CN114931955A - High-temperature-resistant catalyst for preparing formaldehyde by methanol oxidation and preparation method thereof - Google Patents

High-temperature-resistant catalyst for preparing formaldehyde by methanol oxidation and preparation method thereof Download PDF

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CN114931955A
CN114931955A CN202210573922.6A CN202210573922A CN114931955A CN 114931955 A CN114931955 A CN 114931955A CN 202210573922 A CN202210573922 A CN 202210573922A CN 114931955 A CN114931955 A CN 114931955A
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oxide
catalyst
temperature
parts
magnesium
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乔莎
苏敏
张明胜
赵丹
张新波
郑珩
杜勇
李季
陈鹏
赵安民
华波
郭雄
李倩
李启强
颜智
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Southwest Research and Desigin Institute of Chemical Industry
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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
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/633—Pore volume less than 0.5 ml/g
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    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • 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
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Abstract

The invention provides a high-temperature-resistant catalyst for preparing formaldehyde by methanol oxidation and a preparation method thereof, belonging to the field of catalysts. The catalyst comprises a high-temperature resistant material, an active component, an active assistant and a forming assistant. The high-temperature resistant material comprises a composite oxide of magnesium oxide and aluminum oxide or aluminum oxide and silicon oxide, the active component comprises iron oxide and molybdenum oxide, the active auxiliary agent comprises silver oxide, niobium oxide, zinc oxide and erbium oxide, and the forming auxiliary agent comprises aluminum stearate, calcium stearate, magnesium stearate and graphite. The invention also provides a preparation method of the catalyst. According to the invention, the high-temperature resistant material and the active auxiliary agent are added in the preparation process of the catalyst, so that the catalyst still keeps higher strength and catalytic activity after long-period operation under a high-temperature condition, the yield of formaldehyde prepared by methanol oxidation is high, the thermal stability of the catalyst is good, the service life of the catalyst is prolonged, and the catalyst has a wide industrial application prospect.

Description

High-temperature-resistant catalyst for preparing formaldehyde by oxidizing methanol and preparation method thereof
Technical Field
A high-temperature-resistant catalyst for preparing formaldehyde by methanol oxidation and a preparation method thereof, belonging to the field of catalysts.
Background
Formaldehyde is widely used as a raw material for products such as resins (phenol formaldehyde, urea formaldehyde, melamine-formaldehyde, polyacetal), vinylon, urotropine, 1, 4-butanediol, pentaerythritol, dyes, 4' -diphenylmethane diisocyanate, pyridine and derivatives thereof, pesticides, disinfectants, and the like; is used for synthesizing acrylic acid (ester), polyformaldehyde, polyoxymethylene dimethyl ether and other bulk chemicals. Compared with the silver method, the iron-molybdenum method has the advantages of high formaldehyde concentration and the like, and is widely applied to industry.
The iron-molybdenum catalyst prepared by the method is widely disclosed and reported at present. CN100413584C adds chromium and vanadium oxide in the active component, and uses hollow cylinder ring structure, the catalyst has better thermal stability and longer service life. CN103933998B reduces the reaction temperature by adding elements such as Ni, Bi, Co, Ce, Cr, Li and the like, and improves the low-temperature activity of the catalyst, thereby improving the stability of the catalyst to a certain extent. CN105457648B improves the mass transfer and heat transfer of the catalyst by adding Ni as an auxiliary agent in the catalyst and manufacturing more pore channels, and the stability of the catalyst is higher. CN106693981B reduces the reaction temperature of the catalyst by adding auxiliary agent V to the catalyst. The catalyst prepared by CN107262105A has high specific surface area, large pore diameter and pore volume, and good low-temperature activity, and is beneficial to heat transfer. CN107537577B is used to prepare catalyst precursor with uniform particle size distribution by means of highly dispersed precipitation, and the catalyst has high conversion rate, selectivity and stability. CN107952445A reduces free iron ions by adding a humectant in the drying step, and prolongs the service life of the catalyst. CN108097259A adopts macromolecular heterocyclic compounds such as ferroporphyrin molybdatoporphyrin and the like as raw materials, and the distance, the proportion and the distribution of the iron-molybdenum binary active centers are regulated and controlled in a nano self-assembly mode to realize the high-efficiency conversion of methanol. CN108114744A prepares the iron molybdenum active component in the titanium silicon molecular sieve pore canal, and the catalyst obtained by the preparation can realize the high-efficiency conversion of methanol. CN108816241A is subjected to hydrothermal reaction at a high temperature and a high pressure to obtain a precursor with uniform particle size and larger grain size, and the prepared catalyst has high activity and high selectivity. CN109806881A promotes the dispersion of metal by adding an activator in the synthesis process, and the obtained catalyst has better stability. CN1044339C is washed by non-nitric acid acidified solution, so that the process is simplified, and the prepared catalyst has high stability.
The preparation of formaldehyde by methanol oxidation is a highly exothermic reaction, the control of reaction heat becomes crucial, and the high reaction heat will cause the sublimation of molybdenum oxide in the catalyst under the condition of raw material gas. With the continuous precipitation and loss of molybdenum oxide, iron molybdate in the catalyst is gradually decomposed into ferrous molybdate and iron oxide, so that the catalyst is inactivated, the strength of the catalyst is obviously reduced, the catalyst is gradually crushed and pulverized to block a bed layer, the pressure drop of the bed layer is increased, and the reaction cannot be continued. At present, the service life of the industrial catalyst is 10-12 months, and the service life of the catalyst is short. How to maintain both the strength and activity of the catalyst at high temperatures becomes critical.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant catalyst for preparing formaldehyde by methanol oxidation and a preparation method thereof, wherein the catalyst can keep the performance of the catalyst stable under a high-temperature operation condition, and is suitable for a reaction for preparing formaldehyde by methanol air oxidation in a tubular reactor, and the working condition is 0-0.5 MPa, 240-400 ℃, and the gas space velocity is 5000-12000 h -1 The reaction atmosphere is a gas containing 5-10% by volume of methanol in nitrogen and oxygen.
The purpose of the invention is realized by the following technical scheme:
a high temperature resistant methanol oxidation formaldehyde preparation catalyst comprises a high temperature resistant material, an active component, an active assistant and a forming assistant; the high-temperature resistant material comprises magnesium oxide, aluminum oxide and silicon oxide, and the active component comprises iron oxide and molybdenum oxide; the active auxiliary agent comprises silver oxide, niobium oxide, zinc oxide and erbium oxide; the forming aid comprises aluminum stearate, calcium stearate, magnesium stearate and graphite. The catalyst comprises, by weight, 20-60 parts of a high-temperature resistant material, 40-80 parts of an active component, 0.05-0.5 part of an active assistant and 0.5-2 parts of a forming assistant.
Further, the high-temperature resistant material is magnesia-alumina spinel formed by magnesia and alumina or magnesium silicate formed by magnesia and silica, and the high-temperature resistant material comprises 20-50 parts of magnesia and 60-80 parts of alumina, or 30-58 parts of magnesia and 48-70 parts of silica according to weight percentage.
Further, the active components are iron oxide and molybdenum oxide, an iron molybdate crystal phase and a molybdenum oxide crystal phase are formed through preparation, and the active components comprise 70-82 parts by weight of molybdenum oxide and 18-30 parts by weight of iron oxide.
The active auxiliary agent comprises, by weight, 20-50 parts of silver oxide, 10-30 parts of niobium oxide, 10-30 parts of zinc oxide and 10-30 parts of erbium oxide.
Further, the forming auxiliary agent is one or more of aluminum stearate, calcium stearate, magnesium stearate and graphite.
The catalyst for preparing formaldehyde by high-temperature resistant methanol oxidation has the specific surface area of 1-20m 2 Per g, average pore diameter of 10-30nm, pore volume of 0.05-0.3cm 3 /g。
A preparation method of a high-temperature-resistant catalyst for preparing formaldehyde by methanol oxidation comprises the following steps:
1) mixing ferric nitrate, silver nitrate, zinc nitrate and erbium nitrate to prepare a solution, mixing ammonium molybdate and ammonium niobium oxalate to prepare a solution, mixing the two solutions in a reaction kettle, controlling the reaction temperature to be 40-80 ℃, controlling the pH to be 1.5-3.5, aging for 2-6 h, filtering and washing to prepare a filter cake, drying for 8-24 h at 80-130 ℃, roasting for 2-4 h at 300-600 ℃, grinding and sieving to obtain powder A of an active component;
2) dissolving magnesium nitrate and aluminum nitrate in absolute methanol, stirring for 3-5 h, adding epoxypropane and urea, continuing stirring for 1-3 h, aging at room temperature for 2-5 h, drying to form gel, calcining at a certain temperature, grinding by using a ball mill, drying and sieving to obtain powder B of a high-temperature resistant material;
3) or adding anhydrous methanol and ammonium polyacrylate into magnesium nitrate, stirring the solution in a water bath at 40-70 ℃ for 3-5 h, adjusting the pH to a proper value by using glacial acetic acid to obtain a magnesium source solution, adding anhydrous methanol into Tetraethoxysilane (TEOS), stirring for 3-5 h to obtain a silicon source solution, slowly pouring the silicon source solution into the magnesium source solution, continuously heating and stirring in the water bath for 3-5 h, drying to form gel, calcining at a certain temperature, grinding by using a ball mill, drying, and sieving to obtain powder C of the high-temperature-resistant material;
4) and (2) mixing the high-temperature-resistant material B or C with the active component A in a certain ratio, adding the forming aid and a certain amount of water, uniformly mixing, and preparing a ring with the inner diameter of 1-3 mm, the outer diameter of 4-6 mm and the height of 2-5 mm by adopting a tabletting forming method to obtain the catalyst D for preparing formaldehyde by oxidizing methanol.
Further, the concentrations of the nitrate and the ammonium salt in the deionized water are both 0.01-1 mol/L.
Further, the ratio of the addition amount of the propylene oxide to the total amount of the nitrate in the step 2) is 3-8, and the ratio of the addition amount of the urea to the total amount of the nitrate is 0.5-0.8.
Further, the mass ratio of the adding amount of the ammonium polyacrylate to the magnesium nitrate in the step 3) is 0.01-0.2.
Further, the calcining temperature of the B and the C in the step 2) and the step 3) is 600-1200 ℃, the calcining time is 3-5 hours, and the ball milling time is 8-24 hours.
The application of the high-temperature-resistant catalyst for preparing formaldehyde by methanol oxidation comprises the step of placing the catalyst in a tubular reactor for preparing formaldehyde by methanol air oxidation, wherein the working conditions are 0-0.5 MPa, 260-400 ℃ and gas airspeed of 5000-12000 h -1 And the volume fraction of the methanol is 5-10%.
Compared with the prior art, the invention has the following beneficial effects:
the application provides a high temperature resistant methanol oxidation formaldehyde preparation catalyst, which is characterized in that magnesium aluminate spinel or magnesium silicate high temperature resistant materials are added into traditional active components, so that the performance of the catalyst can be kept stable under the high temperature operation condition. Firstly, the magnesium aluminate spinel and the magnesium silicate have excellent high temperature resistance, can be kept stable at high temperature, and simultaneously provide structural support for the catalyst to prevent the catalyst from being crushed and pulverized at high temperature; secondly, the magnesium aluminate spinel and magnesium silicate materials prepared by the sol-gel method have good pore diameter and specific surface area, can maintain the activity of the catalyst, and cannot cause the activity of the catalyst to be reduced due to the addition of the high-temperature resistant material. Meanwhile, four oxides of silver oxide, niobium oxide, zinc oxide and erbium oxide are used as active auxiliaries, so that the stability of the catalyst is improved, the sublimation of molybdenum oxide in a reaction atmosphere is reduced, and the strength of the catalyst is improved.
Drawings
FIG. 1 is a schematic structural diagram of a catalyst performance testing device
Wherein, the device comprises 1-a methanol storage tank, 2-a plunger pump, 3-a ball valve, 4-a mass flowmeter, 5-a pressure reducing valve, 6-a reactor, 7-a needle valve, 8-a emptying absorption liquid storage tank, 9-a primary absorption storage tank, 10-a secondary absorption storage tank, 11-a gas phase product analysis and 12-a liquid phase product analysis.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment discloses a preparation method of the catalyst, which specifically comprises the following steps:
1) 43.88g Fe (NO) 3 ) 3 ·9H 2 O、0.32g AgNO 3 ·6H 2 O、0.20g Zn(NO 3 ) 2 ·6H 2 O、0.30g Er(NO 3 ) 3 ·5H 2 Dissolving O in 900ml of water to form a mixed aqueous solution, mixing the mixed aqueous solution with 400ml of a solution containing 37.21g of ammonium heptamolybdate and 0.37g of ammonium niobium oxalate in a reaction kettle, controlling the reaction temperature to be 50 ℃, controlling the pH to be 1.5, aging for 3h, filtering and washing to obtain a filter cake, drying for 12h at 100 ℃, and roasting for 4h at 420 ℃ to obtain A;
2) 70.34g Mg (NO) 3 ) 2 ·6H 2 O and 205.81g Al (NO) 3 ) 3 ·9H 2 Dissolving O in absolute methanol, stirring for 4h, adding 286.78g of propylene oxide and 29.66g of urea, continuously stirring for 2h, aging for 3h at room temperature, drying to form gel, calcining for 3h at 800 ℃, grinding for 24h by using a ball mill, and screening out particles with the particle size of more than 200 meshes to obtain B;
3) and mixing A and B, adding 1.95g of aluminum stearate and a certain amount of water, uniformly mixing, and preparing a ring with the inner diameter of 2mm, the outer diameter of 5mm and the height of 3mm by adopting a tabletting and forming method to obtain the catalyst D001 for preparing formaldehyde by methanol oxidation.
Example 2
The embodiment discloses a preparation method of the catalyst, which specifically comprises the following steps:
1) 59.24g Fe (NO) 3 ) 3 ·9H 2 O、0.14g AgNO 3 ·6H 2 O、0.53g Zn(NO 3 ) 2 ·6H 2 O、0.82g Er(NO 3 ) 3 ·5H 2 Dissolving O in 800ml of water to form a mixed aqueous solution, mixing the mixed aqueous solution with 800ml of a solution containing 57.42g of ammonium heptamolybdate and 0.22g of ammonium niobium oxalate in a reaction kettle, controlling the reaction temperature to be 60 ℃, controlling the pH to be 2.0, aging for 3h, filtering and washing to obtain a filter cake, drying for 12h at 100 ℃, and roasting for 4h at 500 ℃ to obtain A;
2) 105.51g Mg (NO) 3 ) 2 ·6H 2 O and 308.71g Al (NO) 3 ) 3 ·9H 2 Dissolving O in absolute methanol, stirring for 5h, adding 215.08g of propylene oxide and 37.07g of urea, continuously stirring for 1h, aging for 4h at room temperature, drying to form gel, calcining for 4h at 1200 ℃, grinding for 20h by using a ball mill, and screening out particles with the particle size of more than 200 meshes to obtain B;
3) and mixing A and B, adding 1.95g of graphite and a certain amount of water, uniformly mixing, and preparing a ring with the inner diameter of 2mm, the outer diameter of 5mm and the height of 3mm by adopting a tabletting and forming method to obtain the catalyst D002 for preparing formaldehyde by methanol oxidation.
Example 3
The embodiment discloses a preparation method of the catalyst, which specifically comprises the following steps:
1) 86.74g Fe (NO) 3 ) 3 ·9H 2 O、0.10g AgNO 3 ·6H 2 O、0.24g Zn(NO 3 ) 2 ·6H 2 O、0.18g Er(NO 3 ) 3 ·5H 2 Dissolving O in 1400ml of water to form a mixed aqueous solution, mixing the mixed aqueous solution with 400ml of a solution containing 75.90g of ammonium heptamolybdate and 0.08g of ammonium niobium oxalate in a reaction kettle, controlling the reaction temperature to be 80 ℃, controlling the pH to be 3.0, aging for 6h, filtering and washing to obtain a filter cake, drying the filter cake for 18h at 100 ℃, and roasting for 4h at 360 ℃ to obtain A;
2) 35.62g Mg (NO) 3 ) 2 ·6H 2 O and 104.23g Al (NO) 3 ) 3 ·9H 2 Dissolving O in absolute methanol, stirring for 5h, adding 145.23g of propylene oxide and 20.02g of urea, continuously stirring for 3h, aging for 5h at room temperature, drying to form gel, calcining for 3h at 1100 ℃, grinding for 18h by using a ball mill, and screening out particles with the particle size of more than 200 meshes to obtain B;
3) and mixing the A and the B, adding 0.99g of calcium stearate and a certain amount of water, uniformly mixing, and preparing a ring with the inner diameter of 2mm, the outer diameter of 5mm and the height of 3mm by adopting a tabletting and forming method to obtain the catalyst D003 for preparing the formaldehyde by oxidizing the methanol.
Example 4
The embodiment discloses a preparation method of the catalyst, which specifically comprises the following steps:
1) 52.30g Fe (NO) 3 ) 3 ·9H 2 O、0.27g AgNO 3 ·6H 2 O、0.27g Zn(NO 3 ) 2 ·6H 2 O、0.20g Er(NO 3 ) 3 ·5H 2 Dissolving O in 1000ml of water to form a mixed aqueous solution, mixing the mixed aqueous solution with 500ml of a solution containing 57.73g of ammonium heptamolybdate and 0.08g of ammonium niobium oxalate in a reaction kettle, controlling the reaction temperature to be 70 ℃, controlling the pH to be 2.5, aging for 6h, filtering and washing to obtain a filter cake, drying for 24h at 120 ℃, and roasting for 3h at 450 ℃ to obtain A;
2) 73.93g Mg (NO) 3 ) 2 ·6H 2 O and 216.32g Al (NO) 3 ) 3 ·9H 2 Dissolving O in absolute methanol, stirring for 4h, adding 301.42g of propylene oxide and 31.17g of urea, continuously stirring for 2h, aging for 5h at room temperature, drying to form gel, calcining for 4h at 900 ℃, grinding for 12h by using a ball mill, and screening out particles with the particle size of more than 200 meshes to obtain B;
3) and mixing A and B, adding 1.23g of magnesium stearate and a certain amount of water, uniformly mixing, and preparing into a ring with the inner diameter of 2mm, the outer diameter of 5mm and the height of 3mm by a tabletting method to obtain the catalyst D004 for preparing formaldehyde by methanol oxidation.
Example 5
The embodiment discloses a preparation method of the catalyst, which specifically comprises the following steps:
1) 44.56g Fe (NO) 3 ) 3 ·9H 2 O、0.09g AgNO 3 ·6H 2 O、0.06g Zn(NO 3 ) 2 ·6H 2 O、0.09g Er(NO 3 ) 3 ·5H 2 Dissolving O in 700ml of water to form a mixed aqueous solution, mixing the mixed aqueous solution with 700ml of a solution containing 34.56g of ammonium heptamolybdate and 0.07g of ammonium niobium oxalate in a reaction kettle, controlling the reaction temperature to be 60 ℃, controlling the pH to be 2.4, aging for 3h, filtering and washing to obtain a filter cake, drying for 8h at the temperature of 110 ℃, roasting for 4h at the temperature of 380 ℃, and preparing to obtain A;
2) 174.34g of Mg (NO) 3 ) 2 ·6H 2 Mixing O and anhydrous methanol, adding 8.72g of ammonium polyacrylate, adding 3.5g of glacial acetic acid, stirring for 3h to obtain a magnesium source solution, simultaneously adding the anhydrous methanol into 118.76g of tetraethoxysilane, stirring for 3h to obtain a silicon source solution, slowly pouring the silicon source solution into the magnesium source solution, continuously heating and stirring in a water bath for 3h, drying to form gel, and calcining at 700 ℃ for 4h to obtain C;
3) and mixing A and C, adding 1.23g of magnesium stearate and a certain amount of water, uniformly mixing, and tabletting to obtain a circular ring with the inner diameter of 2mm, the outer diameter of 5mm and the height of 3mm by adopting a tabletting method to obtain the methanol oxidation formaldehyde catalyst D005.
Example 6
The embodiment discloses a preparation method of the catalyst, which specifically comprises the following steps:
1) 61.93g Fe (NO) 3 ) 3 ·9H 2 O、0.09g AgNO 3 ·6H 2 O、0.22g Zn(NO 3 ) 2 ·6H 2 O、0.17g Er(NO 3 ) 3 ·5H 2 Dissolving O in 1000ml of water to form a mixed aqueous solution, mixing the mixed aqueous solution with 500ml of a solution containing 60.03g of ammonium heptamolybdate and 0.21g of ammonium niobium oxalate in a reaction kettle, controlling the reaction temperature to be 40 ℃, controlling the pH to be 1.5, aging for 5h, filtering and washing to obtain a filter cake, drying for 12h at 130 ℃, roasting for 2h at 480 ℃ to prepare A;
2) 116.82g Mg (NO) 3 ) 2 ·6H 2 O and anhydrous methanolMixing, adding 5.84g of ammonium polyacrylate, adding 2.8g of glacial acetic acid, stirring for 5h to obtain a magnesium source solution, simultaneously adding anhydrous methanol into 63.66g of ethyl orthosilicate, stirring for 5h to obtain a silicon source solution, slowly pouring the silicon source solution into the magnesium source solution, continuously heating and stirring in a water bath for 3h, drying to form gel, and calcining at 900 ℃ for 3h to obtain C;
3) and mixing the A and the C, adding 1.84g of graphite and a certain amount of water, uniformly mixing, and preparing a ring with the inner diameter of 2mm, the outer diameter of 5mm and the height of 3mm by adopting a tabletting and forming method to obtain the methanol oxidation formaldehyde catalyst D006.
Example 7
The embodiment discloses a preparation method of the catalyst, which specifically comprises the following steps:
1) 52.47g Fe (NO) 3 ) 3 ·9H 2 O、0.16g AgNO 3 ·6H 2 O、0.60g Zn(NO 3 ) 2 ·6H 2 O、0.61g Er(NO 3 ) 3 ·5H 2 Dissolving O in 1000ml of water to form a mixed aqueous solution, mixing the mixed aqueous solution with 1000ml of a solution containing 35.60g of ammonium heptamolybdate and 0.25g of ammonium niobium oxalate in a reaction kettle, controlling the reaction temperature to be 80 ℃, controlling the pH to be 2.0, aging for 6h, filtering and washing to obtain a filter cake, drying the filter cake for 18h at 100 ℃, and roasting for 2h at 550 ℃ to obtain A;
2) 205.8g of Mg (NO) 3 ) 2 ·6H 2 Mixing O and anhydrous methanol, adding 6.17g of ammonium polyacrylate, adding 4.2g of glacial acetic acid, stirring for 4h to obtain a magnesium source solution, simultaneously adding the anhydrous methanol into 92.81g of tetraethoxysilane, stirring for 4h to obtain a silicon source solution, slowly pouring the silicon source solution into the magnesium source solution, continuously heating and stirring in a water bath for 5h, drying to form gel, and calcining at 1000 ℃ for 3h to obtain C;
3) and mixing the A and the C, adding 0.99g of calcium stearate and a certain amount of water, uniformly mixing, and preparing a ring with the inner diameter of 2mm, the outer diameter of 5mm and the height of 3mm by adopting a tabletting and forming method to obtain the methanol oxidation formaldehyde catalyst D007.
Example 8
The embodiment discloses a preparation method of the catalyst, which specifically comprises the following steps:
1) 40.79g of Fe (NO) 3 ) 3 ·9H 2 O、0.18g AgNO 3 ·6H 2 O、0.68g Zn(NO 3 ) 2 ·6H 2 O、0.34g Er(NO 3 ) 3 ·5H 2 Dissolving O in 800ml of water to form a mixed aqueous solution, mixing the mixed aqueous solution with 800ml of a solution containing 38.43g of ammonium heptamolybdate and 0.28g of ammonium niobium oxalate in a reaction kettle, controlling the reaction temperature to be 55 ℃, controlling the pH to be 2.2, aging for 4h, filtering and washing to obtain a filter cake, drying for 16h at 130 ℃, and roasting for 4h at 460 ℃ to obtain A;
2) 150.44g Mg (NO) 3 ) 2 ·6H 2 Mixing O and anhydrous methanol, adding 9.03g of ammonium polyacrylate, adding 2.5g of glacial acetic acid, stirring for 5h to obtain a magnesium source solution, simultaneously adding 122.98g of tetraethoxysilane to the anhydrous methanol, stirring for 5h to obtain a silicon source solution, slowly pouring the silicon source solution into the magnesium source solution, continuously heating and stirring in a water bath for 5h, drying to form gel, calcining for 3h at 800 ℃, grinding for 12h by using a ball mill, and screening out particles with the particle size of more than 200 meshes to obtain C;
3) and mixing the A and the C, adding 0.99g of magnesium stearate and a certain amount of water, uniformly mixing, and preparing a ring with the inner diameter of 2mm, the outer diameter of 5mm and the height of 3mm by adopting a tabletting and forming method to obtain the catalyst D008 for preparing the formaldehyde by methanol oxidation.
Example 9
This example is comparative example 1, and compared with example 8, this example does not use a high temperature resistant material, specifically:
1) 40.79g of Fe (NO) 3 ) 3 ·9H 2 O、0.18g AgNO 3 ·6H 2 O、0.68g Zn(NO 3 ) 2 ·6H 2 O、0.34g Er(NO 3 ) 3 ·5H 2 Dissolving O in 800ml of water to form a mixed aqueous solution, mixing the mixed aqueous solution with 800ml of a solution containing 38.43g of ammonium heptamolybdate and 0.28g of ammonium niobium oxalate in a reaction kettle, controlling the reaction temperature to be 55 ℃, controlling the pH to be 2.2, aging for 4h, filtering and washing to obtain a filter cake, drying for 16h at the temperature of 130 ℃, roasting for 4h at the temperature of 460 ℃, and preparing to obtain A;
2) adding 0.99g of magnesium stearate and a certain amount of water into the A, uniformly mixing, and preparing a ring with the inner diameter of 2mm, the outer diameter of 5mm and the height of 3mm by adopting a tabletting and forming method to obtain the catalyst D009 for preparing formaldehyde by oxidizing methanol.
Example 10
This example is comparative example 2, and compared to example 8, this example does not use a coagent, specifically:
1) 40.79g of Fe (NO) 3 ) 3 ·9H 2 Dissolving O in 800ml of water to form a mixed aqueous solution, mixing the mixed aqueous solution with 800ml of a solution containing 38.43g of ammonium heptamolybdate in a reaction kettle, controlling the reaction temperature to be 55 ℃, controlling the pH to be 2.2, aging for 4h, filtering and washing to obtain a filter cake, drying for 16h at 130 ℃, roasting for 4h at 460 ℃ to obtain A;
2) 150.44g Mg (NO) 3 ) 2 ·6H 2 Mixing O and anhydrous methanol, adding 9.03g of ammonium polyacrylate, adding 2.5g of glacial acetic acid, stirring for 5h to obtain a magnesium source solution, simultaneously adding 122.98g of tetraethoxysilane to the anhydrous methanol, stirring for 5h to obtain a silicon source solution, slowly pouring the silicon source solution into the magnesium source solution, continuously heating and stirring in a water bath for 5h, drying to form gel, calcining for 3h at 800 ℃, grinding for 12h by using a ball mill, and screening out particles with the particle size of more than 200 meshes to obtain C;
3) and mixing A and C, adding 0.99g of magnesium stearate and a certain amount of water, uniformly mixing, and tabletting to obtain a ring with the inner diameter of 2mm, the outer diameter of 5mm and the height of 3mm by adopting a tabletting method to obtain the catalyst D010 for preparing formaldehyde by oxidizing methanol.
Testing of catalyst Performance
Methanol enters the device from a methanol storage tank through a plunger pump, enters the reactor after being measured by a ball valve and a mass flow meter, is preheated in the reactor and then is converged with reaction gas, and reacts on a catalyst bed layer. The generated formaldehyde and the by-products and the unreacted methanol are absorbed by two-stage absorption liquid and then enter the gas chromatography for analysis together with unabsorbed gaseous substances respectively.
The catalysts prepared in examples 1 to 10 were each placed in a shell-and-tube reactor and testedIts catalytic performance and axial compression strength before and after reaction. Controlling the hot spot temperature of the catalyst bed layer to be 400 ℃ and the space velocity to be 8000h -1 And the activity evaluation is carried out in the air atmosphere containing 5.5 percent of methanol volume fraction under the normal pressure condition, and the test results are detailed in table 1 after the reaction is carried out for 1000 hours.
TABLE 1 catalyst Performance and Strength test results
Figure BDA0003661315660000121
As can be seen from Table 1 above, the catalyst of the present invention has a high formaldehyde yield and a high strength after 1000 hours of operation. The high-temperature resistant material improves the heat resistance of the catalyst, provides good structural support for the catalyst, and the active auxiliary agent reduces the sublimation of molybdenum oxide of the catalyst under the high-temperature condition. In contrast, in comparative examples 1 and 2, the activity and strength of the catalysts D009 and D010 after 1000h of operation were greatly reduced. The D009 is not added with the high temperature resistant material, so that the strength is greatly reduced; d010 has no addition of the active assistant, and the activity reduction range is large. Therefore, the combined action of the high-temperature resistant material and the active assistant is shown, so that the catalyst still keeps higher strength and catalytic activity after long-term operation under the high-temperature condition, and the catalyst can stably operate for a long time.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A high temperature resistant catalyst for preparing formaldehyde by methanol oxidation is characterized by comprising a high temperature resistant material, an active component, an active assistant and a forming assistant; the high-temperature resistant material is a composite oxide consisting of magnesium oxide and aluminum oxide or magnesium oxide and silicon oxide; the active component comprises iron oxide and molybdenum oxide; the active auxiliary agent comprises silver oxide, niobium oxide, zinc oxide and erbium oxide, and the forming auxiliary agent is any one or more of aluminum stearate, calcium stearate, magnesium stearate and graphite; the catalyst comprises, by weight, 20-60 parts of a high-temperature resistant material, 40-80 parts of an active component, 0.05-0.5 part of an active assistant and 0.5-2 parts of a forming assistant.
2. The catalyst for preparing formaldehyde by high-temperature-resistant methanol oxidation according to claim 1, which is characterized in that: the high-temperature resistant material is magnesia-alumina spinel formed by magnesia and alumina; or magnesium silicate formed from magnesium oxide and silicon oxide; the high-temperature resistant material comprises, by weight, 20-50 parts of magnesium oxide and 60-80 parts of aluminum oxide; or 30-58 parts of magnesium oxide and 48-70 parts of silicon oxide.
3. The catalyst for preparing formaldehyde by high-temperature-resistant methanol oxidation according to claim 1 or 2, which is characterized in that: the active component is an iron oxide crystal phase and a molybdenum oxide crystal phase which are prepared from two substances of iron oxide and molybdenum oxide, and comprises 70-82 parts of molybdenum oxide and 18-30 parts of iron oxide in parts by weight; the active auxiliary agent comprises four components of silver oxide, niobium oxide, zinc oxide and erbium oxide, and comprises, by weight, 20-50 parts of silver oxide, 10-30 parts of niobium oxide, 10-30 parts of zinc oxide and 10-30 parts of erbium oxide.
4. The method for preparing the catalyst for preparing formaldehyde by high-temperature-resistant methanol oxidation according to claim 3, which comprises the following steps:
1) mixing ferric nitrate, silver nitrate, zinc nitrate and erbium nitrate to prepare a solution, mixing ammonium molybdate and ammonium niobium oxalate to prepare a solution, mixing the two solutions in a reaction kettle, controlling the reaction temperature to be 40-80 ℃, controlling the pH to be 1.5-3.5, aging for 2-6 h, filtering and washing to prepare a filter cake, drying for 8-24 h at the temperature of 80-130 ℃, roasting for 2-4 h at the temperature of 300-600 ℃, grinding and sieving to obtain powder A of an active component;
2) dissolving magnesium nitrate and aluminum nitrate in absolute methanol, stirring for 3-5 h, adding epoxypropane and urea, continuing stirring for 1-3 h, aging at room temperature for 2-5 h, drying to form gel, calcining at a certain temperature, grinding by using a ball mill, drying and sieving to obtain powder B of a high-temperature resistant material;
3) adding anhydrous methanol and ammonium polyacrylate into magnesium nitrate, stirring the solution in a water bath at 40-70 ℃ for 3-5 h, adjusting the pH value to a proper value by using glacial acetic acid to obtain a magnesium source solution, adding anhydrous methanol into tetraethoxysilane, stirring for 3-5 h to obtain a silicon source solution, slowly pouring the silicon source solution into the magnesium source solution, continuously heating and stirring in the water bath for 3-5 h, drying to form gel, calcining at a certain temperature, grinding by using a ball mill, drying, and sieving to obtain powder C of a high-temperature resistant material;
4) and mixing the high-temperature resistant material B or C with the active component A in a certain proportion, adding the forming aid and a certain amount of water, uniformly mixing, and preparing the catalyst D for preparing formaldehyde by methanol oxidation by adopting a tabletting forming method.
5. The preparation method of the catalyst for preparing formaldehyde through high-temperature-resistant methanol oxidation according to claim 4, wherein the concentrations of the nitrate and the ammonium salt in the deionized water in the step 1) are both 0.01-1 mol/L.
6. The method according to claim 4, wherein the ratio of the amount of propylene oxide to the total amount of nitrates added in step 2) is 3 to 8, and the ratio of the amount of urea to the total amount of nitrates added is 0.5 to 0.8.
7. The method according to claim 4, wherein the ratio of the amount of ammonium polyacrylate added to the amount of magnesium nitrate in step 3) is 0.01-0.2.
8. The preparation method of the catalyst for preparing formaldehyde through high-temperature-resistant methanol oxidation according to claim 4, wherein the calcining temperature of B and C in the steps 2) and 3) is 600-1200 ℃, the calcining time is 3-5 hours, and the ball milling time is 8-24 hours.
9. The catalyst for preparing formaldehyde by the oxidation of methanol with high temperature resistance prepared by any one of claims 4 to 8, wherein the specific surface area of the catalyst is 1 to 20m 2 Per g, average pore diameter of 10-30nm, pore volume of 0.05-0.3cm 3 /g。
10. The application of the high temperature resistant catalyst for preparing formaldehyde by methanol oxidation according to claim 9, wherein the catalyst is placed in a tubular reactor for the reaction for preparing formaldehyde by methanol oxidation, and the working conditions are that the pressure is 0-0.5 MPa, the temperature is 240-400 ℃, and the gas space velocity is 5000-12000 h -1 The reaction atmosphere is a gas containing 5-10% by volume of methanol in nitrogen and oxygen.
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