,14. 2g NH4F和90mL去离子水,充分搅拌混合均匀,通过挤条机混捏均匀后,挤条成型得到成型条。 [0065] company Sasol taken pseudo boehmite SB powder 100g, 3. Og hydroxyethyl cellulose was added, 2g hydroxypropylmethyl cellulose, 3. Og sesbania powder, 14. 2g NH4F and after 90mL of deionized water, sufficiently stirred and mixed uniformly by uniformly kneading extrusion machine, extruding molding to obtain a molded article. 氢氧化铝成型条放置于烘箱中250°C干燥4小时。 Aluminum hydroxide formed article placed in the drying oven at 250 ° C 4 hours. 测定干燥后成型载体的径向压碎强度、吸水率和S值,结果列于表1。 After drying the shaped support was measured radial crushing strength, water absorption, and S values ​​shown in Table 1.

[0066] 实施例6 [0066] Example 6

[0067] 取山东烟台恒辉化工有限公司生产的拟薄水铝石粉100g,加入5. Og羟丙基甲基纤维素,3. Og田菁粉,I. 5g NH4F和90mL去离子水,充分搅拌混合均勾,通过挤条机混捏均匀后,挤条成型得到成型条。 [0067] Take Yantai Fai Chemical Co., Ltd. of pseudoboehmite powder 100g, was added 5. Og hydroxypropylmethylcellulose, 3. Og sesbania powder, I. 5g NH4F and 90mL deionized water, sufficiently stirring and mixing are hooks, by extrusion kneading machine even after the extruding molding to obtain a molded article. 成型条放置于烘箱中120°C干燥4小时。 Molded article placed in a drying oven at 120 ° C 4 hours. 测定干燥后成型载体的径向压碎强度、吸水率和δ值,结果列于表1。 After drying the shaped support was measured radial crushing strength, water absorption and δ values ​​are shown in Table 1.

[0068] 对比例1 [0068] Comparative Example 1

[0069] 取催化剂长岭分公司生产的拟薄水铝石粉100g,加入浓硝酸2. 5mL,3. Og田菁粉, 4. 5g NH/和95mL去离子水,充分搅拌混合均匀,通过挤条机混捏均匀后,挤条成型得到成型条。 [0069] Branch taken Changling Catalyst pseudo-boehmite powder 100g, was added concentrated nitric acid 2. 5mL, 3. Og sesbania powder, 4. 5g NH / and 95mL deionized water, sufficiently stirred and mixed uniformly, by extrusion after uniformly kneading machine, extruding molding to obtain a molded article. 成型条放置于烘箱中80°C干燥4小时。 Molded article placed in a drying oven at 80 ° C 4 hours. 测量干燥条的强度。 Measuring the intensity of the drying section. 称取IOg所得干燥条加入50mL去离子水,用水浸泡30分钟,测定干燥后成型载体的径向压碎强度、吸水率和δ 值,结果列于表1。 The resulting article was dried weighed IOg added 50mL of deionized water, soaked in water for 30 minutes and measured after drying the shaped support radial crush strength, water absorption and δ values ​​are shown in Table 1.

[0070] 对比例2 [0070] Comparative Example 2

[0071] 取Sasol公司生产的拟薄水铝石SB粉100g,加入20ml铝溶胶,3. Og田菁粉14. 2g NH4F和90mL去离子水,充分搅拌混合均匀,通过挤条机混捏均匀后,挤条成型得到成型条。 After the [0071] company Sasol taken pseudo boehmite SB powder 100g, alumina sol was added 20ml, 3. Og and Sesbania NH4F mixed powder 90mL of deionized water, stirred well 14. 2g, by extrusion kneading machine uniformly , extruding molding to obtain a molded article. 成型条放置于烘箱中150°C干燥4小时。 Molded article placed in a drying oven at 150 ° C 4 hours. 成型条放置于烘箱中150°C干燥4小时。 Molded article placed in a drying oven at 150 ° C 4 hours. 测量干燥条的强度。 Measuring the intensity of the drying section. 称取IOg所得干燥条加入50mL去离子水,用水浸泡30分钟,测定干燥后成型载体的径向压碎强度、吸水率和δ值,结果列于表1。 The resulting article was dried weighed IOg added 50mL of deionized water, soaked in water for 30 minutes and measured after drying the shaped support radial crush strength, water absorption and δ values ​​are shown in Table 1.

[0072] 对比例3 [0072] Comparative Example 3

[0073] 取山东烟台恒辉化工有限公司生产的拟薄水铝石粉100g,加入5. OmL醋酸,3. Og 田菁粉,I. 5g NH4F*90mL去离子水,充分搅拌混合均匀,通过挤条机混捏均匀后,挤条成型得到成型条。 [0073] Take Yantai Fai Chemical Co., Ltd. of pseudoboehmite powder 100g, 5. OmL added acetic acid, 3. Og sesbania powder, I. 5g NH4F * 90mL of deionized water, sufficiently stirred and mixed uniformly, by extrusion after uniformly kneading machine, extruding molding to obtain a molded article. 成型条放置于烘箱中180°C干燥4小时。 Molded article placed in a drying oven at 180 ° C 4 hours. 测量干燥条的强度。 Measuring the intensity of the drying section. 称取IOg所得干燥条加入50mL去离子水,用水浸泡30分钟,测定干燥后成型载体的径向压碎强度、吸水率和S值,结果列于表1。 The resulting article was dried weighed IOg added 50mL of deionized water, soaked in water for 30 minutes and measured after drying the shaped support radial crush strength, water absorption, and S values ​​shown in Table 1.

[0074] 对比例4 [0074] Comparative Example 4

[0075] 取催化剂长岭分公司生产的拟薄水铝石粉100g,加入浓硝酸2. 5mL,3. Og田菁粉, 4. 5g NH/和95mL去离子水,充分搅拌混合均匀,通过挤条机混捏均匀后,挤条成型得到成型条。 [0075] Branch taken Changling Catalyst pseudo-boehmite powder 100g, was added concentrated nitric acid 2. 5mL, 3. Og sesbania powder, 4. 5g NH / and 95mL deionized water, sufficiently stirred and mixed uniformly, by extrusion after uniformly kneading machine, extruding molding to obtain a molded article. 成型条放置于烘箱中80°C干燥4小时。 Molded article placed in a drying oven at 80 ° C 4 hours. 干燥条600°C焙烧4小时。 Article dried calcined 600 ° C for 4 hours. 测定焙烧后成型载体的径向压碎强度、吸水率和δ值,结果列于表1。 After firing the shaped support was measured radial crushing strength, water absorption and δ values ​​are shown in Table 1.

[0076]表1 [0076] TABLE 1

Figure CN102861575BD00101

[0078] 实施例7-12与对比例5分别说明本发明提供的催化剂、参比催化剂以及它们的制备方法。 7-12 with the catalysts of the present invention provides, reference catalyst and methods for their preparation are described Comparative Example 5 [0078] Example.

[0079] 对比例5 [0079] Comparative Example 5

[0080] 按照对比例4的方法制备35. 6g圆柱形载体(直径为I. 1mm,颗粒长度为2-5mm) 测其吸水率为〇. 93ml/g。 [0080] 35. 6g cylindrical carrier prepared according to the method of Comparative Example 4 (the diameter I. 1mm, particle length of 2-5 mm) square was measured for water absorption. 93ml / g.

[0081] 用1. 2Ig Na2PdCl4和含有0. 38g HAuCl 4配制成33ml浸渍溶液,用该溶液浸渍载体。 [0081] 1. 2Ig Na2PdCl4 with 0. 38g HAuCl 4 containing 33ml formulated impregnation solution, impregnating the support with the solution. 浸渍5min后,将其置于20ml含有1.5克NaOH的溶液中,室温下静置8h,用去离子水冲洗,直至洗液中不含有Cr为止,之后于120°C干燥2h,350°C氢气还原3h。 After impregnation 5min, placed 20ml of a solution containing 1.5 g of NaOH and allowed to stand at room temperature for 8h, rinsed with deionized water until the washings did not contain far Cr, after drying at 120 ° C 2h, 350 ° C Hydrogen restore 3h. 冷却至室温后, 用等体积含〇. 22g KOAc的水溶液浸渍30min,之后于80°C下干燥4h得到催化剂Al,表征结果见表1。 After cooling to room temperature with an equal volume containing square. 30min 22g KOAc impregnation solution, and then dried at 80 ° C for 4h to obtain a catalyst Al, characterization results are shown in Table 1.

[0082] 实施例7 [0082] Example 7

[0083] 按照实施例1的方法制备50.0 g圆柱形载体(直径为I. 1mm,颗粒长度为2-5mm, 于马弗炉中600°C焙烧4小时后,测得干基为70. 6% ),测其吸水率为0. 85ml/g。 After [0083] 50.0 g of the cylindrical carrier prepared (diameter I. 1mm, 2-5 mm particle length, in a muffle furnace for 600 ° C calcined 4 hours according to the method of Example 1, as measured on a dry basis 70.6 %) measured for the water absorption of 0. 85ml / g.

[0084] 用1. 2Ig Na2PdCl4和含有0. 38g HAuCl 4配制成42ml浸渍溶液,用该溶液浸渍载体。 [0084] 1. 2Ig Na2PdCl4 with 0. 38g HAuCl 4 containing 42ml formulated impregnation solution, impregnating the support with the solution. 浸渍5min后,将其置于20ml含有1.5克NaOH的溶液中,室温下静置8h,用去离子水冲洗,直至洗液中不含有Cr为止,之后于120°C干燥2h,500°C氢气还原3h。 After impregnation 5min, placed 20ml of a solution containing 1.5 g of NaOH and allowed to stand at room temperature for 8h, rinsed with deionized water until the washings did not contain far Cr, after drying at 120 ° C 2h, 500 ° C Hydrogen restore 3h. 冷却至室温后, 用等体积含〇. 22g KOAc的水溶液浸渍30min,之后于80°C下干燥4h得到催化剂Cl,表征结果见表1。 After cooling to room temperature with an equal volume containing square. 30min 22g KOAc impregnation solution, and then dried at 80 ° C for 4h to obtain a catalyst Cl, the characterization results shown in Table 1.

[0085] 实施例8 [0085] Example 8

[0086] 按照实施例3的方法制备50.0 g圆柱形载体(直径为I. 1mm,颗粒长度为2-5mm, 于马弗炉中600°C焙烧4小时后,测得干基为69. 4% ),测其吸水率为0. 89ml/g。 [0086] 50.0 g of the cylindrical support prepared according to the method of Example 3 (having a diameter of I. 1mm, 2-5 mm particle length, in a muffle furnace after firing 600 ° C for 4 hours was measured on a dry basis 69.4 %) measured for the water absorption of 0. 89ml / g.

[0087] 用I. 84g Na2PdClJP 0. 57g HAuCl 4配制成44ml浸渍溶液,用该溶液浸渍载体。 [0087] The impregnation solution to 44ml with I. 84g Na2PdClJP 0. 57g HAuCl 4 formulated, the carrier is impregnated with this solution. 浸渍5min后,将其置于20ml含有1. 5克NaOH的溶液中,室温下静置8h,用去离子水冲洗,直至洗液中不含有Cr为止,之后于120°C干燥2h,500°C氢气还原3h。 After impregnation 5min, placed 20ml containing 1.5 g NaOH solution was allowed to stand at room temperature for 8h, rinsed with deionized water until the washings did not contain far Cr, after drying at 120 ° C 2h, 500 ° C hydrogen reduction 3h. 冷却至室温后,用等体积含0. 33g KOAc的水溶液浸渍30min,之后于80°C下干燥4h得到催化剂C2,表征结果见表1〇 After cooling to room temperature, aqueous solution with an equal volume impregnation 30min 0. 33g KOAc, and then dried at 80 ° C for 4h to obtain a catalyst C2, characterization results are shown in Table 1〇

[0088] 实施例9 [0088] Example 9

[0089] 按照实施例4的方法制备50.0 g圆柱形载体(直径为I. 1mm,颗粒长度为2-5mm, 于马弗炉中600°C焙烧4小时后,测得干基为68. 9% ),测其吸水率为0. 71ml/g。 After [0089] 50.0 g of the cylindrical carrier prepared (diameter I. 1mm, 2-5 mm particle length, in a muffle furnace for 600 ° C calcined 4 hours according to the method of Example 4, as measured on a dry basis 68.9 %) measured for the water absorption of 0. 71ml / g.

[0090] 用I. 20g Na2PdClJP 0. 37g HAuCl 4配制成35ml浸渍溶液,用该溶液浸渍载体。 [0090] I. formulated with 35ml impregnation solution 20g Na2PdClJP 0. 37g HAuCl 4, the support is impregnated with the solution. 浸渍5min后,将其置于20ml含有1. 5克NaOH的溶液中,室温下静置8h,用去离子水冲洗,直至洗液中不含有Cr为止,之后于120°C干燥2h,500°C氢气还原3h。 After impregnation 5min, placed 20ml containing 1.5 g NaOH solution was allowed to stand at room temperature for 8h, rinsed with deionized water until the washings did not contain far Cr, after drying at 120 ° C 2h, 500 ° C hydrogen reduction 3h. 冷却至室温后,得到催化剂C3,表征结果见表1。 After cooling to room temperature, the catalyst C3, characterization results are shown in Table 1.

[0091] 实施例10 [0091] Example 10

[0092] 按照实施例6的方法制备50.0 g圆柱形载体(直径为I. 1mm,颗粒长度为2-5mm, 于马弗炉中600°C焙烧4小时后,测得干基为70. 3% ),测其吸水率为0. 83ml/g。 After [0092] 50.0 g of the cylindrical carrier prepared (diameter I. 1mm, 2-5 mm particle length, in a muffle furnace for 600 ° C calcined 4 hours according to the method of Example 6, as measured on a dry basis 70.3 %) measured for the water absorption of 0. 83ml / g.

[0093] 用0. 60g Na2PdClJP 0. 19g HAuCl 4配制成41ml浸渍溶液,用该溶液浸渍载体。 [0093] with 0. 60g Na2PdClJP 0. 19g HAuCl 4 formulated 41ml impregnation solution, impregnating the support with the solution. 浸渍5min后,将其置于20ml含有1. 5克NaOH的溶液中,室温下静置8h,用去离子水冲洗,直至洗液中不含有Cr为止,之后于120°C干燥2h,500°C氢气还原3h。 After impregnation 5min, placed 20ml containing 1.5 g NaOH solution was allowed to stand at room temperature for 8h, rinsed with deionized water until the washings did not contain far Cr, after drying at 120 ° C 2h, 500 ° C hydrogen reduction 3h. 冷却至室温后,用等体积含0.1 lg KOAc的水溶液浸渍30min,之后于80°C下干燥4h得到催化剂C4,表征结果见表1〇 After cooling to room temperature with an equal volume containing an aqueous solution of 0.1 lg KOAc impregnation 30min, then dried at 80 ° C for 4h to give the catalyst C4, characterization results are shown in Table 1〇

[0094] 催化剂性能评价 [0094] Evaluation of Catalyst Performance

[0095] 在固定床反应器中评价本发明提供催化剂CU C2、C3、C4(实施例11-14)以及参比催化剂Al (对比例6),催化剂用量为30ml。 [0095] Evaluation in a fixed bed reactor of the present invention provides a catalyst CU C2, C3, C4 (Examples 11-14) and the reference catalyst Al (Comparative Example 6), the amount of catalyst 30ml. 原料为乙烯/醋酸/氧气=82/12/6(摩尔比)。 Material is ethylene / vinyl acetate / Oxygen = 82/12/6 (molar ratio).

[0096] 反应条件包括:温度为145°C,反应器入口压力IMPa。 [0096] The reaction conditions comprise: a temperature of 145 ° C, the reactor inlet pressure of IMPa.

[0097] 结果列于表1。 [0097] The results are shown in Table 1.

[0098] 其中: [0098] wherein:

Figure CN102861575BD00111

Figure CN102861575BD00121

[0102] 表1中各组分的含量为实际投料的计算值,即根据实际使用的Pd、Au、KOAc以及含F的Al2O3质量分别与这些组分的质量之和的百分比值。 [0102] The content of each component in Table 1 is the calculated value of the feed, i.e. the value of the sum of the mass percentage of these components in accordance with actual use Pd, Au, KOAc, and F-containing Al2O3 mass. 其中Al以氧化物计,F、PcU Au以元素计,K以KOAc计。 Wherein Al oxide basis, F, PcU Au calculated as element, K in terms KOAc.

Claims (26)

1. 一种壳层分布催化剂,含有载体和负载在该载体上的Pd和Au金属组分,以元素计并以所述催化剂为基准,Pd的质量分数为0. 1-2%,Au的质量分数为0. 1-1%,所述的载体为含氟的水合氧化铝成型物,所述成型物由水合氧化铝、含氟化合物、纤维素醚和淀粉组成,以所述成型物为基准,所述纤维素醚的质量分数为〇. 5-8%,以元素计的含氟化合物的质量分数为0.2-10%,所述淀粉的质量分数为0-8%,所述成型物的径向压碎强度大于等于12N/mm,吸水率为0. 4-1.5,S 值为小于等于10%;其中,S = ((Q1-Q2)/Q1)X100%, Ql为含氟水合氧化铝成型物径向压碎强度,Q2为含氟水合氧化铝成型物经水浸泡30分钟、 经120 °C烘干4小时后的径向压碎强度。 A shell distribution of the catalyst, comprising a carrier and supported on the support Pd and Au metal components, calculated as element and the reference to the catalyst, Pd content of 0. 1-2%, Au of 0. 1-1% mass fraction, the carrier is a fluorine-containing hydrated alumina molded article, said molded article by a hydrated alumina, a fluorine-containing compound, cellulose ether and starch, to the molding material is reference, the mass fraction of the cellulose ether is square. 5-8%, calculated as element content of the fluorine-containing compound is 0.2 to 10%, the starch content of 0-8%, the molded article the radial crushing strength not less than 12N / mm, a water absorption of 0. 4-1.5, S is 10% or less; wherein, S = ((Q1-Q2) / Q1) X100%, Ql is fluorine hydrated radial crush strength of the alumina molded article, Q2 is a fluorine-containing alumina hydrate formed was soaked in water for 30 minutes and dried by 120 ° C for 4 hours after the radial crush strength.
2. 根据权利要求1所述的催化剂,其特征在于,以元素计并以所述催化剂为基准,Pd的质量分数为〇. 2-1. 6%,Au的质量分数为0. 2-0. 8%。 2. The catalyst according to claim 1, wherein, calculated as element and to the reference catalyst, Pd content is square. 2-1. 6%, mass fraction of Au 0. 2-0 . 8%.
3. 根据权利要求1所述的催化剂,其特征在于,所述成型物的径向压碎强度为15N/ mm-30N/mm,吸水率为0. 6-1,5小于等于5%。 3. The catalyst according to claim 1, characterized in that the radial crush strength of the molded article was 15N / mm-30N / mm, 6-1,5 water absorption of 0. 5% or less.
4. 根据权利要求1所述的催化剂,其特征在于,以所述成型物为基准,所述纤维素醚的质量分数为1-6%,以元素计的含氟化合物的质量分数为0. 5-9%。 4. A catalyst according to claim 1, characterized in that, with reference to the molded article, the cellulose ether mass fraction of 1-6%, calculated as element content of fluorine-containing compound is 0. 5-9%.
5. 根据权利要求4所述的催化剂,其特征在于,以所述成型物为基准,所述纤维素醚的质量分数为2-5%,以元素计的含氟化合物的质量分数为1% -8%。 A catalyst as claimed in claim 4, wherein, with reference to the molded article, the cellulose ether mass fraction of 2-5%, calculated as element content of fluorine-containing compound is 1% -8%.
6. 根据权利要求1所述的催化剂,其特征在于,所述纤维素醚选自甲基纤维素、羟乙基甲基纤维素、羟丙基甲基纤维素中一种或几种;所述含氟化合物选自册、順/、(:##、十二氟庚醇、聚四氟乙烯粉末、全氟辛酸、氟乙酸中的一种或几种。 6. The catalyst according to claim 1, wherein the cellulose ether is selected from methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose in one or several of; the said fluorine-containing compound selected volumes, cis / (: ##, dodecafluoroheptyl alcohol, polytetrafluoroethylene powder, perfluorooctanoic acid, fluoro acetic acid is one or more.
7. 根据权利要求6所述的催化剂,其特征在于,所述纤维素醚为甲基纤维素、羟乙基甲基纤维素及它们的混合物;所述含氟化合物为NH 4F、十二氟庚醇、全氟辛酸的一种或几种。 7. The catalyst according to claim 6, wherein the cellulose ether is methyl cellulose, hydroxyethyl methyl cellulose, and mixtures thereof; the fluorine-containing compound is NH 4F, dodecafluoro heptanol, perfluoro-octanoic acid is one or more.
8. 根据权利要求1所述的催化剂,其特征在于,所述水合氧化铝选自拟薄水铝石、薄水铝石、氢氧化铝、三水氢氧化铝中的一种或几种。 8. The catalyst according to claim 1, wherein said hydrated alumina is selected from boehmite pseudoboehmite, boehmite, aluminum hydroxide, aluminum hydroxide trihydrate of one or more.
9. 根据权利要求8所述的催化剂,其特征在于,所述水合氧化铝为拟薄水铝石。 9. The catalyst according to claim 8, wherein the pseudoboehmite alumina hydrate is boehmite.
10. 根据权利要求1所述的催化剂,其特征在于,所述淀粉为田菁粉,以所述成型物为基准,所述淀粉的质量分数不超过5 %。 10. The catalyst according to claim 1, wherein the starch is Sesbania powder, with reference to the molded product, the starch content of less than 5%.
11. 根据权利要求1所述的催化剂,其特征在于,所述催化剂含有选自K、La、Ce、Zr、Cr、 V、B、Mn、Re、Pt、Ru、Ba、Ca中的一种或几种金属助剂组分,以氧化物计并以所述催化剂为基准,所述助剂组分的质量分数不超过5%。 11. The catalyst according to claim 1, wherein said catalyst is selected from the group comprising K, one kind of La, Ce, Zr, Cr, V, B, Mn, Re, Pt, Ru, Ba, Ca in or more metal promoter components, calculated as the oxide and based on the catalyst to the mass fraction of the adjuvant component is not more than 5%.
12. 根据权利要求11所述的催化剂,其特征在于,所述助剂组分选自K和/或Ba,以氧化物计并以所述催化剂为基准,所述助剂组分的质量分数为1-3%。 12. The catalyst according to claim 11, wherein said auxiliary component is selected from K and / or Ba, and in the terms of oxide based on the catalyst, the mass fraction of adjunct components 1-3%.
13. -种制备壳层催化剂的方法,包括制备成型的含氟水和氧化铝载体并在该载体上负载活性金属组分,其中,所述成型的含氟水和氧化铝载体的制备方法包括将水合氧化铝、 含氟化合物、纤维素醚和淀粉混合、成型并干燥;或者是将水合氧化铝、纤维素醚和淀粉混合成型并干燥,之后以浸渍的方式向该成型物中引入含氟化合物并干燥;其中,以所述成型物为基准,所述纤维素醚的质量分数为0.5-8%,以元素计的含氟化合物的质量分数为0. 2-10%,所述淀粉的质量分数为0-8% ;所述成型后的干燥条件包括:温度为80-180°C, 干燥时间为〇. 5-24小时,所述成型物的径向压碎强度大于等于12N/mm,吸水率为0. 4-1. 5, S值为小于等于10% ;其中,S = ((Q1-Q2)/Ql) X 100%,Ql为含氟水合氧化铝成型物径向压碎强度,Q2为含氟水合氧化铝成型物经水浸泡30分钟、经120°C烘干4小时后的 13. - Preparation of seed shell catalyst, comprising preparing a fluorine-containing water and forming the alumina support and the active metal component loaded on the carrier, and a method for preparing a fluorinated alumina support wherein the water, said forming comprising the hydrated alumina, fluorinated compounds, starch and cellulose mixed ethers, molded and dried; or hydrated alumina, cellulose ether and starch are mixed molded and dried, then impregnated in the manner of the introduction of the fluorine-containing molded article in this and drying the compound; wherein, with reference to the molded article, the cellulose ether mass fraction of 0.5 to 8%, calculated as element content of the fluorine-containing compound is from 0.5 to 10%, said starch mass fraction of 0-8%; the drying conditions after molding comprising: a temperature of 80-180 ° C, the drying time is 5-24 hours square, the molded product of the radial crushing strength not less than 12N / mm. , water absorption of 0. 4-1 5, S is 10% or less; where, S = ((Q1-Q2) / Ql) X 100%, Ql is a fluorine-containing molded article radially crushed alumina hydrate after strength, Q2 is a fluorine-containing alumina hydrate formed was soaked in water for 30 minutes and dried by 120 ° C 4 hours 径向压碎强度。 Radial crushing strength.
14. 根据权利要求13所述的方法,其特征在于,所述成型物的径向压碎强度为15N/ mm-30N/mm,吸水率为0. 6-1,5小于等于5%。 14. The method according to claim 13, wherein said molded product of a radial crush strength of 15N / mm-30N / mm, 6-1,5 water absorption of 0. 5% or less.
15. 根据权利要求13所述的方法,其特征在于,以所述成型物为基准,所述纤维素醚的质量分数为1% -6%,以元素计的含氟化合物的质量分数为0. 5% -9%。 15. The method according to claim 13, characterized in that, with reference to the molded article, the mass fraction of the cellulose ether is 1% to 6%, calculated as element content of fluorine-containing compound is 0 5% -9%.
16. 根据权利要求15所述的方法,其特征在于,以所述成型物为基准,所述纤维素醚的质量分数为2% -5%,以元素计的含氟化合物的质量分数为1% -8%;所述成型后的干燥条件包括:温度为100_150°C,干燥时间为1-5小时。 16. The method according to claim 15, characterized in that, with reference to the molded article, the mass fraction of the cellulose ether is 2% -5%, calculated as element content of fluorine-containing compound is a % to 8%; the drying conditions after molding comprising: a temperature 100_150 ° C, the drying time is 1-5 hours.
17. 根据权利要求13所述的方法,其特征在于,所述纤维素醚选自甲基纤维素、羟乙基甲基纤维素、羟丙基甲基纤维素中一种或几种;所述含氟化合物选自册、順/、(:##、十二氟庚醇、聚四氟乙烯粉末、全氟辛酸、氟乙酸中的一种或几种。 17. The method according to claim 13, wherein the cellulose ether is selected from methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose in one or several of; the said fluorine-containing compound selected volumes, cis / (: ##, dodecafluoroheptyl alcohol, polytetrafluoroethylene powder, perfluorooctanoic acid, fluoro acetic acid is one or more.
18. 根据权利要求17所述的方法,其特征在于,所述纤维素醚为甲基纤维素、羟乙基甲基纤维素及它们的混合物;所述含氟化合物为NH 4F、十二氟庚醇、全氟辛酸的一种或几种。 18. The method according to claim 17, wherein the cellulose ether is methyl cellulose, hydroxyethyl methyl cellulose, and mixtures thereof; the fluorine-containing compound is NH 4F, dodecafluoro heptanol, perfluoro-octanoic acid is one or more.
19. 根据权利要求13所述的方法,其特征在于,所述水合氧化铝选自拟薄水铝石、薄水铝石、氢氧化铝、三水氢氧化铝中的一种或几种。 19. The method according to claim 13, wherein said hydrated alumina is selected from boehmite pseudoboehmite, boehmite, aluminum hydroxide, aluminum hydroxide trihydrate of one or more.
20. 根据权利要求19所述的方法,其特征在于,所述水合氧化铝为拟薄水铝石。 20. The method according to claim 19, characterized in that the pseudoboehmite alumina hydrate is boehmite.
21. 根据权利要求13所述的方法,其特征在于,所述在载体上负载活性金属组分的方法为浸渍法,在所述浸渍之后包括干燥的步骤,所述干燥的条件包括:温度为100-200°C, 时间为1-15小时;以元素计并以所述催化剂为基准,所述浸渍液的浓度和用量使所述催化剂中Pd的质量分数为0. 1-2 %,Au的质量分数为0. 1-1%。 21. A method according to claim 13, characterized in that the method of supporting the active metal component on the carrier is impregnation method, comprising the step of drying after the impregnation, the drying conditions include: temperature 100-200 ° C, to 15 hours; calculated as element and with reference to the catalyst, the concentration and amount of immersion liquid so that the content of Pd in ​​the catalyst was 0. 1-2%, Au the mass fraction of 0. 1-1%.
22. 根据权利要求21所述的方法,其特征在于,所述干燥的条件包括:温度为100-200°C,时间为1-15小时;以元素计并以所述催化剂为基准,所述浸渍液的浓度和用量使所述催化剂中Pd的质量分数为0. 1-1%,Au的质量分数为0. 2-0. 8%。 22. The method of claim 21, wherein the drying conditions include: a temperature of 100-200 ° C, to 15 hours; calculated as element and to the catalyst as a reference, the the amount and concentration of the impregnating solution so that the content of Pd in ​​the catalyst was 0. 1-1%, mass fraction of Au and 0. 2-0. 8%.
23. 根据权利要求13所述的方法,其特征在于,所述淀粉为田菁粉,以所述成型物为基准,所述淀粉的引入的质量分数不超过5%。 23. The method according to claim 13, wherein the starch is Sesbania powder, with reference to the molded product, the starch content of less than 5% is introduced.
24. 根据权利要求13所述的方法,其特征在于,包括在所述载体中引入一种或几种助剂组分的步骤。 24. A method according to claim 13, characterized in that, comprising introducing one or more auxiliary components in the carrier of step.
25. 根据权利要求24所述的方法,其特征在于,所述助剂组分选自K、La、Ce、Zr、Cr、V、 B、Mn、Re、Pt、Ru、Ba、Ca中的一种或几种,以氧化物计并以所述催化剂为基准,所述助剂组分的质量分数不超过5%。 25. The method of claim 24, wherein said auxiliary component is selected from K, La, Ce, Zr, Cr, V, B, Mn, Re, Pt, Ru, Ba, Ca in one or more, calculated as the oxide and based on the catalyst to the mass fraction of the adjuvant component is not more than 5%.
26. 根据权利要求25所述的方法,其特征在于,所述助剂组分选自K和/或Ba,以氧化物计并以所述催化剂为基准,所述助剂组分的质量分数为1-3%。 26. A method according to claim 25, wherein said auxiliary component is selected from K and / or Ba, and in the terms of oxide based on the catalyst, the mass fraction of adjunct components 1-3%.
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