EP0850212A1 - Procede de production de methanol et catalyseur utilise a cet effet - Google Patents

Procede de production de methanol et catalyseur utilise a cet effet

Info

Publication number
EP0850212A1
EP0850212A1 EP96907504A EP96907504A EP0850212A1 EP 0850212 A1 EP0850212 A1 EP 0850212A1 EP 96907504 A EP96907504 A EP 96907504A EP 96907504 A EP96907504 A EP 96907504A EP 0850212 A1 EP0850212 A1 EP 0850212A1
Authority
EP
European Patent Office
Prior art keywords
zinc
catalyst
zirconium
solution
copper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP96907504A
Other languages
German (de)
English (en)
Inventor
Alkis Sofianos
Erich Armbruster
Olaf Frei
Josef Heveling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lonza AG
Original Assignee
Lonza AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lonza AG filed Critical Lonza AG
Publication of EP0850212A1 publication Critical patent/EP0850212A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for producing methanol by reacting a gas mixture which contains hydrogen and carbon monoxide and / or carbon dioxide over a catalyst.
  • methanol can be produced from H 2 and CO and / or CO 2 on copper-containing catalysts. It is also known for this purpose to use catalysts which, in addition to copper, also contain zinc oxide, zirconium oxide and optionally further oxides (GB-A 2 151 498, US Pat. No. 5,254,520, Y. Nitta et al., Catal. Lett. 1994, 26, 345-354).
  • the known catalysts often contain additives which make it difficult to dispose of or reprocess the spent catalyst.
  • the object of the present invention to provide a process for the production of methanol with a higher space-time yield by using an improved catalyst, the catalyst preferably not containing any toxic or otherwise questionable components.
  • the object is achieved by the method according to claim 1. It has surprisingly been found that excellent results can be achieved even with a catalyst having a simple composition of 10-70% Cu, 10-50% Zn and 20-80% Zr if the latter is essentially X-ray-amorphous. The percentages indicate the relative proportion of the metallic elements Cu, Zn and Zr, ie the sum of the three values is always 100%, regardless of whether there are any other elements.
  • catalyst is understood to mean only the catalytically active substance in all the information relating to the composition. This can, of course, be applied to a carrier or assembled in some other way.
  • a catalyst is referred to as “essentially X-ray amphib”, the X-ray diffraction pattern of which, like that of a liquid or a glass, has no discrete diffraction lines.
  • the catalyst used according to the invention preferably contains 20-50% Cu, 10-40% Zn and 30-60% Zr.
  • the catalyst is preferably prepared by coprecipitating a precursor from a solution of water-soluble copper, zinc and zirconium salts. This is washed and dried. and then calcined at 300-500 ° C. In this temperature range there is no appreciable crystallization of the amophene Catalyst precursor instead.
  • the catalyst is expediently activated before use for the synthesis of methanol. This is achieved by heating in a hydrogen-containing atmosphere to a final temperature of 200 to 350 ° C.
  • the catalyst is preferably first kept at a lower temperature in an inert atmosphere, for example under nitrogen or argon, and then gradually or continuously exposed to slowly increasing temperatures and hydrogen concentrations until the final temperature is reached.
  • the chlorides or nitrates are preferably used as water-soluble copper, zinc and zirconium salts.
  • the coprecipitation is preferably effected by adding an alkali metal hydroxide solution to the solution of the water-soluble copper, zinc and zirconium salts. The co-precipitation can take place continuously or discontinuously, whereby in any case an intensive mixing of the reactants must be ensured.
  • the methanol synthesis itself can be carried out under the usual temperature and pressure conditions.
  • the temperature is advantageously 200 to 320 ° C, preferably 220 to 280 ° C.
  • the pressure is advantageously in the range from 1 to 10 MPa, preferably from 3 to 7 MPa.
  • the methanol synthesis is preferably carried out at a space velocity (Gas Hourly Space Velocity, GHSV) of 3200 to 40,000 ml / (g-h) (based on normal conditions), particularly preferably at 5000 to 20,000 ml / (g-h).
  • space velocity Gas Hourly Space Velocity, GHSV
  • Example 1 contains the X-ray diffractograms of the catalyst before / after, ie before calcination, from Example 1 (curve 1) and comparative example (2), and the diffraction lines of the crystalline comparative substance (CU Q 2 Zno g ) 5 (CO 3 ) 2 (OH) 6 from the database of the "Joint Committee on Powder Diffraction Standards" (International Center for Diffraction Data, 1601 Park Lane, Swarthmore PA 19081, USA) [JCPDS 380154] (3).
  • 2 contains the X-ray diffractograms of the catalysts from Example 1 (1) and Comparative Example (2) after the calcination and the diffraction lines of synthetic zincite (ZnO) [JCPDS 361451].
  • the following examples illustrate the implementation of the method according to the invention:
  • the catalyst had the following properties: BET surface area: 75 m 2 / g Cu surface area: 10.9 m 2 / g (determined by N 2 O chemiso ⁇ tion) Crystallite size: ⁇ 2 nm (x-ray amorphous), see X-ray diffractogram Fig. 2 (1).
  • Example 2 Analogously to Example 1, a catalyst with the composition 40% Cu, 20% Zn, 40% Zr was produced, the corresponding nitrates being used as starting materials instead of the chlorides.
  • the catalyst thus obtained had a BET surface area of 177 m 2 / g before the calcination and was completely radiopaque.
  • the calcined sample was also completely X-ray and had a BET surface area of 62 m 2 / g Comparative example
  • Example 1 a Cu / Zn / Zr catalyst with the composition 29% Cu, 23% Zn, 48% Zr, but without the addition of chromium, was produced: to a solution of 631 g of ammonium hydrogen carbonate in 30 l of water a solution of 317.4 g of copper (II) nitrate trihydrate, 294.5 g of zinc nitrate hexahydrate and 400.9 g of zirconyl nitrate dihydrate in 10 l of water was added at 60 ° C. while stirring vigorously to 60 ° C. . The mixture was stirred at 60 ° C for 1 h. The temperature was then kept at 80 ° C.
  • the catalysts described in Examples 1 and 2 and Comparative Examples 1 and 2 were tested for their suitability for methanol synthesis.
  • the reaction was carried out in fixed bed microreactors (18 mm 0).
  • the CO + CO 2 conversion, the yield of methanol, the methanol selectivity and the space-time yield were determined.
  • the analysis of the reaction products was carried out by o «- / me gas chromatography.
  • the catalysts were activated in situ as follows: The reactor was slowly heated to 130 ° C. under nitrogen (0.8 MPa). Then 2% hydrogen was added to the nitrogen and the temperature was raised to 200 ° C. at 20 K / h. After 16 hours, the hydrogen content was increased to 12%, the temperature was raised to 240 ° C. and held at this level for 2 hours.
  • the methanol synthesis was carried out at 250 ° C and 5 MPa.
  • a synthesis gas mixture of 32 vol.% Carbon monoxide, 5 vol.% Carbon dioxide and 63 vol.% Hydrogen was used as the starting material.
  • the space velocity was 8000 ml / (gh).
  • the results (conversion, yield, selectivity and space-time yield) are summarized in Table 1 below. These are the current values after a reaction time of 49 hours, i.e. after reaching a steady state.
  • Example 2 Analogously to Example 2, further catalysts of different compositions were produced.
  • the model Polytron® PT45-80 was used as a stirrer for the continuous coprecipitation.
  • the composition in% by weight and the precipitation conditions (temperature ⁇ , pH, concentration c, stirring frequency v and metering speed ⁇ ) are summarized in Table 2 below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé pour la synthèse de méthanol en présence de catalyseurs amorphes aux rayons x et contenant de l'oxyde de cuivre, de l'oxyde de zinc et de l'oxyde zirconium selon les proportions suivantes: 10 à 70 % en poids de cuivre, 10 à 50 % en poids de zinc et 20 à 80 % en poids de zirconium. L'invention concerne également un procédé de production des catalyseurs. Le procédé de synthèse de méthanol se caractérise par ses rendements élevés espace-temps.
EP96907504A 1995-07-21 1996-03-19 Procede de production de methanol et catalyseur utilise a cet effet Ceased EP0850212A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH214695 1995-07-21
CH2146/95 1995-07-21
PCT/EP1996/001180 WO1997003937A1 (fr) 1995-07-21 1996-03-19 Procede de production de methanol et catalyseur utilise a cet effet

Publications (1)

Publication Number Publication Date
EP0850212A1 true EP0850212A1 (fr) 1998-07-01

Family

ID=4226947

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96907504A Ceased EP0850212A1 (fr) 1995-07-21 1996-03-19 Procede de production de methanol et catalyseur utilise a cet effet

Country Status (7)

Country Link
US (1) US6054497A (fr)
EP (1) EP0850212A1 (fr)
JP (1) JP2000512261A (fr)
AU (1) AU5110696A (fr)
CA (1) CA2225449A1 (fr)
WO (1) WO1997003937A1 (fr)
ZA (1) ZA966164B (fr)

Families Citing this family (18)

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Publication number Priority date Publication date Assignee Title
US6514289B1 (en) 2000-01-30 2003-02-04 Diamicron, Inc. Diamond articulation surface for use in a prosthetic joint
DE19809418A1 (de) * 1998-03-05 1999-09-09 Basf Ag Verfahren zur Hydrierung von Carbonylverbindungen
EP1000658B1 (fr) * 1998-11-16 2006-09-13 China Petrochemical Corporation Catalyseur contenant du cuivre, sa préparation et sa utilisation
DE10124962A1 (de) * 2001-05-21 2002-12-05 Basf Ag Katalysatoren für die Reinigung von Ethylen
US6906000B1 (en) * 2001-12-11 2005-06-14 Hydrocarbon Technologies, Inc. Stable carbonous catalyst particles and method for making and utilizing same
EP1737569B1 (fr) * 2004-01-21 2007-12-26 Avantium International B.V. Catalyseurs exempt de chrome, a base de cu metallique et d'au moins un second metal
US7683227B2 (en) * 2004-12-22 2010-03-23 Exxonmobil Chemical Patents Inc. Production of aromatic hydrocarbons from methane
US7977519B2 (en) * 2006-04-21 2011-07-12 Exxonmobil Chemical Patents Inc. Production of aromatic hydrocarbons from methane
CN101945703B (zh) 2008-02-21 2013-05-08 埃克森美孚化学专利公司 由甲烷生产芳烃的方法
US8623927B2 (en) * 2008-07-24 2014-01-07 Hyundai Heavy Industries Co., Ltd. Catalyst for synthesizing methanol from synthesis gas and preparation method thereof
EP2499222A2 (fr) 2009-11-10 2012-09-19 Shell Internationale Research Maatschappij B.V. Procédé de production d'oléfines
BR112012011076A2 (pt) * 2009-11-10 2016-07-05 Shell Int Research processo e sistema integrado para a preparação de um produto de olefina inferior.
WO2011057982A2 (fr) * 2009-11-10 2011-05-19 Shell Internationale Research Maatschappij B.V. Procédé de production d'oléfines
CN102666794B (zh) * 2009-11-10 2015-12-02 国际壳牌研究有限公司 用于制备低级烯烃产品的方法
AU2010318055B2 (en) 2009-11-10 2014-04-03 Shell Internationale Research Maatschappij B.V. Process for producing ethylene oxide
RU2012149861A (ru) 2010-04-23 2014-05-27 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ получения ароматических углеводородов и этилена
DE102018105643B3 (de) 2018-03-12 2019-05-16 Edgar Harzfeld Verfahren zur unterbrechungsfreien Stromversorgung mittels einer Schnellbereitschaftsanlage sowie Schnellbereitschaftsanlage
DE202023100827U1 (de) 2023-02-22 2023-07-10 Edgar Harzfeld Schnellbereitschaftsanlage zur unterbrechungsfreien Stromversorgung einer Elektrotankstelle mit beliebig vielen Ladesäulen

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JPS5371008A (en) * 1976-12-02 1978-06-24 Mitsubishi Gas Chem Co Inc Preparation of methyl formate
FR2529098B1 (fr) * 1982-06-23 1986-12-05 Azote & Prod Chim Procede d'activation des catalyseurs metalliques
JPS60106534A (ja) * 1983-11-14 1985-06-12 Mitsubishi Gas Chem Co Inc メタノ−ル合成用流動触媒
FR2595689B1 (fr) * 1986-03-17 1988-11-04 Inst Francais Du Petrole Procede de fabrication d'un melange d'alcools primaires a partir de gaz de synthese en presence d'un catalyseur contenant du cuivre, du cobalt, du zinc et au moins un metal alcalin et/ou alcalino-terreux
JPH0763624B2 (ja) * 1986-07-24 1995-07-12 三菱瓦斯化学株式会社 メタノ−ル合成用流動触媒の製造法
ATE145837T1 (de) * 1990-09-18 1996-12-15 Csir Katalysator für die methanolsynthese

Non-Patent Citations (1)

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See references of WO9703937A1 *

Also Published As

Publication number Publication date
ZA966164B (en) 1997-02-10
JP2000512261A (ja) 2000-09-19
WO1997003937A1 (fr) 1997-02-06
CA2225449A1 (fr) 1997-02-06
AU5110696A (en) 1997-02-18
US6054497A (en) 2000-04-25

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