CN110860316B - Activation method for hydrocarbon oxidation VPO catalyst - Google Patents
Activation method for hydrocarbon oxidation VPO catalyst Download PDFInfo
- Publication number
- CN110860316B CN110860316B CN201911208323.9A CN201911208323A CN110860316B CN 110860316 B CN110860316 B CN 110860316B CN 201911208323 A CN201911208323 A CN 201911208323A CN 110860316 B CN110860316 B CN 110860316B
- Authority
- CN
- China
- Prior art keywords
- vpo catalyst
- hydrocarbon oxidation
- activation
- activated
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an activation method for a hydrocarbon oxidation VPO catalyst, which comprises the following steps: 1. mixing an activating atmosphere with a hydrocarbon oxidation VPO catalyst and then feeding the mixture into a reaction tube; 2. activating the hydrocarbon oxidation VPO catalyst and the activated atmosphere entering the reaction tube through an activation zone to obtain an activated hydrocarbon oxidation VPO catalyst and tail gas; 3. and discharging the activated hydrocarbon oxidation VPO catalyst and tail gas, and then separating. According to the invention, the hydrocarbon oxidation VPO catalyst and the activation atmosphere are mixed and continuously pass through the activation zones with different temperatures from top to bottom at a constant speed and are simultaneously activated, so that the continuous activation of the hydrocarbon oxidation VPO catalyst is realized, the stability of the continuous activation process is good, the activation treatment capacity of the hydrocarbon oxidation VPO catalyst is improved, the uniformity of the performance of the activated hydrocarbon oxidation VPO catalyst is ensured, the operation steps are simplified, and the activation cost is saved.
Description
Technical Field
The invention belongs to the technical field of catalyst activation, and particularly relates to an activation method for a hydrocarbon oxidation VPO catalyst.
Background
The selective oxidation process of hydrocarbons plays an extremely important role in the petrochemical industry. According to statistics, the products produced by catalytic selective oxidation account for about 25% of various organic chemicals produced by the catalytic process. The VPO system pore structure material has rich structural chemical characteristics and excellent physicochemical properties, shows good potential application value in the modern industrial field, and is a hot spot of international advanced material research. In the reaction of preparing maleic anhydride by oxidizing n-butane, VPO catalyst (vanadium phosphorus oxide catalyst) is considered as the most effective industrial catalyst for preparing maleic anhydride by selectively oxidizing n-butane after being modified or loaded. The VPO-based catalyst can also be used for selective oxidation of other hydrocarbons.
The activation process is a key factor affecting the activity and selectivity of VPO catalysts. In recent years, researchers have been working on improving the activity and selectivity of VPO catalysts.
Patent application publication No. CN106540728A discloses a method for activating a VPO catalyst used in the preparation of maleic anhydride by oxidation of n-butane. The method comprises the steps of putting a VPO catalyst into a fixed bed reactor for activation, and controlling the activation process by adopting different activation atmospheres at different temperature sections to obtain the VPO catalyst with better activity. However, the catalyst activation process of the method is a batch type, and the activation can be carried out only in batches. Because the activation process is discontinuous, part of the catalyst is not activated uniformly. The patent with the application publication number of CN1037096A provides an activation process of a cis-anhydride vanadium phosphorus oxygen catalyst prepared from n-butane. The method activates a catalyst in a fixed bed reactor, the VPO catalyst is doped with quartz sand, the VPO catalyst is heated to a certain temperature at a certain heating rate after being treated, and the catalyst is activated for a certain time under a proper atmosphere to complete the activation of the catalyst. The VPO catalyst activated by the method has better catalytic activity, the addition of quartz sand can improve the catalyst activation condition, but the catalyst activation of the method belongs to a batch mode, and the quartz sand needs to be separated after the activation is completed, so that the catalyst activation treatment capacity is reduced. Patent application publication No. CN104549392a discloses a method of using an ebullated bed for preparation, work-up and activation of VPO catalysts. Adding the catalyst preparation raw materials into a fluidized bed reactor together for reaction for a period of time, then adding concentrated phosphoric acid for continuous reaction, carrying out in-situ drying and roasting on the obtained blue slurry, and then introducing activated gas for activation treatment to finally obtain the VPO catalyst. The VPO catalyst prepared by the method has better catalytic activity, but the cost of an ebullated bed system is high, and the catalyst activation is not continuously carried out.
Much work has been done by researchers, but as mentioned above, the existing VPO catalyst activation technology suffers from the following disadvantages: (1) the activation process of the catalyst is discontinuous and is not easy to operate; (2) the performance of the activated catalyst varies from batch to batch; and (3) the catalyst has low activation treatment capacity.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for activating a VPO catalyst for hydrocarbon oxidation, which addresses the deficiencies of the prior art mentioned above. The method mixes the hydrocarbon oxidation VPO catalyst with the activation atmosphere, continuously passes through the activation areas with different temperatures from top to bottom at a constant speed, and activates the catalyst simultaneously, so that the continuous activation of the hydrocarbon oxidation VPO catalyst is realized, the stability of the continuous activation process is good, the activation treatment capacity of the hydrocarbon oxidation VPO catalyst is improved, the uniformity of the performance of the activated hydrocarbon oxidation VPO catalyst is ensured, the operation steps are simplified, and the activation cost is saved.
In order to solve the technical problems, the invention adopts the technical scheme that: a process for activating a VPO catalyst for the oxidation of hydrocarbons, characterized in that it comprises the following steps:
step one, respectively feeding an activated atmosphere and a hydrocarbon oxidation VPO catalyst into a reactor through a gas inlet and a feeder, mixing at inlets of a plurality of reaction tubes, and then feeding into the plurality of reaction tubes;
step two, the activated atmosphere entering the plurality of reaction tubes and the hydrocarbon oxidation VPO catalyst in the step one sequentially pass through a plurality of activation areas at a constant speed from top to bottom and are activated simultaneously to obtain an activated hydrocarbon oxidation VPO catalyst and tail gas; the temperatures of the multiple activation zones gradually increase from top to bottom;
and step three, discharging the activated hydrocarbon oxidation VPO catalyst and tail gas obtained in the step two from outlets of the plurality of reaction tubes, and then falling into a sieve plate for separation, discharging the tail gas from a gas outlet, and allowing the activated hydrocarbon oxidation VPO catalyst to fall into a catalyst collector along the sieve plate.
The activation method for the VPO catalyst for hydrocarbon oxidation is characterized in that in the first step, the activation atmosphere is one or more of gaseous hydrocarbon with the carbon number less than 5, air, carbon monoxide, inert gas and water vapor, and the inert gas is one or more of nitrogen, argon, carbon dioxide and helium. When the activating atmosphere consists of air and gaseous hydrocarbon with the carbon number less than 5, the molar concentration of the gaseous hydrocarbon with the carbon number less than 5 is preferably 1 to 2 percent; when the activating atmosphere consists of water vapor and air, the molar concentration of the water vapor is preferably 10 to 90 percent, and more preferably 40 to 50 percent; when the activating atmosphere is composed of water vapor and an inert gas, the molar concentration of the inert gas is preferably 10% to 90%, more preferably 50% to 70%.
A process for activating a VPO catalyst for hydrocarbon oxidation as described above, wherein in step one said VPO catalyst for hydrocarbon oxidation is prepared from compound V (M) a O b HPO 4 ·0.5H 2 O and a carrier, wherein compound V (M) a O b HPO 4 ·0.5H 2 M in O is one or more than two elements in IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB and VIIIA group elements, a = 0-0.2, b is the mole ratio of oxygen elements meeting the valence of each element in the formula; the mass percent of the carrier in the hydrocarbon oxidation VPO catalyst is 0-95%.
The activation method for the hydrocarbon oxidation VPO catalyst is characterized in that the carrier is alumina, silica, titania or silicon carbide.
The activation method for the hydrocarbon oxidation VPO catalyst is characterized in that in the step one, the hydrocarbon oxidation VPO catalyst is in a hollow cylinder shape, a bar shape, a spherical shape, a cylindrical shape or a clover shape.
The activation method for the hydrocarbon oxidation VPO catalyst is characterized in that the introduction space velocity of the activation atmosphere in the step one is 100h -1 ～3000h -1 The single-tube feed rate of the hydrocarbon oxidation VPO catalyst is 0.5 kg.h -1 ～3kg·h -1 。
The activation method for the hydrocarbon oxidation VPO catalyst is characterized in that the activation atmosphere in the step one is preheated by raising the temperature to 200 ℃ at the rate of 5-60 ℃/h before being fed into the reactor.
The activation method for the VPO catalyst for hydrocarbon oxidation is characterized in that the number of the activation zones in the second step is 3-30, each activation zone is independently controlled in temperature, and the temperature of the activation zones is 200-440 ℃.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the hydrocarbon oxidation VPO catalyst and the activation atmosphere are mixed and then enter each reaction tube, and then continuously pass through each activation zone with different temperatures at a constant speed from top to bottom and are simultaneously activated, so that the continuous activation of the hydrocarbon oxidation VPO catalyst is realized, the stability of the continuous activation process is good, the activation treatment capability of the hydrocarbon oxidation VPO catalyst is improved, the uniformity of the performance of the activated hydrocarbon oxidation VPO catalyst is ensured, the operation steps are simplified, and the activation cost is saved.
2. In the activation process, the temperature of each activation zone can be independently controlled, and different activation times can be controlled by setting and adjusting the height of the activation zones, so that the stability of the activation conditions is ensured, the difference between catalytic performances obtained by different batches of activation is reduced, and the batch production is easy to realize; in addition, because the activation temperature and time are adjustable, different activation methods can be formulated according to different hydrocarbon oxidation VPO catalysts, the precision of the activation method is improved, and the application range of the activation method is widened.
3. The continuous activation of the hydrocarbon oxidation VPO catalyst is realized by directly taking the hydrocarbon oxidation VPO catalyst and the activation atmosphere as raw materials without adding auxiliary materials, so that the activation efficiency of the hydrocarbon oxidation VPO catalyst is greatly improved, and the activation cost is reduced; in the subsequent process, only a physical method is needed to carry out one-step solid-gas separation on the activated hydrocarbon oxidation VPO catalyst and the tail gas, the method is simple and easy to operate, the activation efficiency of the hydrocarbon oxidation VPO catalyst is further improved, and the catalytic performance of the activated hydrocarbon oxidation VPO catalyst is not adversely affected.
4. The hot spot temperature of the catalytic reaction of the activated hydrocarbon oxidation VPO catalyst obtained by the invention is 30 ℃ lower than that of the existing hydrocarbon oxidation VPO catalyst.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a schematic view of the structure of an activation apparatus according to the present invention.
Description of the reference numerals
1-a reactor; 2-a jacket; 3-a reaction tube;
4-molten salt circulating system; 5, an upper tube plate; 6-a partition plate;
7, a baffle plate; 8, a lower tube plate; 9, a sieve plate;
10-a catalyst collector; 11-an air inlet; 12-air outlet.
13-a housing; 14-a feeder.
Detailed Description
As shown in fig. 1, the activation apparatus of the present invention includes a reactor 1 and a feeder 14 connected to an upper portion of the reactor 1, wherein a plurality of reaction tubes 3 are arranged in parallel in a vertical direction in a cavity surrounded by a shell 13 of the reactor 1, the shell 13 and the plurality of reaction tubes 3 form a jacket 2, an air inlet 11 and an air outlet 12 are respectively opened at an upper end and a lower end of the shell 13, the upper end and the lower end of the plurality of reaction tubes 3 are respectively fixed in an upper tube plate 5 and a lower tube plate 8, the upper ends of the plurality of reaction tubes 3 are communicated with the feeder 14, the interior of the jacket 2 is divided into a plurality of activation regions by a partition plate 6 in a direction perpendicular to the reaction tubes 3, a baffle plate 7 is installed in each activation region in a direction parallel to the partition plate 6, each activation region is controlled in temperature by a molten salt circulation system 4, a lower portion of the lower tube plate 8 is obliquely installed with a baffle plate 9, and a terminal of the sieve plate 9 is connected with a catalyst collector 10.
Example 1
The method of the embodiment comprises the following steps:
step one, raising the temperature of an activated atmosphere to 200 ℃ at a temperature rise rate of 30 ℃/h for preheating, and then raising the temperature of the preheated activated atmosphere to 800h under the pressure of 0.12MPa -1 The hydrocarbon oxidation VPO catalyst is fed into the reactor 1 through the gas inlet 11 and the feeder 14 respectively, mixed at the inlet of the reaction tube 3 and then fed into the reaction tube 3 respectively, wherein the single-tube feeding speed of the hydrocarbon oxidation VPO catalyst is 1 kg.h -1 (ii) a The activation atmosphere is formed by mixing n-butane and air, wherein the molar concentration of the n-butane is 1.7%; the number of the reaction tubes 3 is 7; the hydrocarbon oxidation VPO catalyst comprises a compound VOHPO 4 ·0.5H 2 O, the hydrocarbonsThe VPO oxidation catalyst is hollow cylindrical particles with the outer diameter of 5.5mm, the inner diameter of 2mm and the height of 6 mm;
step two, the activating atmosphere and the hydrocarbon oxidation VPO catalyst which respectively enter the reaction tube 3 in the step one sequentially pass through 5 activation areas at a constant speed from top to bottom and are activated simultaneously to obtain an activated hydrocarbon oxidation VPO catalyst and tail gas; the temperature of 5 activation areas is from top to bottom in proper order: a first activation zone of 250 ℃, a second activation zone of 300 ℃, a third activation zone of 350 ℃, a fourth activation zone of 400 ℃, a fifth activation zone of 440 ℃;
discharging the activated hydrocarbon oxidation VPO catalyst and tail gas obtained in the step three and the step two from the outlet of the reaction tube 3, and then falling into a sieve plate 9 for separation, discharging the tail gas from a gas outlet 12, and allowing the activated hydrocarbon oxidation VPO catalyst to fall into a catalyst collector 10 along the sieve plate 9.
The activated hydrocarbon oxidation VPO catalyst obtained in this example was found to have a specific surface area of 15m 2 The volume of pores is 0.2mL/g, and the average valence of V ion is 4.20.
The activating atmosphere in this embodiment may be a mixed gas of one or two or more of gaseous hydrocarbons having a carbon number of less than 5, air, carbon monoxide, an inert gas and water vapor, in addition to the mixed gas of n-butane and air, the inert gas being a mixed gas of one or two or more of nitrogen, argon, carbon dioxide and helium.
Component V (M) of the Hydrocarbon Oxidation VPO catalyst in this example a O b HPO 4 ·0.5H 2 M in O can also be one or more than two elements in IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB and VIIIA group elements, a is more than 0 and less than or equal to 0.2, b is the molar ratio of oxygen required by satisfying the valence of each element in the formula.
Example 2
The method of the embodiment comprises the following steps:
step one, raising the temperature of an activation atmosphere to 200 ℃ at a temperature rise rate of 5 ℃/h for preheating, and then raising the temperature of the preheated activation atmosphere to 1000h under the pressure of 0.12MPa -1 Space velocity of (3), VPO catalyst for oxidizing hydrocarbonsAre fed into the reactor 1 through the gas inlet 11 and the feeder 14, respectively, mixed at the inlet of the reaction tube 3, and then fed into the reaction tube 3, wherein the single-tube feeding rate of the hydrocarbon oxidation VPO catalyst is 1.2 kg.h -1 (ii) a The activating atmosphere is formed by mixing water vapor and nitrogen, wherein the molar concentration of the water vapor is 50%; the number of the reaction tubes 3 is 7; the hydrocarbon oxidation VPO catalyst comprises a compound VMo 0.2 O 1.6 HPO 4 ·0.5H 2 O, the hydrocarbon oxidation VPO catalyst is spherical particles with the diameter of 3 mm;
step two, the activated atmosphere entering the reaction tube 3 and the hydrocarbon oxidation VPO catalyst in the step one sequentially pass through 3 activation areas at a constant speed from top to bottom and are simultaneously activated to obtain an activated hydrocarbon oxidation VPO catalyst and tail gas; the temperature of 3 activation areas is from last to being down in proper order: a first activation zone of 250 ℃, a second activation zone of 350 ℃, and a third activation zone of 420 ℃;
and step three, discharging the activated hydrocarbon oxidation VPO catalyst and tail gas obtained in the step two from an outlet of the reaction tube 3, and then falling into a sieve plate 9 for separation, discharging the tail gas from a gas outlet 12, and allowing the activated hydrocarbon oxidation VPO catalyst to fall into a catalyst collector 10 along the sieve plate 9.
The activated hydrocarbon oxidation VPO catalyst obtained in the example was tested to have a specific surface area of 18m 2 The volume of pores is 0.18mL/g, and the average valence of V ions is 4.03.
The activating atmosphere in this embodiment may be a mixed gas of one or more of gaseous hydrocarbon having less than 5 carbon atoms, air, carbon monoxide, inert gas and water vapor, the inert gas being a mixed gas of one or more of nitrogen, argon, carbon dioxide and helium, in addition to the mixed gas of water vapor and nitrogen.
Component V (M) of the Hydrocarbon Oxidation VPO catalyst in this example a O b HPO 4 ·0.5H 2 M in O can also be one or more than two elements in IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB and VIIIA group elements except Mo, a = 0-0.2, b is the valence number of each element in the formulaMolar ratio of aerobic elements.
Example 3
The method of the embodiment comprises the following steps:
step one, raising the temperature of an activating atmosphere to 200 ℃ at a temperature raising rate of 60 ℃/h for preheating, and then raising the temperature of the preheated activating atmosphere to 3000h under the pressure of 0.12MPa -1 The hydrocarbon oxidation VPO catalyst is fed into the reactor 1 through the gas inlet 11 and the feeder 14 respectively, mixed at the inlet of the reaction tube 3 and then fed into the reaction tube 3, wherein the single-tube feeding speed of the hydrocarbon oxidation VPO catalyst is 3 kg.h -1 (ii) a The activating atmosphere is formed by mixing water vapor and air, wherein the molar concentration of the water vapor is 50%; the number of the reaction tubes 3 is 3; the hydrocarbon oxidation VPO catalyst consists of V (FeBi) 0.05 O 1.15 HPO 4 ·0.5H 2 The catalyst consists of O and a titanium oxide carrier, wherein the mass percent of the titanium oxide carrier in the hydrocarbon oxidation VPO catalyst is 30 percent, and the hydrocarbon oxidation VPO catalyst is cloverleaf strip-shaped particles with the diameter of 3mm and the length of 3 mm;
step two, the activated atmosphere and the hydrocarbon oxidation VPO catalyst entering the reaction tube 3 in the step one sequentially pass through 4 activation areas at a constant speed from top to bottom and are activated simultaneously to obtain an activated hydrocarbon oxidation VPO catalyst and tail gas; the temperature of 4 activation areas is from top to bottom in proper order: a first activation zone of 250 ℃, a second activation zone of 350 ℃, a third activation zone of 390 ℃, and a fourth activation zone of 440 ℃;
discharging the activated hydrocarbon oxidation VPO catalyst and tail gas obtained in the third step and the second step from outlets of the plurality of reaction tubes 3, and then falling into a sieve plate 9 for separation, discharging the tail gas from a gas outlet 12, and allowing the activated hydrocarbon oxidation VPO catalyst to fall into a catalyst collector 10 along the sieve plate 9.
The activated hydrocarbon oxidation VPO catalyst obtained in the example was found to have a specific surface area of 16m 2 The volume of pores is 0.14mL/g, and the average valence of V ions is 4.01.
The activating atmosphere in this embodiment may also be one or a mixture of two or more of gaseous hydrocarbon having less than 5 carbon atoms, air, carbon monoxide, inert gas and water vapor, excluding the mixture of water vapor and air, wherein the inert gas is one or a mixture of two or more of nitrogen, argon, carbon dioxide and helium.
Component V (M) of the Hydrocarbon Oxidation VPO catalyst in this example a O b HPO 4 ·0.5H 2 M in O can also be one or more than two elements in IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB and VIIIA elements except Fe and Bi, a = 0-0.2, b is the mole ratio of oxygen elements meeting the valence of each element in the formula.
Example 4
The method of the embodiment comprises the following steps:
step one, raising the temperature of the activation atmosphere to 200 ℃ at a rate of 45 ℃/h for preheating, and then raising the temperature of the preheated activation atmosphere at a pressure of 0.12MPa for 100h -1 The hydrocarbon oxidation VPO catalyst is fed into the reactor 1 through the gas inlet 11 and the feeder 14 respectively, mixed at the inlet of the reaction tube 3, and then fed into the plurality of reaction tubes 3, wherein the single-tube feeding speed of the hydrocarbon oxidation VPO catalyst is 0.5 kg.h -1 (ii) a The activating atmosphere is formed by mixing water vapor and nitrogen, wherein the molar concentration of the water vapor is 70%; the number of the reaction tubes 3 is 3; the hydrocarbon oxidation VPO catalyst consists of a compound V (MoFeBi) 0.05 O 1.3 HPO 4 ·0.5H 2 The catalyst consists of O and an alumina powder carrier, wherein the mass percent of the alumina powder in the hydrocarbon oxidation VPO catalyst is 95 percent, and the hydrocarbon oxidation VPO catalyst is cloverleaf particles with the diameter of 3mm and the length of 3 mm;
step two, the activated atmosphere and the hydrocarbon oxidation VPO catalyst entering the plurality of reaction tubes 3 in the step one sequentially pass through 30 activation areas at a constant speed from top to bottom and are activated simultaneously to obtain an activated hydrocarbon oxidation VPO catalyst and tail gas; the temperatures of the 30 activation zones are distributed in an arithmetic progression from 200 ℃ to 440 ℃ from top to bottom;
discharging the activated hydrocarbon oxidation VPO catalyst and tail gas obtained in the step three and the step two from outlets of the plurality of reaction tubes 3, and then falling into a sieve plate 9 for separation, discharging the tail gas from a gas outlet 12, and allowing the activated hydrocarbon oxidation VPO catalyst to fall into a catalyst collector 10 along the sieve plate 9.
The activated hydrocarbon oxidation VPO catalyst obtained in the example has a specific surface area of 17m 2 The volume of pores is 0.15mL/g, and the average valence of V ions is 4.02.
The activating atmosphere in this embodiment may be a mixed gas of one or more of gaseous hydrocarbon having less than 5 carbon atoms, air, carbon monoxide, inert gas and water vapor, the inert gas being a mixed gas of one or more of nitrogen, argon, carbon dioxide and helium, in addition to the mixed gas of water vapor and nitrogen.
Component V (M) of the Hydrocarbon Oxidation VPO catalyst in this example a O b HPO 4 ·0.5H 2 M in O can also be one or more than two elements in IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB and VIIIA elements except Mo, fe and Bi, a = 0-0.2, b is the mole ratio of oxygen elements meeting the valence of each element in the formula.
Example 5
The method of the embodiment comprises the following steps:
step one, raising the temperature of an activated atmosphere to 200 ℃ at a temperature rise rate of 15 ℃/h for preheating, and then raising the temperature of the preheated activated atmosphere to 2000h under the pressure of 0.12MPa -1 The hydrocarbon oxidation VPO catalyst is fed into the reactor 1 through the gas inlet 11 and the feeder 14 respectively, mixed at the inlet of the reaction tube 3 and then fed into the reaction tube 3, wherein the single-tube feeding speed of the hydrocarbon oxidation VPO catalyst is 2 kg.h -1 (ii) a The activating atmosphere is formed by mixing isobutane and air, wherein the molar concentration of the isobutane is 1.1%; the number of the reaction tubes 3 is 4; the hydrocarbon oxidation VPO catalyst is prepared from a compound VOHPO 4 ·0.5H 2 O and a silicon dioxide carrier, wherein the mass percent of the silicon dioxide carrier in the hydrocarbon oxidation VPO catalyst is 60 percent, and the hydrocarbon oxidation VPO catalyst is cylindrical particles with the diameter of 2mm and the length of 3 mm;
step two, the activated atmosphere and the hydrocarbon oxidation VPO catalyst entering the plurality of reaction tubes 3 in the step one sequentially pass through 20 activation areas at a constant speed from top to bottom and are activated simultaneously to obtain an activated hydrocarbon oxidation VPO catalyst and tail gas; the temperatures of the 20 activation areas are distributed in an arithmetic progression from 200 ℃ to 440 ℃ from top to bottom;
discharging the activated hydrocarbon oxidation VPO catalyst and tail gas obtained in the step three and the step two from the outlet of the reaction tube 3, and then falling into a sieve plate 9 for separation, discharging the tail gas from a gas outlet 12, and allowing the activated hydrocarbon oxidation VPO catalyst to fall into a catalyst collector 10 along the sieve plate 9.
The activated hydrocarbon oxidation VPO catalyst obtained in the example has a specific surface area of 19m 2 The volume of pores is 0.21mL/g, and the average valence of V ions is 4.11.
The activating atmosphere in this embodiment may be a mixed gas of one or two or more of gaseous hydrocarbons having a carbon number of less than 5, air, carbon monoxide, an inert gas and water vapor, in addition to the mixed gas of isobutane and air, wherein the inert gas is one or two or more of nitrogen, argon, carbon dioxide and helium.
Component V (M) of the Hydrocarbon Oxidation VPO catalyst in this example a O b HPO 4 ·0.5H 2 M in O can be one or more than two elements in IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB and VIIIA group elements, a is more than 0 and less than or equal to 0.2, and b is the molar ratio of oxygen elements meeting the valence of each element in the formula.
Example 6
The method of the embodiment comprises the following steps:
step one, raising the temperature of an activated atmosphere to 200 ℃ at a temperature rise rate of 50 ℃/h for preheating, and then raising the temperature of the preheated activated atmosphere to 2500h under the pressure of 0.12MPa -1 The hydrocarbon oxidation VPO catalyst is fed into the reactor 1 through the gas inlet 11 and the feeder 14 respectively, mixed at the inlet of the reaction tube 3, and then fed into the plurality of reaction tubes 3, wherein the single-tube feeding speed of the hydrocarbon oxidation VPO catalyst is 0.7 kg.h -1 (ii) a The activating atmosphere is formed by mixing water vapor and air, wherein the molar concentration of the water vapor is 90%; the number of the reaction tubes 3 is 4; the hydrocarbon oxidation VPO catalyst is prepared by a compound VFe 0.1 O 1.15 HPO 4 ·0.5H 2 The catalyst consists of O and a silicon carbide carrier, wherein the mass percent of the silicon carbide carrier in the hydrocarbon oxidation VPO catalyst is 85 percent, and the hydrocarbon oxidation VPO catalyst is spherical particles with the diameter of 3 mm;
step two, the activated atmosphere and the hydrocarbon oxidation VPO catalyst entering the plurality of reaction tubes 3 in the step one sequentially pass through 15 activation areas at a constant speed from top to bottom and are simultaneously activated to obtain an activated hydrocarbon oxidation VPO catalyst and tail gas; the temperatures of the 15 activation zones are distributed in an arithmetic progression from 200 ℃ to 440 ℃ from top to bottom;
discharging the activated hydrocarbon oxidation VPO catalyst and tail gas obtained in the step three and the step two from outlets of the plurality of reaction tubes 3, and then falling into a sieve plate 9 for separation, discharging the tail gas from a gas outlet 12, and allowing the activated hydrocarbon oxidation VPO catalyst to fall into a catalyst collector 10 along the sieve plate 9.
The activated hydrocarbon oxidation VPO catalyst obtained in the example was found to have a specific surface area of 16m 2 The volume of pores is 0.16mL/g, and the average valence of V ions is 4.01.
The activating atmosphere in this embodiment may be a mixed gas of one or more of gaseous hydrocarbon having less than 5 carbon atoms, air, carbon monoxide, inert gas, and water vapor, in addition to the mixed gas of water vapor and air, the inert gas being one or more of nitrogen, argon, carbon dioxide, and helium.
Component V (M) of the Hydrocarbon Oxidation VPO catalyst in this example a O b HPO 4 ·0.5H 2 M in O can also be one or more than two elements in IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB and VIIIA elements except Fe, a = 0-0.2, b is the mole ratio of oxygen elements for satisfying the valence of each element in the formula.
Example 7
The method of the embodiment comprises the following steps:
step one, raising the temperature of an activation atmosphere to 200 ℃ at a temperature raising rate of 25 ℃/h for preheating, and then raising the temperature of the preheated activation atmosphere at a pressure of 0.12MPa for 1500h -1 The hydrocarbon oxidation VPO catalyst is fed into the reactor 1 through the gas inlet 11 and the feeder 14 respectively, mixed at the inlet of the reaction tube 3, and then fed into the plurality of reaction tubes 3, wherein the single-tube feeding speed of the hydrocarbon oxidation VPO catalyst is 2.5 kg.h -1 (ii) a The activating atmosphere is formed by mixing n-butane and air, wherein the molar concentration of the n-butane is 1.6%; the number of the reaction tubes 3 is 2; the hydrocarbon oxidation VPO catalyst comprises a compound VCe 0.05 O 1.1 HPO 4 ·0.5H 2 O, the hydrocarbon oxidation VPO catalyst is spherical particles with the diameter of 2 mm;
step two, the activated atmosphere and the hydrocarbon oxidation VPO catalyst entering the plurality of reaction tubes 3 in the step one sequentially pass through 10 activation areas at a constant speed from top to bottom and are simultaneously activated to obtain an activated hydrocarbon oxidation VPO catalyst and tail gas; the temperatures of the 10 activation areas are distributed in an arithmetic progression from 200 ℃ to 440 ℃ from top to bottom;
discharging the activated hydrocarbon oxidation VPO catalyst and tail gas obtained in the step three and the step two from the outlet of the reaction tube 3, and then falling into a sieve plate 9 for separation, discharging the tail gas from a gas outlet 12, and allowing the activated hydrocarbon oxidation VPO catalyst to fall into a catalyst collector 10 along the sieve plate 9.
The activated hydrocarbon oxidation VPO catalyst obtained in this example was found to have a specific surface area of 19m 2 The volume of pores is 0.18mL/g, and the average valence of V ions is 4.13.
The activating atmosphere in this embodiment may be a mixed gas of one or two or more of gaseous hydrocarbons having a carbon number of less than 5, air, carbon monoxide, an inert gas and water vapor, in addition to the mixed gas of n-butane and air, the inert gas being a mixed gas of one or two or more of nitrogen, argon, carbon dioxide and helium.
Component V (M) of the Hydrocarbon Oxidation VPO catalyst in this example a O b HPO 4 ·0.5H 2 M in O can also be one or more than two elements in IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB and VIIIA elements except Ce, a = 0-0.2, b is the mole ratio of oxygen elements for satisfying the valence of each element in the formula.
The activated hydrocarbon oxidation VPO catalyst obtained in example 1 of the present invention was subjected to X-ray diffraction analysis using an X-ray powder diffractometer from PANalytical, the netherlands, under the following analysis conditions: cu Ka, graphite monochromator, working voltage of 30kV, working current of 30mA, scanning range of 10: ( o )～80( o ) The results show that the main phase before activation of the hydrocarbon oxidation VPO catalyst of example 1 according to the invention is VOHPO 4 ·0.5H 2 The main phase of the activated hydrocarbon oxidation VPO catalyst is (VO) 2 P 2 O 7 。
Respectively selecting a vanadium phosphorus oxygen commercial catalyst produced by Germany southern chemical company and a vanadium phosphorus oxygen commercial catalyst used by Shandong certain maleic anhydride enterprises as a reference substance A and a reference substance B, then detecting the performance of the activated VPO catalyst obtained in the embodiments 1-7 of the invention, the reference substance A and the reference substance B for catalyzing the oxidation of n-butane to maleic anhydride and measuring the hot spot temperature, wherein the detection specific process comprises the following steps: loading the activated hydrocarbon oxidation VPO catalyst/reference substance A/reference substance B in a tubular molten salt heat exchange reactor, taking the mixed gas of n-butane and air with the n-butane molar concentration of 1.7-1.8% as the raw material, and reacting at the temperature of 370-420 ℃ and the volume space velocity of 1800h -1 ～2000h -1 And the reaction pressure was 0.12MPa, and the n-butane conversion and the cis-anhydride selectivity were calculated by analyzing the gas phase composition in the off-gas generated by the reaction and the off-gas absorbing liquid composition, and the results are shown in table 1 below. Wherein, the calculation formulas of the normal butane conversion rate and the cis-anhydride selectivity are as follows:
TABLE 1 activated VPO catalysts and control obtained in inventive examples 1 to 7
A. Hot Point temperature and catalytic Performance of control B
| Examples | Hotspot temperature (. Degree.C.) | N-butane conversion (%) | Maleic anhydride selectivity (%) |
| Example 1 | 384 | 84.9 | 71.3 |
| Example 2 | 392 | 85.3 | 66.6 |
| Example 3 | 395 | 83.4 | 66.7 |
| Example 4 | 398 | 82.9 | 68.2 |
| Example 5 | 382 | 85.1 | 69.8 |
| Example 6 | 396 | 83.5 | 70.4 |
| Example 7 | 383 | 84.2 | 67.5 |
| Control A | 410 | 84.5 | 65.1 |
| Control B | 415 | 82.9 | 65.6 |
It can be seen from table 1 that the activated VPO catalysts obtained in examples 1 to 7 of the present invention have higher n-butane conversion and good maleic anhydride selectivity than those of control a and control B, and the n-butane conversion and the maleic anhydride selectivity of the activated VPO catalysts obtained in examples 1 to 7 are equivalent to or even better than those of control a and control B, and the hot spot temperature is lower, wherein the n-butane conversion and the maleic anhydride selectivity of the activated VPO catalyst obtained in example 5 are improved by 0.6% and 4.7% as compared with control a, and are improved by 2.2% and 4.2% as compared with control a, and the hot spot temperature is lower by about 30 ℃.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (6)
1. A process for activating a VPO catalyst for the oxidation of hydrocarbons, characterized in that it comprises the following steps:
step one, respectively feeding an activated atmosphere and a hydrocarbon oxidation VPO catalyst into a reactor (1) through a gas inlet (11) and a feeder (14), mixing at inlets of a plurality of reaction tubes (3), and then feeding into the plurality of reaction tubes (3); the hydrocarbon oxidation VPO catalyst is in a hollow cylinder shape, a bar shape, a spherical shape, a cylindrical shape or a clover shape; the introduction space velocity of the activating atmosphere is 100h -1 ~3000h -1 The single-tube feed rate of the hydrocarbon oxidation VPO catalyst is 0.5 kg.h -1 ~3kg·h -1 ；
Step two, the activated atmosphere entering the plurality of reaction tubes (3) and the hydrocarbon oxidation VPO catalyst in the step one sequentially pass through a plurality of activation areas at a constant speed from top to bottom and are simultaneously activated to obtain an activated hydrocarbon oxidation VPO catalyst and tail gas; the temperatures of the plurality of activation zones gradually increase from top to bottom;
discharging the activated hydrocarbon oxidation VPO catalyst and tail gas obtained in the step two from outlets of the reaction tubes (3) and then falling into a sieve plate (9) for separation, discharging the tail gas from a gas outlet (12), and allowing the activated hydrocarbon oxidation VPO catalyst to fall into a catalyst collector (10) along the sieve plate (9).
2. The activation method of a VPO catalyst for hydrocarbon oxidation according to claim 1, wherein in step one, the activation atmosphere is one or more of gaseous hydrocarbon with carbon number less than 5, air, carbon monoxide, inert gas and water vapor, and the inert gas is one or more of nitrogen, argon, carbon dioxide and helium.
3. A process according to claim 1 for the activation of a hydrocarbon oxidation VPO catalyst, characterized in that in step one the hydrocarbon oxidation VPO catalyst is formed from compound V (M) a O b HPO 4 ·0.5H 2 O and a carrier, wherein compound V (M) a O b HPO 4 ·0.5H 2 M in O is one or more than two elements in IA, IB, IIA, IIB, IIIA, IIIB, IVA, IVB, VA, VB, VIA, VIB and VIIIA group elements, a =0 to 0.2, b is the molar ratio of oxygen elements meeting the valence of each element in the formula; the mass percent of the carrier in the hydrocarbon oxidation VPO catalyst is 0-95%.
4. A process according to claim 3, wherein the support is alumina, silica, titania or silicon carbide.
5. A process according to claim 1, wherein in step one the activating atmosphere is preheated by raising the temperature to 200 ℃ at a rate of 5-60 ℃/h before being fed into the reactor (1).
6. The activation method for a hydrocarbon oxidation VPO catalyst according to claim 1, wherein in step two, the number of the activation zones is 3 to 30, each activation zone is independently temperature-controlled, and the temperature of the activation zones is 200 to 440 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911208323.9A CN110860316B (en) | 2019-11-30 | 2019-11-30 | Activation method for hydrocarbon oxidation VPO catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911208323.9A CN110860316B (en) | 2019-11-30 | 2019-11-30 | Activation method for hydrocarbon oxidation VPO catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110860316A CN110860316A (en) | 2020-03-06 |
| CN110860316B true CN110860316B (en) | 2023-02-14 |
Family
ID=69657236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911208323.9A Active CN110860316B (en) | 2019-11-30 | 2019-11-30 | Activation method for hydrocarbon oxidation VPO catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110860316B (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5326886A (en) * | 1991-12-09 | 1994-07-05 | The Standard Oil Company | Maintaining VPO catalyst performance by aluminizing reactor internals in oxidation of butane to maleic anhydride |
| US6475943B1 (en) * | 1995-11-08 | 2002-11-05 | Shell Oil Company | Catalyst activation process |
| US7615510B2 (en) * | 2004-05-12 | 2009-11-10 | Chevron Phillips Chemical Company Lp | Methods of activating chromium catalysts |
| CN103151537B (en) * | 2013-03-20 | 2014-11-26 | 辽宁金谷炭材料股份有限公司 | Production method of graphite felt for vanadium cell |
| CN106540728B (en) * | 2016-10-13 | 2018-11-06 | 西安元创化工科技股份有限公司 | A kind of activation method of vpo catalyst used when preparing cis-butenedioic anhydride by n butane oxidation |
| CN110518260A (en) * | 2019-08-29 | 2019-11-29 | 辽宁金谷炭材料股份有限公司 | A kind of production method of modified vanadium cell porous electrode graphite felt |
-
2019
- 2019-11-30 CN CN201911208323.9A patent/CN110860316B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110860316A (en) | 2020-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5225575A (en) | Oxidation process and apparatus | |
| US8048820B2 (en) | Shaped catalyst body for partial oxidation reactions | |
| CN101622068B (en) | Process for regeneration of a catalyst bed deactivated in the context of a heterogeneously catalyzed partial dehydrogenation of a hydrocarbon | |
| US7429678B2 (en) | Composite-oxide catalyst and process for production of acrylic acid using said catalyst | |
| CS203158B2 (en) | Process for preparing ethylenoxide | |
| EP3490962B1 (en) | Oxidative dehydrogenation (odh) of ethane | |
| US4489204A (en) | Catalyst for the preparation of phthalic anhydride | |
| JPS62431A (en) | Manufacture of 1,2-dichloroethane | |
| JP2003519673A (en) | Gas phase catalytic oxidation method for obtaining maleic anhydride. | |
| CN110860316B (en) | Activation method for hydrocarbon oxidation VPO catalyst | |
| KR20120098834A (en) | Gas phase reaction method | |
| KR20060101323A (en) | Method of producing unsaturated acid from olefin | |
| KR20030082407A (en) | Method for reactivating catalyst for production of methacrylic acid | |
| CN106540728B (en) | A kind of activation method of vpo catalyst used when preparing cis-butenedioic anhydride by n butane oxidation | |
| EP3778560B1 (en) | Method for producing acrylonitrile | |
| KR20140114773A (en) | Process for producing methacrylic acid | |
| JP4557378B2 (en) | Method for producing phthalic anhydride | |
| CN116003262A (en) | Synthesis method of N, N-dimethylaniline | |
| KR101987482B1 (en) | Process for producing alkyl methacrylate | |
| CN1260237A (en) | Catalyst conducting exothermic reaction using fixed bed | |
| Guo et al. | One-step synthesis of methylmethacrylate from methacrolein over Keggin-type heteropoly compounds | |
| KR20060066074A (en) | Method for the production of maleic anhydride | |
| KR102084768B1 (en) | Method of producing unsaturated aldehyde and unsaturated caboxylic acid | |
| US3962322A (en) | Process for unsaturated aldehyde oxidation using a supported catalyst | |
| US4501907A (en) | Maleic anhydride production using high butane feed concentration |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |