CN111229242B - Iron-molybdenum-based catalyst for preparing formaldehyde by oxidizing cerium-doped methanol, preparation and application thereof - Google Patents
Iron-molybdenum-based catalyst for preparing formaldehyde by oxidizing cerium-doped methanol, preparation and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
Abstract
The invention relates to a preparation method and application of an iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation. The preparation of the iron-molybdenum-based catalyst is based on the regulation of the pH value of the raw materials, and a trace advection pump is adopted to accurately control the mixing speed of molybdenum salt and iron salt, thereby accurately controlling the Fe as the second active component 2 (MoO 4 ) 3 With MoO 3 And a cocatalyst component CeO 2 The spatial position relationship and the ratio of (c). By CeO 2 Further modulate MoO 3 The number and distribution of oxygen vacancies. In addition, the sample is dried by respectively adopting vacuum drying and freeze-drying methods, so that the inactive phase Fe can be effectively avoided 2 O 3 And (4) generating. The iron-molybdenum-based catalyst is used, the reaction temperature is 220-350 ℃, the volume content of the imported methanol is 6-10 percent, and the space velocity of the carrier is 7500-12500h under normal pressure ‑1 Under the condition, the high-efficiency conversion of the methanol can be realized, and simultaneously, higher stability is obtained. The preparation method is simple to operate and easy to amplify. Can be applied to the fields of preparing formaldehyde by oxidizing methanol and the like, and has better industrial application prospect.
Description
Technical Field
The invention belongs to the field of novel catalytic material preparation, and particularly relates to a cerium-doped iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by methanol oxidation 2 /MoO 3 -Fe 2 (MoO 4 ) 3 ) The preparation method of (1).
Background
Formaldehyde is an important bulk chemical product and is widely applied to a plurality of fields such as chemical industry, medicine and the like. In the existing formaldehyde industrial production process, a methanol oxidation route is adopted. The "silver method" and the "iron-molybdenum method" are classified according to the catalyst used. Compared with the silver method, the iron-molybdenum method adopts a fixed bed process in the process, has larger production capacity of a device, higher methanol conversion efficiency, low reaction temperature and small unit consumption of methanol, and can produce high-concentration formaldehyde and the like. Therefore, most of formaldehyde devices built and expanded globally in recent years adopt the iron-molybdenum method production process.
The existing iron-molybdenum catalyst in China generally has the problems of short service life, easy sublimation of an active Mo component and the like; secondly, the catalyst used in the domestic iron-molybdenum process depends heavily on import abroad. Therefore, the development of the iron-molybdenum catalyst with proprietary intellectual property rights is of great significance.
The existing iron-molybdenum catalyst preparation method mostly adopts a coprecipitation method to prepare, and an iron salt aqueous solution is directly added into a molybdenum salt aqueous solution in a dropwise manner. CN 107952445A reports a coprecipitation preparation method of iron-molybdenum catalyst for preparing formaldehyde by methanol oxidation, wherein a humectant is added in the drying step of the preparation, so that active phase iron molybdate can be better formed, free iron ions are reduced, and the activity and stability of the catalyst are improved. The service life of the catalyst is prolonged to a certain extent. However, simple co-precipitation mixing, the pH of the system varying from time to time, and lack of control over the active phase. Meanwhile, various metal oxides such as rubidium, cesium, magnesium, strontium and the like need to be introduced, and the preparation process is complex. CN 108435192A reports a non-coprecipitation preparation method for preparing a formaldehyde catalyst by methanol oxidation, which adopts a mechanochemical synthesis method to mix solid molybdate and iron salt according to a certain proportion to obtain a mixture. And ball milling by a ball mill to obtain the ball grinding material. Finally, the iron-molybdenum catalyst is obtained through drying, cooling and roasting. The method can effectively reduce water consumption and preparation cost. However, the catalyst has low activity, increases the energy consumption in the reaction process, and limits the further industrial application of the catalyst.
In conclusion, the existing iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation is generally prepared by a method of directly dripping, mixing and precipitating. During the mixing process, the pH value of the system is always in a changing state, and the two active components (Fe) cannot be effectively controlled 2 (MoO 4 ) 3 With MoO 3 ) Composition and distribution of (a). In addition, the iron component is easily Fe due to sublimation loss of Mo 2 O 3 Is segregated out. Aiming at the problems, the invention develops a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by oxidizing methanol. The mixing speed of molybdenum salt and iron salt is accurately controlled by adopting a micro advection pump, the two raw material solutions are blended at a certain temperature, and the pH value of the mixture is always in a constant state. By CeO 2 Further modulate MoO 3 The number and distribution of oxygen vacancies. The vacuum drying and freeze-drying method is adopted to replace the prior common drying method, so that the Fe of the inactive phase can be effectively avoided 2 O 3 And (4) generating. The preparation method is simple to operate and easy to amplify.
Disclosure of Invention
The invention aims to provide a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation, which can effectively regulate and control two active components Fe 2 (MoO 4 ) 3 With MoO 3 And a cocatalyst component CeO 2 The spatial positional relationship of (a). The sample is dried by adopting a vacuum drying and freeze-drying method, so that the inactive phase Fe can be effectively avoided 2 O 3 Thereby effectively improving the stability of the product.
The invention provides a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation, which comprises the following specific synthetic steps: a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation is characterized by comprising the following steps: firstly, respectively dissolving molybdenum salt, ferric salt and cerium salt into water, and adding nitric acid into a molybdenum salt solution to adjust the pH value to 1.0-2.5;
respectively heating molybdenum salt and iron salt aqueous solution to 40-90 ℃, and then mixing; then aging the sample for 1-48h at 60-90 ℃; regulating the pH value of the cerium salt solution to 8-11, and then dropwise adding the cerium salt solution into the iron-molybdenum mixed solution; then, the mixture is filtered and separated, and dried. Treating at 350-450 deg.C for 2-48h to obtain a series of iron-molybdenum-based catalysts (CeO) with different components for preparing formaldehyde by methanol oxidation 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
The invention provides a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation, which is characterized by comprising the following steps: mixing the molybdenum salt and iron salt aqueous solutions by adopting a micro advection pump respectively, injecting the molybdenum salt and iron salt aqueous solutions into a window respectively, and controlling the flow rate of the micro advection pump at 0.1-1000mL/min.
The invention provides a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation, which is characterized by comprising the following steps: the molar ratio of molybdenum atoms to iron atoms in the catalyst is controlled to be between 1.5 and 6.5, generally between 1.5 and 4.5, and optimally between 1.5 and 2.5.
The invention provides a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by oxidizing methanol, which is characterized by comprising the following steps ofIn the following steps: catalyst promoter component CeO 2 The mass content of (A) is controlled to be 0.1-25%, generally 0.1-10%, optimally 0.5-5%.
The invention provides a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation, which is characterized by comprising the following steps: the molybdenum salt specifically includes: ammonium molybdate, sodium molybdate, lithium molybdate and potassium molybdate, or one or more of the above components;
the iron salt specifically comprises: ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, or a mixture of one or more of the above components;
the cerium salt specifically includes: cerium nitrate, ammonium ceric nitrate, cerium oxalate, cerium acetate, cerium fluoride, cerium sulfate, or one or more of the above components.
The invention provides a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by oxidizing methanol, which is characterized by comprising the following steps:
the mass concentration of the molybdenum salt solution is 0.01-10g/mL, generally 0.1-5g/mL, and optimally 0.2-2g/mL;
the mass concentration of the ferric salt solution is 0.01-10g/mL, generally 0.05-5g/mL, optimally 0.1-2g/mL;
the mass concentration of the cerium salt solution is 0.01-5g/mL, generally 0.05-3g/mL, and optimally 0.1-1g/mL;
the invention provides a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation, which is characterized by comprising the following steps: the drying method comprises the steps of liquid nitrogen freeze-drying, vacuum drying and the like, or two drying methods are used simultaneously.
The invention provides a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation, which is characterized by comprising the following steps: under the condition of normal pressure, the reaction temperature is 220-350 ℃, the volume content of imported methanol is 6-10%, and the space velocity of the carrier is 7500-12500h -1 Under the condition, the conversion rate of methanol is 95-99%, and the yield of formaldehyde is 94-98%.
The invention provides a preparation method of an iron-molybdenum-based catalyst for preparing formaldehyde by oxidizing methanol, which is characterized by comprising the following steps: the catalyst can be applied to the chemical industry fields of preparing formaldehyde by oxidizing methanol and the like.
Compared with the reported preparation method of the iron-molybdenum-based catalyst for preparing formaldehyde by oxidizing methanol, the invention has the following advantages: the preparation method is simple to operate and easy to amplify. The prepared catalyst has the advantages of high reaction activity, difficult inactivation of active components and the like, and can be applied to the field of industrial production of formaldehyde by methanol oxidation.
Detailed Description
Example 1:
dissolving 1.3g of ammonium molybdate into 100mL of deionized water at 80 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 60 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 12 hours under the condition of 90 ℃. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 400 deg.C for 4 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 2: different ferromolybdenum atomic ratio (Mo/Fe = 6.5)
Dissolving 5.7g of ammonium molybdate into 100mL of deionized water at 90 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 70 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 12 hours under the condition of 90 ℃. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 400 deg.C for 4 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 3: different ferromolybdenum atomic ratio (Mo/Fe = 2.5)
Dissolving 2.2g of ammonium molybdate into 100mL of deionized water at 60 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; 2.0g of ferric nitrateDissolving the mixture into 100mL of deionized water at 60 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 24 hours under the condition of 60 ℃. Dissolving 0.2g of cerous nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2h. Filtering, vacuum drying, and roasting at 450 deg.C for 2 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 4: constant flow pump flow rate (0.1 mL/min)
Dissolving 1.3g of ammonium molybdate into 100mL of deionized water at 80 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 80 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by a constant flow pump at the flow rate of 0.1mL/min respectively, and then aged for 48 hours at the temperature of 80 ℃. Dissolving 0.2g of cerous nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2h. Filtering, vacuum drying, and roasting at 350 deg.C for 24 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 5: constant flow pump flow rate (1000 mL/min)
1.3g of ammonium molybdate is dissolved in 100mL of deionized water at 90 ℃, and concentrated nitric acid is added to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 90 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed at a flow rate of 1000mL/min by respectively adopting an advection pump, and then aged for 4 hours at the temperature of 90 ℃. Dissolving 0.2g of cerous nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2h. Filtering, vacuum drying, and roasting at 400 deg.C for 6h. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 6: ceO (CeO) 2 Content (0.1%)
1.3g of ammonium molybdate is dissolved in 100mL of deionized water at 70 ℃, and concentrated nitric acid is added to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 70 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 24 hours under the condition of 70 ℃. Dissolving 4mg of cerium nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 350 deg.C for 6 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 7: ceO (CeO) 2 Content (25%)
1.3g of ammonium molybdate is dissolved in 100mL of deionized water at 70 ℃, and concentrated nitric acid is added to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 70 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 24 hours under the condition of 70 ℃. Dissolving 0.5g of cerous nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2h. Filtering, vacuum drying, and roasting at 350 deg.C for 24 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 8: molybdenum salt species and concentration
Dissolving 1.8g of sodium molybdate into 20mL of deionized water at the temperature of 80 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 80 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 6 hours under the condition of 80 ℃. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 8 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 420 deg.C for 4 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 9: molybdenum salt species and concentration
Dissolving 0.7g of ammonium molybdate and 0.9g of sodium molybdate into 90mL of deionized water at the temperature of 90 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 90 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 12 hours under the condition of 90 ℃. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 11 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 400 deg.C for 4 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 10: type and concentration of iron salt
1.3g of ammonium molybdate is dissolved in 10mL of deionized water at 80 ℃, and concentrated nitric acid is added to adjust the pH value of the solution to 1.5; dissolving 1.3g of ferric chloride into 100mL of deionized water at 80 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 12 hours under the condition of 90 ℃. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 11 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 350 deg.C for 48 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 11: type and concentration of iron salt
Dissolving 1.3g of ammonium molybdate into 140mL of deionized water at 80 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 1.4g of ferrous sulfate into 100mL of deionized water at 90 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed at a flow rate of 10mL/min by respectively using an advection pump, and then aged for 12 hours at 90 ℃. Dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirringStirring for 2h. Filtering, vacuum drying, and roasting at 380 deg.C for 24 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 12: type and concentration of iron salt
Dissolving 1.3g of ammonium molybdate into 100mL of deionized water at 90 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 0.7g of ferrous sulfate and 1.0g of ferric nitrate into 10mL of deionized water at 60 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed at a flow rate of 5mL/min by respectively adopting an advection pump, and then aged for 6h at the temperature of 90 ℃. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 350 deg.C for 4 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 13: cerium salt species and concentration
Dissolving 1.3g of ammonium molybdate into 100mL of deionized water at 80 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 90 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed at a flow rate of 5mL/min by respectively adopting an advection pump, and then aged for 12h at the temperature of 90 ℃. And dissolving 0.2g of cerium chloride into 20mL of deionized water, adjusting the pH value to 8 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 400 deg.C for 12h. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 14: cerium salt species and concentration
Dissolving 1.3g of ammonium molybdate into 100mL of deionized water at 80 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 80 ℃; mixing the ammonium molybdate solution and the ferric nitrate solution at a flow rate of 5mL/min by respectively adopting an advection pump, and then aging at 90 DEG CAnd (4) 12h. And dissolving 0.2g of ammonium ceric nitrate into 2mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 450 deg.C for 4 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 15: cerium salt species and concentrations
1.3g of ammonium molybdate is dissolved in 100mL of deionized water at 80 ℃, and concentrated nitric acid is added to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 70 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 12 hours under the condition of 90 ℃. And dissolving 0.1g of cerium nitrate and 0.1g of ammonium ceric nitrate into 1mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the mixture into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 350 deg.C for 4 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 16: drying mode
1.3g of ammonium molybdate is dissolved in 100mL of deionized water at 80 ℃, and concentrated nitric acid is added to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 80 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 12 hours under the condition of 80 ℃. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 11 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, drying in common air atmosphere, and roasting at 400 deg.C for 24 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 17: drying mode
Dissolving 1.3g of ammonium molybdate into 100mL of deionized water at 60 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; 2.0g of ferric nitrate was dissolved in 100mL of solution at 60 deg.CIonized water; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 12 hours under the condition of 60 ℃. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, freeze drying with liquid nitrogen, and roasting at 400 deg.C for 4 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 18: drying mode
Dissolving 1.3g of ammonium molybdate into 100mL of deionized water at 60 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 60 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed by respectively adopting an advection pump at the flow rate of 5mL/min, and then are aged for 12 hours under the condition of 90 ℃. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 9 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. After suction filtration, the mixture is freeze-dried by liquid nitrogen and then vacuum-dried, and is roasted for 4 hours at 400 ℃. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 19: temperature of roasting
Dissolving 1.3g of ammonium molybdate into 100mL of deionized water at 80 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 80 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed at a flow rate of 5mL/min by respectively adopting an advection pump, and then aged for 12h at the temperature of 90 ℃. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 350 deg.C for 4 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
Example 20: temperature of roasting
Mixing 1.3g of molybdenumDissolving ammonium into 100mL of deionized water at 80 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 70 ℃; the ammonium molybdate solution and the ferric nitrate solution are mixed at a flow rate of 5mL/min by respectively using an advection pump, and then aged for 12 hours at 80 ℃. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 10 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 450 deg.C for 4 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。。
Example 21: drop wise mixing
Dissolving 1.3g of ammonium molybdate into 100mL of deionized water at 80 ℃, and then adding concentrated nitric acid to adjust the pH value of the solution to 1.5; dissolving 2.0g of ferric nitrate into 100mL of deionized water at 60 ℃; the above ferric nitrate solution was added dropwise to an aqueous ammonium molybdate solution to mix, followed by aging at 90 ℃ for 12 hours. And dissolving 0.2g of cerium nitrate into 5mL of deionized water, adjusting the pH value to 8 by using ammonia water, dropwise adding the solution into the aged iron-molybdenum mixed phase, and continuously stirring for 2 hours. Filtering, vacuum drying, and roasting at 400 deg.C for 4 hr. Obtaining the iron-molybdenum-based catalyst (CeO) for preparing formaldehyde by oxidizing methanol 2 /MoO 3 -Fe 2 (MoO 4 ) 3 )。
The catalysts obtained in examples 1, 3, 4, 6, 9, 16, 18, 20 and 21 were subjected to tablet forming to obtain 40 to 60 mesh samples. Under the condition of normal pressure, the reaction temperature is 260 ℃, the volume content of imported methanol is 8.50 percent, and the space velocity of the carrier is 9000h -1 Under the condition, the components of the product are analyzed by on-line chromatography, the conversion rate of the raw material methanol alcohol can reach more than 90 percent, and the selectivity of the formaldehyde can also reach more than 90 percent.
The following table shows the corresponding reaction results of a portion of the catalysts prepared by the process of the present invention
Claims (15)
1. A preparation method of iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation is characterized by comprising the following steps: firstly, respectively dissolving molybdenum salt, ferric salt and cerium salt into water, and adding nitric acid into a molybdenum salt solution to adjust the pH value to 1.0-2.5;
respectively heating the molybdenum salt and the iron salt aqueous solution to 40-90 ℃, and mixing; then aging the sample for 1-48h at 60-90 ℃; regulating the pH value of the cerium salt solution to 8-11, and then dropwise adding the cerium salt solution into the iron-molybdenum mixed solution; then, carrying out suction filtration separation and drying; treating for 2-48h at 350-450 ℃ to obtain a series of iron-molybdenum-based catalysts for preparing formaldehyde by methanol oxidation;
mixing the molybdenum salt and the iron salt aqueous solution by adopting a micro advection pump respectively, injecting the molybdenum salt and the iron salt aqueous solution into a container respectively, and controlling the flow rate of the micro advection pump to be 0.1-1000mL/min.
2. The process for preparing an iron-molybdenum-based catalyst according to claim 1, wherein: the mol ratio of molybdenum atom to iron atom in the catalyst is 1.5-6.5.
3. The process for preparing an iron-molybdenum-based catalyst according to claim 1 or 2, wherein: catalyst promoter component CeO 2 The mass content of the active carbon is controlled to be 0.1-25%.
4. The process for preparing an iron-molybdenum-based catalyst according to claim 1, wherein: the molybdenum salt specifically includes: ammonium molybdate, sodium molybdate, lithium molybdate, potassium molybdate, or one or more of the above components;
the iron salt specifically comprises: ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, or a mixture of one or more of the above components;
the cerium salt specifically includes: cerium nitrate, ammonium ceric nitrate, cerium oxalate, cerium acetate, cerium fluoride, cerium sulfate, or one or more of the above components.
5. The process for preparing an iron-molybdenum-based catalyst according to claim 1 or 4, wherein:
the mass concentration of the molybdenum salt solution is 0.01-10 g/mL;
the mass concentration of the ferric salt solution is 0.01-10 g/mL;
the mass concentration of the cerium salt solution is 0.01-5 g/mL.
6. The process for preparing an iron-molybdenum-based catalyst according to claim 1, wherein: the drying method comprises liquid nitrogen freeze-drying, vacuum drying or two drying methods.
7. The process for preparing an iron-molybdenum-based catalyst according to claim 2, wherein: the mol ratio of molybdenum atom to iron atom in the catalyst is 1.5-4.5.
8. The process for preparing an iron-molybdenum-based catalyst according to claim 5, wherein: the molar ratio of molybdenum atoms to iron atoms in the catalyst is 1.5-2.5.
9. A process for preparing an iron-molybdenum-based catalyst according to claim 3, wherein: catalyst promoter component CeO 2 The mass content of the active carbon is controlled to be 0.1-10%.
10. The process for preparing an iron-molybdenum-based catalyst according to claim 7, wherein: catalyst promoter component CeO 2 The mass content of the active carbon is controlled to be 0.5-5%.
11. The process for preparing an iron-molybdenum-based catalyst according to claim 5, wherein:
the mass concentration of the molybdenum salt solution is 0.1-5g/mL, the mass concentration of the iron salt solution is 0.05-5g/mL, and the mass concentration of the cerium salt solution is 0.05-3 g/mL.
12. The process for preparing an iron-molybdenum-based catalyst according to claim 9, wherein:
the mass concentration of the molybdenum salt solution is 0.2-2g/mL, the mass concentration of the iron salt solution is 0.1-2g/mL, and the mass concentration of the cerium salt solution is 0.1-1 g/mL.
13. A catalyst obtained by the production method according to any one of claims 1 to 12.
14. Use of the catalyst of claim 13 in the oxidation of methanol to formaldehyde.
15. Use of a catalyst according to claim 14, wherein: under the condition of normal pressure, the reaction temperature is 220-350 ℃, the volume content of the imported methanol is 6-10%, and the reaction space velocity is 7500-12500h -1 Under the condition, the conversion rate of methanol is 95-99%, and the yield of formaldehyde is 94-98%.
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