WO1994019099A1 - Dispositif d'oxychloration - Google Patents

Dispositif d'oxychloration Download PDF

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Publication number
WO1994019099A1
WO1994019099A1 PCT/EP1994/000407 EP9400407W WO9419099A1 WO 1994019099 A1 WO1994019099 A1 WO 1994019099A1 EP 9400407 W EP9400407 W EP 9400407W WO 9419099 A1 WO9419099 A1 WO 9419099A1
Authority
WO
WIPO (PCT)
Prior art keywords
tubes
gas
fluidized bed
nozzles
catalyst
Prior art date
Application number
PCT/EP1994/000407
Other languages
German (de)
English (en)
Inventor
Reinhard Krumböck
Jürgen Eichler
Wenzel KÜHN
Thomas Wild
Manfred Stöger
Original Assignee
Hoechst Aktiengesellschaft
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 Hoechst Aktiengesellschaft filed Critical Hoechst Aktiengesellschaft
Publication of WO1994019099A1 publication Critical patent/WO1994019099A1/fr

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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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
    • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/44—Fluidisation grids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
    • C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
    • C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00141—Coils

Definitions

  • Oxychlorination means the reaction of ethylene with hydrogen chloride and oxygen or an oxygen-containing gas, where
  • EDC 1,2-dichloroethane
  • the hydrogen chloride obtained in the thermal cleavage of EDC to vinyl chloride is usually used as the hydrogen chloride.
  • catalysts which contain metal halides, preferably copper chloride, on dust-fine supports such as aluminum oxide.
  • the catalyst particles here have an average diameter of about 50 ⁇ m and form a fluidized bed which is either carried only by the reaction gas streams, if appropriate with portions of inert gas, or additionally by a recycle gas stream. In this process, the heat of reaction is distributed in the fluidized bed and dissipated on cooling surfaces, as a result of which a uniform temperature distribution in the fluidized bed reactor is achieved.
  • the catalyst particles must have a high abrasion resistance. This property is essentially given by the carrier material, for which silica, kieselguhr or pumice stone are used in addition to the aluminum oxide already mentioned.
  • the catalyst particles are ground, in particular by the Gas jets of the gas introduction device, and the catalyst carrier dust thus occurring is discharged from the oxychlorination reactor by the upward gas stream. This not only causes a loss of catalyst, but also creates increased abrasion in the equipment.
  • the stability of the catalyst particles and the abrasion caused by them must also be ensured that the catalyst particles do not agglomerate, since clumping as a result leads to disruption of the fluidized bed.
  • the consequences would be an uneven temperature distribution in the fluidized bed with a correspondingly more unfavorable reaction and possibly blockages at narrow points in the apparatus, for example in cyclones for dust separation above the fluidized bed or in downpipes for returning the dust from these cyclones to the fluidized bed.
  • this tendency to clump depends in particular on the concentration of the reaction gases in the fluidized bed.
  • the invention relates to a device for oxychlorination, which is characterized by a Improved introduction of at least one of the gaseous reactants to be converted, at least one of the reactants being guided in such a way that the gas jet has a horizontal component (transverse to the flow direction leading upward in the entire fluidized bed). Due to its shape, the device according to the invention enables the reactor internals to be protected and the resulting long idle times, largely avoids clumping in due to its favorable gas distribution
  • Fluidized catalyst bed and allows such a favorable reaction that the yield of EDC is significantly increased by suppressing the formation of by-products and the undesirable combustion of ethylene with oxygen.
  • the distribution of the gas flows entering the fluidized bed over the entire reactor cross-section takes place via nozzles.
  • a pressure loss which is controlled in these nozzles is important in such a way that the gas quantities of the reactants flowing in are kept as constant as possible at any point in the cross section.
  • the speeds in the nozzles are necessarily so high to maintain the mentioned pressure loss that a high material removal takes place at these nozzles in a short time when there is carrier dust in the gas stream, which in turn is ground in a sharp gas jet at the nozzle outlet. This phenomenon occurs particularly with simple ones
  • Perforated plates with perforated pipes and with nozzles, which are arranged at the end of gas supply pipes.
  • the device for oxychlorination according to the invention is characterized by
  • nozzles (5) open into tubes (6) which give the emerging gas stream a horizontal component in the flow direction, preferably by at the end of the tubes (6) baffles (7) with outlet openings (8) are arranged, and
  • a special embodiment of the device according to the invention is characterized by pipes (10) which are passed through the boundary (2), in which nozzles (11) are arranged below the boundary (2) but above the lower end of (10).
  • FIG. 1 shows a reactor according to the invention with the special configuration of the tubes (6) described above in cross section, which is shown in detail in FIG.
  • FIG. 3 shows a corresponding reactor in which the horizontal component in the gas flow direction is imparted by ends of the tubes (6) lying in front of or behind the plane of the drawing, as is shown, for example, in detail in FIG.
  • the deflection device (7) can be designed as a flat plate or curved, for example conical, so that the gas jets are deflected obliquely downwards.
  • the tubes (6) themselves or the outlet openings (8) of adjacent tubes (6) are expediently arranged in such a way that the outflowing gas jets do not meet head-on and / or do not meet an adjacent tube (6).
  • the gas inlet (9) - as shown in FIGS. 1 and 3 - can be a tube directed towards the reactor floor, which is preferably curved. However, this embodiment is not essential to the invention.
  • the gas can also be introduced in another form, for example by leading the gas inlet (9) vertically through the reactor floor and distributing it in the lower part of the reactor by means of a deflection device, for example a baffle plate. In any case, care must be taken to ensure that the reaction component (s) introduced or introduced by (9) reaches the fluidized bed (3) as evenly as possible through the inflow floor (2).
  • a device as shown in FIGS. 1 and 3 is preferred.
  • the arrangement of the nozzles (11) in the tubes (10) is advantageously carried out on the basis of simple preliminary tests. An arrangement below half the height of the tubes (10) is preferred.
  • the oxychlorination reaction can take place due to the reduced
  • the reaction can also be carried out very safely.
  • the hydrogen chloride can be added to one of the two components or both.
  • the oxygen or the oxygen-containing gas optionally in a mixture with hydrogen chloride, can be introduced through (9), again above (2) first forming a mixing zone with the catalyst in the fluidized bed (3) before contact with the other Mixing zone is possible, which is formed by the gas jets emerging from (6) or (8).
  • an inert gas or cycle gas can be metered in in a manner known per se — expediently through the introduction pipe (9).
  • the inert gas, a recycle gas or, for example, the hydrogen chloride as a separate component to the reactor (1) via separate inlet devices.
  • FIGS. 1 and 2 An apparatus according to FIGS. 1 and 2 is used.
  • the reactants preheated to 160 ⁇ C are introduced in gaseous form into a reactor vessel (1) 0.5 m in diameter and 24 m high: a mixture of 190.5 kg / h of hydrogen chloride (HCl) and 45.2 kg / h of oxygen (0 2 ) flows through the line (4) via the nozzles (5) into the distributor pipes (6). From there, this gas mixture reaches the catalyst bed via the openings (8).
  • the baffle plates (7) cause this to be deflected Horizontal gas flow.
  • the openings (8) are arranged on the circumference of the distributor pipes in such a way that the gas stream emerging from the openings (8) in the fluidized bed does not cause any abrasion on the devices located therein.
  • Distributed reactor cross section and mixing zones are formed between the individual reactants and the catalyst.
  • the reactants flow from bottom to top in the reactor. In this way they meet and react with the participation of the existing one
  • the gas stream at the reactor head consisting of the reaction products and the cycle gas, leaves the reaction vessel (1) via two cyclones for further Processing.
  • the two cyclones connected in series serve to separate the entrained catalyst dust from the gas stream at the reactor head above the catalyst fluidized bed.
  • the distribution pipes for the introduction of hydrogen chloride and oxygen are arranged at the lower end of the cooling coils (12).
  • the oxychlorination reaction begins here, and the heat generated in this way can be dissipated from here via the cooling coils (12). In this way it is excluded that higher temperatures occur in the fluidized bed below the cooling coil (12) if the reaction has already started there.
  • a uniform temperature distribution throughout the reactor has a favorable effect on ethylene utilization and thus the EDC yield.
  • FIGS. 3 and 4 An apparatus according to FIGS. 3 and 4 is used.
  • the reactants preheated to 160 # C are introduced in gaseous form into a reactor vessel (1) 2.8 m in diameter and 26 high: a mixture of 2 525 kg / h of ethylene (C 2 H 4 ) and 6 230 kg / h of hydrogen chloride (HCl ) via the lines (4) with the nozzles (5) and via the distributor pipes (6). 9,400 kg / h of air are passed through the reactor vessel (1) 2.8 m in diameter and 26 high: a mixture of 2 525 kg / h of ethylene (C 2 H 4 ) and 6 230 kg / h of hydrogen chloride (HCl ) via the lines (4) with the nozzles (5) and via the distributor pipes (6). 9,400 kg / h of air are passed through the
  • the reactants flow from bottom to top in the reactor (1).
  • hydrogen chloride and ethylene meet with the air and react with the help of the catalyst to EDC and water.
  • the resulting heat of reaction of 238.5 kJ / mol is dissipated via the fluidized bed (3) to the cooling coil (12), in which water evaporates at 189 ° C.
  • the reaction temperature is 226 * C at an overpressure of 3.2 bar in the reactor.
  • the gas stream at the reactor head consisting of the reaction products and the nitrogen, leaves the reaction vessel (1) via three
  • Cyclones and a line for further processing are used to separate the entrained catalyst dust from the gas stream at the reactor head above the catalyst fluidized bed.
  • the distributor pipes (6) which are directed downwards at an angle of 45 "to the vertical, for introducing the hydrogen chloride / ethylene mixture, result in a good distribution of this gas mixture over the
  • the distributor tube (6) is across the cross section of the reactor distributed and offset from one another so that the gas stream emerging from the distributor tubes (6) in the fluidized bed does not cause any abrasion at the devices located therein.
  • the energy of these gas jets swirls in the fluidized bed and causes an intimate mixing of the gases with the catalyst. This results in longer runtimes of the reactor between two shutdowns. While with conventional gas distribution systems this erosion limited the service life to an average of six months, the device according to FIGS. 3 and 4 results in service life of more than five years.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

On obtient un rendement élevé en 1,2-dichloréthane par la réaction d'éthylène avec du gaz hydrochlorique et de l'oxygène (oxychloration) en introduisant des courants croisés des composants réactifs éthylène et oxygène dans le lit fluidisé du catalyseur et en imprimant une composante horizontale à un des courants de gaz qui pénètrent dans le lit fluidisé. De manière avantageuse, on veille à ce que les courants de gaz en écoulement ne se rencontrent pas frontalement et ne rencontrent pas sur un dispositif adjacent d'introduction de gaz.
PCT/EP1994/000407 1993-02-18 1994-02-12 Dispositif d'oxychloration WO1994019099A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4305001.8 1993-02-18
DE4305001A DE4305001A1 (de) 1993-02-18 1993-02-18 Vorrichtung zur Oxichlorierung

Publications (1)

Publication Number Publication Date
WO1994019099A1 true WO1994019099A1 (fr) 1994-09-01

Family

ID=6480790

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/000407 WO1994019099A1 (fr) 1993-02-18 1994-02-12 Dispositif d'oxychloration

Country Status (4)

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DE (1) DE4305001A1 (fr)
MX (1) MX9401259A (fr)
WO (1) WO1994019099A1 (fr)
ZA (1) ZA941086B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19505664A1 (de) * 1995-02-20 1996-08-29 Hoechst Ag Vorrichtung und ihre Verwendung zur Oxichlorierung
US7718138B2 (en) 2002-07-18 2010-05-18 Vinnolit Technologie Gmbh & Co. Kg Device for introducing gas into a fluidised bed and a process therefor

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19718871A1 (de) * 1997-05-03 1998-11-12 Krupp Uhde Gmbh Verfahren zur Oxichlorierung von Ethylen in einem Wirbelschicht-Katalysatorbett
DE19849709C2 (de) 1998-10-28 2000-09-14 Krupp Uhde Gmbh Verfahren und Wirbelschicht-Reaktor zur Oxichlorierung von Ethylen, Sauerstoff und HCl
DE19903335A1 (de) * 1999-01-28 2000-08-17 Vinnolit Monomer Gmbh & Co Kg Verfahren für die Herstellung von 1,2-Dichlorethan aus der Oxichlorierung
DE10162318B4 (de) * 2001-12-19 2006-10-19 Air Liquide Deutschland Gmbh Gasleitungsstopfen
PE20140206A1 (es) 2010-12-29 2014-03-08 Ivanhoe Energy Inc Metodo, sistema y aparato para la distribucion de gas de elevacion
DE102011108086A1 (de) * 2011-07-19 2013-01-24 H S Reformer Gmbh Düsenboden

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3466021A (en) * 1967-09-14 1969-09-09 Falconbridge Nickel Mines Ltd Thermal treatments in fluidized beds
DE2846350A1 (de) * 1978-10-25 1980-04-30 Didier Eng Anstroemboden fuer einen wirbelschichtreaktor
EP0081619A1 (fr) * 1981-12-10 1983-06-22 GebràœDer Sulzer Aktiengesellschaft Dispositif de transfert de chaleur à lit fluidisé
US4436507A (en) * 1981-07-16 1984-03-13 Foster Wheeler Energy Corporation Fluidized bed reactor utilizing zonal fluidization and anti-mounding air distributors
GB2236963A (en) * 1989-10-18 1991-04-24 Northern Eng Ind Gas distribution apparatus
EP0482799A1 (fr) * 1990-10-22 1992-04-29 Foster Wheeler Energy Corporation Buse de fluidisation unidirectionnelle et lit fluidifié utilisant celle-ci

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3466021A (en) * 1967-09-14 1969-09-09 Falconbridge Nickel Mines Ltd Thermal treatments in fluidized beds
DE2846350A1 (de) * 1978-10-25 1980-04-30 Didier Eng Anstroemboden fuer einen wirbelschichtreaktor
US4436507A (en) * 1981-07-16 1984-03-13 Foster Wheeler Energy Corporation Fluidized bed reactor utilizing zonal fluidization and anti-mounding air distributors
EP0081619A1 (fr) * 1981-12-10 1983-06-22 GebràœDer Sulzer Aktiengesellschaft Dispositif de transfert de chaleur à lit fluidisé
GB2236963A (en) * 1989-10-18 1991-04-24 Northern Eng Ind Gas distribution apparatus
EP0482799A1 (fr) * 1990-10-22 1992-04-29 Foster Wheeler Energy Corporation Buse de fluidisation unidirectionnelle et lit fluidifié utilisant celle-ci

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19505664A1 (de) * 1995-02-20 1996-08-29 Hoechst Ag Vorrichtung und ihre Verwendung zur Oxichlorierung
WO1996026003A1 (fr) * 1995-02-20 1996-08-29 Hoechst Aktiengesellschaft Dispositif et son utilisation pour l'oxychloration
AU702305B2 (en) * 1995-02-20 1999-02-18 Hoechst Aktiengesellschaft Apparatus and its use for oxychlorination
CN1089026C (zh) * 1995-02-20 2002-08-14 赫彻斯特股份公司 一种设备及其用于氧氯化反应的用途
US7718138B2 (en) 2002-07-18 2010-05-18 Vinnolit Technologie Gmbh & Co. Kg Device for introducing gas into a fluidised bed and a process therefor

Also Published As

Publication number Publication date
ZA941086B (en) 1994-08-29
MX9401259A (es) 1994-08-31
DE4305001A1 (de) 1994-08-25

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