CN114029070A - 一种原位氢解芳醚键催化剂及其制备方法和应用 - Google Patents
一种原位氢解芳醚键催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN114029070A CN114029070A CN202111517205.3A CN202111517205A CN114029070A CN 114029070 A CN114029070 A CN 114029070A CN 202111517205 A CN202111517205 A CN 202111517205A CN 114029070 A CN114029070 A CN 114029070A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrogenolysis
- situ
- nirual
- aryl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920005610 lignin Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 21
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 15
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 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 description 21
- 229910052593 corundum Inorganic materials 0.000 claims description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 7
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical compound C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 claims description 5
- JKSGBCQEHZWHHL-UHFFFAOYSA-N 2-phenoxyethylbenzene Chemical compound C=1C=CC=CC=1OCCC1=CC=CC=C1 JKSGBCQEHZWHHL-UHFFFAOYSA-N 0.000 claims description 4
- -1 aromatic ether compound Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 2
- 150000008378 aryl ethers Chemical class 0.000 claims 5
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 7
- 239000002028 Biomass Substances 0.000 abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 229910009112 xH2O Inorganic materials 0.000 description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
- C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种原位氢解芳醚键催化剂及其制备方法和应用,属于生物质催化氢解领域。本发明催化剂以NiRuAl水滑石为前驱体,经煅烧和还原,制备得到负载型高分散NiRu合金催化剂,以催化剂总质量计,Ni和Ru分别占百分比为20‑40%和1‑5%。该高分散NiRu合金催化剂在木质素及其模型化合物原位氢解反应中展现出优异的催化性能,可以在温和条件下高选择性高活性地断裂木质素及其模型化合物中的芳醚键,明显优于商品化Ru/C催化剂。本发明催化剂制备方法简单,稳定性好,且催化木质素及其模型化合物氢解反应不需要外加氢气,反应条件温和,因而在木质素转化过程中具有良好的应用前景。
Description
技术领域
本发明属于生物质催化氢解领域,具体地说涉及一种高分散高活性NiRu/Al2O3催化剂、其制备方法以及在原位催化氢解芳醚键中的应用。
背景技术
木质素在生物质中的含量仅次于纤维素,是唯一的可再生芳香族化合物来源。在生物质造纸或发酵制乙醇过程中,会产生大量的木质素废液。因此,木质素的高效解聚对生物质的高值化利用至关重要。目前,关于木质素解聚的方法主要有热解、氢解、液化、氧化、水解等。相较于其它解聚方法,氢解具有反应条件温和、产物收率高且组成结构可调等优点,因而受到广泛关注。
低碳醇由于具有供氢能力强、超临界点低、易回收等优点被广泛用于木质素氢解制芳烃、酚、环己醇等平台化合物。研究表明,Ru/C和Ni基及双金属催化剂可促进木质素氢解。然而,传统的双金属负载型催化剂多采用浸渍法制备,分散度较低、活性不高。近年来,水滑石由于具有结构可调变性作为催化剂前体用于制备高分散负载型催化剂引起了人们广泛的关注。因此,水滑石基NiRu双金属催化剂催化木质素原位氢解制平台化合物对木质素的高效利用具有重要的意义。
发明内容
针对现有技术的不足,本发明要解决的技术问题是提供一种高分散高活性NiRu/Al2O3催化剂及其在原位催化氢解芳醚键中的应用,以期实现木质素及其模型化合物的高效氢解。
本发明是通过以下技术方案予以实现的。
本发明催化剂以NiRu合金为催化活性位点,Al2O3为载体;以催化剂总质量计,Ni和Ru分别占百分比为20-40%和1-5%。
本发明提供了上述催化剂的制备方法,具体包括如下步骤:
(1)将摩尔比为1-3:0.5-2:0.02-0.1的Ni(NO3)2 .6H2O、Al(NO3)3 .9H2O和RuCl3 .xH2O加入到水中充分搅拌,与一定浓度(0.5-3mol/L)的NaOH溶液同时逐滴加入到Na2CO3溶液中,升温至60-80℃老化5-20h;之后离心、洗涤并干燥,得到NiRuAl水滑石。
(2)将步骤(1)得到的NiRuAl水滑石在300-600℃下高温煅烧,煅烧时间为2-6小时,得到NiRuAl复合氧化物。
(3)用H2还原步骤(2)得到的NiRuAl复合氧化物,冷却后用O2钝化1-3h,得到目标产物:NiRu/Al2O3催化剂。
进一步的,所述步骤(1)中溶液pH维持在9-11。
进一步的,所述步骤(3)中H2还原升温速率为2℃/min,还原温度为450-600℃,还原时间6h。
本发明同时提供了上述方法制备得到的催化剂在原位氢解芳醚键中的应用,具体包括如下步骤:
将NiRu/Al2O3催化剂、氢源和芳醚类化合物按照用量比20-50mg:5-20mL:1mmol加入到反应釜中,密封后充入10bar的保护性气体,在100-240℃下反应l-8h,得到氢解产物。
进一步的,所述的氢源为甲醇、乙醇和异丙醇中的一种。
进一步的,所述的芳醚类化合物为苯基苄基醚、苯基苯乙基醚、二苯醚和木质素中的一种。
与现有技术相比,本发明具有以下技术效果:
1、本发明的催化剂分散度高(平均粒径为6nm左右,图1和2)、活性高,以醇做氢源,不需要外加H2,能在较低的反应温度(100℃)下,实现芳醚键的氢解断裂。
2、本发明的催化剂制备方法简单,采用共沉淀的方法制备水滑石前驱体,从而制备高分散负载型NiRu合金催化剂。
3、本发明高分散NiRu合金催化剂在木质素及其模型化合物原位氢解反应中展现出优异的催化性能,可以在温和条件下高选择性高活性地断裂木质素及其模型化合物中的芳醚键,明显优于商品化Ru/C催化剂。
4、本发明的催化剂稳定性好,循环使用5次后,仍保持很高的活性,且可通过磁场进行分离。
5、木质素属于造纸和生物炼制副产物,木质素的高效转化对生物质的高值化利用意义重大。本发明催化剂制备方法简单,稳定性好,反应条件温和,因而在木质素转化过程中具有良好的应用前景。
附图说明
图1为本发明实施例1中NiRu/Al2O3催化剂的XRD图;
由图可知,NiRu/Al2O3催化剂中活性组分Ni和Ru高度分散。
图2为本发明实施例1中NiRu/Al2O3催化剂的不同放大倍数的HRTEM图;
通过图2b测量计算得到NiRu/Al2O3催化剂中活性组分NiRu的平均粒径为5.8nm,也说明活性组分分散度较高,从图2c中可看到Ni(111)的晶格条纹与XRD分析结果一致。
具体实施方式
以下是本发明的具体实施例,对本发明的技术方案做进一步的描述,但本发明并不限于这些实施例。
实施例1:
将摩尔比为2:1:0.05的Ni(NO3)2 .6H2O、Al(NO3)3 .9H2O、和RuCl3 .xH2O加入到水中充分搅拌,与1mol/L的NaOH溶液同时逐滴加入到Na2CO3溶液中,维持溶液pH为10,升温至60℃老化20h。老化结束后离心、洗涤并干燥,得到NiRuAl水滑石结构。将NiRuAl水滑石在460℃下高温煅烧,煅烧时间为6小时,得到NiRuAl复合氧化物。用H2在500℃下还原NiRuAl复合氧化物,冷却后用O2钝化1h,即得到NiRu/Al2O3催化剂。通过XRD(图1)和HRTEM(图2)表征表明所制备的NiRu/Al2O3催化剂中活性组分Ni和Ru高度分散,平均粒径为6nm左右。将NiRu/Al2O3催化剂、异丙醇和苯基苄基醚按照用量比25mg:20mL:0.5mmol加入到反应釜中,密封后充入10bar的保护性气体,在100℃下反应4h,得到氢解产物。苯基苄基醚转化率为97.6%,产物主要为甲苯、苯酚和环己醇,收率分别为44.8%、16.2%和36.7%。催化剂循环使用5次后,苯基苄基醚转化率依然高达95.1%。
实施例2:
将摩尔比为2:1:0.05的Ni(NO3)2 .6H2O、Al(NO3)3 .9H2O、和RuCl3 .xH2O加入到水中充分搅拌,与2mol/L的NaOH溶液同时逐滴加入到Na2CO3溶液中,维持溶液pH为10,升温至60℃老化20h。老化结束后离心、洗涤并干燥,得到NiRuAl水滑石结构。将NiRuAl水滑石在460℃下高温煅烧,煅烧时间为6小时,得到NiRuAl复合氧化物。用H2在550℃下还原NiRuAl复合氧化物,冷却后用O2钝化1h,即得到NiRu/Al2O3催化剂。将NiRu/Al2O3催化剂、异丙醇和二苯醚按照用量比25mg:20mL:0.5mmol加入到反应釜中,密封后充入10bar的保护性气体,在140℃下反应3h,得到氢解产物。二苯醚转化率为100%,产物主要为苯、环己烷和环己醇,收率分别为8.0%、39.4%和52.6%。
实施例3:
将摩尔比为2:1:0.05的Ni(NO3)2 .6H2O、Al(NO3)3 .9H2O、和RuCl3 .xH2O加入到水中充分搅拌,与2.5mol/L的NaOH溶液同时逐滴加入到Na2CO3溶液中,维持溶液pH为10,升温至60℃老化20h。老化结束后离心、洗涤并干燥,得到NiRuAl水滑石结构。将NiRuAl水滑石在460℃下高温煅烧,煅烧时间为6小时,得到NiRuAl复合氧化物。用H2在500℃下还原NiRuAl复合氧化物,冷却后用O2钝化1h,即得到NiRu/Al2O3催化剂。将NiRu/Al2O3催化剂、异丙醇和苯基苯乙基醚按照用量比25mg:20mL:0.5mmol加入到反应釜中,密封后充入10bar的保护性气体,在120℃下反应4h,得到氢解产物。苯基苯乙基醚转化率为96.5%,产物主要为乙苯、苯酚和环己醇,收率分别为44.4%、18.8%和20.9%。明显优于商业Ru/C催化剂,相同条件下转化率仅为9.5%。
实施例4:
将摩尔比为3:1:0.05的Ni(NO3)2 .6H2O、Al(NO3)3 .9H2O、和RuCl3 .xH2O加入到水中充分搅拌,与0.5mol/L的NaOH溶液同时逐滴加入到Na2CO3溶液中,维持溶液pH为11,升温至60℃老化20h。老化结束后离心、洗涤并干燥,得到NiRuAl水滑石结构。将NiRuAl水滑石在460℃下高温煅烧,煅烧时间为6小时,得到NiRuAl复合氧化物。用H2在500℃下还原NiRuAl复合氧化物,冷却后用O2钝化1h,即得到NiRu/Al2O3催化剂。将NiRu/Al2O3催化剂、异丙醇和木质素按照用量比250mg:20mL:500mg加入到反应釜中,密封后充入10bar的保护性气体,在200℃下反应4h,得到氢解产物。木质素转化率为62.6%,甲醇可溶物收率为57.2%,其中单体和二聚体占63.6%。
实施例5:
将摩尔比为3:1:0.05的Ni(NO3)2 .6H2O、Al(NO3)3 .9H2O、和RuCl3 .xH2O加入到水中充分搅拌,与3mol/L的NaOH溶液同时逐滴加入到Na2CO3溶液中,维持溶液pH为11,升温至60℃老化20h。老化结束后离心、洗涤并干燥,得到NiRuAl水滑石结构。将NiRuAl水滑石在500℃下高温煅烧,煅烧时间为4小时,得到NiRuAl复合氧化物。用H2在500℃下还原NiRuAl复合氧化物,冷却后用O2钝化1h,即得到NiRu/Al2O3催化剂。将NiRu/Al2O3催化剂、异丙醇和木质素按照用量比250mg:20mL:500mg加入到反应釜中,密封后充入10bar的保护性气体,在220℃下反应4h,得到氢解产物。木质素转化率为65.9%,甲醇可溶物收率为58.1%,其中单体和二聚体占72.8%。
实施例6:
将摩尔比为3:1:0.04的Ni(NO3)2 .6H2O、Al(NO3)3 .9H2O、和RuCl3 .xH2O加入到水中充分搅拌,与2mol/L的NaOH溶液同时逐滴加入到Na2CO3溶液中,维持溶液pH为10,升温至60℃老化20h。老化结束后离心、洗涤并干燥,得到NiRuAl水滑石结构。将NiRuAl水滑石在460℃下高温煅烧,煅烧时间为6小时,得到NiRuAl复合氧化物。用H2在550℃下还原NiRuAl复合氧化物,冷却后用O2钝化1h,即得到NiRu/Al2O3催化剂。将NiRu/Al2O3催化剂、异丙醇和木质素按照用量比250mg:20mL:500mg加入到反应釜中,密封后充入10bar的保护性气体,在180℃下反应4h,得到氢解产物。木质素转化率为59.0%,甲醇可溶物收率为55.9%,其中单体和二聚体占60.5%。
Claims (8)
1.一种原位氢解芳醚键催化剂,其特征在于,该催化剂以NiRu合金为催化活性位点,Al2O3为载体;以催化剂总质量计,Ni和Ru分别占比为20-40%和1-5%。
2.如权利要求1所述的原位氢解芳醚键催化剂的制备方法,其特征在于包括如下步骤:
(1)将摩尔比为1-3:0.5-2:0.02-0.1的Ni(NO3)2 .6H2O、Al(NO3)3 .9H2O和RuCl3 .xH2O加入到水中充分搅拌,与0.5-3mol/L的NaOH溶液同时逐滴加入到Na2CO3溶液中,升温至60-80℃老化5-20h;之后离心、洗涤并干燥,得到NiRuAl水滑石;
(2)将步骤(1)得到的NiRuAl水滑石在300-600℃下高温煅烧,煅烧时间为2-6小时,得到NiRuAl复合氧化物;
(3)用H2还原步骤(2)得到的NiRuAl复合氧化物,冷却后用O2钝化1-3h,得到目标产物:NiRu/Al2O3催化剂。
3.如权利要求2所述原位氢解芳醚键催化剂的制备方法,其特征在于,所述步骤(1)中溶液pH维持在9-11。
4.如权利要求2所述原位氢解芳醚键催化剂的制备方法,其特征在于,所述步骤(3)中H2还原升温速率为2℃/min,还原温度为450-600℃,还原时间6h。
5.如权利要求1所述的催化剂在原位氢解芳醚键中的应用。
6.如权利要求5所述的催化剂在原位氢解芳醚键中的应用,其特征在于包括如下步骤:
将NiRu/Al2O3催化剂、氢源和芳醚类化合物按照用量比20-50mg:5-20mL:1mmol加入到反应釜中,密封后充入10bar的保护性气体,在100-240℃下反应l-8h,得到氢解产物。
7.如权利要求6所述的催化剂在原位氢解芳醚键中的应用,其特征在于,所述的氢源为甲醇、乙醇和异丙醇中的一种。
8.如权利要求6所述的催化剂在原位氢解芳醚键中的应用,其特征在于,所述的芳醚类化合物为苯基苄基醚、苯基苯乙基醚、二苯醚和木质素中的一种。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111517205.3A CN114029070A (zh) | 2021-12-13 | 2021-12-13 | 一种原位氢解芳醚键催化剂及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111517205.3A CN114029070A (zh) | 2021-12-13 | 2021-12-13 | 一种原位氢解芳醚键催化剂及其制备方法和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114029070A true CN114029070A (zh) | 2022-02-11 |
Family
ID=80146794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111517205.3A Withdrawn CN114029070A (zh) | 2021-12-13 | 2021-12-13 | 一种原位氢解芳醚键催化剂及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114029070A (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115041190A (zh) * | 2022-05-13 | 2022-09-13 | 安徽工业大学 | 一种水滑石拓扑转变高分散Ni-Ru/Al2O3催化剂的制备及其应用 |
CN115364862A (zh) * | 2022-09-20 | 2022-11-22 | 南京师范大学 | 一种镍基催化剂及制备方法及在木质素解聚过程中的应用 |
CN115646495A (zh) * | 2022-10-18 | 2023-01-31 | 中国矿业大学 | 一种高活性NiCu/Al2O3催化剂的制备及其在芳醚C-O键催化氢转移裂解方面的应用 |
-
2021
- 2021-12-13 CN CN202111517205.3A patent/CN114029070A/zh not_active Withdrawn
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115041190A (zh) * | 2022-05-13 | 2022-09-13 | 安徽工业大学 | 一种水滑石拓扑转变高分散Ni-Ru/Al2O3催化剂的制备及其应用 |
CN115364862A (zh) * | 2022-09-20 | 2022-11-22 | 南京师范大学 | 一种镍基催化剂及制备方法及在木质素解聚过程中的应用 |
CN115646495A (zh) * | 2022-10-18 | 2023-01-31 | 中国矿业大学 | 一种高活性NiCu/Al2O3催化剂的制备及其在芳醚C-O键催化氢转移裂解方面的应用 |
CN115646495B (zh) * | 2022-10-18 | 2024-03-26 | 中国矿业大学 | 一种高活性NiCu/Al2O3催化剂的制备及其在芳醚C-O键催化氢转移裂解方面的应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN114029070A (zh) | 一种原位氢解芳醚键催化剂及其制备方法和应用 | |
CN113145155B (zh) | 一种应用于组装生物乙醇合成高碳醇的氮掺杂碳包覆镍催化剂及其制备方法 | |
CN110280261B (zh) | 一种由合成气直接合成乙醇的催化剂及其制法和应用 | |
CN113289632B (zh) | 一种用于草酸二甲酯加氢制乙醇的催化剂及其制备方法和应用 | |
CN108048125B (zh) | 一种高选择催化转移氢化木质素衍生物制芳烃的方法 | |
CN113117688A (zh) | 一种mof前驱体钼镍催化剂、其制备方法以及其在木质素降解中的应用 | |
CN113368860B (zh) | 一种木质素催化转化制取环烷烃催化剂及其制备方法与应用 | |
CN112076749B (zh) | 木质素油加氢脱氧制备液体燃料用催化剂及其制备方法和应用 | |
WO2016179974A1 (zh) | 一种纤维素两步法制备乙醇和正丙醇的方法 | |
CN114588910A (zh) | 一种用于木质素解聚的Ni-Zn负载型催化剂的制备方法和应用 | |
Phung | Copper-based catalysts for ethanol dehydrogenation and dehydrogenative coupling into hydrogen, acetaldehyde and ethyl acetate | |
CN101428229B (zh) | 合成气制低碳混合醇催化剂及其制备方法 | |
CN111992213A (zh) | 用于催化愈创木酚加氢脱氧制备环己醇的核壳型催化剂的制备方法 | |
CN112844379B (zh) | 金属有机骨架材料衍生物负载钌催化木质素解聚制备单酚类化学品的方法 | |
WO2016180000A1 (zh) | 一种纤维素两步法制备乙二醇和1,2-丙二醇的方法 | |
CN116618055A (zh) | 一种碳修饰镍基催化剂及在木质素衍生物催化氢化方面的应用 | |
KR101827931B1 (ko) | 1단 반응으로 페놀계 화합물로부터 고탄소 탄화수소를 제조하는 촉매 | |
CN1631527A (zh) | 一种合成气制低碳混合醇的催化剂及其制法 | |
CN115041190A (zh) | 一种水滑石拓扑转变高分散Ni-Ru/Al2O3催化剂的制备及其应用 | |
CN114700092B (zh) | 一种酚类化合物加氢脱氧磷化镍催化剂及其制备方法 | |
CN114832844B (zh) | 一种酚类化合物选择加氢脱氧制备环烷烃催化剂及其制备方法 | |
CN104923285A (zh) | 一种含氧化合物制烃的催化剂及制备方法和应用 | |
CN117504849A (zh) | 一种Ni-Mn/CeZrO2催化剂的制备及在愈创木酚等酚类化合物加氢脱氧的研究方法 | |
CN115532260B (zh) | 一种环状碳酸酯低压加氢催化剂及其制备方法和应用 | |
CN112371188B (zh) | 一种高效甲烷化纳米催化剂的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20220211 |
|
WW01 | Invention patent application withdrawn after publication |