CN114762825B - 一种复合载体负载的Pt基催化剂及其应用 - Google Patents
一种复合载体负载的Pt基催化剂及其应用 Download PDFInfo
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- 239000011865 Pt-based catalyst Substances 0.000 title claims abstract description 6
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- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229940035437 1,3-propanediol Drugs 0.000 claims abstract description 25
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 25
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 24
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 24
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- 239000001257 hydrogen Substances 0.000 claims abstract description 9
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 26
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- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
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- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002839 Pt-Mo Inorganic materials 0.000 description 1
- 229910002835 Pt–Ir Inorganic materials 0.000 description 1
- 229910018885 Pt—Au Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical group [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 description 1
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- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
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- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
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- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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Abstract
本发明专利涉及一种新型复合载体负载的Pt基催化剂在甘油氢解制1,3‑丙二醇中的应用。所述的催化剂制备方法包括:1)通过溶胶凝胶法‑动态晶化法合成新型WO3‑Al2O3复合载体;2)活性组分前驱体溶液通过湿法浸渍在WO3‑Al2O3载体上得到Pt‑A/WO3‑Al2O3催化剂。该方法所制得的催化剂,可以使甘油水溶液在一定的氢气压力和温度下高转化率、高选择性地氢解生成1,3‑丙二醇,且具有良好的循环稳定性。
Description
技术领域
本发明涉及一种新型复合载体负载的Pt基催化剂在甘油氢解制1,3-丙二醇中的应用。
背景技术
近年来,化石能源的日益枯竭和环境污染问题的日趋突出已经严重影响到人类社会的可持续发展,因而寻找可再生的清洁能源受到了各国政府和科学家的高度重视。在这一大背景下,生物柴油由于其无毒、可再生、可降解以及污染排放物少等特点而备受关注。然而,每生产10吨生物柴油就会副产1吨甘油。可以预见,随着生物柴油产业的迅速发展,甘油也将大量过剩。因此,将甘油转化成高附加值的化学品已经成为当今化工领域的研究热点之一。甘油可以通过氢解反应生成1,3-丙二醇、1,2-丙二醇、正丙醇、异丙醇等,其中1,3-丙二醇具有更高的经济价值和市场应用价值。
1,3-丙二醇是一种高附加值的化工原料,是增塑剂、洗涤剂、防腐剂和乳化剂等的重要合成原料,也可用于食品、化妆品和制药行业,其最主要的用途是和对苯二甲酸反应生成新型高端聚酯——聚对苯二甲酸-1,3-丙二醇酯(PTT)。PTT具有优异的回弹性、柔软性、易染性等特点,同时它克服了聚对苯二甲酸乙二醇酯(PET)太硬和聚对苯二甲酸丁二醇酯(PBT)太软的特点,在地毯、纺织、工程塑料等行业具有广阔的应用前景。
相比于传统的环氧乙烷羰基化加氢法(中国专利CN1201407A)以及丙烯醛水合加氢法制备1,3-丙二醇(美国专利US5364984A),甘油直接氢解制备1,3-丙二醇具有工艺简单、环境污染极低的特点,具有极大的竞争力。经过众多研究发现,Pt/WOx/Al2O3催化剂体系可选择性将甘油氢解为1,3-丙二醇,但该催化剂体系的甘油氢解活性仍有待进一步提高。加入合适的第二种金属组分往往能起到调变催化剂活性组分结构的作用,从而提升催化剂的性能,有望推动Pt/WOx/Al2O3催化体系迈向甘油氢解工业化应用的进程。
发明内容
本发明提供了一种高效氢解甘油制1,3-丙二醇的新型复合载体负载的Pt基催化剂的制备方法。
本发明所公开的催化剂以氧化钨-氧化铝为载体,活性组分为铂和记为组分A的钯、铱、钌、铑、金、钼、钽或铌中的一种或二种以上,以载体WO3-Al2O3总重计,Pt占载体的重量百分比为0.01%~10%,优选为0.1%~5%,组分A的质量含量为0.005%~0.5%,优选为0.05%~0.2%;载体中钨的质量分数为1%~30%,优选为5%~20%;铂、钨、组分A均以元素质量为计,其特征在于催化剂活性组分为Pt-A纳米粒子高分散于载体表面,且Pt的平均粒径介于1~2nm,催化剂载体中氧化钨以低聚合态(二聚(两个W物种聚合在一起)、三聚(三个W物种聚合在一起)或四聚(四个W物种聚合在一起))的W物种(WOx,x=2.8~3)形式存在,其在紫外-可见吸收光谱所得到了禁带宽度介于3.0eV和4.5eV之间,该载体具有如下物性:孔容0.3~0.5cm3/g,平均孔径4~10nm,比表面积100~200m2/g;
所述催化剂制备方法,其特征在于首先载体通过溶胶凝胶法-动态晶化法合成,然后活性组分前躯体溶液通过湿法浸渍在WO3-Al2O3载体上,具体制备过程为:
1)将氢氧化铝加入至80℃的0.8~1mol/L稀盐酸水溶液中,用0.3~0.5mol/L氨水调节溶液中pH值至2.5~3.5之间,配制成溶胶状液体,继续搅拌处理60min;
2)将形成的溶胶状液体转移至100ml的水热釜内,向该水热釜中加入溶解好的1~5%偏钨酸铵或仲钨酸铵水溶液,在10~40rpm的转速下,将水热釜于150~170℃动态晶化30~40h,将所得混合物经过滤、洗涤后,在80~120℃烘箱中干燥8~12h,马弗炉中500~800℃煅烧2~4h,得到WO3-Al2O3载体。
3)将配比好的Pt前驱体与组分A前驱体混合水溶液湿法浸渍到上WO3/Al2O3载体上,浸渍时间为10~24h,然后在80~120℃烘箱中干燥2~12h后获得Pt-A/WO3-Al2O3催化剂。
所述的催化剂中Pt的前驱体为氯铂酸,组分A前驱体为氯金酸、氯化钯、氯铱酸、氯化铑、氯化钌、钼酸铵、氯化钽、氯化铌中的一种或二种以上。
所述的催化剂使用前用含H2体积百分数10%-100%的H2/He混合气还原,还原温度为200-400℃,还原压力为0.1MPa~5.0MPa,还原时间为0.5-5h。
对本发明催化剂的活性测试方法如下:甘油氢解制备1,3-丙二醇的反应中,采用高压间歇釜式反应器、固定床或流化床反应器中进行,反应原料为甘油水溶液,其中甘油质量浓度为3~80%,氢气压力为0.1~10MPa,反应温度为160~220℃。
本发明与现有技术相比,可以显著提高甘油的转化率和1,3-丙二醇的收率。
该方法所制得的催化剂,可以使甘油水溶液在一定的氢气压力和温度下高转化率、高选择性的氢解生成1,3-丙二醇,且具有良好的循环稳定性。
附图说明
图1为实施例1催化剂载体紫外-可见吸收光谱图。
图2为1)Pt/WO3-Al2O3催化剂(对比例3);2)Pt-Au/WO3-Al2O3催化剂(实施例2);3)Pt-Ir/WO3-Al2O3催化剂(实施例4);4)Pt-Mo/WO3-Al2O3催化剂(实施例7)高分辨球差校正电镜谱图。
具体实施方式
实施例1
将1克氢氧化铝加入至80℃的50mL 1mol/L稀盐酸水溶液中,用0.5mol/L氨水调节溶液中pH值至3,配制成溶胶状液体,继续搅拌处理60min;将形成的溶胶状液体转移至100ml的水热釜内,向该水热釜中加入溶解好的钨质量含量为2%的偏钨酸铵水溶液10mL,在20rpm的转速下,将水热釜于160℃动态晶化36h,将所得混合物经过滤、洗涤后,在100℃烘箱中干燥8h,马弗炉中800℃煅烧4h,得到7.5%WO3-Al2O3载体。由物理吸附表征可知得到的载体孔容为0.41cm3/g,平均孔径4.3nm,比表面积134.7m2/g。由图1可知载体的禁带宽度约为3.4eV,表明载体上W的状态为低聚合态。
实施例2
将氯铂酸和氯金酸按比例配成一定体积的混合水溶液等体积浸渍到7.5%WO3-Al2O3载体上,浸渍24h,110℃烘箱中干燥8h,将得到的样品在氢气还原炉中220℃纯氢气氛下还原活化1h,制得催化剂质量含量为2%Pt-0.1%Au/7.5%WO3-Al2O3。通过球差矫正高分辨电镜观察及能谱分析后发现所制得的催化剂上Pt的尺寸为1.8±0.1nm,W以2~4个原子形成的团簇形式存在,尺寸介于0.4~1nm,表明W物种以低聚合态的形式存在,未发现Au的聚集体存在,表明Au以单原子或准单原子形式存在于载体上。选用间歇高压釜式反应器,3%甘油水溶液15g,催化剂量为0.3g,反应温度180℃,反应压力5MPa,反应时间12h。
实施例3
将氯金酸换成氯化钯,其他条件与实施例2相同。
实施例4
将氯金酸换成氯铱酸,其他条件与实施例2相同。
实施例5
将氯金酸换成氯化铑,其他条件与实施例2相同。
实施例6
将氯金酸换成氯化钌,其他条件与实施例2相同。
实施例7
将氯金酸换成钼酸铵,其他条件与实施例2相同。
实施例8
将反应底物甘油水溶液质量浓度改为10%,其他条件与实施例2相同。
实施例9
保持Pt的质量分数不变,将Pt/Au质量比改为100:1,其他条件与实施例8相同。
实施例10
保持Pt的质量分数不变,将Pt/Au质量比改为40:1,其他条件与实施例8相同。
实施例11
保持Pt的质量分数不变,将Pt/Au质量比改为10:1,其他条件与实施例8相同。
实施例12
将烘干后的催化剂还原温度升高为300℃,其他条件与实施例8相同。
实施例13
将烘干后的催化剂还原温度升高为400℃,其他条件与实施例8相同。
实施例14
将反应温度改为160℃,其他条件与实施例8相同。
实施例15
将反应温度改为200℃,其他条件与实施例8相同。
实施例16
将反应温度改为220℃,其他条件与实施例8相同。
实施例17
将反应压力改为3MPa,其他条件与实施例8相同。
实施例18
将反应压力改为4MPa,其他条件与实施例8相同。
实施例19
将反应压力改为6MPa,其他条件与实施例8相同。
对比例1
将1克氢氧化铝加入至80℃的50mL 1mol/L稀盐酸水溶液中,用0.5mol/L氨水调节溶液中pH值至3,配制成溶胶状液体,继续搅拌处理60min;将形成的溶胶状液体转移至100ml的水热釜内,向该水热釜中加入溶解好的钨质量含量为2%的偏钨酸铵水溶液10mL,在0rpm的转速下,将水热釜于160℃静态晶化36h,将所得混合物经过滤、洗涤后,在100℃烘箱中干燥8h,马弗炉中800℃煅烧4h,得到7.5%WO3-Al2O3载体。
对比例2
将水热釜静态晶化改为在50rpm的转速下动态晶化36h,其他条件与对比例1相同。
对比例3
将氯铂酸等体积浸渍到7.5%WO3-Al2O3载体上,浸渍24h,110℃烘箱中干燥8h,将得到的粉末样品在氢气还原炉常压下220℃纯氢气氛下还原活化1h,制得催化剂质量含量为2%Pt/7.5%WO3-Al2O3。选用间歇高压釜式反应器,甘油水溶液质量浓度为3%,催化剂量为0.3g,反应温度180℃,反应压力5MPa,反应时间12h。
对比例4
将反应底物甘油水溶液质量浓度改为10%,其他条件与对比例3相同。
表1不同晶化转速下得到的载体的物性对比
由表1可知,水热釜晶化转速对于载体的物性有着明显的影响。当静态晶化时得到的载体孔容及平均孔径大,但比表面积小,这会导致担载贵金属活性组分后贵金属分散度下降,从而使催化剂活性位点数目下降,催化剂性能降低;当动态晶化的转速过高时得到的载体比表面积大,但载体孔容及平均孔径小,这会导致反应过程中反应物、中间体及产物在催化剂上的传质能力下降,不利于反应物吸附及产物脱附的发生,从而使得催化剂性能降低。因此,采用适中的晶化转速(优选为10~40rpm)有利于得到物理性质优良的催化剂载体。
表2 3%甘油氢解制备1,3-丙二醇的催化性能对比
其他包括少量丙烷,甲醇,乙醇,乙二醇,总体物料守恒。
由表2实施例2-7与对比例3可以看出,通过对Pt/WO3-Al2O3催化剂添加第二金属组分后可以明显提高甘油溶液的转化率和1,3-丙二醇的收率,其中Au的促进作用最为显著。
表3 10%甘油氢解制备1,3-丙二醇的催化性能对比
*其他包括少量丙烷,甲醇,乙醇,乙二醇,总体物料守恒。
由表3实例8-11可以看出,Au的引入量不同也会明显的影响甘油的转化率和1,3-丙二醇的收率,当催化剂中Pt/Au的质量比为20左右时1,3-丙二醇的收率最高。
由实例8,12,13可以看出,催化剂的还原温度不同也会明显影响甘油的转化率和1,3-丙二醇的收率,当还原温度为220℃左右时1,3-丙二醇的收率最高。
由实例8,14-16可以看出,反应温度不同也会明显影响甘油的转化率和1,3-丙二醇的收率,反应温度越高,甘油转化率越高,但温度超过180℃后高温会导致1,3-丙二醇发生过度氢解使得1,3-丙二醇的选择性降低,从而导致1,3-丙二醇收率下降。因此在80~300℃的反应温度区间内优选140℃~240℃为较适宜的反应温度。
由实例8,17-19可以看出(甘油水溶液浓度为10%),反应压力不同也会明显影响甘油的转化率和1,3-丙二醇的收率,反应压力越高,甘油的转化率和1,3-丙二醇的收率越高,但压力越高带来的投资成本也就越高,因此在0.1~10MPa的反应压力区间内优选3~8MPa为较适宜的反应压力。
Claims (2)
1.一种复合载体负载的Pt基催化剂在甘油氢解制1,3-丙二醇中的应用,其特征在于:所述催化剂以氧化钨-氧化铝为载体,活性组分为铂和记为组分A的金,所述催化剂的制备过程如下:
将1克氢氧化铝加入至80℃的50mL 1mol/L稀盐酸水溶液中,用0.5mol/L氨水调节溶液中pH值至3,配制成溶胶状液体,继续搅拌处理60min;将形成的溶胶状液体转移至100mL的水热釜内,向该水热釜中加入溶解好的钨质量含量为2%的偏钨酸铵水溶液10mL,在20rpm的转速下,将水热釜于160℃动态晶化36h,将所得混合物经过滤、洗涤后,在100 ℃烘箱中干燥8h,马弗炉中800 ℃煅烧4h,得到7.5%WO3-Al2O3载体;
将氯铂酸和氯金酸按比例配成一定体积的混合水溶液等体积浸渍到7.5%WO3-Al2O3载体上,浸渍24h,110℃烘箱中干燥8h,将得到的样品在氢气还原炉中220℃纯氢气氛下还原活化1h,制得催化剂2%Pt-0.1%Au/7.5%WO3-Al2O3,铂、钨、组分A均以元素质量为计;
所述的催化剂用于甘油氢解制备1,3-丙二醇的反应中,该反应采用高压间歇釜式反应器中进行,反应原料为甘油水溶液,甘油水溶液的质量为15g,催化剂用量为0.3g,其中甘油质量浓度为3%,反应温度180℃,反应压力5MPa,反应时间12h。
2.根据权利要求1所述的应用,其特征在于:催化剂活性组分为Pt-A纳米粒子高分散于载体表面,且Pt的平均粒径介于1.8±0.1nm,催化剂载体中氧化钨以低聚合态形式存在,其中低聚合态的W为两个W物种聚合在一起、三个W物种聚合在一起或四个W物种聚合在一起,WOx,x=2.8~3。
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