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WO1996016011A1 - Procede de production de methanol - Google Patents

Procede de production de methanol Download PDF

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Publication number
WO1996016011A1
WO1996016011A1 PCT/JP1995/002379 JP9502379W WO9616011A1 WO 1996016011 A1 WO1996016011 A1 WO 1996016011A1 JP 9502379 W JP9502379 W JP 9502379W WO 9616011 A1 WO9616011 A1 WO 9616011A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
oxide
methanol
copper
lanthanide
Prior art date
Application number
PCT/JP1995/002379
Other languages
English (en)
Japanese (ja)
Inventor
Susumu Tsuchiya
Yoshihisa Sakata
Satoshi Nobukuni
Kyoji Ohdan
Ryoji Sugise
Takashi Atoguchi
Original Assignee
Ube Industries, Ltd.
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 Ube Industries, Ltd. filed Critical Ube Industries, Ltd.
Publication of WO1996016011A1 publication Critical patent/WO1996016011A1/fr

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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/122—Halides of 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/25—Nitrates
    • 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 carbon monoxide, carbon dioxide, or a mixture thereof with hydrogen.
  • Methanol is a very useful compound that is widely used as a synthesis raw material such as formalin, or as a solvent or fuel. Background art
  • synthesis gas is used as a starting material.
  • M A1 or Cr
  • a catalyst composed of a support of a noble metal such as Pd or Rh or a Group VIII metal such as Ni on a carrier also exhibits activity in a methanol synthesis reaction using carbon monoxide or carbon dioxide as a starting material.
  • the synthesis gas is introduced into the solvent in which the catalyst is suspended to carry out the reaction, so that the heat control is relatively easy and the methanol conversion is higher than in the gas phase method. Can be manufactured.
  • both the gas phase method and the liquid phase method decrease the selectivity and the amount of produced methanol due to concurrent side reactions. There is a problem of doing.
  • the present invention provides a method for producing methanol from carbon monoxide and Z or carbon dioxide and hydrogen in the presence of a catalyst having excellent activity and selectivity. It is for the purpose of. Disclosure of the invention
  • FIG. 1 shows an X-ray diffraction pattern of the copper oxide containing ytterbium oxide obtained in Example 1.
  • Figure 2 shows the X-ray photoelectron spectroscopy spectrum (Cu2p spectrum) of the reduced copper containing ytterbium oxide obtained in Example 1.
  • Figure 3 shows the X of the reduced copper containing ytterbium oxide obtained in Example 1. Shows the X-ray photoelectron spectroscopy spectrum (Yb4d spectrum). BEST MODE FOR CARRYING OUT THE INVENTION
  • the lanthanide compound-containing copper oxide used in the production of the catalyst used in the method of the present invention includes Dy (disposium), Ho (holmium), Er (erbium), and Tb (terbium). ), At least one compound of a lanthanide element selected from the group consisting of Tm (thulium), Yb (ytterbium) and Lu (lutetium), and copper nitrate and Z or chloride.
  • the mixture obtained is mixed with a predetermined amount, and the obtained mixture is mixed with 150 to 650. C, preferably by heat treatment at 250-450.
  • the compound of the lanthanide element can be selected from oxides, nitrates and chlorides of the lanthanide element. If the heating temperature exceeds 650 ° C., CuO and Z or oxides of Dy, Ho, Er, Tb, Tm, Yb or Lu are not preferred. On the other hand, when the above-mentioned heating temperature is lower than 150 ° C., the formation reaction of the lanthanide compound-containing copper oxide from various metal salts does not proceed smoothly, which is not preferable.
  • the above heat treatment is performed by using a normal heating device such as an electric furnace, It is preferable to carry out the treatment while removing volatile decomposed products under a flow of gas such as nitrogen or air or under reduced pressure.
  • the heating time is appropriately selected within the range of 1 minute to 50 hours.
  • the copper oxide containing the lanthanide compound thus prepared was found to have a force of 20 to 16.0 to 16.8 in its X-ray diffraction spectrum. , 29.5-34.0 °, 37.8-39.5 °, 41.0-43.0 °, 54.6-57.0. It has characteristic peaks. These peaks are assigned to the plane indices 111, 222, 400, 331, and 440 of the cubic crystal, respectively. The axial length a of this crystal is about 9.2 to 9.8A.
  • this La printer Roh I de compounds containing copper oxide, if it is a cubic system crystal having a composition similar to Ag? 0 8 (N0 3) Is recognized.
  • the lanthanide compound-containing copper oxide (for example, i-type) is obtained from the X-ray diffraction spectrum shown in FIG. It is recognized that copper atoms and lanthanide atoms represented by M (for example, ytterbium atoms) are regularly arranged in a cubic crystal lattice of copper oxide containing a ytterbium compound). Is received. Therefore, the lanthanide compound-containing copper oxide is recognized as a compound in which copper atoms and lanthanide atoms (ytterbium atoms) are mixed at an atomic level.
  • the lanthanide-containing reduced copper used in the method of the present invention can be prepared by reducing the lanthanide compound-containing copper oxide prepared as described above at a relatively low temperature. Can be. If the reduction temperature is too high, thinning occurs, and if the reduction temperature is low, the reduction does not proceed, so this reduction removes the lanthanide compound-containing copper oxide from 200 to 400 ° C, Preferably, it is carried out by contacting with a gas containing a reducing gas such as hydrogen at a temperature of 250 to 350 ° C. Good.
  • the above-described reduction treatment can be performed under any of normal pressure, increased pressure, and reduced pressure.
  • the reduction time varies depending on the reduction conditions, but is usually 0.1 to 10 hours.
  • This reduction treatment may be carried out while a copper oxide containing a lanthanide compound is put in a reactor different from the reactor for producing methanol and a reducing gas is passed therethrough.
  • a copper oxide containing a lanthanide compound and a reducing gas may be charged into a reactor for producing methanol, and the reaction may be performed before the production of methanol.
  • the mixture of reduced copper, in which copper is reduced to metallic copper, and lanthanide are mixed As shown in the X-ray photoelectron spectroscopy spectrum (for example, Figs. 2 and 3), the mixture of reduced copper, in which copper is reduced to metallic copper, and lanthanide are mixed.
  • the production of methanol is carried out by reacting carbon monoxide and / or carbon dioxide with hydrogen in a gas phase or a liquid phase in the presence of the lanthanide-containing reduced copper.
  • the form of the lanthanide-containing reduced copper catalyst to be present in the reaction system is not limited at all.
  • it may be present in a granular or fine powder form. It may be used in the form of being supported on a finely divided carrier.
  • the lanthanide-containing reduced copper is preferably present in the above-mentioned form in a fixed bed or a fluidized bed.
  • the reaction temperature is usually 150 to 300 ° C in the presence of the above-mentioned lanthanide-containing reduced copper in an ordinary atmospheric or pressurized circulation system or a reduced-pressure closed circulation system. , is preferred and rather to 180 to 250 ° C, 100 to the gas space velocity 20000Hr ', it is preferable and rather the reaction under the conditions of 3000 ⁇ 1 OOOOhr 1 is performed.
  • Reaction pressure if the reaction is carried out under pressure usually 1 ⁇ 120kgZcnf G, and preferred rather is 10 ⁇ 120kg / cm 2 G, is rather further preferred Te 20 ⁇ 50kg / orf G: Yes, the reaction is carried out at reduced pressure In this case, it is usually from 5 torr to less than 760 torr, preferably from 50 to 500 torr.
  • reduced pressure In the case of a liquid phase reaction, the same temperature, pressure, gas composition, or gas space velocity as in the gas phase reaction is used in the presence of the lanthanum oxide-containing reduced copper in a pressurized flow system or a pressurized batch system. The reaction takes place.
  • the reaction temperature is usually 150 to 300 ° C, preferably 180 to 250 ° C
  • the reaction pressure is 10 to 120 kgZcrfG, preferably 20 to 50 kgZcnfG.
  • the reaction is carried out at a gas space velocity of usually 100 to 20000 hr— ', preferably 3000 to 100 hr— 1 .
  • the reaction is carried out in a reaction solvent.
  • the reduced copper containing lanthanide oxide is usually 1 to 60% by weight, preferably 5 to 50% by weight, based on the reaction solvent. It is used by suspending in a solvent at a ratio of weight%.
  • the reaction solvent is not particularly limited as long as it is stable under the reaction conditions and can suspend the catalyst.
  • hexane, heptane, octane, decane, dodecane, etc. having 6 to 20 carbon atoms Halogen-free aliphatic hydrocarbons, (2) aromatic hydrocarbons having 6 to 12 carbon atoms such as benzene, toluene and xylene; (3) ethers such as dimethyl ether, getyl ether and diisopropyl ether; (4) Select from ketones such as acetate, methylethylketone and methylisobutylketone, and (5) aliphatic hydrocarbons such as dichloromethane, chloroform and dichloroethane. At least one selected reaction solvent can be used. It is also possible to use a commercially available mixed paraffinic or naphthenic mineral oil as it is as a reaction solvent.
  • the carbon monoxide, carbon dioxide, and hydrogen used in the production of the methanol of the present invention may be pure gases, respectively, but are usually obtained industrially as synthetic gas or water gas. Are preferably used.
  • the volume ratio of hydrogen to carbon monoxide or carbon dioxide is usually hydrogen: carbon monoxide (H 2 : CO) or hydrogen: carbon dioxide (H 2 : CO 2 ) 10: 1 to 1: 5.
  • Preferably 5: 1 to 1: 2 wide range It can be.
  • the hydrogen volume ratio [H 2 : (C 0 + C 0 2 )] to the total amount thereof is within the above range, that is, 10: 1 to 1 : If it is 5, any value can be taken.
  • concentrations of nitrogen, methane, etc. which coexist in these gases.
  • the resulting Lee Tsu terbium compound containing copper oxide [(Yb l / 7 Cu 6 7 0 u N0 3 ] 0.05g was charged in a glass reaction tube having an inner diameter of 12 mm, under pressure of 400 torr, hydrogen gas in a closed circulation system While circulating at a flow rate of 100 ml / min, the temperature was gradually increased and reduced at 250 ° C for 2 hours to obtain reduced copper containing lanthanide oxide and reduced copper containing ytterbium oxide.
  • Table 1 shows the results of Example 1 and Comparative Example 1.
  • a catalyst was prepared in the same manner as in Example 1. However, 5.52 g (14.4 mmol) of erbium oxide was used instead of ytterbium oxide, and the amount of copper nitrate trihydrate used was changed to 41.8 g (173 ol). Erbium compounds containing copper oxide [(Er 1/7 Cu 6/7) 7 0 B N0 3 ] 21.2g was obtained. The obtained erbium compound-containing copper oxide had a cubic X-ray diffraction pattern similar to that of FIG. Next, 0.05 g of the erbium compound-containing copper oxide was reduced in the same manner as in Example 1 to obtain erbium oxide-containing reduced copper as lanthanum oxide-containing reduced copper. From the X-ray photoelectron spectrum, it was confirmed that copper was present as a metal and erbium was present as an oxide.
  • Example 2 the same methanol generation reaction and analysis as in Example 2 were performed. However, instead of the reduced copper catalyst containing ytterbium oxide, a catalyst composed of the above reduced copper containing erpium oxide was used. As a result, the amount of methanol produced was 320 ⁇ mol Z g—cat.
  • a catalyst prepared by reducing 0.05 g at 250 ° C was used to produce a methanol at 250 ° C.
  • the yield of methanol was 170 imol / g—cat.
  • a catalyst prepared by reducing 0.05 g at 250 ° C was used to produce methanol at 250 ° C.
  • the amount of methanol produced was 220 lmo1 / g / cat.
  • Table 2 shows the results of Examples 2 to 5 and Comparative Examples 2 to 4. (Table 2)
  • Example 1 1.48 g of the ytterbium compound-containing copper oxide described in Example 1 was reduced in the same manner as in Example 1 to obtain 1.15 g of ytterbium oxide-containing reduced copper. 100 ml of this ytterbium oxide-containing reduced copper was placed under a nitrogen atmosphere. Transfer to a magnetically stirred autoclave, add 30 ml of n-dodecane, then inject 15 kg of Zcnf G hydrogen gas and further inject carbon monoxide until the total pressure reaches 30 kg / cnf G . After stirring the inside of the autoclave at room temperature for 10 minutes, the temperature was raised to 200 ° C with stirring, and at this temperature, a metal mold was manufactured for 2 hours.
  • the autoclave was cooled to recover methanol present in the gas phase and the liquid phase, which was analyzed by gas chromatography.
  • the conversion of carbon monoxide was 16.7 mol%
  • the conversion of methanol The selectivity was over 98 mol%.
  • Example 8 For the production of methanol, the same reaction and analysis as in Example 6 were performed. However, the above-mentioned reduced copper containing yttrium oxide was used as the reduced copper containing lanthanum oxide. As a result, the conversion of carbon monoxide was 1 mol%, and the selectivity for methanol was 96 mol% or more.
  • Example 8 For the production of methanol, the same reaction and analysis as in Example 6 were performed. However, the above-mentioned reduced copper containing yttrium oxide was used as the reduced copper containing lanthanum oxide. As a result, the conversion of carbon monoxide was 1 mol%, and the selectivity for methanol was 96 mol% or more. Example 8
  • a catalyst was prepared in the same manner as in Example 1. However, 1.47 g of the copper oxide containing the erbium compound described in Example 3 was reduced to obtain 1.15 g of reduced copper containing erbium oxide.
  • Example 6 In the production of methanol, the same reaction and analysis as in Example 6 were performed. However, instead of the reduced copper containing ytterbium oxide, the reduced copper containing oxidized rubidium was used, and the reaction time was changed to 3 hours. As a result, the conversion of carbon oxide was 11 mol%, and the selectivity of the male was 95 mol% or more.
  • a catalyst was prepared in the same manner as in Example 1. However, 2.52 g (6.57 mmol) of holmium oxide was used instead of ytterbium oxide, and the amount used for copper nitrate trihydrate was changed to 19.38 g (80 mmol).
  • Formyl um compound containing copper oxide [Ho, Cu 6 c) 7 0 8 N0 3] 21.2g was obtained as a La Ntano Lee de compounds containing copper oxide.
  • the obtained holmium compound-containing copper oxide had a cubic X-ray diffraction pattern similar to that of FIG.
  • 1.46 g of this holmium compound-containing copper oxide was used in the same manner as in Example 1. After reduction, 1.15 g of reduced copper containing holmium oxide was obtained as reduced copper containing lanthanum oxide.
  • the X-ray photoelectron spectrum confirmed that copper exists as a metal and holmium exists as an oxide.
  • Example 6 In the production of methanol, the same reaction and analysis as in Example 6 were performed. However, the reduced copper containing formium oxide was used instead of the reduced copper containing ytterbium oxide. As a result, the conversion of carbon monoxide was 10 mol%, and the selectivity for methanol was 97 mol% or more.
  • Example 6 In the production of methanol, the same reaction and analysis as in Example 6 were performed. However, instead of the reduced copper containing ytterbium oxide, 1.26 g of the reduced catalyst described in Comparative Example 1 was used. As a result, the conversion of carbon monoxide was 38.3 mol%, and the selectivity for methanol was 86.6 mol%.
  • Table 3 shows the results of Examples 6 to 9 and Comparative Example 5.
  • Example 7 Containing ytterbium oxide 1 7> 96
  • Example 9 Form oxide-containing reduction 10> 97 Comparative Example 5 CuO-ZnO-A0 :, reduced product 38.38.6.6 Industrial applicability
  • a lanthanide compound-containing copper which is a cubic crystal as a catalyst is used as a catalyst.
  • lanthanide-containing reduced copper obtained by reducing an oxide
  • methanol can be produced with high selectivity in both gas phase and liquid phase reactions.
  • the method of the present invention makes it possible to improve the conversion of carbon monoxide in the liquid phase reaction and to produce methanol with high selectivity, so that the liquid phase is relatively easy to control the heat. The production of methanol by reaction has become possible.

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

Abstract

Procédé de production de méthanol qui consiste à faire réagir un monoxyde de carbone et/ou un dioxyde de carbone avec de l'hydrogène en présence d'un catalyseur comprenant un mélange de cuivre réduit et d'un oxyde de lanthanide, préparé par réduction d'un oxyde de cuivre contenant un composé lanthanide, de formule générale (MxCuy)7OzAw dans laquelle M représente au moins un atome de lanthanide sélectionné parmi Dy, HO, Er, Tb, Yb et Lu; A représente un atome d'halogène et/ou NO3; et x+y = 1, O < x/y « 10, 6 « z « 8m et 0,5 « w « 9.
PCT/JP1995/002379 1994-11-22 1995-11-22 Procede de production de methanol WO1996016011A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP6/288156 1994-11-22
JP28815694 1994-11-22
JP7/228336 1995-09-05
JP22833695 1995-09-05

Publications (1)

Publication Number Publication Date
WO1996016011A1 true WO1996016011A1 (fr) 1996-05-30

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PCT/JP1995/002379 WO1996016011A1 (fr) 1994-11-22 1995-11-22 Procede de production de methanol

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54154706A (en) * 1978-05-15 1979-12-06 Standard Oil Co Manufacture of alcohol from synthetic gas
JPS5929037A (ja) * 1982-07-19 1984-02-16 シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ 変性された銅および亜鉛−含有触媒および該触媒を使用するメタノ−ル製造法
JPS6087233A (ja) * 1983-10-18 1985-05-16 Idemitsu Kosan Co Ltd メタノ−ルの製造方法
JPS60190232A (ja) * 1984-01-27 1985-09-27 アンステイテユ・フランセ・デユ・ペトロール 合成ガスからのメタノールの製造に使用しうる、銅、亜鉛およびアルミニウムを含む触媒の製造方法
JPH04122444A (ja) * 1990-09-13 1992-04-22 Agency Of Ind Science & Technol 二酸化炭素からのメタノールの製造法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54154706A (en) * 1978-05-15 1979-12-06 Standard Oil Co Manufacture of alcohol from synthetic gas
JPS5929037A (ja) * 1982-07-19 1984-02-16 シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ 変性された銅および亜鉛−含有触媒および該触媒を使用するメタノ−ル製造法
JPS6087233A (ja) * 1983-10-18 1985-05-16 Idemitsu Kosan Co Ltd メタノ−ルの製造方法
JPS60190232A (ja) * 1984-01-27 1985-09-27 アンステイテユ・フランセ・デユ・ペトロール 合成ガスからのメタノールの製造に使用しうる、銅、亜鉛およびアルミニウムを含む触媒の製造方法
JPH04122444A (ja) * 1990-09-13 1992-04-22 Agency Of Ind Science & Technol 二酸化炭素からのメタノールの製造法

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