CN108579750B - 一种铜掺杂Ni/SiO2纳米复合催化剂及其制备方法 - Google Patents
一种铜掺杂Ni/SiO2纳米复合催化剂及其制备方法 Download PDFInfo
- Publication number
- CN108579750B CN108579750B CN201810331565.6A CN201810331565A CN108579750B CN 108579750 B CN108579750 B CN 108579750B CN 201810331565 A CN201810331565 A CN 201810331565A CN 108579750 B CN108579750 B CN 108579750B
- Authority
- CN
- China
- Prior art keywords
- copper
- catalyst
- solution
- sio
- nickel
- 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 85
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000010949 copper Substances 0.000 claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- 239000002114 nanocomposite Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 21
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 26
- 150000001879 copper Chemical class 0.000 claims description 20
- 150000002815 nickel Chemical class 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002159 nanocrystal Substances 0.000 claims description 19
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- 229910020489 SiO3 Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000002431 foraging effect Effects 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 230000000694 effects Effects 0.000 abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000001914 filtration Methods 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 8
- 238000002407 reforming Methods 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 239000004115 Sodium Silicate Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003345 natural gas Substances 0.000 abstract description 3
- 238000006057 reforming reaction Methods 0.000 abstract description 3
- 229910018054 Ni-Cu Inorganic materials 0.000 abstract description 2
- 229910018481 Ni—Cu Inorganic materials 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 44
- 239000012153 distilled water Substances 0.000 description 43
- 239000000047 product Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 description 25
- 239000000203 mixture Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 238000005303 weighing Methods 0.000 description 14
- 238000007865 diluting Methods 0.000 description 11
- 238000003760 magnetic stirring Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 239000003755 preservative agent Substances 0.000 description 7
- 230000002335 preservative effect Effects 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000013112 stability test Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000012716 precipitator Substances 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003077 lignite Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- GSWGDDYIUCWADU-UHFFFAOYSA-N aluminum magnesium oxygen(2-) Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 power generation Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种通过以介孔二氧化硅为载体、镍纳米晶为主为活性组分,通过铜掺杂提高所制Ni‑Cu/SiO2纳米复合催化剂甲烷干法重整稳定性的方法,属于催化剂制备技术领域。该纳米复合催化剂以硝酸镍、硅酸钠和稀硝酸等原料,采用简单的沉淀法,经过老化、过滤洗涤、干燥、研磨,还原制得,制备过程简单,无需高温煅烧,原料廉价易得,成本低;本发明所得催化剂具有催化活性高、稳定性好等优点,在700℃条件下反应140h后活性无明显下降,抗烧结和抗积碳能力强。将该催化剂应用于甲烷干法重整反应,为天然气有效利用和CO2减排两个等问题提供了一种有效解决途径。
Description
技术领域
本发明属于催化剂制备技术领域,具体涉及一种铜掺杂Ni/SiO2纳米复合催化剂及其制备方法。
背景技术
天然气作为一种优质高效的清洁能源和化工原料,广泛应用于城市燃气、工业燃料、发电和化工等行业。由于石油资源日益短缺和环保要求日趋严格,利用甲烷合成油、烯烃、含氧化合物、氢气等成为甲烷利用的重要途径,受到国内外政府、企业、学术机构的特别关注,对于缓解能源危机、减轻由于温室气体的排放而导致的全球性气候变暖具有重要意义。目前,用于甲烷二氧化碳重整制合成气的催化剂多以负载金属催化剂为主,主要分为贵金属和非贵金属催化剂两大类。贵金属如Pt、Ir、Ru、Rh等,尽管具有优异的反应性能,但价格昂贵,高温条件下还容易烧结流失。非贵金属催化剂是以镍或钴为活性组分负载于氧化铝、氧化硅、氧化镁、氧化锆、氧化钛等载体上,这种体系的优点是反应性能良好,催化剂制备成本低,但催化剂抗积碳能力低,会因积碳、烧结而导致失活。
CN 101352687 A公开了一种改性的双金属催化剂,该催化剂以一种改性的γ-Al2O3为载体,以质量百分比为1~20%的Ni及1~20%的Co为活性组分,采用浸渍法制备得到该催化剂;但是该制备工艺比较复杂,成本较高。CN 106391020 A公开了一种以碳材料作为载体负载钴的催化剂,将褐煤粉碎成颗粒与钴等其他金属加水均匀混合,放入高压反应釜反应后,经抽滤、干燥、炭化后进行低温活化处理而成;但所述碳材料是褐煤进行改性后生成的碳材料并且还需低温活化,制备过程复杂。CN 105709724 A公开了一种镁铝氧化物固溶体负载贵金属钌的甲烷干法重整催化剂及其制备方法,以镁铝层状复合氢氧化物为前驱体,经焙烧、浸渍制得;该催化剂中Ru的重量百分含量为0.5~4wt%,尽管稳定性较好,但制备过程繁琐,且贵金属含量较高,不利于推广应用。CN103816913 A公开了一种炭基负载金属催化剂,以活性炭为载体,钴、锆、钼多金属物质为活性物质;其中活性炭占80~89%,钴、锆、钼多金属活性物占11~20%;其中载体活性炭由经氧化、水洗、干燥、粉碎后的褐煤与经水洗、干燥、真空炭化、粉碎后的玉米芯混合物,通过炭化、水洗、干燥步骤制得。采用超声浸渍的方法将钴、锆、钼等金属负载于载体活性炭上,之后经干燥、焙烧、还原得到催化剂;虽然该催化剂催化活性良好,但是其主要的活性来自于钴、锆、钼等金属组分,催化剂中金属组分复杂且用量较大,制备过程繁琐复杂。
发明内容
本发明的主要目的是提供了一种活性高、抗积碳能力强、稳定性好的铜掺杂Ni/SiO2纳米复合催化剂,且涉及的制备工艺简单、制备过程易操作控制、成本低。
为实现上述目的,本发明采用的技术方案为:
一种铜掺杂Ni/SiO2纳米复合催化剂,它以介孔二氧化硅为载体,镍纳米晶为活性组分,镍纳米晶分布在介孔二氧化硅表面;其中镍纳米晶表面掺杂铜,铜纳米颗粒附着在镍纳米晶表面。
上述方案中,所述镍纳米晶的平均尺寸大小为4~5nm,铜纳米颗粒平均尺寸为2~3nm;介孔二氧化硅的介孔孔径为17~49nm。
上述方案中,所述铜纳米颗粒在铜掺杂Ni/SiO2纳米复合催化剂中的掺杂量为0.5-1mol%。
上述一种铜掺杂Ni/SiO2纳米复合催化剂的制备方法,包括如下步骤:
1)配制Na2SiO3溶液(硅源);然后在搅拌条件下加入稀酸,调节pH值为5~7,得混合液I;
2)分别配制镍盐溶液和铜盐溶液,在搅拌过程中依次滴加至混合液I中,
3)向混合液II中滴加碱液,然后加热进行老化处理;
4)收集老化处理所得固体产物,然后依次进行洗涤、干燥、研磨,得所述催化剂。
上述方案中,所述混合液II中Na2SiO3、镍盐和铜盐的摩尔比为(8-10):(0.8-1):0.1。
上述方案中,所述碱液的添加量为添加至所得溶液体系的pH为6~7。
上述方案中,所述碱液为稀氨水或Na2SiO3溶液(碱液选用Na2SiO3时,其用量也计入硅源的添加量)。
上述方案中,稀酸可选用稀硝酸等;其质量浓度为15~25%。
上述方案中,所述老化处理工艺为加热至温度为80-100℃,时间为18~24h。
上述方案中,所述研磨工艺为研磨至200目。
本发明的原理为:
甲烷二氧化碳重整反应是一个强吸热过程,该反应需在高温下才能发生,且整个过程中伴随着副反应的产生;高温反应导致三个方面的问题产生:该反应需要消耗大量能源;过程中发生CH4裂解反应与CO歧化反应形成积碳,导致催化剂失活;高温造成催化剂活性组分和载体的烧结,使催化剂活性组分颗粒增大、表面积大幅度降低,导致催化剂失活;解决催化剂的抗积炭性为本领域的关键难题。
本发明所述铜掺杂Ni/SiO2纳米复合催化剂中,通过对Ni/SiO2复合材料进行铜掺杂,使铜纳米颗粒对镍纳米晶表面进行修饰改变其表面电子状态和几何结构,抑制与积炭有关的基元反应的,并利用介孔二氧化硅载体对镍纳米晶进行局部限域,使其铆固在介孔中,阻止这些纳米晶在高温表面下迁移、晶粒生长,同时利用简单的沉淀法,有效控制镍纳米晶和铜纳米颗粒的尺寸,有效提高活性组分的比表面积,进一步提升所得镍基纳米复合催化剂的稳定性以及抗积炭能力;将该催化剂应用于甲烷干法重整反应,为天然气有效利用和CO2减排两个等问题提供了有效解决途径。
与现有技术相比,本发明的有益效果为:
1)金属镍、铜廉价易得,来源广泛、从极大地降低了生产成本;且涉及的制备方法工艺简单,制备过程易操作,反应条件温和,无需高温煅烧,具有显著的能耗效应;
2)所得催化剂具有很高的孔隙率和比表面积,有良好的催化活性,且抗积碳与抗烧结性能优异;
3)制得的催化剂在温度700℃条件下,CH4和CO2转化率较高,且活性可稳定140h无明显下降;具有优异的催化活性和稳定性能。
附图说明
图1为实施例1和对比例5所得产物的XRD图谱;
图2为实施例1所得产物的TEM图谱;
图3为实施例1所得催化剂的活性测试所得CH4和CO2的转化率与温度的关系;
图4为实施例1所得催化剂的稳定性测试所得CH4和CO2的转化率随时间的变化曲线;
图5为实施例2所得催化剂的活性测试所得CH4和CO2的转化率与温度的关系;
图6为实施例3所得催化剂的活性测试所得CH4和CO2的转化率与温度的关系;
图7为对比例1所得催化剂的活性测试所得CH4和CO2的转化率与温度的关系;
图8为对比例2所得催化剂的活性测试所得CH4和CO2的转化率与温度的关系;
图9为对比例3所得催化剂的活性测试所得CH4和CO2的转化率与温度的关系;
图10为对比例5所得催化剂的TEM图谱;
图11为对比例5所得催化剂稳定性测试所得CH4和CO2的转化率随时间的变化曲线。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
实施例1
一种铜掺杂Ni/SiO2纳米复合催化剂,其制备方法包括如下步骤:
1)称取25.578g Na2SiO3·9H2O放入烧杯中,加入84.402g蒸馏水超声溶解得Na2SiO3溶液;将分析纯浓硝酸与蒸馏水按体积比1:4稀释后滴加至所得Na2SiO3溶液中,边滴加边进行磁力搅拌,至pH=6,得混合液I;
2)称取2.617g Ni(NO3)2·6H2O放入烧杯中,加入13.833g蒸馏水超声溶解,得镍盐溶液;称取0.2416g Cu(NO3)2·3H2O放入烧杯中,加入10g蒸馏水超声溶解,得铜盐溶液;然后将所得镍盐溶液和铜盐溶液溶液依次滴加入混合液I中,边滴加边进行磁力搅拌,得混合液II;
3)将分析纯浓氨水与蒸馏水按体积比1:5稀释,取7ml稀释后的氨水滴入所得混合液II 中,边滴边进行磁力搅拌;然后用保鲜膜密封,加热至90℃老化24h;
4)将老化产物进行过滤、洗涤,180℃烘干24h,研磨至过200目,即得所述催化剂(掺杂1mol%铜的Ni/SiO2纳米复合催化剂)。
本实施例所得产物的XRD图谱见图1(Ni-Cu/SiO2);图中在2θ=21.9°处,有一个宽化的衍射峰,对应二氧化硅的微晶态;在衍射角为2θ=44.5°、2θ=51.8°和2θ=76,4°处的三个峰与镍的PDF卡片(PDF#65-2865)一致,说明这三个峰分别对应镍晶面{111}、{200}、{220};证明本发明所得产物为铜/Ni/SiO2复合材料(由于铜的掺杂量较少,低于XRD能够识别的最低水平,因此仅从XRD图上看不到铜的衍射峰)。
本实施例所得产物的透射电镜图见图2,可以看出所得产物中二氧化硅表面均匀分散铜 /Ni颗粒,且分散的颗粒粒径较小。
结合XRD和TEM测试结果,计算得本实施例所得产物中镍纳米晶的平均尺寸大小为4.2nm,铜颗粒平均尺寸为2.3nm;经BET测试得介孔二氧化硅的介孔孔径为17.06~48.23nm。经DFT方法计算推断所得铜颗粒附着在镍纳米晶表面。
将本实施例所得产物进行活性测试,具体包括如下步骤:
1)称取0.05g催化剂与0.5g石英砂混合均匀后填充于石英管反应器中(石英管内径为 8mm,长度为300mm);并使催化剂床层位于加热炉的恒温区部位;固定床石英管反应器放置于一个温度可控的管式炉中;
2)升温前,先通入V(CH4)/V(CO2)/V(Ar)=1/1/8的混合原料气,通过质量流量计将流速调为30ml/min;然后开始升温,催化温度以10℃/min的速度上升,先从室温升至700℃,保温30min(此过程催化剂被还原),此后每上升50℃,保温30min,至750℃保温后自然降温至550℃,保温30min,依次每将50℃保温30min,至400℃;
3)将反应尾气通入气相色谱仪,进行在线检测分析。
在本实施例所得催化剂的作用下,所得CH4和CO2的转化率与温度的关系见图3;结果表明CH4和CO2的转化率在750℃条件下均可达90%以上。
将本实施例所得产物进行稳定性测试,具体包括如下步骤:
i)称取实施例1所得催化剂0.05g与0.5g石英砂混合均匀后填充于石英管反应器的中间 (石英管内径为8mm,长度为300mm)。并使催化剂床层位于加热炉的恒温区部位。固定床石英管反应器放置于一个温度可控的管式炉中。
ii)升温前,先通入V(CH4)/V(CO2)/V(Ar)=1/1/8的混合原料气,通过质量流量计将流速调为30ml/min。然后开始升温,催化温度以10℃/min的速度上升,直接从室温升至700℃,保温140h;
iii)将反应尾气通入气相色谱仪,进行在线检测分析。
在本实施例所得催化剂的作用下,CH4和CO2的转化率随时间的变化见图4;结果表明在700℃条件下,140h内CH4和CO2的转化率稳定在85%和91%。
实施例2
一种铜掺杂Ni/SiO2纳米复合催化剂,其制备方法包括如下步骤:
1)称取25.578g Na2SiO3·9H2O放入烧杯中,加入84.402g蒸馏水超声溶解得Na2SiO3溶液;将分析纯浓硝酸与蒸馏水按体积比1:4稀释后滴加至所得Na2SiO3溶液中,边滴加边进行磁力搅拌,至pH=6,得混合液I;
2)称取2.7825g Ni(NO3)2·6H2O放入烧杯中,加入14.5825g蒸馏水超声溶解,得镍盐溶液;称取0.1208g Cu(NO3)2·3H2O放入烧杯中,加入10g蒸馏水超声溶解,得铜盐溶液;然后将所得镍盐溶液和铜盐溶液溶液依次滴加入混合液I中,边滴加边进行磁力搅拌,得混合液 II;
3)将分析纯浓氨水与蒸馏水按体积比1:5稀释,取7ml稀释后的氨水滴入所得混合液II 中,边滴边进行磁力搅拌;然后用保鲜膜密封,加热至90℃老化24h;
4)将老化产物进行过滤、洗涤,180℃烘干24h,研磨至200目,即得所述催化剂
将本实施例所得产物进行活性测试,具体测试步骤同实施例1;所得CH4和CO2的转化率与温度的关系见图5;结果表明使用氨水作为沉淀剂掺杂0.5mol%(相对催化剂产物的摩尔百分含量)铜的Ni/SiO2纳米复合催化剂据有较高的催化活性。
实施例3
一种铜掺杂Ni/SiO2纳米复合催化剂,其制备方法包括如下步骤:
1)称取22.736g Na2SiO3·9H2O放入烧杯中,加入75.024g蒸馏水超声溶解得Na2SiO3溶液;将分析纯浓硝酸与蒸馏水按体积比1:4稀释后滴加至所得Na2SiO3溶液中,边滴加边进行磁力搅拌,至pH=6,得混合液I;
2)称取2.617g Ni(NO3)2·6H2O放入烧杯中,加入13.833g蒸馏水超声溶解,得镍盐溶液;称取0.2416g Cu(NO3)2·3H2O放入烧杯中,加入10g蒸馏水超声溶解,得铜盐溶液;然后将所得镍盐溶液和铜盐溶液溶液依次滴加入混合液I中,边滴加边进行磁力搅拌,得混合液II;
3)2.5578gNa2SiO3·9H2O放入烧杯中,加入8.4402g蒸馏水超声溶解作为沉淀剂,缓慢滴入所得混合液II中,边滴边进行磁力搅拌;然后用保鲜膜密封,加热至90℃老化24h;
4)将老化产物进行过滤、洗涤,180℃烘干24h,研磨至200目,即得所述催化剂
将本实施例所得产物进行活性测试,具体测试步骤同实施例1;所得CH4和CO2的转化率与温度的关系见图3;结果表明使用硅酸钠作为沉淀剂掺杂1mol%铜的Ni/SiO2纳米复合催化剂据有较高的催化活性。
将本实施例所得产物进行稳定性测试,具体实验步骤与实施例1的活性测试大致相同,不同之处在于测试温度区间为500-750℃。所得CH4和CO2的转化率随时间的变化见图6;结果表明本实施例所得产物可表现出较好的稳定性能。
对比例1
一种铜掺杂Ni/SiO2纳米复合催化剂,其制备方法包括如下步骤:
1)称取25.578g Na2SiO3·9H2O放入烧杯中,加入84.402g蒸馏水超声溶解得Na2SiO3溶液;将分析纯浓硝酸与蒸馏水按体积比1:4稀释后滴加至所得Na2SiO3溶液中,边滴加边进行磁力搅拌,至pH=6,得混合液I;
2)称取2.326g Ni(NO3)2·6H2O放入烧杯中,加入12.296g蒸馏水超声溶解,得镍盐溶液;称取0.4832g Cu(NO3)2·3H2O放入烧杯中,加入10g蒸馏水超声溶解,得铜盐溶液;然后将所得镍盐溶液和铜盐溶液溶液依次滴加入混合液I中,边滴加边进行磁力搅拌,得混合液II;
3)将分析纯浓氨水与蒸馏水按体积比1:5稀释,取7ml稀释后的氨水滴入所得混合液II 中,边滴边进行磁力搅拌;然后用保鲜膜密封,加热至90℃老化24h;
4)将老化产物进行过滤、洗涤,180℃烘干24h,研磨至200目的粉末,即得所述催化剂;
将本对比例所得产物进行活性测试,具体实验步骤与实施例1的活性测试大致相同,不同之处在于测试温度区间为500-750℃。所得CH4和CO2的转化率随温度的变化见图7;结果表明使用氨水作为沉淀剂掺杂2mol%铜的Ni/SiO2纳米复合催化剂据活性有所下降,即当铜的掺杂含量增大时,对催化活性有影响。
对比例2
一种铜掺杂Ni/SiO2纳米复合催化剂,其制备方法包括如下步骤:
1)称取22.736g Na2SiO3·9H2O放入烧杯中,加入75.024g蒸馏水超声溶解得Na2SiO3溶液;将分析纯浓硝酸与蒸馏水按体积比1:4稀释后滴加至所得Na2SiO3溶液中,边滴加边进行磁力搅拌,至pH=6,得混合液I;
2)称取2.1809g Ni(NO3)2·6H2O放入烧杯中,加入11.5283g蒸馏水超声溶解,得镍盐溶液;称取0.604g Cu(NO3)2·3H2O放入烧杯中,加入10g蒸馏水超声溶解,得铜盐溶液;然后将所得镍盐溶液和铜盐溶液溶液依次滴加入混合液I中,边滴加边进行磁力搅拌,得混合液 II;
3)称取2.5578gNa2SiO3·9H2O放入烧杯中,加入8.4402g蒸馏水超声溶解作为沉淀剂,缓慢滴入所得混合液II中,边滴边进行磁力搅拌;然后用保鲜膜密封,加热至90℃老化24h;
4)将老化产物进行过滤、洗涤,180℃烘干24h,研磨至200目,即得所述催化剂
将本实施例所得产物进行稳定性测试,具体实验步骤与实施例1的活性测试大致相同,不同之处在于测试温度区间为500-750℃。所得CH4和CO2的转化率随时间的变化见图8;结果表明使用硅酸钠作为沉淀剂掺杂2.5mol%铜的Ni/SiO2纳米复合催化剂据活性有所下降,当铜的掺杂含量增大时,对催化活性有影响。
对比例3
一种铜掺杂Ni/SiO2纳米复合催化剂,其制备方法包括如下步骤:
1)称取22.736g Na2SiO3·9H2O放入烧杯中,加入75.024g蒸馏水超声溶解得Na2SiO3溶液;将分析纯浓硝酸与蒸馏水按体积比1:4稀释后滴加至所得Na2SiO3溶液中,边滴加边进行磁力搅拌,至pH=6,得混合液I;
2)称取1.454g Ni(NO3)2·6H2O放入烧杯中,加入10g蒸馏水超声溶解,得镍盐溶液;称取1.208g Cu(NO3)2·3H2O放入烧杯中,加入10g蒸馏水超声溶解,得铜盐溶液;然后将所得镍盐溶液和铜盐溶液溶液依次滴加入混合液I中,边滴加边进行磁力搅拌,得混合液II;
3)称取2.5578gNa2SiO3·9H2O放入烧杯中,加入8.4402g蒸馏水超声溶解作为沉淀剂,缓慢滴入所得混合液II中,边滴边进行磁力搅拌;然后用保鲜膜密封,加热至90℃老化24h;
4)将老化产物进行过滤、洗涤,180℃烘干24h,研磨至200目,即得所述催化剂
将本实施例所得产物进行稳定性测试,具体实验步骤与实施例1的活性测试大致相同,不同之处在于测试温度区间为600-750℃。所得CH4和CO2的转化率随时间的变化见图9;结果表明使用硅酸钠作为沉淀剂掺杂5mol%铜的Ni/SiO2纳米复合催化剂据活性有所下降,即当铜的掺杂含量增大时,对催化活性有影响。
对比例4
一种甲烷干法重整催化剂,其制备方法包括如下步骤:
1)称取25.578gNa2SiO3·9H2O放入烧杯中,加入84.402g蒸馏水超声溶解;
2)再将分析纯浓硝酸与蒸馏水按体积比1:4稀释后缓慢滴入步骤(1)所得溶液中,边滴加边进行磁力搅拌,至pH=6;
3)称取2.416gCu(NO3)2·3H2O放入烧杯中,加入16.344g蒸馏水超声溶解;
4)将步骤3)所配溶液依次缓慢滴加入步骤2)所配溶液中,边滴加边进行磁力搅拌;
5)将分析纯浓氨水与蒸馏水按体积比1:5稀释,取7ml稀释后的氨水缓慢滴入步骤5) 所配溶中,边滴边进行磁力搅拌;
6)用保鲜膜密封,90℃老化24h,过滤,洗涤,180℃烘干24h,研磨。
活性测试:具体实验步骤与实施例1的活性测试相同;测试结果表明,本对比例所得产物不具备催化活性。
对比例5
一种甲烷干法重整催化剂,其制备方法包括如下步骤:
1)称取5.468g硅胶粉放入烧杯中,加入装有40ml蒸馏水的烧杯中,超声溶解;
2)称取2.617g Ni(NO3)2·6H2O放入烧杯中,加入15g蒸馏水搅拌均匀;
3)将II中溶液缓慢倒入I中,搅拌均匀;
4)称取1g NaOH放入烧杯中,加入10g蒸馏水搅拌均匀;
5)直接过滤洗涤后在180℃下烘干12h,研磨至细小粉末。
本实施例所得产物的XRD图谱见图1(R-Ni/SiO2),与实施例1相比,本对比例所得镍纳米晶颗粒明显大于实施例1所得复合材料中镍纳米晶的粒径。
本对比例所得产物的TEM图见图10,与实施例1相比,所得产物中分布的颗粒较大,分布不均匀。
热稳定性测试:具体实验步骤与实施例2的热稳定性测试相同。测试结果表明(见图11),本对比例在300分钟内CH4和CO2的转化率迅速下降,催化剂快速失活。
显然,上述实施例仅仅是为清楚地说明所作的实例,而并非对实施方式的限制。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。这里无需也无法对所有的实施方式予以穷举。而因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。
Claims (7)
1.一种铜掺杂Ni/SiO2纳米复合催化剂,它以介孔二氧化硅为载体,镍纳米晶为活性组分,镍纳米晶分布在介孔二氧化硅表面;其中镍纳米晶表面掺杂铜,铜纳米颗粒附着在镍纳米晶表面;
所述镍纳米晶的平均尺寸大小为4-5nm,铜纳米颗粒平均尺寸大小为2-3nm;介孔二氧化硅的介孔孔径为17-49nm;
所述铜纳米颗粒的掺杂量为0.5-1mol%;
其制备方法包括如下步骤:
1)配制Na2SiO3溶液;然后在搅拌条件下加入稀酸,调节pH值为5-7,得混合液I;
2)分别配制镍盐溶液和铜盐溶液,在搅拌过程中依次滴加至混合液I中,
3)向混合液II中滴加碱液,然后加热进行老化处理;
4)收集老化处理所得固体产物,然后依次进行洗涤、干燥、研磨,得所述催化剂;
所述混合液II中Na2SiO3、镍盐和铜盐的摩尔比为(8-10):(0.8-1):0.1。
2.一种如权利要求1所述铜掺杂Ni/SiO2纳米复合催化剂的制备方法,其特征在于,包括如下步骤:
1)配制Na2SiO3溶液;然后在搅拌条件下加入稀酸,调节pH值为5-7,得混合液I;
2)分别配制镍盐溶液和铜盐溶液,在搅拌过程中依次滴加至混合液I中,
3)向混合液II中滴加碱液,然后加热进行老化处理;
4)收集老化处理所得固体产物,然后依次进行洗涤、干燥、研磨,得所述催化剂。
3.根据权利要求2所述的制备方法,其特征在于,所述碱液的添加量为添加至pH为6-7。
4.根据权利要求2所述的制备方法,其特征在于,所述碱液为稀氨水或Na2SiO3溶液。
5.根据权利要求2所述的制备方法,其特征在于,所述稀酸的质量浓度为15-25%。
6.根据权利要求2所述的制备方法,其特征在于,所述老化处理工艺为加热至温度为80-100℃,时间为18-24h。
7.根据权利要求2所述的制备方法,其特征在于,所述研磨工艺为研磨至200目。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810331565.6A CN108579750B (zh) | 2018-04-13 | 2018-04-13 | 一种铜掺杂Ni/SiO2纳米复合催化剂及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810331565.6A CN108579750B (zh) | 2018-04-13 | 2018-04-13 | 一种铜掺杂Ni/SiO2纳米复合催化剂及其制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108579750A CN108579750A (zh) | 2018-09-28 |
CN108579750B true CN108579750B (zh) | 2021-08-24 |
Family
ID=63622474
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810331565.6A Expired - Fee Related CN108579750B (zh) | 2018-04-13 | 2018-04-13 | 一种铜掺杂Ni/SiO2纳米复合催化剂及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108579750B (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109701543A (zh) * | 2019-01-30 | 2019-05-03 | 武汉理工大学 | 一种La2O3团簇修饰Ni/SiO2纳米复合催化剂及其制备方法 |
CN110013854B (zh) * | 2019-05-09 | 2021-06-22 | 福州大学 | 一种负载型镍系催化剂的制备及在c5/c9石油树脂催化加氢中的应用 |
CN111111684B (zh) * | 2020-01-17 | 2020-09-15 | 成都理工大学 | 乙酸自热重整制氢用介孔氧化硅负载钨促进镍基催化剂 |
CN112473716A (zh) * | 2020-11-30 | 2021-03-12 | 同济大学 | 负载铜镍合金颗粒的掺氮介孔碳基纳米材料及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106513000A (zh) * | 2016-11-30 | 2017-03-22 | 中国科学院上海高等研究院 | 一种负载型镍基催化剂及其制备方法及应用 |
CN106944067A (zh) * | 2017-04-22 | 2017-07-14 | 武汉理工大学 | 一种用于甲烷二氧化碳重整制合成气的催化剂的制备方法 |
-
2018
- 2018-04-13 CN CN201810331565.6A patent/CN108579750B/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106513000A (zh) * | 2016-11-30 | 2017-03-22 | 中国科学院上海高等研究院 | 一种负载型镍基催化剂及其制备方法及应用 |
CN106944067A (zh) * | 2017-04-22 | 2017-07-14 | 武汉理工大学 | 一种用于甲烷二氧化碳重整制合成气的催化剂的制备方法 |
Non-Patent Citations (1)
Title |
---|
Influence of preparation method on supported Cu–Ni alloys and their catalytic properties in high pressure CO hydrogenation;Qiongxiao Wu等;《Catal.Sci.Technol.》;20131104(第4期);第378-386页 * |
Also Published As
Publication number | Publication date |
---|---|
CN108579750A (zh) | 2018-09-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Gao et al. | CrPd nanoparticles on NH2-functionalized metal-organic framework as a synergistic catalyst for efficient hydrogen evolution from formic acid | |
CN108579750B (zh) | 一种铜掺杂Ni/SiO2纳米复合催化剂及其制备方法 | |
Fu et al. | Oxygen-vacancy generation in MgFe2O4 by high temperature calcination and its improved photocatalytic activity for CO2 reduction | |
Cao et al. | Enhanced photocatalytic H 2-evolution by immobilizing CdS nanocrystals on ultrathin Co 0.85 Se/RGO–PEI nanosheets | |
CN109126844B (zh) | 一种碳化钼纳米片及其制备方法和应用 | |
Zhang et al. | Cotton stalk activated carbon-supported Co–Ce–B nanoparticles as efficient catalysts for hydrogen generation through hydrolysis of sodium borohydride | |
Feng et al. | Copper oxide hollow spheres: synthesis and catalytic application in hydrolytic dehydrogenation of ammonia borane | |
Azam et al. | In-situ synthesis of TiO2/La2O2CO3/rGO composite under acidic/basic treatment with La3+/Ti3+ as mediators for boosting photocatalytic H2 evolution | |
Zhang et al. | High dispersed Pd supported on CeO2 (1 0 0) for CO oxidation at low temperature | |
Wang et al. | Microwave pyrolysis-engineered MOFs derivatives for efficient preferential CO oxidation in H2-rich stream | |
CN113813963A (zh) | 一种抗积碳型镍基催化剂及其制备方法和应用 | |
CN114345324B (zh) | 生物质碳基金属单原子复合催化剂、制备方法及其应用 | |
Lan et al. | Facile construction of a hierarchical Bi@ BiOBr–Bi 2 MoO 6 ternary heterojunction with abundant oxygen vacancies for excellent photocatalytic nitrogen fixation | |
Yin et al. | Insight into the factors influencing the photocatalytic H 2 evolution performance of molybdenum sulfide | |
Liu et al. | CoNi bimetallic alloy cocatalyst-modified TiO2 nanoflowers with enhanced photocatalytic hydrogen evolution | |
CN114602474A (zh) | 层状硅酸镍催化剂的制备方法 | |
Wang et al. | The synthesis of Ni–Cu alloy nanofibers via vacuum thermal Co-reduction toward hydrogen generation from hydrazine decomposition | |
Mu et al. | Hollow cubic TiO2 loaded with copper and gold nanoparticles for photocatalytic CO2 reduction | |
CN109261183B (zh) | 一种用于二氧化碳甲烷化的钴基催化剂及应用 | |
CN112408320A (zh) | 一种负载型双活性金属复合载氧体及其制备方法和应用 | |
CN115591541A (zh) | 一种高价态金属铌离子掺杂CeO2的制备方法及其应用 | |
CN113000057B (zh) | 负载有Cu/ZnO/CeO2催化剂的多孔材料的制备方法及其应用 | |
CN110787821B (zh) | 一种毛刺球状结构的石墨相碳化氮/硫化镉光催化纳米复合材料及其制备方法与用途 | |
Wu et al. | Synergistic metal-support interaction promoting the formation of oxygen vacancies and their role in CO-PROX over CuO/NiO-CeO2 catalyst | |
Zhang et al. | Hydrogen production from complete dehydrogenation of hydrazine borane on carbon-doped TiO 2-supported NiCr catalysts |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210824 |
|
CF01 | Termination of patent right due to non-payment of annual fee |