CN116060064B - Catalyst for preparing phthalic anhydride by oxidation of o-xylene, and method for preparing phthalic anhydride by oxidation of o-xylene - Google Patents
Catalyst for preparing phthalic anhydride by oxidation of o-xylene, and method for preparing phthalic anhydride by oxidation of o-xylene Download PDFInfo
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- 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
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Abstract
The invention relates to the technical field of phthalic anhydride preparation by o-xylene, in particular to a catalyst for phthalic anhydride preparation by o-xylene oxidation and a method for phthalic anhydride preparation by o-xylene oxidation. The catalyst comprises at least 3 sequentially arranged catalyst beds, wherein the weight ratio of active components to carriers in catalytic media filled in each catalyst bed is 8-20:100, S n of each catalyst bed is sequentially decreased along the flow direction, P n of each catalyst bed is sequentially increased, S n is the total surface area of the carriers in unit volume of the nth catalyst bed along the flow direction, P n is the surface area of the single carrier of the nth catalyst bed along the flow direction, and n is a positive integer. The method for preparing phthalic anhydride by oxidizing o-xylene by using the catalyst provided by the invention can effectively improve the conversion rate of o-xylene and the yield of phthalic anhydride.
Description
Technical Field
The invention relates to the technical field of phthalic anhydride preparation by o-xylene, in particular to a catalyst for phthalic anhydride preparation by o-xylene oxidation and a method for phthalic anhydride preparation by o-xylene oxidation.
Background
Phthalic Anhydride (PA), which is considered one of the most important organic chemical raw materials, is mainly used as an intermediate for the production of plasticizers, alkyd resins and Unsaturated Polyester Resins (UPR). The phthalic anhydride is produced by two oxidation methods, namely naphthalene or ortho-xylene oxidation method, one is obtained by mixing naphthalene or ortho-naphthalene as raw materials and carrying out air catalytic oxidation, namely naphthalene phthalic anhydride for short, and the other is obtained by carrying out air oxidation on ortho-xylene as raw materials under the action of a vanadium catalyst to obtain phthalic anhydride for short, namely ortho-phthalic anhydride.
Currently, the oxidation to phthalic anhydride patent is focused mainly on the screening of auxiliaries and optimization of the formulation, and BASF corporation discloses a gas phase oxidation process wherein a gas stream comprising at least one hydrocarbon and molecular oxygen is passed over a catalyst produced using antimony trioxide containing a significant proportion of stibine. However, the method cannot specifically optimize the functions of each bed layer, and the catalytic efficiency is required to be improved.
The south chemical company developed a multilayer catalyst for the preparation of phthalic anhydride, which catalyst was carried out with a catalyst arrangement having a first catalyst layer on the gas inlet side and at least one second catalyst layer with different catalytic activity downstream of the first catalyst layer in the direction of gas flow through. However, the method has the problem that the catalytic efficiency of the catalyst reaches the bottleneck and is insufficient to improve the weight yield of phthalic anhydride products.
The imported phthalic anhydride catalyst of the o-xylene method used in China is mainly from BASF company and southern chemical company, the catalyst is divided into 3-6 sections of beds, the feeding amount of raw materials is 90-100g/Nm 3, and the pure yield of phthalic anhydride is 113-114% in the first year. However, this method has a problem that the catalytic efficiency of each bed catalyst is not optimized and the feed amount of raw materials is limited.
Disclosure of Invention
The invention aims to solve the problems of low catalytic efficiency of a catalyst in a catalyst bed, low phthalic anhydride yield and the like in the prior art, and provides a catalyst for preparing phthalic anhydride by oxidizing o-xylene and a method for preparing phthalic anhydride by oxidizing o-xylene.
In order to achieve the above object, the first aspect of the present invention provides a catalyst for preparing phthalic anhydride by oxidizing o-xylene, the catalyst comprising up to 3 catalyst beds arranged in sequence, wherein the weight ratio of active components and carriers in a catalytic medium filled in each catalyst bed is 8-20:100;
in the catalyst, along the flow direction, S n of each catalyst bed is gradually decreased, and P n of each catalyst bed is gradually increased, wherein S n is the total surface area of carriers in unit volume of the nth catalyst bed along the flow direction, P n is the surface area of a single carrier of the nth catalyst bed along the flow direction, and n is a positive integer;
wherein the total surface area of the carriers per unit volume is defined as the total number of carriers per 100mL volume in a cylindrical container having a diameter of 29mm x the individual carrier surface area;
Wherein the single support surface area is defined as the support surface area of the catalytic media packed in the nth catalyst bed.
In a second aspect, the invention provides a method for preparing phthalic anhydride by oxidizing o-xylene, which comprises introducing o-xylene and an oxygen-containing gas into the catalyst provided in the first aspect, and sequentially contacting and reacting the o-xylene and the oxygen-containing gas with a catalytic medium in each catalyst bed.
Compared with the prior art, the invention has the following advantages:
(1) According to the catalyst provided by the invention, the S n and P n change rules of each catalyst bed are limited, namely, along the logistics direction, the S n of each catalyst bed is sequentially decreased, the P n of each catalyst bed is sequentially increased, and especially, the relation formula that S n and P n meet the formula (1) is further limited, and the deep oxidation of a product can be avoided by optimizing the catalyst beds, so that the reaction load, the selectivity and the catalytic performance of a catalytic medium are improved;
(2) The catalyst provided by the invention is used for the method for preparing phthalic anhydride by oxidizing o-xylene, and can effectively improve the conversion rate of o-xylene and the yield of phthalic anhydride, namely, the conversion rate of o-xylene is up to 99.95%, and the yield of phthalic anhydride is up to 115.2%.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a catalyst for preparing phthalic anhydride by oxidizing o-xylene, which comprises at least 3 catalyst beds which are sequentially arranged, wherein the weight ratio of active components to carriers in a catalytic medium filled in each catalyst bed is 8-20:100;
in the catalyst, along the flow direction, S n of each catalyst bed is gradually decreased, and P n of each catalyst bed is gradually increased, wherein S n is the total surface area of carriers in unit volume of the nth catalyst bed along the flow direction, P n is the surface area of a single carrier of the nth catalyst bed along the flow direction, and n is a positive integer;
wherein the total surface area of the carriers per unit volume is defined as the total number of carriers per 100mL volume in a cylindrical container having a diameter of 29mm x the individual carrier surface area;
Wherein the single support surface area is defined as the support surface area of the catalytic media packed in the nth catalyst bed.
In the invention, the catalyst medium is a phthalic anhydride catalyst prepared by oxidizing o-xylene, unless otherwise specified.
In the present invention, unless otherwise specified, in the catalyst, the progressive decrease of S n of each catalyst bed in the flow direction means that S n+1 of the n+1th catalyst bed and S n of the n catalyst bed satisfy the condition that S n+1＜Sn is satisfied, wherein S n+1 is the total surface area of the carriers in unit volume of the n+1th catalyst bed in the flow direction, S n is the total surface area of the carriers in unit volume of the n catalyst bed in the flow direction, and n is a positive integer.
In the present invention, without specifying the special cases, in the catalyst, the sequential increasing of P n of each catalyst bed along the flow direction means that P n+1 of the n+1th catalyst bed and P n of the n catalyst bed satisfy P n+1＞Pn, where P n+1 is the single support surface area of the n+1th catalyst bed along the flow direction, P n is the single support surface area of the n catalyst bed along the flow direction, and n is a positive integer.
In some embodiments of the present invention, preferably, in the catalyst, S n and P n of each catalyst bed satisfy the relationship of formula (1):
Wherein S n is the total surface area of the carriers per unit volume along the nth catalyst bed in the flow direction, P n is the surface area of the single carrier along the nth catalyst bed in the flow direction, n is a positive integer, and m is any value from 50 to 200.
In some embodiments of the invention, the catalyst preferably comprises 3 to 8 catalyst beds, preferably 4 catalyst beds.
In some embodiments of the invention, it is preferred that in the catalyst, the S 1 of the first catalyst bed is 500-650cm 2, preferably 580-620cm 2, the S 2 of the second catalyst bed is 480-620cm 2, preferably 500-600cm 2, the S 3 of the third catalyst bed is 380-550cm 2, preferably 400-520cm 2, and the S 4 of the fourth catalyst bed is 280-480cm 2, preferably 350-420cm 2, along the flow direction.
In some embodiments of the invention, preferably, in the catalyst, the first catalyst bed has a P 1 of 100-250mm 2, preferably 150-250mm 2, the second catalyst bed has a P 2 of 100-350mm 2, preferably 150-300mm 2, the third catalyst bed has a P 3 of 200-400mm 2, preferably 250-350mm 2, and the fourth catalyst bed has a P 4 of 300-500mm 2, preferably 300-400mm 2, along the direction of flow.
In the present invention, the individual catalyst surface area parameters were measured using a 3-pass calculation averaging method, without special instruction.
According to a preferred embodiment of the present invention, in the catalyst, along the flow direction, the catalysts in the first to fourth catalyst beds are respectively catalytic medium a, catalytic medium B, catalytic medium C and catalytic medium D, wherein the first catalyst bed has a S 1 of 580-620cm 2, the second catalyst bed has a S 2 of 500-600cm 2, the third catalyst bed has a S 3 of 400-520cm 2, the fourth catalyst bed has a S 4 of 350-420cm 2, the first catalyst bed has a P 1 of 150-250mm 2, the second catalyst bed has a P 2 of 150-300mm 2, the third catalyst bed has a P 3 of 250-350mm 2, and the fourth catalyst bed has a P 4 of 300-400mm 2.
In some embodiments of the present invention, preferably, the height ratio of the first catalyst bed, the second catalyst bed, the third catalyst bed and the fourth catalyst bed in the catalyst is 10-50:10-40:10-40:0-30, preferably 30-45:20-30:20-30:0-20, along the flow direction. The adoption of the preferable conditions is more beneficial to improving the load of o-xylene, the yield of phthalic anhydride and the conversion rate of o-xylene, thereby reducing impurities or excessive oxidation.
In some embodiments of the invention, preferably, the weight ratio of the active component to the support in the catalytic medium is 10-18:100. In the invention, when the loading amount of the active component in the catalytic medium is too low, the conversion rate of o-xylene is relatively low, and when the loading amount of the active component in the catalytic medium is too high, the catalytic medium can be severely subjected to deep oxidation, so that more byproducts are generated, and the yield of phthalic anhydride is obviously reduced.
In one embodiment of the invention, the catalytic media a-D each independently comprise a support and an active component supported on the support, wherein the weight ratio of the active component to the support is from 8 to 20:100, preferably from 10 to 18:100.
In some embodiments of the invention, the active component preferably comprises a primary active component, tiO 2 and an adjunct, and further preferably the primary active component comprises V 2O5, a phosphorus compound, a potassium compound and optionally a cesium compound.
In some embodiments of the present invention, preferably, the V 2O5 content is 5 to 18wt%, the phosphorus compound content is 0.01 to 0.3wt%, the potassium compound content is 0.01 to 0.5wt%, the cesium compound content is 0 to 1wt%, the adjuvant content is 0.1 to 10wt%, and the balance is TiO 2, based on the total weight of the active components, the phosphorus compound content is 0.01 to 0.3wt%, the potassium compound content is 0.01 to 0.5wt%, the cesium compound content is 0 to 1wt%, the adjuvant content is 0.1 to 10wt%, based on the oxide.
The method for preparing the catalytic medium according to the present invention is not particularly limited, and the preparation of the catalytic medium may be performed according to a method commonly used in the art. Preferably, the preparation method of the catalytic medium filled in each catalyst bed comprises the steps of loading slurry containing a vanadium source, a phosphorus source, a potassium source, an optional cesium source, a titanium source and an auxiliary agent on a carrier, drying and roasting to obtain the catalytic medium.
In some embodiments of the present invention, preferably, the slurry comprises a vanadium source, a phosphorus source, a potassium source, a cesium source, a titanium source, and an auxiliary agent in an amount of 5-18:0.01-0.3:0.01-0.5:0-1:85.88-93.2:0.1-10, wherein the vanadium source is calculated as V 2O5, the phosphorus source is calculated as P, the potassium source is calculated as K, the cesium source is calculated as Cs, the titanium source is calculated as TiO 2, and the auxiliary agent is calculated as an oxide.
According to the present invention, the mixing method is not particularly limited, and wet milling may be used, and milling convenience and timeliness are combined, preferably, the mixing is performed in a ball mill, and more preferably, milling is performed in a ball mill for a period of 1 to 5 hours, preferably, 2 to 4 hours.
According to a preferred implementation of the present invention, preferably, the preparation method of the catalytic medium in each catalyst bed layer includes:
(1) Mixing a vanadium source, a phosphorus source, a potassium source, an optional cesium source, a part of auxiliary agent and a solvent to obtain a solution A;
(2) Mixing the solution A with a titanium source, the rest of auxiliary agents and a binder to obtain slurry;
(3) And loading the slurry on a carrier, and drying and roasting to obtain the catalytic medium.
In the invention, in the step (1), the mode of mixing has a wider selection range, so long as the vanadium source, the phosphorus source, the potassium source, the optional cesium source, part of auxiliary agent and the solvent are uniformly mixed.
In the invention, in the step (2), the mode of mixing has a wider selection range, and the solution A, the titanium source, the rest of auxiliary agent and the binder are uniformly mixed.
According to the invention, in order to avoid precipitation by reaction of the vanadium source with the auxiliary agent in solution a, it is preferred that oxalic acid is also contained in solution a. Further preferably, the weight ratio of oxalic acid to vanadium source is 1:0.2-0.8.
In the present invention, the kind of the carrier has a wide selection range, that is, the carrier is a kind conventional in the art. Preferably, the support is a non-porous inert support, preferably at least one selected from the group consisting of alumina, talc, silicon carbide, aluminum silicate, quartz and ceramic.
In the present invention, the shape of the carrier is not particularly limited, and may be, for example, cylindrical, spherical, annular, or granular. Preferably, the carrier is in the shape of a ring-shaped carrier.
In some embodiments of the invention, the support preferably has an outer diameter of 3-13mm, e.g., 3mm, 5mm, 7mm, 9mm, 11mm, 13mm, and any value in the range of any two values, preferably 5-9mm, a height of 2-12mm, e.g., 2mm, 3mm, 5mm, 7mm, 8mm, 10mm, 12mm, and any value in the range of any two values, preferably 3-8mm, a void fraction of 0.5-10%, e.g., 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, and any value in the range of any two values, preferably 2-8%. In the invention, under no special condition, the outer diameter parameter is measured by a method of measuring 3 times of average value by using a vernier caliper, the height parameter is measured by a method of measuring 3 times of average value by using the vernier caliper, and the porosity parameter is measured by using a porosity measuring instrument.
In some embodiments of the invention, the surface area of the support is preferably in the range of from 100 to 500mm 2, for example, 100mm 2、150mm2、200mm2、300mm2、400mm2、500mm2, and any value in the range of any two values, preferably 150 to 400mm 2.
In the present invention, the kind of the vanadium source has a wide selection range. Preferably, the vanadium source is selected from at least one of ammonium metavanadate, vanadium pentoxide and sodium vanadate, preferably ammonium metavanadate.
In the present invention, the kind of the phosphorus source has a wide selection range. Preferably, the phosphorus source is selected from at least one of monoammonium phosphate, triammonium phosphate and phosphorus pentoxide, preferably monoammonium phosphate.
In the present invention, the kind of the potassium source has a wide selection range. Preferably, the potassium source is selected from at least one of potassium nitrate, potassium sulfate, potassium chloride and potassium bicarbonate, preferably potassium sulfate.
In the present invention, the cesium source has a wide selection range for the species. Preferably, the cesium source is selected from at least one of cesium nitrate, cesium sulfate, cesium chloride and cesium carbonate, preferably cesium sulfate.
In the present invention, the titanium source is selected from a wide range of types. Preferably, the titanium source is titanium dioxide, and further, the titanium dioxide is anatase TiO 2 having a specific surface area of 10-30m 2/g, for example, 10m 2/g、15m2/g、17m2/g、20m2/g、26m2/g、30m2/g, and any value in the range of any two values, preferably 17-26m 2/g.
In the invention, the types of the auxiliary agents have a wider selection range, so long as the auxiliary agents contain corresponding auxiliary agent elements, and the auxiliary agents are substances capable of obtaining corresponding auxiliary agent element oxides through subsequent treatment. Preferably, the promoter contains at least one selected from rubidium, cerium, niobium, chromium, tungsten, iron, silver, cobalt, gold, gallium, indium, antimony, bismuth, zirconium, erbium, tungsten, and tin.
According to the invention, the promoter may comprise a metal oxide and/or a metal water-soluble salt capable of providing the above-mentioned metal element, further preferably the metal oxide is an oxide of silver and/or an oxide of antimony, and the metal water-soluble salt is at least one of water-soluble salts of rubidium, cerium, niobium, chromium, tungsten, iron, cobalt, gold, gallium, indium, bismuth, zirconium, erbium, tungsten and tin elements.
In the present invention, the metal water-soluble salt may be nitrate, carbonate, sulfate, oxalate, chloride, or the like unless otherwise specified.
According to the present invention, preferably, the water-soluble salt of cesium is at least one of cesium nitrate, cesium sulfate and cesium chloride, more preferably cesium sulfate.
In some embodiments of the present invention, preferably, the solvent comprises water and optionally a water-soluble organic solvent, wherein the water-soluble organic solvent comprises at least one of, but not limited to, methanol, ethanol, ethylene glycol dimethyl ether, formamide, and N, N-dimethylamide.
In some embodiments of the invention, preferably, the weight ratio of water to water-soluble organic solvent in the solvent is in the range of 1:0 to 0.3, for example, 1:0.1, 1:0.15, 1:0.2:1:0.25, 1:0.3, and any value in the range of any two values, preferably 1:0.1 to 0.2.
According to the present invention, it is preferable that the slurry further contains a binder, and it is further preferable that the binder is at least one of a vinyl acetate-acrylic ester copolymer emulsion, a vinyl acetate-ethylene copolymer emulsion, a vinyl acetate-maleic ester copolymer emulsion, and an acrylic acid-maleic acid copolymer emulsion, and it is preferable that the binder is a vinyl acetate-ethylene copolymer emulsion.
The amount of the binder used in the present invention is selected in a wide range in order to more uniformly load the active ingredient on the carrier. Preferably, the binder is added in an amount such that the viscosity of the slurry is 10-40 mPa-s, for example, any value in the range of 10 mPa-s, 12 mPa-s, 15 mPa-s, 20 mPa-s, 25 mPa-s, 30 mPa-s, 35 mPa-s, 40 mPa-s, and any two values, preferably 12-25 mPa-s. The binder may be used in any form as long as the viscosity of the slurry can be made within a defined range, preferably the binder is used in the form of an emulsion, and further preferably the binder has a solid content of 10 to 15wt%.
In the present invention, the manner of loading is not particularly limited as long as the slurry can be loaded onto a carrier. Preferably, the loading is by spraying.
According to the present invention, in order to accelerate the evaporation of the water and the organic solvent in the slurry and thereby to rapidly and effectively attach the active ingredient to the carrier, it is preferable to dry with hot air at 90 to 160 ℃ during the spraying process, and more preferable to dry with hot air at 100 to 130 ℃.
In some embodiments of the invention, it is preferred that the spray rate is from 30 to 60mL/min, e.g., from 30mL/min, 35mL/min, 40mL/min, 45mL/min, 50mL/min, 55mL/min, 60mL/min, and any value in the range of any two values for each 2000 grams of carrier, preferably from 35 to 50mL/min. Controlling the spraying rate within the above-defined range can prevent the waste of the slurry and the falling-off of the active ingredient from the carrier.
According to the present invention, in order to make the slurry more easily adhere to the carrier. Preferably, the carrier is heated prior to spraying to maintain the temperature of the carrier at any value in the range of 80-130 ℃, e.g., 80 ℃, 90 ℃,100 ℃, 110 ℃, 120 ℃, 130 ℃, and any two values, preferably 110-130 ℃.
According to the invention, the conditions for the calcination may be selected in a wide range, preferably the conditions for the calcination include 400-450 ℃ for 2-24 hours.
The high temperature can make the adhesive disappear, and the adhesive force of the active component on the catalytic medium is reduced, so that the active component falls off in the process of filling the catalytic medium, so that in order to avoid the active component falling off in the process of filling the catalytic medium, the catalytic medium precursor is filled in a catalyst bed layer, and then the catalytic medium is obtained by roasting.
The device used for the spraying according to the present invention is not particularly limited as long as it can satisfy the requirement of the spraying. Preferably, the device used for spraying comprises an air heater, a coating host, an exhaust fan, a slurry spraying system, a control system and a strong-current power supply cabinet. The coating host machine comprises a coating rotary drum and a power mechanism thereof, the coating rotary drum is sealed in the coating host machine, and the rotation speed can be adjusted. The coating drum adopts a horizontal hollow columnar structure, and the structure can improve the contact opportunity of active components and inert carrier materials. Circular meshes with the aperture of 1-8mm, preferably 3-4mm, are arranged on the horizontal hollow columnar structure, and the purpose of the circular meshes is to ensure that hot air penetrates into the coating drum, and after evaporating the solvent in the slurry on the carrier, the solvent is taken away by penetrating out of the coating drum, preferably, the rotating speed of the coating drum is 5-10rpm. The slurry spraying system consists of a nozzle and a feeding system, wherein the feeding system consists of a charging bucket, a stirring and feeding pump and a conveying pipeline. The feeding pump can adjust the spraying rate, and the nozzle can ensure that the slurry can be uniformly sprayed on the surface of the inert carrier material after passing through the feeding pump to form a smooth and flat catalytic active substance coating, so that the catalyst is prepared.
According to the invention, the spraying amount of the active component in the catalytic medium is controlled by the rotating speed of the rotating drum, the spraying speed, the loss rate and the spraying time, so that the content of the active component in the catalytic medium is controlled.
According to a particularly preferred embodiment of the invention, the catalyst comprises at least 3 catalyst beds arranged in sequence, wherein the weight ratio of active components to carriers in the catalytic medium filled in each catalyst bed is 8-20:100;
Wherein, in the catalyst, along the flow direction, S n of each catalyst bed decreases in sequence, and P n of each catalyst bed increases in sequence, wherein, S n is the total surface area of the carriers in unit volume of the nth catalyst bed along the flow direction, P n is the surface area of the single carrier of the nth catalyst bed along the flow direction, and n is a positive integer;
wherein the total surface area of the carriers per unit volume is defined as the total number of carriers per 100mL volume in a cylindrical container having a diameter of 29mm x the individual carrier surface area;
Wherein the single support surface area is defined as the support surface area of the catalytic media packed in the nth catalyst bed;
wherein, in the catalyst, S n and P n of each catalyst bed layer satisfy the relation of formula (1):
wherein m is any value from 50 to 200.
In a second aspect, the invention provides a method for preparing phthalic anhydride by oxidizing o-xylene, which comprises introducing o-xylene and an oxygen-containing gas into the catalyst provided in the first aspect, and sequentially contacting and reacting the o-xylene and the oxygen-containing gas with a catalytic medium in each catalyst bed.
According to the invention, the reaction conditions preferably include a molten salt temperature of 300-450 ℃, preferably 330-400 ℃, a volume space velocity of 700-5000h -1, preferably 2200-4000h -1, and a concentration of ortho-xylene of 60-120g/m 3, preferably 80-110g/m 3. Wherein the volume space velocity is the volume space velocity of the oxygen-containing gas.
According to the invention, the gas may be an oxygen-containing gas, preferably the gas is air.
According to the present invention, the reaction for producing phthalic anhydride by oxidation of o-xylene may be carried out in a fixed bed or in a fluidized bed, preferably, the reaction for producing phthalic anhydride by oxidation of o-xylene is carried out in a fixed bed single tube reactor, and more preferably, the fixed bed single tube reactor has a tube length of 3000 to 4800mm and an inner diameter of 20 to 30mm. The outside of the reaction tube of the fixed bed single tube reactor adopts circulating flowing molten salt to exchange reaction heat forcedly, a thermowell with the outer diameter of 5-10mm is arranged in the reaction tube, and a plurality of thermocouples with the same interval are arranged in the thermowell and are used for measuring the temperature of a reaction bed layer and the temperature of the molten salt. The outlet of the fixed bed single-tube reactor is connected with a product trapping device, and a sampling port is arranged at the outlet of the lower end of the reaction tube.
According to the invention, the catalytic medium in the reaction tube of the fixed bed single tube reactor is preferably filled in a sectional manner, the total filling height is 2400-3400mm, the first catalytic medium filling height is 10-50% of the total filling height, the second catalytic medium filling height is 10-40% of the total filling height, the third catalytic medium filling height is 10-40% of the total filling height, and the fourth catalytic medium filling height is 0-30% of the total filling height.
The invention optimizes the function of the catalyst bed layer by limiting the change rule of the total surface of the carriers in unit volume in each catalyst bed layer, namely, adopting the multi-size carrier to load active components to prepare the catalytic medium, avoids the deep oxidation of the product and improves the selectivity of the catalytic medium, thereby improving the performance of the catalytic medium. By adopting the method provided by the invention, the concentration of the reaction raw materials can be improved by 5-10g/Nm 3, the conversion rate of the raw materials can reach 99.95%, and the actual mass yield of the phthalic anhydride in industrial production can be improved by 1-3%.
The present invention will be described in detail by examples.
The molecular formula of ammonium metavanadate is NH 4VO3, and the relative molecular weight of the ammonium metavanadate is 116.98;
The molecular formula of the ammonium dihydrogen phosphate is NH 4H2PO4, and the relative molecular weight of the ammonium dihydrogen phosphate is 115.03;
Cesium sulfate has the molecular formula Cs 2SO4 and a relative molecular weight of 361.87;
the molecular formula of the potassium sulfate is K 2SO4, and the relative molecular weight of the potassium sulfate is 174.24;
The titanium dioxide is anatase titanium dioxide, and the specific surface area is 19m 2/g;
the vinyl acetate-ethylene copolymer emulsion had a solids content of 50% by weight.
The catalytic product is analyzed by a chromatographic analysis method;
the conversion (%) of o-xylene was calculated as:
the yield (%) of phthalic anhydride was calculated as:
the amounts of the respective active components in the following catalytic media were calculated by the amounts fed, and the amounts of the respective active components in the catalytic media are shown in Table 1.
Preparation example 1
(1) A solution was prepared of 50g of ammonium metavanadate, 115.4g of oxalic acid, 4.62g of cesium sulfate, 0.1g of monoammonium phosphate, 5g of niobium oxalate, 0.2g of potassium sulfate, 220mL of formamide and 2200mL of water.
(2) The solution was poured into a ball mill together with 625g of titanium dioxide, 12.22g of antimony trioxide, and an appropriate amount of vinyl acetate/ethylene copolymer emulsion was added, ball-milled for 4 hours to form a uniform slurry, and the concentration of the slurry was controlled to 15 mPas.
(3) 2000G of talcum ring inert carrier (with the outer diameter of 6mm, the height of 5mm, the wall thickness of 1.5mm and the surface area of 183.7mm 2) is placed in a rotary drum, the speed of the rotary drum is controlled to be 5rpm, the prepared emulsion is added into a stirring tank of a feed liquid spraying system to be stirred, a hot air blower is started, hot air with the temperature of 100 ℃ penetrates into the rotary drum to preheat the carrier, a feeding nozzle is started when the temperature of the carrier reaches 110 ℃, the feed liquid spraying speed is controlled to be 30mL/min, slurry is sprayed on the surface of the carrier through the nozzle, the slurry is rapidly dried through the hot air, the content of active components reaches 10wt% of the weight of the carrier, the spraying is completed, and the catalyst medium A1 is obtained after roasting for 5 hours at the temperature of 400 ℃.
Preparation example 1'
According to the method of production example 1, except that 2000g of talc ring inert carrier (outer diameter 6mm, height 5mm, wall thickness 1.5mm, surface area 183.7mm 2) was replaced with 2000g of talc ring inert carrier (outer diameter 8mm, height 6mm, wall thickness 1.5mm, surface area 306.2mm 2), the remaining conditions were the same, to obtain catalytic medium A2.
Preparation example 2
(1) A solution was prepared from 55.75g of ammonium metavanadate, 128.67g of oxalic acid, 3.21g of cesium sulfate, 0.1g of monoammonium phosphate, 5.25g of niobium oxalate, 0.1g of potassium sulfate, 220mL of formamide and 2200mL of water.
(2) The solution was poured into a ball mill together with 625g of titanium dioxide, 12.22g of antimony trioxide, and an appropriate amount of vinyl acetate/ethylene copolymer emulsion was added, ball-milled for 4 hours to form a uniform slurry, and the concentration of the slurry was controlled to 13 mPas.
(3) 2000G of talcum ring inert carrier (with the outer diameter of 6mm, the height of 6mm, the wall thickness of 1.5mm and the surface area of 212mm 2) is placed in a rotary drum, the speed of the rotary drum is controlled to be 5rpm, the prepared emulsion is added into a stirring tank of a feed liquid spraying system to be stirred, a hot air blower is started, hot air with the temperature of 100 ℃ penetrates into the rotary drum to preheat the carrier, a feeding nozzle is started when the temperature of the carrier reaches 90 ℃, the feed liquid spraying speed is controlled to be 50mL/min, slurry is sprayed on the surface of the carrier through the nozzle, the slurry is quickly dried through the hot air, the content of active components reaches 13 weight percent of the carrier, the spraying is completed, and the catalyst medium B1 is obtained after roasting for 5 hours at 400 ℃.
Preparation example 2'
According to the method of production example 2, except that 2000g of talc ring inert carrier (outer diameter 6mm, height 6mm, wall thickness 1.5mm, surface area 212mm 2) was replaced with 2000g of talc ring inert carrier (outer diameter 8mm, height 6mm, wall thickness 1.5mm, surface area 306.2mm 2), the remaining conditions were the same, to obtain catalytic medium B2.
Preparation example 3
(1) A solution was prepared from 60.08g of ammonium metavanadate, 138.66g of oxalic acid, 2.14g of cesium sulfate, 4.12g of monoammonium phosphate, 3.86g of niobium oxalate, 0.05g of potassium sulfate, 3.59g of zirconium sulfate tetrahydrate, 220mL of formamide and 2200mL of water.
(2) The solution was poured into a ball mill together with 625g of titanium dioxide, 17.45g of antimony trioxide, and an appropriate amount of vinyl acetate/ethylene copolymer emulsion was added, ball-milled for 4 hours to form a uniform slurry, and the slurry concentration was controlled to be 14mpa·s.
(3) 2000G of talcum ring inert carrier (with the outer diameter of 7mm, the height of 7mm, the wall thickness of 1.5mm and the surface area of 293.6mm 2) is placed in a rotary drum, the speed of the rotary drum is controlled to be 5rpm, the prepared emulsion is added into a stirring tank of a feed liquid spraying system to be stirred, a hot air blower is started, hot air with the temperature of 100 ℃ penetrates into the rotary drum to preheat the carrier, a feeding nozzle is started when the temperature of the carrier reaches 130 ℃, the feed liquid spraying speed is controlled to be 60mL/min, slurry is sprayed on the surface of the carrier through the nozzle, the slurry is rapidly dried through the hot air, the content of active components reaches 14 weight percent of the carrier, the spraying is completed, and the catalyst medium C1 is obtained after roasting for 5 hours at 400 ℃.
PREPARATION EXAMPLE 3'
According to the method of production example 3, except that 2000g of talc ring inert carrier (outer diameter 7mm, height 7mm, wall thickness 1.5mm, surface area 293.6mm 2) was replaced with 2000g of talc ring inert carrier (outer diameter 8mm, height 6mm, wall thickness 1.5mm, surface area 306.2mm 2), the remaining conditions were the same, to obtain catalytic medium C2.
Preparation example 4
(1) 72.28G of ammonium metavanadate, 166.82g of oxalic acid, 0.4g of cesium sulfate, 5.18g of monoammonium phosphate, 6.68g of niobium oxalate, 4.39g of zirconium sulfate tetrahydrate, 220mL of formamide and 2200mL of water were prepared as a solution.
(2) The solution was poured into a ball mill together with 625g of titanium dioxide, 2.57g of antimony trioxide, and an appropriate amount of vinyl acetate/ethylene copolymer emulsion was added, ball-milled for 4 hours to form a uniform slurry, and the slurry concentration was controlled to 12mpa·s.
(3) 2000G of talcum ring inert carrier (with the outer diameter of 8mm, the height of 6mm, the wall thickness of 1.5mm and the surface area of 306.2mm 2) is placed in a rotary drum, the speed of the rotary drum is controlled to be 5rpm, the prepared emulsion is added into a stirring tank of a feed liquid spraying system to be stirred, a hot air blower is started, hot air with the temperature of 100 ℃ penetrates into the rotary drum to preheat the carrier, a feeding nozzle is started when the temperature of the carrier reaches 100 ℃, the feed liquid spraying speed is controlled to be 30mL/min, slurry is sprayed on the surface of the carrier through the nozzle, the slurry is quickly dried through the hot air, the content of active components reaches 15wt% of the weight of the carrier, the spraying is completed, and the catalyst medium D1 is obtained after roasting for 5 hours at 400 ℃.
TABLE 1
Example 1
Filling catalytic media by adopting a fixed bed single-tube reactor simulating industrial production conditions, wherein the inner diameter of the fixed bed single-tube reactor is 29mm, the tube length is 4400mm, the filling height is 3400mm, the fixed bed single-tube reactor sequentially comprises a first catalyst bed layer, a second catalyst bed layer and a third catalyst bed layer in the raw material flow direction, wherein the catalytic media A1, the catalytic media C1 and the catalytic media D1 are sequentially filled in the first catalyst bed layer, the second catalyst bed layer and the third catalyst bed layer, and the filling lengths of the first catalyst bed layer, the second catalyst bed layer and the third catalyst bed layer are sequentially 1600mm, 800mm and 1000mm;
Wherein, the S 1 of the first catalyst bed layer is 618cm 2, the S 2 of the second catalyst bed layer is 500cm 2, the S 3 of the third catalyst bed layer is 400cm 2, that is, the S n of each catalyst bed layer is gradually decreased along the flow direction;
Wherein, the P 1 of the first catalyst bed layer is 183.7mm 2, the P 2 of the second catalyst bed layer is 293.6mm 2, the P 3 of the third catalyst bed layer is 306.2mm 2, namely, the P n of each catalyst bed layer is gradually increased along the flow direction;
Wherein S 1 and P 1 of the first catalyst bed satisfy the relationship of formula (1): Wherein m= 163.58, S 2 and P 2 of the second catalyst bed satisfy the relationship of formula (1): Wherein m= 163.03, and S 3 and P 3 of the third catalyst bed satisfy the relation of formula (1): where m= 119.37.
Example 2
Filling catalytic media by adopting a fixed bed single-tube reactor simulating industrial production conditions, wherein the inner diameter of the fixed bed single-tube reactor is 29mm, the tube length is 4400mm, the filling height is 3400mm, the fixed bed single-tube reactor sequentially comprises a first catalyst bed layer, a second catalyst bed layer and a third catalyst bed layer in the raw material flow direction, wherein the catalytic media A1, the catalytic media B1 and the catalytic media D1 are sequentially filled in the first catalyst bed layer, the second catalyst bed layer and the third catalyst bed layer, and the filling lengths of the first catalyst bed layer, the second catalyst bed layer and the third catalyst bed layer are 1400mm, 1200mm and 800mm in sequence;
Wherein, the S 1 of the first catalyst bed layer is 603cm 2, the S 2 of the second catalyst bed layer is 585cm 2, the S 3 of the third catalyst bed layer is 405cm 2, that is, the S n of each catalyst bed layer is gradually decreased along the flow direction;
Wherein, the P 1 of the first catalyst bed layer is 183.7mm 2, the P 2 of the second catalyst bed layer is 212mm 2, the P 3 of the third catalyst bed layer is 306.2mm 2, namely, the P n of each catalyst bed layer is gradually increased along the flow direction;
Wherein S 1 and P 1 of the first catalyst bed satisfy the relationship of formula (1): Wherein m= 171.75, S 2 and P 2 of the second catalyst bed satisfy the relationship of formula (1): wherein m=57.39, and S 3 and P 3 of the third catalyst bed satisfy the relation of formula (1): where m= 117.73.
Example 3
Filling catalytic media by adopting a fixed bed single-tube reactor simulating industrial production conditions, wherein the inner diameter of the fixed bed single-tube reactor is 29mm, the tube length is 4400mm, the filling height is 3400mm, the fixed bed single-tube reactor sequentially comprises a first catalyst bed layer, a second catalyst bed layer, a third catalyst bed layer and a fourth catalyst bed layer in the raw material flow direction, wherein the catalytic media A1, the catalytic media B1, the catalytic media C1 and the catalytic media D1 are sequentially filled in the first catalyst bed layer, the second catalyst bed layer, the third catalyst bed layer and the fourth catalyst bed layer, and the filling lengths of the first catalyst bed layer, the second catalyst bed layer, the third catalyst bed layer and the fourth catalyst bed layer are 1400mm, 700mm, 800mm and 500mm in sequence;
Wherein, the S 1 of the first catalyst bed layer is 610cm 2, the S 2 of the second catalyst bed layer is 589cm 2, the S 3 of the third catalyst bed layer is 495cm 2, the S 4 of the fourth catalyst bed layer is 400cm 2, namely, the S n of each catalyst bed layer is gradually decreased along the material flow direction;
Wherein, the P 1 of the first catalyst bed layer is 183.7mm 2, the P 2 of the second catalyst bed layer is 212mm 2, the P 3 of the third catalyst bed layer is 293.6mm 2, the P 4 of the fourth catalyst bed layer is 306.2mm 2, namely, the P n of each catalyst bed layer is gradually increased along the flow direction;
Wherein S 1 and P 1 of the first catalyst bed satisfy the relationship of formula (1): Wherein m= 167.94, S 2 and P 2 of the second catalyst bed satisfy the relationship of formula (1): Wherein m=55.5, and S 3 and P 3 of the third catalyst bed satisfy the relationship of formula (1): Wherein m=81.4, and S 4 and P 4 of the fourth catalyst bed satisfy the relationship of formula (1): Where m= 69.37.
Example 4
According to the method of example 1, except that the first catalyst bed, the second catalyst bed and the third catalyst bed are sequentially filled with the catalytic medium A1, the catalytic medium B1 and the catalytic medium C1, the remaining conditions are the same;
Wherein, the S 1 of the first catalyst bed layer is 605cm 2, the S 2 of the second catalyst bed layer is 592cm 2, the S 3 of the third catalyst bed layer is 500cm 2, that is, the S n of each catalyst bed layer is gradually decreased along the flow direction;
Wherein, the P 1 of the first catalyst bed layer is 183.7mm 2, the P 2 of the second catalyst bed layer is 212mm 2, the P 3 of the third catalyst bed layer is 293.6mm 2, namely, the P n of each catalyst bed layer is gradually increased along the flow direction;
Wherein S 1 and P 1 of the first catalyst bed satisfy the relationship of formula (1): Wherein m= 170.66, S 2 and P 2 of the second catalyst bed satisfy the relationship of formula (1): wherein m=54.08, and S 3 and P 3 of the third catalyst bed satisfy the relationship of formula (1): where m=79.7.
Comparative example 1
According to the method of example 1, except that the first catalyst bed, the second catalyst bed and the third catalyst bed are sequentially filled with the catalytic medium A2, the catalytic medium C2 and the catalytic medium D1, the remaining conditions are the same;
Wherein, the S 1 of the first catalyst bed layer is 611cm 2, the S 2 of the second catalyst bed layer is 608cm 2, the S 3 of the third catalyst bed layer is 400cm 2, that is, the S n of each catalyst bed layer is gradually decreased along the flow direction;
wherein, the P 1 of the first catalyst bed layer is 306.2mm 2, the P 2 of the second catalyst bed layer is 306.2mm 2, the P 3 of the third catalyst bed layer is 306.2mm 2, that is, the P n of each catalyst bed layer does not meet the requirement of sequential increasing along the flow direction;
Wherein S 1 and P 1 of the first catalyst bed do not satisfy the relationship of formula (1): wherein m= 300.46, S 2 and P 2 of the second catalyst bed satisfy the relationship of formula (1): Wherein m= 134.77, and S 3 and P 3 of the third catalyst bed satisfy the relation of formula (1): where m= 119.37.
Comparative example 2
According to the method of example 2, except that the first catalyst bed, the second catalyst bed and the third catalyst bed are sequentially filled with the catalytic medium A2, the catalytic medium B2 and the catalytic medium D1, the remaining conditions are the same;
wherein, the S 1 of the first catalyst bed layer is 614cm 2, the S 2 of the second catalyst bed layer is 616cm 2, the S 3 of the third catalyst bed layer is 405cm 2, that is, the S n of each catalyst bed layer is not gradually decreased along the flow direction;
wherein, the P 1 of the first catalyst bed layer is 306.2mm 2, the P 2 of the second catalyst bed layer is 306.2mm 2, the P 3 of the third catalyst bed layer is 306.2mm 2, that is, the P n of each catalyst bed layer does not meet the requirement of sequential increasing along the flow direction;
Wherein S 1 and P 1 of the first catalyst bed do not satisfy the relationship of formula (1): Wherein m= 299.48, S 2 and P 2 of the second catalyst bed do not satisfy the relationship of formula (1): Wherein m= 298.82, and S 3 and P 3 of the third catalyst bed satisfy the relation of formula (1): where m= 117.73.
Comparative example 3
According to the method of example 3, except that the first catalyst bed, the second catalyst bed, the third catalyst bed and the fourth catalyst bed are sequentially filled with the catalytic medium A2, the catalytic medium B2, the catalytic medium C2 and the catalytic medium D1, the remaining conditions are the same;
Wherein, the S 1 of the first catalyst bed layer is 611cm 2, the S 2 of the second catalyst bed layer is 615cm 2, the S 3 of the third catalyst bed layer is 607cm 2, the S 4 of the fourth catalyst bed layer is 400cm 2, that is, the S n of each catalyst bed layer is gradually decreased along the material flow direction;
Wherein, the P 1 of the first catalyst bed layer is 306.2mm 2, the P 2 of the second catalyst bed layer is 306.2mm 2, the P 3 of the third catalyst bed layer is 306.2mm 2, the P 4 of the fourth catalyst bed layer is 306.2mm 2, namely, the P n of each catalyst bed layer does not increase gradually along the flow direction;
Wherein S 1 and P 1 of the first catalyst bed do not satisfy the relationship of formula (1): wherein m= 300.46, S 2 and P 2 of the second catalyst bed satisfy the relationship of formula (1): Wherein m= 132.48, and S 3 and P 3 of the third catalyst bed satisfy the relation of formula (1): Wherein m=51.76, and S 4 and P 4 of the fourth catalyst bed satisfy the relationship of formula (1): Where m= 69.37.
Test case
The fixed bed single tube reactors filled with the catalytic medium of the above examples and comparative examples were evaluated by charging ortho-xylene and air. The conditions for evaluation included a volume space velocity of 3000 to 4000h -1 and the test results are shown in Table 2.
TABLE 2
As can be seen from the data in Table 2, when the catalyst provided by the invention is used for the reaction of oxidizing o-xylene to prepare phthalic anhydride, the conversion rate of o-xylene is as high as 99.95%, and the yield of phthalic anhydride is as high as 115.2%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
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| CN101166572A (en) * | 2004-05-29 | 2008-04-23 | 苏德-化学股份公司 | Multi-layered catalyst for producing phthalic anhydride |
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