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 PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 31
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 19
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 150000002603 lanthanum Chemical class 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 150000003303 ruthenium Chemical class 0.000 claims description 7
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims description 2
- 229910002249 LaCl3 Inorganic materials 0.000 claims description 2
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 2
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical group Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 2
- 238000010792 warming Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000003643 water by type Substances 0.000 description 5
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002254 LaCoO3 Inorganic materials 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- -1 ammonia compound Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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
- B01J23/89—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)
- Catalysts (AREA)
Abstract
本发明属于催化剂材料制备领域，具体涉及一种钌基钙钛矿型复合氧化物氨合成催化剂及其制备方法。本发明制备的钌基钙钛矿型复合氧化物氨合成在400 oC和1 MPa下呈现出优异的氨合成性能和较好的热稳定性，钌掺杂在钙钛矿的B位上相比于直接用Ru浸渍在钙钛矿上呈现出较高的催化性能，同时且该类催化剂具有极高的热稳定性，相对于钌负载型的催化剂，具有明显的工业应用价值。
The invention belongs to the field of catalyst material preparation, in particular to a ruthenium-based perovskite-type composite oxide ammonia synthesis catalyst and a preparation method thereof. The ruthenium-based perovskite-type composite oxide prepared by the present invention exhibits excellent ammonia synthesis performance and good thermal stability at 400 o C and 1 MPa, and ruthenium is doped on the B-site of the perovskite. Compared with directly impregnating perovskite with Ru, it shows higher catalytic performance, and at the same time, this type of catalyst has extremely high thermal stability, and has obvious industrial application value compared with ruthenium-supported catalyst.
Description
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.
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| CN116116412A (en) * | 2023-02-02 | 2023-05-16 | 安徽枡水新能源科技有限公司 | Preparation method of catalyst for synthesizing ammonia at low temperature and low pressure |
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