CN112121867A - 一种加氢催化剂的载体和应用 - Google Patents
一种加氢催化剂的载体和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 17
- 239000001301 oxygen Substances 0.000 abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 5
- -1 ethylene, propylene Chemical group 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 11
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
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- 229910002328 LaMnO3 Inorganic materials 0.000 description 3
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- 239000004215 Carbon black (E152) Substances 0.000 description 2
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- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
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- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002321 LaFeO3 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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Abstract
一种加氢催化剂的载体和应用。本发明属于载体技术领域，采用钙钛矿作为载体，担载活性组分应用于加氢制备乙烯、丙烯、丁烯。载氧体担载后的催化剂表现出良好的低碳烯烃选择性。说明钙钛矿作为载体应用到加氢反应中，具有潜在的工业价值。
Description
技术领域
本发明属于载体技术领域，具体涉及钙钛矿作为载体，担载活性组分应用于加氢制备乙烯、丙烯、丁烯。
背景技术
钙钛矿型金属氧化物因其较强的氧选择性和离子传导能力而被用作过滤膜、化学反应或高温空气分离的催化剂和吸附剂。钙钛矿型金属氧化物具有这种优势主要是由于其独特的氧传输机制，通过掺杂使钙钛矿型金属氧化物结构中产生一定的氧缺陷（即氧空位），氧离子在晶格中从一个氧空位跳到另一个氧空位上从而实现氧离子的传输。掺杂是指以一种金属离子部分占据另一种金属离子的位置，如果两种金属离子的价态不同，则会形成电荷缺陷，进而形成氧空位。氧空位的存在使钙钛矿型金属氧化物可以捕获并活化气相氧，为燃料的氧化反应提供活性的氧。钙钛矿前躯体中B位离子的还原（或部分还原）可使金属态的B更好地高分散于A的氧化物（或钙钛矿复合氧化物）上。通过控制还原温度所制备的这种结构有利于催化剂的稳定性和积碳气化。
钙钛矿基催化剂直接应用于加氢反应时，烯烃选择性较差。且钙钛矿应用到加氢制备烯烃的反应鲜有报道。
发明内容
本发明从钙钛矿作为载体的角度出发，研究了ABO3型钙钛矿作为载体，经过实验多次验证，催化剂活性组分在钙钛矿型载氧体提供的晶格氧、氧缺位、孤对电子等作用下，催化活性显著提高。
技术方案中，ABO3型钙钛矿作为催化剂载体，会发挥活性组分更好的性能。另一方面载体也发挥了助催化作用，使得活性组分更加具备适宜的CO或CO2吸附解离能力，抑制烯烃的再吸附，降低烯烃的二次反应，提高烯烃选择性。为突破A-S-F产物分布，高选择性获得低碳烯烃和抑制副产物甲烷，C5 ＋等副产物提供有力基石。本发明报道的载体，也能一定程度上抑制初级烯烃二次加氢反应，调控出附加值高的产物分布。在考察LaFeO3、LaMnO3、LaFeMnO3、SrMnO3、SrLaFeO3、LaFeCoO3、LaCeFeO3、LaCeFeMnO3时，发现La或Sr或Ce元素相邻铁或锰原子附近位点存在缺陷，富集晶格氧，巩固晶体堆叠取向，影响钙钛矿暴露特定晶面，显著增强材料吸附位点和催化活性。
技术方案中，Mg，Na、Zn、K的元素浸渍修饰，可以进一步调控材料的吸附性能及加氢性能，制备出高性能的钙钛矿功能材料。
为了实现本发明的上述目的，本发明采用的技术方案如下：本发明催化剂载体是ABO3型钙钛矿，A元素包括镧、锶、镁、铜、钡、铈、钙、镓、钆的至少一种；B元素包括铁、锰、钴、镍的至少一种；催化剂活性组分是Fe2O3、分子筛、市售制低碳烯烃催化剂的至少一种；ABO3型钙钛矿载体担载催化剂组分，应用于加氢制备低碳烯烃。催化剂载体的制备方法是溶胶凝胶法制备，按量称取硝酸盐溶液与柠檬酸在80℃水浴后形成的凝胶；凝胶经105-120℃干燥，在600-900℃焙烧获得。CO加氢时，反应条件为H2/CO=1~4，250~400℃、1~8MPa，1000~4000 h–1。CO2加氢时，反应条件为H2/CO2 =1~4，250~450℃、1~5MPa，1000~4000 h–1。
此外通过控制反应温度，如150-250℃，以钙钛矿催化剂作为载体，还可获得低碳醇。
具体实施方式
下面通过实施案例对本发明作进一步详细说明。本实施案例在以本发明技术为前提下进行实施，现给出详细的实施方式和具体的操作过程来说明本发明具有创造性，但本发明的保护范围不限于以下的实施案例。
根据本申请包含的信息，对于本领域技术人员来说可以轻而易举地对本发明的精确描述进行各种改变，而不会偏离所附权利要求的精神和范围。应该理解，本发明的范围不局限于所限定的过程、性质或组分，因为这些实施方案以及其他的描述仅仅是为了示意性说明本发明的特定方面。实际上，本领域或相关领域的技术人员明显能够对本发明实施方式作出的各种改变都涵盖在所附权利要求的范围内。
下述各实施例中，若无特殊说明，所有原料组分无特殊说明，均为本领域技术人员熟知的市售产品。
实施例1
称取6.5g硝酸镧、10.1g硝酸铁、8.9g硝酸锰，用蒸馏水溶解，再加入19.21g柠檬酸，蒸馏水溶解后，于水浴条件下机械搅拌，水浴温度80℃，搅拌速度500r/min。搅拌至凝胶状态后，于100℃干燥 12h。将粉末置于马弗炉，按10℃/min 的速率升温，在800℃保温4h，冷却后研磨得LaFeMnO3钙钛矿。称取Fe(NO3)3•9H2O 200 g，量取25%NH3•H2O 200 mL，分别配制成400mL溶液，常温下并流沉淀，搅拌4h，静置12h。沉淀经过滤、洗涤，于80℃恒温箱中干燥，研磨后450℃焙烧90min，即得Fe2O3。按质量分数计，称取30% Fe2O3和70%LaFeMnO3，机械混合。记为样品1。
实施例2
称取6.5g硝酸镧、8.9g硝酸锰，用蒸馏水溶解，再加入19.21g柠檬酸，蒸馏水溶解后，于水浴条件下机械搅拌，水浴温度80℃，搅拌速度500r/min。搅拌至凝胶状态后，于100℃干燥12h。将粉末置于马弗炉，按10℃/min 的速率升温，在800℃保温4h，冷却后研磨得LaMnO3钙钛矿。Fe2O3制备同实施例1。按质量分数计，称取30% Fe2O3和70%LaMnO3，机械混合。记为样品2。
实施例3
称取5.29g硝酸锶、7.27g硝酸钴、10.1g硝酸铁，用蒸馏水溶解，再加入19.21g柠檬酸，蒸馏水溶解后，于水浴条件下机械搅拌，水浴温度80℃，搅拌速度500r/min。搅拌至凝胶状态后，于100℃干燥 12h。将粉末置于马弗炉，按10℃/min 的速率升温，在900℃保温4h，冷却后研磨得SrFe0.5Co0.3O3钙钛矿。选择市售的制备低碳烯烃的铁基催化剂，简称市售。按质量分数计，称取30% 市售催化剂和70% SrFe0.5Co0.3O3，机械混合。记为样品3。
实施例4
称取5.29g硝酸锶、8.9g硝酸锰，用蒸馏水溶解，再加入19.21g柠檬酸，蒸馏水溶解后，于水浴条件下机械搅拌，水浴温度80℃，搅拌速度500r/min。搅拌至凝胶状态后，于100℃干燥 12h。将粉末置于马弗炉，按10℃/min 的速率升温，在850℃保温4h，冷却后研磨得SrMnO3钙钛矿。选择市售的制备低碳烯烃的分子筛催化剂，简称市售。按质量分数计，称取30% 市售催化剂和70% SrMnO3，机械混合。记为样品4。
实施例5
称取5.29g硝酸锶、5.2g硝酸铁、8.9g硝酸锰，用蒸馏水溶解，再加入25.21g柠檬酸，蒸馏水溶解后，于水浴条件下机械搅拌，水浴温度80℃，搅拌速度500r/min。搅拌至凝胶状态后，于100℃干燥 12h。将粉末置于马弗炉，按10℃/min 的速率升温，在400℃恒温1h，在850℃保温4h，冷却后研磨得SrFeMnO3钙钛矿。选择市售的制备低碳烯烃的分子筛催化剂，简称市售。按质量分数计，称取20% 市售催化剂和80% SrFeMnO3，机械混合。记为样品5。
催化剂性能测试：
实施例1～5制备的催化剂均制成20～40目的催化剂颗粒。在微型固定床反应器中进行性能评价，具体操作步骤如下：称取1.0 mL样品催化剂装入反应管中部恒温区，原料气H2/CO2=3，温度为320°C，压力为2.0MPa、空速（GHSV）为1000 h-1，达到稳定状态后，采样分析，间隔3 h采样一次。利用气相色谱对原料气和产物经行定量和定性分析。
表1为本发明上述实施例制备的样品的加氢催化工艺参数及性能测试结果对比表。由表1可以看出所制样品表现出较好的CO2加氢活性，在产物分布中，烃类产物变化明显。低碳烯烃选择性保持在50%以上，烯烷比（O/P）可达6.33。
表1实施例1～5制备的样品加氢催化反应结果对比表
Claims (4)
1.一种加氢催化剂的载体和应用，其特征在于：所述催化剂载体是ABO3型钙钛矿，A元素包括镧、锶、镁、铜、钡、铈、钙、镓、钆的至少一种；B元素包括铁、锰、钴、镍的至少一种；催化剂活性组分是Fe2O3、分子筛、市售制低碳烯烃催化剂的至少一种；
ABO3型钙钛矿载体担载催化剂组分，应用于加氢制备低碳烯烃。
2.根据权利要求1所述的一种加氢催化剂的载体和应用，其特征在于催化剂载体的制备方法是溶胶凝胶法制备，按量称取硝酸盐溶液与柠檬酸在80℃水浴后形成的凝胶；凝胶经105-120℃干燥，在600-900℃焙烧获得。
3.根据权利要求1所述的一种加氢催化剂的载体和应用，其特征在于CO加氢时，反应条件为H2/CO=1~4，250~400℃、1~8MPa，1000~4000 h–1。
4.根据权利要求1所述的一种加氢催化剂的载体和应用，其特征在于CO2加氢时，反应条件为H2/CO2 =1~4，250~450℃、1~5MPa，1000~4000 h–1。
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| GB2608594A (en) * | 2021-06-30 | 2023-01-11 | Univ Cape Town | Catalyst support structures and methods of manufacture and use |
| CN115779895A (zh) * | 2022-11-08 | 2023-03-14 | 清华大学 | 一种钙钛矿型催化剂及其制备方法和应用 |
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| GB2608594A (en) * | 2021-06-30 | 2023-01-11 | Univ Cape Town | Catalyst support structures and methods of manufacture and use |
| CN115779895A (zh) * | 2022-11-08 | 2023-03-14 | 清华大学 | 一种钙钛矿型催化剂及其制备方法和应用 |
| CN115779895B (zh) * | 2022-11-08 | 2024-04-30 | 清华大学 | 一种钙钛矿型催化剂及其制备方法和应用 |
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