Method for production of ethyleneamines

Abstract

To provide a heterogeneous catalyst for the amination of monoethylene glycol and / or monoethanolamine in the liquid phase, which exhibits sufficient activity and selectivity in the conversion of monoethylene glycol to monoethanolamine and / or ethylenediamine.SOLUTION: The present invention provides a method for preparing alkanolamines and ethyleneamines in the liquid phase by reacting ethylene glycol and / or monoethanolamine with ammonia in the presence of an amination catalyst obtained by reducing a catalyst precursor, wherein the preparation of the catalyst precursor comprises: step a) in which the catalyst precursor comprises one or more catalytically active components selected from Sn, Cu, and Ni; and step b) in which the catalyst precursor prepared in step a) is contacted with a soluble Re compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for preparing alkanolamines and ethylenediamines, especially ethylenediamine.

Background Art

[0002] For the industrial-scale preparation of ethylenediamine (EDA), two methods are commonly used.

[0003] First, EDA can be prepared by reacting 1,2-dichloroethane with ammonia to eliminate HCl (EDC method). A further industrial-scale method for preparing EDA is the reaction of monoethanolamine (MEA) with ammonia in the presence of an amination catalyst (MEA method).

[0004] As an alternative to the established methods, EDA can also be prepared by the reaction of monoethylene glycol (MEG) with ammonia.

[0005] Such a method can have various advantages. One of the advantages is the better availability of MEG compared to MEA.

[0006] MEA is prepared on an industrial scale by the reaction of ethylene oxide (EO) and ammonia. What is generally formed is a reaction mixture that includes, along with MEA, higher alkanolamines such as diethanolamine (DEOA) and triethanolamine (TEOA). These by-products must be separated from MEA by separate distillation steps. Ethylene oxide is a highly flammable gas that can form an explosive mixture with air. The handling of EO is accordingly complex. The preparation of MEA thus requires a technically complex EO plant that is purified by distillation downstream.

[0007] In contrast, MEG can be produced based on petrochemical raw materials or renewable raw materials. MEG is also prepared from EO by reaction with water by petrochemical means. Similar to the reaction of EO with ammonia, in the reaction of EO with water, it is impossible to prevent the already formed MEG from reacting with EO to produce by-products such as di- and triethylene glycol. However, the selectivity for MEG is about 90%, which is clearly higher than that for MEA, which is generally 70 - 80%. The Shell Omega process also clearly increased the selectivity for MEG to about 99%. In the Omega process, EO is reacted with CO2 to obtain ethylene carbonate, which is selectively hydrolyzed to MEG in a second step.

[0008] MEG can also be prepared via the syngas route, for example, by oxidatively carbonylating methanol to obtain dimethyl oxalate and subsequent hydrogenation thereof. Therefore, additional petrochemical raw materials considered for preparing MEG are also natural gas or coal.

[0009] Alternatively, MEG can be prepared from renewable raw materials such as corn or sugarcane by fermentation to ethanol, subsequent dehydration to ethene, and subsequent reaction with oxygen to obtain ethylene oxide.

[0010] Due to many manufacturing variations, the availability of MEG is generally high and generally has a positive effect on raw material costs.

[0011] The prior art discloses that reacting MEG with ammonia to obtain EDA can be carried out either in the liquid phase or in the gas phase.

[0012] The amination of MEG in the gas phase is disclosed in two Chinese patents CN102 190 588 and CN 102 233 272.

[0013] For example, CN 102 190 588 describes the one-step conversion of MEG and ammonia in the presence of a Cu catalyst. According to the description, the reaction pressure is within the range of 3 to 30 bar. The reaction temperature is in the range of 150 to 350 °C.

[0014] Patent CN102 233 272 discloses the reaction of MEG and ammonia in the gas phase on a catalyst containing Cu and Ni as main components and Zr, Zn, Al, Ti, Mn, and Ce as secondary components. However, the composition of the resulting reaction mixture was not disclosed.

[0015] As an alternative to conversion in the gas phase, the reaction of MEG with ammonia and hydrogen can also be carried out in the liquid phase. However, there are generally significant differences in the reaction characteristics of the catalyst in the gas phase and the liquid phase, and thus generally, it is not allowed to apply conclusions from the reaction characteristics of MEG in the gas phase to the reaction characteristics of MEG in the liquid phase.

[0016] An overview of the metal-catalyzed amination of MEG in the liquid phase is given in the Diplom thesis “Reaktionskinetische Untersuchungen zur metallkatalysierten Aminierung von Ethylenglykol in der fluessigen Phase” [Studies of Reaction Kinetics of the Metal-Catalyzed Amination of Ethylene Glycol in the Liquid Phase] by Carsten Wolfgang Ihmels (Carl von Ossietzky University of Oldenburg, Diplom thesis, dated March 17, 2000). Ihmels describes a number of further reactions and side reactions that can occur in the amination of MEG, such as the formation of di- and triethanolamine, disproportionation, nitrile formation, carbonyl condensation, and fragmentation reactions. In the case of dihydric alcohols, condensation and disproportionation can ultimately also cause the formation of oligomers such as diethylenetriamine (DETA), triethylenetetramine (TETA), and polymers. An important further side reaction is cyclization. For example, diethanolamine or DETA can be further reacted to obtain piperazine (PIP). High temperatures promote dehydrogenation following cyclization to give aromatics. Thus, the reaction of MEG with ammonia gives a wide range of product spectra, and some of the products in this product spectrum are of greater commercial interest than others. For example, the commercial demand for EDA, DETA, and TETA is higher than that for PIP or aminoethylethanolamine (AEEA). The aim of many studies in the reaction of MEG with ammonia is therefore to find catalysts and reaction conditions that give a favorable product spectrum.

[0017] Ihmels himself studied the conversion of MEG over supported cobalt / silicon dioxide catalysts. Amination to obtain the desired MEA and EDA target products was not successful. Instead, polymeric reaction products were formed. The conversion of MEG was still incomplete even under milder conditions, and the target products MEA and EDA were obtained in low yields. The main product was an oligomeric compound.

[0018] US4,111,840 discloses the reaction of MEG with ammonia and hydrogen over supported Ni / Re catalysts at pressures from 500 to 5000 psig (about 34 to 340 bar). A supported silica / alumina catalyst with a surface area of 60 m 2 / g led to better results here than a supported silica / alumina catalyst with a specific surface area of 150 m 2 / g.

[0019] US3,137,730 discloses the reaction of MEG with ammonia in the liquid phase over a Cu / Ni catalyst at a temperature of 200 - 300 °C and a pressure above 1000 psig (about 69 bar).

[0020] DE1 172 268 discloses the conversion of ethylene glycol over a catalyst containing at least one of the metals Cu, Ag, Mn, Fe, Ni, and Co. In one example, MEG was reacted with ammonia over a Co catalyst at 180 °C and a pressure of 300 bar in the presence of hydrogen.

[0021] WO2007 / 093514 discloses a two - step preparation method of EDA, where in the first step of the method, amination is carried out over a hydroamination catalyst up to an MEA conversion rate of 40% or less, and in the second step of the method, a supported Ru / Co catalyst compact with a small shape is used, and the second step is carried out at a temperature at least 10 °C higher than the first step of the method.

[0022] Catalysts for the amination of alcohols containing Sn are also disclosed in WO2011067200. The catalysts described therein contain not only Sn, but also the elements Co, Ni, Al and Cu.

[0023] Further catalysts for the amination of alcohols are disclosed in WO200908051, WO2009080508, WO200006749 and WO20008006750. The catalysts contain not only Zr and Ni, but also Cu, Sn, Co and / or Fe. Further components are the elements for example V, Nb, S, O, La, B, W, Pb, Sb, Bi and In.

[0024] WO2013072289 discloses the reaction of alcohols and nitrogen compounds on a catalyst containing the element Sn in addition to Al, Cu, Ni and Co. The preferred alcohols mentioned are ethylene glycol and monoethanolamine. The catalyst is obtained by precipitatively applying a solution of the respective metal salts onto a catalyst support.

[0025] US4,855,505 discloses the amination of MEG and MEA in the presence of a catalyst containing Ni and / or Co and Ru. This involves contacting a catalyst precursor containing Ni oxide and / or Co oxide with a halogenated Ru, for example Ru chloride, and then reducing this in a hydrogen stream.

[0026] EP0839 575 discloses catalysts containing Co, Ni and mixtures thereof, and Ru on a porous metal oxide support. The catalysts are prepared by impregnating the support with the metal, drying the impregnated support, calcining it, and reducing the calcined support in a hydrogen stream. It is further disclosed that the support may be impregnated with the metal compounds in any order. In one example, the support was first impregnated with solutions of nickel nitrate, cobalt nitrate and copper nitrate, then calcined, and further impregnated with an aqueous solution of ruthenium nitrate.

[0027] WO96 / 38226 discloses a catalyst for the amination of alcohols containing Re, Ni, Co, B, Cu and / or Ru. In one example, a support of SiO2 was impregnated with a solution of NH4ReO4, nickel nitrate, H3BO3, cobalt nitrate and copper nitrate and then calcined. In a further impregnation step, the calcined and impregnated support is impregnated with ruthenium chloride.

[0028] A catalyst for the amination of ethylene glycol is disclosed in WO2018 / 224321, which is obtained by impregnating a catalyst precursor containing at least one metal selected from Sn, Cu or Ni with a soluble Ru-compound and a soluble Co-compound. SUMMARY OF THE INVENTION

[0029] It was an object of the present invention to develop a heterogeneous catalyst for the amination of MEG and / or MEA in the liquid phase, which shows sufficient activity and selectivity in the conversion of MEG to MEA and / or EDA.

[0030] More particularly, the formation of valuable products, namely ethanolamines or ethylenediamines with high commercial significance, in particular MEA and EDA, should be promoted, and the formation of cyclic ethylenediamines, in particular PIP, and higher ethanolamines, in particular AEEA, should be kept low, since the commercial demand for PIP or AEEA is less than that for EDA and MEA.

[0031] More particularly, the concentration of certain undesirable by-products, such as NMEDA, NEEDA and ethylamine (EA), should be reduced. NMEDA has a volatility that is almost indistinguishable from that of EDA, and thus the two components can only be separated by a very complex separation. Therefore, it can be advantageous if only a small amount of NMEDA is formed even if it is produced. The conventional production specification for EDA requires that the NMEDA present in EDA be less than 500 ppm.

[0032] Furthermore, the catalyst should have high activity to achieve good space-time yields and enable high MEG conversion rates.

[0033] Thus, overall, a good spectrum of properties regarding overall selectivity, selectivity quotient, and formation of unwanted by-products should be achieved.

[0034] The object of the present invention is a method for preparing alkanolamines and ethyleneamines in the liquid phase by reacting ethylene glycol and / or monoethanolamine with ammonia in the presence of an amination catalyst obtained by reducing a catalyst precursor, wherein the preparation of the catalyst precursor comprises step a) of preparing a catalyst precursor containing one or more catalyst active components of Sn, Cu, and Ni, and step b) of contacting the catalyst precursor prepared in step a) with a soluble Re compound.

[0035] The amination catalyst prepared according to the present invention by contacting a catalyst precursor containing Ni, Sn, or Cu with a soluble Re-compound has high selectivity for the linear amination products MEA and EDA, but is unexpectedly found to have low selectivity for the cyclic amination products PIP and the higher alkanolamine AEEA compared to the amination catalyst prepared by contacting a catalyst precursor containing Ni, Sn, and / or Cu with a Ru-compound and a Co-compound.

[0036] Furthermore, it has been found that the catalyst of the present invention forms unwanted by-products, such as NMEDA, at lower levels. Furthermore, the amination catalyst used in the method of the present invention has high activity for the conversion of MEG and thus enables high space-time yields during conversion.

Mode for Carrying Out the Invention

[0037] The following abbreviations are used above and below: AEEA: Aminoethylethanolamine AEP: Aminoethylpiperazine DETA: Diethylenetriamine EA: Ethylamine EDA: Ethylenediamine EO: Ethylene oxide HEP: Hydroxyethylpiperazine NEEDA: N-Ethylethylenediamine NMEDA: N-Methylethylenediamine MEA: Monoethanolamine MEG: Monoethylene glycol PIP: Piperazine TEPA: Tetraethylenepentamine TETA: Triethylenetetramine

[0038] Amination catalyst: The method for preparing alkanolamines and ethyleneamines by the reaction of MEG and / or MEA with NH3 according to the present invention is carried out in the presence of an amination catalyst.

[0039] Catalyst precursor: The amination catalyst is obtained by reduction of the catalyst precursor.

[0040] The preparation of the catalyst precursor includes two steps.

[0041] In step a), a catalyst precursor containing one or more catalyst active components among Sn, Cu, and Ni is first prepared.

[0042] The catalyst precursor obtained in step a) is further contacted with a soluble Re compound in step b).

[0043] Step a) Preparation of the catalyst precursor: Active composition: The catalyst precursor contains an active composition.

[0044] The active composition of the catalyst precursor includes one or more active metals, and optionally one or more added catalyst elements, and optionally one or more carrier materials.

[0045] Active metal: According to the present invention, the active composition of the catalyst precursor used in the method of the present invention includes one or more active metals selected from the group consisting of Sn, Cu, and Ni.

[0046] Added catalyst element: The active composition of the catalyst precursor used in the method of the present invention may optionally include one or more added catalyst elements.

[0047] The added catalyst elements are metals or metalloids, element P, and rare earth metals selected from Groups 1 to 8, 9, 10 (excluding Ni), 11 (excluding Cu), and 12 to 13, 14 (excluding Sn), and 15 to 17 of the periodic table.

[0048] Preferred added catalyst elements are Co, Zr, Al, Fe, Sb, Pb, Bi, In, Ga, V, Nb, S, P, B, W, La, Ce, Y, and Hf.

[0049] Particularly preferred added catalyst elements are Co, Zr, Al, and Fe.

[0050] In a particularly highly preferred embodiment, the added catalyst element is Co.

[0051] Catalytic active component: In the catalyst precursor, the active metal and the added catalyst element are generally in the form of their oxygen compounds, such as carbonates, oxides, mixed oxides, or hydroxides of the active metal or the added catalyst element.

[0052] The oxygen compounds of the active metal and the added catalyst element are hereinafter referred to as catalytic active components.

[0053] However, the term "catalytic active component" is not intended to imply that these compounds themselves are already catalytically active. The catalytic active component generally has catalytic activity only after reduction of the catalyst precursor in the conversion of the present invention.

[0054] Generally, the catalytic active component is obtained by conversion through calcination of a soluble compound of an active metal or an added catalyst element, or a precipitate of an active metal or an added catalyst element, and the conversion is generally carried out by dehydration and / or decomposition.

[0055] Support material: The catalytic active composition may further comprise one or more support materials.

[0056] The support material is generally an added catalyst element used in the preparation of the catalyst precursor in solid form, on which a soluble compound of an active metal and / or an added catalyst element is precipitated, or the added catalyst element is impregnated with a soluble compound of an active metal or an added catalyst element. Generally, the support material is a solid having a high surface area.

[0057] It is preferred to use a support material already having the preferred forms and shapes described below (see the section "Forms and Shapes of Support Materials and Catalyst Precursors").

[0058] The catalytic active component can be applied to the support material, for example, by precipitation application in the form of a poorly soluble compound of an active metal or an added catalyst element, such as a carbonate, bicarbonate or hydroxide, or by impregnating the support material with a soluble compound of an active metal or an added catalyst element.

[0059] The support material used can be carbon of an added catalyst element, for example, in the form of graphite, carbon black and / or activated carbon.

[0060] Preferred carrier materials can be oxides of the added catalytic elements Al, Ti, Zn, Zr and Si or mixtures thereof, such as aluminum oxide (gamma, delta, theta, alpha, kappa, chi or mixtures thereof), titanium dioxide (anatase, rutile, brookite or mixtures thereof), zinc oxide, zirconium dioxide, silicon dioxide (e.g., silica, fumed silica, silica gel or silicate), aluminosilicate, minerals such as hydrotalcite, chrysotile and sepiolite.

[0061] Particularly preferred carrier materials are aluminum oxide or zirconium dioxide, or mixtures thereof.

[0062] Particularly preferred carrier material is aluminum oxide.

[0063] Composition of the catalyst precursor: The catalyst precursor used in this method, when the catalyst precursor is used in the form of a shaped body, is preferably used in the form of a catalyst precursor consisting only of a catalytically active composition and optionally a shaping aid (e.g., graphite or stearic acid).

[0064] The proportion of the catalytically active composition is typically 70 wt% to 100 wt%, preferably 80 wt% to 100 wt%, more preferably 90 wt% to 100 wt%, even more preferably 95 wt% to 100 wt%, more preferably 97 wt% to 100 wt% based on the total mass of the catalyst precursor.

[0065] The composition of the catalyst precursor can be measured by known elemental analysis methods, such as atomic absorption spectrometry (AAS), atomic emission spectrometry (AES), X-ray fluorescence analysis (XFA) or ICP-OES (inductively coupled plasma optical emission spectrometry).

[0066] The concentration values (wt%) of the catalytically active components related to the present invention are reported as the corresponding oxides.

[0067] The added catalytic elements of Group 1 (alkali metals) are calculated as M2O, such as Na2O.

[0068] The added catalyst element of Group 2 (alkaline earth metals) is calculated as MO, for example, MgO or CaO.

[0069] The added catalyst element of Group 13 (boron group) is calculated as M2O3, for example, B2O3 or Al2O3.

[0070] In Group 14 (carbon group), Si is calculated as SiO2, Ge as GeO, Sn as SnO, and Pb as PbO.

[0071] In Group 15 (nitrogen group), P is calculated as H3PO4, As as As2O3, Sb as Sb2O3, and Bi as Bi2O3.

[0072] In Group 16 (chalcogen group), Se is calculated as SeO2 and Te as TeO2.

[0073] In Group 3 (scandium group), Sc is calculated as Sc2O3, Y as Y2O3, and La as La2O3.

[0074] In Group 4 (titanium group), Ti is calculated as TiO2, Zr as ZrO2, and Hf as HfO2.

[0075] In Group 5 (vanadium group), V is calculated as V2O5, Nb as Nb2O5, and Ta as Ta2O5.

[0076] In Group 6 (chromium group), Cr is calculated as CrO2, Mo as MoO3, and W as WO2.

[0077] In Group 7 (manganese group), Mn is calculated as MnO2 and Re as ReO3.

[0078] In Group 8 (iron group), Fe is calculated as Fe2O3, Ru as RuO2, and Os as OsO4.

[0079] In the cobalt group (Group 9), Co is calculated as CoO, Rh as RhO2, and Ir as IrO2.

[0080] In the nickel group (Group 10), Ni is calculated as NiO, Pd as PdO, and Pt as PtO.

[0081] In the copper group (Group 11), Cu is calculated as CuO, Ag as AgO, and Au as Au2O3.

[0082] In the zinc group (Group 12), Zn is calculated as ZnO, Cd as CdO, and Hg as HgO.

[0083] The concentration values (weight %) of the components of the catalyst precursor are, unless otherwise specified, based on the catalytically active composition of the catalyst precursor after its final calcination and before contacting the calcined catalyst precursor with a soluble Re compound.

[0084] The composition of the catalyst precursor is generally determined by the preparation methods (coprecipitation or precipitation application or impregnation) described below.

[0085] The catalyst precursor prepared by coprecipitation does not contain any carrier material. When the precipitation described below is carried out in the presence of a carrier material, the precipitation is referred to as precipitation application in the context of the present invention.

[0086] The catalyst precursor prepared by coprecipitation generally contains from 1 to 3, more preferably from 1 to 2, and particularly preferably 1 active metal.

[0087] Regardless of the number of active metals present in the active composition, in the case of a catalyst precursor prepared by coprecipitation, the composition of the catalytically active component of the active metal is preferably in the range of 1 wt% to 95 wt%, more preferably 10 wt% to 90 wt%, even more preferably 20 wt% to 85 wt%, and particularly preferably 50 wt% to 80 wt% based on the total mass of the catalyst precursor, and the catalytically active component is calculated as an oxide.

[0088] The catalyst precursor prepared by coprecipitation generally contains from 1 to 5, more preferably from 1 to 4, and particularly preferably from 1 to 3 different additional catalyst elements.

[0089] Regardless of the number of additional catalyst elements present in the active composition, in the case of a catalyst precursor prepared by coprecipitation, the composition of the catalytically active component of the additional catalyst element is preferably in the range of 1 wt% to 90 wt%, more preferably 5 wt% to 80 wt%, and most preferably 10 wt% to 60 wt% based on the total mass of the catalyst precursor, and the catalytically active component is calculated as an oxide.

[0090] The catalyst precursor prepared by precipitation application generally contains from 5 wt% to 95 wt%, preferably from 10 wt% to 80 wt%, and more preferably from 15 wt% to 60 wt% of a carrier material.

[0091] The catalyst precursor prepared by precipitation application generally contains from 1 to 3, more preferably from 1 to 2, and particularly preferably 1 active metal.

[0092] Regardless of the number of active metals present in the active composition, in the case of a catalyst precursor prepared by precipitation application, the composition of the catalytically active component of the active metal is preferably in the range of 5 wt% to 90 wt%, more preferably 10 wt% to 70 wt%, and most preferably 15 wt% to 60 wt% based on the total mass of the catalyst precursor, and the catalytically active component is calculated as an oxide.

[0093] The catalyst precursor prepared by precipitation application generally contains from 1 to 5, more preferably from 1 to 4, and particularly preferably from 1 to 3 different additional catalyst elements.

[0094] Regardless of the number of added catalyst elements present in the active composition, in the case of a catalyst precursor prepared by precipitation application, the composition of the catalytically active component of the added catalyst element is preferably in the range of 1 wt% to 80 wt%, more preferably 5 wt% to 70 wt%, and most preferably 10 wt% to 50 wt% based on the total mass of the catalyst precursor, and the catalytically active component is calculated as the oxide.

[0095] Catalyst precursors prepared by impregnation generally contain 50 wt% to 99 wt%, preferably 75 wt% to 98 wt%, more preferably 90 wt% to 97 wt% of a carrier material.

[0096] Catalyst precursors prepared by impregnation generally contain 1 to 3, more preferably 1 to 2, and particularly preferably 1 active metal.

[0097] Regardless of the number of active metals present in the active composition, in the case of a catalyst precursor prepared by impregnation, the composition of the catalytically active component of the active metal is preferably in the range of 1 wt% to 50 wt%, more preferably 2 wt% to 25 wt%, and most preferably 3 wt% to 10 wt% based on the total mass of the catalyst precursor, and the catalytically active component is calculated as the oxide.

[0098] Catalyst precursors prepared by impregnation generally contain 1 to 5, more preferably 1 to 4, and particularly preferably 1 to 3 different added catalyst elements.

[0099] Regardless of the number of added catalyst elements present in the active composition, in the case of a catalyst precursor prepared by impregnation, the composition of the catalytically active component of the added catalyst element is preferably in the range of 1 wt% to 50 wt%, more preferably 2 wt% to 25 wt%, and most preferably 3 wt% to 10 wt% based on the total mass of the catalyst precursor, and the catalytically active component is calculated as the oxide.

[0100] Preferred catalyst precursor compositions: Composition 1: In a preferred embodiment, a catalyst precursor is prepared in which the catalytically active composition comprises catalytically active components of Zr, Cu and Ni, and one or more catalytically active components of Sn, Pb, Bi and In. This type of catalyst precursor is disclosed, for example, in WO2008 / 006749.

[0101] In a particularly preferred variant of this embodiment, a catalytically active component of zirconium in an amount of 10% to 75% by weight, preferably 25% to 65% by weight, more preferably 30% to 55% by weight, calculated as ZrO2, a catalytically active component of copper in an amount of 1% to 30% by weight, preferably 2% to 25% by weight, more preferably 5% to 15% by weight, calculated as CuO, a catalytically active component of nickel in an amount of 10% to 70% by weight, preferably 20% to 60% by weight, more preferably 30% to 50% by weight, calculated as NiO, a catalyst precursor is prepared which contains a catalytically active component of one or more metals selected from Sb, Pb, Bi and In in the range of 0.1% to 10% by weight, in particular in the range of 0.2% to 7% by weight, more particularly in the range of 0.4% to 5% by weight, very particularly in the range of 2% to 4.5% by weight, each calculated as Sb2O3, PbO, Bi2O3 and In2O3.

[0102] Composition 2: In a preferred embodiment, a catalyst precursor is prepared in which the catalytically active composition comprises catalytically active components of Zr, Cu, Ni and Co, and one or more catalytically active components of Pb, Bi, Sn, Sb and In. This type of catalyst precursor is disclosed, for example, in WO2008 / 006750.

[0103] In a particularly preferred variant of this embodiment, a catalytically active component of zirconium in an amount of 10% to 75% by weight, preferably 25% to 65% by weight, more preferably 30% to 55% by weight, calculated as ZrO2, A catalytic active component of copper calculated as CuO is from 1 wt% to 30 wt%, preferably from 2 wt% to 25 wt%, more preferably from 5 wt% to 15 wt%, and A catalytic active component of nickel calculated as NiO is from 10 wt% to 70 wt%, preferably from 13 wt% to 40 wt%, more preferably from 16 wt% to 35 wt%, A catalytic active component of cobalt calculated as CoO is from 10 wt% to 50 wt%, preferably from 13 wt% to 40 wt%, more preferably from 16 wt% to 35 wt%, and A catalyst precursor containing a catalytic active component of one or more metals selected from Pb, Bi, Sn, Sb, and In is prepared, calculated as PbO, Bi2O3, SnO, Sb2O3, and In2O3 respectively, in the range of 0.1 wt% to 10 wt%, specifically in the range of 0.2 wt% to 7 wt%, and more specifically in the range of 0.4 wt% to 5 wt%.

[0104] Composition 3: In a further preferred embodiment, a catalyst precursor is prepared that contains catalytic active components of Zr, Ni, and Fe, and catalytic active components of one or more of Sn, Pb, Bi, Mo, Sb, and / or P in the range of 0.2 wt% to 5.5 wt% calculated as SnO, PbO, Bi2O3, MoO3, Sb2O3, and H3PO4 respectively. This type of catalyst precursor is disclosed, for example, in WO2009 / 080506.

[0105] In a particularly preferred variant of this embodiment, A catalytic active component of zirconium calculated as ZrO2 is from 20 wt% to 70 wt%, A catalytic active component of nickel calculated as NiO is from 15 wt% to 60 wt% and A catalytic active component of iron calculated as Fe2O3 is from 0.5 wt% to 14 wt%, preferably from 1.0 wt% to 10 wt%, more preferably from 1. 5 wt% to 6 wt%, andA catalyst precursor containing catalytically active components of tin, lead, bismuth, molybdenum, antimony and / or phosphorus in an amount of 0.2 wt% to 5.5 wt%, preferably 0.5 wt% to 4.5 wt%, more preferably 0.7 wt% to 3.5 wt% calculated as SnO, PbO, Bi2O3, MoO3, Sb2O3 and H3PO4 respectively is prepared.

[0106] Composition 4: In a further preferred embodiment, the catalytically active composition comprises catalytically active components of Zr, Cu, Ni, and a catalytically active component of cobalt in the range of 0.2 wt% to 40 wt% calculated as CoO, a catalytically active component of iron in the range of 0.1 wt% to 5 wt% calculated as Fe2O3, and a catalyst precursor is prepared which contains catalytically active components of lead, tin, bismuth and / or antimony in the range of 0.1 wt% to 5 wt% calculated as PbO, SnO, Bi2O3 and Sb2O3 respectively.

[0107] This type of catalyst precursor is disclosed, for example, in WO2009 / 080508.

[0108] In a particularly preferred variant of this embodiment, a catalytically active component of zirconium in the range of 20 wt% to 85 wt%, specifically 25 wt% to 70 wt%, more specifically 30 wt% to 60 wt% calculated as ZrO2, a catalytically active component of copper in the range of 0.2 wt% to 25 wt%, specifically 3 wt% to 20 wt%, more specifically 5 wt% to 15 wt% calculated as CuO, a catalytically active component of nickel in the range of 0.2 wt% to 45 wt%, specifically 10 wt% to 40 wt%, more specifically 25 wt% to 35 wt% calculated as NiO, a catalytically active component of cobalt in the range of 0.2 wt% to 40 wt%, preferably 1 wt% to 25 wt%, more preferably 2 wt% to 10 wt% calculated as CoO, A catalytically active component of iron, calculated as Fe2O3, is from 0.1 wt% to 5 wt%, preferably from 0.2 wt% to 4 wt%, more preferably from 0.5 wt% to 3 wt%, and A catalyst precursor is prepared that contains catalytically active components of lead, tin, bismuth, and / or antimony, calculated as PbO, SnO, Bi2O3, and Sb2O3 respectively, from 0.1 wt% to 5.0 wt%, specifically from 0.3 wt% to 4.5 wt%, more specifically from 0.5 wt% to 4 wt%.

[0109] Composition 5: In a further preferred embodiment, the catalytically active composition contains catalytically active components of Zr, Cu, and Ni, and a catalytically active component of cobalt in the range of 1.0 wt% to 5.0 wt% calculated as CoO, and a catalyst precursor is prepared that contains catalytically active components of vanadium, niobium, sulfur, phosphorus, gallium, boron, tungsten, lead, and / or antimony in the range of 0.2 wt% to 5.0 wt% calculated as V2O5, Nb2O5, H2SO4, H3PO4, Ga2O3, B2O3, WO3, PbO, and Sb2O3 respectively.

[0110] This type of catalyst precursor is disclosed, for example, in WO2009 / 080508.

[0111] In a particularly preferred variation of this embodiment, a catalytically active component of zirconium, calculated as ZrO2, is from 46 wt% to 65 wt%, specifically from 47 wt% to 60 wt%, more specifically from 48 wt% to 58 wt%, a catalytically active component of copper, calculated as CuO, is from 5.5 wt% to 18 wt%, specifically from 6 wt% to 16 wt%, more specifically from 7 wt% to 14 wt%, a catalytically active component of nickel, calculated as NiO, is from 20 wt% to 45 wt%, specifically from 25 wt% to 40 wt%, more specifically from 30 wt% to 39 wt%, A catalytically active component of cobalt in the range of 1.0 wt% to 5.0 wt%, specifically in the range of 1.5 wt% to 4.5 wt%, more specifically in the range of 2.0 wt% to 4.0 wt%, calculated as CoO, and A catalyst precursor containing catalytically active components of vanadium, niobium, sulfur, phosphorus, gallium, boron, tungsten, lead and / or antimony, each in the range of 0.2 wt% to 5.0 wt%, specifically in the range of 0.3 wt% to 4.0 wt%, more specifically in the range of 0.5 wt% to 3.0 wt%, calculated as V2O5, Nb2O5, H2SO4, H3PO4, Ga2O3, B2O3, WO3, PbO and Sb2O3 respectively, is prepared.

[0112] Composition 6: In a further preferred embodiment, a catalyst precursor is prepared which contains catalytically active components of Al, Cu, Ni, Co and Sn, and Catalytically active components of yttrium, lanthanum, cerium and / or hafnium in the range of 0.2 wt% to 5.0 wt%, calculated as Y2O3, La2O3, Ce2O3 and Hf2O3 respectively.

[0113] This type of catalyst precursor is disclosed, for example, in WO2011 / 067200.

[0114] In a particularly preferred variant of this embodiment, A catalytically active component of tin in the range of 0.2 wt% to 5.0 wt%, specifically in the range of 0.4 wt% to 4.0 wt%, more specifically in the range of 0.6 wt% to 3.0 wt%, even more specifically in the range of 0.7 wt% to 2.5 wt%, calculated as SnO, A catalytically active component of cobalt in the range of 10 wt% to 30 wt%, more specifically in the range of 12 wt% to 28 wt%, very specifically in the range of 15 wt% to 25 wt%, calculated as CoO, A catalytically active component of aluminum in the range of 15 wt% to 80 wt%, specifically in the range of 30 wt% to 70 wt%, more specifically in the range of 35 wt% to 65 wt%, calculated as Al2O3, A catalytically active component of copper calculated as CuO is from 1 wt% to 20 wt%, specifically from 2 wt% to 18 wt%, more specifically from 5 wt% to 15 wt%, and A catalytically active component of nickel calculated as NiO is from 5 wt% to 35 wt%, specifically from 10 wt% to 30 wt%, more specifically from 12 wt% to 28 wt%, and very specifically from 15 wt% to 25 wt%, A catalyst precursor containing yttrium, lanthanum, cerium and / or hafnium as catalytically reactive components is prepared, calculated as Y2O3, La2O3, Ce2O3 and Hf2O3 respectively, in the range of 0.2 wt% to 5.0 wt%, specifically in the range of 0.4 wt% to 4.0 wt%, more specifically in the range of 0.6 wt% to 3.0 wt%, and even more specifically in the range of 0.7 wt% to 2.5 wt%.

[0115] Composition 7: In a further preferred embodiment, a catalyst precursor is prepared which contains catalytically active components of Sn, Cu, Ni, Co and Al. Such a catalyst precursor preferably has the following components: A catalytically active component of tin calculated as SnO is from 0.2 wt% to 5 wt%, A catalytically active component of copper calculated as CuO is from 1 wt% to 20 wt%, A catalytically active component of nickel calculated as NiO is from 5 wt% to 35 wt%, and A catalytically active component of cobalt calculated as CoO is from 5 wt% to 35 wt%, It contains an aluminum catalytically active component and / or zirconia as a carrier material calculated as Al2O3 or ZrO2 in the range of 15 wt% to 80 wt%. In a particularly highly preferred variant of this embodiment, the catalyst precursor having the aforementioned composition is obtained by precipitation application on the carrier material. Preferably, the soluble compounds of Co and Sn are precipitated on a finely divided carrier material as disclosed in WO2013 / 072289. The soluble compounds of Sn, Co, Cu and / or Ni are preferably used in the form of their nitrates or nitrosyl nitrates.

[0116] The precipitation application is more preferably carried out in the presence of a complexing agent.

[0117] The complexing agent is preferably selected from the group consisting of glycolic acid, lactic acid, hydroacrylic acid, hydroxybutyric acid, hydroxyvaleric acid, malonic acid, mandelic acid, citric acid, sugar acid, tartronic acid, tartaric acid, oxalic acid, malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, glycine, hippuric acid, EDTA, alanine, valine, leucine or isoleucine.

[0118] The carrier material is preferably aluminum oxide or zirconium oxide, or a mixture thereof.

[0119] The median diameter d of the particles of the carrier material used 50 is preferably in the range of 1 to 500 μm, preferably 3 to 400 μm, more preferably 5 to 300 μm.

[0120] The standard deviation of the particle diameter is generally in the range of 5% to 200%, preferably 10% to 100%, particularly preferably 20% to 80% of the median diameter d. 50

[0121] After the precipitation application, the catalyst precursor is generally post-treated by separating the catalyst precursor from the solution in which the precipitation application was carried out, washing, drying, calcining, and optionally converting it into the desired form in the step of forming.

[0122] Preferably, after calcination, the step of forming follows, where the catalyst precursor is processed to obtain a formed body, particularly a tablet.

[0123] The height of the tablet is preferably in the range of 1 to 10, more preferably in the range of 1.5 to 3 mm. The ratio of the height h of the tablet to the diameter D of the tablet is preferably 1:1 to 1:5, more preferably 1:1 to 2.5, and most preferably 1:1 to 1:2.

[0124] When the catalyst precursor is used in the form of a powder or a chip, the median diameter d of the particles 50 is generally in the range of 50 to 2000 μm, preferably 100 to 1000 μm, more preferably 300 to 700 μm. The standard deviation of the particle diameter is generally 5% to 200% of the median diameter d 50 , preferably 10% to 100%, particularly preferably 20% to 80%.

[0125] In a particularly preferred embodiment, the median diameter d of the powder or chip particles used 50 is preferably in the range of 1 to 500 μm, preferably 3 to 400 μm, more preferably 5 to 300 μm. The standard deviation of the particle diameter is generally 5% to 200% of the median diameter d 50 , preferably 10% to 100%, particularly preferably 20% to 80%.

[0126] Preparation of the catalyst precursor: The catalyst precursor can be prepared in step a) by known processes, for example by precipitation reactions (such as coprecipitation or precipitation application) or impregnation.

[0127] Precipitation reaction - coprecipitation: The catalyst precursor can be prepared via coprecipitation of a soluble compound of the active metal or an added catalyst element with a precipitating agent. For this purpose, one or more soluble compounds of the corresponding active metal and optionally one or more soluble compounds of the added catalyst element in a liquid are admixed with the precipitating agent while heating and stirring until precipitation is complete.

[0128] The liquid used is generally water.

[0129] Useful soluble compounds of the active metal are typically the corresponding metal salts, such as nitrates or nitrosyl nitrates, chlorides, sulfates, carboxylates, especially acetates of the aforementioned metals, or those containing nitrates or nitrosyl nitrates.

[0130] The soluble compounds of the added catalyst elements used are generally water-soluble compounds of the added catalyst elements, such as water-soluble nitrates or nitrosyl nitrates, chlorides, sulfates, carboxylates, especially acetates, or nitrates or nitrosyl nitrates.

[0131] Precipitation reaction - Precipitation application: The catalyst precursor can also be prepared by precipitation application.

[0132] Precipitation application means a preparation method in which one or more carrier materials are suspended in a liquid, and then soluble compounds of the active metal, such as soluble metal salts of the active metal, and optionally soluble compounds of the added catalyst elements are added, and these are then applied by precipitation application to the suspended carrier material by adding a precipitant (for example, described in EP-A2-1 106 600, page 4 and A. B. Stiles, Catalyst Manufacture, Marcel Dekker, Inc., 1983, page 15).

[0133] The soluble compounds of the active metal or added catalyst elements used are generally water-soluble compounds of the active metal or added catalyst elements, such as water-soluble nitrates or nitrosyl nitrates, chlorides, sulfates, carboxylates, especially acetates, or nitrates or nitrosyl nitrates.

[0134] The carrier material is generally in the form of powder or chips.

[0135] The particle size generally ranges from 50 to 2000 μm, preferably from 100 to 1000 μm, more preferably from 300 to 700 μm.

[0136] The carrier material used for precipitation application can be used, for example, in the form of chips, powder or shaped bodies, such as strands, tablets, spheres or rings. It is preferred to use a carrier material that already has the preferred forms and shapes described below (see the section "Form and Shape of the Carrier Material and Catalyst Precursor").

[0137] The liquid used, in which the carrier material is suspended, is typically water.

[0138] Precipitation reaction - general: Typically, in a precipitation reaction, a soluble compound of an active metal or an added catalytic element precipitates as a poorly soluble or insoluble basic salt by the addition of a precipitant.

[0139] The precipitant used is preferably an alkali, especially an inorganic base such as an alkali metal base. Examples of precipitants are sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide.

[0140] The precipitant used may also be an ammonium salt, such as ammonium halide, ammonium carbonate, ammonium hydroxide or ammonium carboxylate.

[0141] The precipitation reaction can be carried out, for example, at a temperature of from 20 to 100 °C, in particular from 30 to 90 °C, especially from 50 to 70 °C.

[0142] The precipitate obtained in the precipitation reaction is generally chemically heterogeneous and generally contains a mixture of oxides, oxide hydrates, hydroxides, carbonates and / or bicarbonates of the metals or metalloids used. With regard to the filterability of the precipitate, it may prove advantageous for the precipitate to be aged, i.e. optionally, under elevated temperature conditions or by passing air through, and the precipitate is left to stand for a certain time after precipitation.

[0143] Impregnation: The catalyst precursor can also be prepared by impregnating a carrier material with a soluble compound of an active metal or an added catalytic element (impregnation).

[0144] The carrier material used for impregnation can be used, for example, in the form of small pieces, powders or shaped bodies, such as strands, tablets, spheres or rings. It is preferred to use a carrier material already having the preferred form and shape of the shaped bodies described below (see the section "Form and shape of the carrier material and catalyst precursor").

[0145] The carrier materials mentioned above can be impregnated by customary processes (A. B. Stiles, Catalyst Manufacture - Laboratory and Commercial Preparations, Marcel Dekker, New York, 1983), for example, by applying salts of active metals or added catalyst elements in one or more impregnation steps.

[0146] Useful salts of active metals or added catalyst elements generally include water-soluble salts of the corresponding active metals or added catalyst elements, such as carbonates, nitrates or nitrosyl nitrates, carboxylates, especially nitrates or nitrosyl nitrates, acetates or chlorides, which are generally at least partially converted to the corresponding oxides or mixed oxides under calcination conditions.

[0147] Impregnation can also be carried out by the "incipient wetness method", in which the carrier material is wetted with the impregnating solution to maximum saturation according to its water absorption capacity, or the impregnating solution is sprayed onto the carrier material. Alternatively, impregnation may be carried out in a supernatant solution.

[0148] In the case of a multi-stage impregnation process, it is appropriate to dry and, optionally, calcine between individual impregnation steps. Multi-stage impregnation should preferably be used when the carrier material is to be brought into contact with a relatively large amount of salt.

[0149] When applying a plurality of active metals and / or added catalyst elements and / or basic elements to the carrier material, impregnation can be carried out simultaneously with all the salts or successively with the individual salts in any order.

[0150] Method for preparing a preferred combination of a composition and a catalyst precursor: In a preferred embodiment, the catalyst precursor having the composition described above is prepared by coprecipitation or precipitation application, more preferably by precipitation application.

[0151] In a particularly preferred embodiment, the catalyst precursor having one of the preferred compositions 1 to 7 is prepared by coprecipitation or precipitation application. Most preferably, the catalyst precursor of one of the compositions 1 to 7 is prepared by precipitation application.

[0152] Post-treatment of the catalyst precursor: The catalyst precursor prepared in step a) by the impregnation method or precipitation method described above is typically further processed by performing one or more of the following aa) Liquid separation, and ab) Washing, ac) Drying, ad) Calcination, and ae) Shaping processing steps, and then step b) is applied to the catalyst precursor.

[0153] Preferably, the further processing of the catalyst precursor includes all of the processing steps mentioned above, but it is possible to omit one or more of the steps mentioned above and, optionally, perform the processing steps omitted after the post-impregnation step b).

[0154] Separation and washing steps: The impregnated catalyst precursor or the precipitate obtained by the precipitation method is generally separated from the liquid in which the catalyst precursor was prepared and washed.

[0155] The process of separating and washing the catalyst precursor is known, for example, from the treatise "Heterogenous Catalysis and Solid Catalysts, 2. Development and Types of Solid Catalysts" in Ullmann's Encyclopedia of Industrial Chemistry (DOI: 10.1002 / 14356007.o05_o02).

[0156] The washing liquid used is generally a liquid in which the separated catalyst precursor is sparingly soluble but is a good solvent for impurities adhering to the catalyst, such as the precipitating agent. A preferred washing liquid is water.

[0157] In batch preparation, the separation is generally carried out with a frame filter press. Washing of the filter residue with a washing liquid can be carried out here by passing the washing liquid in a countercurrent direction to the filtration direction.

[0158] In continuous preparation, the separation is generally carried out with a rotary drum vacuum filter. Washing of the filter residue is typically carried out by spraying the washing liquid onto the filter residue.

[0159] The catalyst precursor can also be separated by centrifugation. Generally, washing can be carried out here by adding the washing liquid during the course of centrifugation.

[0160] Drying: The separated catalyst precursor is generally dried.

[0161] The process of drying the catalyst precursor is known, for example, from the treatise "Heterogenous Catalysis and Solid Catalysts, 2. Development and Types of Solid Catalysts" in Ullmann's Encyclopedia of Industrial Chemistry (DOI: 10.1002 / 14356007.o05_o02).

[0162] Drying is preferably carried out here at a temperature in the range of 60 to 200 °C, especially 80 to 160 °C, more preferably 100 to 140 °C, and the drying time is preferably 6 h or more, for example, in the range of 6 to 24 h. However, depending on the water content of the material to be dried, there can also be short drying times, for example, about 1, 2, 3, 4 or 5 h.

[0163] The separated and washed catalyst precursor may be dried, for example, in a chamber oven, a drum dryer, a rotary kiln or a belt dryer.

[0164] The catalyst precursor can also be dried by spray-drying a suspension of the catalyst precursor.

[0165] Firing: Generally, the catalyst precursor is fired after drying.

[0166] During firing, thermally unstable compounds of the active metal or added catalyst elements, such as carbonates, bicarbonates, nitrates or nitrosyl nitrates, chlorides, carboxylates, oxide hydrates or hydroxides, are at least partially converted into the corresponding oxides and / or mixed oxides.

[0167] Firing is generally carried out at a temperature in the range of 250 to 1200 °C, preferably 300 to 1100 °C, especially 500 to 1000 °C.

[0168] Firing can be carried out under any suitable gas atmosphere, and air and / or air mixtures, such as lean air, are preferred. Firing can alternatively be carried out in the presence of hydrogen, nitrogen, helium, argon and / or steam, or mixtures thereof.

[0169] Firing is generally carried out in a muffle furnace, rotary kiln and / or tunnel kiln, and the firing time is preferably 1 h or more, more preferably in the range of 1 to 24 h, most preferably in the range of 2 to 12 h.

[0170] Form and shape of the support material or catalyst precursor: The catalyst precursor or support material is preferably used in the form of a powder or chip, or in the form of a shaped body.

[0171] When the catalyst precursor is used in the form of a powder or chip, the median diameter d of the particles 50 is generally in the range of 50 to 2000 μm, preferably 100 to 1000 μm, more preferably 300 to 700 μm. The standard deviation of the particle diameter is generally in the range of 5% to 200% of the median diameter d 50 preferably 10% to 100%, especially preferably 20% to 80%.

[0172] In a particularly preferred embodiment, the median diameter d of the powder or chip particles used 50 is preferably in the range of 1 to 500 μm, preferably 3 to 400 μm, more preferably 5 to 300 μm. The standard deviation of the particle diameter is generally 5% to 200% of the median diameter d 50 and preferably in the range of 10% to 100%, particularly preferably in the range of 20% to 80%.

[0173] When the catalyst precursors are used in the form of shaped bodies, these are preferably used in the form of tablets.

[0174] The height of the tablet is preferably in the range of 1 to 10, more preferably in the range of 1.5 to 3 mm. The ratio of the height h of the tablet to the diameter D of the tablet is preferably 1:1 to 1:5, more preferably 1:1 to 2.5, and most preferably 1:1 to 1:2.

[0175] However, the carrier material or the catalyst precursor can preferably also be used in the method of the present invention in the form of a shaped body.

[0176] Suitable shaped bodies are shaped bodies having any shape or form. Preferred forms are tablets, rings, cylinders, star extrudates, wagon wheels or spheres, with tablets, rings, cylinders, spheres or star extrudates being particularly preferred. More specifically, a cylindrical shape is preferred.

[0177] In the case of spheres, the diameter of the sphere is preferably 20 mm or less, more preferably 10 mm or less, even more preferably 5 mm or less, and particularly preferably 3 mm or less.

[0178] In a preferred embodiment, in the case of spheres, the diameter of the sphere is preferably in the range of 0.1 to 20, more preferably 0.5 to 10 mm, even more preferably 1 to 5 mm, and particularly preferably 1.5 to 3 mm.

[0179] In the case of a strand or a cylinder, the length: diameter ratio is preferably in the range of 1:1 to 20:1, more preferably 1:1 to 14:1, even more preferably 1:1 to 10:1, and particularly preferably 1:2 to 6:1.

[0180] The diameter of the strand or cylinder is preferably 20 mm or less, more preferably 15 mm or less, even more preferably 10 mm or less, and particularly preferably 3 mm or less.

[0181] In a preferred embodiment, the diameter of the strand or cylinder is preferably in the range of 0.5 to 20 mm, more preferably 1 to 15 mm, and most preferably 1.5 to 10 mm.

[0182] In the case of a tablet, the height h of the tablet is preferably 20 mm or less, more preferably 10 mm or less, even more preferably 5 mm or less, and particularly preferably 3 mm or less.

[0183] In a preferred embodiment, the height h of the tablet is preferably in the range of 0.1 to 20 mm, more preferably 0.5 to 15 mm, even more preferably 1 to 10 mm, and particularly preferably 1.5 to 3 mm.

[0184] The ratio of the height h (or thickness) of the tablet to the diameter D of the tablet is preferably 1:1 to 1:5, more preferably 1:1 to 1:2.5, and most preferably 1:1 to 1:2.

[0185] The shaped body to be used preferably has a bulk density (in accordance with EN ISO 6) in the range of 0.1 to 3 kg / l, preferably 1.0 to 2.5 kg / l, and particularly preferably 1.2 to 1.8 kg / l.

[0186] Shaping: In the production of the catalyst precursor by impregnation or by precipitation application, it is preferred to use a carrier material which already has the preferred forms and shapes described above.

[0187] Carrier materials or catalyst precursors that do not have the preferred form described above can be subjected to a shaping step.

[0188] During the shaping process, the carrier materials or catalyst precursors are generally conditioned by grinding them down to a specific particle size.

[0189] After grinding, the conditioned carrier materials or conditioned catalyst precursors can be mixed with further additives, such as shaping aids, for example graphite, binders, pore formers, and pasting agents, and further processed to obtain shaped bodies. Preferably, the catalyst precursor is mixed only with graphite as a shaping aid, and no further additives are added during the shaping process.

[0190] Standard shaping processes are described, for example, in Ullmann [Ullmann's Encyclopedia Electronic Release 2000, chapter: "Catalysis and Catalysts", pages 28 - 32], and also by Ertl et al. [Ertl, Knoezinger, Weitkamp, Handbook of Heterogeneous Catalysis, VCH Weinheim, 1997, pages 98 ff].

[0191] Standard shaping processes are, for example, extrusion, tableting, i.e., mechanical pressing, or pelletization, i.e., compression by circular and / or rotational motion.

[0192] The shaping operation results in a shaped body having the shape mentioned above.

[0193] Shaping can alternatively be carried out by spray drying a suspension of the catalyst precursor.

[0194] Conditioning or shaping is generally followed by a heat treatment. The temperature in the heat treatment typically corresponds to the temperature in calcination.

[0195] Step b): The step of contacting the catalyst precursor prepared in step a) with a Re compound: According to the present invention, the catalyst precursor prepared in step a) is contacted with a soluble Re compound.

[0196] In a preferred embodiment, the catalyst precursor is contacted with at least one additional active metal and / or at least one additional promoter element.

[0197] Preferably, the catalyst precursor prepared in step a) is contacted simultaneously with a soluble Re compound and at least one soluble compound of an active metal and / or a promoter element other than Re.

[0198] In another preferred embodiment, the catalyst precursor prepared in step a) is contacted with at least one soluble compound of an active metal and / or a promoter element other than Re before or after being contacted with the soluble Re compound.

[0199] Preferred additional active metals or additional promoter elements to be contacted with the catalyst precursor prepared in step a) are Ru, Co, Ni, and Cu. More preferred additional active metals or additional promoter elements are Co and Ru.

[0200] The contact of the catalyst precursor with the soluble Re compound and optionally at least one soluble compound of an active metal and / or a promoter element is usually accomplished by contacting the catalyst precursor with one or more impregnation solutions. The impregnation solution is a solution containing the soluble Re compound and / or a soluble compound of an active metal and / or a promoter element, and a solvent for each soluble compound.

[0201] The solvent used in the preparation of the impregnation solution is preferably water, but other solvents such as organic solvents like alcohols and ethers may also be used.

[0202] When the impregnating solution contains a soluble Re compound, the Re content of the impregnating solution is typically in the range of 0.1 to 50% by weight, preferably 1 to 40% by weight, more preferably 2 to 15% by weight.

[0203] When the impregnating solution contains a soluble compound of an active metal or an added catalyst element other than Re, the content of each active metal or added catalyst element is typically in the range of 0.1 to 50% by weight, preferably 1 to 40% by weight, more preferably 2 to 15% by weight, and the total of all active elements or added catalyst elements in the impregnating solution is typically in the range of 0.1 to 70% by weight, preferably 1 to 60% by weight, more preferably 2 to 50% by weight.

[0204] When the impregnating solution contains a soluble Ru compound, the Ru content of the impregnating solution is typically in the range of 0.1 to 50% by weight, preferably 1 to 40% by weight, more preferably 2 to 15% by weight.

[0205] When the impregnating solution contains a soluble Co compound, the Co content of the impregnating solution is typically in the range of 0.1 to 20% by weight, preferably 0.1 to 5% by weight, more preferably 0.15 to 2% by weight.

[0206] Preferably, the impregnating solution contains three components, namely a soluble Re compound, a soluble Ru compound, and a soluble Co compound.

[0207] As the soluble Re compound, perrhenic acid is preferably used.

[0208] The soluble compound of the active metal or added catalyst element is generally used in the form of its water-soluble salt, such as its carbonate, halide, nitrate, nitrosyl nitrate, or carboxylate. Preferably, the water-soluble salts of the active metal or added catalyst element are used as soluble compounds in the form of their respective nitrates or nitrosyl nitrates, acetates, or chlorides. Most preferably, nitrates or nitrosyl nitrates are used as the soluble compounds of the active metal or added catalyst element.

[0209] When the catalyst precursor is to be contacted with a Co and / or Ru compound, preferably, cobalt nitrate hexahydrate is used as a soluble compound of Co, and ruthenium nitrosyl nitrate is used as a soluble compound of Ru.

[0210] The contact of the catalyst precursor prepared in step a) with the impregnation solution in step b) is preferably carried out after calcining the catalyst precursor prepared in step a), or after heat treatment after shaping, and before reduction / passivation of the catalyst precursor.

[0211] The contact of the catalyst precursor prepared in step a) with the impregnation solution is hereinafter referred to as post-impregnation.

[0212] The catalyst precursor used for post-impregnation can be used, for example, in the form of small pieces, powders or shaped bodies, such as strands, cylinders, tablets, spheres or rings. It is preferred to use a catalyst precursor having the forms and shapes described above (see the section "Form and Shape of Support Materials and Shaped Bodies"). In particular, it is preferred to use a catalyst precursor in the form of a tablet.

[0213] The height of the tablet is preferably in the range of 1 to 10, more preferably in the range of 1.5 to 3 mm. The ratio of the height h of the tablet to the diameter D of the tablet is preferably from 1:1 to 1:5, more preferably from 1:1 to 2.5, and most preferably from 1:1 to 1:2.

[0214] In a particularly preferred embodiment, the median diameter d of the powder or small piece particles used 50 is preferably in the range of 1 to 500 μm, preferably 3 to 400 μm, more preferably 5 to 300 μm. The standard deviation of the particle diameter is generally from 5% to 200%, preferably from 10% to 100%, and particularly preferably from 20% to 80% of the median diameter d 50 .

[0215] The catalyst precursor can be post-impregnated by conventional processes (A. B. Stiles, Catalyst Manufacture - Laboratory and Commercial Preparations, Marcel Dekker, New York, 1983).

[0216] The post-impregnation of the catalyst precursor can be carried out by the "incipient wetness method", in which the catalyst precursor is wetted with the impregnation solution up to maximum saturation according to its solvent absorption capacity, specifically water. Alternatively, the post-impregnation can be carried out in the supernatant solution.

[0217] In a preferred embodiment, the post-impregnation of the catalyst precursor is carried out by the "incipient wetness method" by first determining the saturation capacity (SC) of the catalyst precursor with respect to the solvent used in the impregnation solution, most preferably water, and then contacting the catalyst precursor with an amount of the impregnation solution corresponding to 50 to 100%, preferably 60 to 95%, more preferably 70 to 90% of the previously determined saturation capacity (SC).

[0218] The post-impregnation can be carried out in one or more steps.

[0219] If the post-impregnation is to be carried out in one step, the impregnation solution should contain all the compounds that come into contact with the catalyst precursor, such as soluble compounds of Re, and optionally at least one additional soluble compound of an active metal or a promoter element. As described above, the impregnation solution used for one-step impregnation preferably contains soluble compounds of Co and / or Ru in addition to the soluble Re compound.

[0220] If the post-impregnation is to be carried out in two or more steps, the post-impregnation can be repeated one or more times using an impregnation solution having the same composition as that previously contacted with the catalyst precursor. Alternatively, the catalyst precursor can be subsequently post-impregnated with impregnation solutions of different compositions.

[0221] Preferably, the post-impregnation is carried out in two or more steps using an impregnation solution of the same composition.

[0222] In the most preferred embodiment, the post-impregnation is carried out by applying the incipient wetness method. In the first step, the catalyst precursor is contacted with an amount of the impregnation solution corresponding to 50 to 100%, preferably 60 to 95%, more preferably 70 to 90% of the solvent capacity (SC) of the catalyst precursor. In the second step, the catalyst precursor obtained in the first step is contacted with an amount of the impregnation solution having the same composition as the impregnation solution used in the first step, corresponding to 50 to 100%, preferably 60 to 95%, most preferably 70 to 90% of the originally determined solvent capacity (SC) of the catalyst precursor.

[0223] When the post-impregnation is carried out in two or more steps, the catalyst precursor is preferably dried after each post-impregnation step. The conditions of the drying step carried out after each post-impregnation step are usually the same as the conditions described above in the "Drying" section.

[0224] Optionally, calcination may follow each drying step after each post-impregnation step. However, it is preferred that no subsequent calcination follows each drying step.

[0225] Preferably, the catalyst precursor is reduced after the last drying step as described below.

[0226] When the catalyst precursor is contacted with a soluble compound of Re, the proportion of Re in the catalyst precursor increases by about 0.1 wt% to 10 wt%, preferably 0.5 wt% to 7 wt%, most preferably 1 wt% to 5 wt% with respect to the total mass of the catalyst precursor in each case.

[0227] In a preferred embodiment where the catalyst precursor is contacted with a soluble compound of an active metal other than Re or an added catalyst element, the amount of the added active metal or added catalyst element generally increases by 0.1 to 10% by weight, preferably 0.5 to 7% by weight, more preferably 1 to 5% by weight, based on the total mass of the catalyst precursor in each case.

[0228] In a most preferred embodiment where the catalyst precursor is contacted with a soluble compound of Co, the amount of Co generally increases by 0.1 to 5% by weight, preferably 0.3 to 4% by weight, more preferably 0.5 to 3% by weight, based on the total mass of the catalyst precursor in each case.

[0229] In a most preferred embodiment where the catalyst precursor is contacted with a soluble compound of Ru, the amount of Ru generally increases by 0.1 to 5% by weight, preferably 0.3 to 4% by weight, more preferably 0.5 to 3% by weight, based on the total mass of the catalyst precursor in each case.

[0230] After the catalyst precursor is contacted with a soluble compound of Re, the catalyst precursor preferably contains 0.1% to 20% by weight, more preferably 0.5% to 15% by weight, and particularly preferably 1% to 10% by weight of the catalytically active component of Re, calculated as ReO3, after the final drying step (the weight values are based on the total mass of the catalyst precursor).

[0231] When the catalyst precursor is contacted with a soluble compound of an active metal other than Re or an added catalyst element, the catalyst precursor preferably contains 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, and most preferably 1 to 10% by weight of the catalytically active component of each active metal or added catalyst element, calculated as the respective oxide, after the final drying step (the weight values are based on the total mass of the catalyst precursor).

[0232] When the catalyst precursor is brought into contact with a soluble compound of Ru, the catalyst precursor preferably contains, calculated as RuO2, from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, and most preferably from 1 to 10% by weight of the catalytically active component of Ru after the last drying step (the weight value is based on the total mass of the catalyst precursor).

[0233] When the catalyst precursor is brought into contact with a soluble compound of Co, the catalyst precursor preferably contains, calculated as CoO, from 0.1% to 50% by weight, more preferably from 10% to 45% by weight, and particularly preferably from 20% to 40% by weight of the catalytically active component of Co after the last drying step (the weight value is based on the total mass of the catalyst precursor).

[0234] Preferably, the last impregnation in step b) is followed by a drying step (described above), as well as a reduction and / or passivation step.

[0235] According to the present invention, the conversion of MEG and / or MEA, and ammonia is carried out on the reduced catalyst precursor.

[0236] Reduction generally converts the catalyst precursor into its catalytically active form.

[0237] Therefore, after drying the catalyst precursor obtained in step b), the following processing steps: ba) reduction, and bb) passivation One or more of these are preferably carried out.

[0238] Reduction: The reduction of the catalyst precursor is preferably carried out at a high temperature.

[0239] The reducing agent used is typically hydrogen or a gas containing hydrogen.

[0240] Hydrogen is generally used in technical grade purity. Hydrogen can also be used in the form of a gas containing hydrogen, i.e., as a mixture with other inert gases such as nitrogen, helium, neon, argon or carbon dioxide. In a preferred embodiment, hydrogen is used together with nitrogen, and the volume ratio of hydrogen is preferably in the range of 1% to 50% by volume, more preferably 2.5% to 30% by volume, and particularly preferably 5% to 25% by volume. The hydrogen stream can optionally be recycled as cycle gas for reduction after being mixed with fresh hydrogen and optionally removing water by condensation.

[0241] It is even more preferable that the proportion of hydrogen in the mixture with the inert gas is increased gradually or in a stepwise manner, for example from 0% by volume of hydrogen to 50% by volume of hydrogen. For example, during the course of heating, the proportion relative to the volume of hydrogen can be 0% by volume, and when the reduction temperature is reached, it can be increased to 50% by volume in one or more steps or gradually.

[0242] The reduction is preferably carried out in a muffle furnace, a rotary kiln, a tunnel kiln or a moving or fixed reduction oven.

[0243] The catalyst precursor is preferably also reduced in a reactor, where the catalyst precursor is arranged as a fixed bed. It is particularly preferred to reduce the catalyst precursor in the same reactor in which the subsequent reaction of MEG and / or MEA with NH3 is carried out.

[0244] Furthermore, the catalyst precursor may be reduced in a fluidized bed reactor, in a fluidized bed.

[0245] The catalyst precursor is generally reduced at a reduction temperature of 50 to 600 °C, particularly 100 to 500 °C, more preferably 150 to 450 °C, and particularly preferably 200 to 300 °C.

[0246] The hydrogen partial pressure is generally from 1 to 300 bar, in particular from 1 to 200 bar, more preferably from 1 to 100 bar, and the pressure values here and below relate to the pressure measured in absolute terms.

[0247] The duration of the reduction is generally determined by the size and shape of the reactor and is generally carried out only at a rate such that a significant temperature rise in the reactor is avoided. This means that depending on the shape and size of the reactor, the reduction can take from several hours to several weeks.

[0248] During the reduction, the solvent can be supplied in order to remove the water of the reaction formed, and / or to enable, for example, more rapid heating of the reactor, and / or to enable good removal of the heat during the reduction. The solvent can also be supplied here in supercritical form.

[0249] Suitable solvents that can be used are the solvents described above. Preferred solvents are water; ethers such as methyl tert-butyl ether, ethyl tert-butyl ether, dioxane or tetrahydrofuran. Water or tetrahydrofuran is particularly preferred. Suitable solvents also include suitable mixtures.

[0250] [[ID=1৬]]After the reduction, the reduced catalyst can be brought into direct contact with reactants such as MEG, MEA and NH3. This is particularly advantageous when the reduction is carried out in a reactor in which the subsequent conversion of MEG and / or MEA is also carried out.

[0251] Alternatively, the catalyst reduced in this way is handled under inert conditions after the reduction. The catalyst precursor can preferably be handled and stored under an inert gas such as nitrogen, or an inert liquid such as alcohol, water, or the product of the particular reaction in which the catalyst is used. In this case, it may be necessary to remove the inert liquid from the catalyst before the actual start of the reaction. The storage of the catalyst under an inert substance enables the safe and uncomplicated handling and storage of the catalyst.

[0252] Passivation: After reduction, the catalyst may be contacted with a gas stream containing oxygen, such as air or a mixture of air and nitrogen.

[0253] Thereby, a passivated catalyst is obtained. The passivated catalyst generally has a protective oxide layer. This protective oxide layer simplifies the handling and storage of the catalyst, and as a result, for example, the installation of the passivated catalyst into a reactor is simplified.

[0254] In passivation, after the reduction step, the reduced catalyst is contacted with an oxygen-containing gas, preferably air.

[0255] The oxygen-containing gas can be used while adding an inert gas, such as nitrogen, helium, neon, argon or carbon dioxide. In a preferred embodiment, air is used together with nitrogen, and the volume ratio of air is preferably in the range of 1% to 80% by volume, more preferably 20% to 70% by volume, and particularly preferably 30% to 60% by volume. In a preferred embodiment, the volume ratio of air in the mixture with nitrogen is gradually increased from 0% to about 50% by volume.

[0256] Passivation is preferably carried out at a temperature up to 50 °C, preferably up to 45 °C, and most preferably up to 35 °C.

[0257] Activation: Before contacting with the reactants, the passivated catalyst is preferably reduced by treating the passivated catalyst with hydrogen or a gas containing hydrogen. The conditions in activation generally correspond to the reduction conditions used for reduction. Activation generally removes the protective passivation layer.

[0258] Reactants: According to the present invention, the conversion of ethylene glycol (EG) and / or monoethanolamine (MEA) of the present invention, and ammonia (NH3) is carried out in the presence of an amination catalyst reduced or activated in the liquid phase.

[0259] Ethylene glycol: The ethylene glycol used for the amination of MEG in the present invention is preferably industrial ethylene glycol having a purity of at least 98%, most preferably ethylene glycol having a purity of at least 99%, and most preferably at least 99.5%.

[0260] The ethylene glycol used in the process can be prepared from ethylene obtainable from petrochemical processes. For example, generally, ethene is oxidized to ethylene oxide in a first step, which is then reacted with water to obtain ethylene glycol. The obtained ethylene oxide can, alternatively, be reacted with carbon dioxide in the so-called omega process to obtain ethylene carbonate, which can then be hydrolyzed with water to obtain ethylene glycol. The omega process is characterized by a higher selectivity for ethylene glycol since fewer by-products, such as di- and triethylene glycol, are formed.

[0261] The ethylene used for the preparation of MEG can, alternatively, be prepared from renewable raw materials. For example, ethylene can be formed by the dehydration of bioethanol.

[0262] Ethylene glycol can also be prepared via the syngas route, for example, by the oxidative carbonylation of methanol to form dimethyl oxalate and subsequent hydrogenation thereof. Thus, petrochemical raw materials that can also be considered for the preparation of MEG are natural gas or coal.

[0263] MEA: MEA can also be used in the method of the present invention.

[0264] MEA can be prepared by reacting ethylene oxide with ammonia as described above.

[0265] Preferably, MEA can be prepared by reacting MEG with ammonia. For example, by the method of the present invention, MEG is first reacted with ammonia, the MEA formed in addition to EDA is separated from EDA, and the separated MEA can be recycled to the preparation method of the present invention, optionally together with unreacted MEG.

[0266] When MEA is used in the method of the present invention without MEG, MEA is preferably used with a purity of at least 97%, most preferably at least 98%, most preferably at least 99%.

[0267] When MEA is used together with MEG in the method of the present invention, the weight ratio of MEA with respect to the mass of MEA and MEG is preferably in the range of 0 wt% to 60 wt%, more preferably 10 wt% to 50 wt%, most preferably 20 wt% to 40 wt%.

[0268] Ammonia: According to the present invention, ethylene glycol and / or monoethanolamine are reacted with ammonia.

[0269] The ammonia used can be conventional commercially available ammonia, for example, ammonia having a content of more than 98% by weight, preferably more than 99% by weight, preferably more than 99.5% by weight, specifically more than 99.8% by weight.

[0270] Hydrogen: The method of the present invention is preferably carried out in the presence of hydrogen.

[0271] Hydrogen is generally used at technical grade purity. Hydrogen can be used in the form of a gas containing hydrogen, i.e., with the addition of other inert gases such as nitrogen, helium, neon, argon, or carbon dioxide. The gas containing hydrogen used can be, provided that these gases do not contain any catalyst poisons for the catalyst used, such as CO, and provided they do not contain, for example, reformed off-gas, refinery gas, etc. However, it is preferred to use pure hydrogen or essentially pure hydrogen in the process, for example, hydrogen having a hydrogen content of more than 99% by weight, preferably more than 99.9% by weight, more preferably more than 99.99% by weight, especially more than 99.999% by weight.

[0272] Reaction in the liquid phase: According to the present invention, ethylene glycol is reacted with ammonia and an amination catalyst in the liquid phase.

[0273] In connection with the present invention, "reaction in the liquid phase" means that the reaction conditions, such as pressure and temperature, are adjusted so that ethylene glycol is present in the liquid phase and flows around the amination catalyst in liquid form.

[0274] The reaction of MEG and / or with ammonia can be carried out continuously or batch by batch. A continuous reaction is preferred.

[0275] Reactor: A reactor suitable for the reaction in the liquid phase is generally a tubular reactor. The catalyst can be arranged as a moving bed or a fixed bed in the tubular reactor.

[0276] It is particularly preferred to react ethylene glycol and / or monoethanolamine with NH3 in a tubular reactor in which the amination catalyst is arranged in the form of a fixed bed.

[0277] When the catalyst is arranged in the form of a fixed bed, mixing the catalyst with an inert random packing can, so to speak, "dilute" the catalyst in the reactor, which can be advantageous for the selectivity of the reaction. The proportion of the random packing in such a catalyst preparation can be 20 to 80, preferably 30 to 60, more preferably 40 to 50 parts by volume.

[0278] Alternatively, the reaction is preferably carried out in a shell and tube reactor or a once-through plant. In a once-through plant, the tubular reactor in which the reaction is carried out can consist of a series connection of a plurality (for example, 2 or 3) of individual tubular reactors. Advantageous options that can be considered here are the intermediate introduction of the feed (containing reactants and / or ammonia and / or H2) and / or the recycle gas and / or the reactor effluent from the downstream reactor.

[0279] Reaction conditions: When carried out in the liquid phase, MEG and / or ammonia in addition thereto are generally introduced simultaneously in the liquid phase containing hydrogen, on the catalyst, typically in a fixed bed reactor preferably heated externally, at a pressure generally of 5 to 30 MPa (50 to 300 bar), preferably 5 to 25 MPa, more preferably 15 to 25 MPa, and generally at a temperature of 80 to 350 °C, in particular 100 to 300 °C, preferably 120 to 270 °C, more preferably 130 to 250 °C, especially 160 to 230 °C.

[0280] The hydrogen partial pressure is preferably 0.25 to 20 MPa (2.5 to 200 bar), more preferably 0.5 to 15 MPa (5 to 150 bar), even more preferably 1 to 10 MPa (10 to 100 bar), and particularly preferably 2 to 5 MPa (20 to 50 bar).

[0281] Reactor feed: MEG and / or MEA and ammonia are preferably fed to the reactor in liquid form and contact the amination catalyst in liquid form.

[0282] A trickle mode or a liquid phase mode can be considered.

[0283] Even before the reactants are fed into the reaction vessel, it is advantageous to heat the reactants, preferably to the reaction temperature.

[0284] Ammonia is preferably used in a molar amount of from 0.90 to 100 times, especially from 1.0 to 20 times, the molar amount of MEG or MEA used in each case.

[0285] The catalyst hourly space velocities are generally in the range of from 0.05 to 0.5, preferably from 0.1 to 2, more preferably from 0.2 to 1 kg (MEG + MEA) per kg of catalyst and per hour.

[0286] At the stated catalyst hourly space velocities, the conversion rate of MEG or MEA is generally in the range of from 20% to 75%, preferably from 30% to 60%, most preferably from 35% to 65%.

[0287] During the course of the reaction, the water of reaction formed, 1 mol per mol of alcohol groups converted in each case, generally has no detrimental effect on the degree of conversion, the reaction rate, the selectivity or the catalyst life, so that it is beneficially removed from the reaction product only when the product is worked up, for example by distillation.

[0288] Reactor effluent: The effluent from the amination reactor or the reactor effluent contains the products of the amination reaction, unconverted reactants such as ethylene glycol and ammonia, and also hydrogen and water.

[0289] As products of the amination reaction, the effluent from the amination reactor also contains the corresponding ethanolamines and / or ethyleneamines based on MEG.

[0290] The effluent from the amination reactor preferably contains MEA and / or EDA.

[0291] As a product from the amination reaction, the reaction effluent preferably has the general formula R-CH2-CH2-NH2 (wherein R is a group of the formula -(NH-CH2-CH2) X -NH2, and x is an integer in the range of 1 to 4, preferably 1 to 3, and most preferably 1 to 2) and also includes higher linear ethyleneamines. Preferably, the reaction effluent contains DETA, TETA, and TEPA, more preferably DETA and TETA, and most preferably DETA.

[0292] As a product of the amination reaction, the effluent from the amination reactor has the formula R-CH2-CH2-OH (wherein R is a group of the formula -(NH-CH2-CH2) X -NH2, and x is an integer in the range of 1 to 4, preferably 1 to 3, and most preferably 1 to 2) and may also include higher linear ethanolamines.

[0293] An example of a higher linear ethanolamine is AEEA.

[0294] As a product of the amination reaction, the reaction effluent has the formula

[0295]

Chemical formula

[0296] As a product of the amination reaction, the reaction effluent has the general formula

[0297]

Chemical formula

[0298] Examples of the cyclic ethyleneamine present in the reaction effluent are piperazine and AEPIP.

[0299] The effluent preferably contains 1 wt% to 60 wt% of MEA, 1 wt% to 90 wt% of EDA, 0.1 wt% to 30 wt% of higher cyclic ethyleneamines such as PIP and AEPIP, and 0.1 wt% to 30 wt% of higher linear ethyleneamines such as DETA, TETA, and TEPA.

[0300] More preferably, the effluent contains 10 wt% to 50 wt% of MEA, 25 wt% to 85 wt% of EDA, 0.25 wt% to 10 wt% of cyclic ethyleneamines such as PIP and AEPIP, and 1 wt% to 30 wt% of higher linear ethyleneamines such as DETA, TETA, and TEPA.

[0301] Most preferably, the effluent contains 15 wt% to 45 wt% of MEA, 30 wt% to 70 wt% of EDA, 0.5 wt% to 5 wt% of cyclic ethyleneamines such as PIP and AEPIP, and 5 wt% to 25 wt% of higher linear ethyleneamines such as DETA, TETA, and TEPA.

[0302] The method of the present invention can achieve a selectivity index SQ of 1.5 or more, preferably 4 or more, more preferably 8 or more. This means that the product ratio of the desired linear ethyleneamines and ethanolamines, such as MEA and EDA, to the undesired cyclic ethyleneamines and undesired higher ethanolamines, such as PIP and AEEA, can be increased by the method of the present invention.

[0303] The effluent is generally post-treated so that the different components are separated from each other.

[0304] For this purpose, the reaction effluent is appropriately depressurized.

[0305] Components that are in gaseous form after depressurization, such as hydrogen and inert gases, are generally separated from the liquid components in a gas-liquid separator. The gaseous components can be recycled into the amination reactor individually (after further post-treatment steps) or together.

[0306] After hydrogen and / or inert gases are separated, the effluent from the amination reactor optionally contains ammonia, unreacted ethylene glycol, water, and the amination product.

[0307] Preferably, the effluent from the amination reactor is separated in two separation sequences, each separation sequence including multi-stage distillation. Such post-treatment is described, for example, in EP-B1-198699. Thus, in the first separation sequence, water and ammonia are first separated, and in the second separation sequence, it is separated into unreacted MEG, and MEA, EDA, PIP, DETA, AEEA, and higher ethyleneamines. In this case, components with lower and higher boiling points compared to the azeotropic mixture of MEG and DETA are first removed, and then the mixture concentrated in MEG and DETA is separated into the stream containing MEG and DETA by extractive distillation using triethylene glycol (TEG) as a selective solvent.

[0308] MEA can be recycled partially or completely into the process of the invention, together with or separately from unconverted MEG.

[0309] Advantages: In the process of the invention, it is possible to convert MEG with high selectivity to the linear amination products MEA and EDA, but with low selectivity to the cyclic amination products PIP and the higher ethanolamine AEEA.

[0310] The measurement of this effect is the selectivity index SQ, which is defined as the quotient of the sum of the selectivities to DETA and EDA and the sum of the selectivities to PIP and AEEA (SQ = (S(DETA) + S(EDA)) / (S(PIP) + S(AEEA)).

[0311] Achieving a high selectivity index SQ is industrially advantageous because the market demand for the linear amination products MEA and EDA and their higher homologues, such as DETA and TETA, is higher than the demand for PIP or AEEA.

[0312] Furthermore, the process of the invention forms undesirable by-products at lower levels. Undesirable by-products are, for example, gaseous decomposition products or insoluble or poorly soluble oligomers and polymers based on MEA and EDA. The formation of such by-products results in a decrease in the carbon balance and thus a decrease in the economic viability of the process. The formation of poorly soluble or insoluble by-products can cause deposition on the amination catalyst, thereby reducing the activity of the amination catalyst.

[0313] The process of the invention also reduces the amount of N-methylethylenediamine (NMEDA). NMEDA is an undesirable by-product. In many industrial applications, a purity of EDA with a proportion of NMEDA less than 500 ppm by weight is specified.

[0314] Furthermore, the catalyst precursor used in the process of the invention has been found to have high activity in the process, so that a favorable space-time yield can be achieved.

[0315] Generally, the method of the present invention can achieve an advantageous spectrum of properties regarding total selectivity, selectivity index, activity and the formation of unwanted by-products.

Example

[0316] The present invention is illustrated by the following examples:

[0317] [Example 1] Preparation of the catalyst precursor (step a)) The catalyst precursor was obtained according to Example B3 of WO2013 / 072289. The tablets (3×3 mm) thus obtained were crushed into small pieces with a size of 1 to 2 mm. The solvent capacity SC of the small pieces with respect to water was determined to be 0.29 ml / g.

[0318] [Examples 2 to 13] Preparation of the catalyst by post-impregnation of the catalyst precursor prepared in Example 1 (step b)) The aqueous metal salt solution (impregnation solution) was prepared according to Table 1 and used for the post-impregnation of the catalyst precursor obtained in Example 1. The metal content of the aqueous metal salt solution was as follows: Perrhenic acid: 50 g Re per 100 g Nitrosyl ruthenium nitrate: 20 g Ru per 100 g Cobalt(II) nitrate hexahydrate: 20 g Co per 100 g.

[0319] The impregnation solution was obtained by mixing the aqueous metal salt solutions of each metal in the amounts described in columns 2 to 4 of Table 1 and adding additional water to obtain an impregnation solution having the total volume set in column 5 of Table 1.

[0320] Post-impregnation was carried out in the impregnation apparatus by the initial wetting method, and each impregnation solution was added to the apparatus in an amount corresponding to x% of the solvent volume SC determined in Example 1 (see column 9 of Table 1). The post-impregnated chips were rotated in the impregnation apparatus for 30 minutes to achieve homogeneous absorption of the metal salt solution by the chips. In the case of one-step post-impregnation, the post-impregnated chips were then dried in a drying chamber at 120 °C for 16 hours. In the case of two-step post-impregnation, before the second post-impregnation step, the post-impregnated chips obtained during the first post-impregnation step were dried in the impregnation apparatus at 120 °C for 4 hours under water jet vacuum. The second post-impregnation step was also carried out by the initial wetting method by adding an amount of metal salt solution corresponding to x% of the solvent volume determined in Example 1 (see column 9 of Table 1). The drying step after the second post-impregnation step was carried out at 120 °C for 4 hours under water jet vacuum.

[0321] The theoretical metal content of the catalyst precursor after the last drying step is depicted in columns 6 to 8 of Table 1.

[0322]

Table 1

[0323] The catalyst precursor obtained by this means was reduced by reduction calcination according to Comparative Example 4 in WO2018 / 224316 and then passivated as in WO2018 / 224316, Comparative Example 1.

[0324] Testing of the catalyst: The testing of the catalyst was carried out as described in WO2018 / 224316, page 37, except that the test was carried out at a temperature of 170 °C and a catalyst space velocity in the range of 0.3 to 0.6 kg / l / h (see column 3 of Table 2).

[0325] The results of the tests are summarized in Table 2.

[0326] For better comparison, the test results at different space velocities (selectivity S of each product) were evaluated by linearly interpolating the measured values that depend on the loadings in the ranges of 25 to 35% conversion and 35 to 45% conversion to a conversion of 35%.

[0327]

Table 2

[0328] It is clear that the post-impregnation with Co and Ru of the catalyst precursor (Comparative Example 12) already increased the selectivity index SQ (SQ = (S(DETA)+S(EDA)) / (S(PIP)+S(AEEA)) from 3.8 to 4.4 compared to the non-impregnated catalyst precursor (Comparative Example 13).

[0329] The increase in SQ corresponds to an increase in the total selectivity of the desired products EDA and DETA, as well as a decrease in the total selectivity of the undesired products PIP and AEEA.

[0330] When the post-impregnation is carried out with Re (Example 11) instead of Co and Ru, it becomes clear that the SQ further increases from 4.4 to 4.7 when post-impregnated with Re without post-impregnation with Co and Ru.

[0331] When the post-impregnation is carried out with Re combined with Ru and Co (Examples 2 to 10), a further increase in SQ to a value of up to 5.6 is achieved.

Claims

1. A method for preparing alkanolamines and ethyleneamines in a liquid phase by reacting ethylene glycol and / or monoethanolamine with ammonia in the presence of an amination catalyst obtained by reducing a catalyst precursor, wherein the preparation of the catalyst precursor includes step a) of preparing a catalyst precursor containing one or more catalyst active components selected from Sn, Cu, and Ni, and step b) of contacting the catalyst precursor prepared in step a) with a soluble Re compound.

2. The method according to claim 1, wherein the catalyst precursor prepared in step a) further contains a catalyst active component of Co.

3. The method according to claim 1 or 2, wherein in step a), the catalyst precursor is prepared by coprecipitation, and in each case, based on the total mass of the catalyst precursor, it contains catalyst active components of Sn, Cu, and / or Ni in the range of 1 wt% to 95 wt% calculated as CuO, NiO, and SnO, respectively.

4. The method according to claim 1 or 2, wherein the catalyst precursor is prepared by precipitation application in step a), and in each case, based on the total mass of the catalyst precursor, it contains a carrier material in the range of 5 wt% to 95 wt% and catalyst active components of Sn, Cu, and / or Ni in the range of 5 wt% to 90 wt% calculated as CuO, NiO, and SnO, respectively.

5. The method according to claim 1 or 2, wherein the catalyst precursor is prepared by impregnation in step a), and in each case, based on the total mass of the catalyst precursor, it contains a carrier material in the range of 50 wt% to 99 wt% and catalyst active components of Sn, Cu, and / or Ni in the range of 1 wt% to 50 wt% calculated as CuO, NiO, and SnO, respectively.

6. The catalyst precursor prepared in step a) contains, based on the total mass of the catalyst precursor - a catalyst active component of tin in the range of 0.2 wt% to 5 wt% calculated as SnO, - a catalyst active component of copper in the range of 1 wt% to 20 wt% calculated as CuO, - a catalyst active component of nickel in the range of 5 wt% to 35 wt% calculated as NiO, and - a catalyst active component of cobalt in the range of 5 wt% to 35 wt% calculated as CoO, and - Al 2 O 3 calculated as, the catalytically active component of aluminum as a carrier material of 15% to 80% by weight The method according to claim 2 or 4.

7. The method according to claim 6, wherein the catalyst precursor is prepared in the presence of tin nitrate and a complexing agent.

8. In step b), the catalyst precursor is post-impregnated with an impregnation solution containing a soluble Re compound, wherein the Re concentration in the impregnation solution ranges from 0.1 to 50% by weight, so that the catalyst precursor is brought into contact with the soluble Re compound. The method according to any one of claims 1 to 7.

9. In step b), the catalyst precursor is brought into contact with a soluble compound of an active metal other than Re and / or an added catalyst element. The method according to any one of claims 1 to 8.

10. In step b), the catalyst precursor is post-impregnated with an impregnation solution containing a soluble Ru compound and / or a soluble Co compound, wherein the Ru concentration in the impregnation solution ranges from 0.1 to 50% by weight, and / or the Co concentration in the impregnation solution ranges from 0.1 to 20% by weight, so that the catalyst precursor is brought into contact with the soluble Ru compound and / or the soluble Co compound. The method according to any one of claims 1 to 9.

11. After step b), before reduction of the catalyst precursor, the catalyst precursor is dried to obtain an aminated catalyst. The method according to any one of claims 1 to 10.

12. After the last drying step, the catalyst precursor contains, calculated as ReO with respect to the total mass of the catalyst precursor, from 0.1% to 20% by weight of the catalytically active component Re. 3 The method according to claim 11, wherein the catalyst precursor contains from 0.1% to 20% by weight of the catalytically active component Re, calculated as ReO with respect to the total mass of the catalyst precursor after the last drying step.

13. After the last drying step, the catalyst precursor contains a catalytically active component of Co of 0.1% to 50% by weight calculated as CoO, based on the total mass of the catalyst precursor, and / or after the last drying step, the catalyst precursor contains a catalytically active component of Ru of 0.1% to 50% by weight calculated as RuO 2 The method according to claim 11 or 12, wherein the catalyst precursor contains a catalytically active component of Ru of 0.1% to 50% by weight calculated as RuO, based on the total mass of the catalyst precursor, after the last drying step.

14. Before subjecting the catalyst precursor to step b), the catalyst precursor prepared in step a) is further processed by performing one or more of the following aa) liquid separation, ab) washing, ac) drying, ad) calcination, and ae) shaping processing steps. The method according to any one of claims 1 to 13.

15. The reaction of ethylene glycol and / or monoethanolamine with ammonia is carried out in the liquid phase at a pressure of 5 to 30 MPa and a temperature in the range of 80 to 350 °C. The method according to any one of claims 1 to 15.

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