CN110013848B - 一种用于乙酰丙酸加氢制γ-戊内酯的催化剂及其制备方法 - Google Patents
一种用于乙酰丙酸加氢制γ-戊内酯的催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种用于乙酰丙酸加氢制γ‑戊内酯的催化剂及其制备方法,属于催化剂制备技术领域。本发明的催化剂包括活性组分内核、包裹在活性组分内核外的活性组分层;所述活性组分内核为M‑B非晶态合金,M选自Zn、Cu、Fe、Co、Ni中的至少一种;所述活性组分层为Ru‑B非晶态合金;M‑B非晶态合金中M原子和Ru‑B非晶态合金中Ru原子的物质的量之比为1:0.05~1.5。本发明的用于乙酰丙酸加氢制γ‑戊内酯的催化剂的亲水性好,具有高活性和高γ‑戊内酯选择性。
Description
技术领域
本发明涉及一种用于乙酰丙酸加氢制γ-戊内酯的催化剂及其制备方法,属于催化剂制备技术领域。
背景技术
随着世界范围内现代工业和交通技术发展,能源和燃料的需求量大幅增加。目前为止,80%以上的需求源自于存量减少而价格升高的化石燃料。因此,寻求更清洁、持续性更强的能源原料显得尤为重要,而木质纤维素生物质作为碳储量最大的可再生能源,是化石燃料最有可能的替代品。
在木质纤维素生物质化工中,γ-戊内酯是非常重要的平台化合物,它可以直接用作燃料添加剂、绿色溶剂、香料等,也可以继续反应生成汽油、柴油和航空燃料等。目前,合成γ-戊内酯最佳反应路线为乙酰丙酸加氢,加氢过程可以使用氢气,也可以使用甲酸或多元醇等作为替代氢源。而乙酰丙酸可以通过简单的纤维素和半纤维素水解产生,同时纤维素水解过程中会产生与乙酰丙酸等摩尔比例的甲酸。所以,从碳原子经济性和分离成本上考虑,开发能够在水相中采用甲酸或氢气进行乙酰丙酸加氢的高活性、选择性的催化剂至关重要。
现有技术中,《Co/γ-Al2O3催化乙酰丙酸加氢合成γ-戊内酯的研究》一文中公开了一种用于乙酰丙酸加氢合成γ-戊内酯的催化剂,(张琳,陆晓蕾等.Co/γ-Al2O3催化乙酰丙酸加氢合成γ-戊内酯的研究[J].2013.21(7):68-71.)该文献的催化剂的制备方法是将由等体积浸渍法制备的Co/γ-Al2O3催化剂、1.67g乙酰丙酸和40mL甲醇加入高压釜,通氢气置换高压釜中空气,然后通氢气至反应压力,缓慢升温至反应温度进行反应得到。采用该催化剂催化乙酰丙酸加氢制γ-戊内酯时,γ-戊内酯的选择性最高仅能达到81.4%,其选择性较差。
此外,现有技术中,乙酰丙酸加氢制γ-戊内酯多数是在有机相中进行的,由于原料乙酰丙酸一般利用生物质水解产生,采用有机相时需要对水解产生的乙酰丙酸进行分离,并且产物γ-戊内酯的极性较小,采用有机相也加大了产物从体系中分离的难度。
发明内容
本发明的目的是提供一种用于乙酰丙酸加氢制γ-戊内酯的催化剂。该催化剂的亲水性好、γ-戊内酯的选择性好。
本发明还提供一种用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法,该方法工艺简单,易于实现。
为实现上述目的,本发明的用于乙酰丙酸加氢制γ-戊内酯的催化剂的技术方案是:
一种用于乙酰丙酸加氢制γ-戊内酯的催化剂,包括活性组分内核、包裹在活性组分内核外的活性组分层;所述活性组分内核为M-B非晶态合金,M选自Zn、Cu、Fe、Co、Ni中的至少一种;所述活性组分层为Ru-B非晶态合金;M-B非晶态合金中M原子和Ru-B非晶态合金中Ru原子的物质的量之比为1:(0.05~1.5)。
该催化剂亲水性好,具有高活性和高γ-戊内酯选择性。
所述用于乙酰丙酸加氢制γ-戊内酯的催化剂还包括包裹在活性组分层外的助剂外壳;所述助剂外壳为氧化铝。以氧化铝作为助剂外壳可以进一步提高γ-戊内酯的选择性,使γ-戊内酯的选择性高于97%。
助剂外壳中Al原子与M-B非晶态合金中M原子的物质的量之比为(0.05~1.5):1。该物质的量之比的Al原子和M原子可以增强催化剂的γ-戊内酯选择性。
本发明的用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的技术方案是:
一种上述用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法,包括如下步骤:
1)将M-B非晶态合金加入Ru溶胶中,在保护气氛下进行凝胶化;
2)加入硼氢化物进行反应,反应完全得到沉淀,将沉淀进行洗涤,得Ru-B包裹的M-B催化剂。
该制备方法操作简单,易于实现。
所述M-B非晶态合金的制备方法,包括如下步骤:在金属M的可溶性盐水溶液中加入硼氢化物进行反应得到沉淀,将沉淀洗涤至中性即得。该方法的目的是将金属M元素转化为M-B化合态的形式,得到M-B非晶态合金,为下一步反应做准备。
所述金属M的可溶性盐水溶液中M原子与硼氢化物中B原子的物质的量之比为1:(5~50)。该物质的量的比例可以使反应均匀、稳定地进行。
所述Ru溶胶中Ru原子与硼氢化物中B原子的物质的量之比为1:(5~50)。该物质的量的比例可以使反应均匀、稳定地进行。
步骤2)中,加入硼氢化物进行反应的温度为0~50℃。该反应温度下可以使反应更稳定。
所述Ru溶胶的制备方法为:在Ru的可溶性盐溶液中加入强碱溶液至不再产生沉淀,然后加入柠檬酸溶液至沉淀完全溶解,即得;所述强碱溶液中OH-的浓度为0.1~10mol/L;所述柠檬酸溶液中柠檬酸的浓度为0.01~5mol/L。上述浓度保证Ru溶胶在催化剂表面的高分散性,以确保催化剂的高活性。
上述用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法,还包括步骤:将Ru-B包裹的M-B催化剂加入到Al溶胶中,在保护气氛下进行凝胶化,固液分离得固体,将固体洗涤即得。通过该方法制得的催化剂γ-戊内酯的选择性高达97%以上。
附图说明
图1为本发明用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例1中Zn-B@Ru-B@Al2O3催化剂的TEM测试图;
图2为本发明用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例2中Cu-B@Ru-B@Al2O3催化剂的TEM测试图;
图3为本发明用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例3中Fe-B@Ru-B@Al2O3催化剂的TEM测试图;
图4为本发明用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例4中Co-B@Ru-B@Al2O3催化剂的TEM测试图;
图5为本发明用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例5中Ni-B@Ru-B@Al2O3催化剂的TEM测试图。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
下面实施例中,M-B非晶态合金的制备中,可溶性M盐可以为M的盐酸盐、硝酸盐或硫酸盐等,优选为盐酸盐、硝酸盐。从原料的成本方面考虑,优选的,硼氢化物为硼氢化钠或硼氢化钾。
Ru溶胶的制备:
取2.4g RuCl3·3H2O加入到50mL蒸馏水中配成RuCl3溶液,将4mol/L的NaOH溶液滴加到RuCl3溶液中,直至不再有沉淀生成为止;再加入1mol/L的柠檬酸溶液,直至沉淀完全溶解,即得Ru溶胶。
上述Ru溶胶的制备过程中,可溶性Ru盐还可以为Ru的硝酸盐或硫酸盐等,氢氧化钠也可以替换为氢氧化钾,Ru溶胶为水合氢氧化钌胶状溶液。
在Pt溶胶的凝胶化过程中,为形成稳固的凝胶结构,优选的,凝胶化是在温度为50~150℃、保护气体压力为1~5MPa下保持1~5h。保护气体可选择氮气、氩气、氢气等,从抗氧化效果方面考虑,优选的,所述保护气体选择氢气。
Al溶胶的制备:
取0.41g AlCl3溶于50mL蒸馏水中,将4mol/L的NaOH溶液滴加到AlCl3溶液中,直至不再有沉淀生成为止;再加入4mol/L的NaOH溶液直至沉淀完全溶解,即得Al溶胶。
上述Al溶胶的制备过程中,可溶性Al盐溶液还可以为Al的硝酸盐或硫酸盐溶液等。所述氢氧化钠也可以替换为氢氧化钾。Al溶胶为水合氢氧化铝胶状溶液。在Al溶胶的凝胶化过程中,优选的,凝胶化是在温度为50~150℃、保护气体压力为1~5MPa下保持1~5h。保护气体可选择氮气、氩气、氢气等,优选的,所述保护气体选择氢气。
本发明的用于乙酰丙酸加氢制γ-戊内酯的催化剂经BET测得的比表面积为50~70cm2/g。催化剂中,B的质量含量为0.02%~0.05%。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的实施例1
本实施例的用于乙酰丙酸加氢制γ-戊内酯的催化剂,包括活性组分内核Zn-B非晶态合金、包裹在活性组分内核外的活性组分层Ru-B非晶态合金以及包裹在活性组分层外的助剂外壳Al2O3;Zn-B非晶态合金中Zn原子和Ru-B非晶态合金中Ru的物质的量之比为1:0.6;Zn-B非晶态合金中Zn原子和Al2O3中Al原子的物质的量之比为1:0.2。催化剂中B的质量含量为0.03%。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的实施例2
本实施例的用于乙酰丙酸加氢制γ-戊内酯的催化剂,包括活性组分内核Cu-B非晶态合金、包裹在活性组分内核外的活性组分层Ru-B非晶态合金以及包裹在活性组分层外的助剂外壳Al2O3;Cu-B非晶态合金中Cu原子和Ru-B非晶态合金中Ru的物质的量之比为1:0.6;Cu-B非晶态合金中Cu原子和Al2O3中Al原子的物质的量之比为1:0.2。催化剂中B的质量含量为0.03%。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的实施例3
本实施例的用于乙酰丙酸加氢制γ-戊内酯的催化剂,包括活性组分内核Fe-B非晶态合金、包裹在活性组分内核外的活性组分层Ru-B非晶态合金以及包裹在活性组分层外的助剂外壳Al2O3;Fe-B非晶态合金中Fe原子和Ru-B非晶态合金中Ru的物质的量之比为1:0.6;Fe-B非晶态合金中Fe原子和Al2O3中Al原子的物质的量之比为1:0.2。催化剂中B的质量含量为0.02%。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的实施例4
本实施例的用于乙酰丙酸加氢制γ-戊内酯的催化剂,包括活性组分内核Co-B非晶态合金、包裹在活性组分内核外的活性组分层Ru-B非晶态合金以及包裹在活性组分层外的助剂外壳Al2O3;Co-B非晶态合金中Co原子和Ru-B非晶态合金中Ru的物质的量之比为1:0.6;Co-B非晶态合金中Co原子和Al2O3中Al原子的物质的量之比为1:0.2。催化剂中B的质量含量为0.03%。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的实施例5
本实施例的用于乙酰丙酸加氢制γ-戊内酯的催化剂,包括活性组分内核Ni-B非晶态合金、包裹在活性组分内核外的活性组分层Ru-B非晶态合金以及包裹在活性组分层外的助剂外壳Al2O3;Ni-B非晶态合金中Ni原子和Ru-B非晶态合金中Ru的物质的量之比为1:0.6;Ni-B非晶态合金中Ni原子和Al2O3中Al原子的物质的量之比为1:0.2。催化剂中B的质量含量为0.05%。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的实施例6
本实施例的用于乙酰丙酸加氢制γ-戊内酯的催化剂,其结构和催化剂的实施例4相同,区别仅在于,催化剂中Co-B非晶态合金中Co原子和Ru-B非晶态合金中Ru的物质的量之比为1:0.07;Co-B非晶态合金中Co原子和Al2O3中Al原子的物质的量之比为1:1.3。催化剂中B的质量含量为0.02%。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的实施例7
本实施例的用于乙酰丙酸加氢制γ-戊内酯的催化剂,其结构和催化剂的实施例5相同,区别仅在于,催化剂中Ni-B非晶态合金中Ni原子和Ru-B非晶态合金中Ru的物质的量之比为1:1.2;Ni-B非晶态合金中Ni原子和Al2O3中Al原子的物质的量之比为1:0.04。催化剂中B的质量含量为0.04%。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的实施例8
本实施例的用于乙酰丙酸加氢制γ-戊内酯的催化剂,包括活性组分内核Ni-B非晶态催化剂、包裹在活性组分内核外的活性组分层Ru-B非晶态催化剂;Ni-B非晶态催化剂中Ni原子和Ru-B非晶态催化剂中Ru的物质的量之比为1:0.6。催化剂中B的质量含量为0.05%。
以下催化剂的制备方法实施例1-8分别对应合成上述催化剂实施例1-8涉及的催化剂。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例1
本实施例用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法,包括以下步骤:
(1)Zn-B非晶态合金的制备:
取2.1g ZnCl2加入到50mL蒸馏水中配成溶液,取5.8g NaBH4溶于50mL蒸馏水中配成溶液,在30℃下将NaBH4溶液滴加到ZnCl2溶液中反应得黑色固体,滴加过程中同时搅拌,将黑色固体用蒸馏水洗涤至洗涤液为中性,所得黑色固体即为Zn-B非晶态合金;ZnCl2和NaBH4的物质的量之比为1:10。
(2)Ru溶胶的制备:
取2.4g RuCl3·3H2O加入到50mL蒸馏水中配成RuCl3溶液,将4mol/L的NaOH溶液滴加到RuCl3溶液中,直至不再有沉淀生成为止;再加入1mol/L的柠檬酸溶液直至沉淀完全溶解,即得Ru溶胶。
(3)Ru-B包裹的Zn-B催化剂的制备:
将步骤(1)制备好的Zn-B非晶态合金加入到Ru溶胶中,在150℃、氢气压力1MPa下以800r/min的转速搅拌反应3h,得混合液;
取5.8g NaBH4溶于50mL蒸馏水中配成NaBH4溶液,在30℃、搅拌下将该NaBH4溶液滴加到上述混合液中;继续搅拌30min,使Ru完全还原,固液分离,得黑色固体;NaBH4与混合液中Ru的物质的量比为10:1;将所得黑色固体用蒸馏水洗涤至洗涤液为中性,所得黑色固体即为Ru-B包裹的Zn-B催化剂。
(4)Al溶胶的制备:
取0.41g AlCl3溶于50mL蒸馏水中,将4mol/L的NaOH溶液滴加到AlCl3溶液中,直至不再有沉淀生成为止;再加入4mol/L的NaOH溶液直至沉淀完全溶解,即得Al溶胶。
(5)Zn-B@Ru-B@Al2O3催化剂的制备:
将步骤(3)制得的Ru-B包裹的Zn-B催化剂加入到Al溶胶中,Zn-B催化剂中的Zn与Al溶胶中Al的物质的量的比为1:0.2,在150℃、氢气压力5MPa下以800r/min的转速搅拌反应3h,得黑色固体,将黑色固体用蒸馏水洗涤至洗涤液为中性,即得。该催化剂的微晶尺寸在5nm左右,如图1所示。
乙酰丙酸的转化率和γ-戊内酯选择性检测
以氢气为氢源,在间歇反应釜中催化乙酰丙酸加氢制γ-戊内酯反应的步骤如下:取0.5g步骤(5)所得催化剂和12.5g乙酰丙酸加入到反应釜中,再加入250mL蒸馏水,用氮气置换釜内空气,然后维持氢气压力为1MPa,以800r/min的速率进行搅拌,以1℃/min的速率升温至150℃,反应5h后得产物。采用气相色谱仪分析产物的组成,采用FID检测器及面积校正法计算产物浓度,进而计算乙酰丙酸的转化率和γ-戊内酯选择性,结果见表1。
以甲酸为氢源,在间歇反应釜中催化乙酰丙酸加氢制γ-戊内酯反应的步骤如下:取0.5g步骤(5)所得催化剂、10.4g乙酰丙酸和1.4g甲酸加入到反应釜中,再加入250mL蒸馏水,以800r/min的速率进行搅拌,以1℃/min的速率升温至150℃,反应24h后得产物,采用气相色谱仪分析产物的组成,FID检测器及面积校正法计算产物浓度,进而计算乙酰丙酸的转化率和γ-戊内酯选择性,结果见表1。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例2
本实施例与用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例1的区别在于:
1)、将实施例1中步骤(1)的ZnCl2替换为CuCl2,制得本实施例的Al2O3包裹Ru-B包裹的Cu-B催化剂,该催化剂微晶尺寸在5nm左右,如图2所示。乙酰丙酸的转化率和γ-戊内酯选择性测试结果如表1所示。
2)、将实施例1中步骤(2)Ru溶胶的制备过程中NaOH溶液的浓度4mol/L替换为0.1mol/L,柠檬酸溶液的浓度1mol/L替换为0.01mol/L。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例3
本实施例与用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例1的区别仅在于:
1)、将实施例1中步骤(1)的2.1g的ZnCl2替换为2.0g的FeCl2,制得本实施例的Al2O3包裹Ru-B包裹的Fe-B催化剂,该催化剂微晶尺寸在5nm左右,如图3所示。乙酰丙酸的转化率和γ-戊内酯选择性测试结果如表1所示。
2)、将实施例1中步骤(2)Ru溶胶的制备过程中NaOH溶液的浓度4mol/L替换为10mol/L,柠檬酸溶液的浓度1mol/L替换为5mol/L。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例4
本实施例与用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例1的区别仅在于:将实施例1中的2.1g的ZnCl2替换为2.0g的CoCl2,制得本实施例的Al2O3包裹Ru-B包裹的Co-B催化剂,该催化剂微晶尺寸在5nm左右,如图4所示。乙酰丙酸的转化率和γ-戊内酯选择性测试结果如表1所示。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例5
本实施例与用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例1的区别仅在于:将实施例1中的2.1g的ZnCl2替换为2.0g的NiCl2,制得本实施例的Al2O3包裹Ru-B包裹的Ni-B催化剂,该催化剂微晶尺寸在5nm左右,如图5所示。乙酰丙酸的转化率和γ-戊内酯选择性测试结果如表1所示。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例6
本实施例与用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例1的制备步骤基本相同,区别仅在于:
步骤(1)中,CoCl2和NaBH4的物质的量之比为1:6。
步骤(3)中,将步骤(1)制备好的Co-B非晶态合金加入到Ru溶胶中,在100℃、氢气压力3MPa下以400r/min的转速搅拌反应5h得混合液。
取5.8g NaBH4溶于50mL蒸馏水中配成NaBH4溶液,在50℃、搅拌下将该NaBH4溶液滴加到上述混合液中;继续搅拌30min,使Ru完全还原,固液分离,得黑色固体;NaBH4与混合液中Ru的物质的量比为7:1。
步骤(5)中,将Ru-B包裹的Co-B催化剂加入到Al溶胶中,在100℃、氢气压力3MPa下以400r/min的转速搅拌反应5h。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例7
本实施例与用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例1的制备步骤基本相同,区别仅在于:
步骤(1)中,NiCl2和NaBH4的物质的量之比为1:20。
步骤(3)中,将步骤(1)制备好的Ni-B非晶态合金加入到Ru溶胶中,在50℃、氢气压力4MPa下以1000r/min的转速搅拌反应2h得混合液。
取5.8g NaBH4溶于50mL蒸馏水中配成NaBH4溶液,在10℃、搅拌下将该NaBH4溶液滴加到上述混合液中;继续搅拌30min,使Ru完全还原,固液分离,得黑色固体;NaBH4与混合液中Ru的物质的量比为30:1。
步骤(5)中,将Ru-B包裹的Ni-B催化剂加入到Al溶胶中,在60℃、氢气压力4MPa下以1000r/min的转速搅拌反应2h。
用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例8
参考用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法的实施例7的步骤(1)~步骤(3),即得不含助剂外壳的催化剂。
表1催化剂制备方法的实施例1~8的评价结果
从表1结果可以看出,利用本发明制备的催化剂,以氢气为氢源,乙酰丙酸的转化率达到了100%,γ-戊内酯的选择性达到了97.8%以上;以甲酸为氢源,实现了γ-戊内酯的水相催化合成,原料的转化率和产物的选择性均处于较高水平,表现出良好的工业应用价值。
Claims (8)
1.一种用于乙酰丙酸加氢制γ-戊内酯的催化剂,其特征在于:包括活性组分内核、包裹在活性组分内核外的活性组分层;所述活性组分内核为M-B非晶态合金,M选自Zn、Cu、Fe、Co、Ni中的至少一种;所述活性组分层为Ru-B非晶态合金;M-B非晶态合金中M原子和Ru-B非晶态合金中Ru原子的物质的量之比为1:(0.05~1.5);
所述用于乙酰丙酸加氢制γ-戊内酯的催化剂还包括包裹在活性组分层外的助剂外壳;所述助剂外壳为氧化铝;
助剂外壳中Al原子与M-B非晶态合金中M原子的物质的量之比为(0.05~1.5):1。
2.一种如权利要求1所述的用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法,其特征在于:包括如下步骤:
1)将M-B非晶态合金加入Ru溶胶中,在保护气氛下进行凝胶化;
2)加入硼氢化物进行反应,反应完全得到沉淀,将沉淀进行洗涤,得Ru-B包裹的M-B催化剂。
3.根据权利要求2所述的用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法,其特征在于:所述M-B非晶态合金的制备方法,包括如下步骤:在金属M的可溶性盐水溶液中加入硼氢化物进行反应得到沉淀,将沉淀洗涤至中性即得。
4.根据权利要求3所述的用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法,其特征在于:所述金属M的可溶性盐水溶液中M原子与硼氢化物中B原子的物质的量之比为1:(5~50)。
5.根据权利要求2所述的用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法,其特征在于:所述Ru溶胶中Ru原子与硼氢化物中B原子的物质的量之比为1:(5~50)。
6.根据权利要求2所述的用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法,其特征在于:步骤2)中,加入硼氢化物进行反应的温度为0~50℃。
7.根据权利要求2所述的用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法,其特征在于:所述Ru溶胶的制备方法包括:在Ru的可溶性盐溶液中加入强碱溶液至不再产生沉淀,然后加入柠檬酸溶液至沉淀完全溶解,即得;所述强碱溶液中OH-的浓度为0.1~10mol/L;所述柠檬酸溶液中柠檬酸的浓度为0.01~5mol/L。
8.根据权利要求2所述的用于乙酰丙酸加氢制γ-戊内酯的催化剂的制备方法,其特征在于:还包括步骤:将Ru-B包裹的M-B催化剂加入到Al溶胶中,在保护气氛下进行凝胶化,固液分离得固体,将固体洗涤即得。
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