WO2014199349A2 - Silicates amorphes imprégnés de métal pour la conversion sélective de l'éthanol en butadiène - Google Patents

Silicates amorphes imprégnés de métal pour la conversion sélective de l'éthanol en butadiène Download PDF

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Publication number
WO2014199349A2
WO2014199349A2 PCT/IB2014/062203 IB2014062203W WO2014199349A2 WO 2014199349 A2 WO2014199349 A2 WO 2014199349A2 IB 2014062203 W IB2014062203 W IB 2014062203W WO 2014199349 A2 WO2014199349 A2 WO 2014199349A2
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WIPO (PCT)
Prior art keywords
catalyst
gas stream
butadiene
weight
range
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PCT/IB2014/062203
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English (en)
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WO2014199349A3 (fr
Inventor
Mathias Feyen
Kirsten SPANNHOFF
Ulrich Müller
Xinhe Bao
Weiping Zhang
Dirk De Vos
Hermann Gies
Takashi Tatsumi
Feng-Shou Xiao
Yokoi TOSHIYUKI
Yilmaz BILGE
Original Assignee
Basf Se
Basf (China) Company Limited
Tokyo Institute Of Technology
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Application filed by Basf Se, Basf (China) Company Limited, Tokyo Institute Of Technology filed Critical Basf Se
Publication of WO2014199349A2 publication Critical patent/WO2014199349A2/fr
Publication of WO2014199349A3 publication Critical patent/WO2014199349A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/14—Silica and magnesia
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a process for the preparation of butadiene using a catalyst comprises Hf and two or more further catalytically active metals M1 and M2, wherein the two or more two further catalytically active metals M 1 and M2 are selected from the group consisting of Zr, Zn, Cu and combinations of two or more thereof, and wherein M1 is different from M2.
  • the present invention further relates to a catalyst comprising Hf and two or more further catalytically active metals M1 and M2 as such, and to its use as a catalytically active material for the preparation of butadiene, preferably from a gas stream comprising ethanol and optionally acetaldehyde
  • butadiene is widely used in the chemical industry, for example as monomer and/or co- monomer for the polymerization of elastomers.
  • Catal. Sci. Technol. 201 1 , 1 , 267-272 a variety of silica impregnated bi- and trimetallic catalysts for the conversion of ethanol into 1 ,3-butadiene is described. The highest selectivity observed was 67% at 45% conversion using a Cu, Zr, Zn, Si02 system. Further, Catal. Sci. Technol. 201 1 , 1 , 267-272 discloses the use of catalysts impregnated with Hf and Zn, wherein low selectivities to butadiene in the range of from 4.9 to 6.7 % and conversions in the range of from 15 to 26 % were achieved. Furthermore, all catalysts tended to show a reduced conversion rate over a period of 3 h.
  • WO 2012/015340 A1 a process for the preparation of butadiene is disclosed by use of a solid catalyst containing metals chosen from the group of silver, gold or copper, and metal oxides, chosen from the group of magnesium, titanium, zirconium, tantalum or niobium oxide.
  • metals chosen from the group of silver, gold or copper
  • metal oxides chosen from the group of magnesium, titanium, zirconium, tantalum or niobium oxide.
  • the present invention relates to a catalyst for the preparation of butadiene comprising Hf and two or more further catalytically active metals M 1 and M2, wherein the two or more further catalytically active metals M 1 and M2 are selected from the group consisting of Zr, Zn, Cu and combinations of two or more thereof, and wherein M 1 is different from M2.
  • Hf and the two or more further catalytically active metals comprised in the catalyst are disposed on a support. Therefore, according to a preferred embodiment of the present invention, Hf and the two or more further catalytically active metals are disposed on a support.
  • the two or more further catalytically active metals M 1 and M2 no specific restrictions exist concerning the combinations of M 1 and M2 selected from the group consisting of Zr, Zn, Cu, and combinations of two or more thereof. Therefore, according to the present invention, all combinations of Hf, Zr, Zn and Cu are conceivable.
  • the catalyst may comprise Hf, Zr, Zn and Cu, or the catalyst may comprise Hf, Zr and Zn, or the catalyst may comprise Hf, Zr and Cu, or the catalyst comprise Hf, Zn and Cu.
  • the catalyst comprises Hf, Zn and Cu, which are disposed on the on a support.
  • the support comprises one or more metal oxides, preferably one or more metal oxides selected from the group consisting of alumina, silica, titania, titania-alumina, zirconia, zirconia-alumina, titania- zirconia, and mixtures of two or more thereof, more preferably from the group consisting of alumina, silica, titania-alumina, zirconia-alumina, and mixtures of two or more thereof, wherein more preferably the support comprises silica and/or alumina, preferably silica.
  • the catalyst com- prises Hf, Zr, Zn and Cu disposed on a silica support or the catalyst comprises Hf, Zr and Zn disposed on a silica support or the catalyst comprises Hf, Zr and Cu disposed on a silica support or the catalyst comprises Hf, Zn and Cu disposed on a silica support.
  • the catalyst comprises Hf, Zn and Cu disposed on a silica support.
  • the molar ratio of Hf : M 1 : M2 may be anywhere in the range of from 1 : (0.002 - 20) : (0.0015 - 15), preferably from (0.0015 - 15), more preferably from 1 : (0.02 - 10) : (0.01 - 8).
  • the molar ratio Hf : M 1 : M2, calculated as the respective element is in the range of from 1 : (0.2 - 3.0) : (0.1 - 2.0), preferably from 1 : (0.5 - 2.5) : (0.3 - 1.5), more preferably from 1 : (0.9 - 1.9) : (0.5 - 1).
  • the molar ratio Hf : M1 : M2, calculated as the respective element is in the range of from 1 : (0.002 - 20) : (0.0015 - 15), preferably from 1 : (0.02 - 10) : (0.01 - 8), preferably 1 : (0.2 - 3.0) : (0.1 - 2.0), more preferably from 1 : (0.5 - 2.5) : (0.3 - 1.5), more preferably from 1 : (0.9 -1.9) : (0.5 - 1).
  • the content of Hf in the catalyst is in the range of from 0.05 to 30.0 weight-%, preferably in the range of from 0.1 to 15.0 weighted, more preferably in the range of from 0.3 to 10.0 weight-%, more preferably in the range of from 0.5 to 5.0 weight-%, more preferably in the range of from 1 to 4.0 weight-%, more preferably in the range of from 1.4 to 3.2 weight-%, wherein Hf is calculated as the element and based on the total weight of the catalyst.
  • M 1 in the catalyst is the same applies to the content of M 1 in the catalyst.
  • the content of M 1 in the catalyst is in the range of from 0.02 to 20.0 weight- %, preferably in the range of from 0.05 to 10.0 weight-%, more preferably in the range of from 0.1 to 5.0 weight-%, more preferably in the range of from 0.3 to 3.0 weight-%, preferably in the range of from 0.6 to 1.8 weight-%, more preferably in the range of from 0.8 to 1.2 weight-%, wherein M 1 is calculated as the element and based on the total weight of the catalyst.
  • the content of M2 in the catalyst is in the range of from 0.01 to 15.0 weight-%, preferably in the range of from 0.05 to 10.0 weight-%, more preferably in the range of from 0.08 to 5.0 weight-%, more preferably in the range of from 0.1 to 2.0 weight-%, preferably in the range of from 0.2 to 1.2 weight-%, more preferably in the range of from 0.4 to 0.7 weight-%, wherein M2 is calculated as the element and based on the total weight of the catalyst.
  • M 1 which is selected from the group consisting of Zr, Zn, Cu and combinations of two or more thereof, comprises Cu and M2, which is selected from the group consisting of Zr, Zn, Cu and combinations of two or more thereof, comprises Zn. Further, it is particularly preferred according to the present invention that M 1 is Cu and M2 is Zn.
  • M 1 comprises Cu and M2 comprises Zn, wherein preferably M 1 is Cu and M2 is Zn.
  • the catalyst comprising Hf and two or more further catalytically active metals further comprises Ba in an amount of from 0.1 to 15 weight-%, preferably from 0.5 to 10 weight-%, more preferably from 1 to 5 weight-%, based on the total weight of the catalyst Further, according to a particularly preferred embodiment of the present invention, the catalyst comprising Hf and two or more further catalytically active metals, does not contain Ba.
  • the content of Cu in the catalyst is in the range of from 0.02 to 20.0 weight-%, preferably in the range of from 0.05 to 10.0 weight-%, more preferably in the range of from 0.1 to 5.0 weight- %, more preferably in the range of from 0.3 to 3.0 weight-%, preferably in the range of from 0.6 to 1.8 weight-%, more preferably in the range of from 0.8 to 1.2 weight-%, wherein Cu is calculated as the element and based on the total weight of the catalyst.
  • the con- tent of Zn in the catalyst is in the range of from 0.01 to 15.0 weight-%, preferably in the range of from 0.05 to 10.0 weight-%, more preferably in the range of from 0.08 to 5.0 weight-%, more preferably in the range of from 0.1 to 2.0 weight-%, preferably in the range of from 0.2 to 1.2 weight-%, more preferably in the range of from 0.4 to 0.7 weight-%, wherein Zn is calculated as the element and based on the total weight of the catalyst.
  • the molar ratio Hf : Cu : Zn, calculated as the respective element is in the range of from 1 : (0.002 - 20) : (0.0015 - 15), preferably from 1 : (0.02 - 10) : (0.01 - 8), preferably 1 : (0.2 - 3.0) : (0.1 - 2.0), more preferably from 1 : (0.5 - 2.5) : (0.3 - 1.5), more preferably from 1 : (0.9 -1.9) : (0.5 - 1 ).
  • Hf and the two or more further catalytically active metals comprised in the catalyst no specific restrictions exist concerning the method by which Hf and the two or more further catalytically active metals are disposed on the support. Therefore, it may be con- ceivable to dispose Hf and the two or more further catalytically active metals on the support by impregnation, ion-exchange incipient wetness impregnation and/or by dry impregnation. According to a preferred embodiment of the present invention Hf and the two or more further catalytically active metals are disposed on support by incipient wetness impregnation, dry impregnation and/or by ion exchange. According to the present invention, it is particular- ly preferred to dispose Hf and the two or more further catalytically active metals on the support by incipient wetness impregnation.
  • the incipient wetness impregnation is conducted with the aid of a solvent or solvent mixture in which Hf and the two or more further catalytically active metals to be disposed on the support are suitably dissolved.
  • a solvent or solvent mixture in which Hf and the two or more further catalytically active metals to be disposed on the support are suitably dissolved.
  • Hf and the two or more further catalytically active metals to be disposed on the support are may be solvated therein.
  • the solvent or mixture of solvents which may be used include water and alcohols, and in particular short chain alcohols selected among Ci-C 4 , and preferably C1-C3 alcohols, in particular methanol, ethanol or propanol, including mixtures of two or more thereof.
  • 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.
  • alcohols such as methanol and ethanol or methanol and propanol or ethanol and propanol or methanol and ethanol and propanol or water and ethanol and propanol.
  • water or a mixture of water and one or more alcohols is preferred, wherein a mixture of water and ethanol is further preferred, deionized water being particularly preferred as the solvent for the one or more ion-exchange proce- dures.
  • incipient wetness impregnation may be achieved with a volume of solvent or a solvent mixture which slightly exceeds or approximately corresponds to or is slightly inferior to the porous volume of the crystalline material such that Hf and the two or more further catalytically active metals M1 and M2 are solvatized in the solvent or solvent mixture enters the porous system of the support by capillary action.
  • the impregnation is conducted by use of a liquid to solid weight ratio ranging anywhere from 0.1 to 50.
  • the liquid to solid weight ratio being the weight ratio of the solvent or solvent mixture to the support, is comprised in the range of from 1 to 45, more preferably of from 5 to 40, more preferably of from 10 to 35, more preferably of from 12 to 30, and even more preferably of from 15 to 25.
  • the liquid to solid weight ratio employed in the impreg- nation is comprised in the range of from 18 to 22.
  • Hf and the two or more further catalytically active metals are disposed on the support by impregnation, preferably by incipient wetness.
  • Hf, Cu and Zn are disposed on the support by impregnation, preferably by incipient wetness.
  • impregnation no particular restrictions exist concerning the compounds comprising Hf and the two or more further catalytically active metals which are used to dispose Hf and the two or more further catalytically active metals on the support by impregnation, preferably by incipient wetness impregnation. According to the present invention, it is preferred to carry out the impregnation by use of one or more inorganic or organic salts as sources for one or more of the catalytically active metals.
  • the one or more inorganic or organic salts used in the impregnation procedure are selected from the group consisting of halides, nitrates, sulfates, phosphates, hydroxides, carbonates, carboxylates, alcoholates, and combinations of two or more thereof, more pref- erably selected from the group consisting of chlorides, nitrates, acetates, and combinations of two or more thereof.
  • impregnation is carried out using one or more inorganic or organic salts of one or more of the catalytically active metals, wherein these salts are preferably selected from the group consisting of halides, nitrates, sulfates, phosphates, hydroxides, carbonates, carboxylates, alcoholates, and combinations of two or more thereof, more preferably selected from the group consisting of chlorides, nitrates, acetates, and combinations of two or more thereof.
  • the Hf source is preferably selected from the group consisting of, hafnium halides, hafnium hydroxides, hafnium nitrates, hafnium alkoxides, and mixtures of two or more thereof, more preferably from the group consisting of hafnium bromide, chloride, hafnium nitrate, C1 -C4 alkoxides of Hf, and mixtures of two or more thereof, more preferably from the group consisting of hafnium chloride, bromide, hafnium nitrate, C2-C3 alkoxides of Hf, more preferably selected from the group consisting of hafnium chloride, bromide, hafnium nitrate and mixtures of two or more thereof, wherein more preferably the Hf source is hafni- um(IV)chlor
  • the Zn source is preferably selected from the group consisting of zinc halides, zinc hydroxides, zinc nitrates, zinc alkoxides, and mixtures of two or more thereof, more preferably from the group consisting of zinc bromide, chloride, fluoride, zinc nitrate, C1 -C4 alkoxides of Zn, and mixtures of two or more thereof, more preferably from the group consisting of zinc chloride, fluoride, zinc nitrate, C2-C3 alkoxides of Zn, more preferably selected from the group consisting of zinc chloride, fluoride, zinc nitrate and mixtures of two or more thereof, wherein more preferably the Zn source is zinc(ll)nitrate.
  • the Cu source is preferably selected from the group consisting of copper halides, copper hydroxides, copper nitrates, copper alkoxides, and mixtures of two or more thereof, more preferably from the group consisting of copper bromide, chloride, fluoride, copper nitrate, C1 -C4 alkoxides of Cu, and mixtures of two or more thereof, more preferably from the group consisting of copper chloride, copper nitrate, C2-C3 alkoxides of Cu, more preferably selected from the group consisting of copper chloride, copper nitrate, copper(ll)acetate, and mixtures of two or more thereof, wherein more preferably the Cu source is copper(ll)acetate According to a preferred embodiment of the present invention, wherein one or more inor- ganic or organic salts as sources for one or more of the cata
  • impregnation is carried out by use of hafnium(IV)chloride, copper(ll)acetate, and zinc(ll)nitrate.
  • the catalyst comprising Hf and two or more further catalytically active metals M 1 and M2 selected from the group consisting of Zr, Zn, Cu and combinations of two or more thereof, wherein M 1 is different from M2, is provided by a impregnation process comprising
  • the support used in (a) comprises one or more metal oxides, preferably one or more metal oxides selected from the group consisting of alumina, silica, titania, titania-alumina, zirconia, zirconia-alumina, titania- zirconia, and mixtures of two or more thereof, more preferably from the group consisting of alumina, silica, titania-alumina, zirconia-alumina, and mixtures of two or more thereof, wherein more preferably the support comprises silica and/or alumina, preferably silica.
  • the one or more Hf sources, one or more M1 sources and one or more M2 sources used in (a) are inorganic or organic salts wherein these salts are preferably selected from the group consisting of halides, nitrates, sulfates, phosphates, hydroxides, carbonates, carboxylates, alcoholates, and combinations of two or more thereof, more preferably selected from the group consisting of chlorides, nitrates, acetates, and combinations of two or more thereof.
  • the present invention relates to a process for the preparation of butadiene comprising
  • the catalyst comprises Hf and two or more further catalytically active metals M 1 and M2, wherein the two or more further catalytically active metals M1 and M2 are selected from the group consisting of Zr, Zn, Cu and combinations of two or more thereof, and wherein M 1 is different from M2.
  • the inventive catalyst for the preparation of butadiene used in the inventive process the inventive catalyst according to any of the particular and preferred embodiments as described in the present application may be employed therein. According to preferred embodiments of the inventive process, the catalyst for the preparation of butadiene according to preferred and particularly preferred embodiments of the inventive catalyst as described in the present application are preferably used.
  • a gas stream G-1 comprising ethanol is provided in step (i) and subsequently contacted with a catalyst in step (ii).
  • the gas stream provided in step (i) additionally comprises acetaldehyde.
  • the molar ratio of ethanol to acetaldehyde in the gas stream G-1 is in the range of 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.
  • 70 vol.-% or more, preferably 75 vol.-% or more, more preferably 80 vol.-% or more of the gas stream G-1 comprises ethanol or a mixture of ethanol and acetal- dehyde. It is further preferred that prior to contacting with the catalyst, 85 vol.-% or more, preferably 90 vol.-% or more, more preferably 95 vol.-% or more of the gas stream G-1 comprises ethanol or a mixture of ethanol and acetaldehyde.
  • 80 vol.-% or more of the gas stream G-1 com- prises ethanol or of a mixture of ethanol and acetaldehyde, wherein preferably 90 vol.-% or more, more preferably 95 vol.-% or more of the gas stream G-1 comprises ethanol or of a mixture of ethanol and acetaldehyde.
  • a gas stream G-2 comprising butadiene is obtained.
  • said contacting of the gas stream in step (ii) may be conducted according to the inventive process at a tem- perature in the range of from 200 to 500 °C, preferably from 220 to 470 °C, more preferably from 250 to 450 °C, more preferably from 270 to 420 °C, more preferably from 300 to 400 °C.
  • contacting the gas stream G-1 with the catalyst is carried out at a temperature in the range of from 200 to 500 °C, preferably from 250 to 450 °C, more preferably from 300 to 400 °C.
  • contacting of the gas stream G-1 with the catalyst is carried out at a pressure in the range of from 1 to 5 bar, preferably from 1 to 2 bar.
  • the gas stream G-1 is contacted with a catalyst according to the present invention in step (ii) at a tempera- ture in the range of from 200 to 500 °C, preferably from 250 to 450 °C, more preferably from 300 to 400 °C at a pressure in the range of from 1 to 5 bar, preferably from 1 to 2 bar.
  • contacting gas stream G-1 with the catalyst is carried out in a continuous mode.
  • Preferred continuous process set-ups include the use of one or more fixed-bed reactor.
  • contacting the gas stream G-1 with the catalyst is carried out in one or more reactors, wherein preferably the one or more reactors contain the catalyst in the form of a fixed bed.
  • the gas stream prior to contacting the gas stream G-1 with the catalyst, is heated prior to contacting.
  • the heating of the gas stream G-1 prior to contacting with the catalyst may be conducted at a temperature in the range of from 50 to 300 °C, preferably from 100 to 250 °C, and more preferably from 120 to 180 °C.
  • the gas stream G-1 prior to contacting the gas stream G-1 with the catalyst, is heated, preferably to a temperature in the range of from 100 to 250 °C, more preferably from 120 to 180°C.
  • an activation of the catalyst takes place prior to contacting the gas stream G-1 with the catalyst, wherein, for example, the activation may be conducted by heating of the catalyst.
  • the catalyst prior to contacting the gas stream G-1 with the catalyst, the catalyst is activated, preferably by heating.
  • said activation of the catalyst prior to contacting with the gas stream G-1 may be conducted according a preferred embodiment of the inventive process at a temperature in the range of from 250 to 700 °C, preferably from 350 to 600 °C, more preferably from 440 to 510 °C.
  • the activation prior to contacting with the gas stream G-1 is conducted for a period in the range of from 0.5 to 10 h, more preferably from 1 to 7 h, more preferably from 2 to 5 h.
  • the catalyst is activated by heating to a temperature in the range of from 250 to 700 °C, preferably from 350 to 600 °C, more preferably from 440 to 510 °C, preferably for a period in the range of from 0.5 to 10 h, more preferably from 1 to 7 h, more preferably from 2 to 5 h.
  • a heating ramp is used for reaching the temperature of activation, wherein 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.
  • the catalyst is heated with a temperature ramp in the range of from 0.5 to 10 K/min, preferably 1 to 5 K/min, more preferably from 1 to 3 K/min.
  • the catalyst is activated in the one or more reactors. It is preferred that during heating the catalyst is flushed with an inert gas. As to the chemical nature of the inert gas, no particular restrictions exist. According to a particularly preferred embodiment of the present invention, preferably the catalyst is flushed during heating with an inert gas, more preferably with an inert gas selected from the group consisting of helium, nitrogen, argon, and mixtures of two or more thereof, wherein the inert gas is more prefera- bly nitrogen.
  • a gas stream G-2 is obtained containing butadiene in an amount of from 10 to 90 vol-%, preferably from 20 to 80 vol-%, more preferably from 30 to 70 vol-%, based on the total volume of the gas stream G-2.
  • the gas stream G-2 contains butadiene in an amount of from 10 to 90 vol-%, preferably from 20 to 80 vol-%, more prefera- bly from 30 to 70 vol-%, based on the total volume of the gas stream G-2.
  • the process for the preparation of butadiene further comprises a separation of butadiene from the gas stream G-2 obtained from step (ii) of the present invention, wherein a purified gas stream G-3 comprising butadiene is obtained.
  • a purified gas stream G-3 comprising butadiene is obtained.
  • Such methods may include thermal separation.
  • the separation of butadiene from the gas stream G-2 is achieved by thermal separation, more preferably by distillation.
  • the gas stream G-2 comprising butadiene obtained from step (ii) of the present invention may comprise further compounds resulting from contacting the gas stream G-1 with the catalyst.
  • the gas stream G-2 comprising butadiene further comprises diethyl ether. If the gas stream G-2 comprising butadiene further comprises diethyl ether, it is preferred that the diethyl ether is separated from the gas stream G-2 comprising butadiene.
  • the separation is carried out by thermal separation, preferably by distillation.
  • the separated diethyl ether may be recycled to the process for the preparation of butadiene according to the present invention, wherein it is preferred to recycle the separated diethyl ether as a component of the gas stream G-1 which is contacted with a catalyst in step (ii). Therefore, according to a preferred embodiment of the present invention, the separated diethyl ether is recycled to the process for the preparation of buta- diene according to the present invention, wherein the separated diethyl ether is preferably recycled as a component of the gas stream G-1 which is contacted with the catalyst in step (ii) to obtain butadiene.
  • the gas stream G-2 further comprises diethyl ether, and wherein the diethyl ether is separated from the gas stream G-2, preferably by thermal separation, more preferably by distilla- tion, and recycling the separated diethyl ether to the gas-phase process for the preparation of butadiene, preferably as component of the gas stream G-1.
  • G-2 further comprises diethyl ether which is preferably separated from G-2 and recycled preferably as compo- nent of the gas stream G-1
  • the gas stream G-2 prior to separating the diethyl ether contains diethyl ether in an amount of from 1 to 65 vol.-%, preferably from 2 to 35 vol.-%, more preferably from 5 to 30 vol.-%, based on the total volume of the gas stream G-2.
  • the gas stream G-2 contains the diethyl ether in an amount of from 1 to 65 vol.-%, preferably from 2 to 35 vol.-%, more preferably from 5 to 30 vol.-%, based on the total weight of the gas stream G-2.
  • the process for the preparation of butadiene further comprises hydrolyzing at least a portion of the separated diethyl ether to ethanol prior to its recycling to the gas-phase process for the preparation of butadiene, preferably as compo- nent of the gas stream G-1.
  • the separated diethyl ether is hydrolyzed under acidic conditions, more preferably in the presence of a solid catalyst.
  • the gas stream G-2 may further comprise crotonaldehyde.
  • the gas mixture G-2 further comprises crotonaldehyde.
  • the gas stream G-2 further comprises crotonaldehyde
  • the gas stream G- 2 contains crotonaldehyde in an amount of from 0.1 to 15 vol.-%, preferably from 0.5 to 10 vol.-%, more preferably from 1 to 5 vol.-%, based on the total weight of the gas stream G-2.
  • the gas stream G-2 comprising butadiene is free of crotonaldehyde or essentially free of crotonaldehyde, i.e. contains crotonaldehyde only in traces.
  • the gas stream G-2 comprising butadiene contains 0.1 vol.-% or less crotonaldehyde, preferably contains butadiene in the range of from 0.0001 to 0.1 vol.-%, more preferably in the range of from 0.0005 to 0.05 vol.-%, more preferably in the range of from 0.001 to 0.01 vol.-%.
  • the catalyst is subjected to regeneration, wherein regeneration may be conducted by any suitable method.
  • Conceivable methods are, for example to regenerate the catalyst by thermal treatment, preferably in the presence of oxygen. Further, there are no particular restrictions concerning the temperature under which the regeneration is conducted.
  • the thermal treatment is conducted, for example, at a temperature in the range of from 100 to 700 °C, preferably from 350 to 600 °C, more preferably from 450 to 570 °C.
  • the process for the preparation of butadiene according to the present invention further comprises regenerating the catalyst, preferably by thermal treatment in the presence of oxygen, wherein the thermal treatment is preferably performed at a temperature in the range of from 100 to 700 °C, preferably from 350 to 600 °C, more preferably from 450 to 570 °C.
  • the catalyst comprising Hf and two or more further active metals M 1 and M2 selected from the group consisting of Zr, Zn, Cu and combinations of two or more thereof, wherein M 1 is different from M2, obtained or obtainable according to the present invention can be used as such for any suitable purpose and in particular as a catalyti- cally active material, such as a catalytically active material in a process for the preparation of butadiene according to the present invention.
  • the present invention also relates to the use of a catalyst comprising Hf and two or more further catalytically active metals M 1 and M2, wherein the two or more further catalytically active metals M1 and M2 are selected from the group consisting of Zr, Zn, Cu and combinations of two or more thereof, and wherein M 1 is different from M2, as a catalytically active material in a process for the preparation of butadiene, preferably from a gas stream comprising ethanol and optionally acetaldehyde.
  • the catalyst 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:
  • the catalyst used as a catalytically active mate- rial in a process for the preparation of butadiene, preferably from a gas stream comprising ethanol and optionally acetaldehyde is a catalyst comprising Hf and two or more further catalytically active metals M 1 and M2 as defined according to any of the particular and preferred embodiments of the present invention.
  • the catalysts according to the present invention are used in a process for the preparation of butadiene according to the present invention, wherein the selectivity of the process relative to butadiene is at least 10 %, preferably in the range of from 10 to 90 %, more preferably from 20 to 80 %, more preferably from 30 to 70 %.
  • the selectivity of the process relative to butadiene generally designates any suitable process for the preparation of butadiene, and accordingly the selectivity relative to butadiene obtained by such a process. It is, however, preferred according to the present invention, that the selectivity relative to butadiene designates a selectivity as obtained according to any of the particular and preferred embodiments of the process for the preparation of butadiene according to present invention as defined in the present application.
  • the present invention includes the following embodiments, wherein these include the specific combinations of embodiments as indicated by the respective interdependencies defined therein:
  • a catalyst for the preparation of butadiene comprising Hf and two or more further catalytically active metals M 1 and M2, wherein the two or more further catalytically active metals M1 and M2 are selected from the group consisting of Zr, Zn, Cu and combinations of two or more thereof, and wherein M 1 is different from M2.
  • the catalyst of embodiment 1 wherein Hf and the two or more further catalytically active metals are disposed on a support.
  • the support comprises one or more metal oxides, preferably one or more metal oxides selected from the group consisting of alumina, silica, titania, titania-alumina, zirconia, zirconia-alumina, titania-zirconia, and mixtures of two or more thereof, more preferably from the group consisting of alumina, silica, titania-alumina, zirconia-alumina, and mixtures of two or more thereof, wherein more preferably the support comprises silica and/or alumina, preferably silica.
  • the catalyst of any of embodiments 1 to 3, wherein the molar ratio Hf : M 1 : M2, calculated as the respective element is in the range of from 1 : (0.002 - 20) : (0.0015 - 15), preferably 1 : (0.02 - 10) : (0.01 - 8), preferably from 1 : (0.2 - 3.0) : (0.1 - 2.0), more preferably from 1 : (0.5 - 2.5) : (0.3 - 1.5), more preferably from 1 : (0.9 -1.9) : (0.5 - 1).
  • impregnation is carried out using one or more inorganic or organic salts, wherein these salts are preferably selected from the group consisting of halides, nitrates, sulfates, phosphates, hydroxides, carbonates, carbox- ylates, alcoholates, and combinations of two or more thereof, more preferably selected from the group consisting of chlorides, nitrates, acetates, and combinations of two or more thereof.
  • a catalyst according to any of embodiments 1 to 10 as a catalytically active material in a process for the preparation of butadiene, preferably from a gas stream comprising ethanol and optionally acetaldehyde.
  • the selectivity to butadiene is in the range of from 10 to 90 %, preferably from 20 to 80 %, more preferably from 30 to 70 %.
  • Figure 1 shows the product formation and ethanol conversion indicated by " ⁇ " in the
  • Figure 2 shows the product formation and ethanol conversion indicated by "*"in the graph as function of time by use of the catalyst having a hafnium loading of 1.5 weight-
  • Example 2 a Cab- O-Sil M5 support obtained from Example 2, according to the present invention.
  • percent values are shown for the conversion of ethanol, as well as for the selectivity relative to ethylene, propylene, acetaldehyde, butadi- ene, other C4 compounds, diethylether, and oxygen-containing C4 compounds, and on the y axis, the time in minutes is indicated.
  • Figure 3 shows the product formation and ethanol conversion indicated by "*"in the graph as function of time by use of the catalyst having a hafnium loading of 3.0 weight- %, a zinc loading of 0.5 weight-% and a copper loading of 1 weight-% on a Cab-
  • O-Sil M5 support obtained from Example 3, according to the present invention.
  • percent values are shown for the conversion of ethanol, as well as for the selectivity relative to ethylene, propylene, acetaldehyde, butadiene, other C4 compounds, diethylether, and oxygen-containing C4 compounds, and on the y axis, the time in minutes is indicated.
  • Figure 4 shows the product formation and ethanol conversion indicated by "*"in the graph as function of time by use of the catalyst having a galium loading of 1.5 weight- %, a zinc loading of 0.5 weight-% and a copper loading of 1 weight-% on a Cab- O-Sil M5 support obtained from Comparative Example 1.
  • the percent values are shown for the conversion of ethanol, as well as for the selectivity relative to ethylene, propylene, acetaldehyde, butadiene, other C4 compounds, diethylether, and oxygen-containing C4 compounds, and on the y axis, the time in minutes is indicated.
  • Figure 5 shows the product formation and ethanol conversion indicated by "*"in the graph as function of time by use of the catalyst having a hafnium loading of 3 weight- %, a barium loading of 0.5 weight-% and a copper loading of 1 weight-% on a Cab-O-Sil M5 support obtained from Comparative Example 2.
  • the percent values are shown for the conversion of ethanol, as well as for the selectivity relative to ethylene, propylene, acetaldehyde, butadiene, other C4 compounds, diethylether, and oxygen-containing C4 compounds, and on the y axis, the time in minutes is indicated.
  • Figure 6 shows the product formation and ethanol conversion indicated by "*"in the graph as function of time by use of the catalyst having a hafnium loading of 3.0 weight- % and a copper loading of 1 weight-% on a Cab-O-Sil M5 support obtained from Comparative Example 3.
  • the percent values are shown for the conversion of ethanol, as well as for the selectivity relative to ethylene, propylene, acetaldehyde, butadiene, other C4 compounds, diethylether, and oxygen- containing C4 compounds, and on the y axis, the time in minutes is indicated.
  • Example 1 Preparation of a catalyst loaded with 0.75 weight-% Hf, 0.5 weight-% Zn and 1 weight-% Cu
  • hafnium (IV) chloride 0.02274 g zinc nitrate hexahydrate and 0.03142 g cop- per(ll) acetate monohydrate were dissolved in 20 mL deionized water.
  • 1 g of Cab-O-Sil M5 was added and water was slowly evaporated under stirring.
  • the obtained material was cal- cined in air at 500 °C for 6 h with a heating rate of 1 K/min.
  • the obtained calcined material had a hafnium loading of 0.75 weight-%, a zinc loading of 0.5 weight-% and a copper loading of 1 weight-%.
  • Example 2 Preparation of a catalyst loaded with 1.5 weight-% Hf, 0.5 weight-% Zn and 1 weight-% Cu
  • Example 3 Preparation of a catalyst loaded with 3 weight-% Hf, 0.5 weight-% Zn and 1 weight-% Cu 0.05384 g hafnium (IV) chloride, 0.02274 g zinc nitrate hexahydrate and 0.03142 g cop- per(ll) acetate monohydrate were dissolved in 20 mL deionized water. 1 g of Cab-O-Sil M5 was added and water was slowly evaporated under stirring. The obtained material was calcined in air at 500 °C for 6 h with a heating rate of 1 K/min. The obtained calcined material had a hafnium loading of 3 weight-%, a zinc loading of 0.5 weight-% and a copper loading of 1 weight-%.
  • Comparative Example 1 Preparation of a catalyst with 1.5 weight-% Ga, 0.5 weight-% Zn and 1 weight-% Cu
  • Comparative Example 2 Preparation of a catalyst with 3 weight-% Hf, 0.5 weight-% Ba and 1 weight-% Cu
  • hafnium (IV) chloride, 0.00758 g barium (II) chloride dihydrate and 0.03142 g copper(ll) acetate monohydrate were dissolved in 20 mL deionized water.
  • 1 g of Cab-O-Sil M5 was added and water was slowly evaporated under stirring.
  • the obtained material was calcined in air at 500 °C for 6 h with a heating rate of 1 K/min.
  • the obtained calcined mate- rial had a hafnium loading of 3 weight-%, a barium loading of 0.5 weight-% and a copper loading of 1 weight-%.
  • Comparative Example 3 Preparation of a catalyst with 3 weight-% Hf and 1 weight-% Cu 0.05384 g hafnium (IV) chloride and 0.03142 g copper(ll) acetate monohydrate were dissolved in 20 mL deionized water. 1 g of Cab-O-Sil M5 was added and water was slowly evaporated under stirring. The obtained material was calcined in air at 500 °C for 6 h with a heating rate of 1 K/min. The obtained calcined material had a hafnium loading of 3 weight- % and a copper loading of 1 weight-%.
  • Example 5 The process according to the present invention was carried out according to Reference Example 1 by use of the catalyst obtained from Example 1 , i.e. a catalyst having a hafnium loading of 0.75 weight-%, a zinc loading of 0.5 weight-% and a copper loading of 1 weight-%, wherein Cab-O-Sil M5 is used as support. The result of this experiment is shown in figure 1.
  • Example 5 a catalyst having a hafnium loading of 0.75 weight-%, a zinc loading of 0.5 weight-% and a copper loading of 1 weight-%, wherein Cab-O-Sil M5 is used as support. The result of this experiment is shown in figure 1.
  • Example 5 Example 5:
  • the process according to the present invention was carried out according to Reference Example 1 by use of the catalyst obtained from Example 2, i.e. a catalyst having a hafnium loading of 1.5 weight-%, a zinc loading of 0.5 weight-% and a copper loading of 1 weight-%, wherein Cab-O-Sil M5 is used as support.
  • the result of this experiment is shown in figure 2.
  • Example 6 The process according to the present invention was carried out according to Reference Example 1 by use of the catalyst obtained from Example 3, i.e. a catalyst having a hafnium loading of 3 weight-%, a zinc loading of 0.5 weight-% and a copper loading of 1 weight-%, wherein Cab-O-Sil M5 is used as support. The result of this experiment is shown in figure 3. Comparative Example 4:
  • Figure 4 displays the result of Comparative Example 4, which was carried out by use of a catalyst having a galium loading of 1.5 weight-%, a zinc loading of 0.5 weight-% and a cop- per loading of 1 weight-%, wherein a conversion of ethanol of less than 90 weight-% and a selectivity to butadiene of less than 10 weight-% are achieved.
  • figure 5 displays the result of Comparative Example 5, which was carried out by use of a catalyst having a hafnium loading of 3 weight-%, a barium loading of 0.5 weight-% and a copper loading of 1 weight-%.
  • the conversion of ethanol as well as the selectivity to butadiene decreases with time. After 300 minutes on stream the conversion of ethanol is below 50 % and decreases below a value of 40 % after 1000 minutes on stream, wherein after 300 minutes on stream the selectivity to butadiene is approximately 30 % and decreases to a value of below 20 % after 1000 minutes on stream.
  • this catalyst does not exhibit long time stability.
  • figure 6 displays the result of Comparative Example 6, which was carried out by use of a catalyst comprising Hf and one further catalytically active metal, i.e. a catalyst having a hafnium loading of 3 weight-% and a copper loading of 1 weight-%.
  • a catalyst comprising Hf and one further catalytically active metal, i.e. a catalyst having a hafnium loading of 3 weight-% and a copper loading of 1 weight-%.

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Abstract

L'invention concerne un catalyseur de préparation de butadiène, qui comprend Hf et deux ou plusieurs métaux additionnels M1 et M2 catalytiquement actifs choisis dans le groupe constitué par Zr, Zn, Cu et des combinaisons d'au moins deux d'entre eux, M1 étant différent de M2. L'invention concerne également un procédé de préparation de butadiène qui consiste (i) à utiliser un flux gazeux G-1 comprenant de l'éthanol; (ii) à placer le flux gazeux G-1 de l'étape (i) au contact du catalyseur de l'invention pour obtenir un flux gazeux G-2 comprenant du butadiène, ledit catalyseur comprenant Hf et deux ou plusieurs métaux additionnels M1 et M2 catalytiquement actifs choisis dans le groupe constitué par Zr, Zn, Cu et des combinaisons d'au moins deux d'entre eux, M1 étant différent de M2. L'invention concerne en outre l'utilisation dudit du catalyseur comprenant Hf et deux ou plusieurs autres métaux M1 et M2 catalytiquement actifs choisis dans le groupe constitué par Zr, Zn, Cu et des combinaisons d'au moins deux d'entre eux, M1 étant différent de M2.
PCT/IB2014/062203 2013-06-13 2014-06-13 Silicates amorphes imprégnés de métal pour la conversion sélective de l'éthanol en butadiène WO2014199349A2 (fr)

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WO2016043209A1 (fr) * 2014-09-16 2016-03-24 積水化学工業株式会社 Dispositif et procédé de production de butadiène
WO2017009105A1 (fr) 2015-07-13 2017-01-19 IFP Energies Nouvelles Catalyseur oxyde mixte mesoporeux comprenant du silicium
WO2017009108A1 (fr) 2015-07-13 2017-01-19 IFP Energies Nouvelles CATALYSEUR Ta-Nb POUR LA PRODUCTION DE 1,3-BUTADIÈNE
JP2017144359A (ja) * 2016-02-15 2017-08-24 積水化学工業株式会社 １，３−ブタジエン合成用触媒、１，３−ブタジエンの製造装置及び１，３−ブタジエンの製造方法
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JP2019043943A (ja) * 2017-08-30 2019-03-22 積水化学工業株式会社 １，３−ブタジエン及びアセトアルデヒドジエチルアセタールの製造方法
WO2019065924A1 (fr) 2017-09-27 2019-04-04 積水化学工業株式会社 Catalyseur, dispositif de fabrication de diène conjugué et procédé de fabrication de diène conjugué
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WO2016043209A1 (fr) * 2014-09-16 2016-03-24 積水化学工業株式会社 Dispositif et procédé de production de butadiène
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JP2019043943A (ja) * 2017-08-30 2019-03-22 積水化学工業株式会社 １，３−ブタジエン及びアセトアルデヒドジエチルアセタールの製造方法
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