阅读说明：本技术 制备亚乙基胺的方法 (Process for preparing ethyleneamines ) 是由 R·H·贝本塞 T·海德曼 B·贝克尔 E·科赫 H·鲁肯 J-P·梅尔德 于 2018-05-24 设计创作，主要内容包括：本发明涉及一种在液相中制备链烷醇胺和/或亚乙基胺的方法,包括使乙二醇和/或单乙醇胺与氨在包含一种或多种选自Sn和元素周期表第8、9、10和11族元素的活性金属的胺化催化剂存在下反应。所述制备链烷醇胺和/或亚乙基胺的方法的特征在于,胺化催化剂是通过催化剂前体的还原煅烧方法获得的。催化剂前体优选通过使常规或催化载体材料与一种或多种活性金属的可溶化合物以及任选地一种或多种催化剂添加剂元素的可溶化合物接触而制备。本发明进一步涉及一种制备胺化催化剂的方法,所述胺化催化剂包含一种或多种选自Sn和元素周期表第8、9、10和11族元素的活性金属,其中所述胺化催化剂通过催化剂前体的还原煅烧方法获得。所述制备胺化催化剂的方法的特征在于,在其中进行催化剂前体的还原煅烧方法的反应器连接至脱硝系统。本发明还涉及脱硝系统在胺化催化剂的制备中的用途。(The invention relates to a method for producing alkanolamines and/or ethyleneamines in the liquid phase, comprising reacting ethylene glycol and/or monoethanolamine with ammonia in the presence of an amination catalyst comprising one or more active metals selected from Sn and elements of groups 8, 9, 10 and 11 of the periodic Table of the elements. The method for producing alkanolamines and/or ethyleneamines is characterized in that the amination catalyst is obtained by a method of reductive calcination of a catalyst precursor. The catalyst precursor is preferably prepared by contacting a conventional or catalytic support material with soluble compounds of one or more active metals and optionally soluble compounds of one or more catalyst additive elements. The invention further relates to a process for preparing an amination catalyst comprising one or more active metals selected from Sn and elements of groups 8, 9, 10 and 11 of the periodic table of the elements, wherein the amination catalyst is obtained by a process of reductive calcination of a catalyst precursor. The method for preparing an amination catalyst is characterized in that a reactor in which a reductive calcination method of a catalyst precursor is performed is connected to a denitration system. The invention also relates to the use of the denitrification system in the preparation of amination catalysts.)

1. A process for preparing alkanolamines and/or ethyleneamines in the liquid phase comprising reacting ethylene glycol and/or monoethanolamine with ammonia in the presence of an amination catalyst comprising one or more active metals selected from Sn and elements of groups 8, 9, 10 and 11 of the periodic table of the elements, wherein the amination catalyst is obtained by reductive calcination of a catalyst precursor.

2. The process according to claim 1, wherein the catalyst precursor is prepared by contacting a conventional or catalytic support material with one or more soluble compounds of the active metal and optionally one or more soluble compounds of the added catalyst element.

3. The process according to claim 2, wherein the catalytic or conventional support material is contacted with soluble compounds of the active metals and optionally with soluble compounds of the added catalyst elements by soaking or impregnation.

4. A method according to any one of claims 1 to 3, wherein the one or more active metals are selected from Co, Ru, Sn, Ni and Cu.

5. The method according to any one of claims 1 to 4, wherein one of the one or more active metals is Ru or Co.

6. A process according to any one of claims 1 to 5, wherein the soluble compound of the active metal contacted with the support material is used partially or completely in the form of its nitrate or nitrosylnitrate.

7. A process according to any one of claims 2 to 5, wherein the support material comprises Al and/or Zr.

8. A process according to any one of claims 2 to 7 wherein the support material is contacted simultaneously or sequentially with a soluble Ru compound and a soluble Co compound, wherein the soluble cobalt compound is cobalt nitrate.

9. The process according to any one of claims 1 to 8, wherein the reactor in which the reductive calcination is carried out is a shaft reactor, a rotary furnace, a multi-layer furnace or a fluidized bed reactor.

10. The process of any of claims 1-9, wherein the reductive calcination is carried out in the presence of hydrogen.

11. A process according to any one of claims 1 to 10 wherein the oxygen content in the reduction is less than 0.1% by volume.

12. The process as claimed in any one of claims 1 to 11, wherein the temperature in the reductive calcination is 100-300 ℃.

13. The method of any one of claims 1 to 12, wherein the reductive calcination is carried out in a reactor connected to a denitrification facility.

14. The process as claimed in any of claims 1 to 13, wherein the catalyst is passivated and activated after the reductive calcination and the temperature in the activation is 100-300 ℃.

15. A method for producing an amination catalyst comprising one or more active metals selected from Sn and elements of groups 8, 9, 10 and 11 of the periodic table, the amination catalyst being obtained by reductive calcination of a catalyst precursor, wherein a reactor in which the catalyst precursor is subjected to reductive calcination is connected to a denitration device.

16. A process according to claim 21, wherein the reductive calcination is carried out according to any one of claims 9 to 14.

17. The method according to claim 15 or 16, wherein the denitration unit is configured as a scrubbing or a selective catalytic reduction.

18. Use of a denitration device in the preparation of an amination catalyst.

The prior art discloses that the reaction of MEG with ammonia to EDA can be carried out in the liquid or gas phase.

Two chinese applications CN 102190588 and CN 102233272 disclose the amination of MEG in the gas phase.

For example, CN 102190588 describes the one-step conversion of MEG and ammonia in the presence of a Cu catalyst. The reaction pressure is, as stated, from 3 to 30 bar. The reaction temperature is 150-350 ℃.

Application CN 102233272 discloses the reaction of MEG with ammonia in the gas phase over a catalyst comprising Cu and Ni as main components and Zr, Zn, Al, Ti, Mn and Ce as minor components. However, the composition of the resulting reaction mixture is not disclosed.

As an alternative to gas phase conversion, the reaction of MEG with ammonia and hydrogen can also be carried out in the liquid phase. However, the reaction characteristics of the catalyst in the gas and liquid phases are usually quite different and therefore it is generally not allowed to apply the conclusions drawn from the reaction characteristics of MEG in the gas phase to the reaction characteristics of MEG in the liquid phase.

An overview of the metal-catalyzed amination of MEG in the liquid Phase is given in the diapom paper "kinetics study of metal-catalyzed amination of ethylene glycol in the liquid Phase" for the reaction kinetics of ethylene glycol in the liquid Phase ", the carbonstituent of methylene in fl ü ssigen Phase", the "reaction kinetics study of metal-catalyzed amination of ethylene glycol in the liquid Phase", the "carbonstituent of methylene in fl ü ssigen Phase", the "dipom paper, the Carl von osidezkyy University of Oldenburg, date 03.17.2000.

Ihmels, i, investigated the conversion of MEG over a supported cobalt/silica catalyst. Amination to give the desired MEA and EDA target products was unsuccessful. In contrast, a highly polymerized reaction product is formed. Under milder conditions MEG is not yet fully converted and the desired products MEA and EDA are obtained in low yield. The main product is an oligomeric compound.

US 4,111,840 discloses the reaction of MEG with ammonia and hydrogen over a supported Ni/Re catalyst at a pressure of 500-5000psig (about 34-340 barg). The catalyst was calcined at 300-500 ℃ prior to reduction. It is disclosed that the calcination can be carried out under an inert atmosphere.

US 3,137,730 discloses the reaction of MEG with ammonia in the liquid phase over a Cu/Ni catalyst at temperatures of 200 ℃. and pressures above 1000psig (about 69 bar). In the examples, the catalyst was calcined at a temperature of 400 ℃ and 800 ℃.

DE 1172268 discloses the conversion of ethylene glycol over a catalyst comprising at least one of the metals Cu, Ag, Mn, Fe, Ni and Co. In one embodiment, MEG is reacted with ammonia at 180 ℃ and 300 bar pressure in the presence of hydrogen over a Co catalyst. The catalyst is prepared by sintering suitably at a temperature above 700 ℃.

WO 2007/093514 discloses a two-step process for the preparation of EDA, wherein in a first process step, the amination is carried out over a hydroamination catalyst until the MEA conversion does not exceed 40%; in a second process step, a supported Ru/Co catalyst shaped body with a small geometry is used and the second step is carried out at a temperature at least 10 ℃ higher than the first process step. The catalyst was calcined at 200 ℃ and 500 ℃. In the examples, the calcination is carried out in the presence of air.

WO 2013072289 discloses the reaction of alcohols with nitrogen compounds over catalysts which contain the element Sn in addition to Al, Cu, Ni and Co. Preferred alcohols mentioned are ethylene glycol and monoethanolamine. Calcination is typically carried out at a temperature of 300-800 ℃. In one embodiment, air is passed through the calcination.

WO 2011067200 likewise discloses catalysts for the amination of alcohols, which comprise Sn. The catalyst described therein contains not only Sn but also the elements Co, Ni, Al and Cu. Calcination is typically carried out at a temperature of 300-800 ℃.

WO 200908051, WO 2009080508, WO 200006749 and WO 20008006750 disclose further catalysts for the amination of alcohols. The catalyst contains not only Zr and Ni but also Cu, Sn, Co and/or Fe. The other components are elements such as V, Nb, S, O, La, B, W, Pb, Sb, Bi and In.

WO 96/38226 discloses catalysts for alcohol amination comprising Re, Ni, Co, B, Cu and/or Ru. In one embodiment, SiO₂NH for supports₄ReO₄Nitric acid Ni, H₃BO₃Co nitrate and Cu nitrate, followed by calcination. In a further impregnation step, the calcined and impregnated support is impregnated with Ru chloride. Before the reduction, calcination is optionally carried out at 200-500 ℃, wherein according to the disclosure the calcination is preferably carried out in the presence of air.

US 4,701,434 and US 4,855,505 disclose the amination of MEG and MEA in the presence of a catalyst comprising Ni and/or Co and Ru. This involves contacting a catalyst precursor comprising Ni oxide and/or Co oxide with a halogenated Ru, for example Ru chloride, which is then reduced in a hydrogen stream. According to this disclosure, the calcination of the catalyst precursor is carried out in an air stream at 300-600 ℃. The subsequent reduction of the Ru-halide treated catalyst precursor is carried out in two steps, first at 150-300 ℃ and second at a temperature of up to 300-600 ℃.

EP 0839575 discloses a catalyst comprising Co, Ni and mixtures thereof and Ru on a porous metal oxide support. The catalyst is prepared by impregnating a support with a metal, drying and calcining the impregnated support and reducing the calcined support in a hydrogen stream. It is further disclosed that the support may be impregnated with the metal compound in any order. In one example, the support is first impregnated with a solution of Ni nitrate, Co nitrate and Cu nitrate, then calcined and further impregnated with an aqueous solution of Ru nitrate and calcined again at 400 ℃.

US 5,958,825 discloses a catalyst comprising Ni and Co and Ru, which is prepared by impregnation of a support material and subsequent drying and calcination of the impregnated catalyst. In example 1 of US 5,958,825, the alumina support was first impregnated with NiO, CoO and CuO and, after calcination at 400 ℃, the catalyst precursor was sprayed with a solution of Ru nitrate. The catalyst precursor obtained in this way was dried and calcined at 400 ℃.

It is 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.

More particularly, the formation of the valuable products, i.e. those ethanolamines or ethyleneamines of high commercial significance, especially MEA and EDA, will be promoted, and the formation of cyclic ethyleneamines, especially PIP, and higher ethanolamines, especially AEEA, will be kept at low levels, since the commercial demand for PIP or AEEA is lower than for EDA and MEA.

More particularly, the concentration of certain undesired by-products, such as NMEDA, NEEDA and Ethylamine (EA), will also decrease. The volatility of NMEDA is hardly different from EDA, so that the two components can only be separated with a high degree of separation complexity. It is therefore advantageous to form only even small amounts of NMEDA in the preparation. Conventional product specifications for EDA require that less than 500ppm of NMEDA be present in EDA.

Furthermore, the catalyst should also have a high activity and be able to achieve high MEG conversion in order to achieve good space-time yields.

Overall, a good performance spectrum relating to the overall selectivity, the selectivity quotient and the formation of undesired by-products is thus obtained.

The object of the invention is achieved by a process for preparing alkanolamines and ethyleneamines in the liquid phase, which comprises reacting ethylene glycol and/or monoethanolamine with ammonia in the presence of an amination catalyst comprising one or more active metals selected from Sn and elements of groups 8, 9, 10 and 11 of the periodic table of the elements, wherein the amination catalyst is obtained by reductive calcination of a catalyst precursor.

It has surprisingly been found that reductive calcination of an amination catalyst according to the invention at MEG with NH₃Has high selectivity to linear amination products MEA and EDA, and low selectivity to cyclic amination products PIP and higher ethanolamine AEEA.

Furthermore, it has been found that the catalysts of the invention form lower levels of undesirable by-products, such as NMEDA. Furthermore, it has been found that the amination catalysts used in the process of the invention have a high activity for the conversion of MEG and therefore enable high space-time yields in the conversion.

In preparing an amination catalyst suitable for use in the reaction of the present invention by reductive calcination, reductive calcination of the catalyst precursor may produce nitrogen oxides, which may form an explosive mixture. Especially in the preparation of catalyst precursors, nitrogen oxides can be formed when catalytic or non-catalytic support materials have been contacted with nitrates or nitrosyl nitrates of active metals or added catalyst elements during preparation.

It is therefore also an object of the present invention to provide a process for preparing amination catalysts which meets high safety standards.

The object is achieved by a process for preparing an amination catalyst comprising one or more active metals selected from the group consisting of Sn and elements of groups 8, 9, 10 and 11 of the periodic table of the elements, wherein the amination catalyst is obtained by reductive calcination of a catalyst precursor, wherein a reactor in which the catalyst precursor is subjected to reductive calcination is connected to a denitrification apparatus.

The following abbreviations are used above and below:

AEEA: aminoethylethanolamine

AEP: aminoethylpiperazines

DETA: diethylenetriamine

EA: ethylamine (ethylamine)

EDA (electronic design automation): ethylene diamine

EO: ethylene oxide

EDC: ethylene dichloride

HEP: hydroxyethyl piperazine

NEEDA: N-Ethylenediamine

NMEDA: n-methyl ethylenediamine

MEA: monoethanolamine

MEG: monoethylene glycol

PEHA: pentaethylenehexamine

PIP: piperazine derivatives

TEPA: tetraethylenepentamine

TETA: triethylenetetramine

Amination catalyst

By MEG and/or MEA with NH₃The process of the present invention for the reaction to produce an alkanolamine and an ethyleneamine is carried out in the presence of an amination catalyst.

Catalyst precursor

The amination catalyst is obtained by reductive calcination of the catalyst precursor.

Active composition

The catalyst precursor used comprises the active composition.

The active composition of the catalyst precursor comprises an active metal and optionally one or more added catalyst elements, and optionally one or more support materials.

Reactive metal

The active composition of the catalyst precursor comprises one or more active metals selected from the group consisting of Sn and elements of groups 8, 9, 10 and 11 of the periodic table of the elements.

Preferably, the active composition of the catalyst precursor comprises one or more active metals selected from Fe, Ru, Co, Ni, Cu and Sn.

Most preferably, the active composition of the catalyst precursor comprises one or more active metals selected from Ru, Co, Ni, Cu and Sn.

In a particularly preferred embodiment, one of the one or more active metals is Ru or Co.

In a very particularly preferred embodiment, one of the one or more active metals is Ru.

In a further very particularly preferred embodiment, the amination catalyst comprises one of the following combinations of active metals:

ru and Co;

ru and Sn;

ru and Cu;

ru and Ni;

ru and Co and Sn;

ru and Co and Cu;

ru and Co and Ni;

ru and Sn and Cu;

ru and Sn and Ni;

ru and Cu and Ni;

ru and Co and Sn and Cu;

ru and Co and Sn and Ni;

ru and Co and Sn and Cu and Ni;

co and Sn;

co and Cu;

co and Ni;

co and Sn and Cu;

co and Sn and Ni;

co and Cu and Ni; or

Co and Sn and Cu and Ni;

in a very particularly preferred embodiment, the amination catalyst comprises one of the following combinations comprising both Ru and Co:

ru and Co;

ru and Co and Sn;

ru and Co and Cu;

ru and Co and Ni;

ru and Co and Sn and Cu;

ru and Co and Sn and Ni;

ru and Co and Sn and Cu and Ni.

Added catalyst elements

The active composition of the catalyst precursor used in the process of the present invention may optionally comprise one or more added catalyst elements.

The added catalyst elements are metals or semimetals (excluding active metals) selected from groups 1 to 17 of the periodic table of the elements, the element P and rare earth metals.

Preferred additional catalyst elements are Zr, Al, Pb, Bi, Ce, Y and Mn.

Particularly preferred added catalyst elements are Zr, Al and Mn.

Very particularly preferred additional catalyst elements are Zr and Al.

Catalytically active component

In the catalyst precursor, the active metal and the added catalyst element are generally present in the form of their oxygen compounds, for example carbonates, oxides, mixed oxides or hydroxides of the added catalyst element or active metal.

The oxygen compounds of the active metal and the added catalyst elements are referred to hereinafter as catalytically active components.

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

Typically, the catalytically active component is converted into the catalytically active component by calcination from soluble compounds of the active metal or added catalyst element or from a precipitate of the active metal or added catalyst element, wherein the conversion is typically carried out by dehydration and/or decomposition.

Carrier material

The catalytically active composition may further comprise one or more support materials.

In the context of the present invention, a distinction is made between catalytic support materials and conventional support materials.

Conventional support materials

Conventional support materials are usually added catalyst elements which are used in solid form in the preparation of the catalyst precursor and on which the active metal and/or soluble compounds of the added catalyst elements are precipitated or impregnated with the active metal or soluble compounds of the added catalyst elements. Typically, conventional support materials are solids having a high surface area.

Conventional support materials used may be added catalyst element carbon, for example in the form of graphite, carbon black and/or activated carbon.

Preferred conventional support materials are the oxides of the added catalyst elements Al, Ti, Zn, Zr and Si or mixtures thereof, for example alumina (γ, δ, θ, α, κ, χ or mixtures thereof), titania (anatase, rutile, brookite or mixtures thereof), zinc oxide, zirconia, silica (for example silica, fumed silica, silica gel or silicates), aluminosilicates, minerals (for example hydrotalcites, chrysotiles and sepiolites).

Particularly preferred support materials are alumina or zirconia or mixtures thereof.

In a particularly preferred embodiment, the conventional support material is the median diameter d of the particles₅₀Alumina, zinc oxide or mixtures thereof in the range of 50-2000 μm, preferably 100-1000 μm, more preferably 300-700 μm. In a particularly preferred embodiment, the median diameter d of the particles₅₀Is 1 to 500. mu.m, preferably 3 to 400. mu.m, more preferably 5 to 300. mu.m. In a preferred working example, the standard deviation of the particle diameters is generally the median diameter d₅₀5 to 200%, preferably 10 to 100%, particularly preferably 20 to 80%.

Catalytic support material

In a very particularly preferred embodiment, the support material is a catalytic support material.

The catalytic support material is a solid comprising one or more active metals. The catalytic support material is in particular a compound which is itself prepared by coprecipitation, precipitation application or impregnation, is then generally worked up by separation, washing, drying and calcination, and is optionally converted by shaping steps into the desired shape and geometry described below.

Preparation of catalytic support materials

The catalytic support material can be prepared by known methods, for example by precipitation reactions (e.g. coprecipitation or precipitation application) or impregnation.

The catalytic support material may be prepared by co-precipitation of soluble compounds of the active metal or added catalyst elements with a precipitating agent. To this end, one or more soluble compounds of the corresponding active metal and optionally one or more soluble compounds of the added catalyst element are mixed in a liquid with a precipitant while heating and stirring until precipitation is complete.

The liquid used is usually water.

Soluble compounds of the active metals which may be used generally include the corresponding metal salts, for example the nitrates or nitrosylnitrates, chlorides, sulfates, carboxylates, especially the acetates or nitrates or nitrosylnitrates, of the abovementioned metals.

The soluble compounds of the added catalyst elements used are usually water-soluble compounds of the added catalyst elements, for example water-soluble nitrates or nitrosylnitrates, chlorides, sulfates, carboxylates, in particular acetates or nitrates or nitrosylnitrates.

The catalytic support material may also be prepared by precipitation application.

By precipitation application is understood a preparation method wherein one or more support materials, preferably conventional support materials, are generally suspended in a liquid, then soluble compounds of the active metals, for example soluble metal salts of the active metals, are suspended, and optionally added soluble compounds of the Catalyst elements, and these are then applied to the suspended support materials by precipitation application methods by adding a precipitating agent (as described, for example, in EP-a2-1106600, page 4 and ABStiles, Catalyst Manufacture, Marcel Dekker, inc., 1983, page 15).

The soluble compounds of the active metals or of the added catalyst elements used are generally water-soluble compounds of the active metals or of the added catalyst elements, for example water-soluble nitrates or nitrosylnitrates, chlorides, sulfates, carboxylates, in particular acetates or nitrates or nitrosylnitrates.

The support material used in the deposit application can be used, for example, in the form of chips, powders or shaped bodies, such as wires, flakes, spheres or rings. Preference is given to using support materials which already have the preferred shape and geometry of the shaped bodies described below (see section "shape and geometry of support materials").

In general, in the precipitation reaction, soluble compounds of the active metals or added catalyst elements are precipitated as sparingly soluble or insoluble basic salts by addition of a precipitating agent.

The precipitating agent used is preferably a base, especially an inorganic base, for example an alkali metal base. Examples of precipitants are sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide.

The precipitant used may also be an ammonium salt, for example an ammonium halide, ammonium carbonate, ammonium hydroxide or ammonium carboxylate.

The precipitation reaction can be carried out, for example, at temperatures of from 20 to 100 deg.C, in particular from 30 to 90 deg.C, in particular from 50 to 70 deg.C.

The precipitates obtained in the precipitation reaction are usually chemically inhomogeneous and usually comprise mixtures of the oxides, oxide hydrates, hydroxides, carbonates and/or bicarbonates of the metals or semimetals used. In terms of filterability of the precipitates, it may prove advantageous to age them — meaning that they are left to stand for a certain time after precipitation, optionally under hot conditions or with the passage of air.

Catalytic support materials can also be prepared by impregnating the support material with active metals or soluble compounds of added catalyst elements (impregnation).

The support material used in the impregnation can be used, for example, in the form of chips, powder or shaped bodies, such as wires, flakes, spheres or rings. Preference is given to using support materials which already have the preferred shape and geometry of the shaped bodies described below (see section "shape and geometry of support materials").

The above-mentioned support materials can be impregnated by conventional methods ((a.b. stiles, Catalyst management-Laboratory and Commercial Preparations, Marcel Dekker, new york, 1983), for example by applying salts of active metals or salts of added Catalyst elements in one or more impregnation steps.

Useful salts of the active metal or added catalyst element generally include water-soluble salts of the corresponding active metal or added catalyst element, for example carbonates, nitrates or nitrosylnitrates, carboxylates, especially nitrates or nitrosylnitrates, acetates or chlorides, which are usually at least partially converted under calcination conditions into the corresponding oxide or mixed oxide.

Impregnation can also be carried out by the "incipient wetness method", in which, depending on their water absorption capacity, the support material is wetted to the maximum saturation with an impregnation solution or sprayed with an impregnation solution. Alternatively, the impregnation may be carried out in the supernatant.

In the case of a multi-stage impregnation process, drying and optionally calcination between the impregnation stages is suitable. When the support material is contacted with a relatively large amount of salt, it is advantageous to employ a multi-stage impregnation.

In order to apply the various active metals and/or the added catalyst elements and/or the basic elements to the support material, impregnation with all salts can be carried out simultaneously or in any order one after the other.

Post-treatment of catalytic support materials

The impregnated catalytic support materials obtained by these impregnation methods or the precipitates obtained by the precipitation methods are generally prepared by separating them from the liquid in which the impregnation or precipitation is carried out, then washing, drying, calcining and optionally conditioning, and subjecting them to a shaping process.

Separation and washing

After the preparation of the catalytic support material, the precipitate thus obtained or impregnated, the conventional support material, is usually separated from the liquid from which the catalyst support has been prepared and washed.

Methods for separating and washing catalytic support materials are known, for example, from the articles "Heterogenous Catalysts and Solid Catalysts, 2.Development and Types of Solid Catalysts", Ullmann's encyclopedia of Industrial Chemistry (DOI:10.1002/14356007.o 05-o 02).

The wash liquid used is typically a liquid in which the isolated catalytic support material is slightly soluble but which is a good solvent for impurities, such as precipitant, that are adhered to the catalyst. The preferred wash liquid is water.

In batch preparation, the separation is usually carried out by a frame filter press. Here, the filter residue can be washed by passing the washing liquid through the washing liquid in a direction opposite to the filtering direction.

In continuous production, separation is usually carried out using a drum filter. The filter residue is usually washed by spraying it with a washing liquid.

The catalytic support material may also be separated by centrifugation. Here, washing is generally carried out by adding a washing solution during centrifugation.

Drying

The separated catalytic support material is typically dried.

Methods for drying catalytic support materials are known, for example, from the articles "Heterogenous Catalysts and Solid Catalysts, 2.Development and Types of Solid Catalysts", Ullmann's encyclopedia of Industrial Chemistry (DOI10.1002/14356007.o 05-o 02).

Here, the drying is carried out at a temperature of preferably from 60 to 200 deg.C, in particular from 80 to 160 deg.C, more preferably from 100 to 140 deg.C, with a drying time of preferably 6 hours or more, for example from 6 to 24 hours. However, depending on the moisture content of the material to be dried, shorter drying times, for example about 1,2, 3, 4 or 5 hours, are also possible.

The separated washed catalytic support material may be dried, for example, in a chamber furnace, drum dryer, rotary kiln, or belt dryer.

The catalytic support material may also be dried by spray drying a suspension of the catalytic support material.

Calcination of

Typically, the catalytic support material is calcined after drying.

During calcination, thermally labile compounds of the active metals or of the added catalyst elements, such as carbonates, bicarbonates, nitrates or nitrosyl nitrates, chlorides, carboxylates, oxide hydrates or hydroxides, are converted at least partially into the corresponding oxides and/or mixed oxides.

Calcination is typically carried out at temperatures of 250-1200 deg.C, preferably 300-1100 deg.C, and especially 500-1000 deg.C.

The calcination may be carried out under any suitable gas atmosphere, preferably air and/or air mixtures, e.g. lean burn air. Alternatively, the calcination may be carried out in the presence of hydrogen, nitrogen, helium, argon and/or steam or mixtures thereof.

Calcination is typically carried out in a muffle, rotary and/or tunnel kiln, preferably for a time period of 1 hour or more, more preferably from 1 to 24 hours, and most preferably from 2 to 12 hours.

Composition of catalytic support material

The composition of the catalytic support material can be measured by known elemental analysis methods, such as Atomic Absorption Spectroscopy (AAS), Atomic Emission Spectroscopy (AES), X-ray fluorescence analysis (XFA), or ICP-OES (inductively coupled plasma emission spectroscopy).

In the context of the present invention, the concentration data (in% by weight) of the catalytically active components are reported as the corresponding oxides.

Group 1 added catalyst element (alkali metal) as M₂O, e.g. Na₂And (4) measuring O.

The catalyst element (alkaline earth metal) added in group 2 is calculated as MO, e.g. MgO or CaO.

Group 13 added catalyst element (boron group) as M₂O₃E.g. B₂O₃Or Al₂O₃And (6) counting.

In the carbon group (group 14), Si is SiO₂In terms of GeO, Sn in terms of SnO and Pb in terms of PbO.

In the nitrogen group (group 15), P is H₃PO₄As is measured As₂O₃Sb is Sb₂O₃Calculated as Bi₂O₃And (6) counting.

In the group of chalcogen elements (group 16), Se is SeO₂In terms of Te is TeO₂And (6) counting.

In the scandium group (group 3), Sc is expressed as Sc₂O₃In terms of Y, Y is Y₂O₃In terms of La₂O₃And (6) counting.

In the titanium group (group 4), Ti is TiO₂Calculated as ZrO₂Hf is HfO₂And (6) counting.

In the vanadium group (group 5), V is as V₂O₅Measured as Nb₂O₅In terms of Ta₂O₅And (6) counting.

In the chromium group (group 6), Cr is in CrO₂Calculated as MoO for Mo₃Measured as WO₂And (6) counting.

In the manganese group (group 7), Mn is expressed as MnO₂Calculated as Re₂O₇And (6) counting.

In the iron group (group 8), Fe is Fe₂O₃Ru in RuO₂Calculated as OsO₄And (6) counting.

In the cobalt group (group 9), Co is calculated as CoO and Rh is calculated as RhO₂In terms of IrO, Ir₂And (6) counting.

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

In the copper family (group 11), Cu is calculated as CuO, Ag is calculated as AgO, and Au is calculated as Au₂O₃And (6) counting.

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

Unless otherwise stated, the concentration data (in% by weight) of the individual components of the catalytic support material are based on the total mass of the catalytic support material after the last calcination.

The composition of the catalytic support material generally depends on the preparation method described below (coprecipitation or precipitation application or impregnation).

The catalytic support material preferably consists exclusively of the active metal or of the catalytically active component of the added catalyst element, for example in the form of a conventional support material, and optionally also a shaping aid (for example graphite or stearic acid) if the catalytic support material is used in the form of shaped bodies.

The proportion of the catalytically active component of the active metal or of the added catalytic element is generally from 70 to 100% by weight, preferably from 80 to 100% by weight, more preferably from 90 to 100% by weight, even more preferably from 95 to 100% by weight, and particularly preferably from 97 to 100% by weight, based on the total mass of the catalytic support material.

The catalytic support material prepared by co-precipitation does not contain any conventional support material. The method of preparation of the catalytic support material is referred to in the context of the present invention as precipitation application if the precipitation is carried out in the presence of conventional support materials as described below.

The catalytic support material prepared by co-precipitation typically comprises 1 to 3, more preferably 1 to 2, and especially preferably 1 active metal.

Irrespective of the amount of active metal present in the active composition, in the case of a catalytic support material prepared by coprecipitation, the composition of the catalytically active components of the active metals is preferably from 1 to 95% by weight, more preferably from 10 to 90% by weight, even more preferably from 20 to 85% by weight, and particularly preferably from 50 to 80% by weight, based on the total mass of the catalytic support material, and in which the catalytically active components are calculated as oxides.

The catalytic support material prepared by coprecipitation generally comprises from 1 to 5, more preferably from 1 to 4, and particularly preferably from 1 to 3, different added catalyst elements.

Irrespective of the amount of added catalyst elements present in the active composition, in the case of a catalytic support material prepared by co-precipitation, the composition of the catalytically active components of the added catalyst elements is preferably in the range from 1 to 90% by weight, more preferably in the range from 5 to 80% by weight, most preferably in the range from 10 to 60% by weight, based on the total mass of the catalytic support material, and wherein the catalytically active components are calculated as oxides.

The catalytic support material prepared by precipitation application generally comprises from 5 to 95% by weight, preferably from 10 to 80% by weight, more preferably from 15 to 60% by weight, of conventional support materials.

The catalytic support material prepared by precipitation application typically comprises 1 to 5, more preferably 1 to 4, especially preferably 1 to 3 active metals.

Regardless of the amount of active metal present in the active composition, in the case of a catalytic support material prepared by precipitation application, the composition of the catalytically active components of the active metals is preferably from 5 to 90% by weight, more preferably from 10 to 70% by weight, most preferably from 15 to 60% by weight, based on the total mass of the catalytic support material, and wherein the catalytically active components are calculated as oxides.

The catalytic support material prepared by precipitation application usually contains 1 to 5, more preferably 1 to 4, particularly preferably 1 to 3 different added catalyst elements.

Irrespective of the amount of added catalyst element present in the active composition, in the case of a catalytic support material prepared by precipitation application, the composition of the catalytically active component of the added catalyst element is preferably from 1 to 80% by weight, more preferably from 5 to 70% by weight, most preferably from 10 to 50% by weight, based on the total mass of the catalytic support material, and wherein the catalytically active component is calculated as oxide.

The catalytic support material prepared by impregnation generally comprises from 50 to 99% by weight, preferably from 75 to 98% by weight, more preferably from 90 to 97% by weight, of conventional support material.

The catalytic support material prepared by impregnation generally comprises from 1 to 5, more preferably from 1 to 4, and particularly preferably from 1 to 3 active metals.

Regardless of the amount of active metal present in the active composition, in the case of a catalytic support material prepared by impregnation, the composition of the catalytically active component of the active metal is preferably from 1 to 50% by weight, more preferably from 2 to 25% by weight, most preferably from 3 to 10% by weight, based on the total mass of the catalytic support material, and wherein the catalytically active component is calculated as oxide.

The catalytic support material prepared by impregnation usually comprises 1 to 4, more preferably 1 to 3, especially preferably 1 to 2 different added catalyst elements.

Irrespective of the amount of added catalyst elements present in the active composition, in the case of a catalytic support material prepared by impregnation, the composition of the catalytically active components of the added catalyst elements is preferably from 1 to 50% by weight, preferably from 2 to 25% by weight, most preferably from 3 to 10% by weight, based on the total mass of the catalytic support material, and wherein the catalytically active components are calculated as oxides.

Preferred composition of catalytic support material

Particularly preferably used catalytic support materials are in particular the following compositions:

I)

in a preferred embodiment, the catalytic support materials used are those compositions 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. Such compositions are for example disclosed in WO 2008/006749.

In a particularly preferred variant of this embodiment, a composition is used which comprises:

with ZrO₂From 10 to 75% by weight, preferably from 25 to 65% by weight, more preferably from 30 to 55% by weight, of a catalytically active component of zirconium,

1 to 30% by weight, preferably 2 to 25% by weight, more preferably 5 to 15% by weight, calculated as CuO, of a catalytically active component of copper,

from 10 to 70% by weight, preferably from 20 to 60% by weight, more preferably from 30 to 50% by weight, based on NiO, of a catalytically active component of nickel,

each independently of Sb₂O₃、PbO、Bi₂O₃And ln₂O₃From 0.1 to 10%, In particular from 0.2 to 7%, more In particular from 0.4 to 5%, very In particular from 2 to 4.5%, by weight of one or more catalytically active components of a metal selected from Sb, Pb, Bi and In.

II)

In a preferred embodiment, the catalytic support material used is a composition In which the catalytically active composition comprises the catalytically active components Zr, Cu, Ni and Co and one or more of Sn, Pb, Bi and In. Such compositions are for example disclosed in WO 2008/006750.

In a particularly preferred variant of this embodiment, a composition is used which comprises:

with ZrO₂From 10 to 75% by weight, preferably from 25 to 65% by weight, more preferably from 30 to 55% by weight, of a catalytically active component of zirconium,

1 to 30% by weight, preferably 2 to 25% by weight, more preferably 5 to 15% by weight, calculated as CuO, of a catalytically active component of copper, and

10 to 70 wt.%, preferably 13 to 40 wt.%, more preferably 16 to 35 wt.% of a catalytically active component of nickel, calculated as NiO,

from 10 to 50% by weight, preferably from 13 to 40% by weight, more preferably from 16 to 35% by weight, calculated as CoO, of a catalytically active component of cobalt, and

respectively adding PbO and Bi₂O₃、SnO、Sb₂O₃And ln₂O₃From 0.1 to 10% by weight, In particular from 0.2 to 7% by weight, more In particular from 0.4 to 5% by weight, of one or more catalytically active components of metals selected from the group consisting of Pb, Bi, Sn, Sb and In.

III)

In a further preferred embodiment, the catalytically active compositions used are those in which the catalytically active composition comprises catalytically active components of Zr, Ni and Fe and from 0.2 to 5.5% of one or more catalytically active components of Sn, Pb, Bi, Mo, Sb and/or P, each in the form of SnO, PbO, Bi, respectively₂O₃、MoO₃、Sb₂O₃And H₃PO₄And (6) counting. Such compositions are for example disclosed in WO 2009/080506.

In a particularly preferred variant of this embodiment, a composition is used which comprises:

with ZrO₂20-70% by weight of a catalytically active component of zirconium,

15 to 60% by weight, calculated as NiO, of a catalytically active component of nickel, and

with Fe₂O₃0.5 to 14% by weight, preferably 1.0 to 10% by weight, more preferably 1.5 to 6% by weight, of a catalytically active component of iron, and

SnO, PbO and Bi are respectively used₂O₃、MoO₃、Sb₂O₃And H₃PO₄0.2 to 5.5% by weight, preferably 0.5 to 4.5% by weight, more preferably 0.7 to 3.5% by weight, of a catalytically active component of tin, lead, bismuth, molybdenum, antimony and/or phosphorus.

IV)

In another preferred embodiment, the catalytic carriers used are those compositions in which the catalytically active composition comprises the following catalytically active components: zr, Cu, Ni, and

0.2 to 40% by weight, calculated as CoO, of a catalytically active component of cobalt,

with Fe₂O₃0.1 to 5% by weight, based on the total weight of the catalyst active component, of iron, and

respectively adding PbO, SnO and Bi₂O₃And Sb₂O₃0.1 to 5% by weight of a catalytically active component of lead, tin, bismuth and/or antimony.

Such compositions are for example disclosed in WO 2009/080508.

In a particularly preferred variant of this embodiment, a composition is used which comprises:

with ZrO₂From 20 to 85% by weight, in particular from 25 to 70% by weight, more particularly from 30 to 60% by weight, of a catalytically active component of zirconium,

0.2 to 25% by weight, in particular 3 to 20% by weight, more particularly 5 to 15% by weight, calculated as CuO, of a catalytically active component of copper,

0.2 to 45 wt.%, in particular 10 to 40 wt.%, more in particular 25 to 35 wt.%, calculated as NiO, of a catalytically active component of nickel,

0.2 to 40% by weight, preferably 1 to 25% by weight, more preferably 2 to 10% by weight, calculated as CoO, of a catalytically active component of cobalt,

with Fe₂O₃0.1 to 5% by weight, preferably 0.2 to 4% by weight, more preferably 0.5 to 3% by weight, of a catalytically active component of iron, and

respectively adding PbO, SnO and Bi₂O₃And Sb₂O₃0.1-5.0 wt.%, in particular 0.3-4.5 wt.%, more in particular 0.5-4 wt.% of a catalytically active component of lead, tin, bismuth and/or antimony.

V)

In a further preferred embodiment, the catalytic support material used is a composition in which the catalytically active composition comprises the catalytically active components Zr, Cu and Ni, and

1.0 to 5.0% by weight, calculated as CoO, of a catalytically active component of cobalt, and

are each respectively provided with V₂O₅、Nb₂O₅、H₂SO₄、H₃PO₄、Ga₂O₃、B₂O₃、WO₃PbO and Sb₂O₃0.2 to 5.0% by weight, calculated on the basis of the total weight of the catalyst, of a catalytically active component of vanadium, niobium, sulphur, phosphorus, gallium, boron, tungsten, lead and/or antimony.

Such compositions are for example disclosed in WO 2009/080508.

In a particularly preferred variant of this embodiment, a composition is used which comprises:

with ZrO₂46-65% by weight, in particular 47-60% by weight, more in particular 48-58% by weight, of a catalytically active component of zirconium,

5.5 to 18% by weight, in particular 6 to 16% by weight, more particularly 7 to 14% by weight, calculated as CuO, of a catalytically active component of copper,

20 to 45 wt.%, in particular 25 to 40 wt.%, more in particular 30 to 39 wt.%, calculated as NiO, of a catalytically active component of nickel,

1.0-5.0 wt.%, specifically 1.5-4.5 wt.%, more specifically 2.0-4.0 wt.% cobalt, calculated as CoO, as a catalytically active component, and

are each respectively provided with V₂O₅、Nb₂O₅、H₂SO₄、H₃PO₄、Ga₂O₃、B₂O₃、WO₃PbO and Sb₂O₃0.2-5.0 wt.%, in particular 0.3-4.0 wt.%, more in particular 0.5-3.0 wt.% of a catalytically active component of vanadium, niobium, sulphur, phosphorus, gallium, boron, tungsten, lead and/or antimony.

VI)

In another preferred embodiment, the catalytic support material used is a composition wherein the catalytically active composition comprises the following catalytically active components: al, Cu, Ni, Co and Sn, and

each independently of the other being Y₂O₃、La₂O₃、Ce₂O₃And Hf₂O₃0.2 to 5.0% by weight of a catalytically active component of yttrium, lanthanum, cerium and/or hafnium.

Such compositions are for example disclosed in WO 2011/067200.

In a particularly preferred variant of this embodiment, a composition is used which comprises:

0.2 to 5.0 wt.%, particularly 0.4 to 4.0 wt.%, more particularly 0.6 to 3.0 wt.%, even more particularly 0.7 to 2.5 wt.% of a catalytically active component of tin, calculated as SnO,

from 10 to 30% by weight, more particularly from 12 to 28% by weight, very particularly from 15 to 25% by weight, calculated as CoO, of a catalytically active component of cobalt,

with Al₂O₃From 15 to 80% by weight, in particular from 30 to 70% by weight, more particularly from 35 to 65% by weight, of a catalytically active component of aluminium,

1 to 20% by weight, in particular 2 to 18% by weight, more particularly 5 to 15% by weight, calculated as CuO, of a catalytically active component of copper, and

5 to 35 wt.%, in particular 10 to 30 wt.%, more in particular 12 to 28 wt.%, very in particular 15 to 25 wt.%, calculated as NiO, of a catalytically active component of nickel,

each independently of the other being Y₂O₃、La₂O₃、Ce₂O₃And Hf₂O₃0.2-5.0 wt.%, in particular 0.4-4.0 wt.%, more in particular 0.6-3.0 wt.%, even more in particular 0.7-2.5 wt.% of a catalytically active component of yttrium, lanthanum, cerium and/or hafnium.

VII)

In a further preferred embodiment, the catalytic support material used is a composition prepared by applying a solution (L) comprising tin nitrate and at least one complexing agent to a support, wherein the solution (L) does not comprise any solids or comprises a solids content of not more than 0.5% by weight, based on the total mass of dissolved components, and the solution (L) additionally comprises at least one further nickel, cobalt and/or copper salt, more preferably nickel, cobalt nitrate and/or copper nitrate.

Such compositions are for example disclosed in WO 2013/072289.

In a preferred variant of this embodiment, a composition is used which comprises:

0.2 to 5 wt.%, calculated as SnO, of a catalytically active component of tin,

with Al₂O₃15-80% by weight, calculated on the basis of the total weight of the catalyst, of a catalytically active component of aluminium,

1 to 20 wt.%, calculated as CuO, of a catalytically active component of copper,

5 to 35% by weight, calculated as NiO, of a catalytically active component of nickel, and

5-35% by weight, calculated as CoO, of a catalytically active component of cobalt.

In a very particularly preferred variant of this embodiment, the composition having the above-described composition is obtained by precipitating a soluble compound of Co and Sn, which is Sn nitrate, onto a finely divided support material, and the precipitation application is carried out in the presence of a complexing agent. The soluble compound of Co is preferably Co nitrate.

The precipitation application is further preferably carried out in the presence of at least one other soluble compound of the added catalyst element, preferably a soluble compound of Cu and/or Ni. Further preferably, the added catalyst elements are likewise used in the form of their nitrates or nitrosylnitrates.

The complexing agent is preferably selected from glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, malonic acid, mandelic acid, citric acid, sugar acids, hydroxymalonic acid, tartaric acid, oxalic acid, malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, glycine, hippuric acid, EDTA, alanine, valine, leucine or isoleucine.

The support material is preferably alumina or zirconia or a mixture thereof.

Shape and geometry of the carrier material used

The support material is preferably used in the form of a powder or of chips or in the form of shaped bodies.

If the support material is used in the form of a powder or of flakes, the median diameter d of the particles₅₀Typically 50-2000. mu.m, preferably 100-1000. mu.m, more preferably 300-700. mu.m. The standard deviation of the particle diameters is generally the median diameter d₅₀5 to 200%, preferably 10 to 100%, particularly preferably 20 to 80%.

In a particularly preferred embodiment, granules of the powders or flakes usedMedian diameter d of₅₀Preferably 1 to 500. mu.m, preferably 3 to 400. mu.m, more preferably 5 to 300. mu.m. The standard deviation of the particle diameters is generally the median diameter d₅₀5 to 200%, preferably 10 to 100%, particularly preferably 20 to 80%.

However, in the process of the invention, the support material can also preferably be used in the form of shaped bodies.

Suitable shaped bodies are shaped bodies having any geometric structure or shape. Preferred shapes are tablets, rings, cylinders, star extrudates, wagon wheels or spheres, particularly preferably tablets, rings, cylinders, spheres or star extrudates. Very particularly preferably cylindrical.

In the case of a ball, the diameter of the ball is preferably 20mm or less, more preferably 10mm or less, even more preferably 5mm or less, and particularly preferably 3mm or less.

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

In the case of a wire or a cylinder, the ratio of length to diameter is preferably from 1:1 to 20:1, more preferably from 1:1 to 14:1, even more preferably from 1:1 to 10:1, particularly preferably from 1:2 to 6: 1.

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

In a preferred embodiment, the diameter of the wire or cylinder is preferably from 0.5 to 20mm, more preferably from 1 to 15mm, most preferably from 1.5 to 10 mm.

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

In a preferred embodiment, the height h of the sheet is preferably from 0.1 to 20mm, more preferably from 0.5 to 15mm, even more preferably from 1 to 10mm, and especially preferably from 1.5 to 3 mm.

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, most preferably 1:1 to 1:2.

The molded bodies used preferably have a bulk density (according to EN ISO 6) of 0.1 to 3kg/l, preferably 1.0 to 2.5kg/l, particularly preferably 1.2 to 1.8 kg/l.

Shaping of

Preference is given to using support materials which already have the preferred shapes and geometries described above.

The shaping step may be carried out on a support material, in particular a catalytic support material, which does not have the desired shape and geometry after preparation.

During the shaping process, the support material is usually adjusted to a specific particle size by grinding.

After milling, the conditioned support material can be mixed with further additives, such as shaping aids, for example graphite, binders, pore formers and pasting agents, and further processed to give shaped bodies. Preferably, the support material is only mixed with graphite as a shaping aid and no further additives are added during shaping.

Standard shaping methods are described, for example, in Ullmann's Encyclopedia Electron Release 2000, chapter: "Catalysis and Catalysis", pages 28 to 32]And Ertl et al [ Ertl,

weitkamp, Handbook of heterogenous Catalysis, VCH Weinheim, 1997, page 98 and subsequent pages]In (1).

Standard shaping methods are, for example, extrusion, tabletting (i.e. mechanical pressing) or granulation (i.e. compaction by circular and/or rotary motion).

The shaping operation may give the shaped body the geometry described above.

Alternatively, shaping can be carried out by spray drying a suspension of the support material.

After conditioning or shaping, a heat treatment is usually carried out.

The heat treatment is typically carried out at a temperature of 250 ℃ to 1200 ℃, preferably 300 ℃ to 1100 ℃, especially 500 ℃ to 1000 ℃.

The heat treatment may be carried out under any suitable gas atmosphere. The heat treatment is preferably carried out in the presence of air, wherein the proportion by volume of air is preferably from 20 to 100% by volume, more preferably from 35 to 90% by volume, and particularly preferably from 30 to 70% by volume.

The heat treatment is generally carried out in a muffle furnace, rotary furnace and/or belt calciner, preferably for a duration of 1 hour or more, more preferably from 1 to 24 hours, most preferably from 2 to 12 hours.

Preparation of the catalyst precursor (impregnation of the conventional or catalytic support material)

The catalyst precursor is preferably prepared by contacting a conventional or catalytic support material with one or more soluble compounds of the active metal and optionally one or more soluble compounds of the added catalyst element, wherein the contacting is preferably performed by soaking or impregnation.

The support material may be contacted with the soluble compounds of the active metal and the added Catalyst element by conventional methods (a.b. stiles, Catalyst manufacturing-Laboratory and commercial Preparations, Marcel Dekker, New York, 1983), for example by using the active metal or a salt of the added Catalyst element in one or more impregnation steps.

Useful salts of the active metal or added catalyst element generally include water-soluble salts, such as carbonates, nitrates or nitrosylnitrates, carboxylates, especially carboxylates, preferably nitrates or nitrosylnitrates and acetates, most preferably nitrates or nitrosylnitrates, of the corresponding active metal or added catalyst element, which are generally at least partially converted under calcination conditions to the corresponding oxide or mixed oxide.

The contacting can also be carried out by the "incipient wetness process", in which the support material is wetted with an impregnation solution to a maximum saturation, or sprayed with an impregnation solution, depending on the water absorption capacity of the support material. Alternatively, the impregnation may be carried out in the supernatant.

In the case of a multi-stage impregnation process, it is suitable to carry out drying between the impregnation stages. When the support material is contacted with a relatively large amount of salt, it is advantageous to employ a multi-stage impregnation.

In order to apply the various active metals and/or the added catalyst elements and/or the basic elements to the support material, impregnation with all salts can be carried out simultaneously or in any order one after the other.

Preferred conventional support materials are support materials comprising the added catalyst elements Al and Zr or mixtures thereof.

In a very particularly preferred embodiment, the soluble compounds of the active metals which are brought into contact with the support material are used partly or completely in the form of their nitrates or nitrosylnitrates. Most preferably, the soluble compound of the active metal used is only the nitrate or nitrosylnitrate of the active metal.

It is also preferred that the soluble compounds of the added catalyst elements are used partly or completely in the form of their nitrates or nitrosylnitrates. Most preferably, the soluble compound of the added catalyst element used is only the nitrate or nitrosylnitrate of the added catalyst element.

In a particularly preferred embodiment, the soluble compounds of the active metal and of the added catalyst element which are brought into contact with the support material are only the corresponding nitrates or nitrosylnitrates.

In another preferred embodiment, the support material used is a catalytic support material comprising as active metal one or more active metals selected from the group consisting of Ru, Co, Sn, Cu and Ni. More preferably, the support material used is a catalytic support material comprising as active metal one or more active metals selected from the group consisting of Co, Sn, Cu and Ni.

Further preferably, the catalytic support material comprises one or more added catalyst elements selected from Zr and Al.

Most preferably, the preferred compositions described above are used as catalytic support materials.

The support material can be used, for example, in the form of chips, powder or shaped bodies, such as wires, flakes, spheres or rings.

It is preferred to use a support material which already has the above-mentioned preferred shape and geometry (see section "shape and geometry of support material").

The soluble compound of the active metal in contact with the support material is preferably present in an amount of from 0.1 to 50% by weight, preferably from 1 to 40% by weight, more preferably from 2 to 15% by weight, of each active metal.

In a particularly preferred embodiment, the at least one active metal used to impregnate the support material is Ru. In this embodiment, it is further preferred that Ru is used in the form of Ru nitrosylnitrate.

In another very particularly preferred embodiment, the support material is impregnated with Ru and Co by impregnating the support material simultaneously or sequentially with a soluble Ru compound and a soluble Co compound, preferably with Ru and Co in the form of their nitrates or nitrosyl nitrates.

The Ru content of the solution which is brought into contact with the support material is generally from 0.1 to 50% by weight, preferably from 1 to 40% by weight, more preferably from 2 to 15% by weight.

The Co content of the solution in contact with the support material is generally from 0.1 to 20% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.15 to 2% by weight.

The contacting of the support material with soluble compounds of Co and Ru is such that:

the proportion of Ru in the catalyst precursor is increased by about 0.1 to 5 wt%, preferably 0.5 to 4 wt%, most preferably 1 to 3 wt%, and

the proportion of Co in the catalyst precursor is increased by about 0.1 to 5% by weight, preferably 0.5 to 3% by weight, most preferably 1 to 2% by weight, based in each case on the total mass of the catalyst precursor.

The support material may be contacted with the soluble Ru compound and the soluble Co compound simultaneously or sequentially.

In a preferred embodiment, the support material is contacted with a solution comprising soluble compounds of Ru and soluble compounds of Co.

In another preferred embodiment, the support material is contacted with a solution of soluble compounds comprising Ru in a first step and then with a solution of soluble compounds comprising Co in a second step.

In another preferred embodiment, the support material is contacted with a solution of soluble compounds comprising Co in a first step and then with a solution of soluble compounds comprising Ru in a second step.

In the case of a multi-step impregnation process, the support material may be separated from the impregnation solution and dried between the impregnation steps, as described below. If the contacting with the soluble Ru compound and the soluble Co compound is performed in two or more impregnation steps, it is preferable that the second impregnation is performed immediately after the drying step of the first impregnation step without any calcination after the drying step between the first and second impregnation.

In this embodiment, the support material is preferably alumina, zirconia or a mixture thereof.

In particular, in this embodiment it is also preferred that the support material is a catalytic support material.

Post-treatment of the catalyst precursor

The impregnated catalyst precursors obtained by these impregnation methods are generally treated by: it is separated from the liquid in which the impregnation has been carried out, and it is washed and dried.

Separation and washing:

the impregnated catalyst precursor is typically separated from the liquid in which the catalyst precursor is prepared and washed.

Methods for separating and washing catalyst precursors are known, for example, from the article "Heterogenous Catalysts and Solid Catalysts", 2.Development and Types of Solid Catalysts ", Ullmann's encyclopedia of Industrial Chemistry (DOI:10.1002/14356007.o 05-o 02).

The washing liquid used is usually a liquid in which the separated catalyst precursor is slightly soluble but which is a good solvent for impurities such as a precipitant adhering to the catalyst. The preferred wash liquid is water.

In batch preparation, the separation is usually carried out by a frame filter press. Here, the filter residue can be washed by passing the washing liquid through the washing liquid in a direction opposite to the filtering direction.

In continuous production, separation is usually carried out using a drum filter. The filter residue is usually washed by spraying it with a washing liquid.

The catalyst precursor may also be separated off by centrifugation. Here, washing is generally carried out by adding a washing solution during centrifugation.

Drying

The separated catalyst precursor is usually dried.

Methods for drying catalyst precursors are known, for example, from the article "Heterogenous Catalysts and Solid Catalysts, 2.Development and Types of Solid Catalysts", Ullmann's encyclopedia of Industrial Chemistry (DOI10.1002/14356007.o 05-o 02).

Here, the drying is carried out at a temperature of preferably from 60 to 200 deg.C, in particular from 80 to 160 deg.C, more preferably from 100 to 140 deg.C, with a drying time of preferably 6 hours or more, for example from 6 to 24 hours. However, depending on the moisture content of the material to be dried, shorter drying times, for example about 1,2, 3, 4 or 5 hours, are also possible.

The separated washed catalyst precursor may be dried, for example, in a chamber furnace, drum dryer, rotary kiln or belt dryer.

The catalyst precursor may also be dried by spray drying a suspension of the catalyst precursor.

In a preferred embodiment, the drying is carried out at a temperature of 300 ℃ or less.

Composition of catalyst precursor

Proportion of active composition

The catalyst precursor used in the process is preferably used in the form of a catalyst precursor consisting only of the catalytically active composition and, if the catalyst precursor is used in the form of shaped bodies, optionally a shaping aid, for example graphite or stearic acid.

The proportion of the catalytically active composition is generally from 70 to 100% by weight, preferably from 80 to 100% by weight, more preferably from 90 to 100% by weight, even more preferably from 95 to 100% by weight, more preferably from 97 to 100% by weight, based on the total mass of the catalyst precursor.

Determination of the composition of the catalyst precursor

The composition of the catalyst precursor can be determined by a known elemental analysis method, for example, Atomic Absorption Spectrometry (AAS), Atomic Emission Spectrometry (AES), X-ray fluorescence analysis (XFA), or ICP-OES (inductively coupled plasma emission spectrometry).

In the context of the present invention, the concentration data (in% by weight) of the catalytically active components are reported as the corresponding oxides.

Group 1 added catalyst element (alkali metal) as M₂O, e.g. Na₂And (4) measuring O.

The catalyst element (alkaline earth metal) added in group 2 is calculated as MO, e.g. MgO or CaO.

Group 13 added catalyst element (boron group) as M₂O₃E.g. B₂O₃Or Al₂O₃And (6) counting.

In the carbon group (group 14), Si is SiO₂In terms of GeO, Sn in terms of SnO and Pb in terms of PbO.

In the nitrogen group (group 15), P is H₃PO₄As is measured As₂O₃Sb is Sb₂O₃Calculated as Bi₂O₃And (6) counting.

In the group of chalcogen elements (group 16), Se is SeO₂Te is calculated as TeO 2.

In the scandium group (group 3), Sc is expressed as Sc₂O₃In terms of Y, Y is Y₂O₃In terms of La₂O₃And (6) counting.

In the titanium group (group 4), Ti is TiO₂Calculated as ZrO₂Hf is HfO₂And (6) counting.

In the vanadium group (group 5), V is as V₂O₅Measured as Nb₂O₅In terms of Ta₂O₅And (6) counting.

In the chromium group (group 6), Cr is in CrO₂Calculated as MoO for Mo₃Measured as WO₂And (6) counting.

In the manganese group (group 7), Mn is expressed as MnO₂Calculated as Re₂O₇And (6) counting.

In the iron group (group 8), Fe is Fe₂O₃On a basis of RuRuO₂Calculated as OsO₄And (6) counting.

In the cobalt group (group 9), Co is calculated as CoO and Rh is calculated as RhO₂In terms of IrO, Ir₂And (6) counting.

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

In the copper family (group 11), Cu is calculated as CuO, Ag is calculated as AgO, and Au is calculated as Au₂O₃And (6) counting.

In the zinc group (group 12), Zn is measured as ZnO, Cd is measured as CdO, Hg is measured as HgO.

Unless otherwise stated, the concentration data (in% by weight) of the catalytically active components of the catalyst precursor are based on the total mass of the catalyst precursor after the final drying step and before the reductive calcination.

Composition of catalyst precursor

When the support material is not a catalytic support material, the catalyst precursor preferably comprises, independently of the active metals used and the amount of catalyst elements added:

0.01-20 wt% of a reactive metal; and

80-99.99 wt% of added catalyst elements; and is

More preferably comprises:

0.1-10 wt% of a reactive metal; and

90-99.9 wt% of added catalyst elements; and is

Most preferably comprises:

1-5 wt% of a reactive metal; and

95-99 wt% of added catalyst elements.

When the support material is a catalytic support material, the catalyst precursor preferably comprises, independently of the active metals used and the amount of catalyst elements added:

5-95 wt% of a reactive metal; and

5-95 wt% of added catalyst elements; and is

More preferably comprises:

10-90 wt% of a reactive metal; and

10-90 wt% of added catalyst elements; and is

Most preferably comprises:

50-80 wt% of a reactive metal; and

20-50 wt% of added catalyst elements.

Preferred catalyst precursor compositions

In a preferred embodiment, the catalyst precursor comprises:

0.01 to 20% by weight, more preferably 0.1 to 15% by weight, and particularly preferably 1 to 10% by weight, calculated as RuO, of a catalytically active component of Ru; and

1 to 50 wt.%, more preferably 10 to 45 wt.%, and particularly preferably 20 to 40 wt.% of a catalytically active component of Co, calculated as CoO; and

0.1 to 5 wt.%, more preferably 0.2 to 4 wt.%, and particularly preferably 1 to 3 wt.% of a catalytically active component of Sn, calculated as SnO.

In a particularly preferred embodiment, the catalyst precursor comprises:

(i) 0.2 to 5 wt.% of a catalytically active component of Sn, calculated as SnO,

(ii) 1-35 wt.% of a catalytically active component of Co, calculated as CoO,

(iii) respectively with Al₂O₃And ZrO₂10-80% by weight of a catalytically active component of Al and/or Zr;

(iv) 1-35 wt% of a catalytically active component of Cu and/or 1-35 wt% of a catalytically active component of Ni, calculated as CuO and NiO, respectively; and

(v) 0.01 to 20% by weight, calculated as RuO, of a catalytically active component of Ru.

In a particularly preferred embodiment, the catalyst precursor comprises:

(i) 0.2 to 5 wt.% of a catalytically active component of Sn, calculated as SnO,

(ii) 5-35 wt.%, calculated as CoO, of a catalytically active component of Co,

(iii) respectively with Al₂O₃And ZrO₂15-80% by weight of a catalytically active component of Al and/or Zr;

(iv) 1 to 20 wt.%, calculated as CuO, of a catalytically active component of Cu,

(v) 5-35 wt% Ni, calculated as NiO, of the catalytically active component; and

(vi) 0.1 to 20% by weight, calculated as RuO, of a catalytically active component of Ru.

Reduction calcination

Typically, drying is followed by reductive calcination of the catalyst precursor according to the invention.

The reductive calcination is carried out in the presence of a reducing gas, especially hydrogen.

Furthermore, the reactive calcination may be carried out in the presence of an inert gas, preferably nitrogen, helium or argon, wherein the volume ratio of the reducing gas, especially hydrogen, in the mixture with the inert gas is preferably from 1 to 50% by volume, more preferably from 2.5 to 40% by volume, most preferably from 5 to 20% by weight.

It is further preferred to increase the proportion of hydrogen in the mixture with inert gas in a gradual or stepwise manner, for example from 0% by volume of hydrogen to 20% by volume of hydrogen. For example, the volume ratio of hydrogen gas may be 0 volume% during heating, and may be increased in one or more steps or gradually to 20 volume% when the calcination temperature is reached.

The temperature in the reduction calcination is preferably 100-400 ℃, more preferably 150-350 ℃, more preferably 180-300 ℃, and most preferably 200-280 ℃.

It is particularly preferable that the temperature in the reduction calcination does not exceed 300 ℃. In this case, a catalyst is obtained which exhibits particularly positive properties with respect to selectivity, activity and avoidance of undesired by-products.

Typically, the reductive calcination is followed by passivation, e.g., as described below.

The reductive calcination is generally carried out in a muffle furnace, a rotary furnace, a shaft reactor, a rotary furnace, a multi-layer furnace, a fluidized bed reactor and/or a belt calciner.

The reductive calcination is preferably carried out in a vertical reactor or a rotary furnace.

The calcination time in the reduction calcination is preferably 1 hour or more, more preferably 1 to 24 hours, and most preferably 2 to 12 hours.

More preferably, the reactor in which the catalyst precursor is reductively calcined is connected to a denitration device, as described below.

Denitration device

In preparing the amination catalyst by reductive calcination, reductive calcination of the catalyst precursor may form nitrogen oxides, which may form explosive mixtures. Nitrogen oxides are formed in particular when, in the preparation of catalyst precursors, catalytic or non-catalytic support materials are brought into contact with nitrates or nitrosyl nitrates of active metals or added catalyst elements.

It is therefore a further object of the present invention to provide a process for the preparation of amination catalysts which meet high safety standards.

This object is achieved by using a denitrification facility in the preparation of the amination catalyst.

The object is also achieved by a process for preparing an amination catalyst comprising one or more elements selected from the group consisting of Sn and elements of groups 8, 9, 10 and 11 of the periodic table of the elements, said amination catalyst being obtained by reductive calcination, wherein the reactor in which the reductive calcination is carried out is connected to a denitrification device.

The preparation of the catalyst precursor and the reductive calcination are preferably carried out as already described above, and in the preparation of the amination catalyst of the invention, in each case also preferably specified as preferred variants and embodiments, respectively.

The method according to the invention is particularly preferably used for preparing amination catalysts when a catalytic or non-catalytic support material is brought into contact with one or more nitrates or nitrosylnitrates of the active metal or of the added catalyst element in the preparation of the catalyst precursor.

In a particularly preferred embodiment, the reactor in which the reductive calcination is carried out is connected to a denitration device. This has the advantage that potentially explosive nitrogen oxides formed during the reduction calcination can be destroyed.

As already mentioned above, the reductive calcination is generally carried out in muffle furnaces, rotary furnaces, shaft reactors, multi-layer furnaces, fluidized bed reactors and/or belt calciners.

The reductive calcination is preferably carried out in a vertical reactor or a rotary furnace.

In a specific arrangement of the present invention, the reactor in which the reduction calcination is carried out is connected to a deoxidation apparatus, and therefore a gas flow is guided from the outlet of the reactor in which the reduction calcination is carried out to the inlet of the denitrification apparatus.

In a denitrator unit, nitrogen oxides that may be present in the gas stream are usually partially or completely destroyed.

The denitration unit may preferably be configured as a scrubbing operation or a selective catalytic reduction.

In selective catalytic reduction, ammonia is generally mixed as a reducing agent into the exhaust gas of the reduction calcination and is led through a denitration catalyst, such as a catalyst containing titanium oxide and vanadium oxide. Here, nitrogen oxides are generally reacted with ammonia to produce water and nitrogen in the form of water vapor.

In a preferred embodiment, the ammonia required for the reduction is fed together with hydrogen. The volume ratio of ammonia in the gas stream of reducing gas and optionally inert gas is generally from 5 to 50% by volume, preferably from 10 to 40% by volume, more preferably from 20 to 30% by volume, based in each case on the total gas stream conducted through the catalyst precursor in the reductive calcination.

In another preferred embodiment, ammonia is not added until outside the reactor in which the reductive calcination is carried out and upstream of the denitration device.

It is less preferred to supply ammonia in the form of an aqueous urea solution, since in this case the hydrolysis reaction of urea will form ammonia and CO₂. CO formed as a catalyst poison₂The activity of the amination catalyst can be reduced.

The temperature of the gas stream passing through the denitration catalyst is preferably 100-400 ℃, more preferably 150-350 ℃, more preferably 180-300 ℃, and most preferably 200-280 ℃. This corresponds substantially to the temperature also employed in the reductive calcination and therefore there is generally no need to further adjust the temperature of the gas stream prior to passing through the denitration catalyst.

The water formed in the reduction with ammonia is generally removed from the gas stream outside the denitration catalyst, preferably by condensation or by drying with a suitable molecular sieve, and this gas stream is recycled in a recycle mode to the reduction calcination, with optional addition of additional hydrogen.

The denitration unit may also be configured for scrubbing operation. In this case, the gas stream containing nitrogen oxides is generally brought into contact with the scrubbing liquid. Useful scrubbing liquids typically comprise aqueous suspensions or solutions of basic substances, such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia and urea. Preference is given to aqueous solutions of alkali metal hydroxides, in particular NaOH and KOH, aqueous solutions or suspensions of alkaline earth metal carbonates or alkaline earth metal hydroxides, in particular Mg hydroxide, Mg carbonate, Ca hydroxide, Ca carbonate, aqueous ammonia solutions or aqueous urea solutions.

Alternatively, the scrubbing liquid used may be aqueous hydrogen peroxide or water.

The contacting of the gas stream comprising nitrogen oxides is preferably carried out in an absorber which can be configured as an exchange scrubber, a spray scrubber, a column with random packing or trays, a jet scrubber, a vortex scrubber, a rotary scrubber or a venturi scrubber. The absorber is preferably configured as a tower or spray scrubber with random packing or trays. The gas stream is preferably treated with scrubbing liquid in a countercurrent manner in the column. Here, the gas stream is generally supplied to the lower region of the column and the scrubbing liquid is generally supplied to the upper region of the column. In a preferred embodiment, the scrubbing step is carried out in the following manner: the gas stream containing nitrogen oxides is treated in a scrubbing step with a scrubbing liquid at a scrubbing temperature of from 20 to 80 ℃, preferably from 20 to 70 ℃, in particular from 30 to 60 ℃. The total pressure in the scrubbing step generally corresponds to the pressure at which the reductive calcination is also carried out, preferably 1 bar (absolute). The exact operating conditions for scrubbing can be determined in a conventional manner by the person skilled in the art.

The scrubbing liquid may be regenerated by membrane processes, heating, expansion to lower pressure or stripping. After the regeneration process, the scrubbing liquid can be reused.

The nitrogen oxide concentration of the gas stream leaving the denitrator is typically lower than the concentration present in the gas stream upstream of the denitrator. The nitrogen oxide-depleted gas stream (optionally with the addition of hydrogen and/or inert gas) may be recycled back to the reductive calcination step.

The reductive calcination is typically followed by passivation, for example as described below.

Passivation of

After the reductive calcination, the catalyst is preferably contacted with an oxygen-containing gas stream, such as air or a mixture of air and nitrogen.

This gives a passivated catalyst. Passivated catalysts typically have a protective oxide layer. The protective oxide layer simplifies handling and storage of the catalyst, thereby simplifying, for example, installation of the passivated catalyst in the reactor.

For passivation, the reduction calcination is followed by contact with an oxygen-containing gas, preferably air. The oxygen-containing gas may be used with the addition of an inert gas such as nitrogen, helium, neon, argon or carbon dioxide. In a preferred embodiment, air is used together with nitrogen, wherein the volume ratio of air is preferably from 1 to 80% by volume, more preferably from 20 to 70% by volume, and particularly preferably from 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.

The passivation is preferably carried out at a temperature of at most 50 ℃, preferably at most 45 ℃, most preferably at most 35 ℃.

Activation of

The passivated catalyst is preferably reduced by treating the passivated catalyst with hydrogen or a hydrogen containing gas prior to contacting with the reactants.

Activation typically removes the protective passivation layer.

Hydrogen is typically used in industrial grade purity. Hydrogen can also be used in the form of a hydrogen-containing gas, i.e. in admixture with other inert gases such as nitrogen, helium, neon, argon or carbon dioxide. In a preferred embodiment, hydrogen is used together with nitrogen, wherein the volume ratio of hydrogen is preferably from 1 to 50% by volume, more preferably from 2.5 to 30% by volume, and particularly preferably from 5 to 25% by volume. The hydrogen stream may also be recycled to the reduction reaction as recycle gas, optionally mixed with fresh hydrogen, and optionally after removal of water by condensation.

The activation is preferably carried out in a mobile or stationary reduction furnace.

More preferably, the catalyst precursor is activated in a reactor in which the catalyst precursor is arranged as a fixed bed. It is particularly preferred to reduce the catalyst precursor in the same reactor, followed by MEG and/or MEA with NH in that reactor₃The reaction of (1).

The catalyst precursor is typically activated at a reduction temperature of 50-600 deg.C, especially 100-500 deg.C, more preferably 150-450 deg.C.

The hydrogen partial pressure is generally in the range from 1 to 300 bar, in particular from 1 to 200 bar, more preferably from 1 to 100 bar, the pressure data here and below relating to the pressure measured in absolute terms.

In a particularly preferred embodiment, the temperature in the activation is in the range in which the reductive calcination is also carried out, i.e., preferably 100-. When the activation is also carried out in this lower temperature range, an amination catalyst with a particularly favorable property profile is obtained.

Reactants

According to the invention, the Ethylene Glycol (EG) and/or Monoethanolamine (MEA) and ammonia (NH) of the invention₃) In the liquid phase in the presence of a reduced or activated amination catalyst.

Ethylene glycol

As the ethylene glycol, preferred is industrial ethylene glycol having a purity of at least 98%, most preferred is ethylene glycol having a purity of at least 99%, most preferred is ethylene glycol having a purity of at least 99.5%.

The ethylene glycol used in the process may be prepared from ethylene available from petrochemical processes. For example, ethylene is typically oxidized to ethylene oxide in a first step, which is then reacted with water to form ethylene glycol. Alternatively, the ethylene oxide obtained can be reacted with carbon dioxide in a so-called ω -process to form ethylene carbonate, which can then be hydrolyzed with water to form ethylene glycol. The omega process is characterized by a higher selectivity to ethylene glycol because less by-products (e.g., diethylene glycol and triethylene glycol) are formed.

Alternatively, ethylene can be produced from renewable feedstocks. For example, ethylene may be formed by dehydration from bioethanol.

Ethylene glycol can also be prepared by the synthesis gas route, for example by oxidative carbonylation of methanol to dimethyl oxalate and subsequent hydrogenation thereof. Thus, another possible petrochemical feedstock for the production of MEG is also natural gas or coal.

MEA

MEAs may also be used in the process of the present invention.

As described above, the MEA can be prepared by reacting ethylene oxide with ammonia.

Preferably, the MEA can be prepared as follows: the MEG is reacted with ammonia, for example by the process of the invention, the MEG is first reacted with ammonia and the MEA formed other than EDA is separated from EDA and the separated MEA is recycled, optionally together with unconverted MEG, to the production process of the invention.

When MEA is used in the process of the present invention without MEG, the MEA is preferably used at a purity of at least 97%, most preferably at least 98%, most preferably at least 99%.

When MEA is used together with MEG in the process of the present invention, the weight proportion of MEA is preferably 0-60 wt%, more preferably 10-50 wt%, most preferably 20-40 wt%, relative to the mass of MEA and MEG.

Ammonia

According to the invention, ethylene glycol and/or monoethanolamine is reacted with ammonia.

The ammonia used may be conventional commercially available ammonia, for example ammonia having an ammonia content of more than 98% by weight ammonia, preferably more than 99% by weight ammonia, preferably more than 99.5% by weight ammonia, in particular more than 99.8% by weight ammonia.

Hydrogen gas

The process of the invention is preferably carried out in the presence of hydrogen.

Hydrogen is typically used in industrial grade purity. Hydrogen can also be used in the form of a hydrogen-containing gas, i.e. with the addition of other inert gases, such as nitrogen, helium, neon, argon or carbon dioxide. The hydrogen-containing gas used can be, for example, reformer off-gases, refinery gases, etc., if and as long as these gases do not contain any catalyst poisons, such as CO, for the catalyst used. However, it is preferred to use pure or substantially pure hydrogen in the process, for example hydrogen having a hydrogen content of more than 99 wt.%, preferably a hydrogen content of more than 99.9 wt.%, more preferably a hydrogen content of more than 99.99 wt.%, in particular a hydrogen content of more than 99.999 wt.%.

Liquid phase reaction

According to the invention, ethylene glycol and/or monoethanolamine are reacted in the liquid phase with ammonia and an amination catalyst.

In the context of the present invention, "reacting in the liquid phase" means adjusting the reaction conditions, such as pressure and temperature, so that both ethylene glycol and monoethanolamine are present in the liquid phase and flow in liquid form around the amination catalyst.

The reaction of MEG and/or MEA with ammonia can be carried out continuously or batchwise. Continuous reaction is preferred.

Reactor with a reactor shell

Suitable reactors for liquid phase reactions are generally tubular reactors. The catalyst can be arranged in a tubular reactor as a moving bed or as a fixed bed.

Particular preference is given to reacting ethylene glycol and/or monoethanolamine with NH₃In a tubular reactor in which the amination catalyst is arranged in the form of a fixed bed.

If the catalyst is arranged in the form of a fixed bed, it can be said to be advantageous for the selectivity of the reaction to be "diluted" by mixing it with an inert random packing. The proportion of random filler in the catalyst formulation may be from 20 to 80 parts by volume, preferably from 30 to 60 parts by volume, more preferably from 40 to 50 parts by volume.

Alternatively, the reaction is advantageously carried out in a shell-and-tube reactor or in a single-flow apparatus. In a single flow arrangement, the tubular reactor in which the reaction is carried out may consist of a series connection of a plurality (e.g. two or three) of individual tubular reactors. Here, a possible and advantageous option is the intermediate introduction of the feed (comprising reactants and/or ammonia and/or H)₂) And/or recycle gas and/or reactor discharge from a downstream reactor.

Reaction conditions

When working in the liquid phase, MEG and/or MEA plus ammonia, including hydrogen, is introduced simultaneously onto the catalyst in the liquid phase, typically in a fixed bed reactor, preferably externally heated, at a pressure typically in the range of from 5 to 30MPa (50 to 300 mbar), preferably in the range of from 5 to 25MPa, more preferably in the range of from 2015 to 25MPa and at a temperature typically in the range of from 80 to 350 ℃, especially in the range of from 100 ℃ to 300 ℃, preferably in the range of from 120 ℃ to 270 ℃, more preferably in the range of from 130 ℃ to 250 ℃, especially in the range of from 160 ℃ to 230 ℃.

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

Feeding of the feedstock

The ME and/or MEA and ammonia are preferably supplied to the reactor in liquid form and contacted with the amination catalyst in liquid form.

Either trickle mode or liquid phase mode is possible.

It is advantageous to heat the reactants (preferably to the reaction temperature) even before they are supplied to the reaction vessel.

The ammonia is preferably used in a molar amount of from 0.90 to 100 times, in particular from 1.0 to 20 times, based in each case on the MEG and/or MEA used.

The catalyst hourly space velocity is generally in the range from 0.05 to 0.5kg (MEG + MEA)/kg catalyst hourly, preferably in the range from 0.1 to 2kg (MEG + MEA)/kg catalyst hourly, more preferably in the range from 0.2 to 0.6kg (MEG + MEA)/kg catalyst hourly.

At the stated catalyst hourly space velocities, the conversion of MEG or MEA is generally in the range of from 20 to 75%, preferably from 30 to 60%, most preferably from 35 to 55%.

The reaction water formed during the reaction (in each case 1 mol per 1 mol of alcohol groups converted) generally has no adverse effect on the conversion, the reaction rate, the selectivity or the catalyst life, and is therefore generally removed from the reaction product (for example by distillation) only when working up the product.

Discharging

The output of the amination reactor contains the products of the amination reaction, unconverted reactants, such as ethylene glycol and ammonia, and hydrogen and water.

The discharge from the amination reactor also contains the corresponding ethanolamine and/or ethyleneamine based on MEG as a product of the amination reaction.

The discharge from the amination reactor preferably comprises MEA and/or EDA.

The reaction output also preferably comprises, as product of the amination reaction, higher linear ethyleneamines of the general formula:

R-CH₂-CH₂-NH₂

wherein R is of the formula- (NH-CH)₂-CH₂)_X-NH₂Wherein x is an integer from 1 to 4, preferably from 1 to 3, most preferably from 1 to 2. Preferably, the reaction output comprises DETA, TETA and TEPA, more preferably DETA and TETA, especially preferably DETA.

The discharge from the amination reactor may also comprise, as a product of the amination reaction, a higher linear ethanolamine of the formula:

R-CH₂-CH₂-OH

wherein R is of the formula- (NH-CH)₂-CH₂)_X-NH₂Wherein x is an integer from 1 to 4, preferably from 1 to 3, most preferably from 1 to 2.

An example of a higher linear ethanolamine is AEEA.

As a product of the amination reaction, the reaction product may also comprise a cyclic ethanolamine of the formula:

wherein R is₁Is of the formula- (CH)₂-CH₂-NH)_X-CH₂-CH₂A group of-OH, wherein x is an integer of 0 to 4, preferably 0 to 3, more preferably 1 to 2, and

R₂independently or simultaneously H or formula- (CH)₂-CH₂-NH)_X-CH₂-CH₂-OH, wherein x is an integer from 0 to 4, preferably from 0 to 3, more preferably from 1 to 2. An example of a cyclic ethanolamine is hydroxyethyl piperazine (HEP).

As a product of the amination reaction, the reaction product may also comprise a cyclic ethyleneamine of the general formula:

wherein R is₁And R₂Independently or simultaneously H or formula- (CH)₂-CH₂-NH)_X-CH₂-CH₂-NH₂Wherein X is an integer of 0 to 4, preferably 0 to 4, more preferably 1 to 2.

Examples of cyclic ethyleneamines present in the reaction discharge are piperazine and AEPIP.

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

The effluent more preferably comprises from 10 to 50 weight percent MEA, from 25 to 85 weight percent EDA, from 0.25 to 10 weight percent cyclic ethyleneamines such as PIP and AEPIP, and from 1 to 30 weight percent higher linear ethyleneamines such as DETA, TETA and TEPA.

The effluent most preferably contains 15-45 wt% MEA, 30-70 wt% EDA, 0.5-5 wt% cyclic ethyleneamines such as PIP and AEPIP, and 5-25 wt% higher linear ethyleneamines such as DETA, TETA and TEPA.

The process of the invention can achieve a selectivity quotient SQ of 1.5 or greater, preferably 4 or greater, more preferably 8 or greater. This means that the product ratio of the desired linear ethyleneamines and ethanolamines (e.g., MEA and EDA) to the desired cyclic ethyleneamines and the undesired higher ethanolamines (e.g., PIP and AEEA) can be increased by the process of the present invention.

The discharge is usually subjected to a post-treatment in order to separate the different components from one another.

For this purpose, the reaction output is suitably depressurized.

The components which are gaseous after the pressure reduction, such as hydrogen and inert gas, are usually separated from the liquid component in a gas-liquid separator. The gaseous components can be recycled to the amination reactor either separately (after further work-up steps) or together.

After separation of hydrogen and/or inert gases, the output of the amination reactor optionally comprises ammonia, unconverted ethylene glycol and/or monoethanolamine, water and amination products.

Preferably, the output of the amination reactor is separated in two separation sequences, wherein each separation sequence comprises a multistage distillation. This aftertreatment is described, for example, in EP-B1-198699. Thus, in the first separation sequence water and ammonia are separated first, and in the second separation sequence unconverted MEG is separated, as well as MEA, EDA, PIP, DETA, AEEA and higher ethyleneamines. In this case, the components which are low-boiling and high-boiling with respect to the MEG and DETA azeotrope are first removed, and the mixture which has been concentrated in MEG and DETA is then separated into streams comprising MEG and DETA by extractive distillation using triethylene glycol (TEG) as selective solvent.

The MEA may be recycled partially or wholly with unconverted MEG into the process of the present invention, optionally together or separately.

Advantages of the invention

In the process of the invention, MEG and/or MEA can be converted with high selectivity to the linear amination products DETA and EDA and low selectivity to the cyclic amination products PIP and the higher ethanolamine AEEA.

A measure of this effect is the selectivity quotient SQ, which is defined as the quotient of the sum of the selectivities of MEA and EDA and the sum of the selectivities of PIP and AEEA (s (deta) + s (EDA))/(s (PIP) + s (AEEA)).

Since the market demand for the linear amination products MEA and EDA and their higher homologues (such as DETA and TETA) is higher than for PIP or AEEA, it is industrially advantageous to obtain a high selectivity quotient SQ.

In addition, the process of the present invention forms lower levels of undesirable by-products. Undesirable by-products are, for example, gaseous decomposition products or insoluble or sparingly soluble oligomers and polymers based on MEA and EDA. The formation of such by-products leads to a reduction in the carbon balance and thus reduces the economic viability of the process. The formation of sparingly soluble or insoluble by-products can lead to deposition on the amination catalyst, which reduces the activity of the amination catalyst.

The process of the invention likewise leads to a reduction in the amount of N-methylethylenediamine (NMEDA). NMEDA is an undesirable by-product. In many industrial applications, the purity of EDA is specified, with a proportion of NMEDA lower than 500ppm by weight.

Furthermore, it has been found that the catalyst precursors used in the process of the present invention have a high activity in the process and therefore a favourable space-time yield can be achieved.

Overall, the process of the invention makes it possible to obtain a profile of properties which is advantageous in terms of overall selectivity, selectivity quotient, activity and formation of undesired by-products.

The process of the present invention for preparing an amination catalyst provides a process which meets high safety standards.

The invention is illustrated by the following examples:

preparation of the catalyst precursor

Comparative example 1:

85.62g of cobalt nitrate hexahydrate were dissolved in approximately 80ml of heat demineralised water and 269.75g of a solution of Ru nitrosylnitrate (16% by weight Ru) were added thereto. The solution thus obtained was made up to a total of 371mL with demineralized water.

The metal salt solution thus obtained is transferred to a spray container.

500g of Al₂O₃The support (1-2mm pieces) was calcined at 900 ℃ in an air atmosphere. Subsequently, the maximum water absorption of the carrier was measured. This was 0.78 mL/g.

The chips are impregnated with a solution of a metal salt prepared beforehand. The amount of solution corresponds to 95% of the maximum water absorption of the chips.

The chips impregnated with the metal salt solution were then dried in an air circulation drying oven at 120 ℃ for 12 hours.

After drying, the catalyst precursor was oxidatively calcined at 600 ℃ in the presence of air.

After oxidative calcination, the catalyst was reduced by passing a stream of hydrogen gas through the catalyst precursor at 200 ℃ for about 6 hours.

After reduction, 98L (STP)/h of N were added at room temperature₂And 2L of (STP)/h of air flow through the catalyst to deactivate the catalyst. Gradually increasing the amount of air while slowly decreasing N₂Amount until 20L (STP) is reachedN of/h₂And 18L (STP)/h of air. The increase in the amount of air is carried out in such a manner that the catalyst temperature does not exceed 35 ℃.

Comparative example 2:

a catalyst precursor was prepared according to example B3 of WO 2013/072289. Thus, the catalyst precursor was oxidatively calcined at a temperature of 450 ℃ under passing air. The thus prepared tablets were pulverized into 1-2mm pieces before reduction.

The catalyst precursor thus obtained was reduced by the following method (see table 1):

table 1:

after reduction, the catalyst precursor is passivated. For this purpose, 50L of N (STP)/h is used₂And 0L (STP)/h of air flow through the reduced catalyst precursor. Gradually increasing the amount of air while slowly decreasing N₂Amount until 20L (STP)/h of N is reached₂And 20L (STP)/h of air. The increase in the amount of air is carried out in such a manner that the catalyst temperature does not exceed 35 ℃.

Comparative example 3:

a catalyst precursor was prepared according to example B3 of WO 2013/072289.

The thus obtained pieces (3X 3mm) were pulverized into 1-2mm pieces. The water absorption of the chips was 0.25 mL/g.

A metal salt solution is prepared. For this purpose, 9.39g of cobalt nitrate hexahydrate (20.25% by weight of Co) were dissolved in hot water and 24.58g of Ru nitrosylnitrate solution were added. The solution thus obtained was made up to 45mL with demineralized water and transferred to a spray container.

The chips were sprayed in an impregnation apparatus in an amount corresponding to 90% of the maximum water absorption of the chips. Subsequently, the catalyst pieces were dried in an air circulation drying oven at 120 ℃ for 16 hours.

After drying, the catalyst precursor was oxidatively calcined at 600 ℃ in the presence of air.

The catalyst precursor thus obtained was reduced by the following method (see table 2):

table 2:

after reduction, the catalyst precursor is passivated. For this purpose, 50L of N (STP)/h is used₂And 0L (STP)/h of air flow through the catalyst precursor. Gradually increasing the amount of air while slowly decreasing N₂Amount until 20L (STP)/h of N is reached₂And 20L (STP)/h of air. The increase in the amount of air is carried out in such a manner that the catalyst temperature does not exceed 35 ℃.

Example 1:

85.62g of cobalt nitrate hexahydrate were dissolved in approximately 80ml of heat demineralised water and 269.75g of a solution of Ru nitrosylnitrate (16% by weight Ru) were added thereto. The solution thus obtained was made up to a total of 371mL with demineralized water.

The metal salt solution thus obtained is transferred to a spray container.

500g of Al₂O₃The support (1-2mm pieces) was calcined at 900 ℃ in an air atmosphere. Subsequently, the maximum water absorption of the carrier was measured. This was 0.78 mL/g.

The chips are impregnated with a solution of a metal salt prepared beforehand. The amount of solution corresponds to 95% of the maximum water absorption of the chips.

The chips impregnated with the metal salt solution were then dried in an air circulation drying oven at 120 ℃ for 12 hours.

After drying, the catalyst precursor was reductively calcined under the conditions listed in table 1.

Table 3:

after reductive calcination, by reacting 98L (STP)/h of N₂And 2L of an air Stream (STP)/h passed over the catalyst at room temperature to deactivate the catalyst. Gradually increasing the amount of air while slowly decreasing N₂Amount until 20L (STP)/h of N is reached₂And 18L (STP)/h of air. Increase of air quantity to makeThe catalyst temperature is not more than 35 ℃.