CN112875724A - Method for synthesizing ammonia by metal oxide catalytic mechanochemistry under normal temperature and pressure water phase condition - Google Patents

Method for synthesizing ammonia by metal oxide catalytic mechanochemistry under normal temperature and pressure water phase condition Download PDF

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CN112875724A
CN112875724A CN202110106532.3A CN202110106532A CN112875724A CN 112875724 A CN112875724 A CN 112875724A CN 202110106532 A CN202110106532 A CN 202110106532A CN 112875724 A CN112875724 A CN 112875724A
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ball milling
reaction
metal oxide
normal temperature
tank
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CN112875724B (en
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何承溧
崔晓莉
陈阳
邱栋
陆雨瑄
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Fudan University
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Fudan University
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    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides 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
    • B01J23/70—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
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
    • B04B—CENTRIFUGES
    • B04B13/00—Control arrangements specially designed for centrifuges; Programme control of centrifuges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
    • B04B—CENTRIFUGES
    • B04B5/00—Other centrifuges
    • B04B5/10—Centrifuges combined with other apparatus, e.g. electrostatic separators; Sets or systems of several centrifuges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
    • B04B—CENTRIFUGES
    • B04B5/00—Other centrifuges
    • B04B5/10—Centrifuges combined with other apparatus, e.g. electrostatic separators; Sets or systems of several centrifuges
    • B04B2005/105—Centrifuges combined with other apparatus, e.g. electrostatic separators; Sets or systems of several centrifuges being a grinding mill
    • 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)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Food Science & Technology (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the technical field of materials, and particularly relates to a method for synthesizing ammonia by catalyzing mechanochemical synthesis by metal oxide under the condition of normal temperature and normal pressure of water phase. The invention carries out mechanochemical ball milling synthesis by a planetary ball mill, stainless steel grinding balls, metal oxide powder and pure water are put into a stainless steel ball milling tank, nitrogen is introduced, ball milling is directly carried out at normal temperature and normal pressure, the solution is stood and centrifuged after the reaction is finished, and the existence of ammonium ions in the solution is verified by ion chromatography(NH4 +). The invention uses metal oxide Fe2O3Or TiO2As an auxiliary catalyst, the potential barrier of the synthetic ammonia reaction is reduced, the synthetic ammonia reaction which is difficult to be carried out at normal temperature and normal pressure is induced and promoted, and the performance of the synthetic ammonia reaction by a mechanochemical method is enhanced. The invention uses nitrogen as nitrogen atom source and water as hydrogen proton source, thus avoiding the environmental pollution caused by preparing hydrogen; the water is used as a reactant, so that the abrasion between the grinding balls and the ball milling tank body is relieved, and the service life of ball milling equipment is prolonged.

Description

Method for synthesizing ammonia by metal oxide catalytic mechanochemistry under normal temperature and pressure water phase condition
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a method for synthesizing ammonia by metal oxide assisted catalysis mechanochemical synthesis under the conditions of normal temperature and normal pressure of water phase.
Background
Currently synthetic ammonia (NH)3) The industry is predominantly carried out by the Haber-Bosch process. The reaction increases the grain yield in the field of agricultural chemical fertilizer production, lives a plurality of global population, is vital in the field of national defense of explosive production, and is known as the most important invention in the 20 th century. The industrial synthesis ammonia reaction needs high temperature and high pressure (300-2Causing serious environmental pollution. Therefore, the development of a green, clean and low-energy-consumption ammonia synthesis process has important social significance. The invention provides a method for synthesizing ammonia by mechanical chemical ball milling under the condition of water phase under normal temperature and pressure and with the assistance of metal oxide catalysis. Performing mechanochemical ball milling synthesis by a planetary ball mill, putting stainless steel grinding balls and metal oxide powder into a stainless steel ball milling tank, introducing pure water and nitrogen, directly performing ball milling at normal temperature and normal pressure, standing and centrifuging the solution after the reaction is finished, and verifying the existence of ammonium ions (NH) in the solution by an ion chromatography method4 +). In contrast to the control experiment without the addition of the metal oxide catalyst, the catalyst having catalytic activity for the reaction of synthetic ammonia, iron (Fe) trioxide, was selected from a large number of metal oxides2O3) And titanium dioxide (TiO)2) Prove Fe2O3And TiO2The catalyst has the function of auxiliary catalysis for the mechanical ball milling synthetic ammonia reaction at normal temperature and normal pressure. Compared with the Haber-Bosch process, the method has the advantages of simple reaction conditions, greenness, safety and low equipment requirement.
Disclosure of Invention
The invention aims to provide a method for synthesizing ammonia by catalyzing mechanochemical synthesis of metal oxide under the conditions of normal temperature and normal pressure water phase, which has simple reaction conditions, is green and safe, and is used for fixing nitrogen and synthesizing ammonia with low energy consumption.
The invention provides a method for synthesizing ammonia by metal oxide catalysis mechanochemistry under the condition of normal temperature and normal pressure water phase, which obtains mechanical force through ball milling process and simultaneously leads metal oxide Fe2O3Or TiO2As an auxiliary catalyst, the potential barrier of the synthetic ammonia reaction is reduced, the synthetic ammonia reaction which is difficult to be carried out at normal temperature and normal pressure is induced and promoted, and the performance of the synthetic ammonia reaction by a mechanochemical method is enhanced. The method comprises the following specific steps:
(1) putting a proper amount of pure water, solid metal oxide powder and stainless steel grinding balls into a stainless steel vacuum ball milling tank, introducing nitrogen into the ball milling tank for a period of time to remove air in the tank, and sealing the ball milling tank to ensure that the tank is in an environment filled with nitrogen at normal temperature and normal pressure;
(2) installing the ball milling tank prepared in the step (1) in a planetary ball mill, carrying out ball milling for 1-12 hours at the speed of 300-600 revolutions per minute, and taking out the ball milling tank after the reaction is finished;
(3) taking out the suspension in the tank body in the step (2), centrifuging twice through a centrifuge at the centrifugal rotation speed of 12000-15000r/min for 4-8min each time, and separating out the solid metal oxide catalyst and the aqueous solution;
(4) detecting the aqueous solution in the step (3) by ion chromatography to detect NH4 +Thereby calculating the ammonia production performance; meanwhile, the metal oxide catalyst is characterized by X-ray diffraction (XRD), and the change of the catalyst before and after reaction is analyzed.
In the invention, the ball milling tank and the milling ball are made of stainless steel.
In the invention, the volume of the ball milling tank is 250mL, grinding balls with different diameters (1 phi 15, 3 phi 12, 6 phi 10, 27 phi 8 and 103 phi 4) are selected, and the ball loading amount is 150g in total.
In the present invention, the metal oxide Fe was found2O3And TiO2All have positive catalytic activity for mechanochemical ammonia synthesis reaction, and Fe2O3Catalytic activity ratio of (3) TiO2And higher.
In the present invention, the amount of water at least submerges the grinding balls.
The invention has the beneficial effects that:
the invention realizes the high-efficiency ammonia synthesis reaction by taking water and nitrogen as raw materials through mechanochemistry at normal temperature and normal pressure.
The invention screens out Fe from a plurality of metal oxides2O3And TiO2As a catalyst, the performance of the mechanochemical ball-milling synthetic ammonia reaction is further improved. At the same time, Fe2O3And TiO2Low cost, easily available source and convenient large-scale production of synthetic ammonia.
The method utilizes nitrogen as a source of nitrogen atoms and water as a source of hydrogen protons, avoids using hydrogen as the source of hydrogen protons in the existing industrial ammonia synthesis method, and avoids environmental pollution caused by preparing hydrogen. Meanwhile, water is used as a reactant, so that the abrasion between the grinding balls and the ball milling tank body is relieved to a certain extent, and the service life of the ball milling equipment is prolonged.
Drawings
FIG. 1 shows the catalysts Fe before and after the reaction in example 12O3XRD pattern of (a).
FIG. 2 shows TiO catalysts before and after the reaction in example 22XRD pattern of (a).
Fig. 3 is an XRD pattern of solid precipitation after the reaction in comparative example 1.
Detailed Description
Example 1
(1) 50mL of pure water and 3gFe2O3Solid powder, stainless steel of different sizes with a total mass of 150gPlacing grinding balls made of stainless steel in a vacuum ball milling tank with the volume of 250mL, introducing nitrogen into the ball milling tank for 30 minutes, removing air in the tank body, sealing the ball milling tank, and enabling the tank body to be in an environment filled with nitrogen at normal temperature and normal pressure, wherein the volume of the nitrogen is 190 mL;
(2) installing the ball milling tank prepared in the step (1) in a planetary ball mill, carrying out ball milling for 5 hours at the speed of 600 revolutions per minute, and taking out the ball milling tank after the reaction is finished;
(3) taking out the suspension in the tank body in the step (2), centrifuging twice by using a centrifugal machine, wherein each time is 15000r/min and 5min, and separating out the solid metal oxide catalyst and the aqueous solution;
(4) detecting the aqueous solution in the step (3) by ion chromatography to detect NH4 +The ammonia generating performance is calculated accordingly. Meanwhile, the metal oxide catalyst is characterized by X-ray diffraction (XRD), and the change of the catalyst before and after reaction is analyzed.
Performing ion chromatography characterization on the obtained water sample, and detecting NH in the water sample4 +And NH4 +The concentration of (B) was 5.93 mg/L. In FIG. 1, Fe after reaction is compared with Fe before reaction2O3In the graph, a new diffraction peak appears at 44.5 ℃, which corresponds to a standard card (PDF- # 06-0696), and shows that Fe powder appears in the catalyst after the reaction.
Example 2
(1) 50mL of pure water and 3g of TiO2Placing solid powder and 150g of stainless steel grinding balls with different sizes in total mass into a vacuum ball milling tank with the volume of 250mL made of stainless steel, introducing nitrogen into the ball milling tank for 30 minutes, removing air in the tank body, sealing the ball milling tank, and enabling the tank body to be in an environment filled with nitrogen at normal temperature and normal pressure, wherein the volume of the nitrogen is 190 mL;
(2) installing the ball milling tank prepared in the step (1) in a planetary ball mill, carrying out ball milling for 5 hours at the speed of 600 revolutions per minute, and taking out the ball milling tank after the reaction is finished;
(3) taking out the suspension in the tank body in the step (2), centrifuging twice by using a centrifugal machine, wherein each time is 15000r/min and 5min, and separating out the solid metal oxide catalyst and the aqueous solution;
(4) detecting the aqueous solution in the step (3) by ion chromatography to detect NH4 +The ammonia generating performance is calculated accordingly. Meanwhile, the metal oxide catalyst is characterized by X-ray diffraction (XRD), and the change of the catalyst before and after reaction is analyzed.
Performing ion chromatography characterization on the obtained water sample, and detecting NH in the water sample4 +And NH4 +The concentration of (B) was 5.12 mg/L. In FIG. 2, the reacted TiO is compared to the pre-reaction, post-reaction TiO2In the graph, a new diffraction peak appears at 44.5 ℃, which corresponds to a standard card (PDF- # 06-0696), and shows that Fe powder appears in the catalyst after the reaction.
Comparative example 1
(1) Placing 50mL of pure water and 150g of stainless steel grinding balls with different sizes and total mass in a stainless steel vacuum ball milling tank with the volume of 250mL, introducing nitrogen into the ball milling tank for 30 minutes, exhausting air in the tank body, sealing the ball milling tank, and enabling the tank body to be in an environment filled with nitrogen at normal temperature and normal pressure, wherein the volume of the nitrogen is 190 mL;
(2) installing the ball milling tank prepared in the step (1) in a planetary ball mill, carrying out ball milling for 5 hours at the speed of 600 revolutions per minute, and taking out the ball milling tank after the reaction is finished;
(3) taking out the suspension in the tank body in the step (2), centrifuging twice by using a centrifugal machine, wherein each time is 15000r/min and 5min, and separating out solid precipitate and aqueous solution;
(4) detecting the aqueous solution in the step (3) by ion chromatography to detect NH4 +The ammonia generating performance is calculated accordingly. And simultaneously carrying out X-ray diffraction (XRD) characterization on the solid precipitate, and analyzing the type and phase of the precipitate.
NH detection in Water sample prepared in this comparative example 14 +The concentration of (B) was 2.71 mg/L. This is due to the absence of a metal oxide catalyst in this comparative example, demonstrating Fe2O3And TiO2The solid powder has the auxiliary catalysis effect on the mechanochemical ball-milling synthetic ammonia reaction. FIG. 3 is an XRD pattern of solid precipitates appearing after the reaction, showing that the solid precipitated powder was ball-milledAnd iron powder falling off from the stainless steel ball milling tank and the grinding balls in the process.

Claims (3)

1. A process for synthesizing ammonia from metallic oxide under the condition of water phase at ordinary temp and pressure features that the mechanical force is obtained by ball grinding while the metallic oxide Fe is used2O3Or TiO2As an auxiliary catalyst, the method reduces the barrier of the synthetic ammonia reaction, induces and promotes the synthetic ammonia reaction which is difficult to be carried out at normal temperature and normal pressure, and enhances the performance of the synthetic ammonia reaction by a mechanochemical method, and comprises the following specific steps:
(1) putting a proper amount of pure water, solid metal oxide powder and stainless steel grinding balls into a stainless steel vacuum ball milling tank, introducing nitrogen into the ball milling tank for a period of time to remove air in the tank, and sealing the ball milling tank to ensure that the tank is in an environment filled with nitrogen at normal temperature and normal pressure;
(2) installing the ball milling tank prepared in the step (1) in a planetary ball mill, carrying out ball milling for 1-12 hours at the speed of 300-600 revolutions per minute, and taking out the ball milling tank after the reaction is finished;
(3) taking out the suspension in the tank body in the step (2), centrifuging twice through a centrifuge at the centrifugal rotation speed of 12000-15000r/min for 4-8min each time, and separating out the solid metal oxide catalyst and the aqueous solution;
(4) detecting the aqueous solution in the step (3) by ion chromatography to detect NH4 +Thereby calculating the ammonia production performance; meanwhile, the metal oxide catalyst is characterized by X-ray diffraction (XRD), and the change of the catalyst before and after reaction is analyzed.
2. The method of claim 1, wherein the ball milling pot and the milling balls are stainless steel.
3. The method of claim 1 wherein the amount of water at least floods the grinding balls.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113634260A (en) * 2021-08-09 2021-11-12 安徽国祯生态科技有限公司 Synthetic ammonia catalyst composition and preparation method and application thereof
CN114605174A (en) * 2022-01-27 2022-06-10 杭州三得农业科技有限公司 System and process for preparing nitrogen ion fertilizer special for chemoautotrophy of plants by using nitrogen
CN114751373A (en) * 2022-04-15 2022-07-15 山东大学 Mechanical catalysis method for preparing hydrogen and carbon by cracking methane

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113634260A (en) * 2021-08-09 2021-11-12 安徽国祯生态科技有限公司 Synthetic ammonia catalyst composition and preparation method and application thereof
CN114605174A (en) * 2022-01-27 2022-06-10 杭州三得农业科技有限公司 System and process for preparing nitrogen ion fertilizer special for chemoautotrophy of plants by using nitrogen
CN114751373A (en) * 2022-04-15 2022-07-15 山东大学 Mechanical catalysis method for preparing hydrogen and carbon by cracking methane
CN114751373B (en) * 2022-04-15 2023-10-27 山东大学 Mechanocatalytic method for preparing hydrogen and carbon by methane pyrolysis

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