CN101455982A - Zeolite-like porous material and preparation method and use thereof - Google Patents
Zeolite-like porous material and preparation method and use thereof Download PDFInfo
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- 239000011148 porous material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- 150000004033 porphyrin derivatives Chemical class 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical class COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical group [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 claims description 2
- YAMIWWIPGQYPFX-UHFFFAOYSA-K samarium(3+);triperchlorate Chemical compound [Sm+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YAMIWWIPGQYPFX-UHFFFAOYSA-K 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- -1 rare earth ions Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 1
- UHDNUPHSDMOGCR-UHFFFAOYSA-N 3-Formylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=O)=C1 UHDNUPHSDMOGCR-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
Description
技术领域 technical field
本发明涉及合成氨技术领域，尤其涉及一种类沸石多孔材料及制备方法与用途。The invention relates to the technical field of ammonia synthesis, in particular to a zeolite-like porous material, a preparation method and application.
背景技术 Background technique
合成氨催化剂虽然已经经历了近一个世纪的研究，但是目前大量使用的仍然是传统的熔铁催化剂，以氧化铝、氧化钾等作为助催化剂，其高温(450～550℃)、高压(10～30MPa)、低活性(转化率15～25％)的特点而必定成为节能降耗的制约因素，并且对设备材料要求苛刻。因此，开发出新一代高效节能型合成氨催化剂势在必行。专利CN1293593、CN1099353、US3839229等主要集中在对原有熔铁催化剂的改良，而专利CN1401426、CN1270081A、DE2748972、GB2034194、WO84-3642、US4142993、US3830753以及US4600571等所报道的催化剂均以钌为活性组分，新型的钌基合成氨催化剂虽然可在低温、低压下操作，而且寿命长，可节省大量能耗，然而由于钌的稀有和昂贵，必然会造成催化剂的成本大幅度提高等问题。因此，开发出一种新型高效、节能、低成本合成氨催化剂是非常重要和迫切的。Although ammonia synthesis catalysts have been researched for nearly a century, the traditional molten iron catalysts are still widely used at present, with alumina, potassium oxide, etc. ), low activity (conversion rate 15-25%), which must become the restrictive factor of energy saving and consumption reduction, and has strict requirements on equipment materials. Therefore, it is imperative to develop a new generation of high-efficiency and energy-saving catalysts for ammonia synthesis. Patents CN1293593, CN1099353, US3839229, etc. mainly focus on the improvement of the original molten iron catalyst, while the catalysts reported in patents CN1401426, CN1270081A, DE2748972, GB2034194, WO84-3642, US4142993, US3830753 and US4600571 all use ruthenium as the active component Although the new ruthenium-based ammonia synthesis catalyst can operate at low temperature and low pressure, and has a long life, it can save a lot of energy consumption. However, due to the rarity and high cost of ruthenium, it will inevitably cause problems such as a substantial increase in the cost of the catalyst. Therefore, it is very important and urgent to develop a novel high-efficiency, energy-saving, and low-cost catalyst for ammonia synthesis.
发明内容 Contents of the invention
本发明的目的是针对现有技术的不足，提供一种类沸石多孔材料及制备方法与用途，该类沸石多孔材料具有在较低的温度和常压，甚至常温常压下合成氨的能力，催化活性高，成本低，可广泛应用于合成氨工业。The purpose of the present invention is to address the deficiencies in the prior art, to provide a zeolite-like porous material and its preparation method and application. High, low cost, can be widely used in the ammonia industry.
本发明的目的是通过以下技术方案来实现的：一种类沸石多孔材料，它主要由卟啉或卟啉衍生物基本载体、过渡金属离子活性组分和金属离子节点组成。The purpose of the present invention is achieved through the following technical solutions: a zeolite-like porous material, which is mainly composed of porphyrin or porphyrin derivative basic carrier, transition metal ion active components and metal ion nodes.
进一步地，所述过渡金属离子活性组分为Fe、Ni、Co、Ru、Pd、Pt、Rh、Ta、Re、Mo、W等；所述催化活性组分位于卟啉的中心；所述卟啉或卟啉衍生物基本载体为卟啉或其羧酸、吡啶、膦酸、磺酸等的衍生物；所述金属离子节点为元素周期表中的所有金属离子。Further, the transition metal ion active components are Fe, Ni, Co, Ru, Pd, Pt, Rh, Ta, Re, Mo, W, etc.; the catalytically active components are located at the center of porphyrin; the porphyrin The basic carrier of porphyrin or porphyrin derivatives is porphyrin or derivatives thereof such as carboxylic acid, pyridine, phosphonic acid, sulfonic acid, etc.; the metal ion nodes are all metal ions in the periodic table of elements.
上述类沸石多孔材料的制备方法，包括以下步骤：The preparation method of the above-mentioned zeolite-like porous material comprises the following steps:
(1)通过吡咯与对应的醛反应制备卟啉或其衍生物。(1) Prepare porphyrin or its derivatives by reacting pyrrole with corresponding aldehyde.
(2)利用对应的金属盐与卟啉或卟啉衍生物在DMF溶剂中通过回流反应得到对应的金属卟啉或金属卟啉衍生物。(2) Using the corresponding metal salt and porphyrin or porphyrin derivative to obtain the corresponding metalloporphyrin or metalloporphyrin derivative by reflux reaction in DMF solvent.
(3)在混合溶剂中，将金属卟啉或金属卟啉衍生物载体与金属盐反应，得到深棕红色溶液，经过一段时间以后得到深棕色晶体，然后过滤、分别用DMF、乙醇以及乙醚等溶剂依次洗涤，最后在空气中晾干，得到本发明类沸石多孔材料。(3) In a mixed solvent, the metal porphyrin or metal porphyrin derivative carrier is reacted with a metal salt to obtain a dark brown-red solution. After a period of time, dark brown crystals are obtained, and then filtered, respectively, with DMF, ethanol and ether, etc. The solvent is washed sequentially, and finally dried in the air to obtain the zeolite-like porous material of the present invention.
进一步地，所述步骤(3)中，所述混合溶剂为DMF、氯苯、甲醇以及醋酸等的混合溶剂；所述金属盐为硝酸隔、氯化轧、硝酸铕、高氯酸钐、氯化铟等。Further, in the step (3), the mixed solvent is a mixed solvent of DMF, chlorobenzene, methanol, and acetic acid; the metal salt is sodium nitric acid, sodium chloride, europium nitrate, samarium perchlorate, Indium etc.
上述类沸石多孔材料可作为合成氨催化剂。The above-mentioned zeolite-like porous material can be used as a catalyst for ammonia synthesis.
本发明与现有的合成氨催化剂相比，具有以下技术效果：Compared with the existing ammonia synthesis catalyst, the present invention has the following technical effects:
1、反应条件温和；1. Mild reaction conditions;
2、不需要高压，可以常压下进行催化反应；2. No high pressure is required, and the catalytic reaction can be carried out under normal pressure;
3、成本低；3. Low cost;
4、转化率高且不受传统的热力学条件的限制；4. High conversion rate and not limited by traditional thermodynamic conditions;
5、易于实现工业化生产，可广泛应用于合成氨工业。5. It is easy to realize industrialized production and can be widely used in the synthetic ammonia industry.
具体实施方式 Detailed ways
本发明提供的是以卟啉或卟啉衍生物为基本载体，以过渡金属离子为活性组分，以过渡金属离子或稀土离子或主族金属离子为节点的催化剂自负载的类沸石多孔材料，可广泛应用于合成氨工业。The present invention provides a zeolite-like porous material with porphyrin or porphyrin derivatives as the basic carrier, transition metal ions as the active component, and transition metal ions or rare earth ions or main group metal ions as the nodes. It can be widely used in synthetic ammonia industry.
本发明的类沸石多孔材料主要由卟啉或卟啉衍生物基本载体、过渡金属离子活性组分以及金属离子节点组成。催化活性组分为过渡金属元素，如：Fe、Ni、Ru、Pd、Pt、Rh、Ta、Re、Mo、W等；催化活性组分位于卟啉的中心；卟啉或其衍生物载体为卟啉或其羧酸、吡啶、膦酸、磺酸等的衍生物；节点金属为元素周期表中的所有金属离子，如：碱土金属元素、稀土金属元素、Cd、Al、In、Pb、Ge等。The zeolite-like porous material of the invention is mainly composed of porphyrin or porphyrin derivative basic carrier, transition metal ion active components and metal ion nodes. The catalytically active component is a transition metal element, such as: Fe, Ni, Ru, Pd, Pt, Rh, Ta, Re, Mo, W, etc.; the catalytically active component is located at the center of porphyrin; the carrier of porphyrin or its derivatives is Porphyrin or its derivatives of carboxylic acid, pyridine, phosphonic acid, sulfonic acid, etc.; node metals are all metal ions in the periodic table, such as: alkaline earth metal elements, rare earth metal elements, Cd, Al, In, Pb, Ge wait.
本发明类沸石多孔催化剂的制备方法，包括以下步骤：The preparation method of zeolite-like porous catalyst of the present invention comprises the following steps:
(1)通过吡咯与对应的醛反应制备卟啉或卟啉衍生物。(1) Prepare porphyrin or porphyrin derivatives by reacting pyrrole with corresponding aldehyde.
所述的醛为对羧基苯甲醛、间羧基苯甲醛、对膦酸基苯甲醛、间膦酸基苯甲醛、对磺酸基苯甲醛、间磺酸基苯甲醛等。The aldehydes are p-carboxybenzaldehyde, m-carboxybenzaldehyde, p-phosphonate benzaldehyde, m-phosphonate benzaldehyde, p-sulfonate benzaldehyde, m-sulfonate benzaldehyde and the like.
(2)利用对应的金属盐与卟啉或卟啉衍生物在DMF溶剂中通过回流反应得到对应的金属卟啉或金属卟啉衍生物。(2) Using the corresponding metal salt and porphyrin or porphyrin derivative to obtain the corresponding metalloporphyrin or metalloporphyrin derivative by reflux reaction in DMF solvent.
所述的金属盐为Fe、Ni、Co、Ru、Pd、Pt、Rh、Ta、Re、Mo、W等金属的硝酸盐、醋酸盐、高氯酸盐、卤化物、硫酸盐等。The metal salts are nitrates, acetates, perchlorates, halides, sulfates and the like of Fe, Ni, Co, Ru, Pd, Pt, Rh, Ta, Re, Mo, W and other metals.
(3)在混合溶剂中，将金属卟啉或卟啉衍生物载体与金属盐反应，得到深棕红色溶液，经过一段时间以后得到深棕色晶体，然后过滤、分别用DMF、乙醇以及乙醚等溶剂依次洗涤，最后在空气中晾干。得到本发明类沸石多孔材料。(3) In a mixed solvent, the metal porphyrin or porphyrin derivative carrier is reacted with a metal salt to obtain a dark brown-red solution. After a period of time, dark brown crystals are obtained, and then filtered, and solvents such as DMF, ethanol and ether are used respectively Wash sequentially and finally air dry. The zeolite-like porous material of the present invention is obtained.
所述混合溶剂为DMF、氯苯、甲醇以及醋酸等的混合溶剂；金属盐为硝酸隔、氯化轧、氯化铟等。The mixed solvent is a mixed solvent of DMF, chlorobenzene, methanol, acetic acid, etc.; the metal salt is nitric acid, sodium chloride, indium chloride, etc.
通过单晶X-射线衍射、PLATON计算以及BET比表面积计算说明该类化合物为多孔的类沸石化合物。热失重及粉末X-射线衍射表明该类化合物在除去孔道中的结晶溶剂以后，化合物的整体骨架是保持不变的。The single crystal X-ray diffraction, PLATON calculation and BET specific surface area calculation show that the compound is a porous zeolite-like compound. Thermal weight loss and powder X-ray diffraction show that the overall skeleton of the compound remains unchanged after removing the crystallization solvent in the pores.
本发明所选用的过渡金属元素活性组分的不同对催化剂的活性影响较大。所选用的金属离子节点的不同以及卟啉或卟啉衍生物载体的种类对合成条件的选择影响较大，如：合成温度、不同溶剂的比例以及溶液的酸碱度等，也同时会影响到催化剂的比表面积大小，进而影响催化剂的催化活性。The difference in the active components of transition metal elements selected in the present invention has a great influence on the activity of the catalyst. The choice of metal ion nodes and the type of porphyrin or porphyrin derivative carrier have a great influence on the selection of synthesis conditions, such as: synthesis temperature, the ratio of different solvents, and the pH of the solution, etc., which will also affect the catalyst. The size of the specific surface area affects the catalytic activity of the catalyst.
反应条件如：温度、压力、气体流速等对催化剂活性的影响各不相同。其中压力、气体流速对合成氨的转化率影响较小。随着温度的升高，合成氨的转化率升高的很快，并且不受热力学因素的影响。Reaction conditions such as: temperature, pressure, gas flow rate, etc. have different effects on the catalyst activity. Among them, pressure and gas flow rate have little influence on the conversion rate of synthetic ammonia. As the temperature increases, the conversion rate of synthetic ammonia increases rapidly and is not affected by thermodynamic factors.
与已有的技术相比，本发明在低温常压下对合成氨反应具有极高的催化活性，并且原料廉价易得、合成简单、催化剂成本低、活性极高，特别是可以节省大量的能耗。Compared with the existing technology, the present invention has extremely high catalytic activity for ammonia synthesis reaction at low temperature and normal pressure, and the raw materials are cheap and easy to obtain, the synthesis is simple, the catalyst cost is low, and the activity is extremely high, especially it can save a lot of energy consumption .
以下实施例将有助于理解本发明，但本发明的保护范围并不限于此内容：The following examples will help to understand the present invention, but protection scope of the present invention is not limited to this content:
实施例1Example 1
在混合溶剂中，如：DMF、氯苯、甲醇以及醋酸，将钯卟啉的苯甲酸衍生物与金属盐硝酸隔在80℃反应得到深棕红色溶液。经过十天以后得到深棕色晶体，然后过滤、分别用DMF、乙醇以及乙醚等溶剂洗涤，最后在空气中晾干。通过单晶X-射线衍射、PLATON计算以及BET比表面积计算说明该化合物为多孔的类沸石化合物。通过加热以及抽真空的方法可以除去该化合物在孔道中的结晶溶剂。热失重及粉末X-射线衍射表明该化合物的整体骨架在失去溶剂分子以后是保持不变的。In a mixed solvent, such as: DMF, chlorobenzene, methanol and acetic acid, react the benzoic acid derivative of palladium porphyrin with the metal salt nitric acid at 80°C to obtain a dark brownish red solution. After ten days, dark brown crystals were obtained, which were then filtered, washed with solvents such as DMF, ethanol and ether, and finally dried in air. The compound is a porous zeolite compound through single crystal X-ray diffraction, PLATON calculation and BET specific surface area calculation. The crystallization solvent of the compound in the channel can be removed by heating and vacuuming. Thermal weight loss and powder X-ray diffraction showed that the overall skeleton of the compound remained unchanged after losing solvent molecules.
实施例2Example 2
催化剂活性评价在MRCS8004装置中进行。反应器内径为2mm的固定床，堆积体积为0.03mL，反应气为1：3的氮气和氢气混合气，气体流速为12mL/min，催化剂在200℃活化30分钟。结果表明，在室温时开始有氨气生成，在310℃的转化率达到7％，并且不受传统热力学条件的限制。Catalyst activity evaluation was carried out in MRCS8004 device. The inner diameter of the reactor is a fixed bed of 2mm, the bulk volume is 0.03mL, the reaction gas is a 1:3 mixture of nitrogen and hydrogen, the gas flow rate is 12mL/min, and the catalyst is activated at 200°C for 30 minutes. The results show that ammonia gas begins to be generated at room temperature, and the conversion rate reaches 7% at 310°C, and is not limited by traditional thermodynamic conditions.
实施例3Example 3
催化剂活性评价在MRCS8004装置中进行。反应器内径为2mm的固定床，堆积体积为0.05mL，反应气为1：3的氮气和氢气混合气，气体流速为20mL/min，催化剂在200℃活化30分钟。结果表明，催化剂的活性几乎不受压力的影响。Catalyst activity evaluation was carried out in MRCS8004 device. The inner diameter of the reactor is a fixed bed of 2mm, the bulk volume is 0.05mL, the reaction gas is a 1:3 mixture of nitrogen and hydrogen, the gas flow rate is 20mL/min, and the catalyst is activated at 200°C for 30 minutes. The results showed that the activity of the catalyst was hardly affected by pressure.
上述实施例用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明作出的任何修改和改变，都落入本发明的保护范围。The above-mentioned embodiments are used to illustrate the present invention, rather than to limit the present invention. Within the spirit of the present invention and the protection scope of the claims, any modification and change made to the present invention will fall into the protection scope of the present invention.
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| CN109833912A (en) * | 2019-03-21 | 2019-06-04 | 南京工业大学 | Metalloporphyrin-loaded titanium silicalite molecular sieve novel catalyst and synthesis method thereof |
| CN110280268A (en) * | 2019-07-03 | 2019-09-27 | 北京氦舶科技有限责任公司 | A kind of synthetic ammonia catalyst and preparation method thereof |
| CN115703076A (en) * | 2021-08-03 | 2023-02-17 | 中国科学院化学研究所 | Catalyst and material for processing fossil energy materials, method for catalytic pyrolysis of fossil energy materials, method for processing oil shale |
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| CN109833912A (en) * | 2019-03-21 | 2019-06-04 | 南京工业大学 | Metalloporphyrin-loaded titanium silicalite molecular sieve novel catalyst and synthesis method thereof |
| CN110280268A (en) * | 2019-07-03 | 2019-09-27 | 北京氦舶科技有限责任公司 | A kind of synthetic ammonia catalyst and preparation method thereof |
| CN115703076A (en) * | 2021-08-03 | 2023-02-17 | 中国科学院化学研究所 | Catalyst and material for processing fossil energy materials, method for catalytic pyrolysis of fossil energy materials, method for processing oil shale |
| CN115703076B (en) * | 2021-08-03 | 2024-03-01 | 中国科学院化学研究所 | Catalyst for processing fossil energy substances, material, method for catalytically pyrolyzing fossil energy substances, and method for processing oil shale |
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