CN105618081A - Rare earth metal La doped copper manganese catalyst and experiment method thereof - Google Patents
Rare earth metal La doped copper manganese catalyst and experiment method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 19
- 238000002474 experimental method Methods 0.000 title claims abstract description 12
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 230000000694 effects Effects 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 27
- 238000001179 sorption measurement Methods 0.000 claims description 23
- 230000009467 reduction Effects 0.000 claims description 19
- 238000012360 testing method Methods 0.000 claims description 19
- 238000006386 neutralization reaction Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 238000003795 desorption Methods 0.000 claims description 4
- 238000002309 gasification Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000012495 reaction gas Substances 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 238000004817 gas chromatography Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 57
- 239000011572 manganese Substances 0.000 abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052802 copper Inorganic materials 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000007423 decrease Effects 0.000 abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052748 manganese Inorganic materials 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 7
- 229910017566 Cu-Mn Inorganic materials 0.000 abstract description 3
- 229910017871 Cu—Mn Inorganic materials 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 19
- 229910052746 lanthanum Inorganic materials 0.000 description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000011029 spinel Substances 0.000 description 6
- 229910052596 spinel Inorganic materials 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- HNLPQEXXXUPULW-UHFFFAOYSA-J copper manganese(2+) disulfate Chemical compound [Mn+2].S(=O)(=O)([O-])[O-].[Cu+2].S(=O)(=O)([O-])[O-] HNLPQEXXXUPULW-UHFFFAOYSA-J 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002604 lanthanum compounds Chemical class 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QHDUJTCUPWHNPK-UHFFFAOYSA-N methyl 7-methoxy-2h-indazole-3-carboxylate Chemical compound COC1=CC=CC2=C(C(=O)OC)NN=C21 QHDUJTCUPWHNPK-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
本发明公开了一种掺杂稀土金属La铜锰催化剂及其实验方法，利用XRD、TPR/s-TPR、CO2-TPD等对所制备的催化剂样品进行了表征。La掺杂量0.5％制备的催化剂与纯的Cu-Mn样品相比，可有效的增加表面铜的分散性而使低温变换反应催化性能明显提高。La掺杂量≥3.0％的催化剂样品中除了有Cu1.5Mn1.5O4晶相外，出现有较为明显的CuO晶相，且表面碱性位随La掺杂量的增加而增加的幅度减小，较高的La掺杂量由于La的聚集覆盖了部分活性位，锰不能有效的抑制铜晶粒的长大，使表面铜的分散度下降而导致水煤气变换反应活性明显降低。
The invention discloses a rare-earth metal La copper-manganese catalyst and an experimental method thereof. The prepared catalyst samples are characterized by XRD, TPR/s-TPR, CO 2 -TPD and the like. Compared with the pure Cu-Mn sample, the catalyst prepared with La doping amount of 0.5% can effectively increase the dispersion of copper on the surface and significantly improve the catalytic performance of the low-temperature shift reaction. In addition to the Cu 1.5 Mn 1.5 O 4 crystal phase, the catalyst samples with La doping amount ≥ 3.0% have a more obvious CuO crystal phase, and the increase of surface basic sites decreases with the increase of La doping amount , the higher La doping amount is due to the accumulation of La covering part of the active sites, manganese cannot effectively inhibit the growth of copper grains, and the dispersion of copper on the surface decreases, resulting in a significant decrease in the water gas shift reaction activity.
Description
技术领域technical field
本发明属于催化剂技术领域，涉及一种掺杂稀土金属La铜锰催化剂及其实验方法。The invention belongs to the technical field of catalysts, and relates to a copper-manganese catalyst doped with rare earth metal La and an experimental method thereof.
背景技术Background technique
CO变换是合成气制造、碳氢比调整及净化除去CO不可缺少的反应过程。随着变换反应在燃料电池中的潜在应用价值，新型变换催化剂的研制工作在国内外得到了很大的重视。在过去的10多年，变换催化剂的研究主要集中在贵金属负载型催化剂上，如负载型贵金属Au、Pt催化剂对水煤气变换反应表现出良好的低温活性。但由于贵金属昂贵的价格，新型变换催化剂的研究重点更多已转向过渡金属催化剂上，铜锰催化剂是除工业化外研究较多的一种变换催化剂，相关研究主要是针对制备方法、原料配比、溶液浓度、加料速度、温度及溶液pH等因素进行。如Tanaka等考察了制备方法、助剂种类、Cu/Mn和焙烧温度对铜锰催化剂变换反应催化性能的影响，发现共沉淀法Cu/Mn为1∶2，焙烧温度为900℃下制备得到的催化剂具有较佳的变换反应催化性能；柠檬酸法可以制备得到高活性的铜锰催化剂，Fe或Al对Mn的部分取代有利于提高其催化性能。最近，T.Tabakova等认为，催化剂活性的提高可通过新的制备方法和添加适当的载体来实现，他采用硝酸尿素燃烧法制备了铜锰变换催化剂，并与共沉淀法对比，发现该法制备的催化剂活性较好。由于制备方法和条件的不同，导致其组成、结构和催化性能会出现很大的差异。尽管经过多年的研究，铜锰催化剂的各项性能有了很大的提高，但距离实际应用仍有较大差距，主要是其低温活性较差，而耐热性也有待进一步提高。CO shift is an indispensable reaction process for syngas production, carbon-hydrogen ratio adjustment and purification to remove CO. With the potential application value of shift reaction in fuel cells, the research and development of new shift catalysts has received great attention both at home and abroad. In the past 10 years, the research on shift catalysts has mainly focused on noble metal-supported catalysts, such as supported noble metal Au and Pt catalysts, which exhibit good low-temperature activity for the water-gas shift reaction. However, due to the high price of precious metals, the research focus of new shift catalysts has shifted to transition metal catalysts. Copper-manganese catalysts are a shift catalyst that has been studied more than industrialization. The relevant research is mainly on preparation methods, raw material ratios, Factors such as solution concentration, feeding speed, temperature and solution pH are carried out. For example, Tanaka et al. investigated the influence of preparation method, additive type, Cu/Mn and calcination temperature on the catalytic performance of copper-manganese catalyst shift reaction, and found that the co-precipitation method Cu/Mn was 1:2, and the calcination temperature was 900 °C. The catalyst has better catalytic performance for shift reaction; the citric acid method can prepare highly active copper-manganese catalyst, and the partial substitution of Fe or Al for Mn is beneficial to improve its catalytic performance. Recently, T. Tabakova et al. believe that the improvement of catalyst activity can be achieved by a new preparation method and adding an appropriate carrier. He prepared a copper-manganese shift catalyst by using the urea nitrate combustion method, and compared it with the co-precipitation method. Catalyst activity is better. Due to the different preparation methods and conditions, there will be great differences in its composition, structure and catalytic performance. Although after years of research, the performance of copper-manganese catalysts has been greatly improved, but there is still a big gap from practical application, mainly because of its poor low-temperature activity, and the heat resistance needs to be further improved.
针对铜锰变换催化剂低温活性及稳定性差的问题，主要通过在其中添加第三种组分来改善其低温催化性能。镧元素因其优良的储放氧能力，添加后可有效提高催化剂的电子传输和转移能力。基于其独特的电子结构，良好的电子转移轨道，许多以其为添加物，过渡金属、贵金属等为活性组分的催化剂都显示出良好的催化性能。镧掺杂改性铜锰水煤气变换催化剂的研究鲜见报道，而掺杂其它体系的报道较多。现有技术报道La掺杂铜铈催化剂，表明La的掺杂对铜铈催化剂的氧化选择性有一定的促进作用。RothmanKamD等研究了La掺杂量对Cu/ZnO催化剂的影响，表明La的掺杂量为2.3wt％的Cu/ZnO催化剂在300℃耐热25h下表现出良好的催化活性和热稳定性，催化活性较Cu/ZnO催化剂高20％左右，同时反应活化能降低。Andreeva等采用沉积沉淀法制备了La，Sm，Gd，Yb等稀土元素掺杂的Au/CeO2催化剂，发现添加Yb和Sm的样品具有较好的WGS反应活性。Herunxia等报道稀土氧化物掺杂的铜锰催化剂，发现La2O3的掺杂可显著改善样品的还原性能，提高其表面铜的分散性，有效提高铜锰体系水煤气变换反应的活性和稳定性。Aiming at the poor low-temperature activity and stability of copper-manganese shift catalysts, the low-temperature catalytic performance is mainly improved by adding a third component therein. Due to its excellent ability to store and release oxygen, the addition of lanthanum can effectively improve the electron transport and transfer ability of the catalyst. Based on its unique electronic structure and good electron transfer orbit, many catalysts with transition metals and noble metals as active components have shown good catalytic performance. There are few reports on lanthanum-doped modified copper-manganese water-gas shift catalysts, but there are many reports on doping other systems. The prior art reports La-doped copper-cerium catalysts, indicating that La doping can promote the oxidation selectivity of copper-cerium catalysts to a certain extent. RothmanKamD et al. studied the effect of La doping amount on Cu/ZnO catalyst, and showed that the Cu/ZnO catalyst with La doping amount of 2.3wt% showed good catalytic activity and thermal stability at 300°C for 25h, and the catalytic The activity is about 20% higher than that of Cu/ZnO catalyst, and the reaction activation energy is lowered at the same time. Andreeva et al prepared Au/CeO2 catalysts doped with La, Sm, Gd, Yb and other rare earth elements by deposition and precipitation method, and found that the samples added with Yb and Sm had better WGS reactivity. Herunxia et al. reported rare earth oxide doped copper-manganese catalysts, and found that the doping of La 2 O 3 can significantly improve the reduction performance of the sample, improve the dispersion of copper on its surface, and effectively improve the activity and stability of the water-gas shift reaction of the copper-manganese system. .
本发明在前期研究工作的基础上，以铜锰硫酸盐和镧硝酸盐为原料制备铜锰水煤气变换催化剂，以期利用镧元素特有的物化性质对铜锰催化剂进行改性研究，以提高其低温变换反应活性。On the basis of previous research work, the present invention uses copper-manganese sulfate and lanthanum nitrate as raw materials to prepare copper-manganese water-gas shift catalyst, in order to use the unique physical and chemical properties of lanthanum to modify the copper-manganese catalyst to improve its low-temperature shift. reactivity.
发明内容Contents of the invention
本发明的目的在于克服上述技术存在的缺陷，提供一种掺杂稀土金属La铜锰催化剂及其实验方法，以硫酸铜、硫酸锰和硝酸镧晶体为原料，氢氧化钠溶液为沉淀剂，采用共沉淀法制备1.2倍碱量下5种稀土La掺杂量的铜锰催化剂。分别对这5种样品进行活性测试，XRD、TPR/s-TPR及CO2-TPD等手段进行表征，考察沉淀反应体系中稀土La掺杂量对铜锰基催化剂结构和性能的影响。The object of the present invention is to overcome the defective that above-mentioned technology exists, provide a kind of doped rare earth metal La copper manganese catalyst and experimental method thereof, take copper sulfate, manganese sulfate and lanthanum nitrate crystal as raw material, sodium hydroxide solution is precipitating agent, adopts Co-precipitation method prepared copper-manganese catalysts with 1.2 times the amount of alkali doped with 5 kinds of rare earth La. The five samples were tested for activity and characterized by means of XRD, TPR/s-TPR and CO 2 -TPD to investigate the influence of the doping amount of rare earth La in the precipitation reaction system on the structure and performance of copper-manganese-based catalysts.
其具体技术方案为：Its specific technical plan is:
一种掺杂稀土金属La铜锰催化剂，掺杂0.5％稀土元素。A copper-manganese catalyst doped with rare earth metal La, doped with 0.5% rare earth element.
一种掺杂稀土金属La铜锰催化剂的实验方法，包括以下步骤：A kind of experimental method of doping rare earth metal La copper manganese catalyst, comprises the following steps:
步骤1：掺杂稀土元素La铜锰催化剂的制备Step 1: Preparation of Rare Earth Element La Copper-Manganese Catalyst
1.1)配液1.1) Dosing
将CuSO4·5H2O、MnSO4.H2O和La(NO3)3·6H2O按一定比例配制成浓度为0.225mol/L的混合液；Prepare CuSO 4 .5H 2 O, MnSO 4 .H 2 O and La(NO 3 ) 3 .6H 2 O in a certain proportion to make a mixed solution with a concentration of 0.225mol/L;
1.2)恒温溶解1.2) Dissolving at constant temperature
将混合液置于45℃的恒温水浴锅中，搅拌速率保持在300rad/min，恒温10分钟使其充分溶解，而且在滴定过程中始终保持该温度不变；Put the mixed solution in a constant temperature water bath at 45°C, keep the stirring rate at 300rad/min, keep the temperature for 10 minutes to fully dissolve it, and keep the temperature constant during the titration process;
1.3)中和1.3) Neutralization
将溶解后的混合液用浓度为4mol/L的NaOH溶液进行中和得到沉淀物，中和温度45℃，中和终点pH值11.5，中和液滴定速率10.5rad/min，保持搅拌速率300rad/min；Neutralize the dissolved mixed solution with a NaOH solution with a concentration of 4mol/L to obtain a precipitate. The neutralization temperature is 45°C, the pH value of the neutralization end point is 11.5, the titration rate of the neutralization solution is 10.5rad/min, and the stirring rate is maintained at 300rad/min. min;
1.4)热煮老化1.4) Hot boiling aging
将得到的沉淀物进行热煮，热煮时的温度为45℃，热煮时间为30min；The obtained precipitate was boiled, the temperature during boiling was 45°C, and the boiling time was 30 minutes;
1.5)洗涤1.5) Washing
对经过热煮的沉淀物进行洗涤，使其pH至7：Wash the boiled precipitate to pH 7:
1.6)干燥1.6) dry
在80℃下进行，干燥4小时；Carry out at 80°C, dry for 4 hours;
1.7)焙烧1.7) Roasting
焙烧介质是空气，焙烧温度550℃，升温速率5℃/min，焙烧时间4h。The roasting medium is air, the roasting temperature is 550°C, the heating rate is 5°C/min, and the roasting time is 4h.
步骤2：催化剂活性测试Step 2: Catalyst Activity Test
催化剂的活性测试实验是在固定床煤燃烧-气化反应装置上完成的。固定床煤燃烧-气化反应装置属于固定床绝热式积分反应器，反应管内径为6mm，活性测试过程为：将来自钢瓶的原料气先经分子筛脱除其中的杂质分子，然后进入脱氧管脱除微量氧气，再经转子流量计计量，自上而下进入反应管对催化剂进行还原，经催化剂层反应后的还原气再经冷凝、硅胶脱水最后排空，还原完成后将原料气经分子筛脱除其中的杂质分子后进入脱氧管脱除微量氧气，然后经转子流量计计量后经饱和蒸汽管增湿成为具有一定水气比的反应气，反应气自上而下进入反应管进行CO的变换反应，经催化剂层反应后的变换气再经冷凝、硅胶脱水后取样，用气相色谱仪在线分析，热导检测出变换反应后的气体组成。The activity test experiment of the catalyst is completed on the fixed bed coal combustion-gasification reaction device. The fixed-bed coal combustion-gasification reaction device is a fixed-bed adiabatic integral reactor, and the inner diameter of the reaction tube is 6mm. In addition to trace oxygen, it is measured by a rotameter, and enters the reaction tube from top to bottom to reduce the catalyst. The reducing gas after the reaction of the catalyst layer is condensed, dehydrated by silica gel, and finally emptied. After removing the impurity molecules, it enters the deoxidation tube to remove trace oxygen, and then is measured by the rotameter and then humidified by the saturated steam tube to become a reaction gas with a certain water-gas ratio. The reaction gas enters the reaction tube from top to bottom for CO conversion. For the reaction, the shifted gas after the reaction of the catalyst layer is condensed and dehydrated on silica gel, then sampled, and analyzed online with a gas chromatograph, and the composition of the gas after the shift reaction is detected by thermal conductivity.
步骤3：XRD/TPR/s-TPR/TPD测试Step 3: XRD/TPR/s-TPR/TPD test
XRD晶相分析在德国BrukerD8advanceX射线粉末衍射仪上进行，Cu靶，Ni滤波，Si-Li探测器，40KV×40mA，扫描范围20°-80°，扫描速度2°/min。XRD crystal phase analysis was carried out on a Bruker D8advance X-ray powder diffractometer in Germany, Cu target, Ni filter, Si-Li detector, 40KV×40mA, scanning range 20°-80°, scanning speed 2°/min.
TPR测试是在常压U型石英管反应器中进行，以8.9％H2/Ar(V/V)混合气体为还原气，还原气流速：30mL/min，试样用量：20mg，粒度：40-80目，催化剂进行TPR测试前，先进行预处理，预处理条件是将催化剂在Ar气气氛下于室温升到120℃，吹扫30min后再降到40℃，然后切换为8.9％H2/Ar(V/V)混合气体，待基线走平后，以10℃/min的速率从室温升温至600℃。The TPR test is carried out in a normal pressure U-shaped quartz tube reactor, with 8.9% H 2 /Ar(V/V) mixed gas as the reducing gas, the reducing gas flow rate: 30mL/min, the sample dosage: 20mg, the particle size: 40 -80 mesh, before TPR test, the catalyst should be pretreated. The pretreatment condition is to raise the catalyst to 120°C at room temperature under Ar gas atmosphere, purging for 30min, then lowering to 40°C, and then switching to 8.9%H 2 /Ar(V/V) mixed gas, after the baseline leveled off, the temperature was raised from room temperature to 600°C at a rate of 10°C/min.
s-TPR测试是样品完成如上TPR步骤后降温至40℃，用Ar气吹扫30分钟至***稳定，通入流量为30mL/min的N2O气体进行表面氧化30分钟至***稳定，再通入流量为50mL/min的8.9％H2/Ar(V/V)混合气，以10℃/min的速率升到600℃。The s-TPR test is that the sample is cooled to 40°C after the above TPR step, purged with Ar gas for 30 minutes until the system is stable, and N 2 O gas with a flow rate of 30mL/min is introduced for surface oxidation for 30 minutes until the system is stable. 8.9% H 2 /Ar (V/V) mixed gas with a flow rate of 50 mL/min was introduced, and the temperature was raised to 600° C. at a rate of 10° C./min.
CO2-TPD测试是样品完成如上TPR步骤后降温至40℃，然后升温至200℃，通入CO2气体，恒温2h进行化学吸附。在Ar气氛下降温至40℃，以10℃/min的速率程序升温脱附至600℃。In the CO 2 -TPD test, the temperature of the sample is lowered to 40°C after the above TPR step, and then the temperature is raised to 200°C, CO 2 gas is introduced, and the temperature is maintained for 2 hours for chemical adsorption. The temperature was lowered to 40°C in an Ar atmosphere, and the temperature was programmed to desorb to 600°C at a rate of 10°C/min.
与现有技术相比，本发明的有益效果为：Compared with prior art, the beneficial effect of the present invention is:
本发明实验所做的5种不同稀土La掺杂量的铜锰基催化剂中，La掺杂量为0.5％的催化剂的低温活性是最好的。Among the copper-manganese-based catalysts with different doping amounts of rare earth La in the experiments of the present invention, the low-temperature activity of the catalyst with a La doping amount of 0.5% is the best.
附图说明Description of drawings
图1是La改性铜锰催化剂的CO转化率，其中，图1a为450℃耐热过程(350min)；图1b为450℃耐热350min后降温过程；Figure 1 is the CO conversion rate of the La modified copper-manganese catalyst, wherein Figure 1a is a heat-resistant process at 450°C (350min); Figure 1b is a cooling process after a heat-resistant 350min at 450°C;
图2是La改性铜锰催化剂的XRD图，其中，图2a为催化剂样品；图2b为变换反应后样品；Fig. 2 is the XRD figure of La modified copper-manganese catalyst, wherein, Fig. 2a is the catalyst sample; Fig. 2b is the sample after shift reaction;
图3是La改性铜锰催化剂的TPR图；Fig. 3 is the TPR figure of La modified copper-manganese catalyst;
图4是La改性铜锰催化剂的s-TPR图，其中，图4a为CuMn催化剂样品；图4b为CuMn/La-0.5催化剂样品；图4c为CuMn/La-3.0催化剂样品；图4d为CuMn/La-5.0催化剂样品；图4e为CuMn/La-10.0催化剂样品；Figure 4 is the s-TPR diagram of La modified copper-manganese catalyst, in which Figure 4a is the CuMn catalyst sample; Figure 4b is the CuMn/La-0.5 catalyst sample; Figure 4c is the CuMn/La-3.0 catalyst sample; Figure 4d is the CuMn /La-5.0 catalyst sample; Figure 4e is a CuMn/La-10.0 catalyst sample;
图5是La改性铜锰催化剂的CO2-TPD图。Fig. 5 is the CO 2 -TPD diagram of the La-modified copper-manganese catalyst.
具体实施方式detailed description
下面结合附图和具体实施例对本发明的技术方案作进一步详细地说明。The technical solution of the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.
实施例1掺杂稀土金属La铜锰催化剂的制备The preparation of embodiment 1 doping rare earth metal La copper manganese catalyst
所用试剂和药品见表1。The reagents and drugs used are listed in Table 1.
表1实验所用化学试剂Table 1 Chemical reagents used in experiments
实验设计experimental design
其制备过程简述如下：将CuSO4.5H2O、MnSO4.H2O和La(NO3)3·6H2O按所设计的比例溶于一定量的蒸馏水中配制成浓度为0.225mol/L的混合液，然后用浓度为4mol/L的NaOH溶液进行中和，生成沉淀物。所得到的混合物经洗涤、抽滤、干燥、焙烧后得到催化剂样品。掺杂稀土元素La铜锰催化剂的制备工艺方案设计The preparation process is briefly described as follows: CuSO 4 .5H 2 O, MnSO 4 .H 2 O and La(NO 3 ) 3 6H 2 O are dissolved in a certain amount of distilled water according to the designed ratio to prepare a concentration of 0.225mol /L of the mixed solution, and then neutralized with a NaOH solution with a concentration of 4mol/L to form a precipitate. The resulting mixture was washed, suction filtered, dried, and calcined to obtain a catalyst sample. Preparation process design of La copper manganese catalyst doped with rare earth element
(1)配液(1) Dosing
为了得到铜、锰、镧比例大致一定的催化剂，配混合溶液时需要称取特定量的CuSO4·5H2O、MnSO4.H2O和La(ON3)3·6H2O，同时为了保证混合液的浓度，还要在混合物中加一定量的水，混合物加水后搅拌10分钟使其成为混合均匀一致的溶液。In order to obtain a catalyst with a roughly constant ratio of copper, manganese, and lanthanum, specific amounts of CuSO 4 ·5H 2 O, MnSO 4 .H 2 O and La(ON 3 ) 3 ·6H 2 O need to be weighed when preparing the mixed solution. To ensure the concentration of the mixed solution, a certain amount of water is also added to the mixture, and the mixture is stirred for 10 minutes after adding water to make it a uniformly mixed solution.
配液过程计算如下：The dosing process is calculated as follows:
假设沉淀只有Cu(OH)2、Mn(OH)2和Mn(OH)3，沉淀之分解为CuO、Mn3O4。令催化剂中铜与锰的摩尔比ncuo：nMn3O4＝1∶1，以制备5克催化剂为基准，以掺杂0.5％La为例：Assuming that the precipitates are only Cu(OH) 2 , Mn(OH) 2 and Mn(OH) 3 , the precipitates are decomposed into CuO and Mn 3 O 4 . Make the mol ratio n cuo of copper and manganese in the catalyst: n Mn3O4 =1: 1, take preparation 5 gram catalysts as benchmark, take doping 0.5%La as example:
则Cu∶Mn∶La＝49.75％∶49.75％∶0.5％＝1∶1∶0.01005Then Cu:Mn:La=49.75%:49.75%:0.5%=1:1:0.01005
设Cu2+的摩尔数为x，则(Mn2++Mn3+)为x，La3+为0.01005xAssuming that the number of moles of Cu 2+ is x, then (Mn 2+ +Mn 3+ ) is x, and La 3+ is 0.01005x
则CuOMn3O4La2O3 Then CuOMn 3 O 4 La 2 O 3
x1/3x0.01005x/2＝0.005025xx1/3x0.01005x/2＝0.005025x
M79.55228.84325.81M79.55228.84325.81
则79.55x+228.84×1/3x+325.81×0.005025x＝5Then 79.55x+228.84×1/3x+325.81×0.005025x＝5
得x＝0.032molGet x=0.032mol
m(CuSO4·5H2O)＝0.032×249.68÷99％＝8.071gm(CuSO 4 ·5H 2 O)=0.032×249.68÷99%=8.071g
m(MnSO4·H2O)＝0.032×169.02÷99％＝5.463gm(MnSO 4 ·H 2 O)=0.032×169.02÷99%=5.463g
m(La(NO3)3.6H2O)＝0.032×0.01005×433.01÷99％＝0.141gm(La(NO 3 ) 3 .6H 2 O)=0.032×0.01005×433.01÷99%=0.141g
设CuSO4溶液的浓度为0.225mol/L，则MnSO4溶液的浓度亦为0.225mol/L，Suppose CuSO The concentration of solution is 0.225mol/L, then MnSO The concentration of solution is also 0.225mol/L,
则0.225v＝0.032，v＝0.1422L＝142.2mLThen 0.225v=0.032, v=0.1422L=142.2mL
由此可知：在溶解药品的过程中所需加入的蒸馏水为142.2mLIt can be seen from this that the distilled water that needs to be added in the process of dissolving the drug is 142.2mL
Cu2+～2OH-Mn2+～2OH-La3+～3OH- Cu 2+ ～2OH - Mn 2+ ～2OH - La 3+ ～3OH -
0.0320.0640.0320.0640.01005×0.0323×0.01005×0.0320.0320.0640.0320.0640.01005×0.0323×0.01005×0.032
在实验过程中所用的NaOH溶液的浓度为4mol/L，1.2倍的碱量。The concentration of NaOH solution used during the experiment is 4mol/L, 1.2 times the amount of alkali.
则，n(OH-)＝0.064+0.064+3×0.01005×0.032＝0.1290molThen, n(OH - )=0.064+0.064+3×0.01005×0.032=0.1290mol
V(NaOH)＝0.1290×1.2÷4＝38.7mLV(NaOH)=0.1290×1.2÷4=38.7mL
所以所要加入NaOH溶液的体积为38.7mL。So the volume of NaOH solution to be added is 38.7mL.
(2)恒温溶解(2) Dissolving at constant temperature
为使混合液与碱液能在恒定温度(45℃)下发生中和反应，需将混合液加热到给定温度后恒温10分钟使其溶解，而且在滴定过程中始终保持该温度不变。In order to enable the neutralization reaction between the mixed solution and the lye at a constant temperature (45°C), it is necessary to heat the mixed solution to a given temperature and then keep the temperature for 10 minutes to dissolve it, and keep the temperature constant during the titration process.
(3)中和(3) Neutralization
中和过程是硫酸铜、硫酸锰及硝酸镧与碱液进行反应生成碱性沉淀物的过程。中和过程中Cu2+与OH-反应生成浅蓝色的Cu(OH)2沉淀，Mn2+与OH-反应首先得到白色的Mn(OH)2沉淀，Mn(OH)2在空气中很快被氧化，生成棕色的Mn2O3和MnO2的水合物。关于Mn(OH)2沉淀的具体氧化过程还不是十分清楚，其推测的反应方程式如下：The neutralization process is a process in which copper sulfate, manganese sulfate and lanthanum nitrate react with lye to form alkaline precipitates. During the neutralization process, Cu 2+ reacts with OH - to form a light blue Cu(OH) 2 precipitate, and Mn 2+ reacts with OH - to form a white Mn(OH) 2 precipitate at first, and Mn(OH) 2 is very stable in air. It is quickly oxidized to produce brown Mn 2 O 3 and MnO 2 hydrates. The specific oxidation process of Mn(OH) 2 precipitation is not very clear, and the speculated reaction equation is as follows:
Cu2++OH-→Cu(OH)2(s)Cu 2+ +OH - → Cu(OH) 2 (s)
Mn2++OH-→Mn(OH)2(s)Mn 2+ +OH - → Mn(OH) 2 (s)
La3++OH-→La(OH)3(s)La 3+ +OH - → La(OH) 3 (s)
Cu(OH)2(s)→CuO.aH2O(s)Cu(OH) 2 (s)→CuO.aH 2 O(s)
La(OH)3(s)→La2O3.bH2O(s)La(OH) 3 (s)→La 2 O 3 .bH 2 O(s)
Mn(OH)2(s)+O2(g)→Mn2O3.cH2O(s)Mn(OH) 2 (s)+O 2 (g)→Mn 2 O 3 .cH 2 O(s)
Mn2O3.xH2O(s)+O2(g)→MnO2.dH2O(s)Mn 2 O 3 .xH 2 O(s)+O 2 (g)→MnO 2 .dH 2 O(s)
在催化剂的制备过程中，当催化剂组成一定时，中和过程的条件对催化剂性能有重要影响。在中和过程中，中和温度、混合液浓度、碱液浓度、加料速度、pH值、搅拌速率等因素中，其中一个条件的变动都可能会对最终催化剂的性能造成影响。本实验的具体工艺条件如表2所示。In the preparation process of the catalyst, when the composition of the catalyst is constant, the conditions of the neutralization process have an important influence on the performance of the catalyst. During the neutralization process, a change in one of the factors such as neutralization temperature, mixed solution concentration, lye concentration, feeding speed, pH value, and stirring rate may affect the performance of the final catalyst. The specific process conditions of this experiment are shown in Table 2.
表2中和工艺条件及参数Table 2 neutralization process conditions and parameters
(4)热煮老化(4) Hot boiling aging
此过程是滴定结束后使其保持一定温度下沉淀物的老化过程，热煮可以完善沉淀物的晶型，对晶粒的长大也有重要作用。热煮时的温度为45℃，热煮时间为30分钟。This process is the aging process of keeping the precipitate at a certain temperature after the titration. Hot boiling can improve the crystal form of the precipitate and also play an important role in the growth of the crystal grain. The temperature during hot boiling is 45 ℃, and the hot boiling time is 30 minutes.
(5)洗涤(5) washing
在催化剂制备过程中，必须对沉淀物进行洗涤，使其pH至7。洗涤催化剂一方面是为了除去催化剂中夹杂的SO4 2-和其它杂质离子。如果洗涤不彻底，在干燥过程中杂质可能受热汽化分解，这样会破坏催化剂的晶体结构，使催化剂结构变得松散，强度下降。另一方面，如果不洗涤或洗涤不彻底会造成催化剂本体含硫量高，影响催化剂的活性。另外，洗涤过程能使沉淀物的晶型更加完善。During catalyst preparation, the precipitate must be washed to bring its pH to 7. On the one hand, washing the catalyst is to remove SO 4 2- and other impurity ions contained in the catalyst. If the washing is not thorough, the impurities may be heated and vaporized and decomposed during the drying process, which will destroy the crystal structure of the catalyst, make the catalyst structure loose and reduce its strength. On the other hand, if it is not washed or washed thoroughly, the sulfur content of the catalyst body will be high, which will affect the activity of the catalyst. In addition, the washing process can make the crystal form of the precipitate more perfect.
(6)干燥(6) dry
干燥主要是固体物料的脱水过程，通常在80℃下进行，干燥4小时。固体物质中的水分有三种：①化学结合水；②吸附水，是固体表面或毛细孔中吸附的水；③游离水，是处于物料颗粒之间的水，干燥过程主要是除去后两种水。干燥一般对催化剂的化学结构影响不大，但对半成品催化剂的物理结构有影响。Drying is mainly the dehydration process of solid materials, usually at 80°C for 4 hours. There are three types of moisture in solid matter: ①Chemically bound water; ②Absorptive water, which is water adsorbed on the solid surface or in capillary pores; ③Free water, which is water between material particles. The drying process is mainly to remove the latter two kinds of water. . Drying generally has little effect on the chemical structure of the catalyst, but has an effect on the physical structure of the semi-finished catalyst.
干燥温度、干燥方法、干燥速率、干燥介质的不同，都将对催化剂的孔径大小，比表面积、机械强度有所影响。另外，干燥温度过高或时间太长，会使催化剂内水分损失过大，催化剂粒子结合紧密，孔结构发生变化，影响催化剂的性能。The difference in drying temperature, drying method, drying rate and drying medium will affect the pore size, specific surface area and mechanical strength of the catalyst. In addition, if the drying temperature is too high or the drying time is too long, the moisture loss in the catalyst will be too large, the catalyst particles will be closely combined, and the pore structure will change, which will affect the performance of the catalyst.
(7)焙烧(7) Roasting
焙烧是催化剂制备过程中一个重要的热处理过程，是氢氧化物分解生成氧化物的过程。焙烧温度、焙烧时间的不同会对催化剂的活性、热稳定性、机械强度等方面有很大影响。焙烧过程可以除去催化剂中的一部分水，使催化剂体积收缩，提高催化剂的机械强度。表3是催化剂的焙烧工艺条件及参数。Roasting is an important heat treatment process in the catalyst preparation process, and it is a process in which hydroxides are decomposed to form oxides. The difference in calcination temperature and calcination time will have a great influence on the activity, thermal stability, mechanical strength and other aspects of the catalyst. The calcination process can remove part of the water in the catalyst, shrink the volume of the catalyst, and improve the mechanical strength of the catalyst. Table 3 is the roasting process conditions and parameters of the catalyst.
表3焙烧工艺条件及参数Table 3 Roasting process conditions and parameters
实施例2掺杂稀土元素La铜锰催化剂的活性测试与表征结果Activity test and characterization result of embodiment 2 doping rare earth element La copper manganese catalyst
图1为所制备催化剂的CO变换反应活性测试结果。图1a为450℃耐热350min过程中的CO转化率，图1b为经450℃耐热350min后降温过程的CO转化率。由图1a图可知，掺La量为0.5％的样品，在耐热过程中CO转化率始终保持在95％以上，而掺La量为10.0％的样品，当耐热时间小于280min时，CO转化率保持在93％左右，超过280min后，CO转化率明显下降。由图1b图可知，不同La掺杂量的样品在整个活性测试温区内的差别较大，在350℃-450℃之间，掺La量小于5.0％的样品，CO转化率变化很小，掺La量大于5.0％的CuMn/La-10.0样品，CO转化率随温度的降低而下降。在200℃-350℃之间，掺La量小于等于3.0％的样品，CO转化率均较CuMn大，尤以CuMn/La-0.5样品最为明显，250℃时CO转化率达到87％，200℃时达到38％，而不掺La的CuMn样，250℃时CO转化率只有40％，200℃时8.0％。掺La量大于3.0％的样品，在整个测试温区中CO转化率均较低，特别是CuMn/La-10.0样品，300℃以下基本失活，说明La掺杂量对催化剂的活性影响较大。Figure 1 shows the CO shift reaction activity test results of the prepared catalysts. Figure 1a shows the CO conversion rate during the 450°C heat-resistant process for 350 minutes, and Figure 1b shows the CO conversion rate during the cooling process after 450°C heat-resistant process for 350 minutes. It can be seen from Figure 1a that the CO conversion rate of the sample doped with 0.5% La is always above 95% during the heat resistance process, while the CO conversion rate of the sample doped with 10.0% La is less than 280min when the heat resistance time is less than 280min. The CO conversion rate remained at about 93%, and after more than 280 minutes, the CO conversion rate dropped significantly. It can be seen from Figure 1b that the samples with different La doping amounts have a large difference in the entire activity test temperature range. Between 350°C and 450°C, the CO conversion rate of the samples with less than 5.0% La doping changes little. For the CuMn/La-10.0 sample doped with more than 5.0% La, the CO conversion rate decreased with the decrease of temperature. Between 200°C and 350°C, the CO conversion rate of the samples with La content less than or equal to 3.0% is higher than that of CuMn, especially the CuMn/La-0.5 sample, the CO conversion rate reaches 87% at 250°C, and the The conversion rate of CO can reach 38% at 250°C and 8.0% at 200°C for CuMn without La doping. For samples doped with more than 3.0% La, the conversion rate of CO is low in the entire test temperature range, especially the CuMn/La-10.0 sample, which is basically inactivated below 300°C, indicating that the doping amount of La has a great influence on the activity of the catalyst .
图2为所制备催化剂和变换反应后样品的XRD图谱，其结构参数见表4。由图2a可见，各样品的主晶相均为尖晶石结构的Cu1.5Mn1.5O4(JCPDS35-1172)，没有出现单独镧类化合物的特征峰，说明La可能呈分散状态存在于催化剂晶粒表面或者进入Cu1.5Mn1.5O4晶格。但表4中数据表明，掺杂La的样品晶面间距均增大，说明有部分La3+进入Cu1.5Mn1.5O4晶格，这是由于La3+的半径(0.1106nm)明显大于Cu+、Cu2+、Mn3+和Mn4+的半径(0.096、0.072、0.062和0.054nm)。La的掺杂量直接影响样品的晶面间距和晶粒大小，CuMn/La-0.5样品由于掺杂的La量较少，晶面间距增加的幅度较小，晶粒大小相比于CuMn变化不大。当La掺杂量≥3.0％时，CuMn/La-m(m＝3.0，5.0，10.0)样品的晶面间距相差不大，但均大于CuMn/La-0.5样品，说明进入晶格中的La量有一定的限度，且晶粒尺寸随掺La量的增加变化不大。La掺杂量≥3.0％的样品中均发现有较为明显的铜氧化物晶相，说明有部分Cu2+没有进入尖晶石Cu1.5Mn1.5O4晶格中，可能是进入晶格中的La阻止了Cu2+的进入。经变换反应后(图2b)，尖晶石结构的Cu1.5Mn1.5O4金属固溶体均被还原分解为Cu(JCPDS04-0836)与MnO(JCPDS07-0230)，高温烧结Cu晶粒均长大。掺La量较少的样品Cu晶粒长大的幅度较小，尤以CuMn/La-0.5样品最为明显，掺La量较多的样品经变换反应后Cu的烧结较严重，尤以CuMn/La-10.0样品最为明显，未掺杂的CuMn样品单质Cu烧结长大的幅度较CuMn/La-10.0小，但远大于CuMn/La-0.5样品。说明在变换反应过程中，少量La的掺入可使铜锰组分分散均匀，锰可有效抑制铜的烧结长大，较多La的掺入(CuMn/La-10.0样品在29.4℃出现有单质La的特征衍射峰)干扰了锰对铜的协同效应，使铜得不到有效的隔离而聚集长大。此外CuMn和CuMn/La-0.5样品在31.5°出现有MnCO3(JCPDS44-1472)特征峰。Figure 2 is the XRD spectrum of the prepared catalyst and the sample after the shift reaction, and its structural parameters are shown in Table 4. It can be seen from Figure 2a that the main crystal phase of each sample is Cu 1.5 Mn 1.5 O 4 (JCPDS35-1172) with a spinel structure, and there is no characteristic peak of a single lanthanum compound, indicating that La may exist in the catalyst crystal in a dispersed state. grain surface or into the Cu 1.5 Mn 1.5 O 4 lattice. However, the data in Table 4 show that the interplanar spacing of the samples doped with La increases, indicating that some La 3+ enters the Cu 1.5 Mn 1.5 O 4 lattice, because the radius of La 3+ (0.1106nm) is significantly larger than that of Cu + , Cu 2+ , Mn 3+ and Mn 4+ radii (0.096, 0.072, 0.062 and 0.054 nm). The doping amount of La directly affects the interplanar spacing and grain size of the sample. Due to the small amount of La doped in CuMn/La-0.5 sample, the increase in interplanar spacing is small, and the grain size changes little compared with CuMn. Big. When the La doping amount is ≥3.0%, the interplanar spacing of the CuMn/La-m (m=3.0, 5.0, 10.0) samples has little difference, but they are all larger than the CuMn/La-0.5 sample, indicating that the La in the lattice There is a certain limit to the amount of doped La, and the grain size does not change much with the increase of La doped amount. Obvious copper oxide crystal phase was found in the samples with La doping amount ≥ 3.0%, indicating that some Cu 2+ did not enter the spinel Cu 1.5 Mn 1.5 O 4 lattice, and it may have entered the lattice La blocks the entry of Cu 2+ . After the transformation reaction (Figure 2b), the Cu 1.5 Mn 1.5 O 4 metal solid solution with spinel structure was reduced and decomposed into Cu (JCPDS04-0836) and MnO (JCPDS07-0230), and the Cu grains all grew up after high-temperature sintering. The sample with less La doping has a smaller Cu grain growth range, especially the CuMn/La-0.5 sample. The Cu sintering of the sample with more La doping is more serious after transformation reaction, especially for CuMn/La-0.5. The -10.0 sample is the most obvious. The undoped CuMn sample has a smaller CuMn/La-10.0 sample than the CuMn/La-10.0 sample, but it is much larger than the CuMn/La-0.5 sample. It shows that in the transformation reaction process, the doping of a small amount of La can make the copper and manganese components dispersed evenly, and the manganese can effectively inhibit the sintering growth of copper, and the doping of more La (CuMn/La-10.0 sample has a simple substance at 29.4 ℃ The characteristic diffraction peak of La) interferes with the synergistic effect of manganese on copper, so that copper cannot be effectively isolated and aggregated. In addition, CuMn and CuMn/La-0.5 samples have MnCO 3 (JCPDS44-1472) characteristic peak at 31.5°.
表4La改性铜锰催化剂的结构参数Table 4 Structural parameters of La modified copper-manganese catalysts
图3为所制备催化剂的H2-TPR谱图。结合现有技术及实验分析可知，各样品的还原主峰温度均在250-350℃之间(β峰)，认为是铜锰尖晶石相Cu1.5Mn1.5O4的还原，相比于现有技术报道的Mn2O3的还原要容易，该现象可解释为铜对锰的还原有促进作用。Morales等认为，在铜锰混合相中存在与氧空位相关的结构缺陷和高分散的Mn2O3更容易还原。此外，在100-250℃之间还观察到有肩峰(α峰)，认为是氧化铜的还原，当La掺杂量小于3.0％时，氧化铜呈高度分散状态存在于样品中(XRD没有检测到CuO的存在)，该结果意味着所有样品中均有少量的Cu2+没有进入到尖晶石晶格中，Cu2+在铜锰尖晶石Cu1.5Mn1.5O4中比在CuO中更难还原，这部分CuO很容易被还原(La掺杂量小于3.0％时，更容易还原)，且在还原反应过程中，因为没有锰的协同作用，生成的铜晶粒很容易结块变大。由图3可知，La掺杂量为0.5％的CuMn/La-0.5样品，还原温度降低，其主峰由CuMn样品的285℃降低到273℃，而掺La量大于3.0％的CuMn/La-m(m＝5.0，10.0)样品，还原主峰温度均较CuMn样品高，可能由于较多La的掺入使得能够与氢气反应的同化学环境位点被包裹，氢气在体相中传质困难，因此还原温度均增大。Fig. 3 is the H 2 -TPR spectrogram of the prepared catalyst. Combined with the existing technology and experimental analysis, it can be seen that the main reduction peak temperature of each sample is between 250-350°C (β peak), which is considered to be the reduction of copper-manganese spinel phase Cu 1.5 Mn 1.5 O 4 . According to technical reports, the reduction of Mn 2 O 3 is easier, and this phenomenon can be explained that copper can promote the reduction of manganese. According to Morales et al., there are structural defects related to oxygen vacancies and highly dispersed Mn2O3 in the copper - manganese mixed phase, which is easier to reduce. In addition, a shoulder peak (α peak) was also observed between 100-250 ° C, which is considered to be the reduction of copper oxide. When the La doping amount is less than 3.0%, copper oxide exists in the sample in a highly dispersed state (XRD has no The existence of CuO was detected), this result means that a small amount of Cu 2+ did not enter into the spinel lattice in all samples, and Cu 2+ was more in copper-manganese spinel Cu 1.5 Mn 1.5 O 4 than in CuO This part of CuO is easily reduced (when the La doping amount is less than 3.0%, it is easier to reduce), and during the reduction reaction, because there is no synergistic effect of manganese, the generated copper grains are easy to agglomerate get bigger. It can be seen from Figure 3 that the reduction temperature of the CuMn/La-0.5 sample with a La doping amount of 0.5% decreases, and its main peak decreases from 285 °C of the CuMn sample to 273 °C, while the CuMn/La-m (m=5.0, 10.0) samples, the main reduction peak temperature is higher than that of CuMn samples, probably due to the incorporation of more La, the same chemical environment sites that can react with hydrogen are wrapped, and the mass transfer of hydrogen in the bulk phase is difficult, so The reduction temperature increased.
图4和表5分别为催化剂的s-TPR曲线及参数计算结果。由图4可知，各样品的二次还原峰峰顶温度都较一次还原峰提前70℃以上，说明H2二次还原的是表面氧化铜。CuMn/La-10.0样品的两次还原温度均是最高的(尤其表面铜的还原温度)，表明其难还原，CuMn样品虽然整体还原温度不高，但表面铜的还原温度较高，CuMn/La-0.5样品的两次还原温度均较低，说明该样品较易还原，与H2-TPR表征结果一致。从表5可看出，各样品具有不同的表面铜分散度(SAcu(m2g-1))，CuMn/La-0.5样品具有最高的表面铜分散度(35.96m2g-1)，其表面铜物种化学活性高，CuMn/La-10.0样品的表面铜分散度(17.58m2g-1)最小，原因是CuMn/La-0.5样品在还原反应过程中由于铜锰之间的协同效应好而得到的Cu晶粒长大的幅度较小，有利于Cu晶粒在催化剂表面的分散，而CuMn/La-10.0样品在反应过程中Cu晶粒烧结严重，不能在其表面进行有效的分散。Figure 4 and Table 5 are the s-TPR curve and parameter calculation results of the catalyst, respectively. It can be seen from Figure 4 that the peak temperature of the secondary reduction peak of each sample is more than 70°C earlier than that of the primary reduction peak, indicating that the surface copper oxide is the secondary reduction of H2. The two reduction temperatures of the CuMn/La-10.0 sample are the highest (especially the reduction temperature of the surface copper), indicating that it is difficult to reduce. Although the overall reduction temperature of the CuMn sample is not high, the reduction temperature of the surface copper is relatively high. CuMn/La The two reduction temperatures of the -0.5 sample are both lower, indicating that the sample is easier to reduce, which is consistent with the H2-TPR characterization results. It can be seen from Table 5 that each sample has different surface copper dispersion (SA cu (m 2 g -1 )), CuMn/La-0.5 sample has the highest surface copper dispersion (35.96m 2 g -1 ), The chemical activity of copper species on its surface is high, and the CuMn/La-10.0 sample has the smallest surface copper dispersion (17.58m 2 g -1 ), which is due to the synergistic effect between copper and manganese during the reduction reaction of CuMn/La-0.5 sample The obtained Cu grains grow smaller, which is beneficial to the dispersion of Cu grains on the surface of the catalyst, while the CuMn/La-10.0 sample has serious sintering of Cu grains during the reaction process, and cannot be effectively dispersed on the surface. .
表5La改性铜锰催化剂的s-TPR计算参数Table 5 La modified copper manganese catalyst s-TPR calculation parameters
图5为所制备催化剂样品的CO2-TPD谱图。由图5可见，掺La后的样品CO2脱附峰均为双峰，说明在样品表面上有两种不同类型的化学吸附位，不同类的吸附位对CO2吸附强度和吸附量不同，第一类吸附位的吸附强度随La掺杂量的增加而减弱，第二类吸附位的吸附强度随La掺杂量的增加而增强，即过多La的掺杂增加了CO2脱附难度。随La掺杂量的增加，CO2吸附量增加，当La掺杂量大于3.0％时，CO2吸附量增加的幅度减小。La掺杂样品对CO2吸脱附结果表明，La掺杂有助于增加该催化剂的表面碱性位，但当La掺杂量超过一定比例时，则其表面碱性位增加的幅度减小。不同类型的两种碱性位吸附强度和吸附量差别的大小，表明催化剂中铜锰组分分散的均匀程度，随La掺杂量的增加，两种碱性位的吸附强度和吸附量差别增大。CuMn/La-0.5样品由于两种碱性位的差别较小，对CO2的吸附量适中，因此表现出较好的催化活性，而CuMn/La-m(5.0，10.0)样品两种碱性位的吸附强度和吸附量差别较大，对CO2的吸附较强，吸附量较大，覆盖了部分活性位，因此表现出的活性较差，CuMn样品对CO2的吸附太少，表现出的活性较CuMn/La-0.5样品差。Fig. 5 is the CO 2 -TPD spectrogram of the prepared catalyst sample. It can be seen from Fig. 5 that the CO desorption peaks of the samples doped with La are double peaks, indicating that there are two different types of chemical adsorption sites on the sample surface, and different types of adsorption sites have different adsorption strength and adsorption capacity for CO . The adsorption strength of the first type of adsorption sites decreases with the increase of La doping amount, and the adsorption strength of the second type of adsorption sites increases with the increase of La doping amount, that is, too much La doping increases the difficulty of CO2 desorption . As the La doping amount increases, the CO2 adsorption amount increases, and when the La doping amount is greater than 3.0%, the magnitude of the CO2 adsorption amount increase decreases. The results of CO2 adsorption and desorption of La doped samples show that La doping helps to increase the surface basic sites of the catalyst, but when the La doping amount exceeds a certain proportion, the increase of the surface basic sites decreases . The difference between the adsorption strength and adsorption amount of two basic sites of different types indicates the uniformity of copper-manganese component dispersion in the catalyst. With the increase of La doping amount, the difference between the adsorption strength and adsorption amount of two basic sites increases Big. The CuMn/La-0.5 sample showed better catalytic activity due to the small difference between the two basic sites and the moderate adsorption capacity of CO2 , while the CuMn/La-m(5.0, 10.0) sample had two basic sites The adsorption strength and adsorption capacity of the sites are quite different, the adsorption of CO2 is stronger, the adsorption capacity is larger, covering part of the active sites, so the activity shown is poor, and the CuMn sample has too little adsorption of CO2 , showing The activity of CuMn/La-0.5 sample is worse than that of CuMn/La-0.5.
本发明研究了不同La掺杂量的Cu-Mn催化剂对水煤气变换反应催化性能的影响，利用XRD、TPR/s-TPR、CO2-TPD等对所制备的催化剂样品进行了表征。结果表明，La掺杂量为0.5％(mol)制备的催化剂与纯的Cu-Mn样品相比，由于铜锰组分分布均匀，金属间的协同效应良好，可有效的增加表面铜的分散性而使低温变换反应催化性能明显提高。La掺杂量≥3.0％的催化剂样品中除了有Cu1.5Mn1.5O4晶相外，还出现有较为明显的CuO晶相，且表面碱性位随La掺杂量的增加而增加的幅度减小，较高的La掺杂量由于La的聚集覆盖了部分活性位，锰不能有效的抑制铜晶粒的长大，使表面铜的分散度下降而导致水煤气变换反应活性明显降低。The present invention studies the influence of Cu-Mn catalysts with different La doping amounts on the catalytic performance of water gas shift reaction, and uses XRD, TPR/s-TPR, CO 2 -TPD to characterize the prepared catalyst samples. The results show that compared with the pure Cu-Mn sample, the catalyst prepared with La doping amount of 0.5% (mol) has a good synergistic effect between the metals due to the uniform distribution of copper and manganese components, which can effectively increase the dispersion of copper on the surface And the catalytic performance of the low-temperature shift reaction is obviously improved. In addition to the Cu 1.5 Mn 1.5 O 4 crystal phase, the catalyst samples with a La doping amount ≥ 3.0% also have a more obvious CuO crystal phase, and the increase of the basic sites on the surface decreases with the increase of the La doping amount. Small and high La doping amount is due to the accumulation of La covering part of the active sites, manganese can not effectively inhibit the growth of copper grains, and the dispersion of copper on the surface decreases, resulting in a significant decrease in the water gas shift reaction activity.
以上所述，仅为本发明较佳的具体实施方式，本发明的保护范围不限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，可显而易见地得到的技术方案的简单变化或等效替换均落入本发明的保护范围内。The above is only a preferred specific embodiment of the present invention, and the scope of protection of the present invention is not limited thereto. Any person familiar with the technical field within the technical scope disclosed in the present invention can obviously obtain the simplicity of the technical solution. Changes or equivalent replacements all fall within the protection scope of the present invention.
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