CN113828321A - 一种新型复合载氧体及其制备方法 - Google Patents
一种新型复合载氧体及其制备方法 Download PDFInfo
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- CN113828321A CN113828321A CN202111428302.5A CN202111428302A CN113828321A CN 113828321 A CN113828321 A CN 113828321A CN 202111428302 A CN202111428302 A CN 202111428302A CN 113828321 A CN113828321 A CN 113828321A
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- oxygen carrier
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- ethylene
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000001301 oxygen Substances 0.000 title claims abstract description 99
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims description 37
- 238000001354 calcination Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 24
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- 238000012216 screening Methods 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 12
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 12
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 36
- 239000005977 Ethylene Substances 0.000 abstract description 36
- 238000000034 method Methods 0.000 abstract description 23
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 20
- 239000003054 catalyst Substances 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000004575 stone Substances 0.000 abstract description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 20
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000001294 propane Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910002846 Pt–Sn Inorganic materials 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical compound [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- IUWCPXJTIPQGTE-UHFFFAOYSA-N chromium cobalt Chemical compound [Cr].[Co].[Co].[Co] IUWCPXJTIPQGTE-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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Abstract
本发明属于载氧体制备技术领域,涉及一种新型复合载氧体及其制备方法,制备的载氧体中含有CrO3、Co2O3和SrO,三种氧化物可以调节Al2O3载体表面的酸性位,同时三种金属元素可以吸引晶格氧到载氧体的表面,与在活性位上的乙烷脱下来的氢反应生成水,促进了反应的正向进行,从而提高了乙烯的选择性;四是在制备载氧体的过程中,载氧体表面形成了CrCoO3结晶石结构,能大大提高乙烯的选择性;用于乙烷化学链脱氢制乙烯时,乙烷的单程转化率在70%以上,乙烯的选择性可以达到98%以上。
Description
技术领域
本发明属于载氧体制备技术领域,涉及一种新型复合载氧体及其制备方法。
背景技术
目前,国内生产的低碳烷烃大多直接用作燃料,其利用价值还有待提高,特别是乙烯还出现了供不应求的现状。因此,研究低碳烷烃脱氢制烯烃,可以实现对石油裂解气的有效利用。2022年国内乙烯需求量预计在3014万吨以上,而在2020年国内乙烯的年产量只有2245万吨,产量远低于需求量,为了满足对乙烯的巨大需求,国内外广泛开展了乙烷生产新技术的研究开发工作。现在已经工业化的乙烷脱氢工艺主要是UOP公司的Oleflex工艺和ABB Lummus公司的Catofin工艺。由于其安全性高,易操作,所以Oleflex工艺应用的最为广泛。我国的烟台万华化学集团(600 kt·a-1)、上海东华能源(700 kt·a-1)和淄博齐翔腾达化工股份有限公司(780 kt·a-1)等近20家企业都引进了该工艺。
在现有技术中,低碳烷烃脱氢反应所使用的催化剂循环利用率较低且对环境污染较大,更重要的是导致催化剂的反应活性下降,进而影响反应的进程。因此开发高活性、高稳定性、循环性能好的催化剂成为该技术的关键。目前低碳烷烃脱氢制低碳烯烃常用的催化剂为Pt-Sn催化剂,如专利CN100464849C所使用的催化剂,是将Pt-Sn负载到氧化铝载体上,结果显示乙烷的转化率仅为18%,选择性为92%;专利CN101066532将贵金属Pt与Sn先后负载到ZSM-5分子筛上,当反应进行完100多小时后,乙烷的转化率低于40%,乙烯的选择性为99.2%,但是该专利并没有提供催化剂在循环再生利用方面的准确数据;专利CN104437485B通过浸渍将贵金属铂负载到氧化铝载体上,之后通过引入氯溴等对该催化剂进行修饰,反应进行144小时后,乙烷的转化率为34.2%,乙烯的选择性为91.7%,催化剂经过循环再生后,催化剂的反应活性下降了40%;专利CN105749986B通过在氧化铝载体中加入氧化钡,然后再将氧化铬负载到载体上,当反应进行12小时后,异丁烷的转化率为56%,异丁烯的选择性为94%。同样,该专利也没有提供催化剂循环再生利用方面的准确数据。上述专利均采用了浸渍法将Pt-Sn催化剂负载到载体上,催化剂易高温积碳失活,在反应过程中催化剂循环利用率低且循环过后催化剂的反应活性也较低。
载氧体表面存在两种氧物种,一种是晶格氧(主要产物是乙烯),一种是吸附态的氧(主要产物是CO与CO2)。晶格氧在一定条件下会转变为吸附态的氧,从而大大降低乙烯的产率,为此如何调节载氧体表面晶格氧的释放规律是当前研究的焦点。在化学链脱氢过程中,对载氧体的释氧特性有较高的要求,目前主要是单金属氧化物研究的较多,例如CN109482174B公开了一种用于丙烷化学链脱氢制丙烯的载氧体制备方法,该方法制备得到的是单金属载氧体,但是由于单金属在反应的过程中研究起来较为容易,单金属氧化物的释氧过程不易控制,在温度较高的时候会发生晶格氧释放较快演变成吸附态的氧,将丙烷深度氧化成CO和CO2;也有部分多金属复合载体用于用于乙烷化学链脱氢制乙烯,例如CN110898844A公开了一种多金属复合载氧体的制备方法,此方法载氧体表面“壳”氧化钡的吸电子能力较低,而且氧化钡在表面形成的孔道结构较为致密,将晶格氧吸引到载氧体表面的能力较弱。因此,寻求一种新型的用于乙烷化学链氧化脱氢制乙烯的载氧体及其制备方法,通过金属与金属之间的强烈的相互作用产生新结构,再利用外层氧化锶的强吸电子作用,进一步使晶格氧不易向吸附态氧方向转化,有效的控制晶格氧的释放,而且当金属之间的比例一定时,晶格氧的迁移与转化规律就容易控制,将乙烷催化氧化脱氢生成乙烯和水,极大地促使向正反应方向进行。
发明内容
本发明目的在于克服现有技术存在的缺点,针对多金属之间复杂的相互作用机理,旨在尽量减少多金属载氧体中晶格氧向吸附态氧方向转化的缺陷,设计提供一种新型复合载氧体及其制备方法,有效控制晶格氧释放,从而抑制其方向转化。
为了实现上述目的,本发明所述新型复合载氧体为核壳结构的Cr-Co基载氧体,具体包括如下质量分数的化学成分:CrO3为40~50%,Co2O3为30~40%,SrO为10~30%,其中活性组分为CrO3和Co2O3,是“核”,在载氧体外层包着SrO,是“壳”。
本发明制备新型复合载氧体的具体过程为:
(1)氧化铝载体的制备:筛选600g粒径为100-500μm 的氧化铝颗粒,加入3-6g田菁粉,混合均匀,滴加100ml 质量分数为2%的硝酸水溶液,充分混合后置于100℃的烘箱中干燥48h后,在马弗炉中于500-600℃下煅烧,制得氧化铝载体颗粒;
(2)先将粘结剂和粘土按照质量比为(1:9)-(5:5)的比例混合溶于去离子水中配置成质量分数为50%-60%的浆液,再将步骤(1)制得的氧化铝载体充分的分散在配制的浆液中,然后将浆液进行喷雾干燥,筛分出粒径在80-600μm的颗粒;
(3)取质量分数为99%的氧化铬(CrO3)120-200g和99.5%六水硝酸钴(Co(NO3)2·6H2O)100-150g与(2)制备好的Al2O3颗粒100g充分混合后置于80℃油浴锅中匀速搅拌,至溶液中水分蒸干至溶胶凝胶物质a,将溶胶凝胶物质a在烘干箱中干燥48h,得到的样品b,再将样品b在马弗炉中煅烧3-5h,煅烧温度为 800-900℃,煅烧后进行筛选,得到粒径为100-500μm、含有CrO3和Co2O3的载氧体c;
(4)将步骤(3)制备好的载氧体c与硝酸锶按照1:1-6:1的质量比混合后加去离子水,得到溶液d,然后将所述溶液d置于80℃油浴锅中匀速搅拌,至溶液d中水分蒸干至溶胶凝胶物质e;
(5)将溶胶凝胶状物质e在烘干箱中干燥48h,得到的样品,将样品在马弗炉中煅烧3-5h,煅烧温度为800-900℃,煅烧后进行筛选,得到粒径为100-200μm的新型复合载氧体。
本发明制备的氧化铝载体颗粒的堆比重为0.3-1g/mL,比表面积为100-200m2/g,孔容为0.5-1mL/g,平均孔径为20-80nm,压碎强度为60-120N•cm-1。
本发明所述Co(NO3)2可用NH4VO3替代。
本发明所述硝酸锶可用La(NO3)3替代。
本发明将备的新型复合载氧体能用于乙烷化学链氧化脱氢制乙烯以及丙烷化学链氧化脱氢制丙烯,其中乙烷化学链氧化脱氢制乙烯的具体过程为:
(1)在反应开始前,先向流化床反应器内通入氮气,排尽反应器内的空气;
(2)打开预热装置与流化床反应器的加热装置,关闭氮气阀门,预热装置的温度设在400-500℃,流化床反应器的温度设在500-750℃。
(3)打开乙烷阀门,乙烷经过预热装置达到反应所需要的温度后进入流化床反应器;
(4)乙烷(流化介质)与新型复合载氧体接触,生成乙烯、甲烷、乙烯、一氧化碳、二氧化碳及未反应的乙烷等气相混合物流;
(5)所述气相混合物流经裂管式冷凝装置冷却至室温后,再经过气液分离装置进行气液分离;
(6)当反应结束后,再向流化床反应器内通入氮气,排尽反应器内的气体后,用气袋收集反应后的气体,之后再用气相色谱来分析气体的成分与含量;
(7)关闭氮气阀门,打开空气阀门,向流化床反应器内通入空气,新型复合载氧体被氧化后能够实现循环再生利用,以便进行第二次化学链脱氢反应;
丙烷化学链氧化脱氢制丙烯过程与上述过程类似。
本发明与现有技术相比,具有以下优点:一是载氧体制备方法工艺简单,且载氧体在制备及循环再生过程中,不会造成环境污染;二是在乙烷化学链脱氢制乙烯的过程中,由于乙烷和乙烯的还原性较强,选择弱氧化性的载氧体进行脱氢反应,制备的铬-钴基复合载氧体可以减少乙烷和乙烯的深度氧化,提高了乙烷的转化率和乙烯的选择性;三是制备的载氧体中含有CrO3、Co2O3和SrO,三种氧化物可以调节Al2O3载体表面的酸性位,同时三种金属元素可以吸引晶格氧到载氧体的表面,与在活性位上的乙烷脱下来的氢反应生成水,促进了反应的正向进行,从而提高了乙烯的选择性;四是在制备载氧体的过程中,载氧体表面形成了CrCoO3结晶石结构,能大大提高乙烯的选择性;用于乙烷化学链脱氢制乙烯时,乙烷的单程转化率在70%以上,乙烯的选择性可以达到98%以上;五是通过实验证明,与单纯的Mn基载氧体相比,Cr-Co复合载氧体增加了载氧体的载氧量,从而延长了载氧体与乙烷的反应时间。
附图说明
图1为本发明所制备的新型复合载氧体(a)和涉及的氧化锶(b)XRD射线衍射的数据图。
图2为本发明所述新型复合载氧体的核壳结构图。
具体实施方式
下面通过实施例并结合附图对本发明做进一说明。
实施例1:
本实施例所述新型复合载氧体为核壳结构的Cr-Co基载氧体,具体包括如下质量分数的化学成分:CrO3为40~50%,Co2O3为30~40%,SrO为10~30%,其中活性组分为CrO3和Co2O3,是“核”,在载氧体外层包着SrO,是“壳”。
本实施例制备新型复合载氧体的具体过程为:
(1)氧化铝载体的制备:筛选600g粒径为100-500μm 的氧化铝颗粒,加入3-6g田菁粉,混合均匀,滴加100ml 质量分数为2%的硝酸水溶液,充分混合后置于100℃的烘箱中干燥48h后,在马弗炉中于500-600℃下煅烧,制得氧化铝载体颗粒;
(2)先将粘结剂和粘土按照质量比为(1:9)-(5:5)的比例混合溶于去离子水中配置成质量分数为50%-60%的浆液,再将步骤(1)制得的氧化铝载体充分的分散在配制的浆液中,然后将浆液进行喷雾干燥,筛分出粒径在80-600μm的颗粒;
(3)取质量分数为99%的氧化铬(CrO3)120-200g和99.5%六水硝酸钴(Co(NO3)2·6H2O)100-150g与(2)制备好的Al2O3颗粒100g充分混合后置于80℃油浴锅中匀速搅拌,至溶液中水分蒸干至溶胶凝胶物质a,将溶胶凝胶物质a在烘干箱中干燥48h,得到的样品b,再将样品b在马弗炉中煅烧3-5h,煅烧温度为 800-900℃,煅烧后进行筛选,得到粒径为100-500μm、含有CrO3和Co2O3的载氧体c;
(4)将步骤(3)制备好的载氧体c与硝酸锶按照1:1-6:1的质量比混合后加去离子水,得到溶液d,然后将所述溶液d置于80℃油浴锅中匀速搅拌,至溶液d中水分蒸干至溶胶凝胶物质e;
(5)将溶胶凝胶状物质e在烘干箱中干燥48h,得到的样品,将样品在马弗炉中煅烧3-5h,煅烧温度为800-900℃,煅烧后进行筛选,得到粒径为100-200μm的新型复合载氧体。
本实施例制备的氧化铝载体颗粒的堆比重为0.3-1g/mL,比表面积为100-200m2/g,孔容为0.5-1mL/g,平均孔径为20-80nm,压碎强度为60-120N•cm-1。
本实施例所述Co(NO3)2可用NH4VO3替代。
本实施例所述硝酸锶可用La(NO3)3替代。
实施例2:
本实施例制备不同氧化锶含量的新型复合载氧体的具体过程为:
(1)氧化铝载体的制备:筛选500g粒径为80-800μm 的氧化铝颗粒,加入3-6g田菁粉,混合均匀,滴加100ml 2%的硝酸水溶液,充分混合后置于100℃的烘箱中干燥48h后,在马弗炉中于500-600℃下煅烧,制得氧化铝载体颗粒;
(2)先将粘结剂和粘土按照质量比为3:7的比例混合溶于去离子水中配置成质量分数为50%的浆液,再将步骤(1)制得的氧化铝载体充分的分散在配制的浆液中,然后将浆液进行喷雾干燥,筛分出粒径在80-600μm的颗粒;
(3)取质量分数为99%的氧化铬(CrO3) 200g和99.9%六水硝酸钴(Co(NO3)2·6H2O)150g与(2)制备好的Al2O3颗粒100g充分混合后置于80℃油浴锅中匀速搅拌,至溶液中水分蒸干至溶胶凝胶物质a,将溶胶凝胶物质a在烘干箱中干燥48h,得到的样品b,再将样品b在马弗炉中煅烧3-5h,煅烧温度为 800-900℃,煅烧后进行筛选,得到粒径为100-200μm的载氧体c;
(4)将步骤(3)制备好的载氧体c与硝酸锶质量比混合后加去离子水,得到溶液d,然后将所述溶液d置于80℃油浴锅中匀速搅拌,至溶液d中水分蒸干至溶胶凝胶物质e;
(5)将溶胶凝胶状物质e在烘干箱中干燥48h,得到的样品,将样品在马弗炉中煅烧7-10h,煅烧温度为 500-600℃,煅烧后进行筛选得到氧化锶含量分别为10wt%、30wt%、0wt%的新型复合载氧体,分别记为A、B和C;分别将A、B和C用于乙烷化学链脱氢制乙烯中,乙烷转化率及乙烯选择性分别如表1所示,将A、B和C经过60次循环后的载氧体颗粒分别记为E、F和G用于乙烷化学链脱氢制乙烯中,乙烷转化率及乙烯选择性分别如表2示,
表1:
载氧体编号 | 乙烷转化率 % | 乙烯选择性 % |
A | 72 | 97.2 |
B | 79.1 | 98.1 |
C | 40.2 | 60.4 |
表2:
载氧体编号(载氧体循环60次后) | 乙烷转化率 % | 乙烯选择性 % |
E | 69.5 | 95.3 |
F | 75.1 | 96.6 |
G | 35.2 | 58.2 |
从表1中可以看出,锶含量(载氧体A、B)对乙烷转化率、乙烯选择性的影响较大,随着锶含量的增加,乙烷的转化率与乙烯的选择性随之增加;与未加入氧化锂所制得的载氧体C相比,增加氧化锶含量的载氧体具有更加良好的脱氢性能,结果表明在乙烷化学链脱氢制乙烯载氧体中加入助活性成分,能够提高载氧体的脱氢能力。
本实施例的结果显示,乙烷转化率和乙烯的选择性均明显高于对比例和现有技术中的催化剂,该方法采用新型载氧体对低碳烷烃脱氢制取低碳烯烃,从表2可以看出,该方法制备的载氧体经过60次循环再生后,载氧体相比于最初反应时,其反应活性只下降了2-4%,说明本发明提供的新型复合载氧体利用化学链技术来对低碳烷烃进行脱氢制低碳烯烃的方案能够满足低碳烃脱氢的工艺要求。
实施例3:
本实施例制备的新型复合载氧体还可用于丙烷脱氢制备丙烯,采用实施例1所述方法制备CrO3为45%、Co2O3为30%、SrO为10%的新型复合载氧体D,将其用于丙烷脱氢制备丙烯过程,丙烷转化率和选择性如表1和表2所示,其中活性组分为CrO3和Co2O3,是“核”,在载氧体外层包着SrO,是“壳”。
表1:
载氧体编号 | 丙烷转化率 % | 丙烯选择性 % |
D | 65.3 | 97.2 |
表2:
载氧体编号(载氧体循环60次后) | 丙烷转化率 % | 丙烯选择性 % |
H | 60.1 | 95.8 |
Claims (2)
1.一种新型复合载氧体,其特征在于,该载氧体为核壳结构的Cr-Co基载氧体,具体包括如下质量分数的化学成分:CrO3为40~50%,Co2O3为30~40%,SrO为10~30%,其中活性组分为CrO3和Co2O3,是“核”,在载氧体外层包着SrO,是“壳”。
2.一种如权利要求1所述新型复合载氧体的制备方法,其特征在于,具体过程为:
(1)氧化铝载体的制备:筛选600g粒径为100-500μm 的氧化铝颗粒,加入3-6g田菁粉,混合均匀,滴加100ml 质量分数为2%的硝酸水溶液,充分混合后置于100℃的烘箱中干燥48h后,在马弗炉中于500-600℃下煅烧,制得氧化铝载体颗粒;
(2)先将粘结剂和粘土按照质量比为(1:9)-(5:5)的比例混合溶于去离子水中配置成质量分数为50%-60%的浆液,再将步骤(1)制得的氧化铝载体充分的分散在配制的浆液中,然后将浆液进行喷雾干燥,筛分出粒径在80-600μm的颗粒;
(3)取质量分数为99%的氧化铬120-200g和99.5%六水硝酸钴100-150g与(2)制备好的Al2O3颗粒100g充分混合后置于80℃油浴锅中匀速搅拌,至溶液中水分蒸干至溶胶凝胶物质a,将溶胶凝胶物质a在烘干箱中干燥48h,得到的样品b,再将样品b在马弗炉中煅烧3-5h,煅烧温度为 800-900℃,煅烧后进行筛选,得到粒径为100-500 μm、含有CrO3和Co2O3的载氧体c;
(4)将步骤(3)制备好的载氧体c与硝酸锶按照1:1-6:1的质量比混合后加去离子水,得到溶液d,然后将所述溶液d置于80℃油浴锅中匀速搅拌,至溶液d中水分蒸干至溶胶凝胶物质e;
(5)将溶胶凝胶状物质e在烘干箱中干燥48h,得到的样品,将样品在马弗炉中煅烧3-5h,煅烧温度为800-900℃,煅烧后进行筛选,得到粒径为100-200μm的新型复合载氧体。
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