CN110743610B - 一种钌/酸改性的分子筛复合物催化剂及其制备方法和应用 - Google Patents
一种钌/酸改性的分子筛复合物催化剂及其制备方法和应用 Download PDFInfo
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 74
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
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- 238000000034 method Methods 0.000 claims abstract description 15
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
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- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
本发明公开了一种钌/酸改性的分子筛复合物催化剂及其制备方法和应用,属于生物质甘油选择性氢解催化剂领域。本发明的钌/酸改性的分子筛复合物催化剂包括0.01%~10%质量分数的活性组分钌纳米颗粒和90%~99.99%质量分数的酸改性的分子筛载体,所述钌纳米颗粒粒径为1‑3nm。由于钌在生物质基甘油氢解体系中活性最高,所以本发明采用钌作为催化剂活性组分。但是目前钌催化剂体系在甘油氢解反应过程中,均存在催化C‑C键氢解的副反应反应,目前的催化剂体系无法解决这一问题。本发明发现钌与酸改性的分子筛间具有协同作用,可以定向地氢解生物质基甘油分子中的C‑O键,从而获得较高的1,3‑丙二醇的选择性。
Description
技术领域
本发明涉及生物质甘油选择性氢解催化剂领域,特别涉及一种钌/酸改性的分子筛复合物催化剂及其制备方法和应用。
背景技术
生物质柴油是一种可以直接替代石油基柴油的绿色、可持续能源。生物质柴油工业的快速发展不但有利于解决目前石油、煤炭、天然气等化石能源枯竭的危机,而且还能避免化石能源使用时所带来的环境污染问题。早在2016年世界生物质柴油已经到达了37亿加仑,但产量远低于预期产量。主要原因就是植物油成本较高,使得每千克生物柴油的利润只有石油基柴油的一半。在生物柴油生产过程中,大约产生10%质量分数的副产物甘油。如果能将这些远远高于市场需求量的甘油转化成其其他附加值更高的物质,将减低生物柴油的成本,提高其市场竞争力。
甘油可以通过氧化、还原等化学方法转化成很多的物质,其中价值较高的包括:乳酸、羟基丙醛、环氧氯丙烷、甘油碳酸酯、丙烯酸、1,2-丙二醇和1,3-丙二醇等。其中1,3-丙二醇是合成聚对苯二甲酸丙三醇酯(PTT)不可或缺的单体,PTT树脂既可以应用于纤维,又可以作为工程塑/料。PTT树脂作为纤维时它同时具有PA、PP和PET纤维的优点;作为工程塑料时具有PET和PBT的优点。预计到2022年PPT全球市场价值将达到7.763亿美元。PTT树脂的产量与能否盈利主要取决于1,3-丙二醇的产量和价格。所以1,3-丙二醇的价值和需求量均很高。
1,3-丙二醇目前市场大约为每年400千吨,预计在今后几年每年增长速率将保持在10%左右。目前1,3-丙二醇的工业生产方法主要包括环氧乙烷法、丙烯醛水合加氢法和微生物发酵法。前两种属于传统的石油化工途径,石油依赖性大,环境污染性大,1,3-丙二醇产量占比逐渐下降。第三种微生物发酵方法属于生物质转化途径,原料来源广且可再生,反应条件温和,但是发酵液中1,3-丙二醇浓度低,副产物多,难以分离提纯,而这些副产物中含有大量有毒有害的微生物排泄产物,这就使得微生物发酵成本大大提高。目前,只有杜邦公司具有相对成熟的微生物发酵法,并凭借此技术垄断了微生物发酵生产1,3-丙二醇及其下游PTT市场。通过生物质,尤其是丙三醇化学氢解反应制备1,3-丙二醇的途径,成为未来需要迫切发展的新兴途径。
自2010年来,有关采用非均相催化剂将甘油选择性氢解得到1,3-丙二醇的文章和专利越来愈多,催化剂中的活性组分主要是贵金属Ru、Pt、Rh、Ir、Pd,载体主要是Al2O3、SiO2、ZrO2、ZnO、固体酸以及金属无机复合物质等。目前为具有较高转化率和选择性的催化剂体系主要有Ir-ReOX/SiO2、Pt-WOX、Rh-ReOX/SiO2、Pt/固体酸(丝光沸石、酸化蒙脱石等)等。
文献(J.Catal.,2006,240(2):213-221)比较了Ru/C、Rh/C、Pt/C、Pd/C作为金属催化剂,/硫酸和盐酸作为酸性催化剂,在温度为393K氢解甘油氢解时,发现金属活性大小是Ru/C﹥﹥Rh/C﹥Pt/C﹥Pd/C,而且Ru/C还能催化甘油发生C-C裂解反应。由于钌的高活性及其较为低廉的价格,需要发展高选择性转化生物质的钌基催化剂。
文献(Applied Catalysis A:General,2014,469:45-51)比较了将HZSM-5(X)作为酸性添加物质加入Ru/Al2O3、Ru/SiO2或者直接作为载体时发现,加入HZSM-5(X)均提高了Ru/Al2O3、Ru/SiO2反应活性,但是降低了液相产物的选择性。其中任何体系中,以钌作为催化剂活性组分,1,3-丙二醇的选择性均小于7%。
通过上述公开资料可以发现钌基催化剂在催化甘油氢解时反应速率最快,加入酸性物质可以提高进一步提高其反应速率。但由于活性物质金属钌前体制备方法,分子筛处理方法以及钌与分子筛的复合方式不恰当,因而不能使金属钌加氢性能和分子筛脱水性能起到协同效应,1,3-丙二醇的选择性很低。因此需要发展高选择性催化甘油转化为1,3-丙二醇的催化剂体系和制备方法。
发明内容
本发明要解决的技术问题是提供一种可用于生物质甘油高选择性得氢解为1,3-丙二醇的高性能钌/酸改性的分子筛复合物催化剂及其制备方法和应用。
为了解决上述技术问题,本发明的技术方案为:
一种钌/酸改性的分子筛复合物催化剂,包括0.01%~10%质量分数的活性组分钌纳米颗粒和90%~99.99%质量分数的酸改性的分子筛载体,所述钌纳米颗粒粒径为1-3nm。
优选的,所述分子筛为Y型分子筛、丝光沸石(MOR)分子筛、ZSM-5(MFI)型分子筛、β型分子筛或Al-MCM-41分子筛。
优选的,所述分子筛为具有不同硅铝比的ZSM-5(X)型分子筛,X=Si:Al。
优选的,所述分子筛为硅铝比为50-90的ZSM-5型分子筛。
一种所述的钌/酸改性的分子筛复合物催化剂的制备方法,包括如下步骤:
(1)使用碱-乙二醇法制备钌纳米胶体;
(2)将所述钌纳米胶体、分子筛和酸混合搅拌,得到混合物;
(3)将所述混合物离心洗涤,将离心洗涤后的固体物于50-300℃烘箱干燥,200-800℃马弗炉焙烧1-240h,即得到钌/酸改性的分子筛复合物催化剂。
优选的,步骤(1)中所述使用碱-乙二醇法制备钌纳米胶体的具体步骤包括:
(1-1)将钌盐溶解到乙二醇中得到溶液A;
(1-2)将氢氧化钠溶于乙二醇中得到溶液B;
(1-3)在常温搅拌的条件下,将所述溶液A和溶液B混合均匀,调节溶液pH值为7-14,在惰性气体氛围保护下升温到120-190℃保持0.5-24小时,冷却后得到钌纳米胶体。
优选的,所述钌盐为氯化钌、硫酸钌、硝酸钌或醋酸钌中的至少一种。
优选的,步骤(2)中所述钌纳米胶体、分子筛和酸加入的质量比为0.6~1.9:1:2~20;所述钌纳米胶体、分子筛和酸混合搅拌0.5~50h;所述酸为醋酸、硝酸、硫酸、盐酸或磷酸中的一种或者多种。
一种所述的钌/酸改性的分子筛复合物催化剂的应用,将钌/酸改性的分子筛复合物催化剂用于甘油转化为1,3-丙二醇的反应。
优选的,所述甘油转化为1,3-丙二醇的反应条件为:反应底物为0.1wt%~99.9wt%甘油的水溶液,温度为120℃~300℃,氢气初始压力为0.1MPa~12MPa,空速0.01~50h-1,反应器采用间歇釜式高压釜或者连续式固定床。
采用上述技术方案,(1)由于钌在生物质基甘油氢解体系中活性最高,所以本发明采用钌作为催化剂活性组分。但是目前钌催化剂体系在甘油氢解反应过程中,均存在催化C-C键氢解的副反应反应,目前的催化剂体系无法解决这一问题。本发明发现钌与酸改性的分子筛间具有协同作用,可以定向地氢解生物质基甘油分子中的C-O键,因而获得较高的1,3-丙二醇的选择性。(2)由于分子筛表面电荷与钌纳米胶体表面电荷趋同,因此钌纳米胶体难以在分子筛表面吸附。酸环境不但可以对分子筛表面进行改性产生正电荷的缺陷吸附位置,促使钌纳米胶体与分子筛复合;而且可以使钌纳米粒子与分子筛的酸性位点处于合适的位置,产生协同效应。因此,本发明提供一种了通过酸作为钌纳米胶体和分子筛复合的“媒介”制备出一种钌/酸改性的分子筛复合物催化剂,并将该催化剂用于甘油催化氢解反应,高选择性地获得了1,3-丙二醇。
附图说明
图1为实施例1中经过酸处理18小时的0.15Ru/ZSM-5(70)催化剂的STEM图;
图2为对比实施例1中未经过酸处理过的0.15Ru/ZSM-5催化剂的STEM图。
具体实施方式
下面结合附图对本发明的具体实施方式作进一步说明。在此需要说明的是,对于这些实施方式的说明用于帮助理解本发明,但并不构成对本发明的限定。此外,下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
钌/酸改性的ZSM-5催化剂及其制备方法和催化甘油加氢反应性能
钌/酸改性的ZSM-5催化剂的制备方法:将8.0g ZSM-5(70)、75ml盐酸和5.04g钌纳米胶体(Ru=0.24wt%)搅拌18h后,离心洗涤8次,在70℃烘干,在马沸炉中220℃焙烧2h。Ru在Ru/HZSM-5质量百分数为0.15。
钌/酸改性的ZSM-5催化剂催化甘油加氢反应:采用间歇式高压反应釜,将25.0g质量分数为4%甘油水溶液加入到100ml不锈钢高压反应釜中,再加入催化剂1.0g;将反应釜密闭后,通入1MPa氢气置换里面空气,置换5次后,通入8MPa氢气进行反应,反应温度为200℃,反应时间为12h,搅拌转速为500rpm。采用气相色谱分析液体产物。
采用连续式固定床,反应压力0.1MPa,甘油质量百分数99.9,反应温度300℃,质量空速5h-1。采用气相色谱分析液体产物。结果如下表:
其它包括:甲醇、乙醇、甲烷、乙烷、丙烷等物质。
对比实施例1
未经过酸处理的Ru/ZSM-5催化剂及其制备方法和催化甘油加氢反应性能
未经过酸处理过的Ru/ZSM-5催化剂的制备,具体步骤如下:
将8.0g ZSM-5(70)、75ml水和5.04g钌纳米胶体(Ru=0.24wt%)搅拌50h后,离心洗涤8次,在70℃烘干,在马沸炉中220℃焙烧2h。
未经过酸处理过的Ru/HZSM-5(70)催化剂催化甘油加氢应用
采用间歇式高压反应釜,将25.0g质量分数为4%甘油水溶液加入到100ml不锈钢高压反应釜中,再加入催化剂1.0g;将反应釜密闭后,通入1MPa氢气置换里面空气,置换5次后,通入8MPa氢气进行反应,反应温度为200℃,反应时间为12h,搅拌转速为500rpm。采用气相色谱分析液体产物,结果如下:
其它包括:甲醇、乙醇、甲烷、乙烷、丙烷等物质。Ru在Ru/HZSM-5质量百分数为0.15。
由结果可以看出本发明的钌/酸改性的ZSM-5催化剂对1,3-丙二醇具有明显的选择性。
实施例2
将实施例1中ZSM-5(70)分子筛换成ZSM-5(21)、ZSM-5(38)、ZSM-5(85)、ZSM-5(130)、ZSM-5(350)或ZSM-5(500),其他条件不变,此处不再赘述。
其它包括:甲醇、乙醇、甲烷、乙烷、丙烷等物质。Ru在Ru/HZSM-5质量分数为0.15%。
结合实施例1的结果可以看出,使用ZSM-5(70)分子筛对1,3-丙二醇的选择效果最佳。
实施例3
将实施例1中的ZSM-5(70)分子筛换成:Y型分子筛、介孔Y型分子筛、丝光沸石(MOR)、Nano ZSM-5、β型分子筛、Al-MCM-41或无定型硅铝(ASA),其他条件不变,此处不再赘述。
其它包括:甲醇、乙醇、甲烷、乙烷、丙烷等物质。Ru在Ru/HZSM-5质量分数为0.15%。
结合实施例1的结果可以看出,ZSM-5(70)分子筛相较于其他类型分子筛也具有更佳的1,3-丙二醇选择性。
实施例4
将实施例1催化制备步骤中钌纳米胶体(Ru=0.24wt%)的质量分别改为1.04、66.67g,其它条件不变,此处不再赘述。
采用间歇式高压反应釜,将25.0g质量分数为4%甘油水溶液加入到100ml不锈钢高压反应釜中,再加入催化剂1.0g;将反应釜密闭后,通入1MPa氢气置换里面空气,置换5次后,通入8MPa氢气进行反应,反应温度为200℃,反应时间为12h,搅拌转速为500rpm。采用气相色谱分析液体产物。
其它包括:甲醇、乙醇、甲烷、乙烷、丙烷等物质。Ru在Ru/HZSM-5质量分数为0.03%,0.40%。
结合实施例1的结果可以看出,Ru在Ru/HZSM-5质量分数为0.15%时,1,3-丙二醇选择性最佳。
实施例5
将实施例1中催化剂制备步骤中搅拌时间分别改为5h,23h。其它条件不变,此处不再赘述。
采用间歇式高压反应釜,将25.0g质量分数为4%甘油水溶液加入到100ml不锈钢高压反应釜中,再加入催化剂1.0g;将反应釜密闭后,通入1MPa氢气置换里面空气,置换5次后,通入8MPa氢气进行反应,反应温度为200℃,反应时间为12h,搅拌转速为500rpm。采用气相色谱分析液体产物。
其它包括:甲醇、乙醇、甲烷、乙烷、丙烷等物质。Ru在Ru/HZSM-5质量分数为0.15%。
结合实施例1的结果可以看出,在酸处理时间为18h时,1,3-丙二醇选择性最佳。
如图1和图2所示,图1为实施例1中经过酸处理18小时的0.15Ru/ZSM-5(70)催化剂的STEM图,图1中0.15表示钌的百分比例为0.15%;图2为对比实施例1中未经过酸处理过的0.15Ru/ZSM-5催化剂的STEM图;可以看出经过酸处理后ZSM-5(70)表面由光滑变得很凹凸不平,这使得Ru更充分的接触位于分子筛内部的酸性位点,加强了二者之间的协同效应,使得1,3-丙二醇的选择性大幅度提高。
(1)由于钌在生物质基甘油氢解体系中活性最高,所以本发明采用钌作为催化剂活性组分。但是目前钌催化剂体系在甘油氢解反应过程中,均存在催化C-C键氢解的副反应反应,目前的催化剂体系无法解决这一问题。本发明发现钌与酸改性的分子筛间具有协调作用,可以定向的氢解生物质基甘油分子中的C-O键,因而获得较高的1,3-丙二醇的选择性。
(2)由于分子筛表面电荷与钌纳米胶体表面电荷趋同,因此钌纳米胶体难以在分子筛表面吸附。酸环境不但可以对分子筛表面进行改性产生正电荷的缺陷吸附位置,促使钌纳米胶体与分子筛复合;而且可以使钌纳米粒子与分子筛的酸性位点处于合适的位置,产生协同效应。因此,本发明提供一种了通过酸作为钌纳米胶体和分子筛的复合“媒介”制备出一种钌/酸改性的分子筛复合物催化剂,并将该催化剂用于甘油催化氢解反应,高选择性地获得了1,3-丙二醇。
以上结合附图对本发明的实施方式作了详细说明,但本实发明不限于所描述的实施方式。对于本领域的技术人员而言,在不脱离本发明原理和精神的情况下,对这些实施方式进行多种变化、修改、替换和变型,仍落入本发明的保护范围内。
Claims (3)
1.一种钌/酸改性的分子筛复合物催化剂,其特征在于:包括0.01%~10%质量分数的活性组分钌纳米颗粒和90%~99.99%质量分数的酸改性的分子筛载体,所述钌纳米颗粒粒径为1-3nm,所述分子筛为硅铝比为50-90的ZSM-5型分子筛;所述钌/酸改性的分子筛复合物催化剂的制备方法,包括如下步骤:
(1)使用碱-乙二醇法制备钌纳米胶体;具体步骤包括:
(1-1)将钌盐溶解到乙二醇中得到溶液A;
(1-2)将氢氧化钠溶于乙二醇中得到溶液B;
(1-3)在常温搅拌的条件下,将所述溶液A和溶液B混合均匀,调节溶液pH值为7-14,在惰性气体氛围保护下升温到120-190℃保持0.5-24小时,冷却后得到钌纳米胶体;所述钌盐为氯化钌、硫酸钌、硝酸钌或醋酸钌中的至少一种;
(2)将所述钌纳米胶体、分子筛和酸混合搅拌,得到混合物,所述钌纳米胶体、分子筛和酸加入的质量比为0.6~1.9:1:2~20;所述钌纳米胶体、分子筛和酸混合搅拌0.5~50h;所述酸为醋酸、硝酸、硫酸、盐酸或磷酸中的一种或者多种;
(3)将所述混合物离心洗涤,将离心洗涤后的固体物于50-300℃烘箱干燥,200-800℃马弗炉焙烧1-240h,即得到钌/酸改性的分子筛复合物催化剂。
2.一种如权利要求1所述的钌/酸改性的分子筛复合物催化剂的应用,其特征在于:将钌/酸改性的分子筛复合物催化剂用于甘油转化为1,3-丙二醇的反应。
3.根据权利要求2所述的钌/酸改性的分子筛复合物催化剂的应用,其特征在于:所述甘油转化为1,3-丙二醇的反应条件为:反应底物为0.1wt%~99.9wt%甘油的水溶液,温度为120℃~300℃,氢气初始压力为0.1MPa~12MPa,空速0.01~50h-1,反应器采用间歇釜式高压釜或者连续式固定床。
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