ZA200100949B - Method for carrying out gas-liquid reactions and corresponding flow reactor. - Google Patents
Method for carrying out gas-liquid reactions and corresponding flow reactor. Download PDFInfo
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- ZA200100949B ZA200100949B ZA200100949A ZA200100949A ZA200100949B ZA 200100949 B ZA200100949 B ZA 200100949B ZA 200100949 A ZA200100949 A ZA 200100949A ZA 200100949 A ZA200100949 A ZA 200100949A ZA 200100949 B ZA200100949 B ZA 200100949B
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- 238000006243 chemical reaction Methods 0.000 title claims description 56
- 238000000034 method Methods 0.000 title claims description 46
- 239000007788 liquid Substances 0.000 title claims description 24
- 239000003054 catalyst Substances 0.000 claims description 36
- 239000012224 working solution Substances 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 150000004056 anthraquinones Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000003068 static effect Effects 0.000 description 5
- 239000002826 coolant Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OTBHDFWQZHPNPU-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1CCCC2 OTBHDFWQZHPNPU-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical group C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 1
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical group C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 1
- 229910000746 Structural steel Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
-
- 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
- B01J19/249—Plate-type reactors
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- 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
- B01J19/32—Packing elements in the form of grids or built-up elements for forming a unit or module inside the apparatus for mass or heat transfer
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- 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
- B01J8/34—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 with stationary packing material in the fluidised bed, e.g. bricks, wire rings, baffles
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2451—Geometry of the reactor
- B01J2219/2453—Plates arranged in parallel
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2451—Geometry of the reactor
- B01J2219/2456—Geometry of the plates
- B01J2219/2458—Flat plates, i.e. plates which are not corrugated or otherwise structured, e.g. plates with cylindrical shape
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2451—Geometry of the reactor
- B01J2219/2456—Geometry of the plates
- B01J2219/2459—Corrugated plates
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2461—Heat exchange aspects
- B01J2219/2462—Heat exchange aspects the reactants being in indirect heat exchange with a non reacting heat exchange medium
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2476—Construction materials
- B01J2219/2477—Construction materials of the catalysts
- B01J2219/2481—Catalysts in granular from between plates
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2491—Other constructional details
- B01J2219/2497—Size aspects, i.e. concrete sizes are being mentioned in the classified document
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2491—Other constructional details
- B01J2219/2498—Additional structures inserted in the channels, e.g. plates, catalyst holding meshes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/322—Basic shape of the elements
- B01J2219/32203—Sheets
- B01J2219/32206—Flat sheets
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/322—Basic shape of the elements
- B01J2219/32203—Sheets
- B01J2219/3221—Corrugated sheets
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/322—Basic shape of the elements
- B01J2219/32203—Sheets
- B01J2219/32213—Plurality of essentially parallel sheets
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/322—Basic shape of the elements
- B01J2219/32203—Sheets
- B01J2219/32255—Other details of the sheets
- B01J2219/32262—Dimensions or size aspects
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/324—Composition or microstructure of the elements
- B01J2219/32466—Composition or microstructure of the elements comprising catalytically active material
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/324—Composition or microstructure of the elements
- B01J2219/32466—Composition or microstructure of the elements comprising catalytically active material
- B01J2219/32475—Composition or microstructure of the elements comprising catalytically active material involving heat exchange
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/33—Details relating to the packing elements in general
- B01J2219/3306—Dimensions or size aspects
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/332—Details relating to the flow of the phases
- B01J2219/3322—Co-current flow
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/332—Details relating to the flow of the phases
- B01J2219/3325—Counter-current flow
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
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- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
. cUuiu7%7/ @¢ ) 1
Process for carrying out gas-liquid reactions and continuous flow reactor for this purpose
The invention relates to a process for carrying out gas- liquid reactions wherein a liquid phase, which represents a reaction component or contains a reaction component in dissolved, emulsified or suspended form, and a gas phase containing a gas to be reacted, are passed through a continuous flow reactor having several reaction chambers in the presence or in the absence of a catalyst. The process relates especially to catalytic hydrogenations and oxidation reactions, such as the production of hydrogen peroxide by the anthraquinone process. The invention further provides a continuous flow reactor having several reaction chambers arranged in parallel for carrying out the process.
Gas-liquid reactions can be carried out in bubble columns of different designs, with or without circulation of the contents of the reactor (cf. Ullmann’s encyclopedia of industrial chemistry, 5th ed., Vol. B4, 276-278 (1992)).
The space-time yield (STY) of gas-liquid reactions of the generic type depends to a considerable extent on the flow conditions in the reactor. An increase in the STY can be brought about by intensifying the mass transport processes by means of turbulences in the main flow. In loop reactors this can, to a certain extent, be brought about by increasing the circulation rate. Better bubble distribution can be achieved by reactor inserts, such as e.g. column trays and packings, including statix [sic] mixer elements.
According to another embodiment, the bubble column can also be divided into individual shafts, arranged in parallel.
Neither a ratio between chamber width and slit width
® WO 00/15550 PCT/EP99/06366 forming the basis of the present invention nor of [sic] the slit width can be derived from this document.
From DE-AS 10 67 783 a contact and rectifying column is known, which is also suitable for carrying out catalytic reactions. The column comprises several column sections with parallel plates, which form chambers that are open in the direction of the main flow. The plate spacing for the m high column given as an example is 1.2 mm. The document does not teach the selection of a much larger 10 plate spacing.
DE-AS 10 55 501 teaches a column for distillation or other mass transfer purposes. The column contains plate stacks. A teaching to use the column for gas-liquid reactions and regarding the plate spacing cannot be taken from the document.
From GB 620 129 a distillation device is known which contains plates aligned parallel to the vapour flow instead of packing in a column. Liquid and vapourflow [sic] in counter-current.
A flow reactor according to DE 195 36 971 contains substantially parallel capillary flow channels in the direction of the main flow. The width of the channels is 0.08 to 0.4 mm.
A technically significant application of a gas-liquid reaction is the anthraquinone process for the production of hydrogen peroxide (cf. Ullmann’s encyclopedia of industrial chemistry, 5th. ed. Vol. A 13, 447-457 (1989)). In the hydrogenation step of this process an anthraguinone reaction support dissolved in a working solution is converted to the anthrahydroquinone form with hydrogen in the presence of a suspension catalyst. According to DE patent specification 15 42 089 (= US 3,423,176) the hydrogenation takes place in a three-phase reaction system
¥ in a meandering reaction chamber of consecutive, vertical, alternately narrow and wide pipes. The increase in the rate of hydrogenation was attributed to the increased turbulence achieved in this reactor. However, as taught by US patent 4,428,923, it was possible to increase the microturbulence, and thus the productivity, corresponding to the space-time yield, in the same process using a meandering tubular reactor consisting of tubes of the same cross section in the rising and falling segments.
The efficiency of the energy transfer (energy dissipation) necessary to produce turbulence is influenced by the turbulence structure. The energy is broken down in cascade fashion via coarse, fine and microturbulences, and the actual chemical processes in a multi-phase system are mainly controlled by microturbulences.
Instead of in a tubular reactor using a suspension catalyst, the hydrogenation step of the anthraquinone process for the production of hydrogen peroxide according to EP-B 0 102 934 can also be carried out using a honeycomb-like catalyst. This catalyst contains many parallel channels, the walls of which are coated with the catalyst. The narrow channels necessarily lead to a considerable pressure drop and, as noted in US patent 5,071,634, to a weak intermixing of the hydrogen with the working solution, optionally also to a phase separation. A disadvantage of catalyst-coated, honeycomb-like elements - the same also applies to catalyst-coated static mixer elements - is that they can be regenerated only with difficulty and at great expense, e.g. by exchanging the elements. Another disadvantage is the inadequate transport of heat outwards from the inner areas of the honeycomb-like catalyst support, conventionally made of a ceramic material. The zones for the catalytic reaction and the elimination of heat are thus separated from one another.
LJ
4
This makes additional apparatus necessary for eliminating heat.
In the anthraquinone process for H;0, production according to US patent 5,071,634, a working solution through which Hp is bubbled is passed through long, narrow static mixer zones with several baffle plates coated with a catalyst.
The static mixer zones guarantee good intermixing of the H; gas bubbles with the working solution and also, owing to the distribution of the flow over the entire cross section, good transport of heat to the cooled external wall, but this version requires greater use of energy owing to the higher pressure drop. In addition, static mixer elements cannot be used if the process is to be operated using a suspension catalyst, because the baffle plates of the static mixer aligned longitudinally and transverse to the direction of flow lead to a catalyst sink (deposit).
In the process of EP-A 0 672 617, a mixture of the working solution and hydrogen is passed at relatively high speed from top to bottom through a fixed bed of catalyst.
According to figure 2 of this document, the reactor can have vertical plates which consist of two nets with catalyst particles in between. Catalyst and nets fill approximately 30% of the cross section of the reactor, so that a large part of the cross section remains free for the gas-liquid dispersion to flow through. The plates must be permeable so that a constant exchange of the working solution on the left and right of such a plate is possible as a pre-condition of the catalyst reaction. A disadvantage is that, generally, hydrogen is used in excess and therefore the latter has to be recycled. Owing to the limited level of catalyst, the reactor volume and thus the hold-up of expensive working solution increase.
The object of the present invention is to set forth a process for carrying out gas-liquid reactions which, through the apparatus design of the reactor, leads to a
« higher space-time yield (STY) than using known tubular continuous flow reactors. The reactor should have as simple a construction as possible and should be suitable for carrying out gas-liquid reactions in the presence of solids 5 suspended in the liquid medium, such as suspension catalysts. According to another object, the STY of the anthraquinone process for producing hydrogen peroxide using a suspension catalyst should be increased compared with the process using known, meandering, tubular reactors.
A process for carrying out gas-liquid reactions was found, wherein a liquid phase which represents a reaction component or contains a reaction component in dissolved, emulsified or suspended form, and a gas phase containing a gas to be reacted, are passed in co-current, in the presence or in the absence of a catalyst, through a continuous flow reactor having at least three slit-shaped reactor chambers arranged parallel to one another and designed for the same direction of flow, the ratio of the width b to the slit width s of which is, on average, greater than 3, which is characterised in that a continuous flow reactor is used, the reactor chambers of which have a slit width s in the range of 5 to 100 mm.
The subclaims relate to preferred embodiments of the process and use of the same for the production of hydrogen peroxide by the anthraquinone process. The ratio b/s of the particularly preferred tubular reactor to be used is usefully in the range of 5 to 100, especially 10 to 50, and the slit width s in the range of 5 to 100 mm, especially 5 to 50 mm.
The continuous flow reactor suitable for carrying out the process comprises a reactor wall in the form of a tube or vessel, an inlet for introducing the reaction components, an outlet for discharging the reacted reaction mixture and at least three slit-shaped reactor chambers arranged parallel to one another and designed for the same direction
® of flow, the ratio of the chamber width b to the slit width s of which is, on average, greater than 3, and characterised in that the slit width s is in the range of 5 to 100 mm.
In the continuous flow reactors according to the invention, microturbulences are produced by simple means, resulting in acceleration of the reaction. It is known that the mass- related dissipation performance (W/kg) decreases as the macro scale of the large-scale turbulence (= dimension of the largest balls of primary turbulence occurring) increases. As a result of the form of the reactor according to the invention it is possible to minimise the large-scale turbulences and to increase the dissipation performance. From the definition deq = 4 A/U, wherein deq is the equivalent diameter in a reaction chamber of a different shape corresponding to the hydraulic diameter in a round tube and A corresponds to the area and U the circumference of the other reaction chamber, the equation deg = 2'b’s / (b+s), wherein s is the slit width, corresponding approximately to the macro scale, and b is the chamber width, follows for rectangular cross sections, such as the slit-shaped reactor chambers according to the invention; for s & b, deg ~ 2s applies.
This equation says that, in the slit-shaped reaction chambers, with the same Reynolds number as in round tubes, only about half the macro scale is present. Thus, in the slit-shaped channels, compared with a tube bundle, the same dissipation is achieved with a much lower pressure drop.
Not only the rate of flow, but also wall friction has an effect on the pressure drop. As the laminar area is approached, the pressure drop in the reactor according to the invention is further reduced. It is surprising that these aspects have never yet been applied in the design of continuous flow reactors for gas-liquid reactions.
¢
The invention is further explained with reference to the figures:
Figure 1 shows a longitudinal section through a tubular continuous flow reactor with two plate stacks rotated by 90° to one another, one stack consisting of simple plates and the other of heat exchanger plates.
Figure 2a shows a perspective view of a tubular continuous flow reactor with a stack of heat exchanger plates.
Figure 2b shows a cross section through the reactor of figure 2a.
Figure 3 shows a cross section through a profile heat exchanger plate.
Figure 4 shows a process diagram for carrying out the process according to the invention using the example of a hydrogenation in the presence of a suspension catalyst.
The construction is elucidated with reference to the preferred continuous flow reactor of figure 1. The tubular continuous flow reactor 1 comprises a reactor wall 2, an inlet 3 and outlet 4 and two plate stacks 5 and 6 arranged in the reactor tube. Each stack has several (n) plates 7/1 to 7/n arranged in parallel, which are aligned in the longitudinal direction to the pipe and thus form n + 1 slit-shaped reaction chambers 8 which are open in the direction of flow. In the reactor of figure 1 the plate stack 5 is rotated by 90° in respect of the plate stack 6.
The slit width corresponds to the plate spacing s - marked in the figure between plates 7/1 and 7/2. The plates are connected to one another by means of distance sleeves 9 and are fixed in the tube by means of anchors 10. The slit- shaped reactor chambers 8 have a width b, which is indicated in the plate stack 6 on the plate 7/m located in the middle of the tube by the plate width b. A feature which is essential for the invention, both of tubular reactors and of reactors with a different cross section, is that the ratio of the width b to the slit width s is, on average, greater than 3, preferably greater than 5 and
¢ - . particularly preferably greater than 10. The ratio b/s is usefully in the range of 5 to 100, especially in the range of 10 to 50, and the slit width in the range of 5 to 100 mm, especially in the range of 5 to 50 mm, particularly preferably 10 to 50 mm.
The plates can be open towards the reactor wall - as can be seen in the plate stack 5 in figure 2 - or closed. In the case of an open construction - as can clearly be seen in figure 2 - it is possible to design a plate stack with a more uniform plate width, and thus chamber width, which corresponds to a particularly simple design. In so far as the plates reach to the reactor wall, the plates necessarily have different widths in the case of a tubular reactor with a round cross section, so that in this case the ratio b/s denotes that of the average plate width per slit width.
In the reactor of figure 1 the plate stack 5 is made up of simple baffle plates, while the plate stack 6 on the other hand is made up of heat exchanger plates, to and from which a heating or cooling medium is fed through the connection pieces 11 and 12. To increase the turbulence, the plates can also be profiled. A reactor can have one or more plate stacks of the same or different designs.
Figure 2a shows a perspective, and partly open, view of a tubular reactor 201 with a stack 205 of several heat exchanger plates 207 of constant width arranged in parallel in the tube 202. The heating or cooling medium is fed to and from the plates through the connection pieces 211 and 212. The parallel arrangement of the plates is guaranteed here by means of the connecting studs or plates 209/1 and 209/2 which simultaneously act as distance sleeves and serve to distribute the heating/cooling medium to the individual plates. In figure 2b, a cross section of the reactor 201 shown in figure 2a is represented with an internal stack 205 of a heat exchanger, the references
«¢ ) 9 corresponding to those in figure 2a. In figure 2b, plate fixings (= anchors) 210 are additionally drawn in. The reaction medium, i.e. the gas-liquid mixture, flows through the reaction chambers 208 formed between the plates and through the tube segments 213 formed below and above the stack, and optionally also through the tube segments 214 formed to the left and right of the stack.
It is possible both with simple baffle plates (according to stack 5 in fig. 1) and with heat exchanger plates (according to stack 6 of fig. 1 and fig. 2a and 2b) to give the plates a profiled shape in order to favour the formation of microturbulence. A profiled plate of this type is represented in cross section in figure 3, which is a welded heat exchanger plate with the channels for the heating/cooling medium.
Although tubular reactors according to the invention are particularly preferred, it is also possible to design block-shaped reactors with one or more plate stacks arranged therein with the feature b/s according to the invention. Block-shaped reactors of this type are useful if the plates consist of welded heat exchanger plates.
A process diagram for carrying out gas-liquid reactions, in this case a hydrogenation of a working solution (AL) in the presence of a suspension catalyst, in a reactor according to this invention is represented in figure 4. The process diagram shown can be applied to any gas-liquid reactions, for example to hydrogenations using a gas that contains hydrogen and a hydrogenation catalyst suspended in the liquid medium and oxidation reactions by means of a gas that contains oxygen. One example of an application relates to a process for the production of hydrogen peroxide by the anthraquinone process, wherein, in a first step, an anthraquinone reaction support dissolved in a working solution is catalytically hydrogenated with hydrogen and, in a subsequent step, the hydrogenated reaction support is
®
N 10 oxidised with an O,-containing gas and finally, hydrogen peroxide that has formed is extracted with water, and wherein the hydrogenation step is carried out in the presence of a suspension catalyst and/or the oxidation step using a reactor according to the invention. In the hydrogenation step of this process, the reaction support to be hydrogenated - usually a 2-alkyl anthraquinone or mixture of 2-alkyl anthraquinones and 2-alkyl tetrahydro- anthraquinones -, dissolved in an organic solvent or mixture of solvents, is converted at least partly to the hydroquinone form in the presence of a suspension catalyst, usually palladium black. This hydrogenation step according to the invention can be performed using reaction supports, solvents and mixtures and suspension catalysts known in the prior art - reference is made in connection with this to the Ullmann citation mentioned above, vol. Al3, 447-457 (1989).
The equipment according to figure 4 comprises two tubular continuous flow reactors 401 connected in series, designed according to the invention. Individual plate stacks 411, which are rotated in respect of one another, are indicated by the alternate grey and white segments. Hydrogen is introduced via a line 402 into the circulation line 404, which contains the reaction components in liquid, suspended or dissolved form and the suspension catalyst. The working solution AL containing a component to be hydrogenated is introduced via line 403 into the circulation line 404. The gas-liquid reaction mixture flows through the reactors 401, wherein the hydrogen is usefully completely converted. The liquid medium leaving the second reactor passes into the intermediate vessel 405 and from there is passed to a filter 408 via line 407 by means of a pump 406. In the filter 408, which contains different filter elements 409, e.g. filter candles, or can be in the form of a cross-flow filter, a partial stream 410 is freed of suspended catalyst by means of the filter elements. The partial stream 410 e ) 11 ~ (= filtrate), a small part of which is also used for back- flushing the filter if necessary (this is indicated by the double arrow of different lengths), is fed into the subsequent or work-up steps. The part of the reacted reaction mixture flowing past the filter which contains the suspended catalyst is fed into the hydrogenation step via line 404. The quantity of liquid medium equivalent to the filtrate that has been drawn off is fed via line 403 to the line 404 before hydrogen is introduced.
As can be seen from Example B according to the invention and comparative example VB, the process according to the invention leads to a large increase in the space-time yield. Not only can the space-time yield be considerably increased by the surprisingly high efficiency of the reactor according to the invention, but at the same time the amount of apparatus needed and the energy requirements are reduced. Whereas, in the known process (according to US patent 4,428,923), many reaction tubes arranged in a meandering shape were needed, the number of tubes could be reduced to less than a third, while maintaining the plant output, if these pipes were equipped with plate stacks according to the invention. Another advantage lies in the fact that the high circulation rate necessary up to now and the pump performance required for it become unnecessary.
Whereas, up to now, only a partial stream was fed to the filter, while the main stream was fed back into the hydrogenation step, the hydrogenated working solution can now be freed of the suspension catalyst in the main stream.
Another advantage is that the reduction in the number of reaction tubes is accompanied by a correspondingly large reduction in the total volume of working solution and suspension catalyst. The reduced number of reaction tubes further leads to lower plant costs owing to a smaller quantity of structural steel. Since only that quantity of the hydrogenated working solution which is not drawn off as filtrate is circulated, and in addition the pressure drop
@. to produce the microturbulence in the plant is smaller than in the known process, the circulating pumps can be given smaller dimensions and thus also energy can be saved.
The combination of a plate stack of simple plates represented in figure 2 - if necessary the plates can also be profiled - and a stack of heat exchanger plates is given dimensions as proved necessary from the thermal balance of the reaction in question.
The surprising effect of the reactor according to the invention is elucidated by the following example and comparative example.
Example (B) and comparative example (VB)
In a device according to figure 4, but with three continuous flow reactors 401 according to the invention = 1 3 loops), the hydrogenation step of the anthraquinone process for the production of hydrogen peroxide was carried out (B). Each of the three tubes contained a stack of simple plates and a stack of heat exchanger plates according to figure 1; the slit spacing was 25 mm, the width of the chambers an average of 350 mm.
For comparison purposes (VB) the process was carried out in a device according to figure 1 of US patent 4,428,923, the reactor comprising 13 tubes (= 6 ¥ loops) and the circulating line 4a shown in figure 1 of the US patent being in operation. The length of the tubes and the tube diameter were the same in the comparative example and the example according to the invention.
The working solution in B and VB was identical. It contained a mixture of 2-ethyl- and 2-amylanthraquinone and the tetrahydroanthraquinones thereof in a solvent mixture of a mixture of alkyl aromatics (Shellsol®) and trioctyl phosphate as the reaction support. The total quinones content was 175 g/l. The working solution contained h RJ 13 palladium black as suspended catalyst in a quantity of approximately 1 g Pd/l working solution. At a temperature of 60°C, H, was introduced and the reaction support was hydrogenated.
In the example according to the invention and in the comparative example, the same quantity of working solution was discharged via the filter (408 in Fig. 4 of this application and 6 in Fig. 1 of the US patent) and fed into the oxidation step, containing a specific proportion of hydroquinone in order to produce approx. 11 to 13 g H;0,/1 working solution over the subsequent process steps.
As a result of the plate pack according to the invention in the reactor tubes, not only could the number of reactor tubes be reduced from 13 to 3, maintaining the plant output, but the volume of working solution contained in the reaction tubes, including the precious metal catalyst, could be reduced to less than a quarter of the quantity required in the comparative example. At the same time, the pressure drop in the plant, and thus the expenditure of energy, was reduced. It was also noted that the third tube in the example according to the invention was superfluous, since the reaction of the reaction support with the hydrogen was already complete in the second tube. As shown by the comparison, the space-time yield of the hydrogenation step (= kg H,O, equivalent per m® reactor volume per hour) is considerably increased.
Claims (14)
1. Process for carrying out gas-liquid reactions, wherein a liquid phase, which represents a reaction component or contains a reaction component in dissolved, emulsified or suspended form, and a gas phase containing a gas to be reacted, are passed in co- current, in the presence or in the absence of a catalyst, through a continuous flow reactor having at least three slit-shaped reaction chambers, arranged parallel to one another and designed for the same direction of flow, the ratio of the width b to the slit width s of which is, on average, greater than 3, characterised in that a continuous flow reactor is used, the reactor chambers of which have a slit width s in the range of 5 to 100 mm.
2. Process according to claim 1, characterised in that a tubular reactor is used, the chambers of which are formed by a plate stack arranged in a tube with a plate spacing s (= slit width) in the range of 5 to 50 mm and the ratio b/s of which is, on average, in the range of 5 to 100, wherein the chambers can be open or closed towards the wall of the reactor, but are open in the direction of flow.
3. Process according to claim 1 or 2, characterised in that a reactor is used in which at least some of the walls located between the reaction chambers are in the form of heat exchanger plates through which a heat exchanger medium flows, and the temperature in the reaction chambers is controlled by means of this medium.
A
4. Process according to claims 2 and 3, characterised in that a reactor is used which has at least one plate stack of simple plates forming chambers which are parallel in the direction of flow and at least one plate stack of heat exchanger plates forming chambers which are parallel in the direction of flow, and the temperature is controlled by means of a medium flowing through the heat exchanger plates.
5. Process according to one of claims 1 to 4, characterised in that a reactor is used, the chambers of which have a slit width s in the range of 10 to 50 mm and on average a ratio b/s in the range of 10 to 50.
6. Process according to one of claims 1 to 5, characterised in that the liquid phase, which contains a dissolved reaction component and, in addition, a suspension catalyst, is passed through the reactor in co-current.
7. Process according to one of claims 1 to 6, characterised in that a catalytic hydrogenation is carried out as the gas- liquid reaction using a hydrogen-containing gas or an oxidation using an oxygen-containing gas.
8. Process according to claim 7, characterised in that as the liquid phase, a working solution containing dissolved anthraquinone reaction supports, suitable for the production of hydrogen peroxide by the anthraquinone process, which contains a suspension hydrogenation catalyst, and as the gas phase, a hydrogen-containing gas is used.
16 PCT/EP99/06366
9. Continuous flow reactor for carrying out the process according to one of claims 1 to 8, comprising a tubular or vessel-shaped reactor wall, an inlet for introducing the reaction components, an outlet for discharging the reacted reaction mixture and at least three slit-shaped reaction chambers, arranged parallel to one another and in the longitudinal direction of the reactor and designed for the same direction of flow, the ratio of chamber width b to slit width s of which is, on average, greater than 3, characterised in that the slit width s is in the range of 5 to 100 mm.
10. Continuous flow reactor according to claim 9, characterised in that it is tubular and the chambers are formed by at least one plate stack arranged in the tube with a plate spacing s (= slit width) in the range of 5 to 50 mm, the ratio of chamber width b to slit width s is, on average, in the range of 5 to 100 and the chambers can be open or closed towards the reactor wall but are open in the direction of flow.
11. Continuous flow reactor according to claim 9 or 10, characterised in that it has at least one plate stack of simple plates forming chambers which are parallel in the direction of flow and at least one plate stack of heat exchanger plates forming chambers which are parallel in the direction of flow.
12. A process according to claim 1, substantially as herein described and illustrated.
13. A reactor according to claim 9, substantially as herein described and illustrated. AMENDED SHEET
17 PCT/EP99/06366
14. A new process for carrying out reactions, or a new reactor, substantially as herein described. AMENDED SHEET
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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DE1998141843 DE19841843A1 (en) | 1998-09-12 | 1998-09-12 | Fluid/gas reactor for hydrogen peroxide production with reaction passages formed by a plate stack of closely defined dimensions. |
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DE10052323A1 (en) | 2000-10-21 | 2002-05-02 | Degussa | Continuous process for hydrogenation |
ATE369909T1 (en) * | 2001-06-13 | 2007-09-15 | Beta Technologie Ag | MASS POLYMERIZATION REACTORS AND POLYMERIZATION PROCESSES |
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GB620129A (en) * | 1945-11-13 | 1949-03-21 | Olaf George Dixon | Improvements in and relating to treating gases or vapours with liquids |
DE1055501B (en) * | 1955-01-11 | 1959-04-23 | Leuna Werke Veb | Column for distillation or other mass transfer purposes |
DE1067783B (en) * | 1956-09-05 | 1959-10-29 | Joseph Graner | Contact and separation column |
SE431532B (en) * | 1982-09-08 | 1984-02-13 | Eka Ab | METHOD OF PRODUCING WHEAT PEROXIDE |
FI95457C (en) * | 1994-03-15 | 1996-02-12 | Kemira Chemicals Oy | Process for the preparation of hydrogen peroxide and the reactor used therein |
DE19536971A1 (en) * | 1995-10-04 | 1997-04-10 | Elwatec Elektrolyse Und Wasser | Flow reactor with capillary flow channels and system for the catalytic reduction of nitrate and / or nitrite in water loaded with hydrogen and method for operating the system |
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1998
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