Method for synthesizing ammonia by activating nitrogen through liquid organic material under mild condition
By using liquid organic materials as hydrogen source and combining the dehydrogenation and nitrogen fixation reaction of transition metal heterogeneous catalysts, the problems of high carbon emissions and high energy consumption in traditional synthesis ammonia technology are solved, and low carbon, low energy consumption and high safety ammonia synthesis is achieved .
Patent Information
- Application Number
- CN202411586882.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-08
- Publication Date
- 2025-02-18
AI Technical Summary
Traditional synthetic ammonia technology has problems such as high carbon emissions, high energy consumption, high transportation costs and low safety, especially during hydrogen production and transportation.
Liquid organic materials are used as hydrogen source, and the nitrogen reaction is reacted under mild conditions, and a transition metal heterogeneous catalyst is used to perform a dehydrogenation and nitrogen fixation reaction to achieve one-step synthesis of ammonia.
It achieves zero carbon emissions, low energy consumption, reduced transportation costs and improved safety, while maintaining a competitive ammonia production rate.
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Figure CN119461413A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of heterogeneous catalysis, and in particular relates to a method for synthesizing ammonia by activating nitrogen with liquid organic materials under mild conditions. Background Art
[0002] Ammonia is a very important compound. In the past 100 years, ammonia has been used as nitrogen fertilizer. In 2008, some scholars pointed out that the growth of ammonia production is closely related to population growth. According to statistical analysis, nitrogen fertilizer produced by artificial nitrogen fixation feeds at least 40% of the world's population (Nature Geosci, 2008, 1, 636-639).
[0003] Today, ammonia is a renewable energy source with strategic value. Because ammonia can achieve zero carbon emissions when it is completely burned, ammonia can be used as engine fuel, which is conducive to solving the carbon emission problem in the transportation sector.
[0004] Traditional marine power systems are mainly fuel-based, and the carbon dioxide emissions they produce account for 3% to 4% of global carbon dioxide emissions (according to the International Maritime Organization). Using an ammonia power system can achieve zero carbon emissions. At present, my country's first ammonia-fueled ship has been internationally recognized.
[0005] Therefore, ammonia is becoming more and more important in our lives, and the technology of synthetic ammonia has also received widespread attention. From the laboratory to industrial production, scientists have been exploring the technology of synthetic ammonia for more than 100 years. Today, the Haber-Bosch method is still the only synthetic ammonia technology with industrial scale. The hydrogen required in the Haber process is generally produced through fossil energy, electrolysis of water, industrial by-products and other methods. However, due to the energy structure of "rich in coal, poor in oil, and little gas" in my country, more than 60% of the hydrogen in synthetic ammonia is produced from coal (China Hydrogen Energy Industry Development Blue Book).
[0006] The gasification process of coal-to-hydrogen production mainly involves three steps: steam reforming, water-gas shift, and carbon dioxide removal. The gas is then transported to the factory under high pressure to synthesize ammonia. In this entire process, not only is the gasification process complicated, the transportation cost is high, and the risk is high, but more importantly, this traditional ammonia synthesis method releases 4 tons of carbon dioxide for every ton of ammonia produced. This high-carbon emission ammonia synthesis model urgently needs to be optimized and improved.
[0007] In view of the above, we propose to use liquid organic materials as hydrogen source for nitrogen synthesis of ammonia. This new strategy of synthesizing ammonia does not require gas separation, and the use of liquid organic materials can achieve zero carbon emissions. In addition, liquid organic matter does not need high-pressure compression during transportation, which reduces transportation costs and improves safety. Summary of the invention
[0008] The object of the present invention is to provide a novel ammonia synthesis strategy to solve the problems raised in the above background technology.
[0009] The technical solution of the present invention:
[0010] A method for synthesizing ammonia by dehydrogenating and activating nitrogen from liquid organic materials under mild conditions, comprising the following steps:
[0011] In the presence of a catalyst, the liquid organic material is heated and nitrogen is introduced to perform a dehydrogenation and nitrogen fixation reaction. The heating temperature is 200°C to 800°C, the reaction pressure is 0.1MPa to 10MPa, and the flow rate of the liquid organic material is 0.01mL min -1 ~10mL min -1 , nitrogen flow rate was 1 mL min -1 ~100mL min -1 .
[0012] The liquid organic material comprises
[0013] One or a combination of two or more of the following, wherein R is a C1-C5 alkyl chain, and X is a N, O or P atom.
[0014] The heating temperature is further 300°C to 700°C.
[0015] The reaction pressure is further 0.1 MPa to 10 MPa.
[0016] The catalyst includes a transition metal heterogeneous catalyst and / or a transition metal homogeneous catalyst.
[0017] The transition metal heterogeneous catalyst is selected from oxides or composite oxides of Pt, Cr, Co, Fe, Mo, W, Ce, Pr, Ru, Rh, Ir, La, Ni, Ti, Pd, Ta, Ag and Sn.
[0018] The transition metal heterogeneous catalyst is selected from carbides or composite carbides of Pt, Cr, Co, Fe, Mo, W, Ce, Pr, Ru, Rh, Ir, La, Ni, Ti, Pd, Ta, Ag, and Sn.
[0019] The transition metal heterogeneous catalyst is selected from the sulfides or composite sulfides of Pt, Cr, Co, Fe, Mo, W, Ce, Pr, Ru, Rh, Ir, La, Ni, Ti, Pd, Ta, Ag, and Sn.
[0020] The transition metal homogeneous catalyst is selected from one or more of Pt, Cr, Co, Fe, Mo, W, Ce, Pr, Ru, Rh, Ir, La, Ni, Ti, Pd, Ta, Ag, and Sn.
[0021] Beneficial effects of the present invention: The embodiments of the present invention use liquid organic materials as a hydrogen source to supply nitrogen for synthesizing ammonia. Traditional ammonia synthesis requires the use of high-purity hydrogen and high-purity nitrogen for reaction, and the production of high-purity hydrogen requires complex processes such as steam reforming, water-gas shift and gas separation. The entire process has high carbon emissions and high energy consumption. This method uses liquid organic materials as a hydrogen source, and does not require processes such as gasification and separation. During the reaction, the liquid organic material can produce hydrogen in situ to achieve the purpose of hydrogen supply, realize one-step synthesis of ammonia, and greatly reduce carbon emissions and energy consumption. In addition, liquid organic materials do not require high-pressure compression during transportation, so the transportation cost is lower and the safety is higher. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 It is a system diagram of the method of the present invention.
[0023] In the figure: 1 high-pressure pump; 2 nitrogen cylinder; 3 fixed bed; 4 back pressure valve. DETAILED DESCRIPTION
[0024] The specific implementation of the present invention is further described below in conjunction with the accompanying drawings and technical solutions.
[0025] Example 1
[0026] Weigh 0.05g PtRu / NaY and fill it into the reaction tube. Pass N2 with a flow rate of 1ml / min and decalin with a flow rate of 0.01ml / min into the reaction tube. React at 200℃ and 10MPa. Collect the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 5440umol / g / h.
[0027] The test results of the synthetic ammonia performance are shown in Table 1.
[0028] Example 2
[0029] Weigh 0.05g PdCo / SAPO-11 and fill it into the reaction tube. Pass N2 with a flow rate of 10ml / min and decalin with a flow rate of 0.1ml / min into the reaction tube. React at 300℃ and 9MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 6260umol / g / h.
[0030] The test results of the synthetic ammonia performance are shown in Table 1.
[0031] Example 3
[0032] Weigh 0.05g IrNi / MCM-41 and fill it into the reaction tube. Pass N2 with a flow rate of 15mL / min and decahydronaphthalene with a flow rate of 0.2mL / min into the reaction tube. React at 400℃ and 8MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Detect the synthetic ammonia yield using cation chromatography. The ammonia yield is 5380umol / g / h.
[0033] The test results of the synthetic ammonia performance are shown in Table 1.
[0034] Example 4
[0035] Weigh 0.05g RhFe / LaCeAlO and fill it into the reaction tube. Pass N2 with a flow rate of 20mL / min and methylcyclohexane with a flow rate of 0.5mL / min into the reaction tube. React at 500℃ and 6MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 6300umol / g / h.
[0036] The test results of the synthetic ammonia performance are shown in Table 1.
[0037] Example 5
[0038] Weigh 0.05g CrTa / LaCoO and fill it into the reaction tube. N2 with a flow rate of 30mL / min and methylcyclohexane with a flow rate of 1mL / min are introduced into the reaction tube. The reaction is carried out at 600℃ and 5MPa. The output liquid is received by a three-necked flask, and the output gas is connected to a 0.5mol / L H2SO4 solution. The synthetic ammonia yield is detected by cation chromatography. The ammonia yield is 7540umol / g / h. The test results of the synthetic ammonia performance are shown in Table 1.
[0039] Example 6
[0040] Weigh 0.05g PtMo / BaTiO and fill it into the reaction tube. N2 with a flow rate of 45mL / min and methylcyclohexane with a flow rate of 3mL / min are introduced into the reaction pipeline. The reaction is carried out at 700℃ and 4MPa. The output liquid is received by a three-necked flask, and the output gas is connected to a 0.5mol / L H2SO4 solution. The synthetic ammonia yield is detected by cation chromatography. The ammonia yield is 8890umol / g / h. The test results of the synthetic ammonia performance are shown in Table 1.
[0041] Example 7
[0042] Weigh 0.05g TaAg / PrWO and fill it into the reaction tube. N2 with a flow rate of 60mL / min and dodecahydro-N-ethylcarbazole with a flow rate of 5mL / min are introduced into the reaction pipeline. The reaction is carried out at 800℃ and 3MPa. The output liquid is received by a three-necked flask, and the output gas is connected to a 0.5mol / L H2SO4 solution. The synthetic ammonia yield is detected by cation chromatography. The ammonia yield is 5190umol / g / h. The test results of the synthetic ammonia performance are shown in Table 1.
[0043] Example 8
[0044] Weigh 0.05g SnIr / BaLiAC and fill it into the reaction tube. N2 with a flow rate of 70mL / min and dodecahydro-N-ethylcarbazole with a flow rate of 7mL / min are introduced into the reaction pipeline. The reaction is carried out at 450℃ and 2MPa. The output liquid is received by a three-necked flask, and the output gas is connected to a 0.5mol / L H2SO4 solution. The synthetic ammonia yield is detected by cation chromatography. The ammonia yield is 8955umol / g / h. The test results of the synthetic ammonia performance are shown in Table 1.
[0045] Example 9
[0046] Weigh 0.05g SnRu / BaS1 and fill it into the reaction tube. Pass N2 with a flow rate of 75mL / min and dodecahydro-N-ethylcarbazole with a flow rate of 8mL / min into the reaction tube. React at 550℃, 1MPa. Receive the output liquid with a three-necked flask, and connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 9251umol / g / h. The test results of the synthetic ammonia performance are shown in Table 1.
[0047] Example 10
[0048] Weigh 0.05g PtO / WO3 and fill it into the reaction tube. Pass N2 with a flow rate of 70mL / min and cyclopentane with a flow rate of 5mL / min into the reaction tube. React at 650℃, 4MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 4551umol / g / h.
[0049] The test results of the synthetic ammonia performance are shown in Table 1.
[0050] Embodiment 11
[0051] Weigh 0.05g Pt / WS2 and fill it into the reaction tube. Pass N2 with a flow rate of 65mL / min and cyclohexane with a flow rate of 3mL / min into the reaction tube. React at 450℃, 5MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 5743umol / g / h.
[0052] The test results of the synthetic ammonia performance are shown in Table 1.
[0053] Example 12
[0054] Weigh 0.05g CoPt / Cr2O3 and fill it into the reaction tube. Pass N2 at a flow rate of 45mL / min and dodecahydrocarbazole at a flow rate of 1mL / min into the reaction tube. React at 550℃, 3MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 8242umol / g / h.
[0055] The test results of the synthetic ammonia performance are shown in Table 1.
[0056] Example 13
[0057] Weigh 0.05g NiRu / Co3O4 and fill it into the reaction tube. N2 with a flow rate of 60mL / min and aminopiperidine with a flow rate of 0.5mL / min are introduced into the reaction tube. The reaction is carried out at 750℃ and 1MPa. The output liquid is collected in a three-necked flask, and the output gas is connected to a 0.5mol / L H2SO4 solution. The synthetic ammonia yield is detected by cation chromatography. The ammonia yield is 6384umol / g / h.
[0058] The test results of the synthetic ammonia performance are shown in Table 1.
[0059] Embodiment 14
[0060] Weigh 0.05g IrRu / CoS and fill it into the reaction tube. Pass N2 with a flow rate of 50mL / min and cyclohexylcyclohexane with a flow rate of 1.5mL / min into the reaction tube. React at 350℃, 7MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 3957umol / g / h.
[0061] The test results of the synthetic ammonia performance are shown in Table 1.
[0062] Embodiment 15
[0063] Weigh 0.05g of RuNi / TiO2 and fill it into the reaction tube. Pass N2 at a flow rate of 45mL / min and n-hexane at a flow rate of 3mL / min into the reaction tube. React at 650℃, 4MPa. Receive the output liquid in a three-necked flask, and connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 4026umol / g / h.
[0064] The test results of the synthetic ammonia performance are shown in Table 1.
[0065] Example 16
[0066] Weigh 0.05g PdNi / MoO and fill it into the reaction tube. Pass N2 at a flow rate of 90mL / min and hexahydropyrazine at a flow rate of 8mL / min into the reaction tube. React at 250℃, 8MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 4778umol / g / h.
[0067] The test results of the synthetic ammonia performance are shown in Table 1.
[0068] Embodiment 17
[0069] Weigh 0.05g PdNi / MoS2 and fill it into the reaction tube. Pass N2 at a flow rate of 100mL / min and octahydro-N-methylindole at a flow rate of 1mL / min into the reaction tube. React at 350℃ and 10MPa. Receive the output liquid in a three-necked flask, and connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 4220umol / g / h.
[0070] The test results of the synthetic ammonia performance are shown in Table 1.
[0071] Embodiment 18
[0072] Weigh 0.05g Rh / Pr2S3 and fill it into the reaction tube. Pass N2 at a flow rate of 60mL / min and tetrahydroquinoline at a flow rate of 10mL / min into the reaction tube. React at 700℃, 3MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 5055umol / g / h.
[0073] The test results of the synthetic ammonia performance are shown in Table 1.
[0074] Embodiment 19
[0075] Weigh 0.05g AgSn / CePrO and fill it into the reaction tube. Pass N2 at a flow rate of 10mL / min and dodecahydrobiphenyl at a flow rate of 0.5mL / min into the reaction tube. React at 650℃, 3MPa. Receive the output liquid in a three-necked flask, and connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 6980umol / g / h.
[0076] The test results of the synthetic ammonia performance are shown in Table 1.
[0077] Embodiment 20
[0078] Weigh 0.05g FeRu / LaPrO and fill it into the reaction tube. Pass N2 at a flow rate of 100mL / min and octahydroquinoxaline at a flow rate of 10mL / min into the reaction tube. React at 200℃ and 0.1MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 5851umol / g / h.
[0079] The test results of the synthetic ammonia performance are shown in Table 1.
[0080] Embodiment 21
[0081] Weigh 0.05g PtSn / LaTiO and fill it into the reaction tube. Pass N2 at a flow rate of 20mL / min and octahydroquinoxaline at a flow rate of 1mL / min into the reaction tube. React at 400℃ and 6MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 6289umol / g / h.
[0082] The test results of the synthetic ammonia performance are shown in Table 1.
[0083] Embodiment 22
[0084] Weigh 0.05g PtFe / LaAlO and fill it into the reaction tube. Pass N2 at a flow rate of 30mL / min and decalin at a flow rate of 1mL / min into the reaction tube. React at 600℃, 2MPa. Receive the output liquid in a three-necked flask. Connect the output gas to a 0.5mol / L H2SO4 solution. Use cation chromatography to detect the synthetic ammonia yield. The ammonia yield is 7960umol / g / h.
[0085] The test results of the synthetic ammonia performance are shown in Table 1.
[0086] Embodiment 23
[0087] Weigh 0.05g of RuRh / LaTiS and fill it into the reaction tube. N2 with a flow rate of 40mL / min and n-hexane with a flow rate of 0.1mL / min are introduced into the reaction tube. The reaction is carried out at 500℃ and 5MPa. The output liquid is collected in a three-necked flask, and the output gas is connected to a 0.5mol / L H2SO4 solution. The synthetic ammonia yield is detected by cation chromatography. The ammonia yield is 5736umol / g / h.
[0088] The test results of the synthetic ammonia performance are shown in Table 1.
[0089] Table 1
[0090]
[0091]
[0092] According to the above results, different catalyst selections in the embodiments of the present invention, as well as the combination of multiple hydrogen sources, can demonstrate a method for synthesizing ammonia by activating nitrogen under mild conditions using liquid organic materials. The above embodiments illustrate that the method of synthesizing ammonia by hydrogenating nitrogen using this liquid organic material as a hydrogen source can be realized. Compared with the traditional ammonia synthesis process, these liquid organic materials as hydrogen sources can greatly reduce energy consumption, reduce carbon emissions, reduce transportation process costs, and improve transportation safety. At the same time, under the premise of low energy consumption, low carbon emissions, and high safety, the ammonia production rate can still be maintained at a competitive level.
[0093] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A method for synthesizing ammonia by dehydrogenating activated nitrogen from liquid organic materials under mild conditions, characterized in that: The steps include: In the presence of a catalyst, the liquid organic material is heated and nitrogen is introduced to carry out a dehydrogenation and nitrogen fixation reaction. The heating temperature is 200 °C to 800 °C, the reaction pressure is 0.1 MPa to 10 MPa, and the flow rate of the liquid organic material is 0.01 mL min-1. 1 ~10 mL min- 1 , nitrogen flow rate was 1 mL min- 1 ~100 mLmin- 1 .
2. The method according to claim 1, characterized in that The liquid organic material comprises One or a combination of two or more of the following, wherein R is a C1-C5 alkyl chain, and X is a N, O or P atom.
3. The method according to claim 1, characterized in that The heating temperature is further 300°C to 700°C.
4. The method according to claim 1, characterized in that: The reaction pressure is further 0.1 MPa to 10 MPa.
5. The method according to claim 1, wherein the catalyst comprises a transition metal heterogeneous catalyst and / or a transition metal homogeneous catalyst.
6. The method according to claim 5, characterized in that The transition metal heterogeneous catalyst is selected from oxides or composite oxides of Pt, Cr, Co, Fe, Mo, W, Ce, Pr, Ru, Rh, Ir, La, Ni, Ti, Pd, Ta, Ag and Sn.
7. The method according to claim 5, characterized in that The transition metal heterogeneous catalyst is selected from carbides or composite carbides of Pt, Cr, Co, Fe, Mo, W, Ce, Pr, Ru, Rh, Ir, La, Ni, Ti, Pd, Ta, Ag, and Sn.
8. The method according to claim 5, characterized in that The transition metal heterogeneous catalyst is selected from the sulfides or composite sulfides of Pt, Cr, Co, Fe, Mo, W, Ce, Pr, Ru, Rh, Ir, La, Ni, Ti, Pd, Ta, Ag, and Sn.
9. The method according to claim 5, characterized in that The transition metal homogeneous catalyst is selected from one or more of Pt, Cr, Co, Fe, Mo, W, Ce, Pr, Ru, Rh, Ir, La, Ni, Ti, Pd, Ta, Ag, and Sn.