Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D301/00—Preparation of oxiranes
  • C07D301/02—Synthesis of the oxirane ring
  • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
  • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
  • C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D301/00—Preparation of oxiranes
  • C07D301/02—Synthesis of the oxirane ring
  • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
  • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
  • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
  • C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D301/00—Preparation of oxiranes
  • C07D301/02—Synthesis of the oxirane ring
  • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
  • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
  • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D301/00—Preparation of oxiranes
  • C07D301/32—Separation; Purification
• • 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
  • Y02P20/10—Process efficiency

Definitions

• the present invention relates to a process for the oxidation of an organic compound having at least one CC double bond or a mixture of two or more thereof, the organic compound or the mixture of two or more thereof using a medium containing molecular oxygen and carbon monoxide in the presence of a heterogeneous Catalyst is implemented.
• the present invention also relates to an integrated process of the above type, in which the catalyst used is regenerated and any unused components are separated off and returned to the reaction.
• EP-A 0 850 936 describes an integrated process for the preparation of epoxides starting from alkanes.
• the epoxidation is carried out by contacting a gas comprising the alkene, hydrogen and unreacted alkane with oxygen in the presence of a catalyst containing Au.
• the primary object of the present invention was to provide a simple process of the type described above which, without the disadvantages of using explosive oxyhydrogen mixtures, is capable of converting olefins into the corresponding epoxides with selectivities well above 60%.
• the present invention relates to a process for the oxidation of an organic compound having at least one C-C double bond or a mixture of two or more thereof, which comprises the following step (II):
• the medium also containing carbon monoxide (CO).
• the molecular oxygen used for the oxidation according to the invention can be air, essentially pure molecular oxygen, as well as oxygen that comes from other sources such as e.g. B. originates ozone and nitrogen oxides, molecular oxygen is preferred.
• the medium contains carbon monoxide (CO).
• CO carbon monoxide
• the CO used preferably originates from a synthesis gas process. Other processes from which the CO can originate are described in K. Weissermel, HJ. Arpe, Industrial Organic Chemistry, 2nd edition (1993), VCH Verlag Weinheim, pp. 14ff. , which is hereby fully incorporated by reference into the context of the present application.
• the medium can contain hydrogen or water, preferably in the form of water vapor, as well as hydrogen and water.
• hydrogen and water there are also no restrictions with regard to the source of hydrogen and water, the hydrogen in particular being produced in situ by, for example, dehydrogenation of alkanes, which are then used as starting materials.
• the medium used in the invention may contain a gaseous or liquid diluent, such as. B. helium, nitrogen, argon, methane, carbon dioxide, water vapor or mixtures thereof, preferably water vapor and / or carbon dioxide (in the gas phase).
• a gaseous or liquid diluent such as. B. helium, nitrogen, argon, methane, carbon dioxide, water vapor or mixtures thereof, preferably water vapor and / or carbon dioxide (in the gas phase).
• a gaseous or liquid diluent such as. B. helium, nitrogen, argon, methane, carbon dioxide, water vapor or mixtures thereof, preferably water vapor and / or carbon dioxide (in the gas phase).
• an oxidation and thermally stable liquid such as. B. chlorinated aliphatic alcohols such as e.g. Chloropropanol, chlorinated aromatics such as. B. chlorine or dichlorobenzene, and liquid polyethers
• the ratio of the essential components of the process according to the invention ie the ratio of organic compound to oxygen to CO, can be chosen freely. It is preferably 1: 0.1-10: 0.1-10, more preferably 1: 1.5-5: 0.3-3 and in particular 1: 2: 0.5 (in each case organic compound: O 2 : CO ).
• organic compound which can be used in the context of the present invention and has at least one CC double bond there are basically no restrictions.
• the term “organic compound having a CC double bond” used in the context of the present invention encompasses all organic compounds which have at least one CC double bond. It can be a low molecular weight organic compound, ie a compound which has a molecular weight of up to approximately 500, and a polymer, ie a compound which has a molecular weight of more than 500.
• the process according to the invention is preferably used for low molecular weight organic compounds of the type described above.
• the organic compound used preferably has 2 to 30 carbon atoms, more preferably 2 to 10 carbon atoms. It is more preferably an aliphatic monoolefin. However, it is also possible for the organic compound used to have more than one ethylenically unsaturated double bond, as is the case, for example, in dienes or trienes. You can additional functional groups such. B.
• the double bond can be terminal or internal. It can also be part of a cyclic structure, such as
• suitable organic compounds include unsaturated fatty acids or their derivatives, such as. B. esters and glycerides of such unsaturated fatty acids, and oligomers or polymers of unsaturated organic compounds, such as Polybutadiene, a.
• organic compounds include the following: Ethylene, propylene, 1-butene, ice and trans-2-butene, isobutylene, butadiene, pentenes, isoprene, 1-hexene, 3-hexene, 1-heptene, 1-octene, diisobutylene, 1-nonen, 1 -Decene, camphene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosen, di-, tri- or tetramers of propylene, styrene and other vinyl aromatic organic compounds with at least one CC double bond, diphenylethylene, polybutadiene, polyisoprene, cyclopentene, cyclohexene,
• Mixtures of two or more such compounds, in particular mixtures of the compounds exemplified above, can also be used.
• the present invention relates in particular to a process of the type in question, the organic compound having at least one CC double bond being selected from the group consisting of a linear or branched chain aliphatic, a linear or branched chain aromatic, a linear or branched chain cyclo aliphatic olefin, each with up to 30 carbon atoms and a mixture of two or more thereof.
• the method according to the invention is particularly suitable for implementation low molecular weight olefins, such as ethylene, propylene, and butenes, with propylene in particular being reacted.
• low molecular weight olefins such as ethylene, propylene, and butenes
• Microporous and / or mesoporous and / or macroporous solids which preferably comprise at least one element from the Villa or Ib group or at least one element from each of the Villa and Ib groups, are preferred as catalysts in step (II) of the process according to the invention those which have silver and / or gold, particularly preferably gold, are used.
• the above catalysts preferably contain Au and / or Ag in the range from about 0.01 to about 20% by weight, preferably from about 0.1 to about 5% by weight and in particular from about 0.3 to about 1% by weight. %.
• the catalysts used can additionally contain the elements Si, Al, Ti, Zr or mixtures thereof.
• the catalysts used additionally contain elements from groups Ia, Ila, lilac, rare earth elements from the series of lanthanides and actinides or mixtures thereof.
• they can also contain elements from groups IVa, Va, Via, Vlla, Ilb, Illb, IVb, Vb, VIb and Vllb.
• Zeolites containing transition metal as described in DE-A 197 23 950; Gold-containing catalysts with a support based on titanium dioxide, as described in EP-A 0 709 360; Gold-containing titanium ilicalite, preferably microporous or mesoporous titanium silicalite, of the structure TS-1, TS-2, Ti- ⁇ , Ti-ZSM-48 or Ti-MCM-41, as described in WO 98/00413; likewise gold-containing catalysts on a titanium-containing carrier material, which additionally contain a "promoter” metal which is selected from the I and II main groups of the Periodic Table of the Elements, and among the rare earth metals from the series of lanthanides and actinides; Carriers suitable for this catalyst include titanium dioxide, titanium silicalites, titanates of the "promoter” metals, titanium dispersed on SiO 2 and silicates of the "promoter”metals; such catalysts are described in WO 98/00414; Catalysts,
• catalysts which comprise a silicon dioxide which has mesopores or mesopores and micropores are the subject of EP-A-0 831 059, the context of which with respect to the catalysts described therein and their preparation is fully incorporated into the context of the present application.
• Silicon dioxide is the subject of application DE-A 198 47 630.2, which is filed in parallel with the present application, the content of which is fully described in the Context of the present application is included.
• EP-A 0 831 059 with regard to the starting compounds and production methods, but in the production of silicon dioxide which has mesopores and micropores, the production, ie the reaction of the starting materials, at a pH ⁇ 7 is carried out.
• the silicon dioxide thus obtained has at least one of the following properties (i) to (iii):
• the upper limit of the pore volumes of the micro and mesopores is 1.5 ml / g.
• the upper limit of the sum of the specific surfaces of the above-mentioned pores is 1000 m 2 / g.
• the maximum pore diameter distribution of the mesopores can be up to 50 nm.
• silicon dioxide with mesopore and micropores, the surface of which is at least 200 g / cm 2 or even at least 100 g / cm 2 , the upper limit preferably being less than 500 g / cm 2 .
• Micropores means pores with a diameter in the range from 2 to 50 nm
• micropores are those with pore diameters smaller than 2 nm.
• the pore diameters and specific surfaces of the mesopores are measured by nitrogen adsorption at 77 K.
• the pore surface can be can be calculated using the BJH model (DIN 66134).
• Catalysts with a zeolite structure as described in DE-A 196 23 611.8, which are also hereby fully incorporated into the context of the present application by reference with regard to the catalysts described therein, are particularly suitable for this purpose.
• the catalysts described therein are principally characterized in that they have been shaped by solidifying shaping processes, and in this regard, too, in principle all methods for a corresponding solidifying molding can be used, as are common in catalysts, such as, for example, extrusion.
• moldings with sufficient stability and containing the above-mentioned active components can be used as a fixed bed reaction.
• the shaped catalyst bodies can either be produced directly from the noble metal-containing catalyst powder, or the aforementioned noble metals are applied to the shaped body which contains the aforementioned activity-increasing elements after the shaping step.
• the noble metal-containing catalyst powders or the noble metal-free powders containing the abovementioned activity-increasing elements can either be applied to molded articles, introduced into them or shaped into them.
• the shaping of the noble metal-containing catalyst powder or the noble metal-free powder containing the abovementioned activity-increasing elements can be carried out by extrusion, extrusion, tableting or the like.
• the powders to be shaped are preferably processed into deformable masses with the aid of a pasting liquid and also optionally using one or more additives by means of a dilution step, such as kneading or milling.
• a dilution step such as kneading or milling.
• one or more additives which among other things have lubricating properties, can also be added to the powder to be shaped.
• inorganic or organic substances can be added to the powder to be deformed during the shaping. These substances can also increase the abrasion resistance if the powder is applied to already existing shaped bodies by a suitable process step, such as spraying, high-coating or the like.
• the powder to be shaped or applied can also be introduced into moldings.
• organic or inorganic substances can be polymerized in the presence of the powder in such a way that the resulting polymer solidly encloses the powder but is accessible to the reactants.
• the noble metal components are applied after the shaping, application or introduction of the powder.
• Methods of applying the noble metal component can be impregnation, impregnation, ion exchange, vapor deposition or the like.
• the noble metal components applied in this way can then, if they are not in active form, by subsequent treatment of the noble metal-containing molded body, e.g. Calcining, reducing, oxidizing or the like can be brought into an active form. Subsequent treatment may also be necessary for molded articles if powders containing precious metals are molded into molded articles.
• the catalysts produced by solidifying shaping processes according to DE-A 196 23 609.6 or DE 197 23 751.7 can be used.
• the corresponding applications cited above are incorporated by reference in their entirety in the context of the present application.
• the reaction in stage (II) within the catalyst according to the invention can be carried out in the gaseous, supercritical or liquid phase.
• the process is generally carried out at temperatures from 0 to 300 ° C, preferably about 40 to about 180 ° C, more preferably about 50 to about 150 ° C and particularly preferably about 60 to about 100 ° C. Temperatures below 100 ° C. are generally used for the implementation in the liquid phase.
• the pressures used in the reaction according to the invention are approximately 0.01 to approximately 1 MPa.
• the process according to the invention can be carried out continuously or batchwise.
• the catalyst can be brought into contact with the organic compound on the one hand and this compound can be brought into contact with the medium containing carbon monoxide and oxygen on the other hand, in a time or space separation.
• the catalyst in particular with a long operating time, when the selectivity and / or activity of the catalyst used has decreased during the reaction, the catalyst can also be regenerated. It is possible to flow the catalyst by treatment with a gas stream suitable for regeneration, in particular with an oxygen-containing gas, more preferably with an oxygen-containing gas stream, the oxygen being produced by decomposing nitrogen oxides at temperatures of 100.degree to regenerate up to 600 ° C. This catalyst can then be used again. The regeneration can also take place in the actual reactor. The composition of the gas flow used for the regeneration will be chosen so that the causes of the deactivation are eliminated. If coking is deactivated, the catalyst will be charged with a gas stream, the oxygen or contains oxygen-providing substances.
• the gas stream can contain reducing substances, such as hydrogen. Furthermore, it may be necessary to redisperse the noble metal component during the regeneration. Correspondingly, compounds will then be used which are suitable for dispersing the aforementioned noble metal components.
• a washing process with solvents such as water, alcohols, aldehydes, ketones etc. can also be carried out. Further details regarding such a regeneration can be found in DE-A 197 23 950 and DE-A 197 23 949.
• the regeneration processes described in EP-A 0 790 075 and EP-A 0 743 094 can also be used.
• the present invention also relates to an integrated process for the oxidation of an organic compound having at least one C-C double bond or a mixture of two or more thereof, which comprises the following steps (I) to (IV):
• step (IV) Carrying out the reaction in step (II) using a catalyst which contains the catalyst regenerated in step (III).
• the integrated method according to the invention can have the following stage (V): (V) separation of unused molecular oxygen or carbon monoxide or of unreacted organic compound or of unused molecular oxygen and carbon monoxide and unused starting material from the medium and recycling of the separated molecular oxygen, the separated carbon monoxide or the unreacted organic compound or a mixture of molecular oxygen, carbon monoxide and unreacted organic compound in step (II).
• the organic compound having at least one CC double bond is selected in the process according to the invention from the group consisting of a linear or branched chain aliphatic, a linear or branched chain aromatic and a linear or branched chain cycloaliphatic olefin, each having up to 30 C atoms, ie if an olefin is used for the reaction with the hydroperoxide, this can be obtained by dehydrogenation of the corresponding saturated organic compound to give the olefin and hydrogen.
• the alkane is split into the olefin, for example propane to propene, and hydrogen in an endothermic reaction.
• Zinc and aluminum spinels with precious metal doping, chromium oxide / aluminum oxide and platinum-supported catalysts are widely used as catalysts.
• chromium oxide / aluminum oxide and platinum-supported catalysts are widely used as catalysts.
• known from DE-A 39 23 026 promoted iron oxide catalysts for carrying out alkane dehydrogenations.
• the olefin preferably used as the starting product in particular propylene
• the olefin preferably used as the starting product can be obtained starting from the corresponding saturated hydrocarbon by steam cracking or catalytic cracking.
• These cracking processes can also be carried out in such a way that they not only provide propene, but also CO in addition to propene.
• Such methods are described in K. Weissermel, H.J. Arpe, Industrial Organic Chemistry, 2nd edition (1993), VCH Verlag Weinheim, pp. 17ff. , which is hereby fully incorporated by reference into the context of the present application.
• the olefin to be used in the epoxidation stage in particular propylene
• the epoxidation stage also contains that which is present in addition to the olefin tolerated unreacted alkane from the dehydrogenation stage and thus saves an expensive alkane / olefin, in particular propane / propene separation.
• the hydrogen originating from the alkane dehydrogenation can be used directly in the hydrogen peroxide formation, for example by the anthraquinone process or a process starting from the elements.
• the CO from the cracking process can also be used.
• the endothermic step of alkane dehydrogenation can be coupled with the exothermic reaction according to stage (II) in a heat and energy network.
• the method according to the invention is particularly suitable for implementation as an integrated method, i.e. as a multi-stage process in which the flows of the various components used during the process are partially or completely closed.
• the above integrated process is further preferably operated with a corresponding heat and energy coupling, in which the amounts of energy released in the exothermic process stages (II) and (III) are used directly to operate the endothermic stage (I).
• the resulting solid was coated with gold by dissolving 0.426 g of tetrachloroauric acid (from Chempur) in 1600 g of water, adjusting the pH to 7.2 with 0.1 mol / 1 sodium hydroxide solution and adding the freshly calcined titanium-containing powder. This suspension was stirred at 70 ° C. for 1 h, then cooled, decanted, filtered and the filter cake washed several times with water.
• tetrachloroauric acid from Chempur
• the resulting solid was dried in vacuo at room temperature and calcined at 400 ° C. in air within 12 hours.
• the pink violet powder contained 0.87 wt% gold, 25 ppm chlorine, 6.2 wt% titanium.
• a gas-phase tubular reactor (internal diameter 6 mm, length 200 mm) was filled with the catalyst from Example 1 (2 g split fraction 0.1 mm) and at a temperature of 60 ° C. with a mixture of 10 Nml / min propene, 20 Nml / min O 2 , 5 Nml / min CO and 10 Nml / min Ar applied.
• the gas stream was saturated with water at room temperature before entering the reactor. After a reaction time of 3 h, the following were found in a gas sample in the discharge: 200 ppm PO, 10 ppm acrolein, 6 ppm acetone and ⁇ 5 ppm propionaldehyde.
• Example 3 Use of CO from synthesis gas
• a gas-phase tubular reactor (internal diameter 6 mm, length 200 mm) was filled with the catalyst from Example 1 (2 g split fraction 0.1 mm) and at a temperature of 60 ° C. with a mixture of 10 Nml / min propene, 20 Nml / min O 2 , 5 Nml / min CO and 10 Nml / min Ar applied. After a reaction time of 3 h, the following were found in a gas sample in the discharge: 153 ppm PO, 5 ppm acrolein, 7 ppm acetone and ⁇ 5 ppm propionaldehyde.
• Example 3 The same catalyst and the same settings as from Example 3 were used, but only oxygen and no synthesis gas were metered in.

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• 1998
  • 1998-10-15 DE DE19847629A patent/DE19847629A1/de not_active Withdrawn
• 1999
  • 1999-10-14 CA CA002346888A patent/CA2346888A1/en not_active Abandoned
  • 1999-10-14 EP EP99970389A patent/EP1121350A1/de not_active Withdrawn
  • 1999-10-14 ID IDW20010852A patent/ID30480A/id unknown
  • 1999-10-14 KR KR1020017004742A patent/KR20010080171A/ko not_active Application Discontinuation
  • 1999-10-14 JP JP2000575851A patent/JP2002527428A/ja not_active Withdrawn
  • 1999-10-14 BR BR9914569-3A patent/BR9914569A/pt not_active Application Discontinuation
  • 1999-10-14 AU AU62027/99A patent/AU6202799A/en not_active Abandoned
  • 1999-10-14 CN CN99814541A patent/CN1330645A/zh active Pending
  • 1999-10-14 US US09/806,514 patent/US6348607B1/en not_active Expired - Fee Related
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