Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/20—Carbon compounds
  • C07C2527/22—Carbides
  • C07C2527/224—Silicon carbide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
• • 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
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
• • 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
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/40—Ethylene production

Definitions

• the present invention relates to a process for the conversion of a gas mixture containing CO and H to olefins using a first catalyst for the conversion of CO and H2 to dimethyl ether, the resulting gas mixture being converted to the olefin-containing product using a second catalyst for the conversion of dimethyl ether to olefins becomes. Furthermore, the present invention relates to a process for the preparation of olefins from carbon or hydrocarbon.
• Haldor-Tops0e-TIGAS process in which from a mixture of natural gas, water vapor and oxygen synthesis gas is first generated by reforming, which is then converted by catalytic reaction to methanol, which is finally in a methanol to gasoline method (MTG method for methanol to gasoline) is converted to gasoline-containing products (see, for example, FJ Keil, Microporous and Mesoporous Materials 1999, Volume 29, pages 49-66).
• the gas mixture (G0) provided in (1) in principle there is no restriction as to its composition, provided that it permits the conversion of at least some of the CO and H2 contained therein to dimethyl ether and CO2 in step (3).
• there is no restriction with regard to the ratio of CO to H2 in the gas mixture (G0) as long as the gas mixture (G0) permits the conversion of at least part of CO and H2 in the gas mixture to dimethyl ether and CO2 in step (3) of the process according to the invention.
• the gas mixture in which CO2 is present in the gas mixture (G0) in addition to CO and H2, the gas mixture preferably has a modulus according to formula (I) to H 2 [vol.%] - C0 2 [vol. -%]
• the gas mixture (G0) provided in step (1) contains CO2 in addition to CO and H2
• the CO.sub.2 content is in a range which, after bringing the gas mixture (G0) into contact with the catalyst (K1 ) to obtain a gas mixture (G1) in step (3), which has a CO 2 content in the range of 44 to 46 vol .-%.
• the catalyst (K1) contains one or more substances selected from the group consisting of copper oxide, aluminum oxide, zinc oxide, ternary oxides and mixtures of two or more thereof as the one or more catalytically active substances for conversion from synthesis gas to methanol.
• the ternary oxide is a spinel compound, wherein the spinel preferably contains Zn and / or Al, and wherein the spinel compound is more preferably a Zn-Al spinel.
• the one or more substances for the conversion of synthesis gas to methanol comprise a mixture of copper oxide, aluminum oxide and zinc oxide.
• mixtures according to the present invention being preferred in which copper oxide is contained in an amount of from 50 to 80% by weight, alumina in an amount from 2 to 8 weight percent and zinc oxide in an amount of from 15 to 35 weight percent based on the total weight of copper oxide, alumina and zinc oxide in the catalytically active material to convert synthesis gas to methanol. More preferably, the mixture contains copper oxide in an amount of 65 to 75% by weight, alumina in an amount of 3 to 6% by weight, and zinc oxide in an amount of 20 to 30% by weight.
• the one or more materials for the conversion of synthesis gas to methanol comprise a mixture of copper oxide, ternary oxide and zinc oxide.
• copper oxide is contained in an amount of from 50 to 80% by weight, the ternary oxide in an amount of 15 to 35% by weight and zinc oxide in an amount of 15 to 35% by weight, based on the total weight of copper oxide, ternary oxide and zinc oxide in the catalytically active material for conversion of synthesis gas to methanol.
• the mixture contains copper oxide in an amount of 65 to 75% by weight, the ternary oxide in an amount of 20 to 30% by weight, and zinc oxide in an amount of 20 to 30% by weight.
• the ternary oxide is a Spinel compound wherein the spinel preferably contains Zn and / or Al, and wherein the spinel compound is more preferably a Zn-Al spinel.
• the one or more catalytically active substances preferably present in the catalyst (K1) for the dehydration of methanol preferably contain one or more compounds selected from the group consisting of aluminum hydroxide, aluminum oxide hydroxide, gamma-alumina, aluminosilicates, Zeolites and mixtures of two or more thereof.
• the zeolites which may be preferably included in the one or more catalytically active substances for dehydrating methanol also include all zeolites suitable for the dehydration of methanol and mixtures thereof, these preferably comprising one or more zeolites selected from the group consisting of zeolite A, zeolite X, zeolite Y, zeolite L, mordenite, ZSM-5, ZSM-1 1, and mixtures of two or more thereof.
• the one or more catalytically active substances for dehydration contains one or more zeolites, the one or more zeolites preferably containing ZSM-5.
• the alumina hydroxide which is preferably contained in the one or more catalytically active substances for dehydration of methanol, it preferably comprises boehmite.
• the preferred catalyst (K1) comprises 70-90% by weight of the one or more catalytically active substances for the conversion of synthesis gas to methanol and 10-30% by weight of the one or more catalytically active substances for dehydrating methanol, and more preferably 75-85% by weight of the one or more catalysts.
• the preferred and particularly preferred particle sizes D90 these have a particle size D 5 o in the range of 40 to 300 ⁇ , more preferably from 40 to 270 ⁇ , and more preferably from 40 to 220 ⁇
• the preferred and particularly preferred particle sizes D90 and D 5 o one or more catalytically active substances to the conversion of synthesis gas to methanol and the one or more catalytically active substances to the dehydration of methanol independently have a particle size D10 in the range of 5 to 140 ⁇ , more preferably from 5 to 80 ⁇ , and more preferably from 5 to 50 ⁇ .
• the particle size may be determined according to any suitable analysis method known to those skilled in the art.
• the use of the measuring devices Mastersizer 2000 or 3000 by Malvern Instruments GmbH should be mentioned.
• the particle size D10 corresponds to a diameter at which 10% by weight of the examined particles have a smaller diameter than this.
• the particle size D 5 o indicates a diameter at which 50% by weight of the examined particles have a smaller diameter than this
• the particle size D90 finally corresponds to the diameter at which 90% by weight of the Particles have a smaller diameter.
• the catalyst (K1) may contain one or more substances for increasing the activity and / or selectivity of the catalyst and in particular one or more promoters.
• the one or more catalytically active substances which are contained in this according to preferred embodiments of the catalyst for the dehydration of methanol, promoters may be present as one or more additional substances in the catalyst (K1) or as doping in one of the catalysts present in the catalyst (K1). be contained substances, wherein according to particularly preferred embodiments of the catalyst (K1) one or more of the catalytically active substances contained therein are doped with one or more promoters.
• the catalytically active substances in the catalyst (K1) which may be doped with one or more promoters, so that one or more or all of the catalytically active substances in the catalyst (K1) have a or more promoters can be doped.
• these may be one or more catalytically active substances for the conversion of synthesis gas to methanol and / or one or more catalytically active substances for the dehydration of methanol, wherein according to particularly preferred embodiments thereof, the one or more catalytically active Substances for the dehydration of methanol are doped with one or more promoters.
• one or more of the catalytically active substances for dehydration of methanol are doped with one or more promoters
• the one or more catalytically active substances for the conversion of synthesis gas to methanol are preferably selected from the group consisting of copper oxide, alumina, zinc oxide, ternary oxides and mixtures of two or more thereof.
• the one or more catalytically active substances for dehydration of methanol are selected from the group consisting aluminum hydroxide, alumina hydroxide, gamma alumina, aluminosilicates, zeolites and mixtures of two or more thereof, wherein aluminum hydroxide and / or alumina hydroxide and / or gamma alumina are preferably doped with niobium, tantalum, phosphorus and / or boron, more preferably with niobium and / or tantalum and / or boron.
• providing the gas mixture (GO) according to (1) comprises recovering the gas mixture from a carbon source selected from the group consisting of oil, coal, natural gas, cellulosic materials and / or waste, landfill waste Agricultural waste and mixtures of two or more thereof and more preferably from the group consisting of oil, coal, natural gas and mixtures of two or more thereof.
• the provision of the gas mixture (GO) according to (1) comprises the recovery of the gas mixture from coal and / or natural gas.
• step (3) the gas mixture (GO) is contacted with the catalyst (K1) to obtain a gas mixture (G1) containing dimethyl ether and CO 2.
• a gas mixture containing dimethyl ether and CO 2 (G1) can be obtained thereby.
• the contacting according to (3) preferably takes place at a temperature in the range of 150 to 400 ° C.
• the contacting according to (3) is more preferably carried out at a temperature in the range from 200 to 350.degree.
• the contacting according to (3) is preferably carried out at a pressure which is higher than the normal pressure of 1. 03 kPa.
• the contacting according to (3) can take place, for example, at a pressure in the range from 2 to 150 bar, the contacting preferably taking place at a pressure in the range from 5 to 120 bar, more preferably from 10 to 90 bar, more preferably from 30 to 70 bar, more preferably from 40 to 60 bar, more preferably from 45 to 55 bar and more preferably from 47 to 53 bar.
• the contacting according to (3) takes place at a pressure in the range from 49 to 51 bar.
• embodiments of the inventive method are preferred in which the contacting according to (3) takes place at a pressure in the range of 2 to 150 bar.
• the one or more zeolites which are preferably present in the catalyst (K2)
• the conversion of at least a portion of the dimethyl ether to at least one olefin can be carried out, preferably zeolites of MFI, MEL and / or of the MWW structure type are included therein.
• the catalyst (K2) contains one or more zeolites of the MFI, MEL and / or MWW structure type.
• zeolites which are preferably present in the catalyst (K2), are of the MWW structure type, then again there is no restriction as to the type and / or number of MWW zeolites which can be used according to the present invention.
• the zeolites of the MEL structure type which are preferably present in the catalyst (K2) according to the present invention, these being selected, for example, from the group consisting of ZSM-1 1, [Si-B-0] -MEL, boron-D (MFI / MEL solid solution), Boralite D, SSZ-46, Silicalite 2, TS-2, and mixtures of two or more thereof.
• those zeolites of the MEL structure type which are suitable for the conversion of dimethyl ether to olefins, in particular [Si-B-0] -MEL, are preferably used.
• zeolites of the MFI structure type are preferably contained in the catalyst (K2).
• the one or more MFI-type zeolites preferably contained in the catalyst (K2) are preferably selected from A group consisting of ZSM-5, ZBM-10, [As-Si-O] MFI, [Fe-Si-O] MFI, [Ga-Si-O] MFI, AMS-1 B, AZ-1, Boron-C, borate C, encilite, FZ-1, LZ-105, monoclinic H-ZSM-5, mutinaite, NU-4, NU-5, silicalite, TS-1, TSZ, TSZ-III, TZ-01, USC-4, USI-108, ZBH, ZKQ-1B, ZMQ-TB and mixtures of two or more thereof.
• the catalyst contains ZSM-5 and / or ZBM-10 as an MFI-type zeolite, more preferably ZSM-5 is used as a zeolite.
• ZSM-5 is used as a zeolite.
• the zeolitic material ZBM-10 and its preparation reference is made, for example, to EP 0 007 081 A1 and to EP 0 034 727 A2, the contents of which, in particular with regard to the preparation and characterization of the material, are included in the present invention.
• embodiments of the catalyst (K2) in which the one or more MFI-type zeolites are preferred are preferred.
• the catalyst (K2) is essentially free of or does not contain any substantial amounts of a specific material in cases where this specific material is present in an amount of 1% by weight or less in the catalyst to the total weight of the catalyst (K2) and preferably to 100% by weight of the total amount of the one or more MFI, MEL and / or MWW structural type zeolites which are preferably present in the catalyst (K2), preferably in one Amount of 0.5 wt% or less, more preferably 0.1 wt% or less, more preferably 0.05 wt% or less, further preferably 0.001 wt% or less preferably 0.0005 wt% or less, and more preferably 0.0001 wt% or less.
• a specific material within the meaning of the present invention particularly denotes a particular element or a particular combination of elements, a specific substance or a specific substance mixture, as well as combinations and / or mixtures of two or more thereof.
• the aluminophosphates (AIPO and APO) generally include all crystalline aluminophosphate phases.
• the aluminosilicophosphates generally include all crystalline aluminosilicophosphate phases and in particular the SAPO materials SAPO-1 1, SAPO-47, SAPO-40, SAPO-43, SAPO-5, SAPO-31, SAPO -34, SAPO-37, SAPO-35, SAPO-42, SAPO-56, SAPO-18, SAPO-41, SAPO-39, and CFSAPO-1A.
• the one or more zeolites contains one or more zeolites several alkaline earth metals.
• the kind and / or the amount of alkaline earth metals which are preferably contained in the one or more zeolites, nor on the way in which they are contained in the one or more zeolites Zeolites can be contained.
• the one or more zeolites may contain one or more alkaline earth metals, for example, selected from the group consisting of magnesium, calcium, strontium, barium and combinations of two or more thereof.
• the one or more alkaline earth metals are preferably selected from the group consisting of magnesium, calcium, strontium, and combinations of two or more thereof, and in particularly preferred embodiments of the catalyst of the present invention, the alkaline earth metal is magnesium.
• the catalyst contains no or no substantial amounts of calcium and / or strontium.
• the one or more MFI, MEL and / or MWW structural type zeolites contain one or more alkaline earth metals, the one or more alkaline earth metals preferably being selected from the group consisting of Group consisting of Mg, Ca, Sr, Ba and combinations of two or more thereof are selected, more preferably consisting of Mg, Ca, Sr and combinations of two or more thereof, wherein the alkaline earth metal is particularly preferably Mg.
• the one or more alkaline earth metals in the micropores of the one or more zeolites, they may be present as an independent compound such as salt and / or oxide and / or as a positive counterion to the zeolite framework.
• the one or more alkaline earth metals are at least partially in the pores and preferably in the micropores the one or more zeolites before, more preferably, the one or more alkaline earth metals are at least partially there as a counterion of the zeolite scaffold, as may arise, for example, in the preparation of the one or more zeolites in the presence of one or more alkaline earth metals and / or by carrying out an ion exchange with the one or more alkaline earth metals on the already prepared zeolite.
• the one or more alkaline earth metals be present in a total amount in the range of 0.5-15% by weight based on 100% by weight of the total amount of the one or more zeolites from 1 to 10% by weight, more preferably from 2 to 7% by weight, more preferably from 3 to 5% by weight, and even more preferably from 3.5 to 4.5% by weight.
• the one or more alkaline earth metals are present in a total amount in the range of 3.8-4.2 wt% in the one or more zeolites. In all of the above-mentioned weight percentages of alkaline earth metal in the one or more zeolites, these are calculated as starting from the one or more alkaline earth metals as metal.
• the catalyst (K2) for the conversion of dimethyl ether to olefins wherein the one or more preferred zeolites of the MFI, MEL and / or MWW structural type contain the one or more alkaline earth metals in one Total contained in the range of 0.1 to 20 wt .-%, each based on the total amount of the one or more zeolites of the MFI, MEL and / or the MWW structure type and calculated as metal.
• the catalyst (K2) further contains particles of one or more metal oxides.
• the type of metal oxides which can be used preferably in the catalyst (K2) nor on the number of different metal oxides which may optionally be contained therein.
• surface information refers to a Materials preferably on their BET (Brunauer-Emmet-Teller) surface, which are preferably determined according to DIN 66131 by nitrogen absorption at 77 K.
• metal oxides which may preferably be present in the catalyst (K2)
• metal oxides which may preferably be present in the catalyst (K2)
• any suitable metal oxide compound as well as mixtures of two or more metal oxide compounds can be used.
• metal oxides which are temperature-stable in processes for the conversion of dimethyl ether to olefins the metal oxides preferably serving as binders.
• the particles of the one or more metal oxides which according to the particular and preferred embodiment as described in the present application contained in the catalyst (K2) include phosphorus.
• the phosphorus is contained in the particles of the one or more metal oxides, there is no particular restriction according to the present invention, provided that at least part of the phosphor is in oxidic form.
• phosphorus is present in oxidic form, provided that it is in combination with oxygen, ie if at least part of the phosphor is at least partially present in a compound with oxygen, in which case in particular a part of the phosphorus is covalently bonded to the oxygen.
• the phosphorus which is at least partially in oxidic form contains oxides of the phosphorus and / or oxide derivatives of the phosphorus.
• oxides of the phosphor of the present invention in particular, phosphorus trioxide, diphosphorus tetraoxide, phosphorus pentoxide, and mixtures of two or more thereof are included.
• the phosphorus and in particular the phosphorus in oxidic form is present at least partially in an amorphous form, wherein the phosphorus and in particular the phosphorus in oxidic form is more preferably substantially in amorphous form.
• the phosphorus may in principle be applied to the one or more metal oxides as element and / or as one or more independent compounds and / or incorporated in the one or more metal oxides, for example in form a doping of the one or more metal oxides, this in particular comprises embodiments in which the phosphorus and the one or more metal oxides at least partially form mixed oxides and / or solid solutions.
• the phosphor is preferably applied partially in the form of one or more oxides and / or oxide derivatives to the one or more metal oxides in the particles, wherein the one or more oxides and / or oxide derivatives of the phosphorus more preferably from a treatment of the one or the plurality of metal oxides with one or more acids of the phosphorus and / or with one or more of their salts.
• the one or more acids of the phosphorus preferably denotes one or more acids selected from the group consisting of phosphinic acid, phosphonic acid, phosphoric acid, peroxophosphoric acid, hypodiphosphonic acid, diphosphonic acid, hypodiphosphoric acid, diphosphoric acid, peroxodiphosphoric acid and mixtures of two or more thereof.
• the one or more phosphoric acids are selected from the group consisting of phosphonic acid, phosphoric acid, diphosphonic acid, diphosphoric acid and mixtures of two or more thereof, more preferably from the group consisting of phosphoric acid, diphosphoric acid and mixtures thereof, wherein according to particularly preferred embodiments present invention, the phosphorus preferably contained in the one or more metal oxides at least partially derived from a treatment of the one or more metal oxides with phosphoric acid and / or with one or more phosphate salts.
• the one or more MFI, MEL and / or MWW structural type zeolites which are preferably contained in the catalyst (K2) also contain phosphorus.
• the phosphorus can be contained in the one or more zeolites, it is the object of the present invention that This is preferably contained in the pores of the zeolite framework and in particular in its micropores, either as a stand-alone phosphorus-containing compound and / or as a counterion to the zeolite framework, wherein the phosphor is particularly preferably present at least partially as an independent compound in the pores of the zeolite framework.
• the catalyst (K2) for the conversion of dimethyl ether to olefins in which the one or more zeolites of the MFI, MEL and / or MWW structure type are preferably present in the catalyst (K2) Phosphorus, wherein the phosphorus is present at least partially in oxidic form.
• the weight ratio of zeolite to metal oxide in the catalyst according to the particular and preferred embodiments of the present invention may range from 10:90 to 95: 5.
• the weight ratio zeolite: metal oxide is preferably in the range from 20:80 to 90:10, more preferably in the range from 40:60 to 80:20 and more preferably in the range from 50:50 to 70:30.
• the weight ratio of zeolite: metal oxide is in the range of 55:45 to 65:45.
• the weight ratio zeolite: metal oxide particularly denotes the weight ratio of the total weight of the one or all of the several zeolites to the total weight of the particles of one or all of the plurality of metal oxides.
• the total amount of phosphorus in the catalyst (K2) according to the present invention may be, for example, in the range of 0.1 to 20% by weight, the total amount of phosphorus being the sum of the total weight of zeolites of MFI, MEL and and / or the MWW structure type and the total weight of the particles of the one or more metal oxides, wherein the phosphorus is calculated as an element.
• embodiments of the catalyst (K2) are preferably used in which the total amount of phosphorus, based on the sum of the total weight of zeolites MFI, MEL and / or MWW structure type and the total weight of the particles of the one or more metal oxides and calculated as element, in the range of 0.1 to 20 wt .-%.
• the catalyst (K2) contains one or more zeolites of the MFI, MEL and / or MWW structure type and particles of one or more metal oxides, the one or more zeolites being preferred of the MFI structure type.
• the one or more MFI, MEL and / or MWW structural type zeolites contain one or more alkaline earth metals, preferably Mg, are furthermore preferred.
• the one or more zeolites the plurality of MFI, MEL and / or MWW-type zeolites contain phosphorus and / or the particles of the one or more metal oxides contain phosphorus, each of the phosphors being at least partially in oxidic form.
• the catalyst (K2) is used in the process according to the invention, there are likewise no restrictions, so that according to the particularly preferred embodiments of the catalyst (K2) used the one or more zeolites and the particles of one or the In principle, a plurality of metal oxides contained therein may in principle be combined to form a catalyst in any possible and suitable manner.
• the catalyst (K2) in step (4) is provided in the form of a shaped body, wherein according to the particularly preferred embodiments of the catalyst used (K2) of the shaped body, a mixture of one or more zeolites of MFI, MEL and / or of the MWW structure type and the particle of the one or more metal oxides, preferably of the one or more zeolites and the particles of the one or more metal oxides according to one of the particular or preferred embodiments as described in the present application.
• the catalyst (K2) is provided in step (4) in the form of an extrudate.
• step (5) of the process according to the invention the dimethyl ether and optionally CO2-containing gas mixture (G1) are brought into contact with the catalyst (K2) to obtain an olefin-containing gas mixture (G2).
• the content of dimethyl ether and optional CO2 which are contained in the gas mixture (G1) in principle there is no restriction, provided that a portion of the dimethyl ether in step (5) converted to at least one olefin can be.
• the gas mixture (G1) may have, for example, a CO 2 content in the range of 20 to 70% by volume based on the total volume of the gas mixture.
• the gas mixture (G1) preferably has a CO2 content which is in the range from 25 to 65% by volume, based on the total volume of the gas mixture, and more preferably from 30 to 60% by volume, more preferably from 35 to 55% by volume, more preferably from 40 to 50% by volume and more preferably from 42 to 48% by volume.
• the gas mixture (G1) has a CO 2 content in the range from 44 to 46% by volume, based on the total volume of the gas mixture.
• the gas mixture (G1) which is brought into contact with (K2) according to (5) a CO 2 content in the range of 20 to 70 vol .-% based on the total volume of the gas mixture having.
• the composition of the gas mixture (G1) according to the specific and preferred embodiments defined herein relates either to the composition of the gas mixture obtained in step (3) after contacting with the catalyst (K1) or to the composition of the present invention Gas mixture (G1) which is brought into contact with the catalyst (K2) according to (5) or also to the composition of the gas mixture (G1) between the steps (3) and (5).
• the term "separation" according to the present invention in particular the targeted removal of a particular component, so that, for example, an inevitable loss of CO2 and / or dimethyl ether in a possible in principle targeted removal of H2O, CO and / or H2 between the steps ( 3) and (5) is preferably not considered as a separation of CO2 and / or dimethyl ether in the context of the present invention.
• no components are separated off from the gas mixture (G1) between steps (3) and (5) and / or no further gas streams are fed, more preferably neither components nor further components being separated from the gas mixture (G1) Gas flows is supplied, so that the composition of the gas mixture (G1) immediately after contacting in step (3) is equal to the composition of the same gas mixture (G1) immediately before contacting the same with the catalyst (K2) in step (5).
• embodiments of the inventive method are preferred in which between the steps (3) and (5) no CO2 from the gas mixture (G1) is separated.
• Embodiments of the method according to the invention are particularly preferred in which neither components are separated off from the gas mixture (G1) between steps (3) and (5) nor further gas streams are supplied.
• the gas mixture (G1) may contain a content of dimethyl ether, which is for example in the range of 20 to 70 vol .-% based on the total volume of the gas mixture.
• embodiments of the method for converting a gas mixture containing CO and H2 to olefins in which the content of dimethyl ether in the gas mixture (G1) is in the range of 25 to 65% by volume, and more preferably 30 to 60% by volume, are preferred %, more preferably from 35 to 55% by volume, more preferably from 40 to 50% by volume, and further preferably from 42 to 48% by volume.
• the gas mixture (G1) has a content of dimethyl ether which is in the range from 44 to 46% by volume, based on the total volume of the gas mixture.
• the gas mixture (G1) has a molar ratio of CO2 to dimethyl ether which is in the range from 10:90 to 90 : 10 is.
• molar ratios of CO2 to dimethyl ether in the gas mixture (G1) are preferred which are in the range from 30:70 to 70:30 and more preferably from 40:60 to 60:40, more preferably from 45:55 to 55:45, more preferably from 48:52 to 52:48 and more preferably from 49:51 to 51:49.
• the gas mixture (G1) when contacted according to step (5) and in particular those substances which were present in the gas mixture (G0), and in particular CO and / or H2, which in step (2 ) were not completely converted to dimethyl ether and CO2, as well as substances, which in addition to dimethyl ether and CO2 on contacting the gas mixture (G0) with the catalyst (K1) in step (3) are formed.
• the gas mixture (G1) when contacting according to step (5) in addition to dimethyl ether and optional CO2 also contain H2.
• the gas mixture (G1) has an H2 content
• there is no restriction with regard to the amounts in which H2 can be contained provided that it brings the gas mixture (G1) into contact with the catalyst (K2 ) in step (5) to convert at least a portion of the dimethyl ether to at least one olefin.
• the gas mixture (G1) an h content of, for example, up to 35 vol .-% based on the total volume of the gas mixture.
• the gas mixture (G1) preferably has an h content which is in the range from 0.1 to 30% by volume, based on the total volume of the gas mixture, more preferably the gas mixture (G1) h content of from 0.5 to 25% by volume, more preferably from 1 to 22% by volume, more preferably from 2 to 20% by volume, still more preferably from 3 to 18% by volume preferably from 4 to 15% by volume and more preferably from 4.5 to 12% by volume.
• the gas mixture (G1) has a molar ratio of H to dimethyl ether ranging from 0 to 64:36 lies. Furthermore, preference is given to molar ratios of H to dimethyl ether in the gas mixture (G1) which are in the range from 0.2: 99.8 to 55:45 and more preferably from 1:99 to 45:55, more preferably from 4: 96 to 36:64, more preferably from 7:93 to 27:73 and more preferably from 9:91 to 22:78. According to particularly preferred embodiments of the process according to the invention, the gas mixture (G1) has a molar ratio of Hb to dimethyl ether, which is in the range of 10:90 to 19:81.
• gas mixture (G1) in addition to CO 2 and dimethyl ether and optionally CO and / or Hb, further substances may also be present in the gas mixture (G1) which, in addition to substances which were in the gas mixture (G 0), are also used as intermediates in step (2). and / or by-product have formed and in the case of the intermediates were not completely converted to dimethyl ether and CO2, in which case in particular methanol is mentioned.
• the gas mixture (G1) in addition to dimethyl ether and CO2 and optionally CO and / or Hb also contain methanol.
• the gas mixture (G1) can contain a methanol content of, for example, up to 20% by volume, based on the total volume of the gas mixture.
• the gas mixture (G1) preferably has a methanol content which is in the range from 0.1 to 15% by volume, based on the total volume of the gas mixture, more preferably the gas mixture (G1) has a methanol content of 0, 5 to 14% by volume, more preferably 1 to 13% by volume, more preferably 1 to 5 to 12% by volume, further preferably 2 to 1 1% by volume, further preferably 3 to 10% by volume, more preferably from 4 to 9% by volume.
• the gas mixture (G1) has a methanol content in the range from 5 to 8% by volume, based on the total volume of the gas mixture.
• the gas mixture (G1) which is brought into contact with (K2) according to (5) has a content of methanol in the Range of 0 to 20 vol .-% based on the total volume of the gas mixture.
• embodiments of the process for the conversion of a gas mixture containing CO or H to olefins are preferred in which in (5) the molar ratio of methanol: dimethyl ether of the gas mixture (G1), which according to (5) with (K2) is in the range of 0.1: 99.9 to 50: 50.
• the substances which, in addition to CO2 and dimethyl ether and optionally CO and / or H2 and / or methanol, may be present in the gas mixture (G1) these may also comprise H2O, these substances already being present in the gas mixture (G0) and / or when the gas mixture (G0) is brought into contact with the catalyst (K1) in step (3) as by-product and / or intermediate due to incomplete conversion of the gas mixture (G0) to dimethyl ether and CO2.
• the gas mixture (G1) when contacting according to step (5) in addition to dimethyl ether and optional CO2 also contain H2O.
• the gas mixture (G1) has an h O content
• the gas mixture (G1) has an h O content in the range from 5 to 8% by volume, based on the total volume of the gas mixture.
• the gas mixture (G1) contacted with (K2) according to (5) has an h O content range of 0 to 20 vol .-% based on the total volume of the gas mixture.
• the gas mixture (G1) has a molar ratio of H 2 O to dimethyl ether of 10:90 to 15: 85 on.
• embodiments of the process for the conversion of a gas mixture containing CO and H2 to olefins are preferred in which in (5) the molar ratio H2O: dimethyl ether of the gas mixture (G1), according to (5) with (K2) in contact is in the range of 0 to 22: 78.
• step (5) the gas mixture (G1) is contacted with the catalyst (K2) to obtain an olefin-containing gas mixture (G2).
• the contacting according to (5) preferably takes place at a temperature in the range of 150 to 800 ° C.
• the contacting according to (5) is carried out at a temperature in the range from 200 to 750 ° C, more preferably from 250 to 700 ° C, more preferably from 300 to 650 ° C, further preferably from 350 to 600 ° C, more preferably from 400 to 580 ° C and more preferably from 430 to 560 ° C.
• the contacting according to (5) takes place at a temperature in the range of 450 to 500 ° C.
• embodiments of the process for converting a gas mixture containing CO and H2 to olefins in which the contacting according to (5) is carried out at a temperature in the range of 150 to 800 ° C are preferred.
• the contacting according to (5) can take place, for example, at a pressure in the range from 0.1 to 20 bar, the contacting preferably taking place at a pressure in the range from 0.3 to 10 bar, more preferably from 0, 5 to 5 bar, more preferably from 0.7 to 3 bar, more preferably from 0.8 to 2.5 bar and more preferably from 0.9 to 2.2 bar.
• the contacting according to (5) takes place at a pressure in the range from 1 to 2 bar.
• embodiments of the process for converting a gas mixture containing CO and H into olefins are preferred in which the contacting according to (5) takes place at a pressure in the range from 0.1 to 20 bar.
• space velocities for contacting the gas mixture (G0) with the catalyst (K1) in step (3) are selected in the range from 2,350 to 2,450 hr.sup.- 1 .
• embodiments of the process for converting a gas mixture containing CO and H to olefins in which the space velocity of contacting in (3) is in the range of 50 to 50,000 hr 1 are preferred.
• the term "space velocity" refers to the loading of the catalyst calculated as grams of dimethyl ether per gram of catalyst per hour relating the contacting of the gas mixture (G1) with the catalyst (K2) in step (5) or the loading of the catalyst in grams of methanol per gram of catalyst per hour for contacting the gas mixture (G0) with the catalyst (K1) in step (3).
• a method for converting a gas mixture containing CO and H2 to olefins comprising
• the process of embodiment 25 wherein the one or more catalytically active species for converting synthesis gas to methanol are selected from the group consisting of copper oxide, alumina, zinc oxide, ternary oxides, and mixtures of two or more thereof.
• the process of embodiment 25 or 26 wherein the one or more catalytically active substances for dehydrating methanol are selected from the group consisting of aluminum hydroxide, aluminum oxide hydroxide, gamma-alumina, aluminosilicates, zeolites, and mixtures of two or more thereof.
• catalyst (K2) contains one or more zeolites of the MFI, MEL and / or MWW structure type and particles of one or more metal oxides, the one or more zeolites preferably being derived from the MFI Are structure type.
• Phosphorus is present at least partially in oxidic form.
• first synthesis step (21) and second synthesis step (23) are carried out at substantially equal pressures.
• the pressure at the outlet of the first synthesis step (21) differs from the pressure at the inlet of the second synthesis step (23) by less than 3 bar, preferably by less than 1 bar.
• Separation step (24) separated carbon dioxide is used to produce synthesis gas (21).
• Method according to one of the embodiments 33 to 40 characterized in that in a second separation step (26) from the third product (15) a predominantly hydrogen, carbon monoxide and methane-containing residual gas (18) is separated.
• the present invention also encompasses a process comprising a first synthesis step wherein carbon or hydrocarbon is converted to a first product (synthesis gas) comprising hydrogen and carbon monoxide, a second synthesis step wherein hydrogen and carbon monoxide convert to a second product comprising dimethyl ether and carbon dioxide and comprising a third step of synthesizing dimethyl ether to a third product comprising olefins (especially ethylene and propylene).
• the second product (DME) will be fed to the third synthesis step (olefin production) without further treatment, except for the optional separation of carbon dioxide from the second product.
• Synthesis gas can be produced in the first synthesis step by coal gasification from carbon and water or oxygen.
• synthesis gas can be produced by autothermal reforming, steam reforming, or partial oxidation of hydrocarbons.
• Synthesis gas is preferably produced in the first synthesis step from methane, more preferably by steam reforming, partial oxidation or dry reforming.
• the second step of the synthesis in the context of the invention means the direct dimethyl ether synthesis in which dimethyl ether is formed directly from hydrogen and carbon monoxide.
• the third synthesis step, the olefin synthesis can be carried out in the presence of suitable catalysts, such as, for example, zeolite or silicon-aluminum-phosphate catalysts.
• suitable catalysts such as, for example, zeolite or silicon-aluminum-phosphate catalysts.
• the first synthesis step and the second synthesis step are carried out at substantially equal pressures, preferably at equal pressures.
• Essentially equal pressures in the understanding of the invention are pressures which differ from one another by no more than 1 bar, preferably 0.5 bar, more preferably still 0.4 bar, 0.3 bar, 0.2 bar and most preferably not more than 0.1 bar.
• equal pressure is understood to mean that the pressure between the two synthesis steps no longer deviates from one another, as caused by the normal pressure loss of the components required therebetween.
• methane is reacted with water or oxygen to form hydrogen and carbon monoxide in the first step of the synthesis.
• Methane according to the invention also includes methane-containing gases such as natural gas.
• the first step of the synthesis is a dry reforming step wherein methane and carbon dioxide are converted to hydrogen and carbon monoxide. Dry reforming in the context of the invention is understood to mean the conversion of methane or natural gas and CO 2 under heat and in the absence of water into synthesis gas having a stoichiometric ratio of H 2 and CO of about 1: 1.
• the dry reforming according to the invention also includes the reaction of CH4 or natural gas and CO2 in the presence of water vapor, water being only in a stoichiometric ratio to methane or natural gas of 1: 2, 1: 3, 1: 4, 1: 5, 1 : 10 or 1:20 is present.
• dry reforming is used when the molar ratio of water to carbon in use is less than 2: 1, preferably less than 1: 1.
• the dry reforming and / or the direct dimethyl ether synthesis can be carried out in the presence of suitable catalysts, such as transition metal catalysts.
• suitable catalysts such as transition metal catalysts.
• Ni-based catalysts are advantageous, as they are also used in other processes of steam reforming.
• dimethyl ether synthesis advantageously copper-based catalysts are used, which are also common in other processes of methanol synthesis.
• the process is carried out at a pressure of 20 bar to 50 bar. Increasing the pressure can shift the equilibrium of the reaction to the product side and thus increase the yield of the reaction.
• carbon monoxide and hydrogen are converted to dimethyl ether and carbon dioxide until a time when dimethyl ether is present in a concentration of at least 60%, 70%, 80%, 90 or 100% of the equilibrium concentration of dimethyl ether ,
• the equilibrium concentration of dimethyl ether in the context of the invention means the dimethyl ether concentration which is present when the reaction of carbon monoxide and hydrogen to dimethyl ether and carbon dioxide is in chemical equilibrium.
• the chemical equilibrium of the reaction is reached when the rate of the forward reaction (3 H2 + 3 CO -> DME + C0 2 ) is equal to the rate of the reverse reaction (DME + C0 2 -> 3 H 2 + 3 CO).
• carbon dioxide is separated from the second product in a first separation step.
• Carbon dioxide can be removed from the second product by conventional separation techniques, for example distillation, e.g. B. by amine or Alkalicarbonatisseschen, washes with organic solvents such as Me- ethanol, N-methyl-2-pyrrolidone or polyethylene glycol dimethyl ether or using a membrane.
• the carbon dioxide separated off in the first separation step is used to produce synthesis gas, with carbon dioxide and methane being converted into hydrogen and carbon monoxide.
• a predominantly hydrogen, carbon monoxide and methane-containing residual gas is separated from the third product, a fourth product comprising olefins (in particular ethylene and propylene) being formed.
• the separated, predominantly hydrogen, carbon monoxide and methane-containing residual gas is supplied to the first synthesis step or the second synthesis step, wherein methane can be converted in the first synthesis step to synthesis gas and hydrogen and carbon monoxide in the second synthesis step to dimethyl ether and carbon dioxide.
• This recycling of the residual gas increases the yield of the process and reduces the amount of waste products.
• the predominantly hydrogen, carbon monoxide and methane-containing residual gas is used to provide thermal energy for synthesis gas production, in particular for steam reforming or dry reforming. Thermal energy can be generated by oxidation of the combustible constituents of the residual gas to water and carbon dioxide. A supply of thermal energy or heat to the endothermic reforming step may shift the chemical equilibrium of the reforming reaction to the product side (hydrogen and carbon monoxide).
• the heat generated in the second and / or third synthesis step is used to generate energy.
• the heat produced in the second synthesis step and / or the third synthesis step in the form of steam is used as drive for turbines, in particular in the second separation step.
• the use of the resulting heat increases the economy of the process.
• a basic idea of the present invention consists in particular in an entanglement of the three process steps synthesis gas production 21, direct DME synthesis 23 and olefin synthesis 25.
• synthesis gas 11 is produced from carbon or hydrocarbon, preferably from methane 21.
• the resulting synthesis gas 1 1 may have a stoichiometric ratio of hydrogen to carbon monoxide of greater than 1: 1 (eg 3: 1).
• the necessary for direct DME synthesis 23 The ratio of hydrogen to carbon monoxide of 1: 1 can be achieved by removing the excess hydrogen 22. If the synthesis gas 11 is produced by dry reforming 21, the removal of hydrogen 22 is eliminated.
• the synthesis gas 11, 12 may also contain unreacted starting materials of synthesis gas production 21, such as methane and carbon dioxide. Subsequently, the synthesis gas 1 1, 12 used in the direct DME synthesis 23.
• the product 13 of the DME synthesis 23 can optionally be freed of carbon dioxide still present 24, 14 or is fed directly to the olefin synthesis 25 without further treatment.
• the product of the olefin synthesis 15 can in turn optionally be freed of carbon dioxide 24 and is then subjected to a separation 26 of olefin 17 and predominantly hydrogen, carbon monoxide and methane-containing residual gas 18.
• the residual gas 18 can in turn be supplied to the synthesis gas production 21.
• Synthesis gas supply 21 and DME synthesis 23 are carried out at the same pressure level (in the range 30-50 bar) (-> no compressor required before DME stage 23),
• the DME direct synthesis is brought close to the chemical equilibrium in this pressure range (preferably at 25 bar to 35 bar),
• Product gas 13 from the direct DME synthesis 23 is fed without further treatment (at most C0 2 removal 24) into the DMTO ⁇ dimethyl ether-to-olefin) stage 25,
• waste heat from the DME-23 and the DMTO stage 25 is combined and used for turbines (preferably in the DMTO separation sequence 26),
• the residual gas 18 from the DMTO stage 25 (H2 / CO / CH4) is recycled materially or energetically to synthesis gas production 21,
• the CO2 formed in DME step 23 is additionally recycled in the dry reforming 21.
• FIGURES shows a block diagram of a method according to the invention, wherein the reference numeral
• An aqueous solution of sodium bicarbonate (20%) was prepared with sodium bicarbonate dissolved in 44 kg of distilled water. Furthermore, a Zn / Al solution was prepared consisting of 6.88 kg of zinc nitrate and 5.67 kg of aluminum nitrate and 23.04 kg of water. Both solutions were heated to 70 ° C. A container filled with 12.1 L of distilled water was also heated to 70 ° C. The prepared solutions were added concurrently with the water introduced, the addition being made so as to maintain a pH of 7 during the addition until the Zn / Al solution was completely added. Subsequently, the resulting mixture was stirred at a pH of 7 for 15 hours.
• the resulting suspension was filtered off and washed with distilled water until the wash water had a sodium oxide content of ⁇ 0.10% and was substantially free of nitrates.
• the filter cake was dried for 24 h at 120 ° C and then calcined for 1 h at 350 ° C under a stream of air.
• An aqueous sodium bicarbonate solution (20%) was prepared, dissolving 25 kg of sodium bicarbonate in 100 kg of distilled water.
• the resulting mixture was then stirred for 10 h, the pH optionally being kept at a pH of 6.7 by addition of the 65% salicylic acid.
• the resulting suspension was then filtered off and washed with distilled water until the wash water had a sodium oxide content ⁇ 0.10% and was substantially free of nitrate.
• the filter cake was dried for 72 h at 120 ° C and then calcined for 3 h under air flow at 300 ° C.
• the resulting catalyst consisted of 70 wt% CuO, 5.5 wt% Al 2 O 3, and 24.5 wt% ZnO.
• Table 1 The results of the experiments are shown in Table 1.
• Table 1 all gas streams were analyzed by on-line gas chromatography. Argon gas was used as an internal standard to correlate incoming and outgoing gas flows.
• the different mixtures of the split fractions (corresponding D10, D 5 o- and Dgo values for ME30 and ZSM5-100H are shown in Table 2) show different CO conversions.
• ⁇ 6 '"residue are compounds formed by the reaction of hydrogen and CO in the reactor except methanol, dimethyl ether or CO2.
• Table 2 Dio, D 50 and Dgo values of the split fractions of Me30 and ZSM5-100H.
• the diluted phosphoric acid solution was then introduced into a dropping funnel and slowly sprayed onto the powder (rotating) via a glass spray nozzle (flooded with 100 l / h N 2).
• the powder was then dried for 8 hours at 80 ° C. in a vacuum drying oven, calcined at 500 ° C. for 4 hours (4 hours heating time) under air, ground to a small size using an analytical mill and sieved through a 1 mm sieve. Elemental analysis of the product showed a phosphorus content of 3.2-3.3 g / 100g).
• the P-ZSM-5 powder thus prepared was further processed into strands with Pural SB (Sasol) as binder so that the zeolite / binder ratio in the calcined product is 60:40.
• Pural SB Pural SB
• 380 g of P-ZSM-5 and 329 g of Pural SB were weighed, mixed, acidified with formic acid, added to Wa- locel and processed with 350 ml of water to a homogeneous mass.
• the dough was pressed by means of an extruder through a 2.5 mm die with about 1 10-1 15 bar.
• these strands were dried for 16 h at 120 ° C in a drying oven, calcined 4 hours at 500 ° C (4 h heating) in a muffle furnace under air and on a screening machine with 2 steel balls (diameter about 2 cm, 258 g / ball) 1, 6-2 mm chips processed.
• the split produced in this way is impregnated with phosphorus in a further step.
• the water absorbency of the exudate was determined (3 ml H2O / 5 g extrudate). Accordingly, a solution of 74 g of 85% phosphoric acid with dist. Water to 292 ml of total fluid filled. The amount of phosphoric acid was calculated so that after calcination 4 wt .-% phosphorus are on the extrudate. 486 g of chippings were placed in a spray drenching drum. The diluted phosphoric acid was slowly sprayed onto the grit (rotating) via a glass spray nozzle (flooded with 100 l / h air).
• the diluted magnesium nitrate solution was then introduced into a dropping funnel and slowly sprayed onto the powder (rotating) via a glass spray nozzle (flooded with 100 l / h N 2). In between, the piston is suspended and shaken the piston by hand to achieve an even distribution. Afterwards approx. 10 min. Post-rotation time, the powder was dried for 16 h at 120 ° C in Quarzfitkugelkolben, calcined for 4 h at 500 ° C (4 h heating) under 20 L / h of air, ground small with the aid of an analytical mill and sieved through a 1 mm sieve. The elemental analysis of the product showed a magnesium content of 3.7 g / 100 g.
• the Mg-ZSM-5 powder thus prepared was further processed into strands with Pural SB as a binder so that the zeolite / binder ratio in the calcined product is again 60:40.
• Pural SB Pural SB
• 58.7 g of zeolite and 50.7 g of Pural SB were weighed, mixed, acidified with formic acid and processed to a homogeneous mass with 38 ml of water.
• the clay was pressed by means of an extruder through a 2.5 mm die at about 1 10 bar.
• these strands were dried for 16 h at 120 ° C in a drying oven, calcined 4 hours at 500 ° C (4 h heating) in a muffle furnace and on a screening machine with 2 steel balls (diameter about 2 cm, 258 g / ball) to 1, 6-2 mm chips processed.
• the BET surface area of the resulting grit was 291 m 2 / g.
• Reference Example 9 Process for converting a gas stream containing dimethyl ether and CO2 to olefins
• the catalysts prepared in Reference Examples 7 and 8 (2 g each) were mixed with silicon carbide (23 g each) and installed in a continuously operated, electrically heated tubular reactor.
• the dimethyl ether / CO 2 feed was reacted with nitrogen in the ratio (% by volume) Dimethyl ether: CO2: N2 of 35: 35: 30 mixed and fed directly into the reactor.
• the gas stream at a temperature of 450 to 500 ° C, a load of 2.2 g of carbon per gram of catalyst and hour (2.2 g C x gKataiysator "1 x Ir 1 ) based on dimethyl ether and in a ( absolute pressure) of 1 to 2 bar, with the reaction parameters being maintained throughout the run.
• the gaseous product mixture was analyzed on-line chromatographically.

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