• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A METHOD FOR PREPARING A CATALYST FOR METHANOL SYNTHESIS, including the coaxialization of carbonates or metal hydroxides by adding to the aqueous solution of the compounds of metals of an aqueous solution of sodium carbonate or sodium hydroxide followed by washing, drying, and shaping the precipitate with a sample of the precipitate, a ra- ture, having a sample, a flow, a flow, a settlement, a sample, a flow, a flow, a flow, a flow, a precipitate, a sample, a flow, a flow, a flow, a precipitate, a flow, a flow, a mixture of the precipitate, a hydrogen, sodium hydroxide and a hydroxide will be used; As metal compounds, copper, zinc, aluminum, and manganese nitrates are used together, or copper, zinc, aliomyne, or chromium nitrates together with a concentration of their marzes; an aqueous solution of 13,014, 8 wt.% and a 10-15% aqueous solution of sodium carbonate or sodium hydroxide is added at a dosage rate of 30.0-45.8 l / hr of 90-100 ° C. C to a final pH of the resulting suspension is 8.5-9.0, the precipitate is washed to a neutral reaction and the molding is carried out by granulation with the addition of 2% by weight of graphite, followed by up to; complete drying with Zr and pelletizing, while in the case of using copper nitrates,, alumini or chromium as metal compounds, the precipitate after mineralization and. drying is calcined at, and granulated with the addition of 2% by weight and 2.85% by weight of an aqueous solution of manganese acid 10% by weight of an aqueous solution of manganese acetate.
    公开号:SU1126205A3
    申请号:SU792784398
    申请日:1979-07-09
    公开日:1984-11-23
    发明作者:Котовски Влодзимеж；Лах Юзеф；Пызиковски Ежи；Кушка Вернер；Магнушевска Софья
    申请人:Институт Ценжкей Сынтэзы Органиинэй "Бляховня" (Инопредприятие)；
    IPC主号:
    专利说明:

    1 The invention relates to a method for producing a copper catalyst intended for methanol synthesis. A method is known for preparing a catalyst for methanol synthesis by mixing copper carbonates and zinc with alumina in the presence of water, followed by drying the catalyst mass L. However, this method of preparation does not ensure the homogeneity of the qualitative composition of the catalyst, which is the reason for the different activity of the catalyst from individual batches. There is also known a method for producing a catalyst for methanol synthesis from a mixture of nitrates or acetates of copper, zinc and aluminum heated to boiling by precipitating hydroxides at noMontH sodium hydroxide with a certain stirring speed, rate of addition and alkali concentration, while the amount of alkali added is such that the alkalinity of the solution after precipitation is 0.08-0.15 n., after which the precipitate is washed with water until the alkalinity is 0.005 n., filtered and dried 2. However, this method does not allow to obtain a catalyst with enhanced activity in the synthesis of methanol. The closest to the invention in its technical essence and the effect achieved is a method for preparing a catalyst for methanol synthesis, including coprecipitation of metal carbonates or hydroxides, adding to the aqueous solution of metal compounds an aqueous solution of sodium carbonate or sodium hydroxide, followed by washing, drying, calcining and forming the resulting precipitate. . In this case, the coprecipitation of carbonates with metal hydroxides leads to the production of, for example, one precipitate of zinc and aluminum hydroxide and another — copper and zinc carbonates, followed by mixing these precipitates and calcining at 300 C 3j. A disadvantage of the known process is the preparation of a catalyst of low activity in methanol synthesis. The known catalyst contains at least 20% ipinel Zn / Al and has the following composition, wt.%: 52 CuO24 ZnO38 AtjO, 37.6, 1 Impurity0.3 This corresponds to the following gram-atomic ratio: Cu 20 Zn-, A1 ( , 9This catalyst is tested by a circulating gas of composition, vol.%: C02 0.4; CO 4.0; H 66.8; CH / j 3.0 N. A 25.6 at -t., P 50 ati, V 12000 cat. H.Ch., has a low activity, amounting to 0.53 kg of SN.ON / kg cat. H. To maintain constant activity, it is necessary to gradually increase the temperature (226-259 C) over 10 weeks. The purpose of the invention is to obtain a catalyst with increased activity. This goal is achieved by the fact that according to the method for producing a catalyst for methanol synthesis by coprecipitating carbonates or hydroxides of methanol by adding to the aqueous solution metal compounds that are used in combination with nitrates of copper, copper, aluminum and manganese or nitrates of copper, zinc, aluminum or chromium with a total concentration of their aqueous solution of 13.0-18.8 wt.%, add 1015% aqueous solution of caobonate or sodium hydroxide at a dosage rate of 30.0-45.8 l / h at 90- 1CO ° C final pH suspension of 8.5-9.0, the precipitate is washed until neutral and molding is carried out by granulating with the addition of 2 wt.% graphite, followed by further drying at 110 ° C and pelletizing, and in the case of using copper or zinc nitrates as metal compounds , aluminum or chromium precipitate after washing and drying is calcined at 300 ° C and granulated with the addition of 2% by weight of graphite and 2.85% by weight of an aqueous solution of manganese acid or 10% by weight of an aqueous solution of manganese acetate. The use of the invention makes it possible to obtain a catalyst with increased activity in the reaction of methanol synthesis. Under similar conditions of the experiment, the catalyst activity is 0.72-0.93 kg CH, OH / KG cat. h.ch. Achieving the increased activity of the catalyst became possible due to the observance of all the specified parameters, a reduced content of copper oxide and the corresponding size of crystallites. Example 1. In 6940 ml of distilled water, 241.6 g of CrCNO ,, RLVO, 397.8 g of Zn (NO) / X 6H, jO, 401.4 g of AKNOj) X 9HjO are dissolved, having obtained a total concentration of 13 wt. The% is then heated, with continuous stirring, to EZ-SE. C. At the same time, 450 g of Na COj are dissolved in 2550 ml of distilled water (Na.COj concentration 15% by weight) and heated to 90-100 C. The sodium carbonate solution is fed into the solution, copper, zinc and aluminum nitrates in 5 minutes at a dosage rate. 30 l / h A blue-green precipitate formed, and the pH of the resulting mixture was 8.5. The precipitated precipitate was washed with hot distilled water until the pH of the industrial liquid was about 7.0. After decanting the last portion of the water, the precipitate is filtered, then dried at 110 ° C and calcined at 300 ° C to decompose the carbonates into oxides. The calcined precipitate is crushed, mixed with 2 wt.% Of graphite and granulated with the addition of 119 g of an aqueous solution of manganese acid at a concentration of 2.85 wt.% To obtain a well-moldable material. After drying the granulated material at 110 ° C, the catalyst is tableted. Pills are crawling in sizes of 5–5 mm with an average compressive resistance of 200 kg / cm2. Get the catalyst of the following composition, wt.%: CuO32,4 ZnO. 44.3 AIjO 22.3 Mn021.0 This corresponds to the following ratio in gram atoms: Cu jcj.g .7 V 0.) The size of crista litas is 50 A. Synthesis of methanol on the prepared catalyst is carried out in a reactor with a diameter of 16 mm and a height of 600 mm 100 g of catalyst are fed to the reactor and are passed under a pressure of 50 at. at a volumetric rate of V 10,000 hours, the synthesis gas is composed. vol.%: Hg CO COj CHj N Catalyst activity presented in kg 100% CH, jOH / Kr cat. H.p., are given below: Working hours, h 200 500 2000 Activity. 0.920 0.930 0.900 Example 2, 230.1 g Cu (NO) 2 ЗН20, 404 g Zn (NO) are dissolved in 7060 ml of distilled water. BNO; 375.2 g AI (NO,) ,. 9H20 and 45.1 g MnCNO). 4 Noo, receiving the total concentration of nitrates 13 wt.%. Then it is heated up, stirring all to 95-100 ° C. At the same time, 337 g of NaOH is dissolved in 3030 ml of distressive water, which gives a NaOH concentration of 10% by weight and is heated to 90-1000 ° C. . Solution of sodium. It is metered into a solution of copper, zinc and manganese nitrates with a speed of 30 l / h, the final pH is 9.0. The precipitate is washed with hot distilled water to remove sodium ions. Then the precipitate is filtered, dried at, crushed, mixed with 2% by weight of graphite, granulated, dried at and tableted. Get the catalyst of the following composition, wt.%: CuO30,3 ZnO44,2 A1203 -20,4 MpO5,1. This corresponds to the following ratio in grams-atoms: Sy.z, Al28,6 fin 5.2,2 average resistance to compression of 250 kg / cm, and bulk density of 1.4 kg / dm. The crystallite size is 150 A. The results of the methanol synthesis test are as follows: Working time, h 200 500 2000 Activity 0.800 0.795 0.78 Example 3. 11.1.6 g Cu (NOp2 ЗН20, 268.7 g ZnCNO) are dissolved in 3950 ml of distilled water. }}) 270.4 g of A1 (Sha) s 9H20, heated, stirring, to 95-100C. The concentration of the mentioned nitrates in salts leaves 14.8 wt.%. At the same time
    390 g of NajCO are dissolved in 221.0 ml (Na2CO3 concentration 15 wt.%). The sodium carbonate solution is metered into a solution of zinc and aluminum copper nitrates at a rate of 40 l / h, and the final pH of the resulting mixture is 9.0. The precipitate is washed with distilled water until the pH of the wash water is about 7.0. After decanting the last portion of the water, the precipitate is filtered, dried at 110 ° C, and also calcined at 300 ° C to decompose the carbonates into oxides.
    The calcined precipitate is crushed, mixed with 2 wt.%. graphite and granularit with a water solution of manganese acetate concentration of 10 wt.%. Then, after drying the granulated material with, the catalyst is tapped. Tablets with dimensions of 5–5 mm are obtained; they are characterized by an average compressive strength of 230 kg / cm and a bulk weight of 1.3 kg / dm.
    The resulting catalyst has the following composition, wt.%:
    CCA 24.5
    ZnO 49.0
    AlgO-j 24.5
    MnO 2.0
    This corresponds to the following ratio of 2 .3) 41.5) in gram atoms:
    42.24 .0
    The crystallite size of CuO is
    em 60 A.
    The results of the methanol synthesis tests are listed below: Work
    time, h 200 500 2000 Activity 0.920 0.930 0.925 Example 4. 364.5 g CuCNO), 416.9 g Zn (N09) 2 are dissolved in 7350 ml of distilled water. 6HjO 315.9 g CrCNOj) 9H20 (nitrate concentration 13 wt.%), Then heated, continuously stirring, to 95100 ° C. 460 g of NaoCOj are simultaneously dissolved in 4140 ml of distilled water to 90-100 ° C, obtaining a concentration of 10 wt.
    The sodium carbonate solution is fed to a solution of copper, zinc and chromium nitrates in 5.5 minutes (dosage rate 45.8 l / h. A blue-green precipitate appears, and the pH of the resulting mixture is 8.9. The precipitate formed is washed with hot water before
    until . The pH of the wash water will not reach a value close to 7.0. After decanting the last portion of water, the precipitate is filtered, then dried at 110 and calcined to decompose the carbonates into oxides.
    The crushed precipitate is crushed, mixed with 2% by weight of graphite and granulated with 19.7 g of No. 1 (C, H.j02) 2 dissolved in such a quantity of water to obtain a material that is good for forming properties (concentration of manganese salt is 10% by weight. %). After drying the granulated material at 110 e, the catalyst is tableted. Tablets with a size of 5 K 5 mm are obtained with an average compression resistance of 150 kg / cm 2.
    The resulting catalyst has the following composition, wt.%:
    SCO40.0
    ZnO38.0
    , 0
    SHO 2.0
    This corresponds to the following ratio in gram-atoms: C, and
    .i) C; 20.8, 2
    The crystallite size of CuO is 70 A.
    . The test results of the catalyst under the conditions of Example 1 are given below: Working time, hours 200 500 2000 Activity 0.720 0.730 0.725 Example 5 (comparative). In this example, the effect of the rate of dosing of the precipitating agent solution on the quality of the catalyst obtained was tested. Operating in the same manner as in Example 1, three catalysts were prepared using different dosage rates of sodium carbonate, i.e. to, 30 and 90 l / h. These catalysts are tested as in example 1. The results are shown below. Speed
    dm / h
    ten
    90
    thirty
    Activity kg CHjOH / kg
    0.500 0.900 0.600 cat. h.ch. The advantage of the proposed method is to obtain a catalyst of increased stability. So for 2000 hours of continuous operation of the catalyst, its activity is preter7P26205
    sings insignificant changes, so obtained by the proposed method
    that it is possible to conduct the process of synthesis catalysts have the strength to
    methanol without increasing the temperature, compression, amounting to 150-250 kg / cm and
    catalyst bed. bulk weight 1, 4 kg / dm.
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING A CATALYST FOR THE SYNTHESIS OF METHANOL, including the coprecipitation of carbonates or metal hydroxides by adding an aqueous solution of carbonate or sodium hydroxide to an aqueous solution of metal compounds, followed by washing, drying and forming the precipitate obtained, characterized in that, in order to obtain a catalyst with increased activity, as metal compounds, copper, zinc, aluminum and manganese nitrates are used together, or copper, zinc, aluminum or chromium nitrates are used together with their total concentration of water th solution 13.0-
    14.8 wt.% And add a 10-15% aqueous solution of carbonate or sodium hydroxide with a dosage rate of 30.0-45.8 l / h at 90-100 ° C to a final pH of the resulting suspension 8.5-9 , 0, the precipitate is washed until neutral and molding is carried out by granulation with the addition of May 2% of graphite, followed by additional drying at 110 ° С and pelletizing; in this case, after the use of copper, cesium, aluminum or chromium nitrates as metal compounds, the precipitate after washing and. drying is calcined at 300 ° C, and granulated with the addition of 2 wt.% graphite and 2.85 wt.% aqueous solution of manganese acid or 10 wt.% aqueous solution of manganese acetate.
    oaSU 1126205>
    类似技术:
    公开号 | 公开日 | 专利标题
    KR100516408B1|2005-11-28|Monoclinic Zirconium Dioxide having a Large Surface Area
    US4111847A|1978-09-05|Methanol synthesis catalyst
    US3303001A|1967-02-07|Low temperature shift reaction involving a zinc oxide-copper catalyst
    CN111330586A|2020-06-26|Novel ethynylation catalyst and method for producing same
    US4305842A|1981-12-15|Preparation of improved catalyst composition
    SU1126205A3|1984-11-23|Method for preparing catalyst of methanol synthesis
    MX2015000225A|2015-08-12|Catalyst for the production of higher alcohols.
    US3961037A|1976-06-01|Process for forming hydrogen and carbon dioxide using a catalyst consisting essentially of oxides of copper, zinc and aluminum or magnesium
    CN104383929A|2015-03-04|2-methyl furan catalyst and preparation method thereof
    US4386017A|1983-05-31|Preparation of improved catalyst composition
    US6054497A|2000-04-25|Process for producing methanol and catalyst therefor
    EP2237882A2|2010-10-13|Iron-based water gas shift catalyst
    CN103551154B|2015-02-18|Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst
    JP3943648B2|2007-07-11|Methanol synthesis method
    US3297588A|1967-01-10|Catalyst comprising a metallic composnent supported on an alumina base
    US4250111A|1981-02-10|Mixed catalyst for the hydrolysis of nitriles to amides
    JP2695663B2|1998-01-14|Method for producing catalyst for methanol synthesis
    JPH0724320A|1995-01-27|Production of catalyst for steam reforming of methanol
    JPH08108072A|1996-04-30|Production of catalyst for hydrogenation reaction of aliphatic alkyl ester
    JPH09141099A|1997-06-03|Methanol synthesis catalyst
    CA2006758C|1998-11-24|Method for preparing catalyst precursor for methanol synthesis
    US3840478A|1974-10-08|Catalyst of copper oxide-zinc-oxide-chromium oxide for methanol synthesis
    SU582829A1|1977-12-05|Method of preparing zinc-copper-aluminium catalyst for carbon monoxide conversion
    JPH08224472A|1996-09-03|Catalyst for hydration reaction of olefin and its production
    JP3510406B2|2004-03-29|Methanol synthesis catalyst
    同族专利:
    公开号 | 公开日
    DD145093A5|1980-11-19|
    GB2025252B|1982-12-22|
    GB2025252A|1980-01-23|
    RO76535A|1981-04-30|
    PL208466A1|1980-03-10|
    PL120574B1|1982-03-31|
    YU146279A|1982-08-31|
    DE2928435A1|1980-01-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2500470C1|2012-11-20|2013-12-10|Открытое акционерное общество "Ангарский завод катализаторов и органического синтеза" |Method of preparing catalyst for methanol synthesis and carbon monooxide conversion|
    DE3005550A1|1980-02-14|1981-08-20|Süd-Chemie AG, 8000 München|METHOD FOR PRODUCING OLEFINS|
    GB8521650D0|1985-08-30|1985-10-02|Ici Plc|Catalyst|
    US5254520A|1990-09-18|1993-10-19|Csir|Catalyst for the synthesis of methanol|
    DE4141199A1|1991-12-13|1993-06-17|Sued Chemie Ag|CHROME-FREE CATALYST FOR HYDRATING ORGANIC COMPOUNDS CONTAINING THE CARBONYL FUNCTIONS|
    DE4142899A1|1991-12-23|1993-06-24|Sued Chemie Ag|METHOD FOR PRODUCING ALCOHOLS BY CATALYTIC HYDRATION OF CARBONIC ACID ALKYL ESTERS|
    CN1048917C|1994-10-20|2000-02-02|中国科学院山西煤炭化学研究所|Method for preparing high-activity methylated copper-zinc/alumina catalyst with metal surfactant by phase transfer|
    US8828903B2|2008-11-10|2014-09-09|Basf Corporation|Copper catalyst for dehydrogenation application|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    PL1978208466A|PL120574B1|1978-07-15|1978-07-15|Method of manufacture of copper catalyst|
    [返回顶部]