CN112121807A - 一种co2加氢催化剂和应用 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- -1 ethylene, propylene Chemical group 0.000 claims abstract description 7
- 229910002321 LaFeO3 Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
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- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
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- 238000005457 optimization Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
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- 238000013329 compounding Methods 0.000 abstract 1
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 description 18
- 238000005303 weighing Methods 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 7
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- 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 6
- 239000011777 magnesium Substances 0.000 description 6
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
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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 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
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- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 2
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
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- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
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- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
一种CO2加氢催化剂和应用。本发明涉及一种钛矿催化剂，应用于CO或CO2加氢制备乙烯、丙烯、丁烯。催化剂组分包括[LaGd]xFeyO3、LaFeO3、金属氧化物，这种复合后的催化剂较大程度上促进CO的吸附和解离，加氢反应中表现出良好的低碳烯烃选择性。具有潜在的经济价值。
Description
技术领域
本发明涉及CO2加氢催化剂制备技术领域，涉及钙钛矿催化剂，及催化剂制备乙烯、丙烯、丁烯或低碳醇的应用。
背景技术
以二氧化碳为原料加氢制备低碳烯烃，不但能够缓解二氧化碳排放带来的环保压力，更能实现二氧化碳资源的有效利用。从热力学方面考虑，低温、高压有利于低碳烯烃的生成，适宜的反应条件应该是温度573～673K、压力2.0～3.0MPa、H2/CO2=3，在该条件下二氧化碳的平衡转化率为72.8%～74.5%。二氧化碳直接加氢制低碳烯烃可分为两个步骤：逆水气转换反应和连续的费托合成。目前在二氧化碳制备低碳烯烃过程中，降低烷烃特别是甲烷的生成以及提高某一烯烃的选择性是研究的重点。
关于反应机理的研究非常多，但结论并不完全一致，这是因为催化剂不同，对二氧化碳的吸附形式就可能不同，产生的中间体就不同，反应机理也就不同。
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。因此，钙钛矿催化剂可以用于CO2加氢反应，并且是一种很有前景的催化剂。
发明内容
本发明提供一种新型催化剂，从钙钛矿出发，通过调配配方，考察产物分布情况，确立了催化剂组成。
本发明催化剂具有适宜的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。本发明催化剂能有效的抑制初级烯烃二次加氢反应，调控出附加值高的产物分布，尤其α烯烃的获得占到C2-C4低碳烯烃中90%以上。Gd、La元素相邻铁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：本发明催化剂组分包括20-70%[LaGd]xFeyO3、2-25%LaFeO3、余量为金属氧化物；x+y≤3；金属氧化物中主要为铁氧化物，包括Fe2O3、Fe3O4。LaFeO3暴露的特定晶面主要为{111}、{120}、{101}晶面。本发明催化剂应用于CO2加氢反应前，须在400-700℃还原活化。CO2加氢反应条件为H2/CO2 =1~4，150~400℃、2~8MPa，1000~4000 h–1。通过改变反应条件，应用于生成低碳醇、低碳烯烃。催化剂的优化通过Mg，Na、Mn、Zn、K的元素浸渍修饰。技术方案中，镧元素可以由锶元素代替。
催化剂中的金属氧化物中因制备条件等因素，自身携带有镧氧化物、钆氧化物、铁氧化物。其中铁氧化物可以通过后引入补充进去。
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。
为了更好地理解本发明而不是限制本发明的范围，在本申请中所用的表示用量、百分比的所有数字、以及其他数值，在所有情况下都应理解为以词语“大约”所修饰。因此，除非特别说明，否则在说明书和所附权利要求书中所列出的数字参数都是近似值，其可能会根据试图获得的理想性质的不同而加以改变。各个数字参数至少应被看作是根据所报告的有效数字和通过常规的四舍五入方法而获得的。
需要说明的是，催化剂组成成分的制备是仅列举了一种比例，其中不同镧、铁、钆的比例也能得到本发明实现的目的。其中配比最佳范围在La：Fe=0.1-5；Gd：Fe=0.2-2，柠檬酸按Fe摩尔量的0.8-3倍称量，焙烧温度范围在600-950℃。
具体实施方式
成分制备方法为：（1）称取10.83g硝酸镧、9.1g硝酸钆、10.1g硝酸铁，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800℃保温4h，冷却后研磨得催化剂样品[LaGd]0.5Fe0.5O3。记为组分A。
（2）称取10.83g硝酸镧、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，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，400℃保温1h后，在升至800℃保温4h，冷却后研磨得LaFeO3。记为组分B。
（3）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。记为组分C。
实施例1
以总量3g催化剂为基数，称取65%组分A、30%组分B、5%组分C，机械混合。
实施例2
以总量3g催化剂为基数，称取50%组分A、45%组分B、5%组分C，机械混合。
实施例3
以总量3g催化剂为基数，称取70%组分A、25%组分B、5%组分C，机械混合。
实施例4
以总量3g催化剂为基数，称取25%组分A、70%组分B、5%组分C，机械混合。
实施例5
以总量3g催化剂为基数，称取70%组分A、20%组分B、10%组分C，机械混合后按质量分数称取2%碳酸钾，即浸渍2%K。
实施例6
以总量3g催化剂为基数，称取70%组分A、25%组分B、5%组分C，机械混合后按质量分数称取10%碳酸钾，即浸渍10%K。
实施例7
以总量3g催化剂为基数，称取70%组分A、25%组分B、5%组分C，机械混合后按质量分数称取10%碳酸镁，即浸渍10%Mg。
实施例8
以总量3g催化剂为基数，称取70%组分A、25%组分B、5%组分C，机械混合后按质量分数称取10%碳酸锌，即浸渍10%Zn。
实施例9
以总量3g催化剂为基数，称取70%组分A、25%组分B、5%组分C，机械混合后按质量分数称取10%碳酸锌，10%碳酸镁，即浸渍10%Mg和Zn。
实施例10
以总量3g催化剂为基数，称取70%组分A、20%组分B、10%组分C，机械混合后按质量分数称取10%碳酸镁，10%碳酸钾，即浸渍10%Mg和K。
催化剂性能测试与表征：
为了使催化剂更好地反应，不堵塞反应管，将本发明上述实施例1～10制备的催化剂均制成20～40目的催化剂颗粒。
本发明采用微型固定床反应器对催化剂进行评价，工艺条件为20～40目催化剂0.5～5 mL，反应温度260～400°C，反应压力0.5～3MPa，原料气H2/CO2=1-4，空速为500～5000·h-1。为了提升催化活性，可以用H2在400-700℃还原3-5h。
例如，在微型固定床反应器中对实施例1制备的催化剂进行性能评价，具体操作步骤如下：称取1.0 mL 实施例1制备的样品催化剂装入反应管中部恒温区，原料气H2/CO2=2，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。利用《煤基费托合成尾气中H2、N2、CO、CO2和C1～C8烃的测定和气相色谱法》甲烷关联法，计算出CO2转化率于各组份物质选择性。
表1为本发明上述实施例1-10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所制样品表现出良好的CO2加氢性能。低碳烯烃选择性保持在40%以上，烯烷比（O/P）可达5.74。催化剂经进一步优化改性，如浸渍K、Mg元素，低碳烯烃选择性还会有所提高。
表1实施例1～10制备的样品加氢催化反应工艺参数及性能测试结果对比表
| 实施例 | CO2转化率(%) | CH<sub>4</sub>(%) | C<sub>2</sub>-C<sub>4</sub><sup>=</sup>(%) | C<sub>2</sub>-C<sub>4</sub><sup>0</sup>(%) | C<sub>5</sub><sup>+</sup>(%) | O/P |
| 实施例1 | 71.45 | 32.21 | 43.52 | 10.06 | 14.21 | 4.33 |
| 实施例2 | 72.54 | 32.12 | 41.21 | 12.19 | 14.48 | 3.38 |
| 实施例3 | 70.33 | 34.48 | 40.78 | 9.17 | 15.57 | 4.45 |
| 实施例4 | 55.48 | 30.78 | 38.62 | 16.32 | 14.28 | 2.37 |
| 实施例5 | 82.45 | 32.45 | 43.35 | 10.33 | 13.87 | 4.20 |
| 实施例6 | 84.58 | 34.41 | 45.45 | 7.92 | 12.22 | 5.74 |
| 实施例7 | 69.78 | 31.45 | 43.47 | 10.63 | 14.45 | 4.09 |
| 实施例8 | 68.45 | 29.68 | 38.78 | 15.09 | 16.45 | 2.57 |
| 实施例9 | 85.45 | 32.45 | 41.47 | 8.66 | 17.42 | 4.79 |
| 实施例10 | 87.17 | 31.84 | 46.45 | 7.15 | 14.56 | 6.50 |
Claims (5)
1.一种CO2加氢催化剂和应用，其特征在于催化剂组分包括1-74.9%[LaGd]xFeyO3、2-25%LaFeO3、余量为金属氧化物；金属氧化物中主要为铁氧化物，包括Fe2O3、Fe3O4；所述催化剂应用于CO2加氢制备低碳烯烃。
2.根据权利要求1所述的一种CO2加氢催化剂，其特征在于催化剂中La、Gd元素共作用，提高烯烃选择性。
3.根据权利要求1所述的一种CO2加氢催化剂应用，其特征在于催化剂应用于CO2加氢反应前，须在400-700℃还原活化。
4.根据权利要求1所述的一种CO2加氢催化剂应用，其特征在于催化剂应用于CO2加氢反应，反应条件为H2/CO2 =1~4，150~400℃、2~8MPa，1000~4000 h–1。
5.根据权利要求1所述的一种CO2加氢催化剂，其特征在于催化剂的优化通过Mg，Mn、Na、Zn、K至少一种元素浸渍修饰。
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