CN109529873A - A kind of ruthenium based perovskite type composite oxides ammonia synthesis catalyst and preparation method thereof - Google Patents

A kind of ruthenium based perovskite type composite oxides ammonia synthesis catalyst and preparation method thereof Download PDF

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CN109529873A
CN109529873A CN201811398031.1A CN201811398031A CN109529873A CN 109529873 A CN109529873 A CN 109529873A CN 201811398031 A CN201811398031 A CN 201811398031A CN 109529873 A CN109529873 A CN 109529873A
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catalyst
ruthenium
ammonia synthesis
soluble
salt
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王秀云
彭渲北
江莉龙
曹彦宁
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Fuzhou University
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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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • 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
    • 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)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention belongs to catalyst material preparation fields, and in particular to a kind of ruthenium based perovskite type composite oxides ammonia synthesis catalyst and preparation method thereof.Ruthenium based perovskite type composite oxides ammonia synthesis prepared by the present invention is 400oExcellent ammonia synthesis performance and preferable thermal stability are showed under C and 1 MPa, ruthenium, which is entrained on the position B of perovskite, shows higher catalytic performance compared to being directly immersed on perovskite with Ru, simultaneously and such catalyst has high thermal stability, relative to the catalyst of ruthenium support type, there is apparent industrial application value.

Description

A kind of ruthenium based perovskite type composite oxides ammonia synthesis catalyst and preparation method thereof
Technical field
The present invention relates to catalyst material preparation fields, and in particular to a kind of ruthenium based perovskite type composite oxides ammonia synthesis Catalyst and preparation method thereof.
Background technique
China is a populous nation, as the increasingly developed and population of society gradually increases, then the demand of ammonia is got over Come bigger, ammonia synthesizing industry also occupies an important position in national economy.Mainly ammonia and the product by ammonia processing is being cured It is all had very important effect in the industrial applications such as medicine, environmental protection, explosive, plastics, and can be used as nitrogenous fertilizer in agricultural Main source can dramatically increase the yield of grain, meet the needs of vast farmers, maintain the stabilization and development of society.At present Traditional Haber-Bosch technique is mainly used in ammonia synthesis industry, i.e., iron catalyst is utilized under conditions of high temperature and pressure To be catalyzed nitrogen and hydrogen synthesis ammonia, it is considered to be one of the important invention in 20th century.Iron catalyst was ground by more than 100 years Study carefully, although obtaining very big raising in catalysis ammonia synthesis, do not change harsh reaction condition, and high energy consumption, The problems such as high cost, is not improved still, and the development of small ammonia compound probability is limited.Ruthenium-based catalyst is in relative low temperature Under show higher ammonia synthesis catalytic performance, be that second generation ammonia synthesis catalyst has been known as since iron catalyst.Nearly 20 Nian Lai, it is expensive due to noble metal Ru although ruthenium-based catalyst is widely studied, and in the item of industrial ammonia synthesis Under part, load ruthenium catalyst is easy sintering, and activity is affected, greatly limits reality of the ruthenium catalyst in ammonia synthesis and answer With.
So seeking one kind in a mild condition, the ammonia synthesis catalyst that can reduce the high stability of energy consumption and cost is The project most challenged.
Summary of the invention
The purpose of the present invention is to provide a kind of ruthenium based perovskite type composite oxides ammonia synthesis catalyst and its preparation sides Method, solve it is generally existing at high cost during ammonia synthesis, it is complicated for operation the problems such as, catalyst produced by the present invention can be in temperature Higher catalytic oxidation activity is showed under the conditions of.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of ruthenium based perovskite type composite oxides ammonia synthesis catalyst, chemical formula LaCo1-xRuxO3, wherein 0≤x≤1.
Using soluble lanthanum salt, soluble cobalt and soluble ruthenium salt as raw material, citric acid leads to the catalyst as complexing agent It crosses sol-gal process to be made, specifically comprise the following steps:
(1) soluble lanthanum salt, soluble cobalt and soluble ruthenium salt are dissolved in deionized water, form mixed solution a；
(2) citric acid is added, stirring forms mixed solution b；
(3) mixed solution b is subjected to heating stirring processing with evaporation water；
(4) product prepared by step (3) is dried；
(5) product of step (4) after dry is placed in Muffle furnace, through high-temperature roasting, obtains the catalyst LaCo1- xRuxO3, wherein 0≤x≤1.
The solubility lanthanum salt is LaCl3、La(NO3)3And La2(SO4)3One of.
The soluble cobalt is CoCl2、Co(NO3)2、CoSO4And CoCO3One of.
The solubility ruthenium salt is RuCl3, one of nitric acid ruthenium and acetic acid ruthenium.
The amount of the substance of total metal ion and citric acid of the solubility lanthanum salt, soluble cobalt and soluble ruthenium salt Ratio is 0.5-1.5.
Heating temperature is 70-90 DEG C in step (3), and the amount of evaporation water is the 1/5-1/2 of original solution weight.
Drying temperature is 90-130 DEG C in step (4), and drying time is 8-24 h.
Roasting process in step (5) is carried out in two steps, and the heating rate of the first one-step baking is 1-4 DEG C/min, roasting temperature Degree is 200-400 DEG C, and calcining time is 2-3 h；The heating rate of second one-step baking is 1-4 DEG C/min, and maturing temperature is 700-900 DEG C, calcining time is 3-5 h.
Using: the catalyst LaCo1-xRuxO3, wherein 0≤x≤1, in low temperature (350-450 DEG C) and low pressure (0.3-5 MPa the synthesis of ammonia is used under).
Remarkable advantage of the invention is:
1. perovskite type composite oxide catalyst (LaCo provided by the invention1-xRuxO3, 0≤x≤1) and answering in ammonia synthesis With noble ruthenium being entrained in perovskite composite oxides be used for ammonia synthesis field for the first time, showed during ammonia synthesis High-caliber catalytic activity and stability out have widened the application field of perovskite type composite oxide catalyst significantly.
2. LaCo has been prepared by sol-gal process in the present invention0.99Ru0.01O3、LaCo0.98Ru0.02O3Catalyst, Gained catalyst shows higher catalytic oxidation activity in lower temperature and low pressure range.
3. catalyst ammonia synthesis effect provided by the invention is better than traditional ammonia synthesis catalyst, and its preparation process Simply, easy to operate, at low cost, ammonia synthesis rate is high, has apparent industrial application value.
Detailed description of the invention
Fig. 1 is embodiment 1-2 and the XRD diagram of comparative example 1-2 gained catalyst.
Fig. 2 is ammonia synthesis rate of the catalyst obtained by embodiment 1-2 and comparative example 1-2 in different temperature points.
Fig. 3 is the stability that embodiment 1 and 2 gained catalyst of comparative example measure catalyst at 450 DEG C and 475 DEG C.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention Technical solution is described further, and exemplary embodiment of the invention and its explanation for explaining only the invention, are not made For limitation of the invention.
Embodiment 1
Step A weighs 0.1429 g Co (NO3)2·6H2O、0.2165 g La(NO3)3·6H2O and 0.0024 g RuCl3·H2O is dissolved in 50mL deionized water, is stirred on magnetic stirring apparatus, and dissolution forms mixed solution a；
Step B, the citric acid for weighing 0.2101 g are added in mixed solution a, and quickly stirring 30 minutes, form mixed solution b；
Mixed solution b is transferred in oil bath pan by step C, is carried out heating stirring, is maintained 80 DEG C of evaporation waters, evaporate Moisture weight be original solution weight 1/5-1/2；
Step D the step C product prepared is dried, through 120 DEG C of dry 12 h；
Product prepared by step D is placed in Muffle furnace by step E, is warming up to 350 DEG C of 2 h of maintenance with the rate of 2 DEG C/min 800 DEG C are warming up to again with the rate of 2 DEG C/min to be labeled as through 4 h of high-temperature roasting to get the catalyst LaCo0.99Ru0.01O3。
Embodiment 2
Step A weighs 0.1412 g Co (NO3)2·6H2O、0.2165 g La(NO3)3·6H2O and 0.0041 g RuCl3·H2O is dissolved in 50 mL deionized waters, is stirred on magnetic stirring apparatus, and dissolution forms mixed solution a；
Step B, the citric acid for weighing 0.2101 g are added in mixed solution a, and quickly stirring 30 minutes, form mixed solution b；
Mixed solution b is transferred in oil bath pan by step C, is carried out heating stirring, is maintained 80 DEG C of evaporation waters, evaporate Moisture weight be original solution weight 1/5-1/2；
Step D the step C product prepared is dried, through 120 DEG C of dry 12 h；
Product prepared by step D is placed in Muffle furnace by step E, is warming up to 350 DEG C of 2 h of maintenance with the rate of 2 DEG C/min 800 DEG C are warming up to again with the rate of 2 DEG C/min to be labeled as through 4 h of high-temperature roasting to get the catalyst LaCo0.98Ru0.02O3。
Comparative example 1
Step A weighs 0.1455 g Co (NO3)2·6H2O and 0.2165 g La (NO3)3·6H2O is dissolved in 50 mL deionizations It in water, is stirred on magnetic stirring apparatus, dissolution forms mixed solution a；
Step B, the citric acid for weighing 0.2101 g are added in mixed solution a, and quickly stirring 30 minutes, form mixed solution b；
Mixed solution b is transferred in oil bath pan by step C, is carried out heating stirring, is maintained 80 DEG C of evaporation waters, evaporate Moisture weight be original solution weight 1/5-1/2；
Step D the step C product prepared is dried, through 120 DEG C of dry 12 h；
Product prepared by step D is placed in Muffle furnace by step E, is warming up to 350 DEG C of 2 h of maintenance with the rate of 2 DEG C/min 800 DEG C are warming up to through 4 h of high-temperature roasting to get catalyst label L aCoO again with the rate of 2 DEG C/min3。
Comparative example 2
Step A weighs 0.1455 g Co (NO3)2·6H2O and 0.2165 g La (NO3)3·6H2O is dissolved in 50 mL deionizations It in water, is stirred on magnetic stirring apparatus, dissolution forms mixed solution a；
Step B, the citric acid for weighing 0.2101 g are added in mixed solution a, and quickly stirring 30 minutes, form mixed solution b；
Mixed solution b is transferred in oil bath pan by step C, is carried out heating stirring, is maintained 80 DEG C of evaporation waters, evaporate Moisture weight be original solution weight 1/5-1/2；
Step D the step C product prepared is dried, through 120 DEG C of dry 12 h；
Product 1 prepared by step D is placed in Muffle furnace by step E, is warming up to 350 DEG C with the rate of 2 DEG C/min and is maintained 2 H is warming up to 800 DEG C through 4 h of high-temperature roasting with the rate of 2 DEG C/min again；
Product 2 prepared by step E is placed in glass dish, uses RuCl by step F3·H2The solution dipping that O is configured to is negative 1 wt%Ru is carried, salting liquid used point is repeatedly impregnated on a small quantity；
Product 3 prepared by step F is dried step G, through 100 DEG C of dry 10 h；
Product 4 prepared by step G is placed in Muffle furnace by step H, is warming up to 300 DEG C with the rate of 2 DEG C/min and is maintained 3 H is labeled as Ru/LaCoO up to catalyst3。
Catalyst performance evaluation
XRD characterization is carried out according to the catalyst that embodiment 1-2 and comparative example 1-2 are synthesized, the result of partial enlargement is shown in figure 1.As can be seen from Figure 1 two main diffraction peaks correspond respectively to LaCoO in 32.9 ° and 33.3 °3(1-10) and (211) crystal face, when Ru is introduced into perovskite LaCoO3The position B on when, it can be found that diffraction maximum to the direction of low angle deviate, Illustrate the biggish Ru of radius3+It enters in the lattice of perovskite.
Each 0.45 g of catalyst of embodiment 1-2 and comparative example 1-2,10,000 mL/ (g of mass space velocity is respectively adopted H), the active measurement of ammonia synthesis is carried out in a stainless steel reactor, ammonia concentration variation is surveyed by ion chromatography in tail gas It is fixed, reaction gas composition are as follows: 25%N2- 75%H2Gaseous mixture.Catalyst is measured at 150-450 DEG C to ammonia synthesis rate, is surveyed Test result is shown in Fig. 2.As can be seen from Figure 2 Ru is introduced into Ru/ of the catalyst on the position B of perovskite relative to load LaCoO3Show higher catalytic activity.
Each 0.45 g of catalyst of embodiment 1 and comparative example 2,60,000 mL/ (gh) of mass space velocity is respectively adopted, The active measurement of ammonia synthesis is carried out in one stainless steel reactor, ammonia concentration variation is by ion chromatography in tail gas, instead Answer gas composition are as follows: 25%N2-75%H2Gaseous mixture.Reaction process is that the stabilization of catalyst is measured at 450 DEG C and 475 DEG C Property, test result is shown in Fig. 3.As can be seen from Figure 3 the Ru catalyst being introduced on the position B of perovskite is shown preferable steady It is qualitative.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (10)

1. a kind of ruthenium based perovskite type composite oxides ammonia synthesis catalyst, it is characterised in that: ruthenium based perovskite type combined oxidation The chemical formula of object catalyst is LaCo1-xRuxO3, wherein 0≤x≤1.
2. a kind of method for preparing ruthenium based perovskite type composite oxides ammonia synthesis catalyst as described in claim 1, special Sign is: using soluble lanthanum salt, soluble cobalt and soluble ruthenium salt as raw material, citric acid leads to the catalyst as complexing agent It crosses sol-gal process to be made, specifically comprise the following steps:
(1) soluble lanthanum salt, soluble cobalt and soluble ruthenium salt are dissolved in deionized water, form mixed solution a；
(2) citric acid is added, stirring forms mixed solution b；
(3) mixed solution b is subjected to heating stirring processing with evaporation water；
(4) product prepared by step (3) is dried；
(5) product of step (4) after dry is placed in Muffle furnace, through high-temperature roasting, obtains the catalyst LaCo1-xRuxO3, Wherein 0≤x≤1.
3. the method according to claim 2, it is characterised in that: the solubility lanthanum salt is LaCl3、La(NO3)3And La2 (SO4)3One of.
4. the method according to claim 2, it is characterised in that: the soluble cobalt is CoCl2、Co(NO3)2、CoSO4 And CoCO3One of.
5. according to the method described in claim 2, it is characterized by: the solubility ruthenium salt is RuCl3, nitric acid ruthenium and acetic acid ruthenium One of.
6. according to the method described in claim 2, it is characterized by: the solubility lanthanum salt, soluble cobalt and soluble ruthenium The ratio of the amount of the substance of total metal ion and citric acid of salt is 0.5-1.5.
7. according to the method described in claim 2, it is characterized by: in step (3) heating temperature be 70-90 DEG C, evaporation water Amount be original solution weight 1/5-1/2.
8. according to the method described in claim 2, it is characterized by: in step (4) drying temperature be 90-130 DEG C, drying time For 8-24 h.
9. according to the method described in claim 2, it is characterized by: the roasting process in step (5) is carried out in two steps, the first step The heating rate of roasting is 1-4 DEG C/min, and maturing temperature is 200-400 DEG C, and calcining time is 2-3 h；Second one-step baking Heating rate is 1-4 DEG C/min, and maturing temperature is 700-900 DEG C, and calcining time is 3-5 h.
10. a kind of application of ruthenium based perovskite type composite oxides ammonia synthesis catalyst as described in claim 1, feature exist In the catalyst LaCo1-xRuxO3, wherein 0≤x≤1, is used for the synthesis of ammonia under 350-450 DEG C and 0.3-5 MPa.
CN201811398031.1A 2018-11-22 2018-11-22 A kind of ruthenium based perovskite type composite oxides ammonia synthesis catalyst and preparation method thereof Pending CN109529873A (en)

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Cited By (1)

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WO2023045218A1 (en) * 2021-09-26 2023-03-30 江南大学 ABO3 TYPE HIGH-ENTROPY PEROVSKITE BAX(FECONIZRY)0.2O3-δ ELECTROCATALYTIC MATERIAL AND PREPARATION THEREFOR

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