EP1858638A1 - Catalytically active porous membrane reactor for reacting organic compounds - Google Patents
Catalytically active porous membrane reactor for reacting organic compoundsInfo
- Publication number
- EP1858638A1 EP1858638A1 EP06707369A EP06707369A EP1858638A1 EP 1858638 A1 EP1858638 A1 EP 1858638A1 EP 06707369 A EP06707369 A EP 06707369A EP 06707369 A EP06707369 A EP 06707369A EP 1858638 A1 EP1858638 A1 EP 1858638A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- membrane
- reactor
- catalytically active
- flow reactor
- hydrogenation
- 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- Withdrawn
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 111
- 150000002894 organic compounds Chemical class 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000002002 slurry Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011552 falling film Substances 0.000 description 3
- -1 for example Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical class [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000079 presaturation Methods 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011555 saturated liquid Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- B01J35/59—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/0215—Silicon carbide; Silicon nitride; Silicon oxycarbide
-
- 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
- B01J19/2475—Membrane reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/10—Specific pressure applied
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
-
- 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
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
-
- 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
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
- B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- Catalytically active membrane pore flow reactor for the conversion of organic compounds.
- the invention relates to a catalytically active membrane pore flow reactor, the membrane used and methods using this reactor.
- the reactors can be roughly divided into fixed bed and slurry reactors.
- the trickle-bed reactor has the greatest industrial importance in catalytic hydrogenation reactions (Al-Dahhan et al., Ind. Engng Chem. Res., 36 (1997) 3292-3314, Saroha et al., Rev. Chem. Eng., 12 (996) 207).
- shell catalysts are used.
- a significant advantage when using a trickle-film reactor is that the separation between the reaction solution and the catalyst after the reaction is not necessary. Furthermore, the reactor can be operated continuously.
- slurry reactor Another industrially used type of reactor for, three-phase hydrogenation is the slurry reactor. Because of its simplicity of construction, ease of implementation, and great flexibility, the slurry reactor is very often used for industrial-scale hydrogenation reactions. Bubble column reactors are also commonly used, especially in the field of organic synthesis e.g. Oxidation, chlorination, hydrogenation. The development of new types of reactors for three-phase reactions, e.g. Membrane reactors are being intensively researched. Kuzin et al. (Kuzin et al., Catalysis Today 79 (2003) 105-111) describe the use of membrane reactors for the hydrogenation of organic compounds.
- the membrane which consists mainly of nickel, acts on the one hand as a carrier and on the other hand as a medium for the meeting of gas and liquid.
- De Vos (de Vos et al., Chem., Eng., 37 (1982) 1719) reports the use of ceramic membranes for a highly exothermic reaction.
- Cini and Harold described a catalytic membrane reactor according to the diffuser principle. In comparison to suspension catalysts, an increase in the reaction rate by a factor of 20 could be achieved.
- the cylindrical membrane consists of macroporous and microporous ceramic material.
- Another type of membrane reactor is the so-called catalytically active membrane flow reactor. In membrane flow reactors, the mass transport can be significantly improved. This then leads to an increase in the reactor power and an increase in the selectivity.
- WO A 98/10865 discloses a membrane flow reactor with an amorphous micropore membrane having pore sizes of 0.5-2 nm. The goal of this membrane was to suppress subsequent reactions by preventing backmixing due to pore sizes of (double) molecular size.
- a membrane reactor has a very large pressure loss due to the very small pore sizes, so that a large-scale operation would be uneconomical.
- US Pat. No. 5,492,873 claims a membrane reactor with a membrane which, however, is permeable only to one reactant and not to the other reactants and catalyst poisons. As a result, catalyst poisoning could be prevented.
- the reaction zone in such an arrangement results only through the surface, so that the catalyst utilization and the space-time yield are very low.
- RU A 2083540 describes carrying out the hydrogenation reactions in which the organic substance is saturated with hydrogen in a separate stirred tank and then the solution is passed through an external bed. Although this reactor concept uses the principle of presaturation of the organic solution, it does not overcome the internal mass transfer limitation. "" .
- the object of the present invention was therefore, starting from the prior art, to provide a so-called catalytic membrane pore flow reactor with, inter alia, hydrogenation reactions to the exclusion of mass transport limitation and with significantly longer service lives become feasible.
- the reactor power of this Membranporendurohhnereaktors should match or exceed the performance of conventional reactors.
- the invention thus relates to a catalytically active membrane pore flow reactor for the reaction, in particular hydrogenation, of organic compounds.
- the inventive reactor comprises the use of ceramic membranes consisting of Al 2 O 3 , TiC> 2 , ZrC> 2 , SiC> 2 , and other known eg MgA ⁇ O 4 and SiC or consisting of binary and ternary mixtures of these materials, with different pore diameter.
- the pore diameter has a crucial role in the optimal (and cost-effective) implementation of hydrogenations.
- the pore diameter of the membrane must be in the order of the pores of particulate catalysts. Accordingly, membranes with a pore diameter in the range of 0.1 ⁇ m to 100 ⁇ m, preferably in the range of 0.1 ⁇ m to 50 ⁇ m, and very preferably in the range of 0.1 ⁇ m to 10 ⁇ m, are used. Significantly smaller pores lead to a large pressure loss and thereby limit the amount required by the membrane. Too large pores subsequently lead to diffusion limitation.
- the optimum residence time in the membrane pores to be set for the processes is 1 ⁇ 10 -6 to 5 seconds, preferably 1 ⁇ 10 -5 to 3 seconds, and very preferably 1 ⁇ 10 -4 to 1 second.
- the necessary flow velocities in the pores are in the range of 0-1 m / s, preferably in the range of 1 * 10 '3 to 0.1 m / s.
- the residence times can be determined by means of the volume flow and the membrane geometry (membrane area, pore diameter and porosity) using methods generally known to the person skilled in the art (see E. Fitzer, W.
- the ceramic membranes are first coated with a catalytic component.
- all hydrogenation-active transition metals such as, for example, Pd, Pt, Ni, Ru, Rh, etc. ... Drying, calcining and reducing are further conditioning steps, which are used here as well as usually for the activation of the catalytic membrane.
- the cost of preparing the catalytically active membranes of the invention by coating is much easier than the production of shell catalysts.
- so-called catalytically active pore flow membranes are obtained, which in turn are clamped in a metallic membrane module.
- the combination of catalytically active pore flow membrane and membrane module describes the membrane pore flow reactor, which is connected to the other plant peripherals.
- Suitable reactive substrates are all organic compounds which have a hydrogenation-active functional group.
- This class includes, for example, CC double bonds, C-C triple bonds, aromatic rings, carbonyl groups, nitrile groups, diolefins, etc.
- all heterogeneously catalyzed gas-liquid reactions, oxidations, alkylations, chlorinations, etc. could in one Such membrane pore flow reactor can be performed.
- Suitable organic solvents are in general all customary organic, protic and aprotic solvents, such as, for example, unsubstituted or substituted aromatic or nonaromatic hydrocarbons, with alkyl radical or halogen as substituent, preferably haloalkanes, alcohols, water, ethers, haloaromatics, etc. into consideration. Particularly preferred are hexane, methylcyclohexane, heptane, cumene, toluene, chlorobenzene, ethanol, i.-propanol, water.
- the temperature at which the hydrogenation is carried out is limited by safety aspects and / or kinetic aspects. For example. Such hydrogenations are carried out in the temperature range of 20-300 0 C, preferably in the range of 40-250 0 C.
- the hydrogen pressure for carrying out the hydrogenation is i.a. determined by kinetic and safety limits. Usually, however, without being limited to this range, hydrogenations are in the range of 1-300 bar.
- the procedure is usually such that the educts (1) are introduced into a built-in storage container (2).
- the starting materials are saturated with hydrogen (3) by means of a gassing stirrer (4).
- the method is not limited to this type of stirrer but can be carried out with all known to those skilled gassing (stirrer, nozzles, etc.).
- the saturated liquid phase is passed by means of a pump (5) into the membrane pore flow reactor (6).
- the saturated educt solution flows through the catalytically active pore flow membrane, where it comes to the reaction at the catalytically active reaction centers.
- the reaction mixture which subsequently emerges from the membrane pore flow reactor (6) is returned to the storage container (2) via a heat exchanger (7) or continuously reacted in a cascade.
- the throughput of the liquid phases is in the range 20 to 500 ml / min, preferably in the range of 100 to 300 ml / min.
- this type of reactor also achieves significantly higher selectivities in hydrogenations with subsequent reactions compared to conventional reactor types (slurry, fixed bed).
- the inventive method is characterized by the high performance of the catalytically active membrane pore flow reactor, which leads as a result to greatly reduced reaction times in combination with significantly increased service life.
- the reduction of mass transport limitation in the membrane pore flow reactor leads to an increase in the effective utilization of the catalysts. Further advantages of the invention are shown as follows.
- the flow rate can be controlled in terms of safety, since this is directly proportional to the conversion rate. Because of their apparatus simplicity resp. In particular, the hydrogenation in the membrane flow reactor proves to be a very advantageous method in the uncomplicated experimental procedure.
- the tubular membranes of Al 2 O 3 used in the process according to the invention have a length of 250 mm.
- the outer diameter is 2.9 mm and the inner diameter is 1.9 mm.
- the membranes have an average weight of 2.9 g and their pore size is in the range of 3.0 microns to 0.6 microns.
- the proportion of educts used is in the range 5 to 100% by volume, preferably in the range 5 to 50% by volume.
- the coating of the ceramic membranes was carried out by wet chemical impregnation.
- the membranes were soaked in a saturated palladium (II) acetate solution.
- the solvent used was toluene, since Pd (OAc) 2 has a satisfactory solubility in toluene.
- the saturation concentration of palladium (II) acetate in toluene at room temperature and atmospheric pressure was determined experimentally to be 10.75 gl '1 . /
- Characteristic of the experimental design of the loop reactor is the local separation of the catalytic chemical reaction in the membrane and the saturation of the liquid phase with hydrogen.
- Suction power results. Hydrogen from the gas space is introduced into the liquid medium via a hollow shaft of the stirrer.
- the stirrer speed can be set on the gassing stirrer and the relative torque can be read off.
- the hydrogen-saturated solution is pumped by means of a pump (2) into the membrane pore flow reactor (3).
- a maximum of three catalytically active pore flow membranes can be placed, which are sealed with Viton O-rings.
- the arrangement of the two reactor inputs and the two reactor outputs can be interchanged so that the flow of current through the tubular pore flow membranes (from inside to outside or from outside to inside) can be varied.
- the reaction solution is passed back to the saturation tank.
- Both the saturation tank and the membrane module can be tempered independently.
- the reactor is embedded in an electrically heatable aluminum block.
- the saturation tank is surrounded by a coil and is tempered by a thermostat. The temperature is recorded via temperature sensors at the inlet and outlet of the membrane module.
- the pressure is displayed at a total of two points, in the saturation vessel and upstream of the membrane pore flow reactor, via pressure transducers and recorded online by the Labview VI software.
- Samples can be taken at the outlet of the membrane pore flow reactor.
- the quantitative analysis of the reaction mixture is carried out by gas chromatography.
- Table 1 shows a summary of the space-time yields in the catalytic hydrogenation of ⁇ -methylstyrene to cumene in various reactor types. It becomes the space-time
- Table 2 lists the change in the space-time yield as a function of the volumetric flow. This results in a linear increase in the space-time yield.
- Diagrams 1 and 2 show the turnover curves for a membrane pore flow reactor and a fixed bed reactor. As can be seen in the diagrams, in contrast to the fixed bed reactor, stable conversion rates are achieved in the membrane pore flow reactor.
- Diagram 4 shows the change in conversion over time in a membrane pore flow reactor for two membranes with different pore diameters.
- the diagram shows that the membrane with the smaller pores has a higher conversion rate, which is due to a better contact of the liquid with the catalyst particles.
- Table 1 Summary of the space-time yield of all reactor types considered in the hydrogenation of ⁇ -methylstyrene.
- FIG. 5 Comparison of conversion-selectivity courses in the hydrogenation of cycloactadiene (COD) (10 bar, 40 ° C., 10% by volume COD in heptane, membrane reactor)
- Fig. 6 conversion curves as a function of the pore diameters for the hydrogenation of cyclooctadiene (COD) in the membrane pores flow reactor (10 bar, 4O 0 C, 10 vol% COD in heptane)
Abstract
Description
Claims
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Application Number | Priority Date | Filing Date | Title |
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DE102005010213A DE102005010213A1 (en) | 2005-03-05 | 2005-03-05 | Catalytically active membrane pore flow reactor for the conversion of organic compounds |
PCT/EP2006/001893 WO2006094699A1 (en) | 2005-03-05 | 2006-03-02 | Catalytically active porous membrane reactor for reacting organic compounds |
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EP1858638A1 true EP1858638A1 (en) | 2007-11-28 |
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EP06707369A Withdrawn EP1858638A1 (en) | 2005-03-05 | 2006-03-02 | Catalytically active porous membrane reactor for reacting organic compounds |
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US (1) | US20080287718A1 (en) |
EP (1) | EP1858638A1 (en) |
CN (1) | CN101171073A (en) |
DE (1) | DE102005010213A1 (en) |
WO (1) | WO2006094699A1 (en) |
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GB0718398D0 (en) * | 2007-09-21 | 2007-10-31 | Robert Gordon The University | Process for the production of alcohols |
DE102018112463A1 (en) | 2018-05-24 | 2019-11-28 | Karlsruher Institut für Technologie | Process for carrying out strong gas-releasing reactions |
TW202045484A (en) * | 2019-02-08 | 2020-12-16 | 德商贏創運營有限公司 | Oxidation of organic compounds |
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GB8609249D0 (en) * | 1986-04-16 | 1986-05-21 | Alcan Int Ltd | Anodic oxide membrane catalyst support |
DE4303610A1 (en) * | 1993-02-09 | 1994-08-11 | Studiengesellschaft Kohle Mbh | Process for the production of poison-proof catalysts |
AU2003286894A1 (en) * | 2002-11-05 | 2004-06-07 | Millennium Cell, Inc. | Hydrogen generator |
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2005
- 2005-03-05 DE DE102005010213A patent/DE102005010213A1/en not_active Withdrawn
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- 2006-03-02 EP EP06707369A patent/EP1858638A1/en not_active Withdrawn
- 2006-03-02 CN CNA2006800152879A patent/CN101171073A/en active Pending
- 2006-03-02 WO PCT/EP2006/001893 patent/WO2006094699A1/en active Application Filing
- 2006-03-02 US US11/817,425 patent/US20080287718A1/en not_active Abandoned
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US20080287718A1 (en) | 2008-11-20 |
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DE102005010213A1 (en) | 2006-09-07 |
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