gas phase process for the preparation of butadiene

专利摘要:
The present invention relates to a gas phase process for the preparation of butadiene comprising (i) providing a gas stream G-1 comprising ethanol; (ii) placing the G-1 gas stream comprising ethanol in contact with a catalyst, thereby obtaining a G-2 gas stream comprising butadiene, wherein the catalyst comprises a zeolitic material with a lattice structure comprising YO2 , Y for one or more tetravalent elements, in which at least a portion of Y comprised in the truss structure is isomorphously replaced by one or more X elements, as well as for a zeolitic material with a YO2 truss structure, Y standing for one or more tetravalent elements, in which at least a portion of Y comprised in the truss structure is isomorphously replaced by one or more X elements, in which the zeolitic material has a specific X-ray powder diffraction pattern . It also concerns the use of this material
公开号:BR112015031174B1
申请号:R112015031174-1
申请日:2014-06-13
公开日:2020-12-01
发明作者:Kirsten Spanhoff；Andrei-Nicolae PARVULESCU；Armin Lange De Oliveira；Stefan Marx；Mathias Feyen；Ulrich Müller；Ekkehard Schwab
申请人:Basf Se；
IPC主号:

专利说明:

[0001] The present invention relates to a gas phase process for the preparation of butadiene using a catalyst comprising a zeolitic material with a lattice structure comprising YO2, wherein at least a portion of Y is isomorphously replaced by one or more X elements. The present invention also relates to a zeolitic material with a specific lattice structure comprising YO2, in which at least a portion of Y is isomorphously replaced by one or more X elements, and the use of that as a catalytically active material for the preparation of butadiene, preferably from a gas stream comprising ethanol and optionally acetaldehyde. INTRODUCTION
[0002] Butadiene is widely used in the chemical industry, for example, as a monomer and / or comonomer for the polarization of elastomers. Currently, butadiene is produced almost entirely as a cracking by-product of ethylene naphtha or diesel raw material. Due to the increase in oil prices, alternative methods for the production of butadiene are of greater interest.
[0003] GB 331482 describes a process for the preparation of butadiene, in which ethanol is placed in contact with aluminum oxide mixed with zinc oxide. However, this process leads to a low yield of 18% butadiene.
[0004] In Ind. Eng. Chem. 41 (1949), pages 1012-1017, the preparation of butadiene by means of a two-step process is described. In the first stage, ethanol is dehydrogenated in acetaldehyde. In the second step, the acetaldehyde obtained is mixed with ethanol and converted to butadiene using impregnated catalysts. By using the most efficient catalyst, which comprises 2.3% by weight of tantalum oxide in amorphous silica, a selectivity of butadiene of up to 69% and the conversion of the starting material in 34% were achieved by 8h in current. However, due to the price of tantalum, the catalyst is relatively expensive.
[0005] Additionally, US 2421361 discloses a process for the preparation of butadiene which comprises passing a mono-olefinic acyclic aldehyde such as crotonaldehyde or acetaldehyde and an ethanol-like monohydric alcohol through a catalyst of the zirconium oxide, tantalum oxide, collutium oxide group and combinations of these oxides with amorphous silica. Through the use of the catalyst containing 2% by weight of zirconium oxide, a single pass yield of 47% of butadiene fraction was obtained, which contained about 93% by weight of butadiene.
[0006] WO 2012/015340 A1 discloses a process for the preparation of butadiene by using a solid catalyst containing metals selected from the silver, gold or copper group and metal oxides, chosen from the oxide group magnesium, titanium, zirconium, tantalum or niobium. However, only low conversion rates in the range of 6 to 64% were achieved in this process, in which these values were determined during only 3 hours of current time.
[0007] The use of a variety of silica impregnated by bi and trimetallic catalysts for the conversion of ethanol and a mixture of ethanol and acetaldehyde to butadiene is described in M.D. Jones et al., Catal. Sci. Technol. 1 (2011), 267-272. However, all catalysts tended to show reduced conversion rates over a 3 hour period. DETAILED DESCRIPTION
[0008] Thus, it was an object of the present invention to provide a process for the preparation of butadiene which does not exhibit the disadvantages of the methods according to the state of the art and in which the high conversion of the starting material, as well as a high selectivity in relation to butadiene is reached. In addition, it was an object of the present invention to improve the long-term activity of the catalyst used.
[0009] It has been found that, by means of a gas phase process for the preparation of butadiene in the presence of a catalyst comprising a zeolitic material with a lattice structure comprising YO2, Y being for one or more tetravalent elements, in which at least at least a portion of Y comprised in the truss structure is isomorphously replaced by one or more elements X, a high conversion of the starting material and, at the same time, high selectivity towards the butadiene is also achieved. In addition, it has been found that the catalysts used in the process of the present invention have a better long-term activity compared to catalysts used in the prior art.
[0010] Therefore, the present invention relates to a gas phase process for the preparation of butadiene comprising: (i) providing a gas stream G-1 comprising ethanol; (j)) placing the G-1 gas stream comprising ethanol in contact with a catalyst, thereby obtaining a G-2 gas stream comprising butadiene, wherein the catalyst comprises a zeolitic material with a lattice structure comprising YO2, Y standing for one or more tetravalent elements, in which at least a portion of Y comprised in the truss structure is isomorphously replaced by one or more elements X.
[0011] In the process of the invention, a gas stream G-1 comprising ethanol is provided in step (i) and is subsequently brought into contact with a catalyst in step (ii). According to a preferred embodiment of the present invention, the gas stream provided in step (i) additionally comprises acetaldehyde.
[0012] With respect to the G-1 gas stream provided in step (i), no particular restrictions apply, according to the present invention, in relation to the composition of the G-1 gas stream relating to ethanol and optionally to acetaldehyde contained therein, provided that after placing the gas stream G-1 in contact with a catalyst in step (ii), the gas stream G-2 comprising butadiene is obtained. Thus, there is generally no specific restriction on the molar ratio of ethanol to acetaldehyde in the G-1 gas stream. According to a preferred embodiment of the present invention, the molar ratio of ethanol to acetaldehyde in the G-1 gas stream ranges from 1: 1 to 6: 1, preferably from 2: 1 to 3.5: 1 and more preferably from 2.5: 1 to 2.9: 1.
[0013] Regarding the composition of the G-1 gas stream, before putting it in contact with the catalyst, there is no specific restriction regarding the amount of ethanol or a mixture of ethanol and acetaldehyde included in the G-1 gas stream. Thus, according to a preferred embodiment of the present invention, 70% by volume or more, preferably 75% by volume or more, more preferably 80% by volume or more of the G-1 gas stream comprises ethanol or a mixture of ethanol and acetaldehyde. It is additionally preferred that before contacting the catalyst, 85% by volume or more, preferably 90% by volume or more, more preferably 95% by volume or more of the G-1 gas stream comprises ethanol or a mixture of ethanol and acetaldehyde. Therefore, according to a preferred embodiment of the present invention, 80% by volume or more of the G-1 gas stream comprises ethanol or a mixture of ethanol and acetaldehyde, in which preferably 90% by volume or more, more preferably 95% in volume or more of the G-1 gas stream comprises ethanol or a mixture of ethanol and acetaldehyde.
[0014] According to the present invention, the gas stream G-1 comprising ethanol provided in step (i) is subsequently brought into contact with a catalyst in step (ii), wherein the catalyst comprises a zeolitic material with a structure truss structure comprising YO2, Y being for one or more tetravalent elements, in which at least a portion of Y comprised in the truss structure is isomorphously replaced by one or more elements X. In general, there is no specific restriction with respect to molar ratio Y: X in the truss structure, as long as the catalyst is able to obtain the gas stream G-2 comprising butadiene. According to a preferred embodiment of the present invention, the molar ratio of Y: X in the truss structure ranges from 10: 1 to 150: 1, preferably from 20: 1 to 80: 1, more preferably from 30: 1 to 50: 1. According to another preferred embodiment of the present invention, the molar ratio of Y: X in the truss structure ranges from 50: 1 to 700: 1, preferably from 100: 1 to 600: 1, more preferably from 170: 1 to 520: 1.
[0015] According to the present invention, X preferably stands for one or more trivalent, tetravalent and / or pentavalent elements, in which there are generally no specific restrictions with respect to the chemical nature of one or more trivalent, tetravalent and / or pentavalent elements . According to a preferred modality, X stands for one or more trivalent, tetravalent and / or pentavalent elements, where the one or more elements X are preferably selected from the group consisting of Zr, Ti, Sn, Ga, Nb, Ta , Sc, Ge, Al, B, Fe and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, Ga, Ge, Ta, and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, Ta, and combinations of two or more of these, where even more preferably X is for Zr and / or Ta.
[0016] There is also no specific restriction regarding the tetravalent Y element included in the truss structure of the zeolitic material. According to a preferred embodiment of the present invention, Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge and combinations of two or more of these, preferably selected from the group consisting of Si, Ti, Ge, and combinations of two or more of these, and most preferably Y stands for Si.
[0017] Regarding the zeolitic material included in the catalyst, there is no specific restriction. Said zeolitic material can be any suitable zeolitic material with a lattice structure BEA, MWW, MFI, MEL, MOR, RUT, DOH, MTN, FER, FAU, CDO, LEV, CHA, as long as this can act as a catalyst in the process for butadiene preparation. According to a preferred embodiment of the present invention, the catalyst comprises a zeolitic material with a lattice structure selected from the group consisting of BEA, MWW, MFI, MEL, MOR, RUT, DOH, MTN, FER, FAU and combinations of two or more of these, preferably selected from the group consisting of BEA, MWW, MFI, MEL and combinations of two or more of these, and most preferably selected from BEA and MWW.
[0018] According to a preferred embodiment of the present invention, the catalyst used in step (ii) of the present invention comprises isomorphically substituted beta zeolite, wherein the trellis structure of the beta zeolite comprises Si and in which at least a portion of Si comprised in the beta zeolite truss structure is isomorphously replaced by one or more elements X, preferably selected from the group consisting of Zr, Ti, Sn, Ga, Ge, and combinations of two or more of these, more preferably selected from the group consisting of Zr, Ti, Sn, and combinations of two or more of these, even more preferably X is for Zr. Additionally, according to a preferred embodiment of the present invention, the catalyst used in step (ii) of the present invention comprises a zeolitic material with a MWW lattice structure, in which the structure comprises Si and in which at least a portion of Si comprises in the truss structure of the zeolitic material isomorphically replaced by one or more elements X, preferably selected from the group consisting of Zr, Ti, Sn, Ga, Ge, Ta, and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, Ta, and combinations of two or more of these, even more preferably X is for Ti and / or Sn and / or Ta.
[0019] The note “X-MWW” and “X-BEA”, as used in the context of the present invention describes the zeolitic materials isomorphically replaced with a lattice structure MWW and BEA, respectively, where X is for the element whereby the zeolitic material is replaced in an isomorphic manner.
In this way, according to a preferred embodiment of the present invention, the catalyst comprises isomorphically substituted beta zeolite, preferably selected from the group consisting of Zr-BEA, Ti-BEA, Sn-BEA and combinations of two or more of these, where more preferably the catalyst comprises Zr-BEA and / or an isomorphic zeolitic material replaced with a MWW lattice structure, preferably selected from the group consisting of Zr-MWW, Ti-MWW, Sn-MWW, Ta-MWW and combinations of two or more of these, where more preferably the catalyst comprises Sn-MWW and / or Ta-MWW.
[0021] According to a particularly preferred embodiment of the present invention, the catalyst comprises isomorphically substituted beta zeolite and / or Sn-MWW and / or Ta-MWW, preferably Zr-BEA and / or Ta-MWW.
[0022] According to a preferred embodiment of the present invention, in which the zeolitic material comprised in the catalyst has a MWW truss structure, the tetravalent Y element comprised in the MWW truss structure of the zeolitic material is selected from the group consisting of Si , Sn, Ti, Zr, Ge and combinations of two or more of these, preferably selected from the group consisting of Si, Ti, Ge, and combinations of two or more of these, more preferably Y stands for Si. Additionally, according to a particularly preferred embodiment of the present invention, in which the zeolitic material comprised in the catalyst has a MWW lattice structure, the one or more trivalent, tetravalent and / or pentavalent X element by which the zeolitic material is isomorphically replaced, is selected from the group consisting of Zr, Ti, Sn, Ga, Nb, Ta, Sc, Ge, Al, B, Fe and combinations of two or more of these, most preferably selected from the go from the group consisting of Zr, Ti, Sn, Ga, Ge, Ta, and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, Ta, and combinations of two or more of these, even more preferably X is for Sn and / or Ti and / or Ta. It is additionally preferred that the zeolitic material comprised in the catalyst has a MWW lattice structure, wherein the tetravalent Y element comprised in the MWW lattice structure is preferably selected from the group consisting of Si, Ti, Ge, and combinations of two or more of these, and preferably Y stands for Si, and in which the one or more element X trivalent, tetravalent and / or pentavalent by means of which the zeolitic material is replaced in an isomorphic manner, is preferably selected from the group consisting of Zr, Ti , Sn, Ta, and preferably X stands for Ti and / or Sn and / or Ta.
[0023] According to a particularly preferred embodiment of the present invention, the zeolitic material comprised in the catalyst has a lattice structure MWW, where Y is Si and X is Ta.
[0024] According to a particularly preferred embodiment of the present invention, the zeolitic material comprised in the catalyst has a MWW lattice structure, where Y is Si and X is Ti.
[0025] In relation to the zeolitic material comprised in the catalyst used in (ii), the zeolitic material may additionally comprise one or more non-lattice elements. Regarding the method by which the one or more non-lattice elements are arranged in the catalyst, there is no specific restriction. Therefore, it may be possible to arrange one or more non-lattice elements in the catalyst by one or more ion exchange procedures, in which the term "ion exchange" according to the present invention generally refers to non-lattice ion elements contained in the zeolitic material.
[0026] With regard to the ion exchange procedure, there is no particular restriction neither in relation to the specific ion exchange method that is applied, nor with respect to whether this step is repeated and, if it is, the number of times that said stage is repeated. In this way, for example, ion exchange can be conducted with the aid of a solvent or a mixture of solvent in which the ion to be exchanged is adequately dissolved. With respect to the type of solvent that can be used, there is again no particular restriction in this regard, as long as the ions to be exchanged can be dissolved in the solvent. Thus, by way of example, the solvent or mixture of solvents that can be used includes water and alcohols, and in particular short-chain alcohols selected from C1-C4, and preferably C1-C3 alcohols, in particular methanol, ethanol or propanol, including mixtures of two or more of these. Examples of mixtures are mixtures of two or more alcohols, such as methanol and ethanol or methanol and propanol or ethanol and propanol or methanol and ethanol and propanol, or mixtures of water and at least one alcohol, such as water and methanol or water and ethanol or water and propanol or water and methanol and ethanol or water and methanol and propanol or water and ethanol and propanol or water and methanol and ethanol and propanol. According to a preferred embodiment of the present invention, however, water or a mixture of water and one or more alcohols is preferred, wherein the mixture of water and ethanol is additionally preferred, deionized water being particularly preferred as the solvent for the one or more more ion exchange procedures.
[0027] Regarding the quantity of one or more solvents preferably used in the ion exchange procedure, in order to dispose the one or more non-lattice elements in the catalyst, again there is no particular restriction, as long as the element does not truss is effectively arranged in the catalyst. Thus, as an example, an excess of solvent or solvent mixtures can be used in the ion exchange procedure, in which one or more dissolved non-lattice elements enter the pore system of the zeolitic material and, on the other hand, ions contained in the zeolitic material against which the one or more non-lattice elements is adequately dissolved in the solvent or in the solvent mixture and, therefore, it is allowed to leave the pore system of the zeolitic material. It is preferred that the ion exchange procedure is conducted with an excess of solvent or solvent mixture, where, for example, a ratio of liquid to solid weight ranging in any range from 0.1 to 50 can be used . According to such preferred embodiments of the present invention, however, it is preferred that the ratio of liquid to solid weight, the ratio of the solvent or solvent mixture to the zeolitic material, is in the range 1 to 45, more preferably from 5 to 43, more preferably from 10 to 40, more preferably from 20 to 38 and even more preferably from 25 to 35. According to particularly preferred embodiments of the present invention, the weight ratio of solid to liquid used in the ion exchange procedure is between 27 and 33.
[0028] According to a preferred embodiment of the present invention, the one or more non-lattice elements are arranged in the catalyst by means of impregnation, more preferably by means of ion exchange.
[0029] According to a preferred embodiment of the present invention, the one or more non-lattice elements comprised in the zeolitic material is selected from the group consisting of Zn, Zr, Sn, Ti, Co, Cu, Fe, and combinations of two or more of these, preferably Zn, Zr, Sn, Ti, and combinations of two or more of these, more preferably Zn, Zr, Sn, and combinations of two or more of these, where even more preferably the non-lattice element is Zn .
Thus, according to a preferred embodiment of the present invention, the zeolitic material additionally comprises Zn as a non-lattice element, where Zn is preferably disposed in the catalyst by means of impregnation, more preferably by means of ion exchange .
[0031] Generally, there are no specific restrictions on how the zeolitic material comprised in the catalyst that is used in step (ii) of the present invention is provided. In particular, any possible process for synthesizing such a zeolite can be employed to provide the zeolitic material. According to a preferred embodiment of the present invention, the zeolitic material comprised in the catalyst that is used in step (ii) is provided by means of a process comprising: (k) providing a zeolitic material with a lattice structure comprising Z2O3 and YO2, where Y stands for one or more tetravalent elements and Z stands for a trivalent element; (l) removing at least a portion of Z when treating the zeolitic material provided in (a) with a liquid solvent system having a pH in the range of 5.5 to 8; (m) isomorphously replacing at least a portion of I comprised in the truss structure of the zeolitic material obtained from (b) by one or more elements X by means of a process comprising (c.1) preparing a synthesis mixture aqueous solution containing the zeolitic material obtained from (b), optionally a model compound, preferably selected from the group consisting of piperidine, hexamethylene imine, N, N, N, N ', N', N'-hexamethyl- 1,5-pentanediammonium, 1,4-bis (N-methylpyrrolidinium) butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, hexyltrimethylammonium hydroxide and a mixture of two or more of these, and an X source; (c.2) hydrothermally synthesize a zeolitic material containing X from the synthesis mixture obtained from (c.1), thus obtaining a zeolitic material containing X in its mother liquor; (c.3) optionally separate the zeolitic material containing X obtained from (c.2) its mother liquor; (n) treating the zeolytic material containing X obtained from (c) with an aqueous solution having a pH of at most 5.
[0032] According to a preferred embodiment of the present invention, YO2 and Z2O3 comprised in the truss structure of the zeolitic materials provided in step (a) are contained in the truss structure as elements forming the structure, as elements opposite to those without truss structure. which can be present in the pores and cavities depending on the truss structure and which can typically be for zeolitic materials in general.
[0033] When it comes to the chemical nature of Z, there are no specific restrictions. In particular Z can be any possible trivalent element or a mixture of two or more trivalent elements. Preferred trivalent elements according to the present invention include, but are not limited to, Al, B, In, Ga and Fe. Preferably, Z is selected from the group consisting of Al, B, In, Ga, Fe and combinations of two or more of these, Z being preferably B.
[0034] There is also no specific restriction with respect to one or more tetravalent elements included in the truss structure of the zeolitic material provided in (a). According to a preferred embodiment of the present invention, Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge and combinations of two or more of these, preferably selected from the group consisting of Si, Ti, Ge , and combinations of two or more of these, more preferably Y stands for Si.
[0035] Therefore, according to a particularly preferred embodiment of the present invention, Y stands for Si and Z stands for B.
[0036] According to preferred embodiments of the present invention, where Y stands for Si, any suitable silicone source can be used to provide the zeolitic material in (a), where preferably the silicone source is smoked silica, a mixture of two or more smoked silicas, a colloidal silica, such as ammonia stabilized colloidal silica, a mixture of two or more colloidal silicas, or a mixture of at least one smoked silica and at least one colloidal silica. Preferably, the silica source comprises a colloidal silica, more preferably an ammonium stabilized colloidal silica. More preferably, the silica source is a colloidal silica, more preferably an ammonia stabilized colloidal silica.
[0037] Additionally, according to preferred embodiments of the present invention, where Z is for B, any suitable source of boron can be used to provide the zeolitic material in (a), where preferably the source of boron is boric acid, a borate, in particular water-soluble borate, a boron halide, boron oxide (B2O3), or a mixture of two or more of these, with boric acid being especially preferred.
[0038] According to a particularly preferred embodiment of the present invention, where Z is for B and Y is for Si, and where the zeolitic material has a MWW lattice structure, a MWW model compound is used in (a), where preferably the model MWW compound is selected from the group consisting of and selected from the group consisting of piperidine, hexamethylene imine, N, N, N, N ', N', N'-hexamethyl-1.5 ion -pentanediamonium, 1,4-bis (N-methylpyrrolidinium) butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, hexyltrimethylammonium hydroxide, N, N hydroxide, N-trimethyl-1-adamantylamonium, and a mixture of two or more of these. Most preferably, the model MWW compound is piperidine.
[0039] Regarding the treatment of the zeolitic material provided in (a) with a liquid solvent system having a pH in the range of 5.5 to 8 according to (b), in order to remove at least a portion of Z, it is preferred that the zeolitic material obtained from (b) be free of Z or essentially free of Z, that is, contain Z only in traces as impurities.
[0040] Therefore, according to a particularly preferred embodiment of the present invention, where Z is for B, zeolitic material obtained from (b) is free of B or essentially free of B, that is, contains B only in strokes as impurities.
[0041] With respect to the model compound used in (c.1), according to a preferred embodiment of the present invention, the model compound used is piperidine.
[0042] According to a preferred embodiment of the present invention, in (c) at least a portion of Y comprised in the truss structure of the zeolitic material is isomorphously replaced by one or more elements X, where X is preferably selected a from the group consisting of Zr, Ti, Sn, Ga, Nb, Ta, Sc, Ge, Al, B, Fe and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, Ga , Ge, Ta, and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, Ta, and combinations of two or more of these.
[0043] According to a preferred embodiment of the present invention, in which the zeolitic material comprised in the catalyst used in (ii) has a MWW lattice structure, X is for Ti and / or Sn, in which the aqueous synthesis mixture prepared in (c.1) comprises a Ti source selected from the group consisting of tetrabutylortotitanate, tetraisopropylortotitanate, tetraethylortotitanate, titanium dioxide, titanium tetrachloride, titanium tert-butoxide, and a mixture of two or more of these, and / or one Sn source selected from the group consisting of SnCl4, Sn (IV) -acetate, Sn (IV) -tert-butoxide, SnBr4, SnCl4, SnF4, Sn (IV) -bisacetylacetonate dichloride, Sn (IV) - bisacetylacetonate dibromide, Sn (II) -acetate, Sn (II) acetylacetonate, Sn (II) -citrate, SnCl2, SnF2, SnI2, SnSO4, and mixtures of two or more of these.
[0044] According to a particularly preferred embodiment of the present invention, in which the zeolitic material comprised in the catalyst used in (ii) has a MWW lattice structure, X stands for Ti and / or Sn, in which the aqueous synthesis mixture prepared in (c.1) comprises tetrabutylortotitanate as source Ti and / or Sn (IV) -tert-butoxide as source Sn.
[0045] As described above, the zeolitic material comprised in the catalyst can additionally comprise one or more non-lattice elements. Thus, according to a preferred embodiment of the present invention, the zeolitic material obtained from (d) is optionally subjected to impregnation with Zn, Zr, Sn, Ti, Co, Cu, Fe, and combinations of two or more of these , preferably Zn, Zr, Sn, Ti, and combinations of two or more of these, more preferably Zn, Zr, Sn, and combinations of two or more of these, preferably impregnation is carried out by ion exchange. According to a particularly preferred embodiment of the present invention, in which the zeolitic material obtained from (d) is optionally subjected to impregnation with Zn, preferably impregnation is carried out by ion exchange.
[0046] According to a particularly preferred embodiment of the present invention, the zeolitic material comprised in the catalyst used in (ii) with a MWW lattice structure, in which at least a portion of Y comprised in the lattice structure is isomorphously substituted by Ta, it is provided by means of a process comprising (a) providing a zeolitic material with a lattice structure comprising Z2O3 and YO2, where Y stands for one or more tetravalent elements and Z stands for a trivalent element; (b) removing at least a portion of Z when treating the zeolitic material provided in (a) with a liquid solvent system having a pH in the range of 5.5 to 8; (c) isomorphously replacing at least a portion of Y comprised in the truss structure of the zeolitic material obtained from (b) by means of Ta by incipient moisture.
[0047] Incipient humidity is conducted with the aid of a solvent or mixture of solvent, in which Ta is properly dissolved. Regarding the type of solvent that can be used, there is no particular restriction. Thus, for example, the solvent or mixture of solvents that can be used includes water and alcohols and in particular short-chain alcohols selected from C1-C4 and preferably C1-C3 alcohols, in particular methanol, ethanol or propanol, including mixtures of two or more of these. Examples of mixtures are mixtures of two or more alcohols, such as methanol and ethanol or methanol and propanol or ethanol and propanol or methanol and ethanol and propanol, or mixtures of water and at least one alcohol, such as water and methanol or water and ethanol or water and propanol or water and methanol and ethanol or water and methanol and propanol or water and ethanol and propanol or water and methanol and ethanol and propanol. According to a preferred embodiment of the present invention, however, water or a mixture of water and one or more alcohols is preferred, in which the mixture of water and ethanol is additionally preferred, deionized water being particularly preferred.
[0048] In accordance with a preferred embodiment of the present invention, incipient moisture is achieved by using one or more inorganic or organic salts as source Ta. It is preferred, according to the present invention, that the one or more inorganic or organic salts are selected from the group consisting of halides, phosphates, hydroxides, carbonates, carboxylates, alcoholates and combinations of two or more of these, most preferably selected from from the group consisting of chlorides, carboxylates and combinations of two or more of these, more preferably the source Ta is oxalate.
[0049] According to a preferred embodiment of the present invention, in which the zeolitic material comprised in the catalyst has a BEA lattice structure comprising X2O3 and YO2, where Y stands for one or more tetravalent elements and X stands for one or more elements trivalent, tetravalent and / or pentavalent, the zeolitic material comprised in the catalyst that is used in step (ii) is preferably supplied by means of a process comprising (a) preparing an aqueous synthesis mixture comprising source Y, source X , and optionally a model compound, preferably selected from the group consisting of piperidine, hexamethylene imine, N, N, N-trimethyl-1-adamantammonium hydroxide, piperidine, hexamethylene imine, dibenzyl-1,4-diazabicyclo [2,2 , 2] octane, dibenzylmethylammonium, tetraethylammonium hydroxide, and combinations of two or more of these; (b) optionally, adding seed crystals and / or an acid to a mixture prepared in (e), wherein an aqueous solution of HF is preferably used as the acid; (c) hydrothermally synthesize a zeolitic material with a BEA lattice structure comprising X2O3 and YO2 from the aqueous synthesis mixture prepared in (e), optionally after step (f), where Y is for one or more elements tetravalent and X stands for one or more trivalent, tetravalent and / or pentavalent elements.
[0050] According to a preferred embodiment of the present invention, in which the zeolitic material comprised in the catalyst used in (ii) has a lattice structure BEA, X stands for one or more trivalent, tetravalent and / or pentavalent elements preferably selected at from the group consisting of Zr, Ti, Sn, Ga, Nb, Ta, Sc, Ge, Al, B, Fe and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, Ga , Ge, and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, and combinations of two or more of these, even more preferably X is for Zr, and Y is for one or more elements tetravalents preferably selected from the group consisting of Si, Sn, Ti, Zr, Ge and combinations of two or more of these, most preferably selected from the group consisting of Si, Ti, Ge, and combinations of two or more of these, plus preferably Y and for you.
[0051] According to a preferred embodiment of the present invention, where Y stands for Si, any suitable source of silicone can be used to prepare the aqueous synthesis mixture in (a), where preferably the source of silicone is selected from from the group consisting of tetraethylorosilicate, a smoked silica, a colloidal silica, such as ammonia-stabilized colloidal silica and combinations of two or more of these, more preferably, the source of silicone is tetraethylorthosilicate.
[0052] According to a preferred embodiment of the present invention, where X is for Zr, any suitable source of Zr can be used to prepare the aqueous synthesis mixture in (a), where preferably the source Zr is selected from from the group consisting of zirconium and zirconyl salts, more preferably from the group consisting of zirconium and zirconyl halides, zirconium hydroxide, zirconyl nitrate, zirconium alkoxides and mixtures of two or more of these, more preferably from the group consisting of zirconium and bromide zirconyl, chloride, fluoride, zirconyl nitrate, C1-C4 Zr alkoxides and mixtures of two or more of these, most preferably the group consisting of zirconium and zirconyl chloride, fluoride, zirconyl nitrate, C2-C3 Zr alkoxides and mixtures of two or more of these, more preferably the group consisting of zirconium and zirconyl chloride, zirconyl nitrate, C3 Zr alkoxides and mixtures of two or more of these, more prefer primarily from the group consisting of zirconyl chloride, zirconyl nitrate, Zn-n-propoxide, and mixtures of two or more of these, where most preferably the source Zr is Zr-n-propoxide.
[0053] Therefore, according to a particularly preferred embodiment of the present invention, where Y is for Si and X is for Zr, the aqueous synthesis mixture prepared in (a) comprises tetraethylortosilicate as the Si and Zr-n-propoxide source as source Zr.
[0054] According to a preferred embodiment of the present invention, wherein the aqueous synthesis mixture prepared in (a) comprises tetraethylorthosilicate and Zr-n-propoxide, the aqueous synthesis mixture prepared in (a) is heated to a temperature in the 50 to 120 ° C, preferably 85 to 100 ° C before optionally adding seed crystals and / or an acid and preferably an aqueous HF solution to a mixture prepared in (a) according to (b) and before hydrothermally synthesizing a zeolitic material with a BEA lattice structure comprising X2O3 and YO2 from the aqueous synthesis mixture prepared in (a) according to (c) to remove one or more alcohols and in particular propanol and / or ethanol, and preferably to remove ethanol from the synthesis mixture by distillation.
[0055] Regarding the particular conditions under which the gas stream G-1 is brought into contact with a catalyst according to the present invention in step (ii), there are no particular restrictions, as long as a gas stream G -2 comprising butadiene is obtained. This, for example, applies to a temperature at which contact occurs in step (ii). Therefore, said contact of the gas stream in step (ii) can be conducted according to the process of the invention at a temperature in the range of 200 to 600 ° C, preferably from 250 to 550 ° C, more preferably from 300 to 500 ° C, more preferably 325 to 425 ° C, more preferably 350 to 400 ° C. According to a particularly preferred embodiment of the present invention, putting the gas stream G-1 in contact with the catalyst is carried out at a temperature in the range of 300 to 500 ° C, preferably from 325 to 425 ° C, more preferably from 350 at 400 ° C.
The same applies, therefore, to the pressure under which the gas stream G-1 is brought into contact with a catalyst according to the present invention in step (ii) of the process of the invention. Thus, in principle, said putting in contact can be conducted under any possible pressures, as long as a stream of G-2 gas comprising butadiene is obtained. According to a preferred embodiment of the present invention, placing the gas stream G-1 in contact with the catalyst is carried out at a pressure in the range of 1 to 5 bar, preferably 1 to 2 bar.
[0057] According to a particularly preferred embodiment of the present invention, the gas stream G-1 is brought into contact with a catalyst according to the present invention in step (ii) at a temperature in the range of 300 to 500 ° C , preferably from 325 to 425 ° C, more preferably from 350 to 400 ° C, at a pressure in the range of 1 to 5 bar, preferably from 1 to 2 bar.
[0058] Additionally, no particular restrictions apply regarding the way in which the process of the invention for the preparation of butadiene is conducted, such that both a non-continuous and a continuous mode can be applied to the process of the invention, in that the non-continuous process can, for example, be conducted as a batch process.
[0059] According to a preferred embodiment of the present invention, placing the gas stream G-1 in contact with the catalyst is carried out in a continuous mode. There is no specific restriction regarding the configuration of the continuous process. Preferred continuous process configurations include the use of one or more fixed reactors. In this way, according to a preferred embodiment of the present invention, putting the gas stream G-1 in contact with the catalyst is carried out in one or more reactors, where the one or more reactors contain the catalyst in the form of a fixed bed .
[0060] In the case of the preferred modalities of the process of the invention, in which putting the gas stream G-1 in contact with the catalyst in step (ii) is carried out in a continuous mode, in principle no restrictions regarding speed hourly spatial liquid (LHSV) in which the process is conducted, provided that a stream of G-2 gas comprising butadiene is obtained. Therefore, hourly spatial velocities of liquid can be chosen to put in contact in step (ii), which are in the range of 0.1 to 30 h-1, in which hourly spatial velocities of liquid are preferably chosen from 0.2 to 15h-1, more preferably from 0.3 to 5h-1, more preferably from 0.4 to 1h-1, and most preferably from 0.5 to 0.7h-1. According to a particularly preferred embodiment of the process of the invention, in which putting the gas stream G-1 in contact with the catalyst in step (ii) is carried out in a continuous mode, hourly spatial velocities of liquid are chosen, varying from 0 , 5 to 0.7 h-1 to bring the gas stream in step (ii) into contact with a catalyst according to the present invention
[0061] Additionally, according to the present invention, it is preferred that before putting the gas stream G-1 in contact with the catalyst, the gas stream is heated. According to a preferred embodiment, heating the gas stream G-1 before coming into contact with the catalyst can be conducted to a temperature in the range of 50 to 300 ° C, preferably from 100 to 250 ° C and more preferably from 120 to 180 ° C. Thus, according to a preferred embodiment of the present invention, before putting the gas stream G-1 in contact with the catalyst, the gas stream G-1 is preferably heated to a temperature in the range of 100 to 250 ° C , more preferably from 120 to 180 ° C.
[0062] Additionally, according to a preferred embodiment of the present invention, an activation of the catalyst occurs before putting the gas stream G-1 in contact with the catalyst, in which, for example, the activation can be conducted at the heat the catalyst. Thus, according to a preferred embodiment of the present invention, before putting the gas stream G-1 in contact with the catalyst, the catalyst is activated preferentially upon heating.
[0063] In the case of specific conditions under which the catalyst is activated, there are no particular restrictions, provided that through the use of the activated catalyst the G-2 gas stream is obtained. Therefore, such activation of the catalyst before coming into contact with the gas stream G-1 can be conducted according to a preferred embodiment of the process of the invention at a temperature in the range of 200 to 550 ° C, preferably from 250 to 500 ° C, more preferably 300 to 450 ° C, more preferably 325 to 425 ° C, more preferably 350 to 400 ° C. The same applies to the activation duration. In this way, according to a preferred embodiment of the present invention, activation before coming into contact with the gas stream G-1 is carried out for a period in the range of 5 to 120 min, more preferably 10 to 60 min, more preferably 20 to 40 min. Thus, according to a preferred embodiment of the present invention, it is preferable that the catalyst is activated by heating to a temperature in the range of 300 to 450 ° C, preferably from 325 to 425 ° C, more preferably from 350 to 400 ° C, preferably for a period in the range of 5 to 120 min, more preferably 10 to 60 min, more preferably 20 to 40 min.
[0064] According to a preferred embodiment of the present invention, a heating ramp is used to reach the activation temperature, where the heating rate preferably ranges from 0.5 to 10 K / min, preferably 1 to 5 K / min, preferably from 1 to 3 K / min. In this way, according to a preferred embodiment of the present invention, the catalyst is heated with a temperature ramp in the range of 0.5 to 10 K / min, preferably 1 to 5 K / min, preferably from 1 to 3 K / min .
[0065] Generally, there is no specific restriction regarding the configuration in which the activation is carried out. According to a particularly preferred embodiment of the present invention, the catalyst is activated in one or more reactors.
[0066] It is preferable that during heating the catalyst is discharged with an inert gas. With regard to the chemical nature of the inert gas, there are no particular restrictions. According to a particularly preferred embodiment of the present invention, during heating the catalyst is discharged with an inert gas, preferably with an inert gas selected from the group consisting of helium, nitrogen, argon and mixtures of two or more of these, in that inert gas is more preferably nitrogen.
[0067] Regarding the amount of butadiene included in the gas stream G-2 obtained from the contact of the gas stream G-1 with the catalyst in step (ii) of the present invention, there are no particular restrictions. However, it has been found that through a process for the preparation of butadiene according to the process of the invention, the gas stream G-2 is obtained containing butadiene in an amount of 10 to 90% by volume, preferably from 20 to 80% by volume, more preferably 30 to 70% by volume, based on the total volume of the G-2 gas stream. Therefore, embodiments of the present invention are preferred, in which the G-2 gas stream contains butadiene in an amount of 10 to 90% by volume, preferably 20 to 80% by volume, more preferably 30 to 70% by volume, based on the total volume of the G-2 gas stream.
[0068] According to preferred embodiments of the present invention, the process for the preparation of butadiene additionally comprises the separation of butadiene from the gas stream G-2 obtained from step (ii) of the present invention, wherein the current of purified gas G-3 comprising butadiene is obtained. There are generally no restrictions regarding the method for separating butadiene from the G-2 gas stream, as long as the purified gas stream G-3 comprising butadiene is obtained. Such methods can include thermal separation. Preferably, the separation of butadiene from the gas stream G-2 is achieved by means of thermal separation, more preferably by means of distillation.
Thus, modalities of the present invention are preferred, in which the process for the preparation of butadiene additionally comprises (iii) separating butadiene from the gas stream G-2, thereby obtaining the purified gas stream G -3 comprising butadiene, in which separation is preferably achieved by means of thermal separation, more preferably by means of distillation.
[0070] According to a preferred embodiment of the present invention, the gas stream G-2 comprising butadiene obtained from step (ii) of the present invention can additionally comprise compounds resulting from placing the gas stream G-1 in contact with the catalyst. Thus, according to preferred embodiments of the invention, the gas stream G-2 comprising butadiene additionally comprises diethyl ether. If the G-2 gas stream comprising butadiene additionally comprises diethyl ether, it is preferred that the diethyl ether be separated from the G-2 gas stream comprising butadiene. It is additionally preferred that the separation is carried out by means of thermal separation, preferably by means of distillation.
[0071] Additionally, it has been found that the separated diethyl ether can be recycled to the gas phase process for the preparation of butadiene according to the present invention, wherein it is preferable to recycle the separated diethyl ether as a component of the gas stream G-1 which is placed in contact with a catalyst in step (ii). Therefore, according to a preferred embodiment of the present invention, the separated diethyl ether is recycled to the gas phase process for the preparation of butadiene according to the present invention, wherein the separated diethyl ether is preferably recycled as a component of the stream of G-1 gas which is put in contact with the catalyst in step (ii) to obtain butadiene. Thus, according to a preferred embodiment of the present invention, the gas stream G-2 additionally comprises diethyl ether, and in which the diethyl ether is separated from the gas stream G-2, preferably by means of thermal separation, more preferably by means of distillation, and recycling of the separated diethyl ether for the gas phase process for the preparation of butadiene, preferably as a component of the G-1 gas stream.
[0072] According to preferred embodiments of the present invention, wherein G-2 additionally comprises diethyl ether which is preferably separated from G-2 and recycled preferably as a component of the G-1 gas stream, it is preferred that the gas stream G-2, before separating the diethyl ether, contain diethyl ether in an amount of 1 to 65% by volume, preferably 1 to 35% by volume, more preferably 2 to 20% by volume, based in the total volume of the G-2 gas stream. Thus, according to a particularly preferred embodiment of the present invention, the gas stream G-2 contains diethyl ether in an amount of 1 to 65% by volume, preferably from 1 to 35% by volume, more preferably from 2 to 20% by volume, based on the total volume of the G-2 gas stream.
[0073] With respect to the diethyl ether separated from the G-1 gas stream, according to a preferred embodiment of the present invention, at least a portion of the separated diethyl ether is hydrolyzed in ethanol before recycling it to the phase process gas for the preparation of butadiene, preferably as a component of the G-1 gas stream. Thus, according to a preferred embodiment of the present invention, the process for the preparation of butadiene additionally comprises hydrolyzing at least a portion of the diethyl ether separated in ethanol before recycling it to the gas phase process for the preparation of butadiene , preferably as a component of the G-1 gas stream.
[0074] With respect to the conditions under which hydrolysis is conducted, according to a preferred embodiment of the present invention, the separated diethyl ether is hydrolyzed under acidic conditions, more preferably in the presence of a solid catalyst.
[0075] According to a preferred embodiment of the present invention, wherein the gas stream G-2 additionally comprises diethyl ether, the gas stream G-2 can additionally comprise crotonaldehyde. Thus, according to a preferred embodiment of the present invention, the G-2 gas mixture additionally comprises crotonaldehyde.
[0076] According to a preferred embodiment of the embodiment of the present invention, in which the G-2 gas stream additionally comprises crotonaldehyde, it is preferred that the G-2 gas stream contains crotonaldehyde in an amount of 0.1 to 15% by volume, preferably from 0.5 to 10% by volume, more preferably from 1 to 5% by volume, based on the total volume of the G-2 gas stream.
[0077] According to a particularly preferred embodiment of the present invention, the G-2 gas stream comprising butadiene is free of crotonaldehyde or essentially free of crotonaldehyde, that is, it contains crotonaldehyde only in strokes.
[0078] According to a preferred embodiment of the present invention, the catalyst is subjected to regeneration, in which the regeneration can be conducted by any suitable method. Possible methods are, for example, to regenerate the catalyst by means of heat treatment, preferably in the presence of oxygen. In addition, there are no particular restrictions on the temperature under which regeneration is conducted. According to a preferred embodiment of the present invention, the heat treatment is conducted, for example, at a temperature in the range of 200 to 600 ° C, preferably from 300 to 550 ° C, more preferably from 400 to 500 ° C. Therefore, according to a preferred embodiment of the present invention, the process for the preparation of butadiene according to the present invention additionally comprises regenerating the catalyst, preferably by means of heat treatment in the presence of oxygen, where the heat treatment is preferably carried out at a temperature in the range of 100 to 700 ° C, preferably from 350 to 600 ° C, more preferably from 450 to 570 ° C.
[0079] According to a particularly preferred embodiment of the present invention, the catalyst placed in contact with the gas stream G-1 in step (ii) comprises a zeolitic material according to any of the particular and preferred embodiments of the present invention, as defined below.
[0080] Thus, it was discovered that when using a catalyst comprising a zeolitic material, with a lattice structure comprising YO2, Y being for one or more tetravalent elements, in which at least a portion of Y comprised in the lattice structure isomorphically replaced by one or more X elements, in which the zeolitic material has an X-ray powder diffraction pattern comprising at least the following reflections:
where 100% concerns the maximum peak intensity in the x-ray powder diffraction pattern in the process of the present invention, a high conversion of ethanol or a mixture of ethanol and acetaldehyde can be achieved, while at the same time a high selectivity in relation to butadiene has been achieved.
[0081] Therefore, in addition to the process for the preparation of butadiene by means of the use of a catalyst comprising a zeolitic material, the present invention also relates to a zeolitic material with a lattice structure comprising YO2, Y being for one or more tetravalent elements, in which at least a portion of Y comprised in the truss structure is isomorphously replaced by one or more X elements, and in which the zeolitic material has an x-ray powder diffraction pattern comprising at least the following reflections:
where 100% refers to the maximum peak intensity in the X-ray powder diffraction pattern.
[0082] Regarding the molar ratio Y: X in the truss structure of the zeolitic material, there are no particular restrictions, provided that at least a portion of Y is isomorphously replaced by one or more X elements. preferred embodiment of the present invention, the molar ratio of Y: X in the truss structure ranges from 100: 1 to 700: 1, preferably from 300: 1 to 600: 1, more preferably from 450: 1 to 550: 1.
[0083] As mentioned above, X stands for one or more trivalent, tetravalent and / or pentavalent elements, in which there are generally no specific restrictions with respect to the chemical nature of one or more trivalent, tetravalent and / or pentavalent elements. According to a particularly preferred embodiment of the present invention, X stands for one or more trivalent, tetravalent and / or pentavalent elements, preferably selected from the group consisting of Zr, Ti, Sn, Ga, Nb, Ta, Sc, Ge, Al, B, Fe and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, Ga, Ge, Ta, and combinations of two or more of these, most preferably selected from the group consisting of in Zr, Ti, Sn, Ta, and combinations of two or more of these, even more preferably X is for Zr.
[0084] There is also no specific restriction with respect to the tetravalent element Y included in the truss structure of the zeolitic material. According to a preferred embodiment of the present invention, Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge and combinations of two or more of these, preferably selected from the group consisting of Si, Ti, Ge, and combinations of two or more of these, where Y is most preferably for Si.
[0085] Therefore, according to a particularly preferred embodiment of the present invention, X stands for Zr and Y stands for Si.
[0086] Additionally, there is no particular restriction, according to the present invention, as to the appropriate physical and / or chemical characteristics of the zeolitic materials of the invention. Thus, as regards, for example, the porosity and / or the surface area of the materials of the invention, they can adopt any conceivable values. In particular, with regard to the BET surface area of the zeolitic materials, as determined according to DIN 66131, it can therefore vary in any range from 20 to 600 m2 / g, more preferably in the range of 30 at 500 m2 / g. According to a particularly preferred embodiment of the present invention, zeolitic material has a specific BET surface area of at least 20 m2 / g, and preferably a specific BET surface area in the range of 20 to 600 m2 / g, more preferably in the range 30 to 500 m2 / g, where the specific surface area is as determined according to DIN 66131.
[0087] Generally, there are no specific restrictions on how the zeolitic material, as defined above, is provided. Any conceivable process for synthesizing such a zeolite can be employed to provide the zeolitic material.
[0088] According to a particularly preferred embodiment of the present invention, where Y is Si, X is Zr, the zeolitic material defined above is preferably provided by means of a process comprising: (a) providing a zeolitic material containing boron with a MWW truss structure comprising SiO2 and B2O3 (B-MWW); (b) deborate the B-MWW by treating the B-MWW provided in (a) with an aqueous solution; (c) isomorphously replacing at least a portion of Si with Zr by means of a process comprising (c.1) preparing an aqueous synthesis mixture containing the deboronated B-MWW obtained from (b), a model compound, preferably selected from the group consisting of piperidine, hexamethylene imine, N, N, N, N ', N', N'-hexamethyl-1,5-pentanediammonium ion, 1,4-bis (N-methylpyrrolidinium) butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, hexyltrimethylammonium hydroxide and a mixture of two or more of these, and a Zr source; (c.2) hydrothermally synthesize a zrolytic material containing Zr from the synthesis mixture obtained from (c.1), thereby obtaining a zeolitic material containing Zr in its mother liquor; (c.3) separate the zeolitic material containing Zr obtained from (c.2) from its mother liquor; (d) treating the zrolytic material containing Zr obtained from (c) with an aqueous solution having a pH of at most 5.
[0089] There are generally no specific restrictions on how B-MWW is provided in (a). Any conceivable process for synthesizing such a zeolite can be employed to provide the zeolitic material. Preferably, the zeolitic material is provided in (a) by means of a process including hydrothermally synthesizing the zeolitic material from suitable sources of B2O3 and SiO2 in the presence of a suitable model compound, also called a structure targeting agent.
[0090] According to a preferred embodiment of the present invention, a precursor B-MWW is provided by means of a process comprising: (a.1) hydrothermally sintering a precursor B-MWW from an aqueous synthesis mixture containing a silicone source, a boron source, and a model MWW compound, preferably selected from the group consisting of piperidine, hexamethylene imine, N, N, N, N ', N', N'-hexamethyl-1 ion, 5-pentanediammonium, 1,4-bis (N-methylpyrrolidinium) butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, hexyltrimethylammonium hydroxide, and a mixture of two or more of these, to obtain a precursor B-MWW in its mother liquor; (a.2) separate a B-MWW precursor from its mother liquor, and calcinate the separate B-MWW precursor, obtaining a B-MWW.
[0091] In the case of the source of silica used in (a.1), there is no specific restriction. Preferably, the silicone source is a smoked silica or a colloidal silica, such as ammonia-stabilized colloidal silica, with ammonium-stabilized colloidal silica being especially preferred.
[0092] In the case of the boron source used in (a.1), there is no specific restriction. Preferably, the boron source is boric acid, a borate, in particular a water-soluble borate, a boron halide, boron oxide (B2O3), with boric acid being especially preferred.
[0093] In the case of the model MWW compound used in (a.1), there is no specific restriction, as long as a precursor B-MWW is obtained. Preferably, the model MWW compound is selected from the group consisting of and selected from the group consisting of piperidine, hexamethylene imine, N, N, N, N ', N', N'-hexamethyl-1,5-pentanediammonium ion , 1,4-bis (N-methylpyrrolidinium) butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, hexyltrimethylammonium hydroxide, N, N, N-trimethyl-1-adamantilammonium hydroxide and a mixture of two or more of these. Most preferably, the model MWW compound is piperidine.
[0094] According to a particularly preferred embodiment of the present invention, the aqueous synthesis mixture according to (a.1) comprises ammonia-stabilized colloidal silica, boric acid and piperidine.
[0095] According to a preferred embodiment of the present invention, the aqueous synthesis mixture is preferably subjected to a hydrothermal synthesis according to (a.1), in which the zeolitic material is crystallized during the hydrothermal synthesis. During hydrothermal synthesis, the crystallization mixture can be stirred. The rate of agitation as such can be appropriately chosen depending, for example, on the volume of the aqueous synthesis mixture, the amount of the starting materials employed, the desired temperature and the like. For example, the agitation rate is in the range of 50 to 300 rpm (revolutions per minute), such as from 100 to 250 rpm or from 130 to 170 rpm Preferably, the crystallization time is in the range of 3 to 8 days , more preferably from 4 to 6 days.
[0096] The temperature applied during hydrothermal synthesis in (a.1) is preferably in the range of 140 to 200 ° C, more preferably from 150 ° C to 190 ° C, more preferably from 160 to 180 ° C, more preferably from 160 less than 180 ° C, more preferably 170 to 177 ° C.
[0097] After hydrothermal synthesis, the precursor B-MWW obtained is preferably adequately separated from its mother liquor according to (a.2). All conceivable methods for separating a B-MWW from its mother liquor are possible. These methods include, for example, filtration, ultrafiltration, diafiltration and centrifugation methods or, for example, spray drying processes and spray granulation processes. A combination of two or more of these methods can be applied.
[0098] According to a preferred embodiment of the present invention, the precursor B-MWW is separated from its mother liquor by filtration, and the material thus obtained, for example, in the form of a filter cake, is preferably subjected to washing with at least one suitable washing agent, preferably when washing with water.
[0099] After separating the precursor B-MWW from the mother liquor, preferably by filtration and preferably after washing, the washed precursor B-MWW is subjected to drying preferably at a temperature in the range of 50 to 200 ° C, more preferably from 70 to 150 ° C, more preferably 90 to 110 ° C.
[00100] After drying, the precursor B-MWW is subjected to calcination to obtain a B-MWW. During calcination, the model MWW compound is preferably at least partially, more preferably essentially completely removed from the truss structure. Preferred calcination temperatures are in the range of 500 to 700 ° C, more preferably from 550 to 675 ° C, more preferably from 600 to 650 ° C. Preferred atmospheres under which calcination is carried out include technical nitrogen, air or poor air. Preferred calcination times are in the range of 1 to 24h, preferably from 5 to 20h, more preferably from 8 to 18h.
[00101] The B-MWW obtained from (a) is subjected to deforestation in (b) by means of a treatment with an aqueous solution. According to a preferred embodiment of the present invention, the aqueous solution has a pH of at most 7, preferably in the range of 0 to 7, more preferably from 0 to 5, more preferably from 0 to 4, more preferably from 0 to 3, more preferably 0 to 2.
[00102] The pH of the aqueous solution used in (b) is adjusted by means of an adequate amount of at least one acid which is dissolved in water. It is generally possible that, in addition to at least one acid, the aqueous solution contains at least one base, as long as the aqueous solution has a pH as defined above. Preferably, the aqueous solution used in (b) comprises water and at least one acid dissolved in the water.
[00103] According to a preferred embodiment of the present invention, the aqueous solution used in (b) comprises at least one organic acid or at least one inorganic acid or a mixture of at least one organic acid and at least one inorganic acid. In principle, any conceivable acid can be comprised in an aqueous solution used in (b). Preferably, the organic acid is selected from the group consisting of oxalic acid, acetic acid, citric acid, methanesulfonic acid and a mixture of two or more of these. Preferably, the inorganic acid is selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid and a mixture of two or more of these. Preferably, at least one inorganic acid is used. Preferably, the inorganic acid is nitric acid.
[00104] In general there is no particular restriction for organic acid and inorganic acid comprised in the aqueous solution used in (b), provided that the pH of the aqueous solution used in (b) is defined as above.
[00105] Preferably, the zeolitic material is treated in (b) with the aqueous solution at a temperature in the range of 20 ° C to 200 ° C, more preferably from 40 ° C to 160 ° C, more preferably from 60 ° C to 140 ° C, more preferably from 80 ° C to 120 ° C.
[00106] Preferably, the zeolitic material is treated in (b) with the aqueous solution for a period ranging from 1 min to 50 h, more preferably from 5 h to 40 h, more preferably from 15 h to 25 h.
[00107] During the treatment according to (b), it is additionally preferable to properly stir the aqueous solution. During (b), the agitation rate is kept essentially constant or altered, the treatment with the liquid solvent system according to (b) being carried out, thus, at two or more different agitation rates.
[00108] After treating the B-MWW with an aqueous solution according to (b), the debored zeolitic material thus obtained is preferably adequately separated from the suspension. All methods for separating the deforested zeolitic material from the suspension are possible. These methods include, for example, filtration, ultrafiltration, diafiltration and centrifugation methods. A combination of two or more of these methods can be applied. According to a preferred embodiment of the present invention, the debored zeolitic material is preferably separated from the suspension by means of a filtration method.
[00109] After separating the debored zeolitic material, it can be subjected to a washing step, in which washing agents include, but are not limited to, water, alcohols such as methanol, ethanol or propanol or mixtures of two or more of these . Examples of mixtures are mixtures of two or more alcohols, such as methanol and ethanol or methanol and propanol or ethanol and propanol or methanol and ethanol and propanol, or mixtures of water and at least one alcohol, such as water and methanol or water and ethanol or water and propanol or water and methanol and ethanol or water and methanol and propanol or water and ethanol and propanol or water and methanol and ethanol and propanol. Water or a mixture of water and at least one alcohol, preferably water and ethanol, is preferred. Especially preferred is water as a single washing agent.
[00110] After deforestation according to (b), at least a portion of Si comprised in the trellis structure of the debored zeolitic material is replaced in an isomorphic manner by Zr.
[00111] In the case of the compound used in (c.1), there is no specific restriction. Preferably, the model compound is selected from the group consisting of piperidine, hexamethylene imine, N, N, N, N ', N', N'-hexamethyl-1,5-pentanediammonium ion, 1,4-bis (N - methylpyrrolidinium) butane, octyltrimethylammonium hydroxide, heptyltrimethylammonium hydroxide, hexyl-trimethylammonium hydroxide and a mixture of two or more of these. Most preferably, the model compound is piperidine.
[00112] Regarding the source Zr used in (c.1) is, there is no specific restriction, as long as Zr is introduced in the deforested B-MWW. According to a preferred embodiment of the present invention, the source Zr is preferably selected from the group consisting of zirconium and zirconyl salts, more preferably from the group consisting of zirconium and zirconyl halides, zirconium hydroxide, zirconyl nitrate, alkoxides of zirconium and mixtures of two or more of these, more preferably from the group consisting of zirconium and zirconyl bromide, chlorine, fluorine, zirconyl nitrate, C1-C4 Zr alkoxides and mixtures of two or more of these, more preferably from the group consisting of zirconium and zirconyl chloride, fluoride and nitrate, C2-C3 Zr alkoxides and mixtures of two or more of these, most preferably the group consisting of zirconium and zirconyl chloride, zirconyl nitrate, C3 Zr alkoxides and mixtures of two or more of these, more preferably from the group consisting of zirconyl chloride, zirconyl nitrate, Zn-n-propoxide and mixtures of two or more of these, where more preferred initially the source Zr is Zr-n-propoxide.
[00113] According to a particularly preferred embodiment of the present invention, the synthesis mixture according to (c.1) comprises the deboronated B-MWW obtained from (b), piperidine and Zr-n-propoxide.
[00114] During the treatment according to (c.1), it is additionally preferable to properly stir the aqueous solution. During (c.1), the rate of agitation is kept essentially constant or is altered, with the result that the treatment with the liquid solvent system according to (c.1) is carried out, thus, in two or more rates of different shaking. For example, the agitation rate is in the range of 50 to 300 rpm (revolutions per minute), such as from 100 to 250 rpm or 130 to 170 rpm.
[00115] According to a preferred embodiment of the present invention, the hydrothermal synthesis according to (c.2) is carried out at a temperature in the range of 80 to 250 ° C, more preferably from 120 to 200 ° C, more preferably from 160 to 180 ° C. In addition, the hydrothermal synthesis according to (c.2) is preferably carried out for a period in the range of 20 to 200 hours, more preferably from 60 to 160 hours, more preferably from 110 to 125 hours.
[00116] After hydrothermal synthesis, the zeolytic material containing Zr obtained is adequately separated from the mother liquor in step (c.3). All methods for separating the zeolitic material containing Zr from its mother liquor are possible. These methods include, for example, filtration, ultrafiltration, diafiltration and centrifugation methods or, for example, spray drying processes and spray granulation processes. A combination of two or more of these methods can be applied. According to the present invention, the zrolytic material containing Zr is preferably separated from its mother liquor by filtration to obtain a filter cake which is preferably subjected to washing, preferably with water.
[00117] Preferably, stage (c.3) comprises drying the zrolytic material containing Zr, where drying is preferably carried out at a temperature in the range of 100 to 180 ° C, more preferably from 110 to 140 ° C. Regarding the duration of drying, the zrolytic material containing Zr having a lattice structure of the MWW type, there is no specific restriction. According to a preferred embodiment of the present invention, drying is carried out for a period ranging from 1 to 30 hours, preferably from 6 to 24 hours, more preferably from 14 to 18 hours.
[00118] According to a preferred embodiment of the present invention, the separate and preferably dry zr zeolitic material obtained from (c) is subjected to stage (d) in which the zr zeolitic material is treated with an aqueous solution having a pH of at most 5.
[00119] Preferably, in (d), the zrolytic material containing Zr obtained from (c) is treated with an aqueous solution, which comprises an organic acid, preferably selected from the group consisting of oxalic acid, acetic acid, acid citric, methanesulfonic acid and a mixture of two or more of these, and / or an inorganic acid, preferably selected from the group consisting of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid and a mixture of two or more of these, the acid inorganic most preferably being nitric acid. Preferably, in (d), the aqueous solution has a pH in the range 0 to 5, preferably 0 to 3, more preferably 0 to 2. The pH values should be understood as being determined with a glass electrode sensitive to pH.
[00120] During the treatment according to (d), it is additionally preferable to properly stir the aqueous solution. During (d), the agitation rate is kept essentially constant or altered, the treatment with the liquid solvent system according to (d), thus being carried out at two or more different agitation rates. For example, the agitation rate is in the range of 50 to 300 rpm (revolutions per minute), such as from 100 to 250 rpm or from 150 to 190 rpm.
[00121] Regarding the temperature of the treatment with the aqueous solution according to (d), there is no specific restriction. Preferably, in (d), the zrolytic material containing Zr is treated with the aqueous solution at a temperature in the range of 50 to 175 ° C, preferably from 70 to 125 ° C, more preferably from 95 to 105 ° C. Preferably, in (d), the zrolytic material containing Zr having a MWW lattice structure is treated with the aqueous solution for a period ranging from 1 to 40 hours, more preferably from 12 to 24 hours, more preferably from 18 to 24 hours. 22 hours.
[00122] The treatment according to (d) preferably comprises adequately separating the zeolytic material containing Zr from the aqueous solution. All methods for separating zeolitic material containing Zr from the aqueous solution are possible. These methods include, for example, filtration, ultrafiltration, diafiltration and centrifugation methods or, for example, spray drying processes and spray granulation processes. A combination of two or more of these methods can be applied. According to a preferred embodiment of the present invention, zrolitic material containing Zr is preferably separated from the aqueous solution by filtration to obtain a filter cake which is preferably subjected to washing, preferably with water.
[00123] It has been found that zeolitic materials obtained or obtainable according to the present invention, in which zeolitic material with a lattice structure comprising YO2, in which at least a portion of Y comprised in the lattice structure is isomorphously substituted by one or more elements X, it can be used as such for any suitable purpose and, in particular, as a catalytically active material, such as a catalytically active material in a process for the preparation of butadiene according to the present invention.
[00124] Thus, the present invention also concerns the use of a zeolitic material with a lattice structure comprising YO2, Y being for one or more tetravalent elements, in which at least a portion of Y comprised in the lattice structure is replaced isomorphically by one or more elements X, as a catalytically active material in a process for the preparation of butadiene, preferably from a gas stream comprising ethanol and, optionally, acetaldehyde.
[00125] According to a preferred embodiment of the present invention, the zeolitic material is used as a catalytically active material in a process for the preparation of butadiene, preferably from a gas stream comprising ethanol and, optionally, acetaldehyde. According to a particularly preferred embodiment of the present invention, the zeolitic material used as a catalytically active material in a process for the preparation of butadiene preferably, preferably from a gas stream comprising ethanol and, optionally, acetaldehyde, is a zeolitic material with a lattice structure comprising YO2 as defined according to any of the particular and preferred embodiments of the present invention.
[00126] It has been found that the zeolitic materials obtained or obtainable according to the present invention can be used in a process for the preparation of butadiene according to the present invention, in which the selectivity of the process in relation to butadiene is at least minus 10%, preferably in the range of 10 to 90%, more preferably 20 to 80%, and most preferably 30 to 70%.
[00127] Therefore, according to a particularly preferred embodiment of the present invention, the zeolitic materials according to the present invention are used in a process for the preparation of butadiene according to the present invention, in which the selectivity of the process in relation to butadiene is at least 10%, preferably in the range of 10 to 90%, more preferably from 20 to 80%, more preferably from 30 to 70%. Within the meaning of the present invention, the selectivity of the process in relation to butadiene generally designates any suitable process for the preparation of butadiene, and, therefore, the selectivity in relation to butadiene obtained by such a process. It is, however, preferential according to the present invention, that selectivity in relation to butadiene designates selectivity as obtained according to any of the particular and preferred modalities of the process for the preparation of butadiene, according to the present invention, as defined in this application.
[00128] The present invention includes the following modalities, where these include specific combinations of modalities as indicated by the respective interdependencies defined therein: 1. A gas phase process for the preparation of butadiene comprising (i) providing a gas stream G -1 comprising ethanol; (ii) placing the G-1 gas stream comprising ethanol in contact with a catalyst, thereby obtaining a G-2 gas stream comprising butadiene, wherein the catalyst comprises a zeolitic material with a lattice structure comprising YO2 , Y standing for one or more tetravalent elements, in which at least a portion of Y comprised in the truss structure is isomorphously replaced by one or more elements X. 2. The process, according to modality 1, in which the gas stream G-1 additionally comprises acetaldehyde. 3. The process, according to modality 2, in which the molar ratio of ethanol to acetaldehyde in the G-1 gas stream is in the range of 1: 1 to 6: 1, preferably from 2: 1 to 3, 5: 1, more preferably from 2.5: 1 to 2.9: 1. 4. The process, according to mode 2 or 3, in which 80% by volume or more of the G-1 gas stream comprises ethanol or a The mixture of ethanol and acetaldehyde, wherein preferably 90% by volume or more, more preferably 95% by volume or more of the G-1 gas stream comprises ethanol or a mixture of ethanol and acetaldehyde. 5. The process, according to any of the modalities 1 to 4, in which the molar ratio to Y: X in the truss structure varies from 10: 1 to 150: 1, preferably from 20: 1 to 80: 1, more preferably from 30: 1 to 50: 1. 6. The process, according to any of modalities 1 to 4, in which the molar ratio of Y: X in the truss structure varies from 50: 1 to 700: 1, preferably from 100: 1 to 600: 1, more preferably from 170: 1 to 520: 1. 7. The process, according to any of the modalities 1 to 6, where X is for one or more trivalent, tetravalent and / or pentavalents, in which the one or more elements X are preferably selected from the group consisting of Zr, Ti, Sn, Ga, Nb, Ta, Sc, Ge, Al, B, Fe and combinations of two or more of these, plus preferably selected from the group consisting of Zr, Ti, Sn, Ga, Ge, Ta and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, Ta and combinations of two or more of these, even more preferably X is for Zr and / or Ta. 8. The process, according to any of modalities 1 to 7, in which Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge and combinations of two or more of these, preferably selected from the group consisting of Si, Ti, Ge and combinations of two or more of these, and most preferably Y is for Si. 9. The process, according to any of modalities 1 to 8, wherein the catalyst comprises a zeolitic material with a structure trellis selected from the group consisting of BEA, MWW, MFI, MEL, MOR, RUT, DOH, MTN, FER, FAU, CDO, LEV, CHA and combinations of two or more of these, preferably selected from the group consisting of BEA, MWW, MFI, MEL and combinations of two or more of these, most preferably selected from BEA and MWW. 10. The process, according to modality 9, in which the catalyst comprises beta zeolite isomorphically substituted and / or Sn-MWW and / or Ta-MWW, preferably Zr-BEA and / or Ta-MWW. 11. The process, according to any one of modalities 1 to 9, in which the zeolitic material comprised in the catalyst has a lattice structure MWW, where Y is Si and X is Ti. 12. The process, according to modality 11, in which the zeolitic material additionally comprises Zn as a non-lattice element, in which Zn is preferably disposed in the catalyst by impregnation, more preferably by ion exchange. 13. The process according to any one of modalities 1 to 4, wherein the catalyst comprises a zeolitic material according to any one of claims 33 to 37. 14. The process, according to any one of modalities 1 to 13, in that placing the gas stream G-1 in contact with the catalyst is carried out at a temperature in the range of 300 to 500 ° C, preferably from 325 to 425 ° C, more preferably from 350 to 400 ° C. 15. The process, according to any of modalities 1 to 14, in which putting the gas stream G-1 in contact with the catalyst is carried out at a pressure in the range of 1 to 5 bar, preferably 1 to 2 bar . 16. The process, according to any of modalities 1 to 15, in which putting the gas stream G-1 in contact with the catalyst is carried out in a continuous mode. 17. The process, according to any of modalities 1 to 16, in which putting the gas stream G-1 in contact with the catalyst is carried out in one or more reactors, in which the one or more reactors contain the catalyst in the in the form of a fixed bed. 18. The process, according to any of the modalities 1 to 17, in which, before putting the gas stream G-1 in contact with the catalyst, the gas stream G-1 is heated, preferably to a temperature in the range from 100 to 250 ° C, more preferably from 120 to 180 ° C. 19. The process, according to any one of the modalities 1 to 18, in which before putting the gas stream G-1 in contact with the catalyst, the catalyst is activated, preferably on heating. 20. The process, according to modality 19, in which the catalyst is activated by heating to a temperature in the range of 300 to 450 ° C, preferably from 325 to 425 ° C, more preferably from 350 to 400 ° C, preferably for a period in the range of 5 to 120 minutes, more preferably 10 to 60 minutes, more preferably 20 to 40 minutes. 21. The process, according to mode 19 or 20, in which the catalyst is heated with a temperature ramp in the range of 0.5 to 10 K / min, preferably 1 to 5 K / min, preferably 1 to 3 K / min. 22. The process, according to any of modalities 19 to 21, in which the catalyst is activated in one or more reactors. 23. The process, according to any of the modalities 19 to 22, in which, during heating, the catalyst is discharged with an inert gas, preferably with an inert gas selected from the group consisting of helium, nitrogen, argon and mixtures of two or more of these, where the inert gas is most preferably nitrogen. 24. The process, according to any one of modalities 1 to 23, in which the gas stream G-2 contains butadiene in an amount of 10 to 90% by volume, preferably from 20 to 80% by volume, more preferably from 30 to 70% by volume, based on the total volume of the G-2 gas stream. 25. The process, according to any one of modalities 1 to 24, additionally comprising (111) separating butadiene from the gas stream G-2, thereby obtaining a stream of purified gas G-3 comprising butadiene, wherein the separation is preferably achieved by thermal separation, more preferably by distillation. 26. The process, according to any one of modalities 1 to 25, in which the G-2 gas stream additionally comprises diethyl ether, and in which the diethyl ether is separated from the G-2 gas stream, preferably by thermal separation, more preferably by distillation, and recycling of the separated diethyl ether for the gas phase process for the preparation of butadiene, preferably as a component of the G-1 gas stream. 27. The process, according to modality 26, in which the gas stream G-2 contains diethyl ether in an amount from 1 to 65% by volume, preferably from 1 to 35% by volume, more preferably from 2 to 2% by volume, based on the total volume of the G-2 gas stream. 28. The process, according to modality 26 or 27, additionally comprising hydrolyzing at least a portion of the diethyl ether separated in ethanol before recycling it to the gas phase process for the preparation of butadiene, preferably as a component of the stream of G-1 gas. 29. The process according to modality 28, in which the separated diethyl ether is hydrolyzed under acidic conditions, more preferably in the presence of a solid catalyst. 30. The process, according to any of modalities 1 to 29, in which the gas stream G-2 additionally comprises crotonaldehyde. 31. The process, according to modality 30, in which the gas stream G-2 contains crotonaldehyde in an amount of 0.1 to 15% by volume, preferably 0.5 to 10% by volume, more preferably 1 to 5% by volume, based on the total volume of the G-2 gas stream. 32. The process, according to any of modalities 1 to 31, additionally comprising regenerating the catalyst, preferably by heat treatment in the presence of oxygen, where the heat treatment is preferably carried out at a temperature in the range of 100 to 700 ° C, preferably 350 to 600 ° C, more preferably 450 to 570 ° C. 33. A zeolitic material with a lattice structure comprising YO2, Y being for one or more tetravalent elements, in which at least a portion of Y comprised in the lattice structure is isomorphously replaced by one or more X elements, and in which the zeolitic material has an x-ray powder diffraction pattern comprising at least the following reflections:
where 100% refers to the maximum peak intensity in the X-ray powder diffraction pattern. 34. The zeolitic material, according to modality 33, in which the molar ratio of Y: X in the truss structure varies from 100: 1 to 700: 1, preferably from 300: 1 to 600: 1, more preferably from 450 : 1 to 550: 1. 35. The zeolitic material, according to modality 33 or 34, where X is for one or more trivalent, tetravalent and / or pentavalent elements, preferably selected from the group consisting of Zr, Ti , Sn, Ga, Nb, Ta, Sc, Ge, Al, B, Fe and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, Ga, Ge, Ta and combinations of two or more of these, most preferably selected from the group consisting of Zr, Ti, Sn, Ta and combinations of two or more of these, even more preferably X is for Zr. 36. The zeolitic material, according to any of the modalities 33 to 35, in which Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge and combinations of two or more of these, preferably selected from the group consisting of Si, Ti, Ge and combinations of two or more of these, more preferably Y is for Si. 37. The zeolitic material, according to any of the modalities 33 to 36, in which the zeolitic material has a surface area specific BET of at least 20 m2 / g, and preferably a specific BET surface area in the range of 20 to 600 m2 / g, more preferably in the range of 30 to 500 m2 / g, where the specific surface area is determined from according to DIN 66131. 38. Use of a zeolitic material with a lattice structure comprising YO2, Y being for one or more tetravalent elements, in which at least a portion of Y comprised in the lattice structure is isomorphously replaced by one or more X elements, like an m catalytically active material in a process for the preparation of butadiene, preferably from a gas stream comprising ethanol and, optionally, acetaldehyde. 39. The use, according to modality 38, in which the zeolitic material is a zeolitic material with a lattice structure comprising YO2 as defined in any of the modalities 5 to 12 or in any of the modalities 33 to 37. 40. The use, according to modality 38 or 39, in which the selectivity of the process in relation to butadiene is at least 10%, preferably in the range of 10 to 90%, more preferably from 20 to 80%, more preferably from 30 to 70%. DESCRIPTION OF THE FIGURES - Figure 1: shows the X-ray diffraction pattern (XRD) (measured using Cu K alpha-1 radiation) of the silicate containing crystalline zirconium (Zr-silicate) obtained from Example 3. In the Figure, the angle diffraction 2 theta in ° is shown along the abscissa and the intensities are plotted along the ordinate. - Figure 2: shows the X-ray diffraction pattern (XRD) (measured using Cu K alpha-1 radiation) of the zeolitic material containing tin (Sn-MWW) obtained from Example 5. In the Figure, the diffraction angle 2 theta in ° is shown along the abscissa and the intensities are plotted along the ordinate. - Figure 3: shows the UV-VIS spectra of Ta-MWW obtained according to Example 8. In the abscissa, the values of wavelength (nanometer) are shown, and the Kubelka-Munk units “KM” are plotted graphically. along the ordinate. - Figure 4: shows the UV-VIS spectra of Ta-MWW obtained according to Example 9. In the abscissa, the wavelength values (nanometer) are shown, and the Kubelka-Munk units “KM” are plotted along of the ordinate. - Figure 5: shows the X-ray diffraction pattern (XRD) (measured using Cu K alpha-1 radiation) of the zeolitic material containing tantalum (Ta-MWW) obtained from Example 8. In the Figure, the diffraction angle 2 theta in ° is shown along the abscissa and the intensities are plotted along the ordinate. - Figure 6: shows product formation and conversion of ethanol / acetaldehyde as a function of time by using the Zr-silicate obtained from Example 3. On the x-axis, the percentage values are shown for the conversion of ethanol, as well as for selectivity in relation to ethylene, crotonaldehyde, ethyl acetate, ethylene, Compounds C1 to C3, compounds C4, diethyl ether, Compounds C6 and other compounds, and on the y axis, the time in hours is indicated. EXAMPLES REFERENCE EXAMPLE 1: DETERMINATION OF CRYSTALLINITY AND THE C NETWORK PARAMETER OF ZEOLYTIC MATERIALS WITH A STRUCTURE IN MWW TRELIQUE
[00129] The crystallinity and the network parameter and the zeolitic materials according to the present invention were determined by XRD analysis. Data is collected using a standard Bragg-Brentano diffractometer with a Cu x-ray source and an energy dispersion point detector. The angular range of 2 ° to 70 ° (2 theta) is examined with a step size of 0.02 °, while the variable divergence groove is defined at a constant illuminated sample length of 20 mm. The data are then analyzed using the TOPAS V4 Software, in which the acute diffraction peaks are modeled using a Pawley adjustment containing a unit cell with the following starting parameters: a = 14.4 Angstrom and c = 25.2 Angstrom in the space group P6 / mmm. These are refined to fit the data. Independent peaks are inserted at the following positions. 8.4 °, 22.4 °, 28.2 ° and 43 °. These are used to describe the amorphous content. The crystalline content describes the intensity of the crystalline signal for the total dispersed intensity. The model includes a linear background, Lorentz and polarization corrections, network parameters, spatial group and crystalline size. REFERENCE EXAMPLE 2: DETERMINATION OF THE CRYSTALLINITY OF ZEOLYTIC MATERIALS WITH A BEA TRELIQUE STRUCTURE
[00130] The crystallinity of zeolitic materials, according to the present invention, was determined by XRD analysis, in which the crystallinity of a given material is expressed in relation to a reference zeolitic material in which a single reflection of the two zeolitic materials is compared. The reference zeolitic material was commercially available beta-type ammonium zeolite under CAS registration number 1318-02-1. The determination of crystallinity was performed on a D8 Advance diffractometer series 2 using Bruker AXS. The diffractometer was configured with a 0.1 ° divergence hole opening and a Lynxeye detector. The samples, as well as the reference zeolitic material, were measured in the range of 19 ° to 25 ° (2 Theta). After baseline correction, the areas of the reflections were determined by using the EVA evaluation software (from Bruker AXS). The proportions of the areas are given as percentage values. REFERENCE EXAMPLE 3: DETERMINATION OF DV50 1. Sample Preparation
[00131] 1.0 g of the micropowder is suspended in 100 g of deionized water and stirred for 1 minute. 2. Apparatus and respective parameters used - Mastersizer S long bed version 2.15, ser. No. 33544-325; supplier: Malvern Instruments GmbH, Herrenberg, Germany - focal width: 300RF mm - beam length: 10.00 mm - module: MS17 - shading: 16.9% - dispersion model: 3 $$ D - analysis model: polydispersed - correction : none REFERENCE EXAMPLE 4: CONVERSION OF A MIXTURE OF ETHANOL AND ACETALDEHYDE FOR BUTADIENE PREPARATION OF THE CATALYST SAMPLES:
[00132] Before testing, the catalyst samples were compacted using 25 kN pressure and sieved to particle size in the range of 315 to 500 μm. CONFIGURATION:
[00133] Experiments were conducted in a Test unit 16 times. For feed-dosing, a mixture of acetaldehyde and ethanol was pumped to an evaporator in which it is heated to 125 ° C inside a stream of nitrogen gas. The trace-heated (170 ° C) feed streams are then distributed to all 16 reactor tubes. Within each reactor tube (stainless steel; 400mm long and 4mm ID), the catalyst sieve fraction (1cc) is stored by an inert upper and lower layer consisting of quartz (315-500μm, 2cc). Through a multiport selection valve, the trace-heated (200 ° C) effluent from each reactor is taken to the GC / MS for product analysis. CATALYST ACTIVATION
[00134] For activation, samples are heated to 375 ° C for 30 minutes under nitrogen. PERFORMANCE
[00135] A mixture of ethanol and acetaldehyde (molar ratio 2.75: 1) was evaporated and mixed with nitrogen to obtain a feed composition of 90% by volume of ethanol / acetaldehyde and 10% by volume of nitrogen. The supply current thus obtained was converted over the catalyst to butadiene at a temperature of 375 ° C and under a pressure in the range of 1 to 2 bar and with LHSV (hourly liquid space velocity) of 0.6 h-1. The mixture of gaseous products was analyzed by line gas chromatography. LHSV (hourly liquid space velocity): 0.6 h-1
[00136] Conversions and average selectivities over an operating time of 110 hours were determined, in which conversions and selectivities were determined in the interval of 8 hours. REFERENCE EXAMPLE 5: UV-VIS SPECTRUM MEASUREMENTS
[00137] Measurements of UV-VIS spectra were performed using a Lambda 950 spectrophotometer from PerkinElmer with 150 mm integrating spheres, in which a white spectralon standard from the company Labsphere was used as a reference. EXAMPLE 1: SYNTHESIS OF ZEOLITHIC MATERIAL CONTAINING ZIRCONIUM WITH A STRUCTURE IN BEA TRELICE (ZR-BEA)
[00138] In a round-bottomed flask 86.30 g of tetraethylorthosilicate (TEOS) were added together with 97.48 g of tetraethylammonium hydroxide (TEAOH). 1.33 g of ZrOCl2 and 3.31 g of distilled water were added to the suspension. The alcohol was distilled under stirring at 95 ° C. After distillation the mixture was cooled to room temperature and transferred to a Teflon coating in a Berghof autoclave (250 ml). To a mixture of 11.59 g of a solution of aqueous hydrogen fluoride (40% by weight in water) and 3.02 g of seeds of a de-aluminized zeolitic material with a BEA lattice structure were added. The autoclave was closed and the zeolite was hydrothermally synthesized in a static oven for 20 days at 140 ° C. After this period, the autoclave was cooled to room temperature and the solid was filtered off and washed with distilled water until the washing water had a pH of 7. The solid was dried in a static oven at 100 ° C for 16 hours. , and calcined at 580 ° C for 4 hours. DESCRIPTION
[00139] The zeolitic material obtained had a zirconium content of 0.75% by weight, a silicon content of 45.0% by weight and a crystallinity of 124%, determined by XRD. The specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 456 m2 / g. EXAMPLE 2: SYNTHESIS OF ZEOLYTIC MATERIAL CONTAINING ZIRCONIUM WITH A STRUCTURE IN BEA TRELICE (ZR-BEA)
[00140] In a round bottom flask 129.60 g of tetraethylorthosilicate (TEOS) were added together with 146.39 g or tetraethylammonium hydroxide (TEAOH). 1.00 g of ZrOCl2 and 5.59 g of distilled water were added to the suspension. The alcohol was distilled under stirring at 95 ° C. After distillation, the mixture was cooled to room temperature and transferred to a Teflon coating in a Berghof autoclave (250 ml). To a mixture of 17.40 g of a solution of aqueous hydrogen fluoride (40% by weight in water) and 4.54 g of dealuminized Beta-type zeolite seeds were added. The autoclave was closed and the zeolite was hydrothermally synthesized in a static oven for 20 days at 140 ° C. After this period, the autoclave was cooled to room temperature and the solid was filtered off and washed with distilled water until the washing water had a pH of 7. The solid was dried in a static oven at 100 ° C for 16 hours. and CALCINATED AT 580 ° C FOR 4 HOURS. DESCRIPTION
[00141] The zeolitic material containing zirconium obtained with a BEA lattice structure had a zirconium content of 0.48% by weight, a silicon content of 46.0% by weight and a crystallinity of 124%, determined by XRD. The specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 472 m2 / g. EXAMPLE 3: SYNTHESIS OF A SILICATE CONTAINING CRYSTALLINE ZIRCON (ZR-SILICATE) EXAMPLE 3.1 SUMMARY OF A ZEOLYTIC MATERIAL CONTAINING BORON WITH A STRUCTURE IN MWW SPLASH (B-MWW)
[00142] 15.75 kg of deionized water and 6.08 kg of piperidine were introduced into a stirring pressure vessel. With stirring 3.63 kg of boric acid was added and the suspension was stirred for 30 minutes added. To the resulting solution, 3.5 kg of Aerosil 200 were added in portions and the suspension was further stirred for 2 hours. Finally, the crystallization vessel was heated to 170 ° C for 2 hours under autogenous pressure and stirred at 150 rpm. The 170 ° C temperature was kept essentially constant for 120 hours. During these 120 hours, the mixture was stirred at 150 rpm. Subsequently, the mixture was cooled to a temperature in the range of 50 to 60 ° C. The aqueous suspension containing boron-containing zeolitic material with a MWW lattice structure (B-MWW) had a pH of 11.3 as determined by measurements with a pH electrode. From said suspension, the B-MWW was separated by filtration. The filter cake was washed with deionized water until the wash water had a conductivity of less than 700 microSiemens / cm. The filter cake was dried in a static oven at 100 ° C for 16 hours and the dry powder was calcined at 600 ° C for 16 hours. DESCRIPTION
[00143] The B-MWW obtained had a boron content of 1.4% by weight, a silicon content of 42% by weight and a total organic carbon (TOC) content of 0.01% by weight. EXAMPLE 3.2: DEBORONATION
[00144] The B-MWW obtained according to Example 3.2 was debored following the procedure below: 122.5 kg of an aqueous solution of HNO3 (30% by weight in water) were introduced together with 4.08 kg of B- MWW in a container equipped with a reflux condenser. The suspension was stirred and heated to 100 ° C and maintained for 20 hours under reflux conditions. Afterwards, the mixture was cooled and the solid was recovered by filtration and washed with distilled water until the washing water had a pH of 7. The filter cake was subsequently dried in a static oven at 120 ° C for 16 hours. DESCRIPTION
[00145] The debored zeolitic material obtained had a boron content of 0.07% by weight and a silicon content of 41.0% by weight. EXAMPLE 3.3 INCORPORATION OF ZIRCONIUM
[00146] 540 g of water and 260.64 g of piperidine were introduced into a glass bottle. The mixture was stirred at 200 rpm and 24.56 g of zirconium n-propoxide was added. The obtained mixture was further stirred for 20 minutes before adding dropwise 180 g of the zeolitic material debored with a MWW lattice structure obtained according to Example 3.2. The suspension was further stirred for 2 hours at 200 rpm until a gel was obtained. The gel formed was transferred to an autoclave. The autoclave was heated to 170 ° C and maintained at this temperature for 120 hours under agitation at 150 rpm. Subsequently, the autoclave was cooled and the solid was filtered off and washed until the washing water had a pH of 7. The filter cake was dried in a static oven at 120 ° C for 16 hours. DESCRIPTION
[00147] The zeolitic material containing zirconium obtained had a zirconium content of 3.2% by weight and a silicon content of 38.5% by weight. EXAMPLE 3.4 ACID TREATMENT OF ZEOLITHIC MATERIAL CONTAINING ZIRCONIUM
[00148] 4200 g of an aqueous solution of HNO3 (30% by weight in water) was provided in a 10 l flask. To this solution was added the zirconium-containing silicate obtained according to Example 3.3 and the mixture was heated at 100 ° C for 20 hours with stirring at 170 rpm. Subsequently, the suspension was filtered and washed until the washing water had a pH of 7. The filter cake was dried in a static oven for 16 hours at 120 ° C and calcined at 550 ° C for 10 hours. DESCRIPTION
[00149] The zeolitic material obtained had a zirconium content of 0.27% by weight and a silicon content of 43% by weight. The specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 38 m2 / g. The XRD of the obtained zeolitic material is shown in Figure 1. The obtained zeolitic material has an XRD pattern having the following reflections:


EXAMPLE 4: SUMMARY OF ZNTI-MWW EXAMPLE 4.1 PREPARATION OF MWW CONTAINING BORON
[00150] 470.4 kg of deionized water were provided in a container. With stirring at 70 ° C, 162.5 kg of boric acid was suspended in the water. The suspension was stirred for another 3 hours. Thereafter, 272.5 kg of piperidine was added and the mixture was stirred for another hour. To the resulting solution, 392.0 kg of Ludox® AS-40 was added and the resulting mixture was stirred at 70 rpm for another hour.
[00151] The finally obtained mixture was transferred to a crystallization vessel and heated to 170 ° C within 5 hours under autogenous pressure and under stirring (50 rpm). The temperature of 170 ° C was kept essentially constant for 120 hours; during these 120 hours, the mixture was stirred at 50 rpm. Subsequently, the mixture was cooled to a temperature of 50 to 60 ° C for 5 hours. The aqueous suspension containing B-MWW had a pH of 11.3 as determined by measurements with a pH electrode.
[00152] From said suspension, the B-MWW was separated by filtration. The filter cake was then washed with deionized water until the washing water had a conductivity of less than 700 microSiemens / cm.
[00153] The filter cake thus obtained was subjected to spray drying in a spray tower with the following spray drying conditions: drying gas, nozzle gas: drying gas temperature: spray tower temperature ( inlet): 288 to 291 ° C spray tower temperature (outlet): 157 to 167 ° C - filter temperature (inlet): - purifier temperature (inlet): - purifier temperature (outlet): difference filter pressure: nozzle: - two-component nozzle 0 - nozzle gas temperature: - nozzle gas pressure: apparatus used: spray tower with one nozzle configuration: spray tower - filter - operating mode: pure nitrogen purifier flow gas: 1,900 kg / h filter material: 20 m2 of Nomex® needled felt dosing by means of a flexible tube pump: SP VF 15 (supplier: Verder)
[00154] The spraying tower was composed of a cylinder arranged vertically with a length of 2,650 mm, a diameter of 1,200 mm, the cylinder of which was conically narrowed at the bottom. The cone length was 600 mm. At the top of the cylinder, the atomizing means (a two-component nozzle) was arranged. The spray-dried material was separated from the drying gas in a filter downstream of the spraying tower, and the drying gas was then passed through a purifier. The suspension was passed through the internal opening of the nozzle and the nozzle gas was passed through the ring-shaped groove surrounding the opening. The spray-dried material was then subjected to calcination at 650 ° C for 2 hours. DESCRIPTION
[00155] The calcined material had a boron content of 1.9% by weight, a silicon content of 41% by weight and a total organic carbon content of 0.18% by weight. The crystallinity determined by XRD was 74%, specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 448 m2 / g, pore volume determined by HG porosimetry, according to with DIN 66133, it was 5.9 ml / g, spray dried particle size distribution determined by Malvern Dv50 was 26.9 μm. 4.2 DEBORONED MWW PREPARATION a) Deforestation
[00156] Based on the spray dried material obtained according to section 4.1 above, 4 lots of MWW of debored zeolite were prepared. In each of the first 3 batches, 35 kg of spray dried material obtained according to section 4.1 and 525 kg of water were used. In the fourth batch, 32 kg of spray dried material obtained according to section 4.1 and 480 kg of water were used. In total, 137 kg of spray dried material obtained according to section 4.1 and 2025 kg of water were used.
[00157] For each batch, the respective amount of water was passed into a container equipped with a reflux condenser. Under stirring at 40 r.p.m., the supplied amount of the spray dried material was suspended in the water. Subsequently, the container was closed and the reflux condenser was put into operation. The stirring rate was increased to 70 r.p.m. Under stirring at 70 r.p.m., the contents of the vessel were heated to 100 ° C for 10 hours and maintained at this temperature for 10 hours. Then, the contents of the container were cooled to a temperature below 50 ° C. The debored zeolitic material resulting from a MWW-type structure was separated from the suspension by filtration under a nitrogen pressure of 2.5 bar and washed four times with deionized water. After filtration, the filter cake was dried in a stream of nitrogen for 6 hours.
[00158] The debored zeolitic material obtained in 4 batches (625.1 kg of nitrogen-dried filter cake in total) had a residual moisture content of 79%, as determined using an IR (infrared) scale at 160 ° C. b) Spray drying of nitrogen-dried filter cake
[00159] From the nitrogen-dried filter cake having a residual moisture content of 79% obtained according to section a) above, an aqueous suspension was prepared with deionized water, the suspension having a solid content of 15% in Weight. This suspension was subjected to spray drying in a spray tower with the following spray drying conditions: drying gas, nozzle gas: drying gas temperature: spray tower temperature (inlet): 304 ° C - temperature spray tower (outlet): 147 to 150 ° C - filter temperature (inlet): 133 to 141 ° C - purifier temperature (inlet): 106 to 114 ° C - purifier temperature (outlet): 13 to 20 ° C pressure difference filter: 1.3 to 2.3 mbar nozzle: two-component nozzle: Niro supplier, dosing diameter by means of a flexible tube pump: VF 10 (supplier: Verder)
[00160] The spraying tower was composed of a vertically arranged cylinder with a length of 2,650 mm, a diameter of 1,200 mm, the cylinder of which was conically narrowed at the bottom. The cone length was 600 mm. At the top of the cylinder, the atomizing means (a two-component nozzle) was arranged. The spray-dried material was separated from the drying gas in a filter downstream of the spraying tower, and the drying gas was then passed through a purifier. The suspension was passed through the internal opening of the nozzle and the nozzle gas was passed through the ring-shaped groove surrounding the opening. DESCRIPTION
[00161] The zeolitic material containing spray dried boron had a boron content of 0.08% by weight, a silicon content of 42% by weight and a total organic carbon content of 0.23% by weight. The specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 476 m2 / g and the crystallinity, determined by XRD, was 81%. EXAMPLE 4.3 PREPARING TIMWW
[00162] Based on the deforested MWW material, as obtained according to section 4.2, a zeolitic material of MWW type structure containing titanium was prepared, referred to below as TiMWW. The synthesis was carried out in two experiments, described below as a) and b): a) First experiment Starting materials: deionized water: 244.00 kg piperidine: 118.00 kg tetrabutyl orthotitanate: 10.90 kg debored zeolitic material: 54.16 kg 54.16 kg of the deforested zeolitic material of MWW type structure were transferred in a first container A.
[00163] In a second container B, 200.00 kg of deionized water were transferred and stirred at 80 rpm 118.00 kg of piperidine were added under stirring and, during the addition, the temperature of the mixture increased by about 15 ° C . Subsequently, 10.90 kg of tetrabutyl orthotitanate and 20.00 kg of deionized water were added. Then, stirring was continued for 60 minutes.
[00164] The mixture from container B was then transferred to container A and stirring was started in container A (70 r.p.m.). Container A was filled with 24.00 kg of deionized water and transferred to container B.
[00165] The mixture was then stirred in container B for 60 minutes at 70 r.p.m. At the beginning of the stirring, the pH of the mixture in container B was 12.6, as determined with a pH electrode.
[00166] After said stirring at 70 r.p.m., the frequency was decreased to 50 r.p.m., and the mixture in vessel B was heated to a temperature of 170 ° C for 5 hours. At a constant stirring rate of 50 r.p.m., the temperature of the mixture in vessel B was maintained at an essentially constant temperature of 170 ° C for 120 hours under autogenous pressure. During this crystallization of TiMWW, a pressure increase of up to 10.6 bar was observed. Subsequently, the suspension obtained containing TiMWW having a pH of 12.6 was cooled for 5 hours.
[00167] The cooled suspension was subjected to filtration and the separated mother liquor was transferred to the discharge of residual water. The filter cake was washed four times with deionized water under a nitrogen pressure of 2.5 bar. After the last washing step, the filter cake was dried in a stream of nitrogen for 6 hours.
[00168] From 246 kg of said filter cake, an aqueous suspension was prepared with deionized water, the suspension having a solid content of 15% by weight. This suspension was subjected to spray drying in a spray tower with the following spray drying conditions: drying gas, nozzle gas: technical nitrogen drying gas temperature: - spray tower temperature (inlet): 304 ° C - spray tower temperature (outlet): 147 to 152 ° C - filter temperature (inlet): 133 to 144 ° C - purifier temperature (inlet): - purifier temperature (outlet): pressure difference filter : nozzle: - top component nozzle: 4 mm - nozzle gas flow: - nozzle gas pressure: operating mode: apparatus used: nozzle configuration: purifier gas flow: filter material: dosing by means of flexible tube pump: VF 10 (supplier: Verder)
[00169] The spray tower was composed of a cylinder arranged vertically with a length of 2,650 mm, a diameter of 1,200 mm, the cylinder of which was conically narrowed at the bottom. The cone length was 600 mm. At the top of the cylinder, the atomizing means (a two-component nozzle) was arranged. The spray-dried material was separated from the drying gas in a filter downstream of the spraying tower, and the drying gas was then passed through a purifier. The suspension was passed through the internal opening of the nozzle and the nozzle gas was passed through the ring-shaped groove surrounding the opening. DESCRIPTION
[00170] The spray dried TiMWW material obtained from the first experiment had a silicon content of 37% by weight, a titanium content of 2.4% by weight and a total organic carbon content of 7.5% in weight. b) Second experiment
[00171] The second experiment was carried out in the same way as the first experiment described in section a) above. The spray dried TiMWW material obtained from the second experiment had a silicon content of 36% by weight, a titanium content of 2.4% by weight and a total organic carbon content of 8.0% by weight. EXAMPLE 4.4 ACID TIMWW TREATMENT
[00172] Each of the two spray dried TiMWW materials as obtained in the first and second experiments described in sections 4.3 a) and 4.3 b) above were subjected to acid treatment as described below in sections a) and b). In section c) below, it is described as a mixture of the materials obtained from a) and b) that are spray dried. In section d) below, it is described how the spray-dried material is calcined. a) Acid treatment of the spray dried material obtained according to section 4.3.a) Starting materials: deionized water: 690.0 kg nitric acid: (53%): 900.0 kg Ti-MWW spray dried 4.3. a): 53.0 kg
[00173] A container was filled with 670.0 kg of deionized water. 900 kg of nitric acid was added and 53.0 kg of spray dried TiMWW were added with stirring at 50 r.p.m. The resulting mixture was stirred for another 15 minutes. Subsequently, the agitation rate was increased to 70 r.p.m. For 1 hour, the mixture in the container was heated to 100 ° C and maintained at this temperature and under autogenous pressure for 20 hours under agitation. The mixture thus obtained was then cooled for 2 hours to a temperature below 50 ° C. The cooled mixture was subjected to filtration, and the filter cake was washed six times with deionized water under a pressure of nitrogen of 2.5 bar. After the last washing step, the filter cake was dried under a stream of nitrogen for 10 hours. The wash water after the sixth wash step had a pH of about 2.7. 225.8 kg of dry filter cake were obtained. b) Acid treatment of the spray dried material obtained in accordance with section 4.3.b) Starting materials: deionized water: 690.0 kg nitric acid: (53%): 900.0 kg Ti-MWW spray dried 4.3. b): 55.0 kg
[00174] The acid treatment of the spray dried material obtained in accordance with section 4.3.b) was carried out in the same way as the acid treatment of the spray dried material obtained in accordance with section 4.3.a) as described in section 4.4 a ). The wash water after the sixth wash step had a pH of about 2.7. 206.3 kg of dry filter cake were obtained. c) Spray drying of the mixture of materials obtained from 4.4.a) and 4.4 b)
[00175] From 462.1 kg of the mixture of the filter cakes obtained from 4.4.a) and 4.4 b), an aqueous suspension was prepared with deionized water, the suspension having a solid content of 15% by weight . This suspension was subjected to spray drying in a spray tower with the following spray drying conditions: drying gas, nozzle gas: technical nitrogen drying gas temperature: - spray tower temperature (inlet): 304 a 305 ° C - spray tower temperature (outlet): 151 ° C - filter temperature (inlet): 141 to 143 ° C - purifier temperature (inlet): 109 to 118 ° C - purifier temperature (outlet): 14 to 15 ° C pressure difference filter: 1.7 to 3.8 mbar nozzle: - two-component nozzle: Niro supplier, dosing diameter by means of a flexible tube pump: VF 10 (supplier: Verder)
[00176] The spraying tower was composed of a cylinder arranged vertically with a length of 2,650 mm, a diameter of 1,200 mm, whose cylinder was conically narrowed at the bottom. The cone length was 600 mm. At the top of the cylinder, the atomizing means (a two-component nozzle) was arranged. The spray-dried material was separated from the drying gas in a filter downstream of the spraying tower, and the drying gas was then passed through a purifier. The suspension was passed through the internal opening of the nozzle and the nozzle gas was passed through the ring-shaped groove surrounding the opening. DESCRIPTION
[00177] The spray dried acid treated TiMWW material had a silicon content of 42% by weight, a titanium content of 1.6% by weight and a total organic carbon content of 1.7% by weight. The specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 435 m2 / g and the crystallinity, determined by XRD, was 80%. d) Calcination of the spray dried material obtained in accordance with 4.4. ç)
[00178] The spray-dried material was then subjected to calcination at 650 ° C in a rotary kiln for 2 hours. DESCRIPTION
[00179] The calcined material had a silicon content of 42.5% by weight, a titanium content of 1.6% by weight and a total organic carbon content of 0.15% by weight. The Langmuir surface is determined by nitrogen adsorption at 77 K according to DIN 66134 was 612 m2 / g, the specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 442 m2 / g. The total penetration volume determined according to HG porosimetry, according to DIN 66133, was 4.9 ml / g (millimeter / gram), the respective total pore area of 104.6 m2 / g. Crystallinity, as determined by XRD, was 80% and the average crystalline size was 31 nm. 4.5 IMPREGNATION OF TIMWW WITH ZN a) Impregnation
[00180] The material treated with acid, spray dried and calcined as obtained according to 4.4 d) was then subjected to an impregnation stage. Starting materials: deionized water: 2610.0 kg dehydrated zinc acetate: 15.93 kg calcined Ti-MWW 4.4.d): 87.0 kg
[00181] Impregnation was carried out in 3 batches a) to c) as follows: a) In a container equipped with a reflux condenser, a solution of 840 kg of deionized water and 5.13 kg dehydrated zinc acetate was prepared for 30 minutes. Under stirring (40 r.p.m.), 28 kg of the calcined Ti-MWW material obtained according to 4.4.d) were suspended. Subsequently, the container was closed and the reflux condenser was put into operation. The stirring rate was increased to 70 r.p.m. b) In a container equipped with a reflux condenser, a solution of 840 kg of deionized water and 5.13 kg of dehydrated zinc acetate was prepared for 30 minutes. Under stirring (40 r.p.m.), 28 kg of the calcined Ti-MWW material obtained according to 4.4.d) were suspended. Subsequently, the container was closed and the reflux condenser was put into operation. The stirring rate was increased to 70 r.p.m. c) In a container equipped with a reflux condenser, a solution of 930 kg of deionized water and 5.67 kg of dehydrated zinc acetate was prepared for 30 minutes. Under stirring (40 r.p.m.), 31 kg of the calcined Ti-MWW material obtained according to 4.4.d) were suspended. Subsequently, the container was closed and the reflux condenser was put into operation. The rate of agitation was increased to 70 r.p.m.
[00182] In all lots a) to c), the mixture in the container was heated to 100 ° C for 1 hour and held under reflux for 4 hours at a stirring rate of 70 rpm. Then, the mixture was cooled for 2 hours at a temperature below 50 ° C. For each batch a) to c), the cooled suspension was subjected to filtration and the mother liquor was transferred to the discharge of residual water. The filter cake was washed five times with deionized water under 2.5 bar nitrogen pressure. After the last washing step, the filter cake was dried in a stream of nitrogen for 10 hours.
[00183] For batch a), 106.5 kg of nitrogen-dried filter cake were finally obtained. For batch b), 107.0 kg of nitrogen-dried filter cake were finally obtained. For batch c), 133.6 kg of nitrogen-dried filter cake were finally obtained. DESCRIPTION
[00184] The TiMWW material impregnated with Zn dried in this way (ZnTi-MWW), for each batch, had a silicon content of 42% by weight, a titanium content of 1.6% by weight, a zinc content 1.4% by weight and a total organic carbon content of 1.4% by weight. b) Spray drying Zn / Ti-MWW powder
[00185] From 347.1 kg of the mixture of the filter cakes obtained from Example 4.5, an aqueous suspension was prepared with deionized water, the suspension having a solid content of 15% by weight. This suspension was subjected to spray drying in a spray tower with the following spray drying conditions: - apparatus used: spray tower with a nozzle - operating mode: pure nitrogen - configuration: dehumidifier - filter - purifier - dosage: flexible tube pump VF 10 (supplier: Verder) nozzle with a diameter of 4 mm (supplier: Niro) filter material: 10 m2 of needle felt Nomex®


[00186] The spraying tower was made up of a vertically arranged cylinder with a length of 2,650 mm, a diameter of 1,200 mm, the cylinder of which was conically narrowed at the bottom. The cone length was 600 mm. At the top of the cylinder, the atomizing means (a two-component nozzle) was arranged. The spray-dried material was separated from the drying gas in a filter downstream of the spraying tower, and the drying gas was then passed through a purifier. The suspension was passed through the internal opening of the nozzle and the nozzle gas was passed through the ring-shaped groove surrounding the opening. DESCRIPTION
[00187] The spray dried material thus obtained had a zinc content of 1.4% by weight, a titanium content of 1.7% by weight, a silicon content of 40% by weight and a carbon content 0.27% by weight. c) Calcination
[00188] The spray-dried product was then subjected to calcination for 2 hours at 650 ° C in air in a rotary kiln, yielding 76.3 kg of ZnTi-MWW dried by calcined spray. DESCRIPTION
[00189] The spray-dried material calcined in this way obtained had a zinc content of 1.4% by weight, a titanium content of 1.7% by weight, a silicon content of 42% by weight and a content of total organic carbon of 0.14% by weight.
[00190] The apparent density of calcined spray dried ZnTi-MWW was 90 g / l (grams / liter). The micropores of the ZnTi-MWW contained in the micropowder had an average pore diameter of 1.13 nm as determined by nitrogen adsorption according to DIN 66134 (Horward-Kawazoe method). The Dv10 value of the micropowder particles, as determined by Malvern, was 5.18 micrometers. The Dv50 value of the micropowder particles was 24.8 micrometers. The Dv90 value of the micropowder particles was 93.53 micrometers. The degree of crystallization determined by XRD was 86% and the average crystalline size was 38.5 nm. The Langmuir surface is determined by nitrogen adsorption at 77 K according to DIN 66134 was 586 m2 / g, the specific BET surface area determined by nitrogen adsorption at 77 K according to DIN 66134 was 423 m2 / g. The total penetration volume determined according to HG porosimetry, according to DIN 66133, was 4.3 ml / g (millimeter / gram), the respective total pore area was 80.7 m2 / g. EXAMPLE 5: SYNTHESIS OF A ZEOLYTIC MATERIAL CONTAINING TIN WITH A STRUCTURE IN THE MWW SPLASH (SN-MWW) EXAMPLE 5.1.PREPARATION OF A B-MWW
[00191] 480 kg of deionized water were provided in a container. Under agitation at 70 rpm (rotations per minute), 166 kg of boric acid were suspended in water at room temperature. The suspension was stirred for another 3 hours at room temperature. Thereafter, 278 kg of piperidine was added and the mixture was stirred for another hour. To the resulting solution, 400 kg of Ludox® AS-40 was added and the resulting mixture was stirred at 70 rpm for another hour at room temperature. The finally obtained mixture was transferred to a crystallization vessel and heated at 170 ° C for 5 hours under autogenous pressure and under agitation (50 rpm). The 170 ° C temperature was kept essentially constant for 120 hours. During these 120 hours, the mixture was stirred at 50 rpm. Thereafter, the mixture was cooled to a temperature of 50 to 60 ° C. The aqueous suspension containing B-MWW had a pH of 11.3 as determined by measurements with a pH sensitive electrode. From said suspension, the B-MWW was separated by filtration. The filter cake was then washed with deionized water at room temperature until the washing water had a conductivity of less than 700 microSiemens / cm. The filter cake thus obtained was subjected to spray drying in a spray tower with the following spray drying conditions: drying gas, nozzle gas: technical nitrogen drying gas temperature: - spray tower temperature ( inlet): 235 ° C spray tower temperature (outlet): 140 ° C nozzle: - two-piece nozzle size 0 - nozzle gas temperature: - nozzle gas pressure: operating mode: apparatus used: nozzle configuration : gas flow scrubber: filter material: Nomex® dosing by means of pump d (supplier: Verder)
[00192] The spraying tower was made up of a cylinder arranged vertically with a length of 2,650 mm, a diameter of 1,200 mm, the cylinder of which was conically narrowed at the bottom. The cone length was 600 mm. At the top of the cylinder, the atomizing means (a two-component nozzle) was arranged. The spray-dried material was separated from the drying gas in a filter downstream of the spraying tower, and the drying gas was then passed through a purifier. The suspension was passed through the internal opening of the nozzle and the nozzle gas was passed through the ring-shaped groove surrounding the opening.
[00193] The spray-dried material was then subjected to calcination at 600 ° C for 10 hours. The calcined material had a molar ratio of B2O3: SiO2 molar ratio of 0.06: 1. EXAMPLE 5.2: DEBORONATION
[00194] 9 kg of deionized water and 600 g of the calcined zeolitic material obtained according to Example 5.1 were refluxed at 100 ° C under agitation at 250 r.p.m. for 10 hours. The resulting debored zeolitic material was separated from the suspension by filtration and washed with 4 liters of deionized water at room temperature. After filtration, the filter cake was dried at a temperature of 120 ° C for 16 hours.
[00195] The dry zeolitic material with a MWW lattice structure had a molar ratio of B2O3: SiO2 of 0.0020: 1. EXAMPLE 5.3 INCORPORATION OF SN
[00196] 776.25 g of deionized water were provided in a glass beaker and 280 g of piperidine were added under agitation and further stirred for 20 minutes. Separately, in a glove box, 5 g of tin (IV) tert-butoxide were dissolved in 95 g of piperidine under a nitrogen atmosphere. The mixture was added to the aqueous piperidine suspension and further stirred for 10 minutes. 172.4 g of zeolitic material obtained according to Example 5.2 were added to the mixture and stirred for 1 hour (200 r.p.m.) at room temperature. Then an autoclave was filled with the obtained suspension. The mixture was treated for 120 hours at a temperature of 170 ° C with stirring (100 r.p.m.).
[00197] Subsequently, the autoclave was cooled to room temperature and the resulting zeolitic material was separated from the suspension by filtration at room temperature and washed with deionized water until the washing water had a conductivity of less than 300 microSiemens / cm. After filtration, the filter cake was dried at a temperature of 120 ° C for 16 hours. DESCRIPTION
[00198] The dry zeolitic material had a silicon content of 37% by weight and a tin content of 0.68% by weight. EXAMPLE 5.4: ACID TREATMENT
[00199] 170 g of zeolitic material obtained according to Example 5.3 were provided in a round bottom flask and 5.1 kg of a 30% by weight aqueous solution of HNO3, having a pH in the range of 0 to 1, have been added. The mixture was stirred at a temperature of 100 ° C for a period of 20 hours (200 r.p.m.). The suspension was filtered and the filter cake was then washed with deionized water at room temperature until the washing water had a pH of approximately 7. The obtained zeolitic material was dried at 120 ° C for 16 hours and calcined when heated to 550 ° C (2 ° C per minute) and heating after 550 ° C for 10 hours. DESCRIPTION
[00200] The dry and calcined zeolitic material had a silicon content of 43.5% by weight and a tin content of 0.78% by weight and a parameter c, as determined by means of XRD, of 27.069 Angstrom. Additionally, the zeolitic material had a BET surface area, determined according to DIN 66131, of 475 m2 / g, the Langmuir area, determined according to DIN 66135, of 657 m2 / g and a total pore area of 189.42 m2 / g. The XRD of the zeolitic material obtained is shown in figure 2. EXAMPLE 6: SYNTHESIS OF A SILICATE CONTAINING CRYSTALLINE ZIRCON (ZR-SILICATE) EXAMPLE 6.1: INCORPORATION OF ZIRCONIUM
[00201] 540 g of water and 260.64 g of piperidine were introduced into a glass bottle. The mixture was stirred at 200 rpm and 24.56 g of zirconium n-propoxide was added. The obtained mixture was further stirred for 20 minutes before adding dropwise 180 g of the debored zeolitic material with a MWW lattice structure obtained according to Example 3.2 .. The suspension was further stirred for 2 hours at 200 rpm until a gel was obtained. The gel formed was transferred to an autoclave. The autoclave was heated to 170 ° C and maintained at this temperature for 120 hours under agitation at 150 rpm. Subsequently, the autoclave was cooled and the solid was filtered off and washed until the washing water had a pH of 7. The filter cake was dried in a static oven at 120 ° C for 16 hours. DESCRIPTION
[00202] The zeolitic material containing zirconium obtained had a zirconium content of 0.73% by weight and a silicon content of 38.5% by weight. The XRD of the zeolitic material obtained is shown in Figure 3. EXAMPLE 6.2 ACID TREATMENT OF ZEOLITHIC MATERIAL CONTAINING ZIRCONIUM
[00203] 4200 g of an aqueous solution of HNO3 (30% by weight in water) were provided in a 10 l flask. To this solution, the zirconium-containing silicate, obtained according to Example 6.1, was added and the mixture was heated at 100 ° C for 20 hours with stirring at 170 rpm. Afterwards, the suspension was filtered and washed until the washing water had a pH of 7. The filter cake was dried in a static oven for 16 hours at 120 ° C and calcined at 550 ° C for 10 hours. DESCRIPTION
[00204] The zeolitic material obtained had a zirconium content of 0.73% by weight and a silicon content of 43% by weight. The specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 100 m2 / g. EXAMPLE 7: REGENERATION OF ZR-SILICATE
[00205] After converting a mixture of ethanol and acetaldehyde according to Example 15, the catalyst was regenerated directly after the reaction inside the reactor. Therefore, the catalyst was heated with a heating ramp of 1 K / min at 500 ° C under an atmosphere of 2% by volume O2. The temperature was maintained at 550 ° C for 7 hours. Thereafter, the catalyst was cooled to 350 ° C and subjected to the conversion of a mixture of ethanol and acetaldehyde according to Example 16. EXAMPLE 8: SUMMARY OF A MWW CONTAINING CRYSTALLINE Tantalum (TA-MWW)
[00206] 0.74 g of tantalum oxalate solution (25.7 g of Ta / L (delivered from HCStarck, Specification ID: D3067 / 02, order number: 1060010508)) was diluted with 7 , 4 ml of distilled water and added to 5 g of debored MWW obtained from Example 4.2 and the suspension was allowed to stand for 2 hours. Thereafter, the suspension was dried at a temperature of 120 ° C for 2 hours followed by drying at a temperature of 500 ° C for 4 hours, using a heating ramp of 1.5 ° C / min. DESCRIPTION
[00207] The zeolitic material obtained had a tantalum content of 1.5% by weight and a silicon content of 41% by weight. The specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 436 m2 / g.
[00208] The material was additionally characterized by UV-VIS measurements (see Figure 3). As can be considered from the spectrum in Figure 3, the maximum absorption is found in the range of 205 to 220 nm, indicating tetrahedrally prevalent coordinated Ta sites as these are found in the truss of the zeolite structure. In addition, no tantalum oxide would appear to be detected in the material obtained since there is no signal above 300 nm. In this way, it is evident from the UV-vis spectrum that the largest portion of the tantalum contained in the material is isomorphously replaced in the truss structure. In this regard, reference is made to Catal Lett (2010) 135: 169-174 regarding the characterization of tantalum sites in a zeolitic material by means of UV-vis measurements.
[00209] The XRD of the zeolitic material obtained is shown in Figure 5, indicating the MWW trellis structure of the material. EXAMPLE 9: SUMMARY OF A MWW CONTAINING CRYSTALLINE TANTALUM (TA-MWW)
[00210] 2.12 g of tantalum oxalate solution (25.7 g of Ta / L (delivered from HCStarck, Specification identification: D3067 / 02, order number: 1060010508)) were diluted with 6 , 2 ml of distilled water and added to 5 g of debored MWW obtained from Example 4.2 and the suspension was allowed to stand for 2 hours. Thereafter, the suspension was dried at a temperature of 120 ° C for 2 hours followed by drying at a temperature of 500 ° C for 4 hours, using a heating ramp of 1.5 ° C / min. DESCRIPTION
[00211] The zeolitic material obtained had a tantalum content of 4.9% by weight and a silicon content of 39% by weight. The specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 416 m2 / g. The material was further characterized by UV-VIS measurements (see Figure 4). As can be considered from the spectrum in Figure 4, the maximum absorption is found in the range of 205 to 220 nm indicating tetrahedrally prevalent coordinated Ta sites as they are found in the zeolite structure lattice. In addition, no tantalum oxide would appear to be detected in the material obtained since there is no signal above 300 nm. In this way, it is evident from the UV-vis spectrum that the largest portion of the tantalum contained in the material is isomorphously replaced in the truss structure. In this regard, reference is made to Catal Lett (2010) 135: 169-174 regarding the characterization of tantalum sites in a zeolitic material by means of UV-vis measurements. COMPARATIVE EXAMPLE 1: SYNTHESIS OF A ZEOLITHIC MATERIAL WITH A STRUCTURE IN MWW SPLIT (Sl-MWW) COMPARATIVE EXAMPLE 1.1: PREPARATION OF MWW CONTAINING BORON
[00212] 480 kg of deionized water were provided in a container. Under stirring at 70 r.p.m., 166 kg of boric acid were suspended in the water. The suspension was stirred for another 3 hours. Thereafter, 278 kg of piperidine was added and the mixture was stirred for another hour. To the resulting solution, 400 kg of Ludox® AS-40 were added and the resulting mixture was stirred at 70 rpm for another hour.
[00213] The mixture finally obtained was transferred to a crystallization vessel and heated to 170 ° C for 5 hours under autogenous pressure and under stirring (50 r.p.m.). The temperature of 170 ° C was kept essentially constant for 120 hours; during these 120 hours, the mixture was stirred at 50 rpm. Afterwards, the mixture was cooled to a temperature of 50 to 60 ° C for 5 hours. The aqueous suspension containing B-MWW had a pH of 11.3 as determined by measurements with a pH electrode. After cooling the reactor, a solution of 10% by weight of HNO3 was added to the suspension until the suspension had a pH in the range of 7 to 8.
[00214] From said suspension, the B-MWW was separated by filtration. The filter cake was then washed with deionized water until the washing water had a conductivity of less than 700 microSiemens / cm.
[00215] From the filter cake thus obtained, an aqueous suspension was prepared with deionized water, the suspension having a solid content of 15% by weight. This suspension was subjected to spray drying in a spray tower with the following spray drying conditions: drying gas temperature: - spray tower temperature (inlet): 206 ° C - spray tower temperature (outlet) : 120 ° C nozzle: - Gerig two-component nozzle; size 0 nozzle gas pressure: 1 bar spray tower with a pure nitrogen nozzle dehumidifier - filter - purifier 45 kg / h
[00216] The spraying tower was composed of a cylinder arranged vertically with a length of 2,650 mm, a diameter of 1,200 mm, whose cylinder was conically narrowed at the bottom. The cone length was 600 mm. At the top of the cylinder, the atomizing means (a two-component nozzle) was arranged. The spray-dried material was separated from the drying gas in a filter downstream of the spraying tower, and the drying gas was then passed through a purifier. The suspension was passed through the internal opening of the nozzle and the nozzle gas was passed through the ring-shaped groove surrounding the opening. The spray-dried material was then subjected to calcination at 650 ° C in a rotary calcine with a flow rate of 0.8 to 1.0 kg / h. DESCRIPTION
[00217] The calcined material had a boron content of 1.3% by weight, a silicon content of 44% by weight and a total organic carbon content of <0.1% by weight. Crystallinity determined by XRD was 88%, specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 464 m2 / g, pore volume determined by HG porosimetry, according to DIN 66133, was 6.3 ml / g, spray dried particle size distribution determined by Malvern Dv50 was 26.9 μm. COMPARATIVE EXAMPLE 1.2: DEBORONED MWW PREPARATION
[00218] 1590 kg of water was passed into a container equipped with a reflux condenser. Under agitation at 40 r.p.m., 106 kg of the spray-dried material obtained according to section 1.1 were suspended in water. Subsequently, the container was closed and the reflux condenser was put into operation. The stirring rate was increased to 70 r.p.m. Under stirring at 70 r.p.m., the contents of the vessel were heated to 100 ° C in 2 hours and maintained at this temperature for 10 hours. Then, the contents of the container were cooled to a temperature below 50 ° C.
[00219] The debored zeolitic material resulting from the MWW type structure was separated from the suspension by filtration and washed with 600 liters of deionized water. After filtration, the filter cake was spray dried. DESCRIPTION
[00220] The obtained dry MWW material had a boron content of 0.04% by weight, a silicon content of 42% by weight and a total organic carbon content of <0.1% by weight. The specific BET surface area determined by nitrogen adsorption at 77 K, according to DIN 66131, was 461 m2 / g, the crystallinity, determined by XRD, was 82%. The particle size distribution obtained from Malvern measurements was Dv50 of 11.1 μm. CONVERSION OF A MIXTURE OF ETHANOL AND ACETALDEHYDE IN THE PRESENCE OF A CATALYST
[00221] The process for the preparation of butadiene by converting a mixture of ethanol and acetaldehyde in the presence of a catalyst according to Reference Example 4 was carried out using several catalysts: Example 10: It was carried out as described in the Example of Reference 4 for the use of the Zr-BEA obtained from Example 1, according to the present invention. Example 11: It was carried out as described in Reference Example 4 by using the Zr-BEA obtained from Example 2, according to the present invention. Example 12: It was carried out as described in Reference Example 4 by using the Zr-silicate obtained from Example 3, according to the present invention. The result of this experiment is shown in Figure 6. Example 13: It was performed as described in Reference Example 4 by using the ZnTi-MWW obtained from Example 4, according to the present invention. Example 14: It was carried out as described in Reference Example 4 by using the Sn-MWW obtained from Example 5, according to the present invention. Example 15: It was carried out as described in Reference Example 4 by using the Zr-silicate obtained from Example 6, according to the present invention. Example 16: It was carried out as described in Reference Example 4 by using the Zr-silicate obtained from Example 7, according to the present invention. Example 17: It was carried out as described in Reference Example 4 by using the Ta-MWW obtained from Example 8, according to the present invention. Example 18: It was carried out as described in Reference Example 4 by using the Ta-MWW obtained from Example 9, according to the present invention. Comparative Example 2: It was performed as described in Reference Example 4 using Si-MWW obtained from Comparative Example 1. Comparative Example 3: It was performed as described in Reference Example 4 using ZrO2 (commercial sample BASF (D9 -89)).
[00222] The selectivities obtained for butadiene, ethyl ether and crotonaldehyde are shown in Table 1, in which the selectivities are calculated based on the total quantity of products obtained and provided in percentage values. TABLE 1: SELECTIVITIES OBTAINED FROM EXAMPLES 10 TO 16 AND EXAMPLES



SUMMARY AND COMPARISON OF THE RESULTS OF EXAMPLES 10 TO 18 AND COMPARATIVE EXAMPLE 2 AND 3
[00223] Examples 10 to 18 are carried out according to the present invention, that is, by a gas phase process for the preparation of butadiene comprising providing a gas stream comprising ethanol and making the gas stream comprising ethanol come into contact with a catalyst, wherein the catalyst comprises a zeolitic material with a lattice structure comprising one or more tetravalent elements, wherein at least a portion of the one or more tetravalent elements comprised in the lattice structure is replaced in an isomorphic manner. In Examples 10 to 12 and 15 to 16 the truss structure comprises silicon, in which a portion of silicon is isomorphously replaced by zirconium. In Example 13 the truss structure comprises silicon, in which a portion of silicon is isomorphically replaced by titanium and in Example 14 the truss structure comprises silicon, in which a portion of silicon is replaced in an isomorphic manner by tin. In addition, in Examples 17 and 18 the truss structure comprises silicon, in which a portion of silicon is isomorphously replaced by tantalum.
[00224] Comparative Examples 2 and 3 are carried out according to a process for the preparation of butadiene comprising making the gas stream of ethanol and acetaldehyde come into contact with a catalyst comprising silicon (Comparative Example 2) or zirconium (Comparative Example 3 ), respectively, in which the tetravalent element comprised in the catalyst is not isomorphically replaced by another element.
[00225] In Examples 10, 11, 12, 15 and 16 which are carried out according to the invention by the use of a catalyst comprising a zeolitic material with a lattice structure comprising zirconium and silicon, high selectivities for butadiene in the range of 38 to 64% are achieved, in which the catalysts containing the zirconium-containing silicate (Zr-silicate) provide an astonishingly high selectivity of 64%, in which, at the same time, high conversions of ethanol and acetaldehyde in the range of 43 to 47% have been achieved . In addition, Example 13 is carried out according to the invention, in which a catalyst comprising ZnTi-MWW is used which leads to a 27% selectivity for butadiene. In addition, in Examples 17 and 18, which are carried out according to the invention by the use of a catalyst comprising a zeolitic material with a MWW lattice structure comprising tantalum and silicon, high selectivities for butadiene of 72% have been achieved and at the same time time, high conversions of ethanol and acetaldehyde in the range of 39 to 42% were achieved. In this way, it has been found that by using catalysts comprising a zeolitic material according to the present invention, very high selectivities for butadiene and, at the same time, high conversions of ethanol and acetaldehyde are achieved.
[00226] In Example 14, which is carried out according to the invention by the use of a catalyst comprising Sn-MWW, and in Comparative Examples 2 and 3, similar selectivities for butadiene are achieved. However, in Example 14 according to the invention, selectivity for 61% diethyl ether is achieved, in Comparative Examples 2 and 3 only a selectivity of 43% and 6%, respectively, is achieved. Diethyl ether is a product of the present invention that can be hydrolyzed and recycled in the gas phase process to obtain butadiene. Therefore, it was found that, although the use of Sn-MWW according to the present invention and the catalysts used in Comparative Examples 2 and 3 lead to similar selectivities for butadiene, the catalyst comprising Sn-MWW according to the present The invention has the advantage that diethyl ether is obtained in a high amount that can be hydrolyzed and recycled in the gas phase process. Therefore, the use of the catalyst used in Example 14 leads to a much better yield compared to the catalysts used in Comparative Examples 2 and 3.
[00227] In Examples 15 and 16, which are carried out according to the invention by the use of a catalyst comprising a zeolitic material with a lattice structure comprising zirconium and silicon, wherein the catalyst used in Example 15 is regenerated and used in the Example 16, selectivities for butadiene of 64% and conversions of the starting material of 47% and 43%, respectively, were achieved. Therefore, the catalyst activity and selectivity of the catalyst according to the present invention was found to remain constant after regeneration.
[00228] Additionally, as can be seen from Figure 6, which shows the results of Example 12, the conversion of ethanol and acetaldehyde as well as selectivity for butadiene remain constant throughout the tested time range. Thus, in addition to exhibiting excellent selectivities, it was found that the catalyst is additionally capable of maintaining these selectivities without any changes over a very long period of time in the chain when considering the long-term test results shown in Figure 6 In particular, it has been found that a highly stable process can be provided by the present invention, in which the product spectrum and the high yield in butadiene shows virtually no change over extended periods of time in the stream.
[00229] Therefore, considering the results detailed in the above and its discussion above, it has been found that the use of a zeolitic material according to the invention leads to a considerable improvement in the process for the preparation of butadiene. STATE OF TECHNIQUE CITED - GB 331482 - US 2421361 - WO 2012/015340 A1 - Catal. Sci. Technol. 1 (2011), 267-272 - Ind. Eng. Chem. 41 (1949), pages 1012-1017.

权利要求:
Claims (24)
[0001]
1. GASEOUS PROCESS FOR THE PREPARATION OF BUTADIENE, characterized by comprising: (i) providing a G-1 gas stream comprising ethanol; (ii) placing the G-1 gas stream comprising ethanol in contact with a catalyst, thereby obtaining a G-2 gas stream comprising butadiene, wherein the catalyst comprises a zeolitic material with a lattice structure comprising YO2 , in which at least a portion of Y comprised in the truss structure is isomorphously replaced by one or more elements X, where Y is Si, where X is Zr and / or Ta, and where said zeolitic material is a zeolitic material that has a lattice structure selected from BEA and MWW, in which the contact of the gas stream G-1 with the catalyst is carried out continuously and in which the catalyst is subject to regeneration by heat treatment in the presence of oxygen.
[0002]
PROCESS according to claim 1, characterized in that the gas stream G-1 additionally comprises acetaldehyde.
[0003]
3. PROCESS, according to claim 2, characterized in that the molar ratio of ethanol to acetaldehyde in the gas stream G-1 is in the range of 1: 1 to 6: 1.
[0004]
PROCESS according to any one of claims 2 to 3, characterized in that 80% or more by volume of the G-1 gas stream comprises ethanol or a mixture of ethanol and acetaldehyde.
[0005]
PROCESS according to any one of claims 1 to 2, characterized in that the molar ratio of Y: X in the truss structure varies from 10: 1 to 150: 1.
[0006]
6. PROCESS according to any one of claims 1 to 2, characterized in that the molar ratio of Y: X in the truss structure varies from 50: 1 to 700: 1.
[0007]
7. PROCESS, according to claim 1, characterized in that the catalyst comprises isomorphically substituted beta zeolite and / or Ta-MWW.
[0008]
PROCESS according to any one of claims 1 to 2, characterized in that the gas stream G-1 in contact with the catalyst is carried out at a temperature in the range of 300 to 500 ° C.
[0009]
9. PROCESS, according to any one of claims 1 to 2, characterized in that the gas stream G-1 in contact with the catalyst is carried out at a pressure in the range of 1 to 5 bar.
[0010]
10. PROCESS, according to any one of claims 1 to 2, characterized in that the gas stream G-1 in contact with the catalyst is carried out in one or more reactors, in which the one or more reactors contain the catalyst in the form of a fixed bed.
[0011]
11. PROCESS according to any one of claims 1 to 2, characterized in that before putting the gas stream G-1 in contact with the catalyst, the gas stream G-1 is heated.
[0012]
12. PROCESS, according to claim 1, characterized in that before placing the gas stream G-1 with the catalyst, the catalyst is activated.
[0013]
13. PROCESS, according to claim 12, characterized in that the catalyst is activated by heating to a temperature in the range of 300 to 450 ° C.
[0014]
14. PROCESS, according to claim 13, characterized in that the catalyst is heated with a temperature ramp in the range of 0.5 to 10 K / min.
[0015]
15. PROCESS, according to any one of claims 12 to 13, characterized in that the catalyst is activated in one or more reactors.
[0016]
16. PROCESS, according to claim 13, characterized in that during heating the catalyst is discharged with an inert gas.
[0017]
17. PROCESS according to any one of claims 1 to 2, characterized in that the gas stream G-2 contains butadiene in an amount of 10 to 90% by volume, based on the total volume of the gas stream G-2.
[0018]
PROCESS according to any one of claims 1 to 2, characterized in that it further comprises (111) separating butadiene from the G-2 gas stream, thereby obtaining a purified gas stream G-3 comprising butadiene.
[0019]
19. PROCESS according to claim 1, characterized in that the gas stream G-2 additionally comprises diethyl ether, and in which the diethyl ether is separated from the gas stream G-2, and the recycling of the diethyl ether separated for the gas phase process for the preparation of butadiene.
[0020]
20. PROCESS according to claim 19, characterized in that the gas stream G-2 contains diethyl ether in an amount of 1 to 65% by volume, based on the total volume of the gas stream G-2.
[0021]
21. PROCESS according to claim 19, characterized in that it further comprises hydrolyzing at least a portion of the diethyl ether separated in ethanol before recycling it to the gas phase process for the preparation of butadiene.
[0022]
22. PROCESS according to claim 21, characterized in that the separated diethyl ester is hydrolyzed under acidic conditions.
[0023]
23. PROCESS, according to claim 1, characterized in that the gas stream G-2 also comprises crotonaldehyde.
[0024]
24. PROCESS, according to claim 23, characterized in that the G-2 gas stream contains the crotonaldehyde in an amount of 0.1 to 15% by volume, based on the total volume of the G-2 gas stream.

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法律状态:
2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-09-29| B09A| Decision: intention to grant|

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2020-12-01| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/06/2014, OBSERVADAS AS CONDICOES LEGAIS. |

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2020-12-22| B16C| Correction of notification of the grant|Free format text: REF. RPI 2604 DE 01/12/2020 QUANTO AO INVENTOR. |

优先权:

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申请号 | 申请日 | 专利标题

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EP13171800|2013-06-13|

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EP13171800.9|2013-06-13|

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PCT/EP2014/062391|WO2014198901A1|2013-06-13|2014-06-13|Process for the preparation of butadiene|

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