CN101676026B - Iron ammonia synthesis catalyst and preparation method - Google Patents

Iron ammonia synthesis catalyst and preparation method Download PDF

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CN101676026B
CN101676026B CN2008102223935A CN200810222393A CN101676026B CN 101676026 B CN101676026 B CN 101676026B CN 2008102223935 A CN2008102223935 A CN 2008102223935A CN 200810222393 A CN200810222393 A CN 200810222393A CN 101676026 B CN101676026 B CN 101676026B
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oxide
catalyst
iron
grams
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CN101676026A (en
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徐显明
林建新
魏可镁
王榕
张忠涛
俞秀金
裴皓天
张永军
林炳裕
李方伟
王斯晗
张宝军
李建功
张学业
李德全
林雪梅
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Fuzhou University
China Petroleum and Natural Gas Co Ltd
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Fuzhou University
China Petroleum and Natural Gas 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 in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0411—Preparation of ammonia by synthesis in the gas phase 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to an iron ammonia synthesis catalyst and a preparation method. The catalyst comprises the following components by weight percent: 89 to 96 percent of iron oxide, 1.5 to 3.0 percent of aluminum oxide, 0.3 to 1.0 percent of potassium oxide, 1.0 to 2.0 percent of calcium oxide, 0.1 to 1.0 percent of magnesium oxide, 0.1 to 2.0 percent of molybdenum oxide, 0.1 to 0.5 percent oftungsten oxide and 0.2 to 1.0 percent of mixed rare-earth metal oxide, and the total amount is 100%; the ratio of molybdenum oxide to tungsten oxide is 1:1-4:1; and the ratio of ferrous iron to ferric iron is 0.4-0.6. By being prepared by a melting method, the catalyst has low temperature, low pressure and high activity. The volume percentage of outlet ammonia is 20.2%, and the heat-resisting andantitoxic performance is good.

Description

A kind of iron ammonia synthesis catalyst and preparation method
Technical field
The present invention relates to be used in a kind of ammonia synthesizing industry by hydrogen and nitrogen is the iron ammonia synthesis catalyst and the preparation method of raw material synthetic ammonia.
Background technology
The ammonia synthesis catalyst of present industrial use both at home and abroad substantially all is the molten iron series catalysts, normally the raw material of being made up of the auxiliary agent of selected magnetite powder and a certain amount of catalyst is through mixing, through high-temperature fusion, cooling, fragmentation are prepared from resistance furnace.Main component has tri-iron tetroxide and ferrous oxide base two classes, the auxiliary agent that is adopted has aluminium oxide, potassium oxide, calcium oxide, magnesia, cobalt oxide, vanadium oxide, rare earth etc., the iron catalyst iron that with the tri-iron tetroxide is the main body composition is controlled between 0.4～0.6 than majority, existing is that the industrial catalyst of main body component has: domestic A106 with the tri-iron tetroxide, A109, its main auxiliary agent of A110 series has aluminium oxide, potassium oxide, calcium oxide, external S6-10, KMIIR, CA-1B ∏ has also added the magnesia auxiliary agent, also have a class to add the catalyst of cobalt such as domestic A201, A202, NCA, the ICI74-1 of Britain and the C73-3-02 of the U.S. add the FA401 that has of rare-earth additive, A203.Chinese patent ZL86107630, U.S. US4308174T have relevant report with US3992328.With the ferrous oxide base is that the iron catalyst of main body composition mainly contains ZA-5 and A301, the auxiliary agent that adds has traditional aluminium oxide, potassium oxide, calcium oxide also to be added with vanadium oxide outward, its iron is controlled between 2.0～10.0 than majority, and relevant report patent has CN10911997A, CN1412113A and CN1113832A.
Summary of the invention
The objective of the invention is to prepare a kind of ammonia synthesis iron catalyst of function admirable, can further improve the activity of tri-iron tetroxide base ammonia synthetic catalyst, this catalyst is on the basis of adding conventional adjuvants aluminium oxide, potassium oxide, calcium oxide, add rare earth, molybdenum oxide and tungsten oxide auxiliary agent, its low-temp low-pressure is active high, antitoxin heat resistance is good, and low cost of manufacture can be widely used in large, medium and small type synthesis ammonia plant.
A kind of iron ammonia synthesis catalyst of the present invention is a main component with the tri-iron tetroxide, is additive with aluminium oxide, potassium oxide, calcium oxide, magnesia, mishmetal, molybdenum oxide and tungsten oxide, and it is mainly formed by weight percentage: ferriferous oxide 89～96; Aluminium oxide 1.5～3.0; Potassium oxide 0.3～1.0; Calcium oxide 1.0～2.0; Magnesia 0.1～1.0; Molybdenum oxide 0.1～2.0; Tungsten oxide 0.1～0.5; Based metallic oxides with mixed rare earth 0.2～1.0, gross weight are 100%.
In the oxide of the iron of a kind of iron ammonia synthesis catalyst of the present invention, ferrous iron and ferric weight ratio are: 0.4～0.6.
A kind of iron ammonia synthesis catalyst of the present invention, its molybdenum oxide is that 0.2～2.5 ratio is 1:1～4:1, preferably 1.5:1～3:1 with the gross weight ratio of tungsten oxide.
A kind of iron ammonia synthesis catalyst of the present invention, mishmetal be La and Ce or and Pr, Nd, Sm rare-earth oxide in one or more mixture, La and Ce oxide content are not less than 5～95% of used rare earth oxide gross weight in the mixture.
The preparation method of a kind of iron ammonia synthesis catalyst of the present invention, selected magnetite powder and aluminium oxide, calcium carbonate, potassium nitrate and other auxiliary agent raw material are mixed together, mix and be placed in the resistance furnace, add metallic iron again, energising makes these material fusions, until completely melted to iron pan with water leg cooling, cooling back fragmentation, angle lap, screening get final product the catalyst finished product of irregular shape.
The advantage of a kind of iron ammonia synthesis catalyst of the present invention is the activity of such catalysts height, compares with existing industrial ammonia synthesis catalyst, has the low-temp low-pressure advantage of high activity.Iron ammonia synthesis catalyst of the present invention relatively sees Table one with the existing A110 activity of such catalysts of using.From table one as seen: in pressure 15.0MPa, 430 ℃ of temperature, air speed 1.0 * 10 4Under the condition, iron ammonia synthesis catalyst of the present invention has improved 1.5% than traditional A110 catalyst outlet ammonia percentage by volume, in pressure 10.0MPa, 400 ℃ of temperature, air speed 1.0 * 10 4Under the condition, iron ammonia synthesis catalyst of the present invention has improved 1.3% than traditional A110 catalyst outlet ammonia percentage by volume.
Table one iron ammonia synthesis catalyst of the present invention compares with existing A110 activity of such catalysts of using and hear resistance
Figure G2008102223935D00031
*Determination of activity condition: air speed 1.0 * 10 4, sample granularity is 1.0～1.4 millimeters, reacting gas is hydrogen nitrogen mixed gas (H 2/ N 2=3V/V).
*Heat-resisting condition: 530 ℃ of following heat-resistant times are 20 hours.
Another advantage of a kind of iron ammonia synthesis catalyst of the present invention is that the heat resistance and the antitoxin performance of catalyst is good.The effect that the mixed rare-earth oxide that adds and molybdenum oxide, tungsten oxide have electron type and structural type auxiliary agent concurrently, can high degree of dispersion the main body of catalyst mutually in, improved activity of such catalysts, heat resistance and antitoxin performance.By table one as seen, iron ammonia synthesis catalyst of the present invention is after under 530 ℃ heat-resisting 24 hours, activity of such catalysts is constant substantially, and its activity shows that also apparently higher than the A110 catalyst iron ammonia synthesis catalyst of the present invention has better heat resistance after heat-resisting.
The mithridatism of iron ammonia synthesis catalyst of the present invention relatively sees Table two.Under the poisoning condition, whole poisoning process tracking is measured outlet ammonia percentage by volume, iron ammonia synthesis catalyst outlet ammonia percentage by volume of the present invention is always than more than the high 1%C of A110, from table two as seen: active fall was less after iron ammonia synthesis catalyst of the present invention was poisoned, through mixing hydrogen and nitrogen gas (H 2/ N 2=3:1V/V) activation recovering of reduction rear catalyst is very fast, and fully, show that iron ammonia synthesis catalyst of the present invention has stronger poison resistance.
Table two iron ammonia synthesis catalyst of the present invention compares with the antitoxin performance of the existing A110 catalyst that uses
A110，NH 3％ This catalyst
Before the poisoning 18.5 20.1
Poisoned back 2 hours 15.6 17.3
After the poisoning reduction 18.1 19.9
Poisoning condition: T=425 ℃, P=15.0MPa, Vs=30000h -1Feed the CO poisonous substance in 2 hours
Concentration is 0～300ppm
The recovery condition: 480 ℃ down with mixing hydrogen and nitrogen gas (H 2/ N 2=3:1V/V) reduced 4 hours
Condition determination: P=15.0Mpa, Vs=10000hh -1, T=430 ℃
Specific embodiments
Embodiment 1
Composition (% meter by weight) aluminium oxide 2.2 with catalyst; Calcium oxide 1.6; Potassium oxide 0.7; Mixed rare-earth oxide 0.6, wherein to account for the part by weight of total amount be La to each rare earth oxide 2O 390.6, CeO 29.23, Pr 6O 110.07, Nd 2O 30.09, Sm 2O 30.01; Magnesia 0.2; Molybdenum oxide 0.4 and tungsten oxide 0.2, other is the ratio batching of the oxide of iron, with selected magnetite powder 1400 grams; Aluminium oxide 32.7 grams; Calcium carbonate 42.5 grams; Potassium nitrate 21.0 grams; Mixed rare-earth oxide 8.9 grams; Magnesia 3.0 grams; Molybdenum trioxide 5.6 grams and tungsten oxide 3.0 grams, be placed in the resistance furnace through full and uniform mixing, energising makes these material fusions, until completely melted to iron pan with the water leg cooling, cooling back fragmentation, angle lap, screening get final product the catalyst finished product of irregular shape.The ferrous iron of this catalyst and ferric ratio are 0.5, at pressure 15MPa, 430 ℃ of temperature, air speed 10000h -1, hydrogen nitrogen is 3:1 than (V/V), the sample granularity of catalyst is under 1.0～1.4mm condition, the outlet ammonia percentage by volume of this catalyst is 20.2%.
Embodiment 2
Chemical composition (% meter by weight) aluminium oxide 2.6 with catalyst; Calcium oxide 1.2; Potassium oxide 0.5; Mixed rare-earth oxide 0.3 wherein each rare earth oxide part by weight of accounting for total amount is La 2O 391.3, CeO 26.25, Nd 2O 32.45; Magnesia 0.2; Molybdenum oxide 0.2 and tungsten oxide 0.1, other is the ratio batching of the oxide of iron, with selected magnetite powder 1400 grams; Aluminium oxide 38.4 grams; Calcium carbonate 31.6 grams; Potassium nitrate 16.1 grams; Mixed rare-earth oxide 4.4 grams; Magnesia 3.0 grams; Molybdenum trioxide 3.0 grams and tungsten oxide 1.5 grams, be placed in the resistance furnace through full and uniform mixing, energising makes these material fusions, until completely melted to iron pan with the water leg cooling, cooling back fragmentation, angle lap, screening get final product the catalyst finished product of irregular shape.The ferrous iron of this catalyst and ferric ratio are 0.44, at pressure 15MPa, 430 ℃ of temperature, air speed 10000h -1, hydrogen nitrogen is 3:1 than (V/V), the sample granularity of catalyst is under 1.0～1.4mm condition, the outlet ammonia percentage by volume of this catalyst be 19.8%, 530 ℃ heat-resisting after the outlet ammonia percentage by volume of this catalyst be 20.1%.

Claims (1)

1. iron ammonia synthesis catalyst is characterized in that: with the composition of catalyst % meter by weight: aluminium oxide 2.2; Calcium oxide 1.6; Potassium oxide 0.7; Mixed rare-earth oxide 0.6; Wherein to account for the part by weight of total amount be La to each rare earth oxide 2O 390.6, CeO 29.23, Pr 6O 110.07, Nd 2O 30.09, Sm 2O 30.01; Magnesia 0.2; Molybdenum oxide 0.4 and tungsten oxide 0.2, other is the ratio batching of the oxide of iron, with selected magnetite powder 1400 grams; Aluminium oxide 32.7 grams; Calcium carbonate 42.5 grams; Potassium nitrate 21.0 grams; Mixed rare-earth oxide 8.9 grams; Magnesia 3.0 grams; Molybdenum trioxide 5.6 grams and tungsten oxide 3.0 grams, be placed in the resistance furnace through full and uniform mixing, energising makes these material fusions, until completely melted to iron pan with the water leg cooling, cooling back fragmentation, angle lap, screening get final product the catalyst finished product of irregular shape; The ferrous iron of this catalyst and ferric ratio are 0.5, at pressure 15MPa, 430 ℃ of temperature, air speed 10000h -1, hydrogen nitrogen is 3: 1 than V/V, the sample granularity of catalyst is under 1.0～1.4mm condition, obtaining the ammonia percentage by volume is 20.2%.
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CN103933986A (en) * 2013-01-18 2014-07-23 济南大学 Molten iron catalyst prepared from blast furnace dust for ammonia industrial synthesis
CN103933985A (en) * 2013-01-18 2014-07-23 济南大学 Fused iron catalyst used for industrial synthetic ammonia and prepared from sulfuric acid residue
CN107185534B (en) * 2017-05-10 2019-09-03 福州大学化肥催化剂国家工程研究中心 A kind of ruthenium system ammonia synthesis catalyst and preparation method thereof
CN109420512A (en) * 2017-09-04 2019-03-05 中国科学院上海硅酸盐研究所 A kind of catalysis material and its preparation method and application based on phosphoric acid modification
DE102020124179A1 (en) * 2020-09-16 2022-03-17 Clariant International Ltd AMMONIA SYNTHESIS CATALYST WITH IMPROVED ACTIVITY
CN113976134B (en) * 2021-11-15 2024-04-09 浙江工业大学 Ferrous oxide-based catalyst and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0174716A1 (en) * 1984-06-19 1986-03-19 Agrimont S.p.A. Process for preparing iron-based catalysts for the synthesis of ammonia and catalysts so obtained
CN1113832A (en) * 1994-06-21 1995-12-27 浙江工业大学 Catalyst for synthesizing ammonia and its preparing method
CN1385238A (en) * 2002-06-03 2002-12-18 福州大学 Process for preparing ammonia synthesis catalyst

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NO317084B1 (en) * 2002-10-02 2004-08-02 Yara Int Asa Catalyst for the synthesis of ammonia

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0174716A1 (en) * 1984-06-19 1986-03-19 Agrimont S.p.A. Process for preparing iron-based catalysts for the synthesis of ammonia and catalysts so obtained
CN1113832A (en) * 1994-06-21 1995-12-27 浙江工业大学 Catalyst for synthesizing ammonia and its preparing method
CN1385238A (en) * 2002-06-03 2002-12-18 福州大学 Process for preparing ammonia synthesis catalyst

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