CN114247464B - 一种镍/稀土分子筛双功能催化剂及其制备和在γ-戊内酯制戊酸酯中的应用 - Google Patents
一种镍/稀土分子筛双功能催化剂及其制备和在γ-戊内酯制戊酸酯中的应用 Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 56
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 35
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229940070710 valerate Drugs 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims description 13
- 229910052761 rare earth metal Inorganic materials 0.000 title abstract description 31
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 23
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- 239000002184 metal Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
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- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
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- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
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- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 4
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- 229910052684 Cerium Inorganic materials 0.000 description 1
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
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- NVPZOOKWNAMVPQ-UHFFFAOYSA-N azanide;nickel Chemical compound [NH2-].[NH2-].[NH2-].[NH2-].[NH2-].[NH2-].[Ni] NVPZOOKWNAMVPQ-UHFFFAOYSA-N 0.000 description 1
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- 229940078494 nickel acetate Drugs 0.000 description 1
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Abstract
戊酸酯是一种新型的生物质基液体燃料分子。本发明提供了一种用于生物质平台分子γ‑戊内酯加氢制备戊酸酯的镍/稀土分子筛催化剂,以经稀土元素离子交换过的分子筛为载体,并担载金属镍构成镍/稀土分子筛双功能催化剂,通过金属位点和分子筛酸性位点协同作用,在γ‑戊内酯加氢制备戊酸酯的反应中可以实现戊酸酯>90%的摩尔收率,选择性>99%;同时,由于稀土元素对分子筛骨架结构的稳定,催化剂可以连续稳定使用>600h而不失活。
Description
技术领域
本发明涉及一种用于γ-戊内酯加氢制备戊酸酯的镍/稀土分子筛双功能催化剂及其制备和应用。
背景技术
戊酸酯可以作为一种新型的绿色能源液体燃料分子,与现有的燃油体系实现良好的兼容。Lange等人将10-20%的戊酸乙酯和现有市场中普通汽油混合后混合燃料的辛烷值可以达到欧洲汽油的规范标准,并在一系列油品指标中表现出了优异的性能,成功地通过了25万公里的路面测试。(J.-P.Lange,R.Price,P.M.Ayoub,J.Louis,L.Petrus,L.Clarkeand H.Gosselink,Valeric Biofuels:A Platform of Cellulosic TransportationFuels,Angew.Chem.Int.Ed.,2010,49,4479-4483.)。
目前,生物质基平台分子制备戊酸酯出发主要是从平台分子乙酰丙酸出发。在加氢-酸双功能催化剂的作用下,通过一步或者多步反应,实现乙酰丙酸加氢到γ-戊内酯,戊内酯开环到戊酸,戊酸酯化到戊酸酯的过程。(Luo W,Cao W,Bruijnincx P C A,etal.Zeolite-supported metal catalysts for selective hydrodeoxygenation ofbiomass-derived platform molecules[J].Green Chemistry,2019,21.)。
区别于传统石油化学中的气相反应过程,生物质转化反应过程通常发生在液相极性溶剂环境中,反应温度在150℃到250℃之间,反应中产生的水热环境往往对于催化剂的稳定性提出了极大的挑战。而相较于贵金属双功能催化剂,镍基催化剂在高温水热反应过程中更容易出现金属团聚,金属溶蚀等问题,导致催化剂的加氢性能下降,进而影响双功能催化剂的活性。另一方面,在液相的反应体系中,分子筛的水热稳定性较气相反应面临更严峻的挑战,反应过程中往往伴随着脱铝现象,导致催化剂酸性位点流失,导致分子筛催化剂的失活(Ravenelle,Ryan M.,et al."Stability of Zeolites in Hot Liquid Water."Journal of Physical Chemistry C 114.46,2010,19582-19595.)。因此,发展稳定的分子筛负载的镍基金属是双功能催化剂设计中亟待解决的关键问题。
发明内容
本发明针对γ-戊内酯到戊酸酯这一关键步骤,设计出了镍/稀土分子筛,可以在固定床反应器中,实现γ-戊内酯加氢到戊酸酯的高选择性转化,戊酸酯的摩尔摩尔收率>90%,选择性>99%,同时避免了生物质转化串联反应这一复杂体系中常见的积炭,催化剂结构破坏等问题,催化剂可以连续稳定使用至少600h而不失活。
本发明提供了镍/稀土分子筛催化剂的制备方法。
为实现上述目的,本发明采取的技术方案为:
本发明一方面,提供一种镍/稀土分子筛催化剂的制备方法,包括以下步骤:
a.制备RE-Y载体分子筛:将稀土元素的硝酸盐溶液与H-Y型分子筛混合,得到的混合悬浊液在20~80℃水浴条件下搅拌2~10h,再经洗涤后,在400-700℃下100mL/min空气中煅烧2~8h,得到RE-Y载体分子筛;
b.将镍盐溶于溶剂中搅拌溶解配制得到浸渍液;
c.向所述浸渍液中边搅拌边加入对应分量的RE-Y载体分子筛;
d.将步骤c得到的溶液升温到20~80℃,继续搅拌1~6h;
e.随后将经过步骤d处理的溶液升温到70~90℃后继续搅拌将水分蒸干,得到粉末状固体;
f.将步骤e中收集到的粉末状固体在300~600℃条件下,在5~20vol.%氢气/氮气气氛中还原2-8h,得到所述的镍/稀土分子筛催化剂。
作为优选的技术方案,步骤a中,
RE-Y载体分子筛为用稀土元素交换过的具有FAU构型的分子筛;
RE为元素镧、铈、镨、钕中的一种或一种以上;
RE在RE-Y载体分子筛中的含量为1~20wt%;
硝酸镧水溶液、硝酸铈水溶液的浓度为0.01~0.2mol/mL。
作为优选的技术方案,步骤b中所述镍盐为硝酸镍、卤化镍、醋酸镍、氯化六氨合镍中的一种或者一种以上;所述溶剂为水、乙醇或者丙酮一种或一种以上的混合溶液。
本发明另一方面,提供上述方法得到的镍/稀土分子筛催化剂。
作为优选的技术方案,其中镍担载在RE-Y载体分子筛上,镍以金属镍的质量计担载量,具体为1~30wt%,镍纳米颗粒尺寸在1~40nm之间。
本发明再一方面,提供上述镍/稀土分子筛催化剂在γ-戊内酯加氢制备戊酸酯加氢反应中的应用。
作为优选的技术方案,在γ-戊内酯加氢制备戊酸酯加氢反应中,所述镍/稀土分子筛催化剂可以连续地稳定使用至少600h以上,且戊酸酯的摩尔收率>90%。
作为优选的技术方案,所述反应在固定床反应器中进行,反应温度为160~250℃,氢气的压力2~10MPa,氢气流量为10~60mL/min,重时空速范围为0.1~10h-1。
作为优选的技术方案,所述反应所采用的反应物可以为纯的γ-戊内酯,或者是由水,甲醇,乙醇等一种或一种以上溶剂稀释过的γ-戊内酯。
戊酸酯是一种新型的生物质基液体燃料分子。本发明提供了一种用于生物质平台分子γ-戊内酯加氢制备戊酸酯的镍/稀土分子筛催化剂,具有制备过程简单、成本低廉,高活性,高选择性,高稳定性等优异性能。以经稀土元素离子交换过的分子筛为载体,并担载金属镍构成镍/稀土分子筛双功能催化剂,通过金属位点和分子筛酸性位点协同作用,在γ-戊内酯加氢制备戊酸酯的反应中可以实现戊酸酯>90%的摩尔收率,选择性>99%;同时,由于稀土元素对分子筛骨架结构的稳定,催化剂可以连续稳定使用>600h而不失活。
下面通过具体实例对本发明进行详细说明,但这些实例并不对本发明的内容构成限制。
附图说明
图1中,a为Ni/La-Y电镜图像;b为Ni/H-Y电镜图像(图中亮点为金属Ni颗粒);
图2为固定床反应管催化剂装填示意图;
图3为镍/分子筛催化γ-戊内酯加氢固定床反应寿命曲线。
具体实施方式
(1)稀土分子筛的制备:将硝酸镧、硝酸铈加入超纯水搅拌溶解,配制硝酸镧、硝酸铈溶液,浓度范围0.01-0.2mol/mL,再分别加入H-Y型分子筛,得到的混合悬浊液在20-80℃水浴条件下搅拌2-10h,后用100mL超纯水过滤洗涤,回收的滤饼在400-700℃下马弗炉煅烧2-8h,得到稀土元素交换过的分子筛La-Y,Ce-Y,稀土元素的含量在1-20wt%。
(2)镍/稀土分子筛的制备:将适量镍盐溶于溶剂中搅拌溶解配制浸渍液,向配好制的浸渍液中边搅拌边加入对应分量的La-Y或Ce-Y,将得到的溶液升温到20-80℃,继续搅拌1-6h,随后将经过处理的溶液升温到70-90℃的继续搅拌下将水分蒸干,将得到的粉末状固体,收集到的粉末在300-600℃条件下,在5-20vol.%氢气/氩气气氛中还原2-8h,最后得到镍/稀土分子筛双功能催化剂,金属载量为1-30wt%。
(3)γ-戊内酯加氢制备戊酸酯:以纯的γ-戊内酯,或者是由水,甲醇,乙醇等一种或一种以上溶剂稀释过的γ-戊内酯为反应原料,在固定床高压加氢装置中进行催化加氢反应,催化剂为镍/稀土分子筛催化剂,反应温度为160-250℃,氢气的压力2-10MPa,氢气流量为10-60mL/min,重时空速范围为0.1-10h-1。
实施例1镍/稀土分子筛催化剂的制备
(1)稀土分子筛的制备:在100mL烧杯中分别加入3.25g的硝酸镧,50mL超纯水在50℃水浴中搅拌溶解,再加入3.00g的H-Y型分子筛,得到的混合溶液在60℃水浴条件下搅拌6h,后用100mL超纯水过滤洗涤,回收的滤饼在600℃于马弗炉中煅烧5h,得到稀土元素交换过的Y型分子筛La-Y。
(2)镍/稀土分子筛催化剂制备:称取硝酸镍1.50g于洁净的50mL的烧杯中,加入30mL的超纯水,将圆底烧瓶置于50℃水浴搅拌30分钟,继续向烧杯中加入制备所得的La-Y分子筛2.70g,并将水浴升温至60℃继续搅拌5h,随后在80℃的水浴搅拌下将烧杯内的水分蒸干,将得到的粉末状固体置于450℃的管式炉中,在10vol.%氢气/氩气气氛中还原5h,最后得到金属负载量为10wt%的Ni/La-Y复合催化剂(附图1a 10wt%Ni/La-Y催化剂STEM图像)。由图中可以看到,Ni金属(图中虚线圆圈所示)以金属颗粒的形式分散在分子筛载体上,粒径在5-50nm之间。
测试例1
实施例1制得的催化剂催化γ-戊内酯加氢反应寿命测试
γ-戊内酯加氢制备戊酸酯反应:将实施例1的步骤(2)中制备的粉末状的金属负载量为10wt%的Ni/La-Y复合催化剂在10MPa的压力下压片,筛选出粒径在20-40目的颗粒进行反应,反应在固定床反应器中进行,按照如附图2所示的方式装填反应管,设定反应温度为200℃,氢气的压力3.0MPa,氢气流量为40mL/min,当反应管温度达到200℃时,开始用高压恒流泵输送反应原料(50wt%γ-戊内酯乙醇溶液),重时空速为5.0h-1,此时视为反应的起点,其反应结果见附图3。
对比例1不含稀土元素的镍/分子筛催化剂的制备
镍/分子筛催化剂制备:称取硝酸镍1.50g于洁净的50mL的烧杯中,加入30mL的超纯水,将圆底烧瓶置于50℃水浴搅拌30分钟,继续向烧杯中加入购买的H-Y分子筛2.70g,并将水浴升温至60℃继续搅拌5h,随后在80℃的水浴搅拌下将烧杯内的水分蒸干,将得到的粉末状固体置于450℃的管式炉中,在10vol.%氢气/氩气气氛中还原5h,最后得到金属负载量为10wt%的Ni/H-Y复合催化剂(附图1b 10wt%Ni/H-Y催化剂STEM图像)。与Ni/La-Y类似,Ni/H-Y中Ni金属(图中虚线圆圈所示)同样以金属颗粒的形式分散在分子筛载体上,粒径在5-50nm之间。
测试例2
对比例1制得的的γ-戊内酯加氢反应寿命反应
γ-戊内酯加氢制备戊酸酯反应:具体步骤同测试例1,催化剂由Ni/La-Y替换为Ni/H-Y,其反应结果见附图3。
从附图3可以看出,在相同的反应条件下,Ni/La-Y及Ni/H-Y催化剂均可以实现对于γ-戊内酯的转化,且戊酸酯的摩尔收率可以长时间维持在>90%,但是对比例1制得的催化剂Ni/H-Y在反应进行到150h后出现明显的失活现象,戊酸酯的摩尔收率下降到了<80%,而实施例1制备的Ni/La-Y催化剂的使用稳定性明显优于Ni/H-Y,即在600h的反应过程中没有出现明显的失活现象,戊酸酯的摩尔收率>90%。
Claims (1)
1.一种镍/镧复合分子筛催化剂的应用,其特征在于:用于γ-戊内酯加氢制备戊酸酯反应;所述反应在固定床反应器中进行,反应温度为200℃,氢气的压力3.0MPa,氢气流量为40mL/min,反应原料50wt%的γ-戊内酯乙醇溶液;重时空速范围为5.0h-1;
所述镍/镧复合分子筛催化剂的制备方法包括:
S1、镧分子筛的制备:在100mL烧杯中分别加入3.25g的硝酸镧,50mL超纯水在50℃水浴中搅拌溶解,再加入3.00g的H-Y型分子筛,在60℃水浴条件下搅拌6h,后用100mL超纯水过滤洗涤,在600℃于马弗炉中煅烧5h,得到Y型分子筛La-Y;
S2、镍/镧复合分子筛催化剂制备:称取硝酸镍1.50g于50mL的烧杯中,加入30mL的超纯水,将圆底烧瓶置于50℃水浴搅拌30分钟,继续向烧杯中加入步骤S1制得的La-Y分子筛2.70g,并将水浴升温至60℃继续搅拌5h,随后在80℃的水浴搅拌下将烧杯内的水分蒸干,置于450℃的管式炉中,在10vol.%氢气/氩气气氛中还原5h,得到金属负载量为10wt%的Ni/La-Y复合催化剂。
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CN108187730A (zh) * | 2018-01-26 | 2018-06-22 | 昆山普瑞凯纳米技术有限公司 | 一种负载型复合金属-酸双功能催化剂 |
CN110117266A (zh) * | 2018-02-06 | 2019-08-13 | 中国科学院大连化学物理研究所 | 一种生物质平台化合物加氢制备生物质燃油分子的方法 |
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