CN109107581A - 一种耐酸合金催化剂 - Google Patents
一种耐酸合金催化剂 Download PDFInfo
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- CN109107581A CN109107581A CN201710481326.4A CN201710481326A CN109107581A CN 109107581 A CN109107581 A CN 109107581A CN 201710481326 A CN201710481326 A CN 201710481326A CN 109107581 A CN109107581 A CN 109107581A
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- catalyst
- parts
- resisting alloy
- alloy catalyst
- acid resisting
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8875—Germanium, tin or lead
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- 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
- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0081—Preparation by melting
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
本发明公开了一种耐酸合金催化剂;它包括镍、一种或多种稀土元素、锡、铝和钼;它廉价、稳定、不需要载体,能稳定应用在工业连续化生产中,并且能使生产成本较低。
Description
技术领域
本发明涉及合金催化剂技术领域。更具体地,涉及一种耐酸合金催化剂。
背景技术
雷尼镍合金催化剂由于其对氢气的强吸附性,高的催化活性和热稳定性使得其被广泛用在很多工业过程和有机合成反应中,如不饱和化合物烯烃,炔烃,腈,二烯烃,芳香烃,含羰基的物质,乃至具有不饱和键的高分子的氢化反应以及可溶性糖的氢化反应,如可溶性糖加氢生产山梨醇和木糖醇。有些反应在反应过程中会产生酸,由于在酸性条件下镍会释放出氢气而生成镍离子Ni2+,导致催化剂缓慢溶解,失去加氢活性。通常,需要向反应体系中加入碱来中和酸以维持镍催化剂的稳定性。碱的加入不但会增加碱原料的成本而且会加大产品的分离和纯化成本,甚至会改变催化剂对目标产物的选择性。如在糖直接加氢裂解制备乙二醇反应中,由于糖极易在高温水相的条件下发生水解副反应,生成小分子物质,如乙酸、乳酸、蚁酸等导致体系酸度增加(Sevilla M,Fuertes A B.Chemical andstructural properties of carbonaceous products obtained byhydrothermalcarbonization of saccharides.Chemistry-A European Journal.2009,15(16):4195-4203.),文献中报道可以通过调节反应体系pH在7以上以维持含镍催化剂的稳定性(CN103667365A)。但高pH条件下,丙二醇的得率会大幅度增加而乙二醇得率会大幅度降低(US5107018,CN101781167A,CN101781171A,CN101781166A),同时水解副反应产生的酸如甲酸,乙酸,乳酸等增多,总二元醇的得率也会相应降低(CN101544537A)。
在pH<5的酸性条件下,还原糖处于较稳定的状态,基本不发生水解副反应(李雁,沈参秋等,非纯糖液中,蔗糖分解机理的研究,中国甜菜糖业,1996(2):11-16),因而在酸性条件下运行糖加氢催化体系可以提高多元醇的得率。但在低pH值条件下,只有Ru,Pt等贵金属是稳定的,可以作为催化活性组分。使用贵金属将会大幅度增加二元醇的生产成本。为了降低贵金属的使用量并提高活性,通常选择高比表面积的载体对其进行固定和分散。但是常用的载体如氧化铝、氧化硅、氧化镁等无机氧化物在酸性条件下不稳定,容易发生中和反应,溶解在反应体系中,导致多元醇收率降低(CN103159587A)。活性炭作为耐酸的材料,也常被作为催化剂的载体使用,以提高催化剂的比表面积(CN103420796A,CN102643165A,CN102731258A,CN10161325A)。但活性炭在高温氢气条件下也不稳定,容易发生加氢反应而被甲烷化(US2002/0169344)。
此外,镍合金材料还有哈氏合金,其主要组成为Ni50-64%,Mo15-30%,Cr14-21%。它对各种化工环境有异常的抵御能力,尤其对各种有机酸具有耐腐蚀的能力,较高的钼和铬含量提高了其耐蚀性。它作为耐蚀性金属结构材料,更注重于力学性能的保证。
因此,需要开发一种耐酸的、廉价的、稳定的不需要载体的镍合金催化剂,它能稳定应用在工业连续化生产中,并且能使生产成本较低。
发明内容
本发明的目的是提供一种耐酸合金催化剂。它能稳定应用在工业连续化生产中,并且能使生产成本较低。
本发明采用下述技术方案:
一种耐酸合金催化剂,包括镍、一种或多种稀土元素、锡、铝和钼;各组分按重量份数计优选分别为10-90份镍、1-5份稀土元素、1-60份锡、5-9份铝和0.1-20份钼。
本发明的耐酸合金催化剂廉价、稳定、不需要载体。
本文中,稀土元素指周期系ⅢB族中原子序数为21、39和57-71的17种化学元素的统称,包括镧(La)、铈(Ce)、钐(Sm)等。
进一步地,所述耐酸合金催化剂包括镍、一种或多种稀土元素、锡、铝、钼和硼或磷,各组分按重量份数计优选分别为10-90份镍、1-5份稀土元素、1-60份锡、5-9份铝、0.1-20份钼和0.01-5份硼或磷。
本催化剂合金中使用了金属元素钼,好处是(与包括镍、一种或多种稀土元素、锡和铝比)有利于反应原料在催化剂上的吸附。反应原料先吸附在钼上,再转移到镍的催化活性发生催化反应。同时,钼的加入可以保持铝成分在反应中不流失,从而保证了催化剂的物理强度和使用寿命。
本催化剂合金中避免使用了金属元素钨,好处是(与包括镍、一种或多种稀土元素、锡、铝和钨比)减少了一种金属使用,降低了催化剂生产的成本,与含有钨的催化剂合金比,可以达到同样的催化效果。
本发明的耐酸合金催化剂可采用化学还原法或者电解沉积法直接制备得到具有高比表面积的活性金属粉末,或者先采用熔炼法形成金属合金,然后采用机械粉碎法,雾化法等形成金属粉末,最后采用常规的雷尼镍催化剂活化方法形成活性金属粉末。例如,将镍、稀土元素、锡、铝、钼、和硼或磷按重量份数计分别为10-90份、1-5份、1-60份、5-9份、0.1-20份、和0.01-5份加入熔炼炉中,升温到1500-2000℃,之后降低温度,充分机械搅拌均匀后出炉,得到金属合金。采用锤式磨粉机将金属合金粉碎成金属粉末,用20wt%-25wt%氢氧化钠水溶液在70-95℃浸泡金属粉末1-2小时,形成具有高比表面积的活性金属粉末。
本发明的耐酸合金催化剂应用在可溶性糖一步法催化加氢裂解制备二元醇的工艺中。
该方法以糖和氢气为原料,在水中与催化剂接触制备二元醇,所采用的催化剂为复合催化剂,所述复合催化剂由主催化剂和助催化剂组成,
其中,
所述主催化剂为本发明的耐酸合金催化剂;
所述助催化剂为可溶性钨酸盐和/或不可溶性钨化合物。
优选地,所述二元醇为乙二醇。
采用本发明的耐酸合金催化剂作为主催化剂,与可溶性钨酸盐和/或不可溶性钨化合物的助催化剂配合使用来作为复合催化剂催化糖来制得二元醇,能在生产成本较低情况下保证二元醇尤其是乙二醇的收率。本发明的耐酸合金催化剂在酸性条件下是稳定的,无需在反应体系加入碱来中和糖水解产生的酸。在工业连续化生产中时,使用这种耐酸合金催化剂作为主催化剂对系统长期、稳定的运行和生产成本的控制尤为重要。
优选地,以上述方法制备乙二醇时,反应体系pH值为1-7;更优选地,反应体系pH值为3-6。通过控制体系pH值<7,不但能避免原料糖在反应过程中发生水解副反应,降低了乙二醇生产中原料糖的消耗量,而且确保了催化剂的使用寿命,可以降低催化剂的使用成本,保证反应系统长期连续运行的稳定性,同时乙二醇的收率高,有机酸和聚合物的产量低。如果反应过程中产生的酸不足以维持低pH值,可向体系中添加乳酸、甲酸、乙酸等有机酸或无机酸来调节反应体系的pH值。通常,有机酸或无机酸随原料糖一起加入。
优选地,所述糖选自五碳单糖、二糖和寡糖,六碳单糖、二糖和寡糖,可溶性的五碳多糖、和可溶性的六碳多糖中的一种或几种。原料糖的最初来源包括但不仅限于糖基物质如甜菜,甘蔗等,淀粉基物质如玉米,小麦,大麦,木薯等,或者木质纤维素基物质如玉米秸秆,玉米芯,麦杆,甘蔗渣,木材等,纤维素类的工业残渣如玉米芯渣等,或者废纸,废包装纸等,或者多糖物质包括海藻等。本文中,可溶性的五碳多糖和可溶性的六碳多糖指在本工艺的反应条件下可溶解的五碳多糖和六碳多糖,不仅仅指在常温下可溶解的五碳多糖和六碳多糖。
优选地,所述糖以糖水溶液(简称糖液)形式与氢气发生反应,糖水溶液浓度为5-60wt%。更优选地,为20-50wt%。在连续化操作中,糖液可通过输送泵来连续进料。通过选用合适的催化剂,使得反应体系对原料糖的浓度限制较小,能采用高浓度糖液为原料,这会大大降低二元醇尤其是乙二醇的生产成本,实现了大规模、经济的生产二元醇。
优选地,所述可溶性钨酸盐为钨酸铵、钨酸钠、磷钨酸钠中的一种或几种;所述不可溶性钨化合物为三氧化钨和/或钨酸。
所述主催化剂与水混合后加入到反应器中。
优选地,所述主催化剂的用量为每小时糖进料量的0.01-10倍。
优选地,反应为连续模式。
优选地,所述主催化剂的补入量为:每进料1000kg糖,补入的主催化剂为0.01-5kg。催化剂的补入可以是通过催化剂出料阀(通常在反应器底部)排放出一部分旧的催化剂,然后通过催化剂进料阀(通常在反应器底部)补入相同量的新催化剂来实现。
所述可溶性助催化剂可先加入糖液中,之后一并加入反应器。优选地,所述可溶性助催化剂的用量为糖水溶液的0.01-5wt%。更优选地,为0.01-2wt%。最优选地,为0.01-1wt%。
所述不可溶性助催化剂可与主催化剂一并加入反应器。优选地,所述不可溶性助催化剂的用量为主催化剂的0.5-50wt%。更优选地,为5-20wt%。
优选地,反应体系反应压力为5-12MPa,反应温度为150-260℃,反应时间≥10min。
更优选地,反应体系反应压力为6-10MPa,反应温度为180-250℃,反应时间0.5-3h。反应时间最优选为0.5-2小时。
优选地,所述反应在浆态床反应器中进行。为保证反应的顺利进行,形成的反应液的总体积不超过反应器容积的80%。
优选地,所述浆态床反应器中设有过滤器,用于将催化剂中的不可溶部分保留在反应器内,而不被经过滤器流出的气体和反应液带走。
反应开始前,向浆态床反应器中加入主催化剂,分别用泵将氢气和糖液同时加入反应器中,进行反应;糖和主催化剂的补入处于连续流动的状态,反应液从反应器中连续流出。对助催化剂,当其为可溶性钨化合物时,与糖液一起加入反应器中;当其为不可溶性钨化合物时,与主催化剂同时加入反应器中。反应器内装有过滤器。该过滤器可以截留催化剂,但气体和反应液会通过过滤器连续流出并进入冷凝器进行气液分离。粗氢气经净化脱除CO,CO2,CH4等,再次成为纯化氢气,返回反应器。从冷凝器流出的流出料进入分离系统,分离得到水、乙二醇、丙二醇、丁二醇、丙三醇、山梨醇和助催化剂等。利用现有技术(例如精馏)可纯化得到乙二醇、丙二醇和丁二醇等产品。水、山梨醇、丙三醇和已溶解在反应体系中的助催化剂返回反应器中循环反应。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1为本发明的耐酸合金催化剂应用在可溶性糖一步法催化加氢裂解制备二元醇时的工艺流程示意图。
图2为实施例2中乙二醇收率随时间变化图。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例和附图对本发明做进一步的说明。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
实施例1
制备耐酸合金催化剂:
本发明的耐酸合金催化剂可采用化学还原法或者电解沉积法直接制备得到具有高比表面积的活性金属粉末,或者先采用熔炼法形成金属合金,然后采用机械粉碎法,雾化法等形成金属粉末,最后采用常规的雷尼镍催化剂活化方法形成活性金属粉末。例如,将镍、稀土元素、锡、铝、钼、和硼或磷按重量份数计分别为10-90份、1-5份、1-60份、5-9份、0.1-20份、和0.01-5份加入熔炼炉中,升温到1500-2000℃,之后降低温度,充分机械搅拌均匀后出炉,得到金属合金。采用锤式磨粉机将金属合金粉碎成金属粉末,用20wt%-25wt%氢氧化钠水溶液在70-95℃浸泡金属粉末1-2小时,形成具有高比表面积的活性金属粉末。
分别制备得到耐酸合金催化剂Ni80Sm1Sn30Al8Mo1(表示耐酸合金催化剂的组成为Ni80份+Sm1份+Sn30份+Al8份+Mo1份,下同)、耐酸合金催化剂Ni10Sm5Sn3Al2Mo5、耐酸合金催化剂Ni70Ce1Sn50Al7Mo0.5B5、耐酸合金催化剂Ni90Ce3Sn60Al9Mo20P0.01、耐酸合金催化剂Ni80La1Ce0.5Sn30Al7Mo10。
实施例2
将6L水和1400g耐酸合金催化剂Ni80Sm1Sn30Al8Mo1(作为主催化剂)边搅拌边加入到10L反应釜中。将反应釜密封,常压下以1000L/h通入氢气置换反应釜内空气5小时后,将氢气压力升高到10MPa,继续通入氢气5小时,反应釜温度升到250℃,开始连续进料。进料组成为:40wt%葡萄糖,0.5wt%钨酸钠,59.5wt%水,糖液的密度约为1.17g/cm3;进料速度为3L/h。糖在反应釜内停留时间为2小时。在反应釜中加入乙酸使反应体系pH值为4.4。反应后的反应液和氢气通过过滤器流出反应釜进入冷凝罐,反应液的出料速度为3L/h,反应液经过冷却后从冷凝罐底部排出,得到流出液。流出液进入精馏分离系统,分别得到水、乙二醇、丙二醇、丙三醇和山梨醇以及钨酸钠,其中未被蒸馏出的重组份包括丙三醇和山梨醇以及钨酸钠返回反应系统循环反应。在冷凝罐底部取样,采用高效液相色谱检测其组成。
高效液相色谱检测采用常规技术即可。本发明提供以下实验参数供参考:
仪器:Waters515HPLCPump;
检测器:Water2414RefractiveIndexDetector;
色谱柱:300mm×7.8mm,AminexHPX-87H离子交换柱;
流动相:5mmol/L硫酸溶液;
流动相流速:0.6ml/min;
柱温:60℃;
检测器温度:40℃。
结果为:葡萄糖转化率为100%;二元醇的收率为85.9%,其中,乙二醇收率为78%,丙二醇收率为6%,丁二醇收率为2.1%;甲醇和乙醇收率为3.7%,其它收率为10.4%。
图1为本发明的耐酸合金催化剂应用在可溶性糖一步法催化加氢裂解制备二元醇时的工艺流程示意图。
图2为乙二醇收率随反应体系运行时间的变化图。从图中可以看出,乙二醇的收率基本保持在78%左右。这说明,复合催化剂能保证反应体系连续运行500小时后,乙二醇的收率仍然稳定。
实施例3
耐酸合金催化剂为Ni10Sm5Sn3Al2Mo5,添加量为1400g。
进料组成为:40wt%葡萄糖,2wt%钨酸钠,48wt%水,糖液的密度约为1.17g/cm3。
反应体系pH=6。
其它操作条件同实施例2。
结果为:葡萄糖转化率为100%;二元醇的收率为62.4%,其中,乙二醇收率为25.4%,丙二醇收率为30.4%,丁二醇收率为6.6%;甲醇和乙醇收率为9.4%,其它收率为28.2%。
实施例4
耐酸合金催化剂为Ni70Ce1Sn50Al7Mo0.5B5,添加量为500g。
三氧化钨为加入量100g。
进料组成为:60wt%葡萄糖,40wt%水,糖液的密度约为1.29g/cm3。
反应体系pH=4.2。
其它操作条件同实施例2。
结果为:葡萄糖转化率为100%;二元醇的收率为20.8%,其中,乙二醇收率为10.9%,丙二醇收率为7.5%,丁二醇收率为2.4%;甲醇和乙醇收率为15.6%,其它收率为63.6%。
实施例5
耐酸合金催化剂为Ni90Ce3Sn60Al9Mo20P0.01,添加量为1000g。
进料组成为:15wt%木糖,40wt%葡萄糖,1wt%麦芽二糖,1wt%麦芽三糖,1wt%磷钨酸钠,42wt%水,糖液的密度约为1.22g/cm3。
反应体系pH=4.8。
其它操作条件同实施例2。
结果为:木糖、葡萄糖、麦芽二糖和麦芽三糖的转化率为100%;二元醇的收率为71.6%,其中,乙二醇收率为65.5%,丙二醇收率为4.3%,丁二醇收率为1.8%;甲醇和乙醇收率为3.4%,其它收率为25%。催化剂运行500小时后,乙二醇收率仍然稳定。
实施例6
耐酸合金催化剂为Ni80La1Ce0.5Sn30Al7Mo10,添加量为5000g。
进料组成为:50wt%木糖,0.1wt%钨酸钠,49.9wt%水,糖液的密度约为1.21g/cm3。
反应体系pH=4.8。
其它操作条件同实施例2。
结果为:木糖的转化率为100%;二元醇的收率为72.1%,其中,乙二醇收率为58.8%,丙二醇收率为12.4%,丁二醇收率为0.9%;甲醇和乙醇收率为6.9%,其它收率为21%。催化剂运行500小时后,乙二醇收率仍然稳定。
实施例7
耐酸合金催化剂为Ni80Sm1Sn30Al8Mo1,添加量为1400g。
进料组成为:40wt%蔗糖,1wt%钨酸钠,59wt%水,糖液的密度约为1.18g/cm3。
反应体系pH=4.7。
其它操作条件同实施例2。
结果为:蔗糖的转化率为100%;二元醇的收率为81.7%,其中,乙二醇收率为52.6%,丙二醇收率为24%,丁二醇收率为5.1%;甲醇和乙醇收率为3.3%,其它收率为15%。催化剂运行500小时后,乙二醇收率仍然稳定。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (5)
1.一种耐酸合金催化剂,其特征在于,所述耐酸合金催化剂包括镍、一种或多种稀土元素、锡、铝和钼。
2.根据权利要求1所述的耐酸合金催化剂,其特征在于,所述耐酸合金催化剂,按重量份数计,包括10-90份镍、1-5份稀土元素、1-60份锡、5-9份铝和0.1-20份钼。
3.根据权利要求1所述的耐酸合金催化剂,其特征在于,所述耐酸合金催化剂包括镍、一种或多种稀土元素、锡、铝、钼和硼或磷。
4.根据权利要求3所述的耐酸合金催化剂,其特征在于,所述耐酸合金催化剂,按重量份数计,包括10-90份镍、1-5份稀土元素、1-60份锡、5-9份铝、0.1-20份钼和0.01-5份硼或磷。
5.根据权利要求1-4任一所述的耐酸合金催化剂,其特征在于,所述稀土元素指周期系ⅢB族中原子序数为21、39和57-71的17种化学元素的统称。
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