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WO1998030323A1 - Reacteur monolithique - Google Patents

Reacteur monolithique Download PDF

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Publication number
WO1998030323A1
WO1998030323A1 PCT/NL1998/000011 NL9800011W WO9830323A1 WO 1998030323 A1 WO1998030323 A1 WO 1998030323A1 NL 9800011 W NL9800011 W NL 9800011W WO 9830323 A1 WO9830323 A1 WO 9830323A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
liquid
catalyst
monolithic
reaction
Prior art date
Application number
PCT/NL1998/000011
Other languages
English (en)
Inventor
Rolf Krister Edvinsson
Jacob Adriaan Moulijn
Original Assignee
Dsm N.V.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dsm N.V. filed Critical Dsm N.V.
Priority to EP98900457A priority Critical patent/EP1089811A1/fr
Priority to AU54994/98A priority patent/AU5499498A/en
Publication of WO1998030323A1 publication Critical patent/WO1998030323A1/fr

Links

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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2485—Monolithic reactors
    • 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
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B01J10/02—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor of the thin-film type
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1887—Stationary reactors having moving elements inside forming a thin film

Definitions

  • the invention relates to a process for carrying out a gas -liquid reaction in the presence of a monolithic catalyst.
  • a process for carrying out a gas -liquid reaction in the presence of a monolithic catalyst is known from EP-A-614 869, which describes how products of peroxidic ozonolysis are reduced in a solution containing hydrogen in the presence of a monolithic catalyst .
  • the monolithic catalyst is contained in the solution and hydrogen is passed through with stirring.
  • the solution and the hydrogen are together contacted with the monolithic catalyst incorporated in a packed column.
  • the monolithic catalyst incorporated in the packed column is in a loop reactor.
  • the aim of the invention is to provide a process that does not show this drawback.
  • This aim is achieved in that the monolithic catalyst rotates around a horizontal shaft and is alternately in the gas and in the liquid phase.
  • An advantage of such a process is that the good wetting of the monolithic catalyst enables better temperature control .
  • a 'monolithic catalyst' is in this specification understood to be a monolith bearing a catalyst.
  • a 'monolith' is in this specification understood to be a one-piece catalyst carrier that is characterised by a structure with a large internal surface.
  • the monolith may in principle consist of any solid material. Examples are metal, metal oxide, ceramic, glass, plastic and carbon.
  • the carrier's large surface may consist of a large number of straight channels having a diameter between approx. 0.5 and 10 mm.
  • the channels' cross section may vary considerably, depending on the type of material used. Known are e.g. round, square, hexagonal, triangular and T-shaped cross-sections and channels with fins on the inside.
  • the catalyst is applied to the channel walls by means of for example vapour deposition or impregnation, which results in a very large catalyst surface.
  • vapour deposition or impregnation which results in a very large catalyst surface.
  • Cybulski and Moulijn describe how a monolithic catalyst can be prepared.
  • the monolithic catalyst revolves around a horizontal shaft and is alternately in the gas phase and in the liquid phase, so that gas and liquid alternately flow through the channels .
  • a good flow through the channels is obtained when the latter are in a plane perpendicular to the horizontal shaft .
  • An even better flow through the channels can be obtained by fitting the ends of the monolithic catalyst facing away from the shaft with vanes so that they guide the liquid to the channel inlets.
  • An advantage of the process according to the invention is that the period of time for which the gas diffuses through the liquid film can easily be varied via the choice of a rotation speed and a liquid level . Especially when the gas dissolves poorly in the liquid, lengthening this period of time may be advantageous to ensure that the gas-liquid reaction at the catalyst surface has proceeded to a sufficient extent before the liquid containing the reaction products is replaced.
  • the monolithic catalysts incorporated in packed columns described in EP-A-614 869 which will hereinafter be referred to as "static monolithic catalysts" present the drawback that the ratio of the gas and the liquid that are contacted with the monolithic catalyst cannot be chosen freely: if there is too much gas, the liquid will not flow through some of the channels, while if there is too little gas the gas will not flow through some of the channels. With certain gas-liquid reaction rates the distribution of gas and liquid will be poor in the case of static monolithic catalysts owing to hydrodynamic instability; a large amount of gas will then flow through some channels while a large amount of liquid will flow through other channels. To obtain a desirable ratio it will often be necessary to circulate an undesirably large quantity.
  • a 'gas-liquid reaction' in this specification this is understood to include not only a reaction between a gas and a liquid, but also between a gas and a substance dissolved in a liquid.
  • This substance may be a gas, a liquid or a solid.
  • a monolith suitable for use as a monolithic catalyst may well have an internal surface of 2500 m 2 /m 3 . If so desired, monoliths can be enlarged by connecting several monoliths in the form of blocks, as a result of which the size of the desired monolith is not limited by the size of a producible monolith.
  • catalyst to be used will depend on the reaction to be carried out. In principle, all the known solid catalysts can be used as monolithic catalysts . Examples of suitable catalysts are the transition metals, their oxides, sulphides or mixtures hereof. Other examples are acid catalysts (e.g. aluminium or silicon oxide) or basic catalysts (e.g. magnesium oxide) . Mixtures of the aforementioned catalysts can also be used.
  • EP-A-384 905 describes a process in which use is made of a gas-liquid reactor fitted with a vertical column packed with a monolithic catalyst .
  • the gas and the liquid can be fed through the reactor in an upward or a downward direction. If the liquid flows downwards, at least a portion of the gas can flow countercurrently upwards.
  • a drawback of such a configuration is that backmixing may take place.
  • 'Backmixing' is understood to be the phenomenon that some portions of liquid with higher concentrations of reaction products are mixed with fresh liquid elements rich in reactants. This often adversely affects the productivity and the selectivity.
  • Another drawback of complete or partial countercurrent flow is that no reaction can take place in the channels that contain exclusively gas or liquid, as a result of which the catalyst's effectiveness factor and hence the productivity decrease.
  • the invention also relates to an apparatus for carrying out a reaction between a gas and a liquid, in the presence of a monolithic catalyst, with one or more monolithic catalysts being connected to a horizontal shaft.
  • Such an apparatus is suitable for carrying out slow gas-liquid reactions in particular, without it being necessary to continuously circulate a gas -liquid mixture .
  • the apparatus according to the invention is used in a configuration in which several apparatuses according to the invention are arranged in series.
  • An advantage of such an apparatus which here and hereinafter is referred to as a "series reactor" is that backmixing has a much smaller effect. Backmixing may occur in the gas phase or in the liquid phase or in both phases .
  • a further advantage of a series reactor is that if the gas and the liquid flow through the series reactor countercurrently, this can lead to a higher yield of the reaction.
  • a further advantage of a series reactor in which countercurrent flow of gas and liquid is used is that there is no risk of the liquid being entrained by the gas. This not only prevents backmixing, but neither can any problems occur in checking the liquid level as with the static monolithic catalyst described above.
  • a "horizontal shaft” is in this specification understood to be a horizontal or virtually horizontal shaft . The use of a virtually horizontal shaft in the series reactor can ensure that the gas-liquid ratio changes over the length of the series reactor. This may be advantageous in the case of reactions in which the amount of one of the two components present has at the end of the reaction decreased more than that of a different component. If the series reactor is placed not entirely horizontal, a lower concentration of for example the gas can be compensated because the volume of the gas in the reactor increases towards the end of the reaction.
  • the invention also relates to the use of the apparatus according to the invention in the catalytic hydrogenation or oxidation of a substance in a liquid phase.
  • Characteristic of these reactions is that the hydrogen or oxygen to be used dissolves poorly in liquids, which is disadvantageous for the reaction rate, which under such conditions is limited by the diffusion of the gas through the liquid layer.
  • these reactions are therefore often carried out in the known reactors at elevated pressure.
  • the greater amount of time taken by the liquid to flow from the channels of the catalyst monolith in the apparatus according to the invention leads to the formation of a much thinner liquid film on the catalyst surface than in the case of a static monolithic catalyst.
  • the invention also relates to the use of the apparatus according to the invention in gas-liquid reactions in which biological matter like enzymes, yeasts or live cells is used as the catalyst. That the use of monoliths may present advantages in immobilising biological matter is known from EP-A-121, 981, in which a feed liquid is circulated past tissue cells immobilised on a monolith, in which a chemical reaction takes place.
  • the feed liquid may also contain solid particles .
  • An advantage of the use of the apparatus according to the invention in biological reactions is that there is no need to circulate any solid particles in a solution, which means that there is less risk of these particles being damaged. Examples of such reactions are oxidation reactions under the influence of air.
  • Figure 1 is a side view of the apparatus according to the invention, hereinafter referred to as "reactor", parallel to the monolithic catalyst's axis of rotation;
  • Figure 2 is a side view of the reactor perpendicular to the monolithic catalyst's axis of rotation;
  • Figure 3 is an enlarged cross-section of part of the monolith;
  • Figure 4 is an enlarged longitudinal section of part of the monolith;
  • Figure 5 is a side view of a series reactor parallel to the monolithic catalyst's axis of rotation.
  • FIG 1 is a reactor partly filled with liquid 2 and partly filled with gas 3.
  • the reactor contains several monolithic catalysts 4 connected to a horizontal shaft 5.
  • Figure 2 shows a round reactor 1 containing eight monolithic catalysts 4, three of which are to varying extents submerged in the liquid 2 while the other 5 are in the gas 3.
  • Figure 3 shows part of the monolith, consisting of the carrier 6 with channels 7. The surface of the channels is covered with a catalyst, not visible in the drawing, on which there is a thin liquid film 8. Otherwise the channels are filled with the gas 3.
  • Figure 4 shows a longitudinal section of the channels, whose surface is covered with the catalyst (not visible in the drawing) and a thin liquid film 8.
  • several reactors are in succession connected to a horizontal shaft.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

La présente invention concerne un procédé permettant de provoquer une réaction entre une phase gazeuse et une phase liquide en présence d'un catalyseur monolithique. L'invention est caractérisée en ce que le catalyseur monolithique tourne autour d'un arbre d'entraînement horizontal et se trouve, en alternance, dans la phase gazeuse et dans la phase liquide. L'invention se rapporte également à un appareil (1) dans lequel peut se produire une réaction gaz-liquide sous l'influence d'un catalyseur monolithique (4) tournant autour d'un arbre d'entraînement horizontal (5).
PCT/NL1998/000011 1997-01-09 1998-01-07 Reacteur monolithique WO1998030323A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP98900457A EP1089811A1 (fr) 1997-01-09 1998-01-07 Reacteur monolithique
AU54994/98A AU5499498A (en) 1997-01-09 1998-01-07 Monolithic reactor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1004961A NL1004961C2 (nl) 1997-01-09 1997-01-09 Monolietreactor.
NL1004961 1997-01-09

Publications (1)

Publication Number Publication Date
WO1998030323A1 true WO1998030323A1 (fr) 1998-07-16

Family

ID=19764185

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL1998/000011 WO1998030323A1 (fr) 1997-01-09 1998-01-07 Reacteur monolithique

Country Status (4)

Country Link
EP (1) EP1089811A1 (fr)
AU (1) AU5499498A (fr)
NL (1) NL1004961C2 (fr)
WO (1) WO1998030323A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1121976A1 (fr) * 2000-02-03 2001-08-08 Engelhard Corporation Procédé chimique dans un réacteur ayant catalyseur structuré
US7074962B2 (en) 2002-02-15 2006-07-11 Air Products And Chemicals, Inc. Catalyst holder and agitation system for converting stirred tank reactor to fixed bed reactor
US7524995B1 (en) 2008-06-12 2009-04-28 E.I. Du Pont De Nemours And Company Continuous process to produce hexafluoroisopropanol
US8084655B2 (en) 2007-06-15 2011-12-27 E. I. Du Pont De Nemours And Company Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2088243A (en) * 1980-11-25 1982-06-09 Rtl Contactor Holding Sa Rotary contactor
WO1991009934A1 (fr) * 1989-12-21 1991-07-11 James Edmund Kitchin Installation de culture d'un materiau biologique
DE4241451A1 (de) * 1991-12-21 1993-12-16 Franz Dietrich Oeste Verfahren und Vorrichtungen zur Reinigung von Gasen, Abgasen, Dämpfen und Solen von unerwünschten chemischen Stoffen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2088243A (en) * 1980-11-25 1982-06-09 Rtl Contactor Holding Sa Rotary contactor
WO1991009934A1 (fr) * 1989-12-21 1991-07-11 James Edmund Kitchin Installation de culture d'un materiau biologique
DE4241451A1 (de) * 1991-12-21 1993-12-16 Franz Dietrich Oeste Verfahren und Vorrichtungen zur Reinigung von Gasen, Abgasen, Dämpfen und Solen von unerwünschten chemischen Stoffen

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1121976A1 (fr) * 2000-02-03 2001-08-08 Engelhard Corporation Procédé chimique dans un réacteur ayant catalyseur structuré
WO2001056692A1 (fr) * 2000-02-03 2001-08-09 Engelhard Corporation Processus chimique
US6800773B2 (en) 2000-02-03 2004-10-05 Engelhard Corporation Chemical process
KR100826346B1 (ko) * 2000-02-03 2008-05-02 바스프 카탈리스트 엘엘씨 화학제품 제조방법
US7074962B2 (en) 2002-02-15 2006-07-11 Air Products And Chemicals, Inc. Catalyst holder and agitation system for converting stirred tank reactor to fixed bed reactor
US8084655B2 (en) 2007-06-15 2011-12-27 E. I. Du Pont De Nemours And Company Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks
US8119847B2 (en) 2007-06-15 2012-02-21 E. I. Du Pont De Nemours And Company Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks
US7524995B1 (en) 2008-06-12 2009-04-28 E.I. Du Pont De Nemours And Company Continuous process to produce hexafluoroisopropanol

Also Published As

Publication number Publication date
EP1089811A1 (fr) 2001-04-11
NL1004961C2 (nl) 1998-07-13
AU5499498A (en) 1998-08-03

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