EP2334593A1 - Procédé de production de chlore en plusieurs étapes - Google Patents

Procédé de production de chlore en plusieurs étapes

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Publication number
EP2334593A1
EP2334593A1 EP09778790A EP09778790A EP2334593A1 EP 2334593 A1 EP2334593 A1 EP 2334593A1 EP 09778790 A EP09778790 A EP 09778790A EP 09778790 A EP09778790 A EP 09778790A EP 2334593 A1 EP2334593 A1 EP 2334593A1
Authority
EP
European Patent Office
Prior art keywords
reaction
reaction stage
zone
stage
process gas
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.)
Withdrawn
Application number
EP09778790A
Other languages
German (de)
English (en)
Inventor
Leslaw Mleczko
Oliver Felix-Karl SCHLÜTER
Aurel Wolf
Stephan Schubert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Intellectual Property GmbH
Original Assignee
Bayer Technology Services GmbH
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Filing date
Publication date
Application filed by Bayer Technology Services GmbH filed Critical Bayer Technology Services GmbH
Publication of EP2334593A1 publication Critical patent/EP2334593A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/04—Preparation of chlorine from hydrogen chloride
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/12—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of actinides
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/07—Purification ; Separation
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions

Definitions

  • the present invention relates to a multi-stage process for the production of chlorine by catalytic gas-phase oxidation of hydrogen chloride with oxygen, wherein the reaction is carried out on at least two different catalyst beds under adiabatic conditions, and a reactor system for carrying out the process.
  • Deacon process developed by Deacon in 1868 and named after him, in which chlorine is formed by the heterogeneous catalytic oxidation of hydrogen chloride with simultaneous formation of water.
  • the main advantage of this process is that it is decoupled from the caustic soda production.
  • the precursor hydrogen chloride is easily accessible; it is obtained in large quantities, for example in phosgenation reactions, such as in the production of isocyanates, in which again the chlorine produced via the intermediate phosgene is preferably used.
  • DE 1 567 788 discloses a catalyst material containing RuCl 3 on a support material which may comprise aluminum oxide or other ceramic materials in which this method of producing chlorine is preferably feasible, are disclosed in ranges of 250 to 500 0 C.
  • WO 2004/052776 discloses a process carried out in a temperature controlled by heat transfer medium tube bundle reactor, which is filled with catalyst material.
  • the disclosed tube bundle reactors are intended to provide a high heat exchange surface to prevent the formation of "hot spots" which, in turn, may result in damage to the catalyst in the above form.
  • the method and the device of WO 2004/052776 are disadvantageous because the desired temperature control is ensured by the highest possible number of tubes (> 10,000), which leads to very complex structural embodiments of the device in which the method is feasible.
  • Such complex structural embodiments inevitably lead to high investment costs and, especially in large reactors, to very complex devices in the periphery of the reaction apparatus; in this case, in particular with regard to the devices for cooling the reaction device.
  • the problems of mechanical strength and uniform thermostating of the catalyst bed increase.
  • the process disclosed in WO 2007/134771 is disadvantageous in that, owing to the catalysts used according to the disclosure, ruthenium oxide, ruthenium chloride, ruthenium oxychloride, rhodium oxide, copper chloride, copper oxide, chromium oxide, bismuth oxide, etc., ensure that the operating temperature of bis to 400 0 C for the reasons mentioned above. It is therefore further disclosed that the reaction is carried out in more than two reaction zones with cooling between the individual reaction zones. Compliance with this limit is further adjusted by selective selection of the reaction conditions (inlet temperature, gas composition, type of catalyst, etc.), which is also complex and therefore at least economically disadvantageous.
  • DE 1 078 100 it is disclosed that also uran category catalysts for the heterogeneous catalytic oxidation of hydrogen chloride to chlorine are used. DE 1 078 100 further discloses that such a process for the heterogeneous catalytic oxidation of hydrogen chloride to chlorine at temperatures of up to 480 0 C is executable.
  • DE 1 078 100 does not disclose whether and to what extent such processes can be carried out in combination with other process variants using catalysts comprising ruthenium.
  • the maximum achievable conversion of the process disclosed in DE 1 078 100 is 62%, which is small and therefore disadvantageous in terms of the conversions possible according to the disclosures set out above.
  • Process gas in the context of the present invention denotes a gas mixture comprising at least oxygen and hydrogen chloride.
  • Process gases may also include minor components as well as the reaction products chlorine and water.
  • Non-exhaustive examples of such minor constituents are, for example, nitrogen, carbon dioxide or carbon monoxide.
  • Oxygen may be pure oxygen or, preferably, an oxygen-containing gas, in particular air.
  • the hydrogen chloride of the process gas may come from other processes, such as for the production of polyisocyanates, and may contain other contaminants, such as phosgene and organic components.
  • organic components are, for example, the solvent residues derived from such processes, such as chlorobenzene.
  • the chlorine produced may e.g. be used for the production of phosgene and possibly recycled in associated production processes.
  • an adiabatic reaction zone means that substantially no heat is supplied to the reaction zone from the outside, nor is heat withdrawn.
  • heat can be supplied or removed by entering or exiting reaction gas.
  • no additional measures are taken to cool / heat the reaction zones from the outside.
  • this is achieved by isolating the reaction zones in a conventional manner.
  • the process according to the invention can be operated continuously or discontinuously. Preferably, however, the process is operated continuously.
  • the catalyst in the first adiabatically operated reaction zone of the at least one reaction stage may be a catalyst, as it is already known from the prior art described in this invention.
  • the catalyst in this first adiabatically operated reaction zone is preferably used immobilized on a support.
  • the catalyst in the first adiabatically operated reaction zone of the at least one reaction stage preferably contains at least one of the elements selected from the list containing copper, potassium, sodium, chromium, cerium, gold, bismuth, ruthenium, rhodium, platinum, and the elements of VIII. Subgroup of the Periodic Table of the Elements. These are preferably used as oxides, halides or mixed oxides / halides, in particular chlorides or oxides / chlorides. These elements or compounds thereof can be used alone or in any combination.
  • Preferred compounds of these elements include copper chloride, copper oxide, potassium chloride, sodium chloride, chromium oxide, bismuth oxide, ruthenium oxide, ruthenium chloride, ruthenium oxychloride, rhodium oxide.
  • the catalyst in the first adiabatically operated reaction zone of the at least one reaction stage particularly preferably consists completely or partially of ruthenium or compounds thereof.
  • the catalyst in this first adiabatically operated reaction zone consists of halide and / or oxygen-containing ruthenium compounds.
  • the support of the catalyst in the first adiabatically operated reaction zone of the at least one reaction stage may consist completely or partially of: titanium oxide, tin oxide, aluminum oxide, zirconium oxide, vanadium oxide, silicon oxide, carbon nanotubes or a mixture or compound of the substances mentioned, in particular mixed oxides such as silicon oxides.
  • Particularly preferred support materials are tin oxide, aluminum oxide and carbon nanotubes.
  • the catalyst in the first reaction zone of the at least one reaction stage may also be doped with a promoter material.
  • suitable promoters are alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, more preferably potassium, alkaline earth metals such as magnesium, calcium, strontium and barium, preferably barium and calcium, particularly preferably Barium, rare earth metals such as scandium, yttrium, lanthanum, cerium, samarium, gadolinium, lutetium, praseodymium and neodymium, preferably scandium, yttrium, lanthanum and cerium, more preferably lanthanum and cerium or mixtures thereof.
  • alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, more preferably potassium, alkaline earth metals such as magnesium, calcium, strontium and barium, preferably barium and calcium, particularly preferably Barium, rare earth metals such as scandium, yttrium, lanthanum, cerium, samarium, ga
  • the catalysts specified here in the first adiabatically operated reaction zone of the first reaction stage are particularly advantageous because they already have a high activity for the oxidation of hydrogen chloride to chlorine at lower temperatures.
  • the catalyst of the second reaction zone of the at least one reaction stage comprising a uranium component may or may not comprise a support material.
  • a catalyst comprising a uranium component in the second reaction zone of the at least one reaction stage of the process according to the invention which comprises a support material
  • suitable support materials are those selected from the list containing silicon oxide, aluminum oxide, titanium oxide, tin oxide, zirconium oxide, cerium oxide or mixtures thereof.
  • the proportion of the uranium component in the catalyst if it additionally comprises a support material, in the range of 0.1 to 90 wt .-%, preferably in the range of 1 to 60 wt .-%, particularly preferably in the range of 1 to 50 wt .-%, based on the total mass of uranium or uranium compound and support material.
  • Uranium components in the context of the present invention refer to uranium oxides, uranium chlorides and / or uranium oxychlorides. Suitable uranium oxides are either UO 3 , UO 2 , UO or the uranium oxides of a non-stoichiometric composition. Preferred uranium oxides of non-stoichiometric composition are those selected from the list containing U 3 O 5 , U 2 O 5 , U 3 O 7 , U 3 Og and U 4 O 9 . Preference is given to uranium oxides or mixtures of uranium oxides having a stoichiometric composition of UO 2, i to UO 5 .
  • Uranium oxychlorides denote in the context of the present invention, materials of the general composition UO x Cl y, wherein x and y are each natural numbers greater than zero. Thus, uranium oxychlorides also do not refer to stoichiometric compositions containing chlorine, oxygen and uranium.
  • the catalyst used in the second reaction zone of the at least one reaction stage contains only one support selected from the list above and one uranium compound and / or uranium. Most preferably, the catalyst used contains only one uranium compound or uranium.
  • Such catalysts are particularly advantageous because it has surprisingly been found that such catalysts also catalyze the oxidation of hydrogen chloride to chlorine even if the temperatures of the process gas at the beginning of the second reaction zone exceed a value that the economic and especially continuous use of catalysts such they are used in the first reaction zone, may appear questionable. In particular, it has surprisingly been found that these catalysts do not tend to sinter or oxidize to volatile compounds at the elevated temperatures in the second reaction zone.
  • the process is particularly advantageous because, without the need for expensive cooling or "dilution" of catalyst material, the reaction can be carried out in at least one reaction stage in two consecutive adiabatic reaction zones, where it is further particularly advantageous that the adiabatic operation of the first reaction zone the energy of the reaction in the second adiabatic reaction zone of the at least one reaction stage can be used for the first time in a particularly advantageous manner.
  • the catalysts in the reaction zones of the reaction stages can be in various forms.
  • Non-conclusive examples of such forms in which the catalysts can be present in the reaction zones of the reaction stages are, for example, the forms of the fixed bed, moving bed or fluidized bed which are generally known to the person skilled in the art.
  • Preferred is a fixed bed arrangement. This comprises a bed of catalyst and packages of the catalyst.
  • catalyst bed also includes contiguous regions of suitable packages on a support material or structured catalyst supports.
  • the catalysts may have any shape, for. As balls, rods, Raschig rings, granules or tablets.
  • the inventive method is in a simple manner in devices, as they are already in operation, executable. It is only necessary to provide a second reaction zone by filling parts of the reaction devices with the catalyst comprising a uranium component. The need for a complex conversion does not exist.
  • the reactors preferably used in the inventive method can also consist of simple containers with one or more thermally insulated catalyst beds, as described for example in Ulimann's Encyclopedia of Industrial Chemistry (Fifth, Completely Revised Edition, VoI B4, page 95-104, page 210-216 ) to be discribed.
  • the catalysts or the catalyst beds thereof are applied in a manner known per se to or between gas-permeable walls of the reactor in the reaction stages or reaction zones.
  • technical devices for uniform gas distribution are installed above, below or above and below the catalyst beds. These may be perforated plates, bubble-cap trays, valve trays, or other internals which cause uniform entry of the gas into the catalyst bed by producing a small but uniform pressure drop.
  • the empty tube velocity of the process gas in a reaction zone in the case of the embodiment as a fixed bed is preferably between 0.1 and 10 m / s.
  • the inventive method is operated so that in the second reaction zone of the at least one reaction stage temperatures of 350 0 C to 800 0 C are present, preferably temperatures of 350 0 C to 700 0 C, more preferably temperatures of 350 0 C to 600 0 C.
  • the first reaction zone becomes So at least one reaction stage so preferably operated so that by the heating of the process gas by the exothermic oxidation of hydrogen chloride to chlorine this at the output of the first reaction zone has a temperature of at least 350 0 C.
  • Non-conclusive examples include the regulation of the composition of the process gas at the beginning of the first reaction zone or the setting of a defined residence time in the first - -
  • Reaction zone by means of the abovementioned regulation of the composition of the process gas at the beginning of the first reaction zone of the reaction stage, for example via a reduced metered addition of hydrogen chloride, a possible increase in temperature in the first reaction zone can be absorbed in a simple manner.
  • the residence time can be reduced by a general increase in the volume flow of process gas, so that the conversion also decreases, and thus the temperature increase can be absorbed in a simple manner.
  • a further reduction in the temperature increase can also be achieved by increasing the proportion of inert gas in the process gas stream.
  • This setting of a specific starting temperature from the first reaction zone of the reaction stage preferably takes place by a combination of the two abovementioned methods.
  • the first reaction zone of a reaction stage according to the invention is therefore operated so that at its input, the process gas has a temperature of 150 to 400 0 C, preferably from 200 to 370 0 C, more preferably from 250 to 35O 0 C.
  • the erf ⁇ ndungswashe method and its preferred developments described below are preferably operated at a pressure of 1 to 30 bar, preferably from 1 to 20 bar, more preferably from 1 to 15 bar in the reaction zones of the reaction stages.
  • a molar ratio of between 0.25 and 10 equivalents of oxygen per equivalent of hydrogen chloride before entry into the first reaction zone of the at least one reaction stage is preferably used.
  • the process comprises more than one reaction stage according to the invention with the two reaction zones according to the invention described above.
  • heat exchange zones are preferably provided between the reaction stages in which the temperature of the process gas originating from the previous reaction stage is reduced.
  • the process gas is cooled in these heat exchange zones to temperatures below 350 0 C.
  • the heat exchange zone may be embodied in forms of heat exchangers which are generally known to the person skilled in the art. These may e.g. Rohrbündel- be, plate, Ringnut-, spiral, finned tube or micro heat exchanger.
  • steam may be generated.
  • Such a generation of steam can be carried out, for example, by first of all, by means of a technical heat transfer medium, e.g. Heat transfer oils or high-temperature molten salts, is cooled, wherein the heat transfer medium is heated.
  • a technical heat transfer medium e.g. Heat transfer oils or high-temperature molten salts
  • the heated heat transfer medium can then be fed to a further heat exchanger of the type described above, in which steam is generated when the heat transfer medium is cooled.
  • the steam is generated directly during the cooling of the process gas stream in the heat exchange zone.
  • Heat exchangers are preferably used in which the product gas and the steam are separated from each other by a double wall (so-called double tube heat exchanger).
  • the gap between the two walls can be traversed for leakage monitoring with a test gas.
  • a heat exchanger is preferably a double tube safety heat exchanger, as e.g. DE 199 59 467 is described in.
  • Such double tube heat exchangers are particularly advantageous because they allow the production of steam in a simple and safe manner already in the course of the process, without the need to use an additional heat transfer fluid (e.g., molten salts, etc.).
  • an additional heat transfer fluid e.g., molten salts, etc.
  • the particularly preferred temperatures of the preferred further development are particularly advantageous because this prevents damage to the catalyst in the first reaction zone of the subsequent reaction stage.
  • At least one further reaction stage with only one reaction zone is behind the at least one reaction stage according to the invention, this at least one further reaction stage containing a second reaction zone according to the invention, and before this further reaction stage comprising a second reaction zone according to the invention, a heat exchange zone as already described in connection with the first preferred development.
  • the process gas is preferably cooled to temperatures of less than 600 ° C., more preferably to temperatures of less than 350 ° C.
  • At least one low-temperature reaction stage having only one reaction zone is behind the at least one reaction stage according to the invention, this at least one further low-temperature reaction stage containing a first reaction zone according to the invention and wherein before this low-temperature reaction stage containing a novel first reaction zone, a heat exchange zone, as has already been described in connection with the first preferred development, is located.
  • the process gas is particularly preferably cooled to temperatures of less than 350 ° C.
  • This third preferred further development of the method according to the invention is particularly advantageous because the equilibrium of the process gas comprising hydrogen chloride and chlorine shifts disadvantageously at too high a temperature on the side of the hydrogen chloride, so that optionally a final oxidation of hydrogen chloride to chlorine by the achieved equilibrium limitation nevertheless is enabled, which further improves the space-time yield of the method. - -
  • the method would thus contain two reaction stages, between which a heat exchange zone is located and in which after and / or before the heat exchange zone, a portion of the process gas, which would otherwise be completely and exclusively fed to the first reaction stage, directly to the second Reaction stage is forwarded.
  • the division into the individual reaction stages contained in the process can be carried out either in equal proportions, or in different from reaction stage to reaction stage rising or falling portions of the total process gas stream, which is fed to the process.
  • a portion of the process gas stream is fed in decreasing proportions the reaction stages.
  • An embodiment of the method according to the alternative embodiment is particularly advantageous because by a distributed limited addition of a portion of the process gas stream, the heat release and thus the temperature rise in the individual reactor stages can be easily controlled.
  • uncontrolled overheating of individual reaction stages and / or reaction zones can not occur, since the exothermic reaction is in the absence of availability of part of the process gas stream, such as, for example, Hydrogen chloride, whose turnover inevitably comes to a standstill. Only with dosing before the next reaction stage then it comes to a further sales.
  • the temperature can be adjusted once again via the process gas stream then composed from the process gas stream from the previous reaction stage and the further portion of the process gas stream, for example by supplying the further portion of the process gas stream at a lower temperature. This reduces the need for cooling in the heat exchange zones, which may be economically advantageous.
  • the abovementioned low-temperature reaction stage is the last reaction stage of the process and before this there is more than one reaction stage according to the invention or one reaction stage according to the invention and at least one further reaction stage according to the further preferred further development.
  • the chlorine formed and / or the hydrogen chloride and / or the oxygen are separated from the process gas in a separation zone.
  • the separation in such a separation zone usually comprises several stages, namely the separation and optionally recycling of unreacted hydrogen chloride from the process gas, drying of the resulting, essentially chlorine and oxygen-containing residual stream and the removal of chlorine from the dried residual stream.
  • the separation can be carried out by methods well known to those skilled in the art, such as by condensing out aqueous hydrochloric acid from the process gas.
  • the hydrogen chloride contained in the process gas can also be absorbed in dilute hydrochloric acid or water.
  • the separated oxygen and optionally also hydrogen chloride are fed back to at least one of the reaction stages.
  • FIGS. 1 to 4 Preferred embodiments of the method according to the invention are shown in FIGS. 1 to 4, without the invention being limited thereto.
  • a hydrogen chloride stream (1) and a gas stream containing oxygen and nitrogen (2) are combined to the process gas stream (3), which is fed to a reactor (29) in which a reaction stage containing a fixed bed of a ruthenium catalyst (I) and a uranium catalyst (VHT).
  • the stream of process gas (4) is then fed to a heat exchanger (36) and as cooled process gas stream (5) to another reactor (30) in which a reaction stage containing a fixed bed of a ruthenium catalyst (IT) and a uranium catalyst ( DC) - 1 - is, fed to the further oxidation of hydrogen chloride to chlorine.
  • the exiting stream of the process gas (6) is fed back to a heat exchanger (37) and enters as a recooled stream of the process gas (7) in a last reactor (31) in which there is a fixed bed of a ruthenium catalyst (HI).
  • the process gas stream (8) output of the reactor (31) forms the process product.
  • FIG. 2 shows a process flow diagram for the process according to Example 4.
  • a hydrogen chloride stream (1) and a gas stream containing oxygen and nitrogen (2) are combined to the process gas stream (3), which is fed to a reactor (29) in which a reaction stage containing a fixed bed of a ruthenium catalyst (I) and a uranium catalyst (VTH).
  • the stream of process gas (4) is then fed to a heat exchanger (36) and as a cooled process gas stream (5) another reactor (30) in which there is a reaction stage containing a fixed bed uranium catalyst (EX), for the further oxidation of hydrogen chloride supplied to chlorine.
  • EX fixed bed uranium catalyst
  • the effluent stream of the process gas (6) is fed back to a heat exchanger (37) and enters as a recooled stream of process gas (7) in another reactor (31), in which a reaction stage containing a fixed bed of a uranium catalyst (X ) is located.
  • the process gas stream (8) outlet of the reactor (31) in turn enters a heat exchanger (38) and enters as a cooled stream of process gas (9) in a last reactor (32.), in which a fixed bed of a ruthenium catalyst (IT) is located.
  • the process gas stream (10) output of the reactor (32) forms the process product.
  • Figure 3 shows the course of conversion of hydrogen chloride and the temperature in the course of the process on the individual reaction steps (S) according to Example 3. Plotted as a thick solid line, the temperature (T) of the process gas against the left y-axis and the turnover (U) to hydrogen chloride over the right y-axis as a thin dashed line.
  • Figure 4 shows the course of conversion of hydrogen chloride and the temperature in the course of the process on the individual reaction steps (S) according to Example 4. Plotted is a thick solid line, the temperature (T) of the process gas against the left y-axis and the conversion (U) to hydrogen chloride over the right y-axis as a thin dashed line.
  • Figure 5 shows the course of conversion of hydrogen chloride and the temperature in the course of the process on the individual reaction steps (S) according to Example 5. Plotted is a thick solid line, the temperature (T) of the process gas against the left y-axis and the turnover (U) to hydrogen chloride over the right y-axis as a thin dashed line.
  • Figure 6 shows the course of conversion of hydrogen chloride and the temperature in the course of the process on the individual reaction steps (S) according to Comparative Example 1. Plotted as a thick solid line, the temperature (T) of the process gas against the left y-axis and the turnover (U) to hydrogen chloride over the right y-axis as a thin dashed line. - -
  • Example 2 Properties of the catalysts according to Example 1 in the oxidation of hydrogen chloride
  • the catalysts from Example 1 were ground to a mean particle size of about 100 microns with a hand mortar in the same way and in a fixed bed in a quartz reaction tube (inner diameter 10 mm) at 540 0 C with a gas mixture of 80 ml / min of hydrogen chloride and 80 ml / min (STP) Oxygen flows through.
  • the quartz reaction tube was heated by an electrically heated sand fluid bed. At intervals according to Table 1, the process gas stream was passed for 10 min in 16% potassium iodide solution. The resulting iodine was then back titrated with 0.1 N thiosulfate standard solution to determine the amount of chlorine contained in the process gas. Table 1 shows the results from the experiment.
  • the ruthenium catalyst is characterized by a strong decrease in activity under the conditions of the process, while the uranium catalyst after 68 h, even in the activity for the oxidation of hydrogen chloride to chlorine, has increased. It is easy to extrapolate that further elevated temperatures and - 1 - prolonged times will lead to the fact that the activity of the ruthenium catalyst will fall below that of the uranium catalyst.
  • EXAMPLE 3 Process comprising two reaction stages according to the invention and one low-temperature reaction stage
  • Two reaction stages according to the invention having two reaction zones arranged one behind the other in a fixed bed reactor are used for the oxidation of hydrogen chloride to chlorine.
  • the reaction steps according to the invention comprise as the first reaction zone a fixed bed of the ruthenium catalyst according to Example 1 and as a second reaction zone a fixed bed of a uranium catalyst according to Example 1. Behind the two reaction stages according to the invention is a low-temperature reaction stage containing only one reaction zone with the ruthenium catalyst. Catalyst according to Example 1 contains.
  • the residence time of the process gas in the first reaction stage is about 2.3 s in total, the residence time in the first reaction zone of the first reaction stage being about 0.9 s and the residence time in the second reaction zone of the first reaction stage being about 1.4 s.
  • the residence time in the second reaction stage is about 3.5 s in total, the residence time in the first reaction zone of the second reaction stage being about 0.9 s and the residence time in the second reaction zone of the second reaction stage being about 2.6 s.
  • the residence time in the low-temperature reaction stage is about 0.7 s.
  • first and second, and second and third reaction stage is a shell and tube heat exchanger, in which the process gases are cooled to about 350 ° C.
  • the process gas at the beginning of the first reaction stage is composed of hydrogen chloride, oxygen and nitrogen in a mutual molar ratio of 4: 4: 2.
  • the process gas is supplied only to the first reaction stage and removed at the output of the third reaction stage.
  • Fig. 3 shows the course of the temperature of the process gas in the process and the conversion in the course of the process.
  • the process gas output of the respective first reaction zone of the reaction stages according to the invention has a temperature of about 370 0 C.
  • the oxidation of hydrogen chloride to chlorine under adiabatic conditions is continued, whereby the temperature in the second reaction zone of the first reaction stage increased to about 470 0 C and in the second reaction zone of the second reaction stage to about 425 ° C. elevated.
  • the degree of conversion of hydrogen chloride achieved in the entire process according to this example is 89% at the end of the last reaction stage. It turns out that with only two series-connected reaction stages according to the invention and a low-temperature reaction stage, a very high conversion can be achieved. The equipment required for this is very low. Furthermore, the first reaction zones of the reaction stages according to the invention and the low-temperature reaction stage are operated at temperatures which cause at least a lesser degradation of the activity of the catalyst.
  • Example 4 Process comprising a reaction stage according to the invention, two reaction stages according to a further preferred development and a low-temperature reaction stage
  • reaction stage according to the invention is used with two successively arranged in a fixed bed reactor reaction zones for the oxidation of hydrogen chloride to chlorine.
  • the reaction stage according to the invention contains as the first reaction zone a fixed bed of the ruthenium catalyst according to Example 1 and as the second reaction zone a fixed bed of a uranium catalyst according to Example 1.
  • Behind the erf ⁇ ndungshielen reaction stage are two reaction stages according to the further preferred development of the inventive method each containing a reaction zone With the uranium catalyst according to Example 1.
  • Hiemach is a low-temperature reaction stage containing only one reaction zone with the ruthenium catalyst according to Example 1.
  • the residence time of the process gas in the first reaction stage is a total of about 2.3 s, wherein the residence time in the first reaction zone of the first reaction stage about 0.9 s and the residence time in the second reaction zone of the first reaction stage is about 1.4 s.
  • the residence time in the second reaction stage is about 1.1 s.
  • the residence time in the third reaction stage is about 1.5 s.
  • the residence time in the low-temperature reaction stage is about 0.7 s.
  • each tube bundle heat exchanger Between the reaction stages are each tube bundle heat exchangers.
  • the process gases are cooled to approximately 400 ° C. each.
  • the process gases are cooled to about 350 0 C.
  • the process gas at the beginning of the first reaction stage is composed according to Example 3.
  • the process gas output of the first reaction zone of the first reaction stage according to the invention has a temperature of about 370 0 C.
  • the oxidation of hydrogen chloride to chlorine is continued under adiabatic conditions, whereby - 1 - the temperature in the second reaction zone of the first reaction stage increased to about 470 0 C.
  • the process gas is cooled as described above to about 400 ° C and is heated in the second reaction stage again under adiabatic conditions to 470 0 C.
  • the process gas heats again under adiabatic conditions in the third reaction stage to about 440 0 C.
  • Example 5 Process with separation of parts of the process gas into the reaction stages A process similar to that in Example 3 is carried out, with the only difference that 57% by volume of the hydrogen chloride contained in the process gas stream are fed before the first reactor stage and the remaining one 43% by volume of the hydrogen chloride is added to the process before the second reaction stage.
  • the residence time of the process gas in the first reaction stage is a total of about 4.3 s, wherein the residence time in the first reaction zone of the first reaction stage about 1.2 s and the residence time in the second reaction zone of the first reaction stage is about 3.1 s.
  • the residence time in the second reaction stage is about 3.7 s in total, the residence time in the first reaction zone of the second reaction stage being about 1 s and the residence time in the second reaction zone of the second reaction stage being about 2.7 s.
  • the residence time in the low-temperature reaction stage is about 0.9 s.
  • Fig. 5 shows the course of the temperature of the process gas in the process, as well as the conversion in the course of the process.
  • the process gas output of the respective first reaction zone of the inventive reaction stages has a temperature of about 370 0 C.
  • the temperature in the second reaction zone of the first reaction stage increased to about 470 0 C and increased in the second reaction zone of the second reaction stage to about 435 ° C.
  • the latter temperature is higher than in the otherwise analogous example 3, since now more hydrogen chloride is oxidized to chlorine under adiabatic conditions.
  • the degree of conversion of hydrogen chloride achieved in the entire process according to this example is likewise 89% at the end of the last reaction stage.
  • Comparative Example 1 Process comprising five reaction stages containing only reaction zones with ruthenium catalyst
  • the process gases are cooled to about 290 0 C to 330 0 C.
  • the process gas at the beginning of the first reaction stage is composed according to Example 3.
  • the residence time of the process gas in the first reaction stage is about 1.1 s, the residence time in the second reaction stage about 1.4 s, in the third about 1.6 s, in the fourth about 1.7 s, in the fifth reaction stage about 1.9 s. Overall, this results in a residence time of about 7.7 s in this process.
  • FIG. 6 shows the profile of the temperature of the process gas in the process and the conversion in the course of the process.
  • the process gas output of the first reaction stage has a temperature of about 365 ° C. Thereafter, the process gas is cooled to about 295 ° C and heated in the subsequent reaction stage back to about 365 ° C by oxidation of hydrogen chloride to chlorine under adiabatic conditions.
  • the sequence of adiabatic oxidation and cooling continues in an oscillating manner, with increasingly higher temperatures being required after cooling in the heat exchangers, since the progressing oxidation of hydrogen chloride to chlorine over the reaction stages reduces the amount of hydrogen chloride in the process gas.
  • Process gas leads to the approximation to the thermodynamic equilibrium; This leads to a decrease in the reaction rate, which must be compensated by increasing the temperature level. From the fifth and final reaction stage, the approximation to the thermodynamic equilibrium is seen by the inflection point and the flattening of the reaction temperature evolution, as well as the corresponding reduction in the increase in conversion.
  • the degree of conversion of hydrogen chloride achieved in the entire process according to this example is about 90% at the end of the fifth and last reaction stage.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé d'oxydation catalytique hétérogène de gaz chlorhydrique en plusieurs étapes dans un gaz de processus dans au moins un étage de réaction comportant deux zones de réaction adiabatiques placées l'une derrière l'autre. Un catalyseur qui est présent dans la deuxième zone de réaction dudit au moins un étage de réaction, contient une composante d'uranium. Cette deuxième zone de réaction fonctionne à des températures de 350°C à 800°C.
EP09778790A 2008-10-09 2009-10-01 Procédé de production de chlore en plusieurs étapes Withdrawn EP2334593A1 (fr)

Applications Claiming Priority (2)

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DE102008050975A DE102008050975A1 (de) 2008-10-09 2008-10-09 Mehrstufiges Verfahren zur Herstellung von Chlor
PCT/EP2009/007040 WO2010040469A1 (fr) 2008-10-09 2009-10-01 Procédé de production de chlore en plusieurs étapes

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JP2014520742A (ja) * 2011-07-05 2014-08-25 バイエル インテレクチュアル プロパティー ゲゼルシャフト ミット ベシュレンクテル ハフツング 断熱反応カスケードにおける酸化セリウム触媒を使用する塩素の製造方法
DE102011081074A1 (de) * 2011-08-17 2013-02-21 Areva Np Gmbh Verfahren zur Herstellung eines Uranoxid als aktive Komponente enthaltenden Katalysators
EP2771108A1 (fr) * 2011-10-24 2014-09-03 Bayer Intellectual Property GmbH Catalyseur et procédé pour produire du chlore par oxydation catalytique en phase gazeuse
CN104592000B (zh) * 2014-12-22 2017-01-11 上海方纶新材料科技有限公司 制备氯甲酰基取代苯的清洁工艺
WO2017130081A1 (fr) * 2016-01-27 2017-08-03 Sabic Global Technologies B.V. Procédés et systèmes pour augmenter la sélectivité pour des oléfines légères dans l'hydrogénation de co2
WO2023094364A1 (fr) * 2021-11-23 2023-06-01 Basf Se Procédé de préparation d'un flux gazeux comprenant du chlore

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CN102177087A (zh) 2011-09-07

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