CN100369670C - 含氧化铁的催化剂的制备方法 - Google Patents

含氧化铁的催化剂的制备方法 Download PDF

Info

Publication number
CN100369670C
CN100369670C CNB021475547A CN02147554A CN100369670C CN 100369670 C CN100369670 C CN 100369670C CN B021475547 A CNB021475547 A CN B021475547A CN 02147554 A CN02147554 A CN 02147554A CN 100369670 C CN100369670 C CN 100369670C
Authority
CN
China
Prior art keywords
nitrate
acid
solution
nitric acid
iron oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB021475547A
Other languages
English (en)
Other versions
CN1411907A (zh
Inventor
K·乔汉森
P·戈德斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
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 Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of CN1411907A publication Critical patent/CN1411907A/zh
Application granted granted Critical
Publication of CN100369670C publication Critical patent/CN100369670C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C01B13/185—Preparing mixtures of oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide [Fe2O3]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
    • 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
    • C07C29/156—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 iron group metals, platinum group metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

一种用于制备含混合金属氧化物的催化剂的方法，包括下述步骤：-将金属Me＝Fe，Ni，Al，Cu，Zn，Cr，溶解在硝酸中，提供一种金属混合的硝酸盐产物的酸性溶液，可以将铝以硝酸盐或氢氧化物加入；-加入糖类，氨基酸和/或羧酸；-在250-700℃自由空气供料下，通过喷射在一或多个旋转窑的内表面上，喷射到喷射烧结流化床中，喷射到塔式窑中或喷射到钢带传送机加热炉中，使酸性溶液分解为氧化铁和NOx；并且可任选地-将生成的NOx再生为硝酸，并将制得的硝酸再循环到第一步中。

Description

含氧化铁的催化剂的制备方法
技术领域
本发明涉及一种用于混合金属氧化物催化剂制备的金属氧化物的制备方法。
背景技术
在本领域中制备混合金属氧化物的方法包括采用沉淀的方法。金属硫化物是一种廉价的纯原料并且通过共沉淀可以获得优良的催化剂，但是含有太高的硫含量。另一方面，金属硝酸盐是一种昂贵的原料，并且将金属溶解在硝酸中需要昂贵的硝酸。
公知的制备混合金属氧化物催化剂的方法在购买酸和碱性原料以及在沉淀、洗涤和废水处理方面费用大。
这方面内容描述在US4482645中，其中Jennings等人制备了一种硝酸铁和硝酸铬的溶液，向其中加入碳酸钠，并且在干燥和分解为氧化物之前将形成的铁和铬的氢氧化物洗去。
发明内容
因此，本发明的总的目的是提供一种以简单且廉价的步骤制备含混合金属氧化物催化剂的改进方法。现在发明和开发了一种基于金属经由硝酸盐和硝酸回收的可供选择的制备路线。
与公知方法相比，本发明的优点在于高质量的催化剂，且进一步在于通过减少生产过程中材料的损失而得到高产率。
本发明的方法包括下述步骤，包括金属Me＝Co，Zn，Fe，Ni，Cr和/或Cu：
(a)通过下述反应(i)将Me溶解在硝酸中，提供一种Me(NO3)3(用三价金属示例说明)的酸性溶液：
2Me+8HNO3→2Me(NO3)3+2NO+4H2O
(b)可选择与不同的金属硝酸盐溶液混合，例如，Fe(NO3)3溶液与Co(NO3)3溶液。铝以硝酸盐或氢氧化物的方式加入。
(c)可选择地，加入促进剂。如果促进剂(PR)诸如PR＝Na，K，Cs，Rb，Mg，Ca，Ba，Sr是在最终产品中所需的，则将它们以金属硝酸盐、碳酸盐、氢氧化物等形式加入到溶解的Me(III)硝酸盐中。促进剂优选以碱＜PR/Me＜0.2的摩尔比加入。
最终的溶液将为Me(NO3)3溶液，任选地含有PR硝酸盐的促进剂。
如果形成NO2则HNO3的消耗量将增加。
(d)组合的金属硝酸盐溶液和促进剂酸硝酸盐溶液热分解为可任选含有氧化物或硝酸盐形式的促进剂的混合金属氧化物Me2O3或氢氧化物MeOOH，这取决于促进剂的化学特性。在反应过程中还产生NOx气体。Me(NO3)3的纯分解反应如反应(ii)：
2Me(NO3)3→Me2O3+6NO2+1.5O2
(e)根据反应(iii)，在一个吸收塔或串连的吸收塔中从反应(i)和(ii)任选地将NOx气体再生为或多或少浓的硝酸：
6NO2+3H2O+15O2→6HNO3
或者对于NO而言为反应(iv)
2NO+H2O+1.5O2→2HNO3
而后，对于铁而言的总反应，即当(i)，(ii)，(iii)和(iv)结合时，为：
总反应：2Me+1.5O2→Me2O3
当仅考虑主组分Me2O3的合成时，我们看到对于总反应而言没有副产物形成并且其它原料氧气通过吸收塔从空气中取出。
当促进剂包含在混合金属硝酸盐溶液中时，总反应会受到某些影响。该影响取决于是否加入了作为硝酸盐、氢氧化物、氧化物等的促进剂PR。如果例如当其以KNO3加入且K/Me的摩尔比＝0.01时总反应方案将为：
2Me+1.5O2+0.02KNO3+0.01H2O→Me2O3+0.01K2O+0.02HNO3
这导致生成可用于溶解的少量HNO3。
在上述反应(i)和(ii)中形成的NO和NO2或通常NOx再次在吸收塔中转化为硝酸。反应(iii)和(iv)导致形成用于再循环和溶解Me的硝酸，其为该过程中的主原料。
由于硝酸的少量损失，必须偶尔地将少量的硝酸加入到再生的酸中，以便保持或增强原料的溶解。
在上述步骤(d)中的分解可通过将步骤(a)，(b)或(c)的酸性溶液喷射到一或多个旋转窑的内表面上，喷射到喷射烧结流化床中，喷射到钢带传送机加热炉中，或喷射到在250-700℃下空气自由供料的塔式颗粒下落窑(tower falling particles kiln)中进行的。但是，通过使用这些方法，为了防止产物粘结到回转窑的内表面上，可采取措施，例如借助一个或多个滑动链。
还可通过其它物理或化学方法防止制得的材料从分解的酸性溶液粘附到所述加热炉或窑的内表面。
金属氧化物产物通过加入少量能够还原硝酸盐的有机化合物得以进一步提高。而后，有机化合物与硝酸盐之间的反应将使硝酸盐加速分解。而且，该粉末微弱地聚结并且可以在低能磨碎设备中破碎。
本发明的方法适于在分解前加入不同的添加剂(例如，在催化剂的情况下加入促进剂，或加入为其它目的的其它组分)。使该溶液分解为金属氧化物的一个方法是连续将储液滴入旋转窑中。旋转窑中的温度可以在250-700℃之间变化，优选为350-600℃。本发明一个主要的特征包括利用添加剂，将选自有机化合物的添加剂加入到硝酸盐储液中。通过调整旋转窑中添加剂的用量和/或温度，可以控制粉末的特性(相含量/晶体结构，表面积，粒径，显微结构等)。当加入此种添加剂时，没有这些有机添加剂，粉末将自由地从回转窑中跑出，从而使连续过程成为可能。优选的添加剂选自碳水化合物或糖类(葡萄糖、果糖、乳糖、蔗糖或其它糖类)，甘氨酸和羧酸。另外，粉末聚结成硬而大的块。这些添加剂的低含量或不含这些添加剂通常会导致α-Fe2O3的形成。当热解温度低时，有机添加剂的含量高将导致形成γ-Fe2O3。
具体地说，本发明涉及以下方面：
1、一种生产混合选自Co，Al，Cu和Cr的氧化物中的一种或多种的氧化铁催化剂的方法，包括下述步骤：
(a)提供带有硝酸铁和选自Co，Al，Cu和Cr的一种或多种金属的硝酸盐的硝酸溶液；
(b)向该硝酸溶液中加入碳水化合物和/或羧酸；
(c)在250-700℃的温度下，在自由空气供入下，使步骤(b)中获得的酸性溶液分解，以得到所述混合的氧化物催化剂，
该方法的特征在于氧化铁为α和/或γ形态的。
2、根据第1项的方法，其中碳水化合物选自葡萄糖，果糖，乳糖和蔗糖，羧酸是柠檬酸和/或甘氨酸。
3、根据第2项的方法，其中分解在300-450℃下进行。
4、根据第2项的方法，其中葡萄糖以化学计量比0.1-0.6的量加入。
5、根据第1项的方法，还包括一个步骤，即向步骤(a)的酸性溶液中加入一种或多种PR(NO3)x形式的促进剂，其中PR选自Na，K，Cs，Mg，Ca，Ba，Sr和Rb。
具体实施方案
实施例
实施例1
铁与促进剂的硝酸盐一起以所需比例溶解在硝酸中，该促进剂是诸如Cr，Cu，K和Na，并且获得储液。该溶液在350℃下以给定的供料速率滴入旋转窑中。粉末特征用XRD分析方法以及用于比表面积的氮吸收等温线来测量(根据Brunauer，Emmett和Teller理论)。合成粉末的表面积(通过氮吸收测量)为73m2/g。
缺陷：粉末牢固地粘附在旋转窑的壁上并且为非常硬的颗粒。
实施例2
储液按照与实施例1相似的方法制备。而后，溶解一定量的葡萄糖，相当于氧化(硝酸盐)和还原(葡萄糖)反应物之间的“化学计量比”为1/6。该溶液在400℃下以给定的供料速率滴入旋转窑中。
X-射线分析结果显示存在α-Fe2O3，其参数为a ＝5.035埃，c＝13.758埃并且微晶尺寸D(024)＝285埃。
合成粉末上的表面积(通过氮吸收测量)为约50m2/g。
SEM研究显示为由空穴高达5μm的大孔隙率组成的独特微结构。采用原子解析(atomic resolution)TEM，发现均匀分布的Fe，Cu和Cr。同时，用TEM检测观察到非常特殊的晶体形态。
实施例3
储液按照与实施例1相似的方法制备。而后，溶解一定量的葡萄糖，相当于氧化(硝酸盐)和还原(葡萄糖)反应物之间的“化学计量比”高于1/2。该溶液在350℃下以给定的供料速率滴入旋转窑中。
X-射线分析结果显示存在立方γ-Fe2O3，其参数为a＝8.333埃并且微晶尺寸D(440)＝97埃。
合成粉末上的表面积(通过氮吸收测量)为70m2/g。
此种粉末用于磁带存储器中。
实施例4
储液按照与实施例1相同的方法制备。而后，溶解一定量的葡萄糖，相当于氧化(硝酸盐)和还原(葡萄糖)反应物之间的“化学计量比”为1/2。该溶液在400℃下以给定的供料速率滴入旋转窑中。
X-射线分析结果显示存在α-Fe2O3和γ-Fe2O3。
实施例5
将摩尔比为1∶1的金属Co与Fe的混合物溶解在浓硝酸中。将氢氧化铝以总摩尔比为Fe∶Co∶Al为1∶1∶2加入。最后，加入KNO3，并使其摩尔百分含量为1％。
该溶液在350℃下以恒定的供料速率滴入旋转窑中。
粉末经破碎，过筛，与石墨混合以及造粒(pelletised)。
小粒(小丸)在传送机加热炉中于550℃下烧结。
该小粒在纯氢下还原，并且可用作合成氨和氨分解的催化剂。
实施例6
金属Cu和氧化锌(ZnO)的混合物溶解在浓HNO3中。其摩尔比为1∶1。氧化铝以总摩尔比为Cu∶Zn∶Al为1∶1∶1加入。浆料在350℃下分解。
粉末经破碎，过筛，与石墨混合，以及造粒。
小粒在稀释的氢中还原，并且可用作合成甲醇或WGS转化的催化剂。

Claims (5)

1.一种生产混合选自Co，Al，Cu和Cr的氧化物中的一种或多种的氧化铁催化剂的方法，包括下述步骤：
(a)提供带有硝酸铁和选自Co，Al，Cu和Cr的一种或多种金属的硝酸盐的硝酸溶液；
(b)向该硝酸溶液中加入碳水化合物和/或羧酸；
(c)在250-700℃的温度下，在自由空气供入下，使步骤(b)中获得的酸性溶液分解，以得到所述混合的氧化物催化剂，
该方法的特征在于氧化铁为α和/或γ形态的。
2.根据权利要求1的方法，其中碳水化合物选自葡萄糖，果糖，乳糖和蔗糖，羧酸是柠檬酸和/或甘氨酸。
3.根据权利要求2的方法，其中分解在300-450℃下进行。
4.根据权利要求2的方法，其中葡萄糖以化学计量比0.1-0.6的量加入。
5.根据权利要求1的方法，还包括一个步骤，即向步骤(a)的酸性溶液中加入一种或多种PR(NO3)x形式的促进剂，其中PR选自Na，K，Cs，Mg，Ca，Ba，Sr和Rb。
CNB021475547A 2001-10-15 2002-10-15 含氧化铁的催化剂的制备方法 Expired - Fee Related CN100369670C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA200101514 2001-10-15
DKPA200101514 2001-10-15

Publications (2)

Publication Number Publication Date
CN1411907A CN1411907A (zh) 2003-04-23
CN100369670C true CN100369670C (zh) 2008-02-20

Family

ID=8160769

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB021475547A Expired - Fee Related CN100369670C (zh) 2001-10-15 2002-10-15 含氧化铁的催化剂的制备方法

Country Status (5)

Country Link
US (2) US6875723B2 (zh)
EP (1) EP1304164A1 (zh)
CN (1) CN100369670C (zh)
RU (1) RU2320409C2 (zh)
ZA (1) ZA200208264B (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7309479B2 (en) * 2005-06-29 2007-12-18 Samsung Engineering Co., Ltd. Cobalt oxide catalysts
DE102018126344A1 (de) * 2018-10-23 2020-04-23 Technische Universität Bergakademie Freiberg Katalysator zur Verwendung bei der Umwandlung von CO2 zu CH4 und Verfahren zur Herstellung eines Katalysators zur Verwendung bei der Umwandlung von CO2 zu CH4
CN112615057B (zh) * 2020-12-15 2022-08-23 广东微电新能源有限公司 固态锂离子电池的制备方法及其固态锂离子电池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4029738A (en) * 1971-12-02 1977-06-14 Societe Francaise Des Produits Pour Catalyse Decomposing nitrogen oxides with nickel-iron-chromium catalysts
US5759936A (en) * 1996-03-21 1998-06-02 Haldor Topsoe As Lanthanide ceramic material
US6136998A (en) * 1996-10-15 2000-10-24 Mitsubishi Rayon Co., Ltd. Retention of activity of molybdenum-containing metallic oxide catalyst
WO2001028986A1 (fr) * 1999-10-18 2001-04-26 Mitsubishi Rayon Co., Ltd. Methode de production d'acrylonitrile, catalyseur employe et methode de preparation dudit produit
CN1306940A (zh) * 2000-02-04 2001-08-08 赫多特普索化工设备公司 氧化铝的生产方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2163830A6 (zh) * 1971-04-19 1973-07-27 Prod Catalyse Fse
JPS52151687A (en) * 1976-06-12 1977-12-16 Agency Of Ind Science & Technol No# reduction catalyst and removal of no# in exhaust gas
NL173387C (nl) * 1979-03-15 1984-01-16 Azote Sa Cie Neerlandaise Werkwijze voor het maken van stabiele, ammoniumnitraat bevattende meststofkorrels.
US4483942A (en) * 1982-10-15 1984-11-20 Nippon Oil Co., Ltd. Process of preparing hydrogenation catalysts
US4490479A (en) * 1983-05-19 1984-12-25 Gulf Research & Development Company Process for preparing catalysts
US4482645A (en) * 1983-05-24 1984-11-13 Imperial Chemical Industries Limited Method of making an iron oxidechromium oxide catalyst
US5061682A (en) * 1990-01-17 1991-10-29 The Washington Technology Center Ceramic precursor mixture and technique for converting the same to ceramic
US5176888A (en) * 1990-03-26 1993-01-05 University Of Delaware Acid rain abatement
US5124295A (en) * 1990-12-13 1992-06-23 Engelhard Corporation Copper chromite catalyst and process for preparation said catalyst
US5565091A (en) * 1993-02-15 1996-10-15 Idemitsu Kosan Co., Ltd. Catalyst composition manufacturing method and sulfur-containing hydrocarbon hydrodesulfurization method using the same catalyst composition
US5360778A (en) * 1993-05-11 1994-11-01 Exxon Research And Engineering Company High surface purity heat transfer solids for high temperature fluidized bed reactions
US5925590A (en) * 1994-05-25 1999-07-20 Eltron Research, Inc. Catalysts utilizing oxygen-deficient metal oxide compound for removal of exhaust gas constituents
US5856261A (en) * 1997-04-22 1999-01-05 Exxon Research And Engineering Company Preparation of high activity catalysts; the catalysts and their use

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4029738A (en) * 1971-12-02 1977-06-14 Societe Francaise Des Produits Pour Catalyse Decomposing nitrogen oxides with nickel-iron-chromium catalysts
US5759936A (en) * 1996-03-21 1998-06-02 Haldor Topsoe As Lanthanide ceramic material
US6136998A (en) * 1996-10-15 2000-10-24 Mitsubishi Rayon Co., Ltd. Retention of activity of molybdenum-containing metallic oxide catalyst
WO2001028986A1 (fr) * 1999-10-18 2001-04-26 Mitsubishi Rayon Co., Ltd. Methode de production d'acrylonitrile, catalyseur employe et methode de preparation dudit produit
CN1306940A (zh) * 2000-02-04 2001-08-08 赫多特普索化工设备公司 氧化铝的生产方法

Also Published As

Publication number Publication date
US6875723B2 (en) 2005-04-05
RU2320409C2 (ru) 2008-03-27
CN1411907A (zh) 2003-04-23
EP1304164A1 (en) 2003-04-23
US20050096216A1 (en) 2005-05-05
ZA200208264B (en) 2003-07-04
US20030073574A1 (en) 2003-04-17

Similar Documents

Publication Publication Date Title
CA1233810A (en) Catalyst composition suitable for synthesis of methanol
JP7352487B2 (ja) アンモニア分解触媒
CN101415509A (zh) 超高纯度金属氧化物、混合金属氧化物、金属以及金属合金的均匀纳米颗粒的制备
Xia et al. Preparation of nickel powders by spray pyrolysis of nickel formate
JPH10194717A (ja) 炭化タングステン粒子生成法
JP2017081812A (ja) マンガン−ジルコニウム系複合酸化物及びその製造方法、並びにその用途
JPS6171840A (ja) 酸化物触媒前駆体組成物及びその製法
CN100369670C (zh) 含氧化铁的催化剂的制备方法
Cordier et al. Synthesis of the metastable α-Al1. 8Fe0. 2O3 solid solution from precursors prepared by combustion
EP0174080B1 (en) Catalystsfor the synthesis of ammonia
EP0462344A1 (en) Method for producing composite oxides for use ad starting materials for ferrites
JP3328845B2 (ja) 水素製造法とそれに用いる触媒
WO2002079091A1 (fr) Procede permettant de produire du nitrate de metal basique
EP3609839B1 (en) Method for the management of phosphogypsum
GB191227955A (en) Improvements in, or connected with, the Manufacture of Hydrogen.
Nilsson et al. Ammoxidation of propane over vanadium-antimony-oxide catalysts. Role of phase cooperation effects
JPS5919546A (ja) メタノ−ル合成用触媒
EP0174079B1 (en) Ammonia synthesis catalysts based on oxides of iron, aluminium and cobalt
US3955961A (en) Carboxylate metals process
CN110668470A (zh) 一种石灰氮的合成方法
JPH0535017B2 (zh)
CN102070207B (zh) 制备纳米氧化镍的方法
JPH0371174B2 (zh)
CN112569977B (zh) 含沉淀型χ碳化铁和θ碳化铁的组合物及制备方法、催化剂和应用及费托合成的方法
Qian et al. Hydrogen reduction studies of members of the system MgFe2− xCrxO4

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080220

Termination date: 20151015

EXPY Termination of patent right or utility model