WO2010031247A1 - 一种铁基氨合成催化剂及其制备方法 - Google Patents

一种铁基氨合成催化剂及其制备方法 Download PDF

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WO2010031247A1
WO2010031247A1 PCT/CN2009/001031 CN2009001031W WO2010031247A1 WO 2010031247 A1 WO2010031247 A1 WO 2010031247A1 CN 2009001031 W CN2009001031 W CN 2009001031W WO 2010031247 A1 WO2010031247 A1 WO 2010031247A1
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oxide
iron
catalyst
ammonia synthesis
rare earth
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French (fr)
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徐显明
林建新
魏可镁
王榕
张忠涛
李文鹏
裴皓天
张永军
林炳裕
李方伟
王斯晗
张宝军
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Petrochina Co Ltd
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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
    • 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
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • 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
    • 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
    • B01J23/83—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 rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis
    • C01C1/0405—Preparation of ammonia by synthesis from N2 and H2 in presence of a catalyst
    • C01C1/0411—Preparation of ammonia by synthesis from N2 and H2 in presence of a catalyst characterised by the catalyst
    • 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
    • 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 invention relates to an iron-based ammonia synthesis catalyst for synthesizing ammonia from hydrogen and nitrogen as raw materials in the synthetic ammonia industry and a preparation method thereof.
  • the ammonia synthesis catalysts currently used in industry at home and abroad are basically molten iron-based catalysts.
  • the raw materials composed of selected magnetite powders and a certain amount of catalyst additives are uniformly mixed and melted at high temperature in an electric resistance furnace. It is prepared by cooling and crushing.
  • the main components are triiron tetroxide and ferrous oxide.
  • the additives used are alumina, potassium oxide, calcium oxide, magnesium oxide, cobalt oxide, vanadium oxide, rare earth, etc., with triiron tetroxide as the main component.
  • the iron catalyst iron ratio is mostly controlled between 0.4 and 0.6.
  • the existing industrial catalysts with triiron tetroxide as the main component are: Domestic A106, A109, A110 series, its main additives are alumina and potassium oxide. Calcium oxide, foreign S6-10, KMIIR, CA- ⁇ also added magnesium oxide auxiliaries, and a class of cobalt-added catalysts such as domestic A201, A202, NCA, ICI74-1 in the United Kingdom and C73-3 in the United States - 02, FA401, A203 are added to the rare earth additive.
  • Chinese patent ZL86107630, US 4308174T and US3992328 have related reports.
  • the iron catalysts with ferrous oxide as the main component are mainly ZA-5 and A301.
  • the added additives are traditional alumina, potassium oxide and calcium oxide, and vanadium oxide is added. The iron ratio is controlled at 2.0 ⁇ 10.0. Between the related reported patents are CN10911997A, CN1412113A and CN1113832A.
  • the object of the present invention is to prepare an ammonia synthesis iron catalyst with excellent performance, which can further improve the activity of a catalyst for synthesizing ferroferric oxide.
  • the catalyst is added with a conventional auxiliary alumina.
  • potassium oxide and calcium oxide rare earth, molybdenum oxide and tungsten oxide additives are added, which have low temperature, low pressure activity, good resistance to poison and heat, low manufacturing cost, and can be widely applied to large, medium and small synthetic ammonia plants.
  • the iron-based ammonia synthesis catalyst of the invention comprises triiron tetroxide as a main component, and uses alumina, potassium oxide, calcium oxide, magnesium oxide, mixed rare earth, molybdenum oxide and tungsten oxide as additives, and the main composition thereof is percentage by weight. : iron oxide 89 ⁇ 96; alumina 1.5 ⁇ 3.0; potassium oxide 0.3 ⁇ : 1.0; calcium oxide 1.0 ⁇ 2.0; magnesium oxide 0.1 ⁇ ; 1.0; molybdenum oxide 0.1 2.0; tungsten oxide 0.1 ⁇ 0.5; mixed rare earth metal oxide 0.2 to 1.0, the total weight is 100%.
  • the weight ratio of the ferrous iron to the ferric iron is 0.4 to 0.6.
  • the iron-based ammonia synthesis catalyst of the present invention has a total weight ratio of molybdenum oxide to tungsten oxide of from 0.2 to 2.5 in a ratio of from 1:1 to 4:1, preferably from 1.5:1 to 3:1.
  • the mixed rare earth is one or a mixture of two or more of La and Ce or a rare earth metal oxide of Pr, Nd, Sm, and the content of La and Ce oxide in the mixture is not lower than
  • the total weight of the rare earth oxide used is 5 to 95%.
  • the selected magnetite powder is mixed with the raw materials of alumina, calcium carbonate, potassium nitrate and other auxiliary materials, uniformly mixed, placed in an electric resistance furnace, and then added with metal. Iron, energized to melt these materials, after being completely melted, poured into an iron pan with water jacket cooling, after cooling, crushing, grinding, and sieving to obtain a catalyst with irregular shape
  • Example 1 The composition of the catalyst (by weight %) alumina 2.2; calcium oxide 1.6; potassium oxide 0.7; mixed rare earth oxide 0.6, wherein the weight ratio of each rare earth oxide to the total amount is L 0 3 90.6, Ce0 2 9.23, Pr 6 O n 0.07, Nd 2 0 3 0.09, Sm 2 0 3 0.01; Magnesium oxide 0.2; Molybdenum oxide 0.4 and Tungsten oxide 0.2, Other ratios of iron oxides, 1400 g of selected magnetite powder; Oxidation 32.7 g of aluminum; 42.5 g of calcium carbonate; 21.0 g of potassium nitrate; 8.9 g of mixed rare earth oxide; 3.0 g of magnesium oxide; 5.6 g of molybdenum trioxide and 3.0 g of tungsten oxide, which were uniformly mixed and placed in an electric resistance furnace, energized These materials are melted, and after being completely melted, they are poured into an iron pan cooled with water jacket.
  • the catalyst After cooling, crushing, grinding, and sieving can obtain a catalyst product of irregular shape.
  • the catalyst has a ratio of divalent iron to ferric iron of 0.5, a pressure of 15 MPa, a temperature of 430 ° C, a space velocity of 10,00011 - 1 , and a hydrogen to nitrogen ratio (V/V) of 3:1.
  • the sample size of the catalyst is 1.0 ⁇ Under the condition of 1.4 mm, the ammonia volume percentage of the outlet of the catalyst was 20.2%.
  • the chemical composition of the catalyst (by weight %) alumina 2.6; calcium oxide 1.2; potassium oxide 0.5; mixed rare earth oxide 0.3 wherein the weight ratio of each rare earth oxide to the total amount is La 2 0 3 91.3, Ce0 2 6.25, Nd 2 0 3 2.45,; Magnesium oxide 0.2; Molybdenum oxide 0.2 and Tungsten oxide 0.1, Other ratios of iron oxides, 1400 g of selected magnetite powder; 38.4 g of alumina; 31.6 g of calcium carbonate; Potassium 16.1 g; mixed rare earth oxide 4.4 g; magnesium oxide 3.0 g; molybdenum trioxide 3.0 g and tungsten oxide 1.5 g, after thorough mixing, placed in an electric resistance furnace, energized to melt these materials, to be completely melted and then poured In the iron pan with water jacket cooling, after cooling, crushing, grinding, and sieving can obtain a catalyst product with irregular shape.
  • the catalyst has a ratio of divalent iron to ferric iron of 0.44, a pressure of 15 MPa, a temperature of 430 ° C, a space velocity of 1000 °H, a hydrogen to nitrogen ratio (V/V) of 3:1, and a catalyst particle size of 1.0 to 1.4 mm. Under the conditions, the catalyst exports ammonia volume The fraction was 19.8%, and the outlet ammonia volume percentage of the catalyst after heat resistance at 530 ° C was 20.1%. Industrial applicability
  • An iron-based ammonia synthesis catalyst of the present invention has the advantages of high activity of the catalyst and low temperature, low pressure and high activity compared with the existing industrial ammonia synthesis catalyst.
  • the activity comparison between the iron-based ammonia synthesis catalyst of the present invention and the conventionally used A110 catalyst is shown in Table 1. It can be seen from Table 1: Under the conditions of pressure 15.0 MPa, temperature 430 ° C and space velocity 1.0 X 10 4 , the iron-based ammonia synthesis catalyst of the invention has a 1.5% increase in the ammonia volume percentage of the conventional A110 catalyst outlet at a pressure of 10.0 MPa. At a temperature of 400 ° C and a space velocity of 1.0 X 10 4 , the iron-based ammonia synthesis catalyst of the present invention has an ammonia volume percentage increase of 1.3% over that of the conventional A110 catalyst.
  • Heat-resisting conditions The heat-resistant time at 530 ° C is 20 hours.
  • an iron-based ammonia synthesis catalyst of the present invention has good heat resistance and poison resistance.
  • the added mixed rare earth oxide and molybdenum oxide and tungsten oxide have the functions of electronic and structural auxiliary agents, and can be highly dispersed in the main phase of the catalyst, thereby improving the activity, heat resistance and anti-toxicity of the catalyst.
  • Table 1 the iron-based ammonia synthesis catalyst of the present invention After heat resistance at 530 ° C for 24 hours, the activity of the catalyst was substantially unchanged, and its activity was also significantly higher than that of the A110 catalyst after heat resistance, indicating that the iron-based ammonia synthesis catalyst of the present invention has superior heat resistance.

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

一种铁基氨合成催化剂及其制备方法
技术领域
本发明涉及一种合成氨工业中用于由氢气和氮气为原料合成氨的铁 系氨合成催化剂及制备方法。
背景技术
国内外现在工业上使用的氨合成催化剂基本都是熔融铁系催化剂， 通常是由精选磁铁矿粉与一定量的催化剂的助剂组成的原料经混合均 匀， 在电阻炉中经高温熔融， 冷却、 破碎制备而成。 主体成份有四氧化 三铁和氧化亚铁基两类， 所采用的助剂有氧化铝、 氧化钾、 氧化钙、 氧 化镁、 氧化钴、 氧化钒、 稀土等， 以四氧化三铁为主体成分的铁催化剂 铁比多数控制在 0.4〜0.6之间，现有的以四氧化三铁为主体组分的工业催 化剂有： 国内的 A106、 A109、 A110系列其主要的助剂有氧化铝、 氧化 钾、 氧化钙， 国外的 S6— 10、 KMIIR、 CA-ΙΒΠ还添加了氧化镁助剂， 还有一类添加钴的催化剂如国内的 A201、 A202、 NCA， 英国的 ICI74-1和 美国的 C73-3- 02，添加稀土助剂的有 FA401、A203。中国专利 ZL86107630、 美国 US4308174T和 US3992328有相关的报道。 以氧化亚铁基为主体成分 的铁催化剂主要有 ZA-5和 A301 ,添加的助剂有传统的氧化铝、氧化钾、 氧化钙外还加有氧化钒， 其铁比多数控制在 2.0〜10.0之间， 相关的报道 专利有 CN10911997A、 CN1412113A和 CN1113832A。
发明内容
本发明的目的是制备一种性能优良的氨合成铁催化剂， 能进一步提 高四氧化三铁基氨合成催化剂的活性， 该催化剂在添加传统助剂氧化铝、 氧化钾、 氧化钙的基础上， 添加稀土、 氧化钼和氧化钨助剂， 其低温.低 压活性高， 抗毒耐热性能好， 制造成本低， 可广泛应用于大、 中、 小型 合成氨厂。
本发明的一种铁系氨合成催化剂， 以四氧化三铁为主要成分， 以氧 化铝、 氧化钾、 氧化钙、 氧化镁、 混合稀土、 氧化钼和氧化钨为添加剂, 其主要组成按重量百分比： 铁氧化物 89〜96； 氧化铝 1.5~3.0； 氧化钾 0.3〜： 1.0;氧化钙 1.0〜2.0；氧化镁 0.1〜； 1.0;氧化钼 0.1 2.0;氧化钨 0.1〜0.5； 混合稀土金属氧化物 0.2〜1.0，总重量为 100%。
本发明的一种铁系氨合成催化剂的铁的氧化物中， 二价铁与三价铁 的重量比为： 0.4〜0.6。
本发明的一种铁系氨合成催化剂,其氧化钼与氧化钨的总重量比为 0.2-2.5比例为 1 :1~4:1， 最好是 1.5:1〜3:1。
本发明的一种铁系氨合成催化剂，混合稀土是 La和 Ce或和 Pr、 Nd、 Sm稀土金属氧化物中的一种或两种以上的混合物， 混合物中 La和 Ce 氧化物含量不低于所用稀土氧化物总重量的 5〜95%。
本发明的一种铁系氨合成催化剂的制备方法， 将精选磁铁矿粉与氧 化铝、 碳酸钙、 硝酸钾和其它助剂原料一起混合， 混合均匀后置于电阻 炉中， 再加金属铁， 通电使这些物料熔融， 待完全熔化后倒至带水夹套 冷却的铁盘中， 冷却后破碎、 磨角、 筛分即可得无规则形状的催化剂成
P 具体实施方案
实施例 1 将催化剂的组成（按重量％计）氧化铝 2.2; 氧化钙 1.6; 氧化钾 0.7; 混合稀土氧化物 0.6,其中各稀土氧化物占总量的重量比例为 L 03 90.6, Ce02 9.23, Pr6On 0.07, Nd203 0.09, Sm203 0.01;氧化镁 0.2;氧化钼 0.4和 氧化钨 0.2,其它为铁的氧化物的比例配料，将精选磁铁矿粉 1400克;氧化 铝 32.7克； 碳酸钙 42.5克； 硝酸钾 21.0克； 混合稀土氧化物 8.9克;氧化 镁 3.0克;三氧化钼 5.6克和氧化钨 3.0克， 经充分均匀混合后置于电阻炉 中， 通电使这些物料熔融， 待完全熔化后倒至带水夹套冷却的铁盘中， 冷却后破碎、 磨角、 筛分即可得无规则形状的催化剂成品。 该催化剂的 二价铁与三价铁的比值为 0.5,在压力 15MPa、温度 430°C 、空速 1000011-1、 氢氮比 （V/V) 为 3: 1， 催化剂的样品粒度为 1.0〜1.4mm条件下，该催化 剂的出口氨体积百分数为 20.2%。
实施例 2
将催化剂的化学组成（按重量％计）氧化铝 2.6; 氧化钙 1.2; 氧化钾 0.5； 混合稀土氧化物 0.3其中各稀土氧化物占总量的重量比例为 La203 91.3, Ce02 6.25, Nd203 2.45,;氧化镁 0.2;氧化钼 0.2和氧化钨 0.1，其它为铁 的氧化物的比例配料， 将精选磁铁矿粉 1400克;氧化铝 38.4克； 碳酸钙 31.6克； 硝酸钾 16.1克； 混合稀土氧化物 4.4克;氧化镁 3.0克;三氧化钼 3.0克和氧化钨 1.5克， 经充分均匀混合后置于电阻炉中， 通电使这些物 料熔融， 待完全熔化后倒至带水夹套冷却的铁盘中， 冷却后破碎、 磨角、 筛分即可得无规则形状的催化剂成品。 该催化剂的二价铁与三价铁的比 值为 0.44,在压力 15MPa、 温度 430°C、 空速 lOOOOh^ 氢氮比（V/V)为 3： 1， 催化剂的样品粒度为 1.0〜1.4mm条件下，该催化剂的出口氨体积百 分数为 19.8%， 530°C耐热后该催化剂的出口氨体积百分数为 20.1%。 工业实用性
本发明的一种铁系氨合成催化剂的优点是催化剂的活性高， 与现有 的工业氨合成催化剂相比， 具有低温低压高活性的特点。 本发明的铁系 氨合成催化剂与现有使用的 A110催化剂的活性比较见表一。 从表一可 见： 在压力 15.0MPa、温度 430°C、空速 1.0 X 104条件下， 本发明的铁系 氨合成催化剂比传统的 A110催化剂出口氨体积百分数提高了 1.5%,在压 力 10.0MPa、温度 400°C、空速 1.0 X 104条件下， 本发明的铁系氨合成催 化剂比传统的 A110催化剂出口氨体积百分数提高了 1.3%。
表一本发明的铁系氨合成催化剂与现有使用的 A110催化剂的活性与耐 热性比较
Figure imgf000006_0001
*活性测定条件：空速 1.0X 104、
混合气 ¾/N2=3 V/V)。
**耐热条件: 530°C下耐热时间为 20小时。
本发明的一种铁系氨合成催化剂的另一个优点是催化剂的耐热性能 及抗毒性能好。 添加的混合稀土氧化物和氧化钼、 氧化钨兼有电子型和 结构型助剂的作用，能高度分散在催化剂的主体相中，提高了催化剂的活 性、 耐热性能及抗毒性能。 由表一可见，本发明的铁系氨合成催化剂经 530°C下耐热 24小时后，催化剂的活性基本不变，并且经耐热后其活性也 明显高于 A110催化剂,表明本发明的铁系氨合成催化剂具有较优良的耐 热性能。
本发明的铁系氨合成催化剂的抗毒性比较见表二。 在中毒条件下， 整个中毒过程跟踪测定出口氨体积百分数， 本发明的铁系氨合成催化剂 出口氨体积百分数一直比 A110催化剂高 1%C 以上， 从表二可见： 本发 明的铁系氨合成催化剂中毒后活性下降幅度较小， 经混合氢氮气 (H2/N2=3: 1 V/V) 还原后催化剂的活性恢复较快， 而且完全， 表明本 发明的铁系氨合成催化剂具有较强的抗毒能力。
表二 本发明的铁系氨合成催化剂与现有使用的 A110催化剂抗毒性能比 较
Figure imgf000007_0001
中毒条件: T=425°C 、 P =15.0MPa、 Vs=30000h_1 2小时内通入 CO毒物 浓度为 0〜300ppm
恢复条件： 480 °C下用混合氢氮气 （H2/N2=3 : 1 V/V) 还原 4小时 测定条件: P =15.0Mpa、 Vs=10000h h"1, T=430°C。

Claims

权利要求书
1. 一种铁系氨合成催化剂， 其特征在于： 其组成按重量％计： 铁氧 化物 89-96； 氧化铝 1.5-3.0;氧化钾 0·3〜1.0;氧化钙 1.0-2.0； 氧化镁 0.1-1.0;氧化钼 0.1 2.0;氧化钨 0.1〜0.5；混合稀土金属氧化物 0.2〜1.0,总 量为 100%; 氧化钼与氧化钨按重量比例为 1~4:1； 二价铁与三价铁按重 量比为 0.4〜0.6。
2.根据权利要求 1所述的铁系氨合成催化剂,其特征在于： 氧化钼与 氧化钨的比例按重量计为 1.5〜3:1。
3.根据权利要求 1所述的铁系氨合成催化剂,其特征在于：混合稀土 是 La和 Ce或和 Pr、 Nd、 Sm稀土金属氧化物中的一种或两种以上的混 合物， 混合物中 La和 Ce氧化物含量不低于所用稀土氧化物总重量的 5-95% o
4. 根据权利要求 1所述的铁系氨合成催化剂的制备方法， 其特征在 于： 取权利要求 1各成分用量， 将精选磁铁矿粉与氧化铝、 碳酸钙、 硝 酸钾、 氧化镁、 氧化钼、 氧化钨、 混合稀土金属氧化物一起混合， 混合 均匀后置于电阻炉中， 再加金属铁， 通电使这些物料熔融， 待完全熔化 后倒至带水夹套冷却的铁盘中， 冷却后破碎、 磨角、 筛分即可得无规则 形状的催化剂成品。
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