WO2015181494A1 - Catalyseur avec une forme externe hélicoïdale améliorant l'hydrodynamique dans des réacteurs - Google Patents
Catalyseur avec une forme externe hélicoïdale améliorant l'hydrodynamique dans des réacteurs Download PDFInfo
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- WO2015181494A1 WO2015181494A1 PCT/FR2015/051394 FR2015051394W WO2015181494A1 WO 2015181494 A1 WO2015181494 A1 WO 2015181494A1 FR 2015051394 W FR2015051394 W FR 2015051394W WO 2015181494 A1 WO2015181494 A1 WO 2015181494A1
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to novel catalyst structures.
- a catalyst is a material that converts reagents into product through repeated and uninterrupted cycles of elemental phases. The catalyst participates in the conversion by returning to its original state at the end of each cycle throughout its lifetime.
- Hollow forms (cylinders or multi-lobes) is perforated with several convex holes of different shapes (circle, angular sector, lobe) or holes with several non-convex holes such as the inner quadrilobe.
- the hydrodynamics of the reactor is mainly due to the stacking of the catalysts and not to their shape, that is to say that the fluid "slides" on the shapes without these generating ejection effects of fluids to increase dispersion and mixing within the bed.
- the stack of catalyst shapes according to the prior art is highly porous, has a high percentage of void fraction for stacking (PFVE) (> 70%) and therefore generates less losses.
- PFVE void fraction for stacking
- the hollow forms (barrels or miniliths) based on a network of channels having symmetries lead to a stack having, statistically, many preferential paths. This induces a low radial dispersion, little turbulence and therefore poor material transfers (extraparticular transfer of reagents) (ie transfer of the gaseous or liquid phases towards the catalyst surface), considering catalytic gas / solid reactions, liquid / solid or gas / liquid / solid.
- the present invention proposes to improve the hydrodynamics of fixed-bed reactors for gas / solid, liquid / solid or gas / liquid / solid reactions; on the one hand, by reducing the pressure losses of fixed beds, on the other hand, by improving the radial dispersion within the reactor.
- a solution of the present invention is a catalyst for catalytic reactors whose shape is a helical helix with n ⁇ l and is such that the percentage of void fraction of the stack (PFVE) is between 75% and 85% and the area / volume ratio (S / V) is greater than 1000 m 2 / m 3 .
- the helical 1 wing corresponds to the shape that is commonly called Archimedean screw; the helical 2 wings corresponds to the form commonly called double helix and the helical 3 wings corresponds to the form commonly called triple helix, etc.
- Each helicoid according to the invention creates turbulence and the use of a stack of helicoidal according to the invention causes gas ejection phenomena from one helical to another improving the mixture locally within the catalytic reactors.
- the percentage of vacuum fraction of the stack (PFVE) is directly related to the pressure drop of the catalytic bed.
- PFVE The percentage of vacuum fraction of the stack
- the S / V ratio is defined as follows:
- the catalyst according to the invention may have one or more of the following characteristics:
- said catalyst has a length of between 5 and 40 mm and an equivalent cylinder diameter of between 5 and 10 mm.
- the surface / volume ratio (S / V) is greater than 2000 m 2 / m 3 .
- said helicoidal catalyst comprises between 1.5 and 10 turns
- said catalyst consists of an oxide-type support or a mixture of inorganic oxides.
- said catalyst consists of a support and an active phase deposited on the support;
- the catalyst support is of the oxide type or of a mixture of inorganic oxides.
- the inorganic oxides are chosen from Al 2 O 3 , MgO, CaO, ZrO 2 , TiO 2 , Ce 2 O 3 , and CeO 2
- the active phase deposited in and / or on the support by all types of techniques consists of metal particles chosen from Ni, Rh, Pt, Pd, Co, Mo, Cu, Fe and or their mixture; the active phase can be deposited in and / or on the support by all types of techniques (impregnation, coprecipitation, ).
- FIG. 1 gives examples of catalyst according to the invention.
- the losses in catalytic reactors are a paramount parameter influencing the performance of certain gas / solid, liquid / solid or gas / liquid / solid processes.
- the pressure drop in a reactor is related to the geometry of the catalyst and the compactness of its stack and / or the formation of fines during filling due to its low mechanical strength.
- Some catalytic gas / solid, liquid / solid or gas / liquid / solid processes involve several catalytic reactors which may have recycles (eg the flow leaving a secondary reactor is returned to the top of a primary reactor). In these cases, compression steps may be necessary and adversely affect the overall efficiency of the process if the pressure drops in the reactors are too great.
- other processes may involve, downstream of the catalytic reactors, units whose performance can be reduced by a too low inlet pressure (eg purification units).
- the invention proposes new geometries with high PFVE (greater than 70%) in order to reduce the pressure drops.
- the catalytic reactions gas / solid, liquid / solid or gas / liquid / solid having a fast intrinsic kinetics are then limited by the transfer of material (transfer of reagents) or gas or liquid phases to the catalyst surface (extraparticular transfer), or from the surface of the catalyst to the active sites within the pores of the catalyst (intraparticular transfer).
- transfer of material transfer of reagents
- gas or liquid phases to the catalyst surface
- extraparticular transfer or from the surface of the catalyst to the active sites within the pores of the catalyst
- intraparticular transfer are, in these cases, slower than the reaction and the step limiting the catalytic efficiency is the transport of the reagents to the active site where the reaction takes place.
- a key catalyst parameter influencing internal and external transfers is the S / M ratio.
- the catalyst according to the invention can be used in any type of reaction (oxidation, hydrogenation, etc.).
- the main targeted reactions of the gas / solid type will be the reforming reactions of a hydrocarbon (natural gas, naphtha, biogas, refinery gas off ...), an alcohol (MeOH, EtOH), of glycerol, with an oxidant such as water vapor, C0 2 , oxygen or their mixture, the reactions of transformation of a synthesis mixture rich in H 2 / CO such as water gas shift reaction, reverse water gas shift reaction, synthesis reaction of an alcohol (MeOH, ..), the methanation reaction.
- the use of the catalyst according to the invention is not limited to the gas / solid type reactions but is applicable to liquid / solid and gas / liquid / solid reactions.
- the catalyst according to the invention can operate under pressure (1 to 60 atm) and temperature (150 - 1000 ° C).
- the subject of the present invention is also a catalytic reactor comprising a stack of catalysts according to the invention.
- Example 1 The advantages of the subject of the invention have been illustrated by the example below.
- Example 1 The advantages of the subject of the invention have been illustrated by the example below.
- the pressure drop and tracing experiments were carried out in a reactor 15 cm in diameter and 2.5 m high (bed volume 46.9 L). This pilot has 5 taps for the pressure drop and 2 taps measurements for the radial dispersion of the gas.
- the gas phase used is air with a flow rate ranging from 0 to 185 m / n (ie 0 to 2.9 m / s) and the tracer is methane. For tracing, methane is injected from the top and center of the bed section ( Figure 2).
- the samples are taken over the entire diameter of the reactor using rods passing through the nozzle of the reactor ( Figure 2).
- the object tested in this example is a 3-wing propeller 0.4 cm and 5 turns and 3.5 cm long. It is compared to commercial objects that are 5mm diameter glass beads and 10-hole 19mm diameter and 15mm height barrels with a 5mm center hole and 9 3mm peripheral holes.
- Table 1 shows the pressure drop of the 10-hole cylinders as a function of volume flow or empty drum speed.
- Table 2 shows the pressure drop of the glass beads as a function of volume flow or empty drum speed.
- Table 3 shows the pressure losses of the propellers as a function of the volume flow rate or the empty drum speed.
- Figure 3 allows a comparison of the results given in Tables 1, 2 and 3.
- the triangles correspond to the losses of loads on the propellers, the squares correspond to the pressure drops on the 10-hole cylinders and the rounds correspond to the pressure losses on the glass balls.
- Table 4 shows the axial dispersion of the 10-hole drums as a function of the empty drum speed.
- Table 5 shows the axial dispersion of the propellers as a function of empty drum speed.
- FIG. 4 allows a comparison of the results given in Tables 4 and 5.
- the triangles correspond to the axial dispersion for the helices and the squares correspond to the axial dispersion for the 10-hole drums.
- Table 6 shows the number of Peclets determined with a flow of 80 m / n for barrels
- the propellers have a higher bedlet than the 10-hole drums (800 and 280 respectively). Consequently, a reactor filled with propellers will have a functioning closer to that of a perfectly piston reactor. This result is supported by the calculations of the axial dispersions as a function of the empty drum speeds. Indeed, as shown in Figure 4 the axial dispersions (Dax) of the propellers are lower than that of 10-hole drums, in other words the deviations from a perfectly piston flow are lower with the propellers.
- the object tested in this example is a 3-wing propeller 0.4 cm and 5 turns and 3.5 cm long. It is compared to commercial objects that are 5mm diameter glass beads.
- the methane concentration profiles are given in Figures 5a) and 5b).
- Propeller-like shapes greatly improve the radial dispersion of stacks compared to stacks of logs. Indeed, the radial dispersion in the helix stack is multiplied by 50 compared to that of the stack of balls.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Fluid Mechanics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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CN201580029384.2A CN106457200A (zh) | 2014-05-30 | 2015-05-27 | 改进反应器中的流体动力学的具有螺旋形外部形状的催化剂 |
US15/314,853 US10005079B2 (en) | 2014-05-30 | 2015-05-27 | Catalyst having a helical outer shape, improving hydrodynamics in reactors |
EP15732808.9A EP3148688A1 (fr) | 2014-05-30 | 2015-05-27 | Catalyseur avec une forme externe hélicoïdale améliorant l'hydrodynamique dans des réacteurs |
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FR1454934 | 2014-05-30 | ||
FR1454934A FR3021557B1 (fr) | 2014-05-30 | 2014-05-30 | Catalyseur avec une forme externe ameliorant l'hydrodynamique des reacteurs |
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WO2015181494A1 true WO2015181494A1 (fr) | 2015-12-03 |
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PCT/FR2015/051394 WO2015181494A1 (fr) | 2014-05-30 | 2015-05-27 | Catalyseur avec une forme externe hélicoïdale améliorant l'hydrodynamique dans des réacteurs |
Country Status (5)
Country | Link |
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US (1) | US10005079B2 (fr) |
EP (1) | EP3148688A1 (fr) |
CN (1) | CN106457200A (fr) |
FR (1) | FR3021557B1 (fr) |
WO (1) | WO2015181494A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170189896A1 (en) * | 2014-05-30 | 2017-07-06 | L'Air Liquide, Société Anonyme pour I'Etude et I'Exploitation des Procédés Georges Claude | Catalyst having a helical outer shape, improving hydrodynamics in reactors |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US20230173444A1 (en) | 2020-06-30 | 2023-06-08 | Dow Technology Investments Llc | Processes for reducing the rate of pressure drop increase in a vessel |
USD968560S1 (en) * | 2020-11-20 | 2022-11-01 | Catmasters LLC | Chemical reactor and tower packing |
CN114177913A (zh) * | 2021-12-03 | 2022-03-15 | 浙江皇马科技股份有限公司 | 一种用于合成聚醚胺的负载型催化剂、制备方法及应用 |
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- 2015-05-27 WO PCT/FR2015/051394 patent/WO2015181494A1/fr active Application Filing
- 2015-05-27 EP EP15732808.9A patent/EP3148688A1/fr not_active Withdrawn
- 2015-05-27 CN CN201580029384.2A patent/CN106457200A/zh active Pending
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Also Published As
Publication number | Publication date |
---|---|
FR3021557B1 (fr) | 2018-01-26 |
EP3148688A1 (fr) | 2017-04-05 |
FR3021557A1 (fr) | 2015-12-04 |
US20170189896A1 (en) | 2017-07-06 |
CN106457200A (zh) | 2017-02-22 |
US10005079B2 (en) | 2018-06-26 |
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