CN108722455B - Preparation method of vanadium phosphorus oxide catalyst - Google Patents

Preparation method of vanadium phosphorus oxide catalyst Download PDF

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CN108722455B
CN108722455B CN201710261218.6A CN201710261218A CN108722455B CN 108722455 B CN108722455 B CN 108722455B CN 201710261218 A CN201710261218 A CN 201710261218A CN 108722455 B CN108722455 B CN 108722455B
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reaction
vanadium
catalyst
ionic liquid
phosphorus oxide
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CN108722455A (en
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薛冬
吕振辉
白富栋
李政
张通
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J35/613—
    • B01J35/633—
    • B01J35/647—
    • B01J35/69—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride

Abstract

The invention discloses a preparation method of a vanadium phosphorus oxide catalyst, which comprises the following steps: (1) mixing the ionic liquid I and vanadium pentoxide, putting into an impinging stream reactor, a fluidized bed reactor or a supergravity reactor, and heating for reaction; (2) introducing concentrated phosphoric acid into the reactor, reacting for 2-4 h, introducing ionic liquid II, continuing to react for 2-4 h, filtering, drying and roasting to obtain a vanadium-phosphorus-oxygen catalyst precursor, and then performing activation molding to obtain the catalyst. The vanadium-phosphorus-oxygen catalyst obtained by the method has double pore channel distribution, and the ionic liquid is used as a solvent and a reducing agent, so that the dosage of the solvent and the reducing agent is effectively reduced; and the impinging stream reactor is adopted, so that the reaction time is short, the mass transfer effect is good, the reaction efficiency is high, and the production cost is saved.

Description

Preparation method of vanadium phosphorus oxide catalyst
Technical Field
The invention relates to a preparation method of a vanadium phosphorus oxide catalyst, which is suitable for being used as a catalyst for a reaction of preparing maleic anhydride by n-butane oxidation.
Background
Maleic anhydride is called maleic anhydride for short, and is also called maleic anhydride, is an important organic chemical raw material and a fine chemical product, is the third anhydride which is only second to phthalic anhydride and acetic anhydride in the world at present, and has very wide development and utilization prospects.
The three basic routes for maleic anhydride production are: benzene oxidation method, butane oxidation method, butene (C)4Fraction) oxidation process. The technology for producing maleic anhydride by using n-butane as a raw material has the advantages of low cost of the raw material, small environmental pollution and low manufacturing cost of the maleic anhydride, and is a main route for producing the maleic anhydride at present. The preparation of maleic anhydride by selective oxidation of n-butane is the only low-carbon alkane selective oxidation reaction for realizing industrial application at present, the catalyst is the key of the process, and the Vanadium Phosphorus Oxide (VPO) catalyst is the most effective catalyst for the reaction.
The VPO catalyst is a catalyst with a complex micro-scaleThe composite oxide catalyst with the structure has various phases prepared from a precursor VOHPO4·0.5H2The crystal appearance and the grain size of the precursor directly influence the crystal appearance and the phase composition of the catalyst. The catalytic activity of the catalyst is greatly related to the preparation method of the precursor, and the preparation process of the catalyst has great influence on the catalytic performance. In order to improve the activity and selectivity of the vanadium phosphorus oxide catalyst and improve the economic benefit of the existing device, people carry out intensive research on the preparation method of the vanadium phosphorus oxide catalyst.
USP4,632,915 provides a method for preparing a vanadium phosphorus oxide catalyst, which comprises the steps of adding isobutanol, phosphoric acid (100%), vanadium pentoxide, lithium chloride and iron powder into a stirring reaction kettle with a reflux cooler under cooling, then introducing hydrogen chloride gas, refluxing for more than 2.5 hours at 102 ℃ to obtain a catalyst precursor, and then drying, roasting, forming and activating to prepare the vanadium phosphorus oxide catalyst. The catalyst has high catalytic activity, the butane conversion rate is more than 78.1 percent, and the molar yield of the maleic anhydride is 54.5 percent.
CN1090224A proposes a preparation method for improving the performance of a vanadium phosphorus oxygen catalyst, which comprises placing vanadium pentoxide and zinc sulfate in a three-neck flask with a stirrer and a spherical reflux condenser, adding a proper amount of concentrated sulfuric acid and an alcohol solvent for mixing, heating and refluxing for 2 hours, then dropwise adding a phosphoric acid solution, and continuously refluxing for 8 hours; and dropwise adding the fourth component or other rare earth metal compounds or transition metal compounds into the bottle, refluxing for 5 hours, and filtering to obtain the lake blue catalyst precursor. After the molding, a fixed bed tubular reactor is adopted for carrying out catalyst activation and evaluation tests: the conversion rate of butane is more than 90 percent, and the molar yield of maleic anhydride is 62 percent.
[ influence of addition of additive Mo on catalytic performance of VPO catalyst-based maleic anhydride ], jiang forest and the like, inner mongolian petrochemical industry, 2006, 9: 25-27 describes a preparation method of a VPO catalyst. A certain amount of V2O5Adding the mixture into a benzyl alcohol solvent, adding metal elements such as Mo, Zr, Cr, Co and the like according to a certain atomic ratio, using isobutanol as a reducing agent, reacting for 6 hours at a reflux temperature, and then adding the mixture into a methanol solvent according to an atomic ratio of V: p = 1: 1.2 dropping a certain amount of 85% H3PO4And continuously heating for reaction for 6 hours to obtain a dark green solution. And filtering and washing the solution, putting the evaporated solution into an oven, and drying at the temperature of 110 ℃ to obtain a dark green catalyst precursor. After the precursor powder is molded, the activation airspeed is 1500h in the mixed gas of n-butane and air with the volume fraction of 1.5 percent-1And after the reaction is activated for 24 hours at the reaction temperature of 400 ℃, the yield of the maleic anhydride is measured to be more than 60 percent.
In the method, the organic solvent is introduced in the synthesis process, the unfavorable impurities are inevitably introduced in the catalyst, and the used solvent and the reducing agent have the defects of low thermal stability and easy volatilization, and easily generate a large amount of toxic and harmful waste liquid and waste gas to cause environmental pollution. In addition, the reaction process adopts a conventional stirring mode, the interphase mass transfer efficiency is low, the reaction time is long, and the production cost is high.
Disclosure of Invention
Aiming at the defects that in the prior art, excessive organic solvents are used in the preparation of the vanadium-phosphorus-oxygen catalyst, impurities are introduced, and environmental pollution is caused, the invention provides the vanadium-phosphorus-oxygen catalyst and a preparation method thereof. The method adopts the ionic liquid as the solvent and the reducing agent, effectively reduces the dosage of the solvent and the reducing agent, reduces the environmental pollution, adopts the impinging stream reactor, has good interphase mass transfer effect, high reaction efficiency and short reaction time, and saves the production cost.
The invention provides a preparation method of a vanadium phosphorus oxygen catalyst, which comprises the following steps:
(1) will M1And M2Adding the mixture into water, stirring, heating, reacting at constant temperature, cooling, centrifuging and filtering after the reaction is finished to obtain ionic liquid I;
will M3And M4Mixing, reacting at constant temperature to obtain intermediate product, cooling, washing, drying, adding into acetone, and adding M1Stirring and reacting at room temperature, performing suction filtration and washing, combining a washing solution with the filtrate, drying by using a drying agent, and performing rotary evaporation to obtain acetone and water to obtain an ionic liquid II;
(2) mixing the ionic liquid I and vanadium pentoxide, putting the mixture into a reactor, wherein the reactor is selected from one of an impinging stream reactor, a fluidized bed reactor and a supergravity reactor, and heating to 95-130 ℃ to react the materials for 1-4 h; introducing concentrated phosphoric acid, continuously reacting for 1-4 h, introducing ionic liquid II, continuously reacting for 2-6 h, and filtering, drying and roasting after the reaction is finished to obtain a vanadium-phosphorus-oxygen catalyst precursor;
(3) the vanadium phosphorus oxide catalyst precursor is subjected to activation and post-forming or treatment of activation and post-forming to obtain the vanadium phosphorus oxide catalyst;
if a vanadium phosphorus oxide catalyst containing a metal oxide is prepared, it can be introduced in three ways: i, in the step (2), adding soluble salt of metal and vanadium pentoxide into the ionic liquid I; II is introduced before or during the forming of the vanadium phosphorus oxide catalyst; III is introduced in a dipping mode after the vanadium phosphorus oxygen catalyst is formed;
the M is1Is at least one of ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium hexafluorophosphate, sodium hexafluorophosphate or potassium hexafluorophosphate;
the M is2Has the general formula (R)1R2R3R4）N+Z-In which R is1、R2、R3And R4Each independently selected from H or C1-C4 alkyl, and R1、R2、R3And R4The sum of C atoms is less than or equal to 4, Z is halogen and is one of F, Cl or Br;
the M is3Is at least one of imidazole, alkyl imidazole, pyridine and alkyl pyridine;
the M is4Is halogenated alkyl alcohol with the general formula Z (CH)2)nCH2OH、Z(CH2)nCHOHCH2OH or Z (CH)2)nCHOHCH2CH2The structure of OH, wherein n is an integer of 0-9, Z is halogen and is F, Cl or Br.
Further, said M1Preferably ammonium hexafluorophosphate and/or tetrakisAmmonium fluoroborate.
Further, said M2In the general formula (II), R1、R2、R3And R4Each independently selected from H, methyl or ethyl, Z is preferably chloro, more preferably, M is2Selected from dimethyl ammonium chloride and/or diethyl ammonium chloride.
Further, said M4Most preferred is chlorohydrin.
In the process of the present invention, M in step (1)1And M2In a molar ratio of 1: 1-1: and 2, the reaction temperature is 60-150 ℃, preferably 70-100 ℃, and the constant-temperature reaction time is 1-4 hours, preferably 1-2 hours.
In the process of the present invention, M in step (1)3And M4In a molar ratio of 1: 1-1: and 2, the reaction temperature is 70-100 ℃, preferably 70-90 ℃, and the constant-temperature reaction time is 20-30 hours, preferably 20-24 hours.
In the method, the drying temperature of the intermediate product in the step (1) is 60-100 ℃, and preferably 70-90 ℃; the drying time is 24-50 h, preferably 30-48 h.
In the process of the present invention, the intermediate in step (1) is reacted with M1In a weight ratio of 0.5: 1-3: 1, preferably 1: 1-2: 1; the weight ratio of the intermediate product to acetone is 0.1: 1-1: 1, preferably 0.2: 1-0.5: 1.
in the method, the weight ratio of the ionic liquid I to the vanadium pentoxide in the step (2) is 5: 1-15: 1; the weight ratio of the ionic liquid II to the vanadium pentoxide is 1: 1-10: 1.
In the method, the mass percentage concentration of the concentrated phosphoric acid in the step (2) is 85-100%; the adding amount of the concentrated phosphoric acid is 0.85 in terms of the molar ratio of phosphorus to vanadium in the system: 1-1.35: 1.
in the method, the reaction temperature in the step (2) is 95-130 ℃, and the reaction time is 1-3 h. And continuing to react for 2-4 h after adding concentrated phosphoric acid. And (4) continuing to react for 2-4 h after adding the ionic liquid II.
In the method, when the impinging stream reactor is used in the step (2), the impinging stream reactor is preferably an immersed circulation type impinging stream reactor, the rotating speed of a propeller in the reaction process is 750 r/min-4500 r/min, preferably 1500 r/min-3500 r/min, and the reaction is normal pressure. When the reactor used in the step (2) is a boiling bed reactor, the reaction materials are kept in a boiling state in the reaction process, and the product can be directly dried, roasted and activated in the boiling bed reactor after the reaction is finished. When the reactor used in the step (2) is a supergravity reactor, the rotating speed is controlled to be 800-2000 r/min in the reaction process.
In the above method, the metal oxide is at least one selected from stable oxides of Co, Ni, Zn, Bi, Zr, Cu, Li, K, Ca, Mg, Ti, La, Mo, Nb, B, Fe, Cr and Ce, and the molar ratio of the metal element to V in the metal oxide is 0.001-0.2.
In the method, the drying agent in the step (1) is anhydrous MgSO4。
In the method of the invention, the drying conditions in the step (2) are as follows: drying for 8-12 hours at the temperature of 95-170 ℃; the roasting conditions are as follows: roasting at 200-280 deg.c for 4-8 hr.
In the method, the activation in the step (3) is carried out in the atmosphere of one or a combination of a nitrogen/air mixed gas, a steam/air mixed gas or a butane/air mixed gas, and the activation temperature is 350-450 ℃, preferably 375-425 ℃; the activation time is 5 to 40 hours, preferably 12 to 20 hours.
In the method, the forming mode in the step (3) is strip extrusion, sheet beating or balling.
The invention also provides the vanadium phosphorus oxygen catalyst prepared by the method, and the catalyst prepared by the method is (VO)2P2O7The vanadium phosphorus oxide catalyst is 80-95% in volume, and has dual pore channel distribution with the pore diameter of 10-20 nm and 20-35 nm, wherein the pore channel with the pore diameter of 10-20 nm accounts for 29-36% of the total pore volume, and the pore channel with the pore diameter of 20-35 nm accounts for 34-45% of the total pore volume. The molar ratio of phosphorus to vanadium in the catalyst is 0.85-1.35, preferably 0.95-1.20, and the specific surface area is 42-64 m2The pore volume is 0.04-0.1 mL/g.
Further, the method comprisesIn the vanadium phosphorus oxide catalyst (VO)2P2O7The content is 85-90% by volume.
The vanadium phosphorus oxygen catalyst can be used as a catalyst in the reaction of preparing maleic anhydride by n-butane oxidation, and has high n-butane conversion rate and good maleic anhydride selectivity. Wherein the reaction for preparing the maleic anhydride by the oxidation of the n-butane can adopt a fixed bed, a fluidized bed or a moving bed reaction mode; the reaction conditions for preparing maleic anhydride by oxidizing n-butane are generally as follows: the reaction temperature is 380-450 ℃, the pressure is normal pressure-0.5 MPa, and the space velocity of the n-butane mixed gas is 1000-3500 h-1The concentration of n-butane is 1.0-1.8% (volume percentage).
Compared with the prior art, the vanadium phosphorus oxide catalyst and the preparation method thereof have the following characteristics:
1. the vanadium phosphorus oxidation catalyst of the invention has a double-pore structure, the pore channels are more abundant, the specific surface area is increased, the diffusion of reaction molecules in the pore channels is accelerated, and the accessible active sites are increased, so the pore channel utilization rate is improved. Meanwhile, due to rich double pore channels, the molecular diffusion path is shortened, the carbon deposition inactivation rate is slowed down, and macromolecules are easy to diffuse, so that the service life of the catalyst is effectively prolonged.
2. The conventional preparation method of the vanadium phosphorus oxide catalyst needs to use a large amount of solvent and reducing agent, has low thermal stability, is easy to volatilize, and is easy to generate a large amount of toxic and harmful waste liquid and waste gas, thereby causing environmental pollution and equipment corrosion. In the method, two ionic liquids are added in the synthesis process of the precursor, one of the ionic liquids is used as a solvent, and the other ionic liquid is used as a reducing agent. The method avoids the introduction of impurities which are unfavorable for the catalyst, the room-temperature ionic liquid has the advantages of non-volatility and good thermal stability, and a large amount of toxic and harmful waste liquid and waste gas are not used and discharged in the reaction, so the method is environment-friendly.
3. In the method, the ionic liquid is easy to separate from the product after the reaction is finished, and can be recycled, so that the production cost is reduced.
4. In the preparation process of the catalyst, the selection of the reactor strengthens the inter-phase transfer effect, so that the contact area between the reaction liquid and the granular solid material is increased, the mass and heat transfer is promoted, the reaction efficiency is greatly improved, and the reaction time is shortened.
Detailed Description
The specific preparation process of the vanadium-phosphorus oxide comprises the following steps:
(1) preparation of ionic liquids
Will M1And M2Adding to water, M1And M2In a molar ratio of 1: 1-1: and 2, heating to the reaction temperature of 60-150 ℃ under the stirring condition, reacting for 1-4 h at constant temperature, cooling to room temperature after the reaction is finished, centrifuging, and filtering to obtain the ionic liquid I.
Will M3And M4Mixing, M3And M4In a molar ratio of 1: 1-1: 2, reacting at the constant temperature of 70-100 ℃ for 20-30 hours to obtain colorless viscous liquid, cooling to room temperature, washing with diethyl ether for 2-6 times, drying at 60-100 ℃ for 24-50 hours to obtain an intermediate product, adding the intermediate product into acetone, and adding M1Stirring at room temperature, filtering, washing, mixing the washing liquid with the filtrate, and adding anhydrous MgSO4Drying, and performing rotary evaporation to remove acetone and water to obtain the ionic liquid II.
(2) Preparation of vanadium phosphorus oxidation catalyst precursor
Mixing the ionic liquid I and vanadium pentoxide, putting into a reactor, and heating to 95-130 ℃ to enable materials to have an impact reaction for 1-4 hours; and then introducing a certain amount of concentrated phosphoric acid into the reactor, continuing to react for 1-4 hours, introducing an ionic liquid II, continuing to react for 2-6 hours, cooling the reaction liquid to room temperature after the reaction is finished, filtering, preferably naturally drying the filter cake at room temperature for 10-24 hours, then drying in a baking oven at 95-170 ℃ for 8-12 hours, and finally roasting in a muffle furnace at 200-280 ℃ for 4-8 hours to obtain a black brown vanadium-phosphorus oxide, namely a vanadium-phosphorus-oxygen catalyst precursor.
(3) Preparation of vanadium phosphorus oxide catalyst
Molding the vanadium phosphorus oxide catalyst precursor obtained in the step (2) to obtain a vanadium phosphorus oxide catalyst intermediate, and then activating; or the obtained vanadium phosphorus oxide catalyst precursor is activated to obtain a vanadium phosphorus oxide catalyst intermediate, and the vanadium phosphorus oxide catalyst is obtained by molding.
The prepared vanadium phosphorus oxide catalyst can be in the shapes of tablets, spheres, extruded strips and the like, and the phase of the catalyst is mainly vanadyl pyrophosphate ((VO)2P2O7) And (4) phase(s).
The above-described forming process may generally include: adding 3-5% graphite powder into vanadium phosphorus oxide catalyst precursor powder (or activated vanadium phosphorus catalyst intermediate), mixing, and extruding into catalyst with certain shape, such as column or other special shapes, by rotary tablet press with proper adjustment of impact force.
For those skilled in the art, the vanadium phosphorus oxide catalyst precursor powder (or the activated catalyst intermediate) can be used to prepare different types of catalysts by other forming methods, and can be applied to a fixed bed, a heat exchange reactor, a fluidized bed reactor or a moving bed reactor. For example, the vanadium phosphorus oxide catalyst precursor powder (or the activated catalyst intermediate) may be formed by extrusion with a suitable binder or lubricant, and the binder or lubricant may be starch, calcium stearate, stearic acid or graphite. Or combined with carrier to prepare supported catalyst, where the carrier can be silicon dioxide or Al2O3、TiO2、ZrO2Molecular sieves, and the like. Similarly, the precursor of the shaped catalyst may be formed into catalyst microspheres for use in fluidized beds and moving beds, and the details of the operation of these reactors are well within the skill of those in the art.
The activation method comprises the following steps: the vanadium phosphorus oxidation catalyst precursor powder (or the molded catalyst intermediate) is placed in a tubular calciner with an activating atmosphere. The activating atmosphere may be a butane/air mixture (butane volume concentration is 0.5% to 1.5%, preferably 0.8% to 1.2%), an air/steam mixture (steam volume concentration is 25% to 75%, preferably 35% to 55%), a nitrogen/steam mixture (steam volume concentration is 25% to 75%, preferably 35% to 55%), or the like. Raising the activation temperature from room temperature to 350-450 ℃, preferably 375-425 ℃; the activation time is generally 5 to 40 hours, preferably 12 to 20 hours. And (5) finishing the activation process to obtain the vanadium-phosphorus-oxygen catalyst.
The performance of the prepared vanadium phosphorus oxide catalyst can be evaluated according to the following method: the prepared vanadium phosphorus oxygen catalyst is loaded into a fixed bed reactor, reaction mixed gas is introduced, and the composition of a reaction product is analyzed by gas chromatography. The reaction conditions were evaluated as follows: the reaction temperature is 380-450 ℃, the pressure is normal pressure-0.5 MPa, and the space velocity of the n-butane mixed gas is 1000-3500 h-1And the butane concentration is 1.0-1.8% (volume percentage), and the activity evaluation test of the catalyst is carried out.
The technical solution of the present invention is further described in detail with reference to the following specific examples. The following examples are not intended to limit the scope of the present invention, and those skilled in the art can make appropriate extensions in combination with the present specification and the entire text, and such extensions should be construed as the scope of the present invention.
The reagents used in examples and comparative examples, ammonium tetrafluoroborate, sodium tetrafluoroborate, Wuhan Haider chemical development Co., Ltd; dimethyl ammonium chloride, methyl ammonium chloride, diethyl ammonium chloride, Qingdao Jinma chemical Co., Ltd; chlorohydrin, N.K., Wen chemical Co., Ltd, Yixing City; chlorobutanol, Jiangsu Yonghua fine Chemicals, Inc.; chlorohexanol, Ziboshenno chemical Co., Ltd; imidazole, methylimidazole, yabang chemical (shanghai) ltd; isobutanol, Tianjin, photo-induced chemical research institute; benzyl alcohol, shinyleaf fine chemical research institute of Tianjin; vanadium pentoxide, fuchen chemical reagent factory, Tianjin; phosphoric acid, Shenyang Tiangang chemical reagent plant. The specific surface area, the pore volume and the pore diameter of the vanadium-phosphorus oxide are measured by an Autosorb3b type full-automatic specific surface area and pore diameter distribution instrument of Quantachrome company in the United states.In the vanadium phosphorus oxide catalyst (VO)2P2O7And fitting the volume content of the crystalline phase according to the peak area in the XRD spectrogram.
Example 1
300g of dimethyl ammonium chloride, 190g of ammonium tetrafluoroborate and 450g of pure water are mixed, heated to 80 ℃ under stirring, kept at the constant temperature for 1 hour, clarified, naturally cooled to about 30 ℃, and centrifugally filtered to obtain 300g of ionic liquid I, wherein the ionic liquid I contains about 3.5wt% of water and the yield is 73 wt%.
Taking 1.92 mol of chloroethanol and 1.28mol of methylimidazole, refluxing for 24h at 80 ℃ under the condition of microwave heating, reacting to obtain viscous colorless transparent liquid, cooling to room temperature, washing with diethyl ether for four times to obtain colorless crystal 1-hydroxyethyl-3-methylimidazole chloride ion liquid, and drying for 48h at 80 ℃ in a vacuum drying oven. Adding 100g (0.6 mol) of dried 1-hydroxyethyl-3-methylimidazole chloride ionic liquid into 600ml of acetone, adding 72g (0.68 mol) of sodium tetrafluoroborate, stirring at room temperature for 24h, carrying out suction filtration, washing filter residues to obtain waxy solid, washing twice with acetone, combining washing liquid and filtrate, and using anhydrous MgSO (MgSO) to obtain the final product4Drying overnight, rotationally evaporating out acetone at 40 ℃, and rotationally evaporating water in an oil bath at 100 ℃ for 2 hours to obtain pure 1-hydroxyethyl-3-methylimidazolium fluoroborate ionic liquid.
Mixing ionic liquid I300g and vanadium pentoxide 30.0g in an immersed circulating impinging stream reactor, putting the mixture into the reactor through a feed inlet, starting the reactor, adjusting the revolution of a propeller to 800r/min, and heating to 95 ℃ to enable the materials to undergo impinging reaction for 2 hours; and then introducing 38.0g of concentrated phosphoric acid with the concentration of 85% into the reactor, wherein the molar ratio of phosphorus to vanadium is 1.0, continuing to react for 2 hours, introducing ionic liquid II, continuing to react for 3 hours, cooling the reaction liquid to room temperature after the reaction is finished, filtering, preferably naturally drying the filter cake for 24 hours at room temperature, then drying the filter cake for 8 hours in a 100 ℃ oven, and finally roasting the filter cake for 4 hours at 220 ℃ in a muffle furnace to obtain the black brown vanadium-phosphorus oxide, namely the vanadium-phosphorus oxide catalyst precursor.
Putting the precursor powder of the vanadium phosphorus oxygen catalyst prepared above into a tubular roasting furnace, introducing a butane/air mixed gas (the volume concentration of butane is 0.8 percent), quickly raising the activation temperature from room temperature to 250 ℃, and then slowly raising the activation temperatureHeating to 400 ℃ and keeping for 20 hours, and finishing the activation process to obtain the vanadium-phosphorus-oxygen catalyst. The obtained catalyst has a crystalline phase (VO) detected by XRD2P2O7Phase (91% by volume). The specific surface area is 60m2The pore volume is 0.06ml/g, the pore distribution is dual, and the pore diameter is 10-20 nm and 20-35 nm; wherein the 10-20 nm pore distribution accounts for 28% of the total pore volume, and the 20-35 nm pore distribution accounts for 40% of the total pore volume.
Adding the catalyst into graphite powder with the mass fraction of 4%, fully mixing, properly adjusting the impact strength by adopting a rotary tablet press, and extruding into a column shape. Crushing and screening the catalyst particles to prepare the catalyst particles. 5mL of catalyst particles (5-10 meshes) are weighed and placed in a stainless steel reaction tube with the inner diameter of 10 mm. At the reaction temperature of 380 ℃, the reaction pressure of 0.25MPa, the reaction gas is n-butane/air mixed gas with butane volume concentration of 1.5 percent, and the gas volume space velocity is 1750h-1The catalytic performance was evaluated under the reaction conditions of (1). Through gas chromatographic analysis, the conversion rate of the n-butane is 95 percent (mol) and the selectivity of the maleic anhydride reaches 73 percent (mol).
Example 2
250g of diethylammonium chloride, 180g of ammonium tetrafluoroborate and 400g of pure water are mixed, heated to 90 ℃ under stirring, kept at the constant temperature for 1.5h, clarified, naturally cooled to about 30 ℃, and centrifugally filtered to obtain 260g of ionic liquid I, wherein the water content is about 3.5wt%, and the yield is 73 wt%.
The procedure for the preparation of 1- (4' -hydroxy) butyl-3-methylimidazolium fluoroborate ionic liquid was the same as in example 1.
Mixing an ionic liquid I250g, vanadium pentoxide 30.0g, an auxiliary agent ferric nitrate hexahydrate 0.3g and an auxiliary agent zirconium nitrate 0.5g in an immersed circulating impinging stream reactor, putting the mixture into the reactor through a feed inlet, starting the reactor, adjusting the rotation number of a propeller to 900r/min, and heating to 95 ℃ to enable the materials to carry out impinging reaction for 2 hours; and then introducing 35.5g of concentrated phosphoric acid with the concentration of 100% into the reactor, wherein the molar ratio of phosphorus to vanadium is 1.1, continuing to react for 2.5 hours, introducing ionic liquid II, continuing to react for 4 hours, cooling the reaction liquid to room temperature after the reaction is finished, filtering, preferably naturally drying the filter cake for 24 hours at room temperature, then drying in an oven at 110 ℃ for 8 hours, and finally roasting in a muffle furnace at 260 ℃ for 4 hours to obtain the blackish brown vanadium-phosphorus oxide, namely the vanadium-phosphorus-oxygen catalyst precursor.
And (3) placing the precursor powder of the vanadium phosphorus oxide catalyst prepared in the above into a tubular roasting furnace, introducing butane/air mixed gas (the volume concentration of butane is 0.8%), quickly raising the activation temperature from room temperature to 250 ℃, then slowly raising the temperature to 420 ℃ and keeping the temperature for 20 hours, and ending the activation process to obtain the vanadium phosphorus oxide catalyst. The obtained catalyst has a crystalline phase (VO) detected by XRD2P2O7Phase (volume content 92%). The specific surface area is 58m2The pore volume is 0.06ml/g, the pore distribution is dual, and the pore diameter is 10-20 nm and 20-35 nm; wherein the 10-20 nm pore distribution accounts for 31% of the total pore volume, and the 20-35 nm pore distribution accounts for 42% of the total pore volume.
Adding the catalyst into graphite powder with the mass fraction of 4%, fully mixing, properly adjusting the impact strength by adopting a rotary tablet press, and extruding into a column shape. Crushing and screening the catalyst particles to prepare the catalyst particles. 5mL of catalyst particles (5-10 meshes) are weighed and placed in a stainless steel reaction tube with the inner diameter of 10 mm. At the reaction temperature of 395 ℃, the reaction pressure of 0.25MPa, the reaction gas is n-butane/air mixed gas with butane volume concentration of 1.5 percent, and the gas space velocity is 3500h-1The catalytic performance was evaluated under the reaction conditions of (1). Through gas chromatographic analysis, the conversion rate of the n-butane is 97 percent (mol) and the selectivity of the maleic anhydride reaches 81 percent (mol).
Example 3
250g of methyl ammonium chloride, 150g of ammonium tetrafluoroborate and 300g of pure water are mixed, heated to 90 ℃ under stirring, kept at the constant temperature for 1.5h, clarified, naturally cooled to about 30 ℃, and centrifugally filtered to obtain 300g of ionic liquid I, wherein the content of water is about 3.5wt%, and the yield is 73 wt%.
The procedure for the preparation of 1-hydroxyethyl-3-methylimidazolium fluoroborate ionic liquid is the same as in example 1.
In an immersed circulating impinging stream reactor, mixing ionic liquid I300g, vanadium pentoxide 30.0g, auxiliary agent zirconium nitrate 0.5g and auxiliary agent nickel nitrate hexahydrate 0.95g, putting into the reactor through a feed inlet, starting, adjusting the rotation number of a propeller to 900r/min, and heating to 100 ℃ to enable the materials to have impinging reaction for 3 hours; and then introducing 34.0g of concentrated phosphoric acid with the concentration of 95% into the reactor, wherein the molar ratio of phosphorus to vanadium is 1.0, continuing to react for 2 hours, then introducing ionic liquid II, continuing to react for 4 hours, cooling the reaction liquid to room temperature after the reaction is finished, filtering, preferably naturally drying the filter cake for 24 hours at room temperature, then drying in an oven at 150 ℃ for 9 hours, and finally roasting in a muffle furnace at 260 ℃ for 6 hours to obtain the black brown vanadium-phosphorus oxide, namely the vanadium-phosphorus-oxygen catalyst precursor.
And (3) placing the precursor powder of the vanadium phosphorus oxide catalyst prepared in the above into a tubular roasting furnace, introducing butane/air mixed gas (the volume concentration of butane is 0.8%), quickly raising the activation temperature from room temperature to 250 ℃, then slowly raising the temperature to 420 ℃ and keeping the temperature for 20 hours, and ending the activation process to obtain the vanadium phosphorus oxide catalyst. The obtained catalyst has a crystalline phase (VO) detected by XRD2P2O7Phase (89% by volume). The specific surface area is 55m2The pore volume is 0.05ml/g, the pore distribution is dual, and the pore diameter is 10-20 nm and 20-35 nm; wherein the 10-20 nm pore distribution accounts for 30% of the total pore volume, and the 20-35 nm pore distribution accounts for 40% of the total pore volume.
Adding the catalyst into graphite powder with the mass fraction of 4%, fully mixing, properly adjusting the impact strength by adopting a rotary tablet press, and extruding into a column shape. Crushing and screening the catalyst particles to prepare the catalyst particles. 5mL of catalyst particles (5-10 meshes) are weighed and placed in a stainless steel reaction tube with the inner diameter of 10 mm. At the reaction temperature of 395 ℃, the reaction pressure of 0.25MPa, the reaction gas is n-butane/air mixed gas with butane volume concentration of 1.5 percent, and the gas space velocity is 3500h-1The catalytic performance was evaluated under the reaction conditions of (1). Through gas chromatographic analysis, the conversion rate of the n-butane is 96 percent (mol) and the selectivity of the maleic anhydride reaches 67 percent (mol).
Example 4
The procedure for the preparation of ionic liquid I was as in example 1.
The procedure for the preparation of 1- (6' -hydroxy) hexyl-3-methylimidazolium fluoroborate ionic liquid was the same as in example 1.
In an immersed circulating impinging stream reactor, mixing an ionic liquid I250g, vanadium pentoxide 30.0g, an auxiliary agent zirconium nitrate 0.5g and an auxiliary agent nickel nitrate hexahydrate 0.95g, putting the mixture into the reactor through a feed inlet, starting, adjusting the revolution of a propeller to be 1000r/min, and heating to 120 ℃ to enable the materials to carry out impinging reaction for 2 hours; then introducing 32.3g of 100% concentrated phosphoric acid into the reactor, wherein the molar ratio of phosphorus to vanadium is 1.0, continuing to react for 2 hours, introducing an ionic liquid II, continuing to react for 2 hours, cooling the reaction liquid to room temperature after the reaction is finished, filtering, preferably naturally drying the filter cake at room temperature for 24 hours, then drying in an oven at 140 ℃ for 8 hours, and finally roasting in a muffle furnace at 250 ℃ for 6 hours to obtain the black brown vanadium-phosphorus oxide, namely the vanadium-phosphorus-oxygen catalyst precursor.
And (3) placing the precursor powder of the vanadium phosphorus oxide catalyst prepared in the above into a tubular roasting furnace, introducing butane/air mixed gas (the volume concentration of butane is 0.8%), quickly raising the activation temperature from room temperature to 250 ℃, then slowly raising the temperature to 420 ℃ and keeping the temperature for 20 hours, and ending the activation process to obtain the vanadium phosphorus oxide catalyst. The obtained catalyst has a crystalline phase (VO) detected by XRD2P2O7Phase (90% by volume). The specific surface area is 61m2The pore volume is 0.09ml/g, the pore distribution is double, and the pore diameter is 10-20 nm and 20-35 nm; wherein the 10-20 nm pore distribution accounts for 31% of the total pore volume, and the 20-35 nm pore distribution accounts for 43% of the total pore volume.
Adding the catalyst into graphite powder with the mass fraction of 4%, fully mixing, properly adjusting the impact strength by adopting a rotary tablet press, and extruding into a column shape. Crushing and screening the catalyst particles to prepare the catalyst particles. 5mL of catalyst particles (5-10 meshes) are weighed and placed in a stainless steel reaction tube with the inner diameter of 10 mm. At the reaction temperature of 395 ℃, the reaction pressure of 0.25MPa, the reaction gas is n-butane/air mixed gas with butane volume concentration of 1.5 percent, and the gas space velocity is 3500h-1The catalytic performance was evaluated under the reaction conditions of (1). Through gas chromatographic analysis, the conversion rate of the n-butane is 87 percent (mol) and the selectivity of the maleic anhydride reaches 75 percent (mol).
Example 5
300g of dimethyl ammonium chloride, 190g of ammonium tetrafluoroborate and 450g of pure water are mixed, heated to 80 ℃ under stirring, kept at the constant temperature for 1 hour, clarified, naturally cooled to about 30 ℃, and centrifugally filtered to obtain 300g of ionic liquid I, wherein the ionic liquid I contains about 3.5wt% of water and the yield is 73 wt%.
Taking 1.92 mol of chloroethanol and 1.28mol of methylimidazole, refluxing for 24h at 80 ℃ under the condition of microwave heating, reacting to obtain viscous colorless transparent liquid, cooling to room temperature, washing with diethyl ether for four times to obtain colorless crystal 1-hydroxyethyl-3-methylimidazole chloride ion liquid, and drying for 48h at 80 ℃ in a vacuum drying oven. Adding 100g (0.6 mol) of dried 1-hydroxyethyl-3-methylimidazole chloride ionic liquid into 600ml of acetone, adding 72g (0.68 mol) of sodium tetrafluoroborate, stirring at room temperature for 24h, carrying out suction filtration, washing filter residues to obtain waxy solid, washing twice with acetone, combining washing liquid and filtrate, and using anhydrous MgSO (MgSO) to obtain the final product4Drying overnight, rotationally evaporating out acetone at 40 ℃, and rotationally evaporating water in an oil bath at 100 ℃ for 2 hours to obtain pure 1-hydroxyethyl-3-methylimidazolium fluoroborate ionic liquid.
In the fluidized bed reactor, ionic liquid I300g and vanadium pentoxide 30.0g are added from a charging opening. Drumming N2The reaction liquid and solid particles are kept in a tumbling state of boiling state in the reactor. Raising the reaction temperature and keeping the temperature at 95 +/-2 ℃ for 2 hours; and introducing 38.0g of concentrated phosphoric acid with the concentration of 85% into the reactor from a feed inlet, keeping the molar ratio of phosphorus to vanadium at 1.0, continuing to keep the boiling-state reaction for 3 hours, introducing ionic liquid II150g from the feed inlet, continuing to keep the boiling-state reaction for 5 hours, and finishing the reaction. The reactor temperature was adjusted and maintained at 120. + -. 2 ℃. Continuously blowing gas, keeping the boiling state for 6h, and evaporating the solvent to obtain catalyst precursor powder. And then roasting the catalyst matrix powder for 5 hours in a boiling state within the temperature range of 240 +/-2 ℃ to obtain a precursor of the vanadium phosphorus oxide catalyst. Further heating at 400 +/-2 deg.c while blowing mixed butane/air gas (butane volume concentration of 0.8%) to activate the catalyst precursor powder in boiling state for 20 hr to obtain vanadium-phosphorus-oxygen catalyst.
The obtained catalyst has a crystalline phase (VO) detected by XRD2P2O7Phase (91% by volume). The specific surface area is 60m2/g，The pore volume is 0.06ml/g, and the porous material has dual pore channel distribution, and the pore diameter is 10-20 nm and 20-35 nm; wherein the 10-20 nm pore distribution accounts for 27% of the total pore volume, and the 20-35 nm pore distribution accounts for 40% of the total pore volume.
Adding the catalyst into graphite powder with the mass fraction of 4%, fully mixing, properly adjusting the impact strength by adopting a rotary tablet press, and extruding into a column shape. The catalyst was measured to have a side pressure strength of 27.7 N.mm-1. The catalyst attrition was 0.02 m%.
Crushing and screening the catalyst particles to prepare the catalyst particles. 5mL of catalyst particles (5-10 meshes) are weighed and placed in a stainless steel reaction tube with the inner diameter of 10 mm. At the reaction temperature of 380 ℃, the reaction pressure of 0.25MPa, the reaction gas is n-butane/air mixed gas with butane volume concentration of 1.5 percent, and the gas volume space velocity is 1750h-1The catalytic performance was evaluated under the reaction conditions of (1). Through gas chromatographic analysis, the conversion rate of the n-butane is 91 percent (mol) and the selectivity of the maleic anhydride reaches 64 percent (mol).
Example 6
250g of diethylammonium chloride, 180g of ammonium tetrafluoroborate and 400g of pure water are mixed, heated to 90 ℃ under stirring, kept at the constant temperature for 1.5h, clarified, naturally cooled to about 30 ℃, and centrifugally filtered to obtain 260g of ionic liquid I, wherein the water content is about 3.5wt%, and the yield is 73 wt%.
The procedure for the preparation of 1- (4' -hydroxy) butyl-3-methylimidazolium fluoroborate ionic liquid was the same as in example 5.
In a fluidized bed reactor, ionic liquid I250g, vanadium pentoxide 30.0g, auxiliary agent ferric nitrate hexahydrate 0.3g and auxiliary agent zirconium nitrate 0.5g are fed from a feed inlet. Drumming N2The reaction liquid and solid particles are kept in a tumbling state of boiling state in the reactor. Raising the reaction temperature and keeping the temperature at 100 +/-2 ℃, and keeping the reaction time for 3 hours; and introducing 35.5g of concentrated phosphoric acid with the concentration of 100% into the reactor from a feed inlet, keeping the molar ratio of phosphorus to vanadium at 1.1, continuously keeping the boiling state for reaction for 3 hours, introducing ionic liquid II200g from the feed inlet, continuously keeping the boiling state for reaction for 6 hours, and finishing the reaction. The reactor temperature was adjusted and maintained at 130. + -. 2 ℃. Continuously blowing gas, keeping boiling state for 7h, evaporating the solvent to obtain catalyst mother liquorA bulk powder. And then roasting the catalyst matrix powder for 5 hours in a boiling state within the temperature range of 220 +/-2 ℃ to obtain a precursor of the vanadium phosphorus oxide catalyst. Further heating at 400 +/-2 deg.c while blowing mixed butane/air gas (butane volume concentration of 0.8%) to activate the catalyst precursor powder for 24 hr to obtain vanadium-phosphorus-oxygen catalyst.
The obtained catalyst has a crystalline phase (VO) detected by XRD2P2O7Phase (90% by volume). Specific surface area of 59m2The pore volume is 0.05ml/g, the pore distribution is dual, and the pore diameter is 10-20 nm and 20-35 nm; wherein the 10-20 nm pore distribution accounts for 30% of the total pore volume, and the 20-35 nm pore distribution accounts for 41% of the total pore volume.
Adding the catalyst into graphite powder with the mass fraction of 4%, fully mixing, properly adjusting the impact strength by adopting a rotary tablet press, and extruding into a column shape. The catalyst had a lateral pressure strength of 29.6 N.mm-1. The catalyst attrition was 0.03 m%.
Crushing and screening the catalyst particles to prepare the catalyst particles. 5mL of catalyst particles (5-10 meshes) are weighed and placed in a stainless steel reaction tube with the inner diameter of 10 mm. At the reaction temperature of 390 ℃, the reaction pressure of 0.25MPa, the reaction gas is n-butane/air mixed gas with butane volume concentration of 1.5 percent, and the gas space velocity is 3500h-1The catalytic performance was evaluated under the reaction conditions of (1). Through gas chromatographic analysis, the conversion rate of the n-butane is 95 percent (mol) and the selectivity of the maleic anhydride reaches 80 percent (mol).
Example 7
250g of methyl ammonium chloride, 150g of ammonium tetrafluoroborate and 300g of pure water are mixed, heated to 90 ℃ under stirring, kept at the constant temperature for 1.5h, clarified, naturally cooled to about 30 ℃, and centrifugally filtered to obtain 300g of ionic liquid I, wherein the content of water is about 3.5wt%, and the yield is 73 wt%.
The procedure for the preparation of 1-hydroxyethyl-3-methylimidazolium fluoroborate ionic liquid is the same as in example 5.
In a fluidized bed reactor, ionic liquid I300g, vanadium pentoxide 30.0g, auxiliary agent zirconium nitrate 0.5g and auxiliary agent nickel nitrate hexahydrate 0.95g are fed into a feed inlet. Drumming intoN2The reaction liquid and solid particles are kept in a tumbling state of boiling state in the reactor. Raising the reaction temperature and keeping the temperature at 100 +/-2 ℃, and keeping the reaction time for 3 hours; and introducing 34.0g of 95% concentrated phosphoric acid into the reactor from a feed inlet, keeping the molar ratio of phosphorus to vanadium at 1.0, continuing to keep the boiling-state reaction for 3 hours, introducing ionic liquid II200g from the feed inlet, continuing to keep the boiling-state reaction for 6 hours, and finishing the reaction. The reactor temperature was adjusted and maintained at 110. + -. 2 ℃. Continuously blowing gas, keeping the boiling state for 8h, and evaporating the solvent to obtain catalyst precursor powder. And then roasting the catalyst matrix powder for 5 hours in a boiling state within the temperature range of 230 +/-2 ℃ to obtain a precursor of the vanadium phosphorus oxide catalyst. Further heating at 400 +/-2 deg.c while blowing mixed butane/air gas (butane volume concentration of 0.8%) to activate the catalyst precursor powder for 24 hr to obtain vanadium-phosphorus-oxygen catalyst.
The obtained catalyst has a crystalline phase (VO) detected by XRD2P2O7Phase (89% by volume). The specific surface area is 55m2The pore volume is 0.06ml/g, the pore distribution is dual, and the pore diameter is 10-20 nm and 20-35 nm; wherein the distribution of 10-20 nm pores accounts for 33% of the total pore volume, and the distribution of 20-35 nm pores accounts for 42% of the total pore volume.
Adding the catalyst into graphite powder with the mass fraction of 4%, fully mixing, properly adjusting the impact strength by adopting a rotary tablet press, and extruding into a column shape. The catalyst was measured to have a lateral pressure strength of 31.5 N.mm-1. The catalyst attrition was 0.02 m%.
Crushing and screening the catalyst particles to prepare the catalyst particles. 5mL of catalyst particles (5-10 meshes) are weighed and placed in a stainless steel reaction tube with the inner diameter of 10 mm. At the reaction temperature of 395 ℃, the reaction pressure of 0.25MPa, the reaction gas is n-butane/air mixed gas with butane volume concentration of 1.5 percent, and the gas space velocity is 3500h-1The catalytic performance was evaluated under the reaction conditions of (1). Through gas chromatographic analysis, the conversion rate of the n-butane is 96 percent (mol) and the selectivity of the maleic anhydride reaches 70 percent (mol).
Example 8
The procedure for the preparation of ionic liquid I was as in example 5.
The procedure for the preparation of 1- (6' -hydroxy) hexyl-3-methylimidazolium fluoroborate ionic liquid was the same as in example 5.
In the fluidized bed reactor, ionic liquid I250g, vanadium pentoxide 30.0g, auxiliary agent zirconium nitrate 0.5g, and auxiliary agent nickel nitrate hexahydrate 0.95g are added through a charging opening. Drumming N2The reaction liquid and solid particles are kept in a tumbling state of boiling state in the reactor. Raising the reaction temperature and keeping the temperature at 110 +/-2 ℃, and keeping the reaction time for 3 hours; and then 32.3g of 100 percent concentrated phosphoric acid is introduced into the reactor from a feed inlet, the molar ratio of phosphorus to vanadium is 1.0, the boiling state reaction is continuously kept for 3 hours, then the ionic liquid II200g is introduced from the feed inlet, the boiling state reaction is continuously kept for 5 hours, and the reaction is finished. The reactor temperature was adjusted and maintained at 120. + -. 2 ℃. And continuously blowing gas, keeping the boiling state for 7h, and evaporating the solvent to obtain catalyst precursor powder. And then roasting the catalyst matrix powder for 5 hours in a boiling state within the temperature range of 250 +/-2 ℃ to obtain a precursor of the vanadium phosphorus oxide catalyst. Further heating at 400 +/-2 deg.c while blowing mixed butane/air gas (butane volume concentration of 0.8%) to activate the catalyst precursor powder for 24 hr to obtain vanadium-phosphorus-oxygen catalyst.
The obtained catalyst has a crystalline phase (VO) detected by XRD2P2O7Phase (90% by volume). The specific surface area is 60m2The pore volume is 0.09ml/g, the pore distribution is double, and the pore diameter is 10-20 nm and 20-35 nm; wherein the 10-20 nm pore distribution accounts for 29% of the total pore volume, and the 20-35 nm pore distribution accounts for 43% of the total pore volume.
Adding the catalyst into graphite powder with the mass fraction of 4%, fully mixing, properly adjusting the impact strength by adopting a rotary tablet press, and extruding into a column shape. The catalyst was measured to have a side pressure strength of 35.1 N.mm-1. The catalyst attrition was 0.03 m%.
Crushing and screening the catalyst particles to prepare the catalyst particles. 5mL of catalyst particles (5-10 meshes) are weighed and placed in a stainless steel reaction tube with the inner diameter of 10 mm. At a reaction temperature of 395 ℃ in the reactionThe reaction pressure is 0.25MPa, the reaction gas is n-butane/air mixed gas with butane volume concentration of 1.5 percent, and the gas space velocity is 3500h-1The catalytic performance was evaluated under the reaction conditions of (1). The gas chromatographic analysis shows that the conversion rate of the n-butane is 89 percent (mol) and the selectivity of the maleic anhydride is 75 percent (mol).
Example 9
250g of diethylammonium chloride, 180g of ammonium tetrafluoroborate and 400g of pure water are mixed, heated to 90 ℃ under stirring, kept at the constant temperature for 1.5h, clarified, naturally cooled to about 30 ℃, and centrifugally filtered to obtain 260g of ionic liquid I, wherein the water content is about 3.5wt%, and the yield is 73 wt%.
The procedure for the preparation of 1- (4' -hydroxy) butyl-3-methylimidazolium fluoroborate ionic liquid was the same as in example 5.
Adding 250g parts of ionic liquid I, 30.0g of vanadium pentoxide, 0.3g of ferric nitrate hexahydrate as an auxiliary agent and 0.5g of zirconium nitrate as an auxiliary agent into a premixing tank, mixing uniformly, pumping into an internal circulation hypergravity rotary bed reactor, heating to 95 ℃, controlling the rotating speed of the hypergravity reactor to be 1500r/min, and reacting for 5 hours; then slowly introducing 33.47g of phosphoric acid with the concentration of 95% into the reactor by virtue of a phosphoric acid storage tank, controlling the phosphorus/vanadium molar ratio to be 1.0, controlling the reaction temperature to be 100 ℃, continuing to react for 2h after the phosphoric acid is added, introducing an ionic liquid II200g into the reactor by virtue of an ionic liquid II storage tank, continuing to keep the reaction temperature at 100 ℃ for reacting for 6h, and finishing the reaction to obtain a slurry-like reaction liquid; and cooling the reaction liquid to room temperature, naturally drying the filter cake for 24 hours at room temperature, then drying the filter cake for 8 hours in a drying oven at 100 ℃, and finally roasting the filter cake for 6 hours in a muffle furnace at 250 ℃ to obtain vanadium-phosphorus oxide powder. And (3) placing the vanadium-phosphorus oxide powder prepared in the above into a tubular roasting furnace, introducing butane/air mixed gas (the butane volume concentration is 0.8%), quickly raising the activation temperature from room temperature to 250 ℃, then slowly raising the temperature to 400 ℃ and keeping the temperature for 20 hours, and finishing the activation process to obtain the vanadium-phosphorus oxide catalyst.
The obtained catalyst has a crystalline phase (VO) detected by XRD2P2O7Phase (91% by volume). The specific surface area is 64m2The pore volume is 0.08ml/g, the double pore channel distribution is realized, and the pore diameter is 10-20 nm and 20-35 nm; 10 to 2 of themThe pore distribution of 0nm accounts for 30% of the total pore volume, and the pore distribution of 20-35 nm accounts for 41% of the total pore volume.
Adding 4% graphite powder into the catalyst intermediate, mixing, adjusting impact force, and extruding into column shape. The catalyst was measured to have a side pressure strength of 34.5 N.mm-1. The catalyst attrition was 0.04 m%.
The resulting catalyst was crushed and sieved. 5mL of catalyst particles (5 mesh to 10 mesh) were weighed into a stainless steel reaction tube having an inner diameter of 10 mm. At the reaction temperature of 380 ℃, the reaction pressure of 0.25MPa, the reaction gas is n-butane/air mixed gas with butane volume concentration of 1.5 percent, and the gas volume space velocity is 1750h-1The catalytic performance was evaluated under the reaction conditions of (1). Through gas chromatographic analysis, the conversion rate of the n-butane is 92 percent (mol) and the selectivity of the maleic anhydride reaches 74 percent (mol).
Comparative example 1
Adding 30.0g of vanadium pentoxide and 600mL of mixed solution of isobutanol and benzyl alcohol into a four-neck flask with a stirrer, wherein the volume ratio of the isobutanol to the benzyl alcohol is 15:1, stirring, heating, and refluxing at 110 +/-2 ℃ for 4 hours; then, 35.5g of 100% phosphoric acid was weighed out to have a phosphorus/vanadium molar ratio of 1.1, and the mixture was put into a flask and refluxed for 6 hours to obtain a reaction solution. Cooling the reaction liquid to room temperature, carrying out vacuum filtration, leaching the filter cake with a small amount of isobutanol for three times, drying in an oven at 120 ℃ for 12h, and roasting in a muffle furnace at 250 ℃ for 5h to obtain a black brown vanadium phosphorus oxide catalyst precursor.
And (3) placing the precursor powder of the vanadium phosphorus oxide catalyst prepared in the above into a tubular roasting furnace, introducing butane/air mixed gas (the volume concentration of butane is 0.8%), quickly raising the activation temperature from room temperature to 250 ℃, then slowly raising the temperature to 420 ℃ and keeping the temperature for 20 hours, and ending the activation process to obtain the vanadium phosphorus oxide catalyst. The obtained catalyst has a crystalline phase (VO) detected by XRD2P2O7Phase (90% by volume). The specific surface area is 18m2(ii)/g; the pore volume is 0.05ml/g and the pore diameter is 17 nm.
Adding the catalyst into graphite powder with the mass fraction of 4%, fully mixing, and tabletting by adopting a rotary tabletting methodAnd (4) properly adjusting the impact force and extruding into a column shape. The catalyst was measured to have a side pressure strength of 6.65 N.mm-1. The catalyst attrition was 0.12 m%.
Crushing and screening the catalyst particles to prepare the catalyst particles. 5mL of catalyst particles (5-10 meshes) are weighed and placed in a stainless steel reaction tube with the inner diameter of 10 mm. At the reaction temperature of 395 ℃, the reaction pressure of 0.25MPa, the reaction gas is n-butane/air mixed gas with butane volume concentration of 1.5 percent, and the gas space velocity is 3500h-1The catalytic performance was evaluated under the reaction conditions of (1). The conversion of n-butane was 72 mol% and the selectivity of maleic anhydride was 52 mol% as determined by gas chromatography.

Claims (11)

1. A preparation method of a vanadium phosphorus oxide catalyst comprises the following steps:
(1) will M1And M2Adding the mixture into water, stirring, heating, reacting at constant temperature, cooling, centrifuging and filtering after the reaction is finished to obtain ionic liquid I;
will M3And M4Mixing, reacting at constant temperature to obtain intermediate product, cooling, washing, drying, adding into acetone, and adding M1Stirring and reacting at room temperature, performing suction filtration and washing, combining a washing solution with the filtrate, drying by using a drying agent, and performing rotary evaporation to obtain acetone and water to obtain an ionic liquid II;
(2) mixing the ionic liquid I and vanadium pentoxide, putting into an impinging stream reactor, and heating to 95-130 ℃ to react materials for 1-4 h; introducing concentrated phosphoric acid, continuously reacting for 1-4 h, introducing ionic liquid II, continuously reacting for 2-6 h, and filtering, drying and roasting after the reaction is finished to obtain a vanadium-phosphorus-oxygen catalyst precursor;
(3) the vanadium phosphorus oxide catalyst precursor is subjected to activation and post-forming or treatment of activation and post-forming to obtain the vanadium phosphorus oxide catalyst;
if a vanadium phosphorus oxide catalyst containing a metal oxide is prepared, it can be introduced in three ways: i, in the step (2), adding soluble salt of metal and vanadium pentoxide into the ionic liquid I; II is introduced before or during the forming of the vanadium phosphorus oxide catalyst; III is introduced in a dipping mode after the vanadium phosphorus oxygen catalyst is formed;
the M is1Is at least one of ammonium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, ammonium hexafluorophosphate, sodium hexafluorophosphate or potassium hexafluorophosphate;
the M is2Has the general formula (R)1R2R3R4）N+Z-In which R is1、R2、R3And R4Each independently selected from H or C1-C4 alkyl, and R1、R2、R3And R4The sum of C atoms is less than or equal to 4, and Z is F, Cl or Br;
the M is3Is at least one of imidazole and pyridine;
the M is4Is halogenated alkyl alcohol with the general formula Z (CH)2)nCH2OH、Z(CH2)nCHOHCH2OH or Z (CH)2)nCHOHCH2CH2The structure of OH is shown, wherein n is an integer of 0-9, and Z is F, Cl or Br.
2. The method of claim 1, wherein: the M is2Selected from dimethyl ammonium chloride and/or diethyl ammonium chloride.
3. The method of claim 1, wherein: the M is4Is chloroethanol.
4. The method of claim 1, wherein: m in step (1)1And M2In a molar ratio of 1: 1-1: 2, the reaction temperature is 60-150 ℃, and the constant-temperature reaction time is 1-4 h.
5. The method of claim 1, wherein: m in step (1)3And M4In a molar ratio of 1: 1-1: 2, the reaction temperature is 70-100 ℃, and the constant-temperature reaction time is 20-30 h.
6. The method of claim 1, wherein: the intermediate product in the step (1) is reacted with M1In a weight ratio of 0.5: 1-3: 1; the weight ratio of the intermediate product to acetone is 0.1: 1-1: 1.
7. the method of claim 1, wherein: the weight ratio of the ionic liquid I to the vanadium pentoxide in the step (2) is 5: 1-15: 1.
8. The method of claim 1, wherein: the weight ratio of the ionic liquid II to the vanadium pentoxide in the step (2) is 1: 1-10: 1.
9. The method according to claim 1, wherein the impinging stream reactor in the step (2) is a submerged circulating impinging stream reactor, the number of revolutions of a propeller during the reaction is 750 to 4500r/min, and the reaction is at normal pressure.
10. A vanadium phosphorus oxide catalyst prepared by the process of any one of claims 1 to 9.
11. Use of a vanadium phosphorus oxide catalyst as claimed in claim 10 in the reaction of n-butane oxidation to maleic anhydride.
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