CN102371187B - External activation method of benzene oxidation to maleic anhydride catalyst - Google Patents
External activation method of benzene oxidation to maleic anhydride catalyst Download PDFInfo
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- CN102371187B CN102371187B CN2010102647319A CN201010264731A CN102371187B CN 102371187 B CN102371187 B CN 102371187B CN 2010102647319 A CN2010102647319 A CN 2010102647319A CN 201010264731 A CN201010264731 A CN 201010264731A CN 102371187 B CN102371187 B CN 102371187B
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Abstract
The invention discloses an ex-situ activation method of a benzene oxidation to maleic anhydride catalyst. The external activation method comprises the following steps: placing the benzene oxidation to maleic anhydride catalyst in an external activation reactor or evaluation reactor; and heating the benzene oxidation to maleic anhydride catalyst to 300 DEG C, then continuously heating to 400-500 DEG C at the speed of 25-40 DEG C/h, performing heat preservation for 4-12 hours, and naturally cooling to room temperature. The catalyst activated by the method can be directly heated to production operation temperature and then material can be added; and compared with the catalyst activated by the previous common method, performances of the catalyst are improved, and evaluation shows that the conversion rate of the catalyst is basically more than 99% and the yield of the catalyst reaches 99-103%.
Description
Technical field
The present invention relates to organic synthesis V-Mo metal oxide catalyst activating process method field.
Background technology
Maleic anhydride (abbreviation cis-butenedioic anhydride) is important Organic Chemicals.Mainly for the production of industry such as synthetic resin, food, agricultural chemicals, medicine, papermaking, coating, weavings, market is growing to the demand of cis-butenedioic anhydride at present.
At present, the production of cis-butenedioic anhydride divides by method, mainly contains fixed bed oxidizing process and fluidized bed process; Divide by raw material route, be mainly two production lines of benzene oxidation and n butane oxidation.Owing to relatively concentrating on several large petrochemical plants in China C4 resource, be unfavorable for carrying, and benzene raw materials relatively more having superiority, so the most of process units of China adopts the benzene oxidizing process, only has the small part device to use the normal butane method.China only has several at present and uses the n butane oxidation method to produce cis-butenedioic anhydride in the maleic anhydride production factory of family more than 30, account for about 20% of production capacity, and other producers all adopt the benzene oxidizing process to produce cis-butenedioic anhydride.
The activation process of benzene preparing cis-butenedioic anhydride by oxidation fixed bde catalyst is divided into the interior activation of device and device activates dual mode outward.Activation refers to that catalyst finishes activation in reactor in the device, and namely catalyst filling is in the tubulation of reactor, and reactor is thrown benzene feedstock after being warmed up to uniform temperature, behind the insulation activation certain hour, reduces the salt temperature again and carries out the normal oxidation reaction.This step needed finish in 2～3 days.This activation process can make maleic anhydride production producer increase the maleic anhydride production cost.The outer activation of device refers to catalyst is just finished activation in the production phase, and being warmed up to after maleic anhydride production factory is complete with Catalyst packing just can directly feed intake after the normal production operation temperature carries out the production of product.Catalyst activates in the cis-butenedioic anhydride reactor, i.e. present industrialized method, and it is at 410～430 ℃ of salt temperature, air speed 1000hr
-1Condition under throw benzene band material activation, belong to activation in the device.Therefore, consumed mass energy.As far back as the eighties in last century, european patent number is just to have proposed once in the patent of EP0196602A2 that V-Mo was the outer activation method of device of maleic anhydride catalyst under the air atmosphere, activation condition is the oxidizing atmosphere under the air, the valence state of active component vanadium raises in the catalyst, reduce catalyst activity, change product yield and feed stock conversion.2005, it was the patent of CN1579631A that there is one piece of publication number in China, was to belong to the outer activation method of device, the method that this patent proposes is to activate with the air that contains ammonia, need control ammonia empty than being 1: 25～1: 5, and because the adding ammonia, input cost can strengthen.
Summary of the invention
The technical problem to be solved in the present invention:
In order to overcome the prior art defective, catalyst adopts the outer activation method of device, catalyst performance can be better than activation method in the device, the invention provides a kind of benzene preparing cis-butenedioic anhydride by oxidation external catalyst activation method, the method does not need to add gas and activates, by the catalyst selfdecomposition gas that is heated, cost is low, and the activation phenomenon good stability.Catalyst after this method activation can directly be warming up to the production operation temperature and feed intake, the performance of the catalyst than before performance of the catalyst of common method therefor activation increases, catalyst reaches more than 99% substantially through estimating conversion ratio, and yield reaches 99～103%.
Technical scheme of the present invention is:
The method that the present invention adopts is to carry out in the activated reactor in reactor or device outside activating outside the device of maleic anhydride catalyst, so that the performance of catalyst obviously improves, and the increase of cis-butenedioic anhydride product yield.
It is V-Mo-auxiliary agent series benzene preparing cis-butenedioic anhydride by oxidation catalyst that device activates catalyst system therefor outward, and concrete preparation method is referring to patent CN1106714A (1995.8.16).According to said method or the V-Mo-auxiliary agent catalyst series of similar approach preparation all applicable.
Device activates concrete grammar outward: at first, in the outer activated reactor of the benzene preparing cis-butenedioic anhydride by oxidation catalyst series loader of said method preparation or assessing reactor, benzene preparing cis-butenedioic anhydride by oxidation catalyst series is heated up, beginning is carried out with 40～70 ℃/hour speed, after temperature reaches about 300 ℃, heat up with 25～40 ℃ of left and right sides temperature per hour, be incubated after reaching 400～500 ℃ of temperature, preferred range is 420～460 ℃; Temperature retention time is 4～12 hours, and preferred time range is 4～8 hours.Naturally be cooled to afterwards room temperature.
Among the present invention in the benzene preparing cis-butenedioic anhydride by oxidation catalyst active component be V, the different atmosphere of V contact has certain impact to the performance of catalyst in activation process.Adopt the import sealing of the outer activator of reactor or device in the experiment, outlet communicates with atmosphere, in the device because catalyst activation when being heated, self pyrolytic generation gas and activation process is carried out under the condition of malleation slightly.
Benzene preparing cis-butenedioic anhydride by oxidation external catalyst activation stove (shown in the accompanying drawing) used among the present invention is cylindric, interior diameter 50～500mm, and height 100～1000mm, volume 1～200L, cylindrical lining net 6 diameters 10～450mm is equipped with in inside, height 50～800mm.Respectively there are an import 1, outlet 2 breather pipes in activation furnace wall both sides, and activation furnace is outside to be the heating of stove silk, and asbestos cloth is incubated 4.
Reasonable for space between activation phenomenon space and catalyst activation stove, reach catalyst and be heated evenly, preferred activation furnace interior diameter 50～300mm, height 100～600mm, volume 1～50L, the diameter 30～200mm of cylindrical lining net 6 is equipped with in inside, height 100～500mm.
Then, maleic anhydride catalyst is packed in the cylindrical lining net 6 of activation furnace, seal top cover flange 3.Breather pipe one end 1 sealing of activator, an end 2 is opened.Cut off the electricity supply.
Catalyst after above step activates carries out evaluating catalyst at the 120ml evaluating apparatus.Directly fused salt is risen to 340～360 ℃ of normal running temperatures with 25 ℃/hour speed during intensification, at air speed 2000hr
-1, benzene concentration 48～54g/M
3Carry out the evaluation of catalyst under the condition, the result is that the benzene conversion ratio is higher than 99%, and the cis-butenedioic anhydride mass yield is higher than 99-103%.
The essential distinction of the present invention and prior art is, in the catalyst activation process provided by the invention, activation phenomenon is under the airtight condition, adjust activation phenomenon by selfdecomposition gas, reach activation effect, and prior art adopts and to pass into other gas, adjusts activation phenomenon such as ammonia etc., and activating cost increases.In addition, the catalyst activation effect that the technology of the present invention reaches is better than prior art, can improve yield of maleic anhydride greater than one percentage point, and prior art improves at most the yield of maleic anhydride one percentage point.
The invention has the beneficial effects as follows: the invention enables maleic anhydride catalyst to activate when producing, saved the cost of manufacturer, simultaneously, improved the performance of catalyst, improved the yield of cis-butenedioic anhydride product, the cis-butenedioic anhydride mass yield can reach 99-103%.
Description of drawings
Fig. 1 is the outer activation furnace schematic top plan view of device;
Fig. 2 is the outer activation furnace generalized section of device.
1. air inlet, 2. gas outlet, 3. top cover flange, 4. external insulation heating, 5. bottom support, 6. cylindrical lining net
The specific embodiment
Adopt method for preparing catalyst among the patent CN1106714A, preparation V-Mo-auxiliary agent catalyst series, for subsequent use.
The used benzene preparing cis-butenedioic anhydride by oxidation external catalyst activation stove of experiment is cylindric among the present invention, interior diameter 100mm, and height 450mm, volume 3530ml, inside fills the diameter 50mm of cylindrical lining net, height 200mm.
Embodiment 1
Measure benzene preparing cis-butenedioic anhydride by oxidation catalyst 150ml, in the cylindrical lining net 6 of the activation furnace of packing into, seal top cover flange 3, sealing activator one end air inlet 1.With per hour 50 ℃ be warming up to 300 ℃, after temperature arrives, with per hour 25 ℃ continue to heat up, temperature is raised to 450 ℃, is incubated 4 hours.Naturally be cooled to room temperature, cut off the electricity supply.Afterwards, take out the catalyst after activating, on the 120ml evaluating apparatus of packing into, at air speed 2000hr
-1, benzene concentration 48～54g/M
3Estimate under the condition.
Embodiment 2
Measure benzene preparing cis-butenedioic anhydride by oxidation catalyst series 260ml, in the cylindrical lining net 6 of the activation furnace of packing into, seal top cover flange 3, sealing activator one end air inlet 1.With per hour 50 ℃ be warming up to 300 ℃, after temperature arrives, with per hour 25 ℃ continue to heat up, temperature is raised to 450 ℃, is incubated 6 hours.Naturally be cooled to room temperature, cut off the electricity supply.Afterwards, with embodiment 1.
Embodiment 3
Measure benzene preparing cis-butenedioic anhydride by oxidation catalyst series 180ml, in the cylindrical lining net 6 of the activation furnace of packing into, seal top cover flange 3, sealing activator one end air inlet 1.With per hour 50 ℃ be warming up to 310 ℃, after temperature arrives, with per hour 25 ℃ continue to heat up, temperature is raised to 460 ℃, is incubated 5 hours.Naturally be cooled to room temperature, cut off the electricity supply.Afterwards, with embodiment 1.
Measure benzene preparing cis-butenedioic anhydride by oxidation catalyst series 120ml, in the 120ml reactor of packing into, close the air feed mouth of an end, the tail gas mouth communicates with atmosphere.Be heated to 100 ℃, then be warming up to 450 ℃ with 25 ℃ of speed per hour, temperature is incubated after arriving, and temperature retention time is 8 hours.Naturally be cooled to afterwards 340 ℃, pass into air, the benzene that feeds intake carries out the test of benzene preparing cis-butenedioic anhydride by oxidation.
Embodiment 5
Measure benzene preparing cis-butenedioic anhydride by oxidation catalyst series 120ml, in the 120ml reactor of packing into, close the air feed mouth of an end, the tail gas mouth communicates with atmosphere.Be heated to 100 ℃, then be warming up to 450 ℃ with 25 ℃ of speed per hour, temperature is incubated after arriving, and temperature retention time is 8 hours.Naturally be cooled to afterwards 350 ℃, pass into air, the benzene that feeds intake carries out the test of benzene preparing cis-butenedioic anhydride by oxidation.
Comparative Examples:
Measure benzene preparing cis-butenedioic anhydride by oxidation catalyst series 120ml, in the 120ml reactor of packing into, carry out band material activation in the device.At first reactor is heated to 300 ℃, begins to pass into air and benzene feedstock, be warming up to 420 ℃ with 25 ℃ of speed per hour again, be incubated 24 hours, be cooled to afterwards 350～360 ℃ of normal running temperatures, at air speed 2000hr
-1, under benzene concentration 48～54g/M3 condition, carry out the test of benzene preparing cis-butenedioic anhydride by oxidation.
Evaluation result is listed in the table below:
Claims (5)
1. the activation method of a benzene preparing cis-butenedioic anhydride by oxidation catalyst, comprise the steps: in the outer activated reactor of benzene preparing cis-butenedioic anhydride by oxidation catalyst series loader or the assessing reactor, benzene preparing cis-butenedioic anhydride by oxidation catalyst series is heated up, beginning is carried out with 40～70 ℃/hour speed, after temperature reaches 300 ℃, heat up with 25～40 ℃ of temperature per hour, be incubated 4～12 hours after reaching 400～500 ℃ of temperature, naturally be cooled to afterwards room temperature;
Wherein activation phenomenon is by the described catalyst selfdecomposition γ-ray emission that is heated.
2. according to claim 1 activation method, wherein heat-preserving range is 420～460 ℃.
3. according to claim 1 and 2 activation method, wherein temperature retention time is 4～8 hours.
4. according to claim 1 activation method, described activation is to carry out in activation furnace, described activation furnace is cylindric, interior diameter 50～500mm, height 100～1000mm, volume 1～200L, cylindrical lining net is equipped with in inside, diameter 10～450mm, height 50～800mm, activation furnace wall one side is provided with an air inlet, and opposite side is provided with a gas outlet, activation furnace is outside to be the heating of stove silk, and asbestos cloth is incubated.
5. according to claim 4 activation method, wherein said activation furnace interior diameter 50～300mm, height 100～600mm, volume 1～50L, the diameter 30～200mm of interior cylindrical lining net, height 100～500mm.
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| CN102371187B true CN102371187B (en) | 2013-05-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037096A (en) * | 1989-06-22 | 1989-11-15 | 天津大学 | The activation process of normal butane system cis-anhydride vanadium-phosphorus oxygen series catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1037096A (en) * | 1989-06-22 | 1989-11-15 | 天津大学 | The activation process of normal butane system cis-anhydride vanadium-phosphorus oxygen series catalysts |
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