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WO1996016011A1 - Process for producing methanol - Google Patents

Process for producing 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
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WO
WIPO (PCT)
Prior art keywords
reaction
oxide
methanol
copper
lanthanide
Prior art date
Application number
PCT/JP1995/002379
Other languages
French (fr)
Japanese (ja)
Inventor
Susumu Tsuchiya
Yoshihisa Sakata
Satoshi Nobukuni
Kyoji Ohdan
Ryoji Sugise
Takashi Atoguchi
Original Assignee
Ube Industries, Ltd.
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Publication date
Application filed by Ube Industries, Ltd. filed Critical Ube Industries, Ltd.
Publication of WO1996016011A1 publication Critical patent/WO1996016011A1/en

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    • 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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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A process for producing methanol by the reaction of carbon monoxide and/or carbon dioxide with hydrogen in the presence of a catalyst comprising a mixture of reduced copper and a lanthanoid oxide and prepared by reducing a copper oxide containing a lanthanoid compound, represented by general formula (MxCuy)7OzAw wherein M represents at least one lanthanoid atom selected from among Dy, Ho, Er, Tb, Tm, Yb and Lu; A represents a halogen atom and/or NO3; and x+y = 1, O < x/y « 10, 6 « z « 8, and 0.5 « w « 9.

Description

明 細 書 メ タノ ールの製造方法 技術分野  Description Manufacturing method of methanol
本発明は、 一酸化炭素、 二酸化炭素、 又はこれらの混合物と水素 とを反応させてメ タノ ールを製造する方法に関する ものである。 メ タノ 一ルはホルマ リ ン等の合成原料と して、 あるいは溶剤や燃料と して広く 用いられきわめて有用な化合物である。 背景技術  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
メ タノ ールの製造方法と しては、 合成ガスを出発原料と して用い As a method for producing methanol, synthesis gas is used as a starting material.
、 かつ触媒と して CuO— ZnO— M203系触媒 （M二 Al， Cr等） を主に 使用 し、 Lurgi法や ICI法に代表される気相法による方法が知られ ている。 また、 この触媒を改良したものと して、 例えば CuO— ZnO _M203触媒 （M = A1又は Cr) に リ ンの酸素酸又はその塩を添加した もの （特開昭 59- 19546号公報） 、 CuO - ZnO 触媒に Al, Cr, V， Mg 及び Mnの酸化物から選ばれた 1 種を添加したもの （特開昭 57— 1305 47号公報） 、 CuO— ZnO 触媒にアルカ リ を添加したもの （特開昭 60 — 190232号公報） 、 CuO - ZnO— Μ203触媒 （Μ =Α1又は Cr) の細孔 径等を制御したもの （特開昭 59— 222232号公報） などが知られてい る And as a catalyst CuO- ZnO- M 2 0 3 catalyst (M two Al, Cr, etc.) mainly used, methods are known by the vapor phase method typified by Lurgi method and ICI method. Further, as a an improvement over this catalyst, e.g. CuO- ZnO _M 2 0 3 catalyst (M = A1 or Cr) in a material obtained by adding oxygen acid or a salt Li down (JP 59-19546 JP ), CuO-ZnO catalyst with addition of one selected from oxides of Al, Cr, V, Mg and Mn (JP-A-57-130547), addition of alkali to CuO-ZnO catalyst the ones (JP 60 - 190232 discloses), CuO - ZnO- Μ 2 0 3 catalyst (Micromax = [alpha] 1 or Cr) that control the pore diameter of the (JP 59-222232 JP), etc. Are known
しかしながら、 このような CuO— ZnO— M 203系触媒 （M = A1， Cr 等） は、 その還元方法や使用形態に拘らず、 いずれも水性ガスシフ ト反応の触媒と しても作用 し （Catal. Today, 23(1995) 29-42、 Ap pi. Catal. A ： General, 112(1994) 57-73)、 更に Boudouard反応 も引き起こすため （Appl. Catal. A ： General, 112(1994) 57-73) 、 この触媒を用いたメ タノ ール合成反応では、 出発原料と して供給 された一酸化炭素および二酸化炭素の間の相互変換反応が常に副反 応して併発するこ とが知られている。 そのため、 メ タ ノ ールの選択 率及び生成量は上記副反応の影響を強く 受け、 殆どの場合、 平衡組 成値より も大幅に低く なる。 更に、 CuO— ZnO— M 203系触媒 （M = Al， Cr等） では、 反応系内の二酸化炭素濃度がある レベル （ 5〜20 モル％程度） を越えると、 メ タノ ールの生成が制御されるという問 題も存在する （Stud. Surf. Sci. Catal. , 64(1991)， 272— 274)。 従って、 CuO— ZnO— M 203系触媒 （M = A1， Cr等） では、 上記の副 反応より もメ タ ノ ール合成反応を優先的に進行させるこ とができる 触媒を開発する必要がある。 However, such CuO- ZnO- M 2 0 3 catalyst (M = A1, Cr, etc.), also act as its regardless of reduction methods or the use forms, for either the aqueous Gasushifu preparative reaction catalyst ( Catal. Today, 23 (1995) 29-42, Ap pi. Catal. A: General, 112 (1994) 57-73) and also cause Boudouard reaction (Appl. Catal. A: General, 112 (1994) 57). -73) However, in the methanol synthesis reaction using this catalyst, it is known that the interconversion reaction between carbon monoxide and carbon dioxide supplied as starting materials always occurs in parallel with side reactions. . For this reason, the selectivity and the amount of formed methanol are strongly affected by the side reaction, and in most cases, are much lower than the equilibrium composition value. Furthermore, CuO- ZnO- the M 2 0 3 catalyst (M = Al, Cr, etc.), exceeds a level (about 5 to 20 mol%) with a carbon dioxide concentration in the reaction system, the generation of main Tano Lumpur There is also a problem that is controlled (Stud. Surf. Sci. Catal., 64 (1991), 272–274). Therefore, CuO- ZnO- M 2 0 in 3 catalysts (M = A1, Cr, etc.), need to develop a catalyst capable and this to proceed preferentially the METHANOL synthesis reaction than side reactions described above There is.
また、 Pdや Rh等の貴金属あるいは Ni等の VI II族金属を担体に担持 して構成された触媒も、 一酸化炭素あるいは二酸化炭素を出発原料 とするメ タノ ール合成反応に活性を示すこ とが知られているが （St ud. Surf. Sci. Catal. , 64(1991)， 266-268、 及び同 290-291 ) 、 実用的に充分な レベルには未だ達していない。  In addition, 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. (Stud. Surf. Sci. Catal., 64 (1991), 266-268, and 290-291), but have not yet reached a practically sufficient level.
メ タ ノ 一ルの製造においては、 上記メ タ ノ ール生成反応が発熱反 応であるため、 反応熱の除去を含む反応器の熱制御が、 プロセス設 計上の障害になるという問題が存在するために、 気相法によるプロ セス以外に、 液相法によるプロセスも試みられている （特開平 2 — 6420号公報） 。 液相法は石炭ガス化複合発電との関連においても興 味がもたれている ものである （Catal. Rev. Sci. Eng. , 36 ( 1994) 558-559)。  In the production of methanol, there is a problem that the heat control of the reactor, including the removal of the heat of reaction, is an obstacle to process design because the above-mentioned reaction for producing methanol is an exothermic reaction. For this purpose, a process using a liquid phase method has been attempted in addition to a process using a gas phase method (Japanese Patent Laid-Open No. 2-6420). The liquid phase method is also of interest in the context of integrated coal gasification combined cycle (Catal. Rev. Sci. Eng., 36 (1994) 558-559).
液相法では、 触媒を懸濁させた溶媒中に合成ガスを導入して反応 を行っているため、 熱制御が比較的容易であって、 気相法より も高 い転化率でメ タノ ール製造を行う こ とができる。 しかしながら、 液 相法においても、 気相法と同様に、 CuO— ZnO— M 203系触媒 （M = Al, Cr等） が用いられるため、 前記のような副反応によ り メ タ ノ 一 ルの選択率及び生成量が低下するという問題が解決されていない。 In the liquid phase method, 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. However, even in the liquid phase method, like the gas phase method, CuO- ZnO- M 2 0 3 catalyst (M = Since Al, Cr and the like are used, the problem that the selectivity and the production amount of methanol decrease due to the side reaction as described above has not been solved.
このように、 従来のメ タ ノ ールの製造方法においては、 気相法、 液相法いずれの方法においても、 併発する副反応のため、 メ タ ノ ー ルの選択率及び生成量が低下する という問題点がある。  As described above, in the conventional method for producing methanol, 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.
上述のような技術背景に鑑み、 本発明は、 活性及び選択性に優れ た触媒の存在下、 一酸化炭素及び Z又は二酸化炭素と水素とからメ タノ 一ルを製造する方法を提供するこ とを目的とする ものである。 発明の開示  In view of the technical background as described above, 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
本発明に係るメ タ ノ ールの製造法は、 一般式 （MxCuy)702A、 （式 中、 Mは Dy， Ho, Er, Tb， Tm, Yb及び Luからなる群から選ばれた少 なく と も一種のラ ンタノ ィ ド原子を表し、 Aはハロゲン原子及び N 03基からなる群から選ばれた少なく と も 1 員を表し、 X + y = 1 , 0 < X / y ≤ 10, 6 ≤ z ≤ 8 、 かつ 0.5 w≤ 9 である） で表され るラ ンタノ ィ ド化学物含有銅酸化物を還元するこ とによって得られ 、 少なく と も 1 種の酸化ラ ンタ ノ ィ ドと還元銅とが混在している酸 化ラ ンタノ イ ド含有還元銅を含む触媒の存在下に、 一酸化炭素及び 二酸化炭素からなる群から選ばれた少なく と も 1 員からなる出発原 料と水素とを反応させるこ とを特徴とする ものである。 図面の簡単な説明 METHANOL manufacturing method according to the present invention have the general formula (M x Cu y) 7 0 2 A, ( where, M is Dy, Ho, Er, Tb, Tm, from the group consisting of Yb, and Lu represents selected small without a kind of La Ntano I de atoms were also, a is also represents one member and less selected from the group consisting of a halogen atom and N 0 3 group, X + y = 1, 0 <X / y ≤ 10, 6 ≤ z ≤ 8 and 0.5 w ≤ 9) by reducing at least one copper oxide containing lanthanide chemicals. At least one member selected from the group consisting of carbon monoxide and carbon dioxide in the presence of a catalyst containing lanthanide-containing reduced copper in which lanthanide and reduced copper are mixed It is characterized by reacting a starting material with hydrogen. BRIEF DESCRIPTION OF THE FIGURES
図 1 は、 実施例 1 で得られた酸化イ ッテルビウム含有銅酸化物の X線回折パターンを示し、  FIG. 1 shows an X-ray diffraction pattern of the copper oxide containing ytterbium oxide obtained in Example 1.
図 2 は、 実施例 1 で得られた酸化イ ッテルビウム含有還元銅の X 線光電子分光スぺク トル （Cu2pスぺク トル） を示し、  Figure 2 shows the X-ray photoelectron spectroscopy spectrum (Cu2p spectrum) of the reduced copper containing ytterbium oxide obtained in Example 1.
図 3 は、 実施例 1 で得られた酸化イ ッテルビウム含有還元銅の X 線光電子分光スぺク トル （Yb4 dスぺク トル） を示す。 発明を実施するための最良の形態 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
本発明の酸化ラ ンタ ノ ィ ド含有還元銅を調製するために使用され るラ ンタノ イ ド化合物含有銅酸化物は、 一般式 （M x Cu y ) 70 z A、、 （式 中、 Mは Dy， Ho, E r, Tb, Tm， Yb及び Luからなる群から選ばれた少 なく と も一種のラ ンタ ノ イ ド原子を表し、 Aはハロゲン原子又は N 03基を示し、 x + y = l， 0 < X / y≤ 10, 6 ≤ z ≤ 8 , かつ 0. 5 ≤ w≤ 9 である） で表されるラ ンタノ ィ ド化合物含有銅酸化物であ つて、 .立方晶系の結晶である。 なお、 Aにより表されるハロゲン原 子と して塩素原子が好ま しい。 このラ ンタ ノ イ ド化合物含有銅酸化 物の一部は、 特開平 5 - 43228 号公報に記載されており、 この明細 書の上記記載は本願明細書の一部と して援用するこ とができる。 本発明方法に用いられる触媒の製造に用いられるラ ンタノ ィ ド化 合物含有銅酸化物は、 Dy (デイ スプロ シゥ ム） 、 H o (ホル ミ ウ ム） 、 Er (エルビウム） 、 Tb (テルビウム） 、 Tm (ツ リ ウム） 、 Yb (ィ ッ テルビウム） 及び Lu (ルテチウム） からなる群から選ばれた少な く と も一種のラ ンタ ノ ィ ド元素の化合物と、 銅の硝酸塩及び Z又は 塩化物との、 所定量を混合し、 得られた混合物を 150〜650 。C、 好 ま し く は 250〜450 で加熱処理するこ とにより調製される。 なお 、 前記ラ ンタ ノ ィ ド元素の化合物は、 前記ラ ンタ ノ ィ ド元素の酸化 物、 硝酸塩及び塩化物から選ぶことができる。 上記加熱温度が 650 °Cを超えると、 CuO及び Z又は Dy, Ho, Er, Tb, Tm, Ybあるいは Lu の酸化物が生成するために好ま し く ない。 また、 上記加熱温度が 1 50°C未満では各種金属塩からの前記ラ ンタ ノ ィ ド化合物含有銅酸化 物の生成反応が円滑に進行しないため、 好ま し く ない。 Oxide La printer Roh be used to prepare the I-de-containing reduced copper Lula Ntano Lee de compounds containing copper oxide of the present invention have the general formula (M x Cu y) 7 0 z A ,, ( wherein, M is Dy, represents Ho, E r, Tb, Tm , a kind of La printer Roh Lee de atom and no less selected from the group consisting of Yb and Lu, a represents a halogen atom or a N 0 3 group, x + y = l, 0 <X / y ≤ 10, 6 ≤ z ≤ 8 and 0.5 ≤ w ≤ 9), which is a copper oxide containing a lanthanide compound. It is a system crystal. Note that a chlorine atom is preferable as the halogen atom represented by A. A part of the lanthanide compound-containing copper oxide is described in JP-A-5-43228, and the above description of this specification may be incorporated as a part of the specification of the present application. it can. 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.
上記加熱処理は、 電気炉等の通常の加熱装置を使用 して、 酸素、 窒素又は空気等のガスの流通下あるいは減圧下で揮発性分解物を除 去しながら行う こ とが好ま しい。 加熱時間は 1 分〜 50時間の範囲で 適宜選定される。 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.
このようにして調製されたラ ンタノ ィ ド化合物含有銅酸化物は、 その X線回折スぺク トルにおいて、 2 0力く 16.0〜16.8。 、 29.5〜34 .0° 、 37.8〜39.5° 、 41.0〜43.0° 、 54.6〜57.0。 に特徴的なピー クを有している。 これらのピークは立方晶系の結晶の面指数 111， 22 2, 400， 331， 440にそれぞれ帰属される。 この結晶の軸長 a は約 9. 2 〜 9.8Aである。  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.
上記のような X線回折スぺク トルのデータから、 このラ ンタ ノ ィ ド化合物含有銅酸化物は、 Ag?08(N03)に類似する組成を有する立方 晶系の結晶であると認められる。 具体的には、 例えばラ ンタノ ィ ド 化合物と して酸化イ ッ テルビウムを用いた場合、 図 1 に示されてい る X線回折スペク トルから、 ラ ンタノ イ ド化合物含有銅酸化物 （例 えばイ ッテルビウム化合物含有銅酸化物） において、 立方晶系の結 晶格子中に銅原子と、 Mにより示されるラ ンタ ノ ィ ド原子 （例えば イ ッテルビウム原子） とが規則正し く配列されているこ とが認めら れる。 従って、 ラ ンタノ ィ ド化合物含有銅酸化物は、 銅原子とラ ン タ ノ ィ ド原子 （イ ッテルビウム原子） が原子的な レベルで混合され ている化合物であると認められる。 From the data of above-described X-ray diffraction scan Bae-vector, 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. Specifically, for example, when ytterbium oxide is used as the lanthanide compound, 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.
本発明の方法に用いられる酸化ラ ンタ ノ ィ ド含有還元銅は、 前記 のよう にして調製されたラ ンタ ノ イ ド化合物含有銅酸化物を、 比較 的低温で還元する こ とによって調製する こ とができる。 還元温度が 高すぎると シ ン夕 リ ングが起こ り、 また還元温度が低いと還元が進 まないため、 この還元は前記ラ ンタ ノ ィ ド化合物含有銅酸化物を、 200 〜400 °C、 好ま し く は 250 〜350 °Cの温度において、 水素等の 還元性ガスを含有するガスと接触させる こ とによって行う こ とが好 ま しい。 上記還元処理は常圧、 加圧、 減圧いずれの条件でも可能で あり、 還元時間は還元条件により異なるが通常 0.1〜10時間で十ゥ である。 なお、 この還元処理は、 メ タ ノ ール製造用反応器とは異な る反応器に、 ラ ンタ ノ ィ ド化合物含有銅酸化物を入れて還元性ガス を流通させながら行ってもよ く 、 又はメ タ ノ ール製造用反応器にラ ンタノ イ ド化合物含有銅酸化物と還元性ガスを仕込み、 メ タ ノ ール 製造の前に行っても差し支えない。 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. Alternatively, 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.
前記のようにして得られた酸化ラ ンタ ノ ィ ド含有還元銅は、 その The lanthanide-containing reduced copper obtained as described above is
X線光電子分光スぺク トル （例えば図 2 ， 3 ) に示されるよう に、 銅が金属銅まで還元されている還元銅と酸化ラ ンタノ ィ ドとが混在 している ものである。 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.
本発明方法では、 前記酸化ラ ンタ ノ ィ ド含有還元銅の存在下に、 一酸化炭素及び/又は二酸化炭素と水素とを、 気相又は液相で反応 させるこ とによってメ タノ ールの製造が行われる。 このとき、 反応 系に存在させる前記酸化ラ ンタノ ィ ド含有還元銅触媒の形態には全 く 制限がな く 、 例えば粒状又は微粉状の形態のまま存在させてもよ く 、 またそれを粒状又は微粉状の担体に担持させた形態で用いても よい。 気相反応においては、 前記酸化ラ ンタノ ィ ド含有還元銅は固 定床又は流動床に上記の形態で存在させるこ とが好ま しい。  In the method of the present invention, 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. Is performed. At this time, the form of the lanthanide-containing reduced copper catalyst to be present in the reaction system is not limited at all. For example, 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. In the gas phase reaction, the lanthanide-containing reduced copper is preferably present in the above-mentioned form in a fixed bed or a fluidized bed.
気相反応の場合、 通常の常圧又は加圧の流通系あるいは減圧の閉 鎖循環系で、 前記酸化ラ ンタ ノ ィ ド含有還元銅の存在下、 通常、 反 応温度が 150〜 300°C、 好ま し く は 180〜 250°Cに、 ガス空間速度 が 100〜 20000hr '、 好ま し く は 3000〜 1 OOOOhr 1の条件で反応が 行われる。 反応圧は、 加圧で反応を行う場合は通常 1 ~ 120kgZcnf G、 好ま し く は 10〜 120kg/cm2 G、 更に好ま し く は 20〜 50kg / orf Gて :あり、 減圧で反応を行う場合は通常 5 torr以上から 760torr 未 満、 好ま し く は 50〜 500torr である。 液相反応の場合、 加圧流通系あるいは加圧バッチ式で、 前記酸化 ラ ンタ ノ ィ ド含有還元銅の存在下に、 前記気相反応における と同様 の温度、 圧力、 ガス組成あるいはガス空間速度で反応が行われる。 即ち、 通常、 反応温度が 150~ 300°C、 好ま し く は 180〜 250°Cで 、 反応圧が 10〜 120kgZcrf G、 好ま し く は 20〜50kgZcnf Gである。 加圧流通系の場合、 ガス空間速度が通常 100〜 20000hr— '、 好ま し く は 3000〜 lOOOOhr— 1の条件で反応が行われる。 液相反応の場合、 反応が反応溶媒中で行われ、 このと き、 前記酸化ラ ンタ ノ イ ド含有 還元銅は、 反応溶媒に対して通常 1 〜60重量％、 好ま し く は 5 〜50 重量％の割合で溶媒中に懸濁させて用いられる。 In the case of a gas phase reaction, 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. 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. That is, the reaction temperature is usually 150 to 300 ° C, preferably 180 to 250 ° C, and the reaction pressure is 10 to 120 kgZcrfG, preferably 20 to 50 kgZcnfG. In the case of a pressurized flow system, the reaction is carried out at a gas space velocity of usually 100 to 20000 hr— ', preferably 3000 to 100 hr— 1 . In the case of a liquid phase reaction, the reaction is carried out in a reaction solvent. At this time, 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%.
反応溶媒は反応条件下で安定でかつ触媒を懸濁し得る ものであれ ばよ く 、 例えば （ 1 ) へキサン、 ヘプタ ン、 オク タ ン、 デカ ン、 ド デカ ン等の炭素数 6 〜 20のハロゲンを含有しない脂肪族炭化水素、 ( 2 ) ベンゼン、 トルエン、 キシ レン等の炭素数 6 〜 12の芳香族炭 化水素、 （ 3 ) ジメ チルエーテル、 ジェチルエーテル、 ジイ ソプロ ピルエーテル等のエーテル、 （ 4 ) アセ ト ン、 メ チルェチルケ ト ン 、 メ チルイ ソプチルケ ト ン等のケ ト ン、 （ 5 ) ジク ロロメ タ ン、 ク ロ ロホルム、 ジク ロロエタ ン等の脂肪族ハ口ゲン化炭化水素から選 択された少なく と も一種からなる反応溶媒を用いるこ とができる。 また、 市販のパラフ ィ ン系あるいはナフテン系の混合鉱物油をその まま反応溶媒と して用いるこ と も可能である。  The reaction solvent is not particularly limited as long as it is stable under the reaction conditions and can suspend the catalyst. For example, (1) 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.
本発明のメ タ ノ ールの製造に使用される一酸化炭素、 二酸化炭素 及び水素は、 それぞれ純ガスであってもよいが、 通常は工業的に合 成ガス又は水性ガスと して得られる ものが好適に使用される。 反応 系中において、 一酸化炭素又は二酸化炭素に対する水素の容積比は 、 水素 ： 一酸化炭素 （H 2 ： CO) 又は水素 ： 二酸化炭素 （H 2 ： CO 2 ) が通常 10 : 1 〜 1 ： 5 、 好ま し く は 5 ： 1 〜 1 ： 2 の広い範囲 とすることができる。 また、 出発原料中に一酸化炭素と二酸化炭素 とが共存する場合は、 それらの合計量に対する水素の容積比 〔H 2 ： (C0+C02)〕 が上記範囲内、 即ち 10 : 1 〜 1 ： 5 であれば任意の 値をとるこ とができる。 なお、 これらガス中に共存する窒素、 メ タ ン等の濃度には格別の制限はない。 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. In the reaction system, 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. When carbon monoxide and carbon dioxide coexist in the starting material, 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. There are no particular restrictions on the concentrations of nitrogen, methane, etc., which coexist in these gases.
気相反応及び液相反応のいずれにおいても、 反応終了後、 生成し たメ タノールは、 例えば蒸留により容易に分離精製される。 実施例  In both the gas phase reaction and the liquid phase reaction, after the reaction is completed, the produced methanol is easily separated and purified, for example, by distillation. Example
本発明を下記実施例により更に説明する。  The present invention is further described by the following examples.
実施例 1 Example 1
酸化イ ッ テルビウム 3.59 g (9. llmmol) と硝酸銅三水和物 26.4 g (109mmol) とをすりつぶしてよ く 混合し、 空気流通下、 330°Cで 2 時間加熱した。 その結果、 ラ ンタノ イ ド化合物含有銅酸化物と して 、 図 1 に示すような立方晶系の X線回折パター ン（CuKa線使用 ： 2 6 = 16.4° 〔111 〕 、 33.2。 〔222 〕 、 38.5° 〔 400 〕 、 42.1° 〔 331 〕 、 55.6° 〔440 〕 ) を有するイ ッ テル ビウム化合物含有銅酸 化物 〔 （Ybl /7Cu6/7)708N03 〕 13.5gが生成した。 3.59 g (9.1 mmol) of ytterbium oxide and 26.4 g (109 mmol) of copper nitrate trihydrate were ground and mixed well, and heated at 330 ° C. for 2 hours under flowing air. As a result, as a lanthanide compound-containing copper oxide, a cubic X-ray diffraction pattern as shown in FIG. 1 (using CuKa line: 26 = 16.4 ° [111], 33.2. [222] , 38.5 ° [400], 42.1 ° [331], is 55.6 ° [440]) Lee Tsu ether Biumu compound containing cuprate compound having [(Yb l / 7 Cu 6/ 7) 7 0 8 N0 3 ] 13.5g Generated.
得られたイ ッ テルビウム化合物含有銅酸化物 〔 （Ybl /7Cu6 70u N03 〕 0.05gを内径 12mmのガラス製反応管に仕込み、 400torrの圧 力下、 閉鎖循環系で水素ガスを 100ml/min で循環させながら、 徐 々 に温度を上げ 250°Cで 2 時間還元して、 酸化ラ ンタ ノ ィ ド含有還 元銅と して酸化ィ ッテルビウ ム含有還元銅を得た。 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.
遝元終了後、 水素ガスを排気し、 得られた酸化イ ッ テルビウ ム含 有還元銅を触媒と して用い、 400torrの圧力下、 閉鎖循環系におい て H 2 ： CO (容積比） = 3 ： 1 の混合ガスを循環させながら、 200 °Cで 8 時間反応させてメ タノ 一ルの製造を行った。 反応終了後、 生成したメ タノ ールを液体窒素で冷却捕集し、 これ をガスク ロマ トグラフ ィ ー（TCD) で分析した。 その結果、 メ タノ ー ル生成量は 560 z mol / g - cat.であり、 ガスク ロマ トグラフ ィ ー 分析における面積の比で表されるメ タ ノ ールと二酸化炭素の生成比 (MeOH： C02)は 69 ： 29であつた。 (4) After the completion of the hydrogen supply, the hydrogen gas is exhausted, and the obtained reduced copper containing ytterbium oxide is used as a catalyst, and H 2 : CO (volume ratio) = 3 in a closed circulation system under a pressure of 400 torr. The reaction was carried out at 200 ° C for 8 hours while circulating the mixed gas of 1 to produce methanol. After the reaction was completed, the produced methanol was collected by cooling with liquid nitrogen, and analyzed by gas chromatography (TCD). As a result, the amount of methanol produced was 560 zmol / g-cat. The production ratio of methanol to carbon dioxide (MeOH: CO2) represented by the area ratio in gas chromatography analysis 2 ) was 69:29.
なお、 上記のようにして得られた酸化ィ ッ テルビウム含有還元銅 は、 金属銅まで還元された銅と酸化イ ッ テルビウムとが混在してい るものであって、 弱い X線回折パター ン（CuK 線使用 ： 2 = 43.3 。 、 50.3。 ） を示し、 図 2 (Cu2pスぺク トル） 及び図 3 (Yb4dスぺ ク トル） に示す X線光電子分光スぺク トルを有していた。  Note that the reduced copper containing ytterbium oxide obtained as described above is a mixture of copper reduced to metallic copper and ytterbium oxide, and has a weak X-ray diffraction pattern (CuK Using lines: 2 = 43.3., 50.3.) And had the X-ray photoelectron spectroscopy spectra shown in Fig. 2 (Cu2p spectrum) and Fig. 3 (Yb4d spectrum).
比較例 1 Comparative Example 1
実施例 1 と同様の反応と分析を行った。 但し、 酸化イ ツテルビゥ ム含有還元銅に代えて、 CuO— ZnO- A 1203 からなる工業用メ タ ノ ール合成触媒 （ CuO： ZnO： A1203 (重量比） = 42.5 ： 47.5 ： 10) 0. 05 gを 350°Cで還元して調製した触媒を使用 し、 250°Cでメ タ ノ 一 ルの製造を行った。 その結果、 メ タ ノ ール生成量は 134〃 mo 1 / g 一 cat.であり、 またメ タノ ールと二酸化炭素の生成比 （MeOH ： C02) は 38 ： 61であった。 The same reaction and analysis as in Example 1 were performed. However, instead of the oxide Lee Tsuterubiu arm containing reduced copper, CuO- ZnO- A 1 2 0 3 consists of industrial METHANOL synthesis catalyst (CuO: ZnO: A1 2 0 3 ( weight ratio) = 42.5: 47.5 : 10) A catalyst prepared by reducing 0.05 g at 350 ° C was used to produce methanol at 250 ° C. As a result, METHANOL production amount is 134〃 mo 1 / g one cat, Matame Tano Lumpur and carbon dioxide production ratio. (MeOH: C0 2) is 38: was 61.
実施例 1 及び比較例 1 の結果を表 1 に示す。  Table 1 shows the results of Example 1 and Comparative Example 1.
〔表 1 〕  〔table 1 〕
Figure imgf000011_0001
実施例 実施例 1 と同様の反応と分析を行った。 但し、 H 2 ： CO (容積比 ) = 3 ： 1 の混合ガスに代えて、 H 2 ： C02 = 3 ： 1 の混合ガスを 使用 した。 その結果、 メ タノ ール生成量は 450 mol /g — cat.で めった o
Figure imgf000011_0001
Example The same reaction and analysis as in Example 1 were performed. However, H 2: CO (volume ratio) = 3: Instead of the gas mixture of 1, H 2: C0 2 = 3: 1 was used in the mixed gas. As a result, the production of methanol was 450 mol / g — cat.
実施例 3 Example 3
実施例 1 と同様にして、 触媒を調製した。 但し、 酸化イ ツテルビ ゥムに代えて酸化エルビウム 5.52 g (14.4mmol) を使用 し、 硝酸銅 三水和物の使用量を 41.8g (173隱 ol) に変えた。 エルビウム化合物 含有銅酸化物 〔 （Er1 /7Cu6/7)70BN03 〕 21.2gが得られた。 得られ たエルビウム化合物含有銅酸化物は図 1 と類似の立方晶系の X線回 折パターンを有していた。 次に、 このエルビウム化合物含有銅酸化 物 0.05gを実施例 1 と同様にして還元し、 酸化ラ ンタノ ィ ド含有還 元銅と して酸化エルビウム含有還元銅を得た。 なお、 その X線光電 子スぺク トルより、 銅は金属と して、 エルビウムは酸化物と して存 在していることが確認された。 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.
次に実施例 2 と同様のメ タ ノ ール生成反応と分析を行った。 但し 、 酸化イ ッテルビウム含有還元銅触媒に代えて上記の酸化エルピウ ム含有還元銅からなる触媒を使用 した。 その結果、 メ タ ノ ール生成 量は 320〃 mol Z g— cat.であった。  Next, 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.
比較例 2 Comparative Example 2
実施例 2 と同様の反応と分析を行った。 但し、 酸化イ ツテルビゥ ム含有還元銅に代えて、 CuO— ZnO- Al 203 からなる工業用メ タ ノ —ル合成触媒 （ CuO : ZnO： Al20:i (重量比） = 42.5 ： 47.5 : 10) 0.05gを 250°Cで還元して調製した触媒を使用 し、 250°Cでメ 夕 ノ —ルの製造を行った。 その結果、 メ タ ノ ール生成量は 170 imol / g— cat.であった。 The same reaction and analysis as in Example 2 were performed. However, instead of the oxide Lee Tsuterubiu arm containing reduced copper, CuO- ZnO- Al 2 0 3 consists of industrial METHANOL - Le synthesis catalyst (CuO: ZnO: Al 2 0 : i ( weight ratio) = 42.5: 47.5 : 10) A catalyst prepared by reducing 0.05 g at 250 ° C was used to produce a methanol at 250 ° C. As a result, the yield of methanol was 170 imol / g—cat.
実施例 4 実施例 1 と同様の反応と分析を行った。 但し、 H 2 ： CO (容積比 ) = 3 ： 1 の混合ガスに代えて、 H 2 ： C02 = 1 ： 1 の混合ガスを 使用 した。 その結果、 メ タノ ール生成量は 420 mol /g 一 cat.で あった。 Example 4 The same reaction and analysis as in Example 1 were performed. However, a mixed gas of H 2 : CO 2 = 1: 1 was used instead of the mixed gas of H 2: CO (volume ratio) = 3: 1. As a result, the amount of methanol produced was 420 mol / g-cat.
比較例 3 Comparative Example 3
実施例 4 と同様の反応と分析を行った。 但し、 酸化イ ツテルビゥ ム含有還元銅に代えて、 CuO— ZnO- A O3 からなる工業用メ タ ノ ール合成触媒 （ CuO ： ZnO： A 1203 (重量比） = 42.5 ： 47.5 : 10) 0. 05gを 250°Cで還元して調製した触媒を使用 し、 250°Cでメ タ ノ ー ルの製造を行った。 その結果、 メ タノ ール生成量は 50〃 mol / g - cat.でめった。 The same reaction and analysis as in Example 4 were performed. However, instead of the oxide Lee Tsuterubiu arm containing reduced copper, CuO- ZnO- consist A O3 industrial METHANOL synthesis catalyst (CuO: ZnO: A 1 2 0 3 ( weight ratio) = 42.5: 47.5: 10 ) A catalyst prepared by reducing 0.05 g at 250 ° C was used to produce methanol at 250 ° C. As a result, the production of methanol was 50 mol / g-cat.
実施例 5 · Example 5
実施例 1 と同様に反応と分析を行った。 但し、 H 2 ： CO (容積比 ) = 3 ： 1 の混合ガスに代えて、 H 2 ： C02 = 6 ： 1 の混合ガスを 使用 した。 その結果、 メ タノ ール生成量は 600〃mol /g — cat.で めった o Reaction and analysis were carried out as in Example 1. However, H 2: CO (volume ratio) = 3: Instead of the gas mixture of 1, H 2: C0 2 = 6: 1 was used in the mixed gas. As a result, the production of methanol was 600 mol / g — cat.
比較例 4 Comparative Example 4
実施例 5 と同様の反応と分析を行った。 但し、 酸化イ ツテルビゥ ム含有還元銅に代えて、 CuO— ZnO- Al 203 からなる工業用メ タ ノ ール合成触媒 （ CuO： ZnO： A 1203 (重量比） = 42.5 ： 47.5 ： 10) 0. 05 gを 250°Cで還元して調製した触媒を使用 し、 250°Cでメ タノ ー ルの製造を行った。 その結果、 メ タノ ール生成量は 220〃 mo 1 / g 一 cat.であった。 The same reaction and analysis as in Example 5 were performed. However, instead of the oxide Lee Tsuterubiu arm containing reduced copper, CuO- ZnO- Al 2 0 3 consists of industrial METHANOL synthesis catalyst (CuO: ZnO: A 1 2 0 3 ( weight ratio) = 42.5: 47.5 : 10) A catalyst prepared by reducing 0.05 g at 250 ° C was used to produce methanol at 250 ° C. As a result, the amount of methanol produced was 220 lmo1 / g / cat.
実施例 2〜 5及び比較例 2 〜 4 の結果を表 2 に示す。 〔表 2〕 Table 2 shows the results of Examples 2 to 5 and Comparative Examples 2 to 4. (Table 2)
Figure imgf000014_0001
Figure imgf000014_0001
実施例 6 Example 6
実施例 1 記載のィ ッテルビウム化合物含有銅酸化物 1.48 gを実施 例 1 と同様に還元して酸化ィ ッテルビウム含有還元銅 1. 15 gを得た この酸化イ ッテルビウム含有還元銅を窒素雰囲気下で 100ml容電 磁攪拌式オー ト ク レーブに移して、 これに n — ドデカ ン 30mlを加え た後、 水素ガスを 15kgZcnf G圧入し、 更に一酸化炭素を全圧が 30kg /cnf Gになるまで圧入した。 室温で 10分間オー ト ク レープ内を攪拌 した後、 攪拌しながら 200°Cまで昇温し、 この温度において、 2 時 間メ 夕ノ ールの製造を行った。  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.
反応終了後、 オー ト ク レープを冷却して気相及び液相に存在する メ タ ノ ールを回収し、 これをガスク ロマ ト グラフ ィ 一で分析した。 その結果、 一酸化炭素の転化率は 16.7モル％であり、 メ タ ノ ールの 選択率は 98モル％以上であった。 After the completion of the reaction, the autoclave was cooled to recover methanol present in the gas phase and the liquid phase, which was analyzed by gas chromatography. As a result, the conversion of carbon monoxide was 16.7 mol%, and the conversion of methanol The selectivity was over 98 mol%.
実施例 7  Example 7
実施例 1 と同様に して触媒を調製した。 但し、 実施例 1 に記載の イ ッテルビウム化合物含有銅酸化物 1.53gを、 H 2 ： N 2 (容積比 ) = 1 ： 5の混合ガスを循環させながら、 350°Cで還元して、 酸化 ィ ッテルビウム含有還元銅 1.15 gを調製した。 A catalyst was prepared in the same manner as in Example 1. However, 1.53 g of the ytterbium compound-containing copper oxide described in Example 1 was reduced at 350 ° C. while circulating a mixed gas of H 2 : N 2 (volume ratio) = 1: 5 to obtain oxides. 1.15 g of reduced copper containing ytterbium was prepared.
メ タ ノ ール製造のために、 実施例 6 と同様の反応と分析とを行つ た。 但し、 酸化ラ ンタノ ィ ド含有還元銅と して前記酸化イ ツテルビ ゥム含有還元銅を使用 した。 その結果、 一酸化炭素の転化率は Πモ ル％であり、 またメ タ ノ 一ルの選択率は 96モル％以上であった。 実施例 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
実施例 1 と同様に して触媒を調製した。 但し、 実施例 3記載のェ ルビゥム化合物含有銅酸化物 1.47 gを還元して酸化エルビウム含有 還元銅 1.15gを得た。  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.
メ タ ノ ールの製造において、 実施例 6 と同様の反応と分析を行つ た。 但し、 酸化イ ッテルビウム含有還元銅に代えて前記酸化工ルビ ゥム含有還元銅を使用 し、 反応時間を 3 時間に変えた。 その結果、 —酸化炭素の転化率は 11モル％であり、 メ 夕 ノ ールの選択率は 95モ ル％以上であつた。  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.
実施例 9 Example 9
実施例 1 と同様に して触媒を調製した。 但し、 酸化イ ツテルビゥ ムに代えて酸化ホルミ ウム 2.52 g (6.57mmol) を使用 し、 硝酸銅三 水和物に使用量を 19.38g (80mmol) に変えた。 ラ ンタノ イ ド化合 物含有銅酸化物と してホルミ ウム化合物含有銅酸化物 〔Ho, Cu6ハ ) 708 N03 〕 21.2gが得られた。 得られたホルミ ウム化合物含有銅酸 化物は図 1 と類似の立方晶系の X線回折パターンを有していた。 次 に、 このホルミ ウム化合物含有銅酸化物 1.46gを実施例 1 と同様に 還元して、 酸化ラ ンタノ ィ ド含有還元銅と して酸化ホル ミ ウ ム含有 還元銅 1. 15 gを得た。 なお、 その X線光電子スぺク トルよ り、 銅は 金属と して、 ホル ミ ウムは酸化物と して存在している こ とが確認さ れた。 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. Next, 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.
メ タノ ール製造において、 実施例 6 と同様の反応と分析を行った 。 但し、 酸化イ ッ テルビウム含有還元銅に代えて前記酸化ホル ミ ゥ ム含有還元銅を使用 した。 その結果、 一酸化炭素の転化率は 1 0モル %であり、 メ タノ 一ルの選択率は 97モル％以上であつた。  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.
比較例 5 Comparative Example 5
メ タノ ール製造において、 実施例 6 と同様の反応と分析を行った 。 但し、 酸化イ ッ テルビウム含有還元銅に代えて比較例 1 記載の、 還元して得られた触媒 1. 26 gを使用 した。 その結果、 一酸化炭素の 転化率は 38. 3モル％であった力く、 メ タ ノ ールの選択率は 86. 6モル％ であった。  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%.
実施例 6 〜 9及び比較例 5 の結果を表 3 に示す。  Table 3 shows the results of Examples 6 to 9 and Comparative Example 5.
〔表 3 〕 触 媒 CO転化率 MeOH選択率  [Table 3] Catalyst CO conversion MeOH selectivity
(モル％ ) (モル％ ) 実施例 6 酸化ィ ッ テルピウ ム含有 1 6. 7 > 98  (Mol%) (mol%) Example 6 Containing ytterbium oxide 16.7> 98
還兀銅  Return
実施例 7 酸化ィ ッ テルピウム含有 1 7 > 96  Example 7 Containing ytterbium oxide 1 7> 96
il兀銅  il vat copper
実施例 8 酸化エルビゥム含有還元 1 1 > 95  Example 8 Erbium oxide-containing reduction 1 1> 95
銅  Copper
実施例 9 酸化ホル ミ ゥ ム含有還元 1 0 > 97 比較例 5 C uO- Z nO - A 0 :, 還元物 38. 3 86. 6 産業上の利用可能性 Example 9 Form oxide-containing reduction 10> 97 Comparative Example 5 CuO-ZnO-A0 :, reduced product 38.38.6.6 Industrial applicability
本発明方法によれば、 一酸化炭素及び Z又は二酸化炭素と水素と を反応させてメ タ ノ ールを製造するに際し、 触媒と して立方晶系結 晶であるラ ンタノ ィ ド化合物含有銅酸化物を還元して得られる酸化 ラ ンタノ イ ド含有還元銅を用いるこ とにより、 気相及び液相反応の いずれにおいても高選択率でメ タ ノ ールを製造するこ とができる。 特に、 本発明方法により、 液相反応において一酸化炭素の転化率を 向上させ、 しかも高選択率でメ タ ノ ールを製造する こ とができるた め、 熱制御の比較的容易な液相反応によるメ タ ノ ールの製造が可能 になった。  According to the method of the present invention, when producing methanol by reacting carbon monoxide and Z or carbon dioxide with hydrogen, a lanthanide compound-containing copper which is a cubic crystal as a catalyst is used as a catalyst. By using lanthanide-containing reduced copper obtained by reducing an oxide, methanol can be produced with high selectivity in both gas phase and liquid phase reactions. In particular, 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.

Claims

請 求 の 範 囲 The scope of the claims
1. 一般式 （MxCuy)70zAw (式中、 Mは Dy, Ho, Er, Tb, Tm, Yb 及び Luからなる群から選ばれた少な く と も一種のラ ンタ ノ ィ ド原子 を表し、 Aはハロゲン原子及び N03基からなる群から選ばれた少な く と も 1 員を表し、 x + y = l ， 0 < X / y ≤ 10, 6 ≤ z ≤ 8 力、 つ 0.5 w 9 である） で表されるラ ンタノ ィ ド化学物含有銅酸化 物を還元する こ とによって得られ、 少な く と も 1 種の酸化ラ ンタ ノ ィ ドと還元銅とが混在している酸化ラ ンタ ノ ィ ド含有還元銅を含む 触媒の存在下に、 一酸化炭素及び二酸化炭素からなる群から選ばれ た少なく と も 1 員からなる出発原料と水素とを反応させるこ とを特 徴とするメ タ ノ ールを製造する方法。 1. General formula (M x Cu y ) 70 z A w (where M is at least one kind of lanthanum selected from the group consisting of Dy, Ho, Er, Tb, Tm, Yb and Lu) It represents I de atom, a is also represents one member and rather less selected from the group consisting of a halogen atom and N0 3 groups, x + y = l, 0 <X / y ≤ 10, 6 ≤ z ≤ 8 force Is obtained by reducing a copper oxide containing a lanthanide chemical represented by the formula (1), and at least one lanthanide oxide and reduced copper are mixed. Reacting at least one member starting material selected from the group consisting of carbon monoxide and carbon dioxide with hydrogen in the presence of a catalyst containing reduced copper containing lanthanum oxide. A method for manufacturing a metallole characterized by the following.
2. 前記酸化ラ ンタノ イ ド含有還元銅を調製する際の還元が、 前 記ラ ンタノ イ ド化合物含有銅酸化物を 200〜 400°Cで還元性ガスと 接触させるこ とによって行われる、 請求の範囲第 1 項に記載の方法 o  2. The reduction in preparing the lanthanide oxide-containing reduced copper is performed by contacting the lanthanide compound-containing copper oxide with a reducing gas at 200 to 400 ° C. The method described in paragraph 1 of the scope o
3. 前記還元性ガスが水素ガスである、 請求の範囲第 2項に記載 の方法。  3. The method according to claim 2, wherein the reducing gas is hydrogen gas.
4. 前記出発原料が一酸化炭素からな り この一酸化炭素に対する 水素の容積比 （ H 2 ： CO) 力 10 ： 1 〜 1 ： 5 である、 請求の範囲第 1 項に記載の方法。 4. The volume ratio of hydrogen the starting material for the carbon monoxide Ri Do carbon monoxide (H 2: CO) Power 10: 1 to 1: 5, The method according to claim 1.
5. 前記出発原料が二酸化炭素からなり、 この二酸化炭素に対す る水素の容積比 （H 2 ： C02 ) 力《10 ： 1 〜 1 ： 5 である、 請求の範 囲第 1 項に記載の方法。 5. The method according to claim 1, wherein the starting material comprises carbon dioxide, and the volume ratio of hydrogen to carbon dioxide (H 2 : C 0 2 ) is << 10: 1 to 1: 5. Method.
6. 前記一酸化炭素及び二酸化炭素から選ばれた少な く と も 1 員 からなる出発原料の合計量に対する水素の容積比 〔H 2 ： (C0+ C0 2)〕 が 10 : 1 - 1 ： 5 である、 請求の範囲第 1 項に記載の方法。 6. The volume ratio of hydrogen [H 2 : (C0 + C0 2 )] to the total amount of at least one-membered starting material selected from the above-mentioned carbon monoxide and carbon dioxide is 10: 1-1: 5. A method according to claim 1.
7. 前記メ タ ノ ール生成反応が、 150〜 300°Cの反応温度、 10〜 120 kgZcnfの反応圧、 及び 100~ 20000hr— 'のガス空間速度におい て気相中で行われる、 請求の範囲第 1 項に記載の方法。 7. The said methanol production reaction is carried out in the gas phase at a reaction temperature of 150 to 300 ° C, a reaction pressure of 10 to 120 kgZcnf, and a gas hourly space velocity of 100 to 20000 hr. The method described in paragraph 1 above.
8. 前記メ タノール生成反応が、 150〜 300°Cの反応温度、 及び 10〜 lSOkgZcnfの反応圧において、 液相中で行われる、 請求の範囲 第 1 項に記載の方法。  8. The method according to claim 1, wherein the methanol-forming reaction is carried out in a liquid phase at a reaction temperature of 150 to 300 ° C and a reaction pressure of 10 to lSOkgZcnf.
9. 前記メ タ ノ ール生成液相反応が、 100〜 20000hr 'のガス空 間速度で行われる、 請求の範囲第 8項に記載の方法。  9. The method according to claim 8, wherein the methanol-forming liquid phase reaction is performed at a gas space velocity of 100 to 20000 hr '.
10. 前記メ タ ノ 一ル生成液相反応が反応溶媒中において行われ、 かつ前記酸化ラ ンタ ノ ィ ド含有還元銅が、 前記反応溶媒に対して 1 〜60重量％の割合で用いられる、 請求の範囲第 8項に記載の方法。  10. The methanol-producing liquid phase reaction is performed in a reaction solvent, and the lanthanide-containing reduced copper is used in a proportion of 1 to 60% by weight based on the reaction solvent. The method according to claim 8.
11. 前記反応溶媒が、 炭素数 6 ~20を有し、 ハロ ゲンを含まない 脂肪族炭化水素、 炭素数 6 〜12の芳香族炭化水素、 エーテル、 ケ 卜 ン、 及び脂肪族ハロゲン化炭化水素からなる群から選ばれる、 請求 の範囲第 10項に記載の方法。  11. The reaction solvent comprises an aliphatic hydrocarbon having 6 to 20 carbon atoms and containing no halogen, an aromatic hydrocarbon having 6 to 12 carbon atoms, an ether, a ketone, and an aliphatic halogenated hydrocarbon. The method of claim 10, wherein the method is selected from the group consisting of:
12. 一般式 （MxCuy)70zAw (式中、 Mは Dy， Ho, Er, Tb, Tm, Yb 及び Luからなる群から選ばれた少なく と も 1 種のラ ンタノ ィ ド原子 を表し、 Aはハロゲン原子又は N03基を表し、 x + y = l , 0 < X / y≤ 10, 6 ≤ z ≤ 8 , かつ 0.5≤ w≤ 9 である） を還元するこ と によって得られ、 酸化ラ ンタノ ィ ドと還元銅とが混在している酸化 ラ ンタ ノ イ ド含有還元銅からなる、 メ タノ ール製造用触媒。 12. General formula (M x Cu y ) 70 z A w (where M is at least one lanthanum selected from the group consisting of Dy, Ho, Er, Tb, Tm, Yb and Lu) It represents a de atom, a represents a halogen atom or a N0 3 group, x + y = l, 0 <X / y≤ 10, 6 ≤ z ≤ 8, and 0.5≤ w≤ is 9) and child reduction A catalyst for producing methanol, comprising lanthanide oxide-containing reduced copper obtained by mixing lanthanide oxide and reduced copper.
PCT/JP1995/002379 1994-11-22 1995-11-22 Process for producing methanol WO1996016011A1 (en)

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JP6/288156 1994-11-22
JP28815694 1994-11-22
JP7/228336 1995-09-05
JP22833695 1995-09-05

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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 (en) * 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 Modified copper- and zinc-containing catalyst and method for producing methanol using the catalyst
JPS6087233A (en) * 1983-10-18 1985-05-16 Idemitsu Kosan Co Ltd Methanol manufacturing method
JPS60190232A (en) * 1984-01-27 1985-09-27 アンステイテユ・フランセ・デユ・ペトロール Production of copper, zinc and aluminum containing catalyst capable of being used in producing methanol from synthetic gas
JPH04122444A (en) * 1990-09-13 1992-04-22 Agency Of Ind Science & Technol Production of methanol from carbon dioxide

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 (en) * 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 Modified copper- and zinc-containing catalyst and method for producing methanol using the catalyst
JPS6087233A (en) * 1983-10-18 1985-05-16 Idemitsu Kosan Co Ltd Methanol manufacturing method
JPS60190232A (en) * 1984-01-27 1985-09-27 アンステイテユ・フランセ・デユ・ペトロール Production of copper, zinc and aluminum containing catalyst capable of being used in producing methanol from synthetic gas
JPH04122444A (en) * 1990-09-13 1992-04-22 Agency Of Ind Science & Technol Production of methanol from carbon dioxide

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