CN110302778A - A kind of charcoal loading ruthenium ammonia synthesis catalyst and preparation method thereof - Google Patents

A kind of charcoal loading ruthenium ammonia synthesis catalyst and preparation method thereof Download PDF

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CN110302778A
CN110302778A CN201910604326.8A CN201910604326A CN110302778A CN 110302778 A CN110302778 A CN 110302778A CN 201910604326 A CN201910604326 A CN 201910604326A CN 110302778 A CN110302778 A CN 110302778A
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ammonia synthesis
carbon materials
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synthesis catalyst
charcoal
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CN110302778B (en
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李瑛�
马永承
韩文锋
刘化章
唐浩东
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Zhejiang University of Technology ZJUT
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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/25—Nitrates
    • 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
    • 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 belongs to catalyst fields, specifically disclose a kind of charcoal loading ruthenium ammonia synthesis catalyst and preparation method thereof, 1) Carbon Materials the following steps are included: be impregnated in metal nitrate saline solution by preparation method, Carbon Materials drying after dipping is placed in tube furnace again, it is warming up to 600~1000 DEG C of 5~30min of roasting under an inert atmosphere, the modified Carbon Materials of metal nitrate are made；2) modified Carbon Materials are impregnated in ruthenium trichloride aqueous solution, precipitating reagent is added, then Carbon Materials modified after dipping are washed, are dried, obtain the charcoal loading ruthenium ammonia synthesis catalyst.The method of the present invention is easy to operate, avoids the use of acid solution, and the ammonia synthesis speed ratio tradition ruthenium catalyst of the catalyst is high by 50% or more, substantially increase catalyst ammino is Viability and heat-resistant stability.

Description

A kind of charcoal loading ruthenium ammonia synthesis catalyst and preparation method thereof
Technical field
The present invention relates to catalyst fields, and in particular to a kind of charcoal loading ruthenium ammonia synthesis catalyst and preparation method thereof.
Background technique
Ammonia synthesis is the pillar industry of chemical industry, as chemical fertilizer and one of the raw material of various nitrogenous chemicals, to agricultural Production has vital influence.In addition to this, ammonia has carbon-free, high-content hydrogen accounting, easily stored and transport property, It can also be used as the energy carrier of hydrogen storage and conversion, therefore, ammonia is considered occupying important function in the future economy.
Ruthenium catalyst is known as the second generation ammonia synthesis catalyst due to excellent performance, and current ratio has wide application prospects Ruthenium catalyst formed with high-area carbon, active metal ruthenium and auxiliary agent three parts.Publication No. CN101053834A, The Patent Application Publication of CN101579627A, CN105413683A, CN108435166A, CN104084197A etc. describe in detail The preparation method of ruthenium catalyst, it can be seen that the active component in ruthenium catalyst is mainly using ruthenium trichloride as precursor, wherein disclosing Number be also well described the method that effectively removes of chloride ion for the Patent Application Publication of CN101053834A, it is adjuvant used mainly with Based on alkali metal, alkaline-earth metal and rare earth metal.
In general, when preparing charcoal loading ruthenium ammonia synthesis catalyst, high-area carbon is placed in hydrogen atmosphere first, in 10-20h is handled at a temperature of 800-1000 DEG C, removes the elements such as chlorine, sulphur, nitrogen, the oxygen on high-area carbon surface, then often selects acid solution Liquid phase oxidation Carbon Materials promote the dispersion of active component ruthenium to become second nature with the ammino for improving ruthenium catalyst to introduce oxygen-containing functional group Energy.However this method can not only generate waste acid liquor and cause serious environmental pollution, but also Catal.Sci.Technol., 2015,5,2829-2838, which reports high-area carbon surface oxygen groups, gasified reverse occurs with high-area carbon under the conditions of ammonia synthesis reaction High-area carbon structure should be destroyed, to reduce the stability of catalyst.
Therefore, for preparing for the ruthenium catalyst with higher ammonia synthesis performance, active component cannot be considered merely It influences, the interaction between dispersion and auxiliary agent and high-area carbon of the auxiliary agent on high-area carbon equally will affect the ammino of ruthenium catalyst At performance.
Summary of the invention
The object of the present invention is to provide a kind of charcoal loading ruthenium ammonia synthesis catalyst and preparation method thereof, the preparation sides Method is easy to operate, not only avoids the use of acid solution, also improve catalyst obtained ammino is Viability and Heat-resistant stable Property.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of preparation method of charcoal loading ruthenium ammonia synthesis catalyst, comprising the following steps:
(1) Carbon Materials are impregnated in metal nitrate saline solution, then Carbon Materials drying after dipping is placed on tube furnace In, it is warming up to 600~1000 DEG C of 5~30min of roasting under an inert atmosphere, the modified Carbon Materials of metal nitrate are made；
(2) the modification Carbon Materials that step (1) obtains are impregnated in ruthenium trichloride aqueous solution, precipitating reagent are added, then will leaching Modified Carbon Materials are washed, are dried after stain, obtain the charcoal loading ruthenium ammonia synthesis catalyst.
The method of the present invention by auxiliary agent nitrate compound and high-area carbon it is compound after be heat-treated, utilize metal nitrate It decomposes, the defect content for not only increasing high-area carbon surface further stabilizes ruthenium nano particle, but also auxiliary agent can be improved and exist The interaction force between dispersion and reinforcing aids and high-area carbon on high-area carbon, improve ruthenium catalyst ammino it is Viability and Heat-resistant stability.
In step (1), the Carbon Materials first pass through pretreatment, pretreatment specifically: Carbon Materials are washed with deionized water It washs, is warming up to 80~140 DEG C of dryings, then be placed in atmosphere of hydrogen and carry out high-temperature process.Above-mentioned preprocessing process first washs removing The dust of charcoal material surface recycles hydrogen high-temperature process to remove the species such as chlorine, sulphur, nitrogen, the oxygen of charcoal material surface.
The Carbon Materials are cocoanut active charcoal, carbon nanotube or high-specific surface area graphite.Carbon Materials are preferably coconut activated Charcoal is Viability higher with heat-resistant stability using the ammino of catalyst made from cocoanut active charcoal.
The metal nitrate is IA or Group IIA metal nitrate, preferably barium nitrate (Ba (NO3)2), potassium nitrate (KNO3) or cesium nitrate (CsNO3)。
Preferably, being warming up to 600~850 DEG C of 10~15min of roasting under an inert atmosphere, roasted under this roasting condition Auxiliary agent can be sufficiently improved afterwards in the dispersion degree of charcoal material surface, further increase the defect level of charcoal material surface.
The inert gas is one of nitrogen, helium or argon gas or a variety of, and the flow of gas is 30~100mL/ min。
In step (2), the precipitating reagent is the dilute ammonia solution that volumetric concentration is 5~20%.With the quality of Carbon Materials Meter, the volumetric usage of the precipitating reagent are 10~20mL/g；Sedimentation time is 6~14h.Precipitating reagent is added by Ru3+It is sunk It forms sediment, and removing precipitating is washed with deionized in benefit, obtains ruthenium-based catalyst after dry.
In step (1) and step (2), the temperature of the dipping is 20~50 DEG C, and dip time is 8~14h.
In step (1) and step (2), the temperature of the drying is 80~140 DEG C, dry to constant weight.
The mass ratio of the metal nitrate, ruthenium trichloride and Carbon Materials is 4~30:5~10:100.
The invention also discloses charcoal loading ruthenium ammonia synthesis catalyst made from above-mentioned preparation method, which has pole Good ammino is Viability and heat-resistant stability, has a good application prospect in ammonia synthesis industry.
Compared with the prior art, the present invention has the following beneficial effects:
(1) the method for the present invention is easy to operate, avoids the use of acid solution, alleviates the pressure of environmental protection caused by waste acid liquor Power facilitates the scale application of ruthenium catalyst.
(2) the method for the present invention substantially increase catalyst ammino is Viability and heat-resistant stability, ruthenium catalysis obtained The ruthenium catalyst that the ammonia synthesis speed ratio tradition of agent is not thermally treated is high by 50% or more；And in 5MPa, 500 DEG C and 30000h-1Item Under part after heat-resisting 14h, the ammonia synthesis rate of catalyst of the present invention be can be further improved, and be demonstrated by good Heat-resistant stable Property.
Detailed description of the invention
Fig. 1 is the TEM phenogram of ammonia synthesis catalyst made from embodiment 1, wherein (a) is that cocoanut active charcoal loads nitre Sour barium (b) loads barium nitrate for the coconut husk charcoal after 850 DEG C of roastings.
Specific embodiment
The present invention is further illustrated by the following examples, but protection scope of the present invention is not limited to following reality Apply example.
Embodiment 1:
(1) 15.2g barium nitrate is taken to be dissolved in the deionized water of 180mL, as maceration extract A；It is dry extremely that 100g is weighed again Cocoanut active charcoal is added in maceration extract A after the pretreatment of constant weight, after impregnating 12h under the conditions of 25 DEG C, in 120 DEG C of forced air drying It dries in case to constant weight；
(2) sample after will be dry in step (1) is placed in tube furnace, is warming up to 850 DEG C of roastings under an argon atmosphere The modified cocoanut active charcoal of barium nitrate is made in 10min；
(3) 10g ruthenium trichloride is taken to be dissolved in the deionized water of 180mL, as maceration extract B；It is again that step (2) is obtained The modified cocoanut active charcoal of barium nitrate is added in maceration extract B, after impregnating 12h under the conditions of 25 DEG C, is directly added into the volume of 1000mL 12h is impregnated in the dilute ammonia solution that concentration is 10%, is finally sufficiently washed using deionized water, until filtrate silver nitrate solution Until detection is without white precipitate, dry to constant weight in 120 DEG C of air dry oven up to charcoal loading ruthenium ammonia synthesis catalyst.
Embodiment 2:
(1) 15.2g barium nitrate is taken to be dissolved in the deionized water of 180mL, as maceration extract A；It is dry extremely that 100g is weighed again Cocoanut active charcoal is added in maceration extract A after the pretreatment of constant weight, after impregnating 12h under the conditions of 25 DEG C, in 120 DEG C of forced air drying It dries in case to constant weight；
(2) sample after will be dry in step (1) is placed in tube furnace, is warming up to 600 DEG C of roastings under an argon atmosphere The modified cocoanut active charcoal of barium nitrate is made in 10min；
(3) 10g ruthenium trichloride is taken to be dissolved in the deionized water of 180mL, as maceration extract B；Step (2) is obtained again The modified cocoanut active charcoal of barium nitrate is added in maceration extract B, after impregnating 12h under the conditions of 25 DEG C, is directly added into the volume of 1000mL 12h is impregnated in the dilute ammonia solution that concentration is 10%, is finally sufficiently washed using deionized water, until filtrate silver nitrate solution Until detection is without white precipitate, dry to constant weight in 120 DEG C of air dry oven up to charcoal loading ruthenium ammonia synthesis catalyst.
Embodiment 3:
(1) 15.2g barium nitrate is taken to be dissolved in the deionized water of 180mL, as maceration extract A；It is dry extremely that 100g is weighed again Cocoanut active charcoal is added in maceration extract A after the pretreatment of constant weight, after impregnating 12h under the conditions of 25 DEG C, in 120 DEG C of forced air drying It dries in case to constant weight；
(2) sample after will be dry in step (1) is placed in tube furnace, is warming up to 1000 DEG C of roastings under an argon atmosphere The modified cocoanut active charcoal of barium nitrate is made in 10min；
(3) 10g ruthenium trichloride is taken to be dissolved in the deionized water of 180mL, as maceration extract B；Step (2) is obtained again The modified cocoanut active charcoal of barium nitrate is added in maceration extract B, after impregnating 12h under the conditions of 25 DEG C, is directly added into the volume of 1000mL 12h is impregnated in the dilute ammonia solution that concentration is 10%, is finally sufficiently washed using deionized water, until filtrate silver nitrate solution Until detection is without white precipitate, dry to constant weight in 120 DEG C of air dry oven up to charcoal loading ruthenium ammonia synthesis catalyst.
Embodiment 4:
(1) 20.6g potassium nitrate is taken to be dissolved in the deionized water of 180mL, as maceration extract A；It is dry extremely that 100g is weighed again Cocoanut active charcoal is added in maceration extract A after the pretreatment of constant weight, after impregnating 12h under the conditions of 25 DEG C, in 120 DEG C of forced air drying It dries in case to constant weight；
(2) sample after will be dry in step (1) is placed in tube furnace, is warming up to 600 DEG C of roastings under an argon atmosphere The modified cocoanut active charcoal of potassium nitrate is made in 10min；
(3) 10g ruthenium trichloride is taken to be dissolved in the deionized water of 180mL, as maceration extract B；Step (2) is obtained again The modified cocoanut active charcoal of barium nitrate is added in maceration extract B, after impregnating 12h under the conditions of 25 DEG C, is directly added into the volume of 1000mL 12h is impregnated in the dilute ammonia solution that concentration is 10%, is finally sufficiently washed using deionized water, until filtrate silver nitrate solution Until detection is without white precipitate, dry to constant weight in 120 DEG C of air dry oven up to charcoal loading ruthenium ammonia synthesis catalyst.
Comparative example 1:
(1) 15.2g barium nitrate is taken to be dissolved in the deionized water of 180mL, as maceration extract A；It is dry extremely that 100g is weighed again Cocoanut active charcoal is added in maceration extract A after the pretreatment of constant weight, after impregnating 12h under the conditions of 25 DEG C, in 120 DEG C of forced air drying It dries in case to constant weight；
(2) 10g ruthenium trichloride is taken to be dissolved in the deionized water of 180mL, as maceration extract B；Step (1) is obtained again Sample is added in maceration extract B, after impregnating 12h under the conditions of 25 DEG C, is directly added into the weak aqua ammonia that the volumetric concentration of 1000mL is 10% 12h is impregnated in solution, is finally sufficiently washed using deionized water, until filtrate is without white precipitate with silver nitrate solution detection Only, it dries in 120 DEG C of air dry oven to constant weight.
Embodiment 5:
(1) 15.2g barium nitrate is taken to be dissolved in the deionized water of 560mL, as maceration extract A；It is dry extremely that 100g is weighed again The pretreatment carbon nanotube of constant weight is added in maceration extract A, after impregnating 12h under the conditions of 25 DEG C, in 120 DEG C of air dry oven It dries to constant weight；
(2) sample after will be dry in step (1) is placed in tube furnace, is warming up to 600 DEG C of roastings under an argon atmosphere 10min obtains barium nitrate modified carbon nano-tube；
(3) 10g ruthenium trichloride is taken to be dissolved in the deionized water of 560mL, as maceration extract B；It is again that step (2) is obtained Barium nitrate modified carbon nano-tube is added in maceration extract B, and after impregnating 12h under the conditions of 25 DEG C, the volume for being directly added into 1000mL is dense Degree is finally sufficiently washed using deionized water, to impregnate 12h in 10% dilute ammonia solution until filtrate is examined with silver nitrate solution Until surveying without white precipitate, dry to constant weight in 120 DEG C of air dry oven up to charcoal loading ruthenium ammonia synthesis catalyst.
Comparative example 2:
(1) 15.2g barium nitrate is taken to be dissolved in the deionized water of 560mL, as maceration extract A；It is dry extremely that 100g is weighed again The pretreatment carbon nanotube of constant weight is added in maceration extract A, after impregnating 12h under the conditions of 25 DEG C, in 120 DEG C of air dry oven It dries to constant weight；
(2) 10g ruthenium trichloride is taken to be dissolved in the deionized water of 560mL, as maceration extract B；It is again that step (1) is obtained Sample is added in maceration extract B, after impregnating 12h under the conditions of 25 DEG C, is directly added into dilute ammonia that the volumetric concentration of 1000mL is 10% 12h is impregnated in aqueous solution, is finally sufficiently washed using deionized water, until filtrate is without white precipitate with silver nitrate solution detection Only, it dries to constant weight in 120 DEG C of air dry oven up to charcoal loading ruthenium ammonia synthesis catalyst.
Performance test:
The activity rating of catalyst carries out in high pressure activating test device, and reactor is the fixed bed of internal diameter 14mm.It urges Catalyst particles are 1.0~1.4mm, and stacking volume 2mL, Catalyst packing is in the isothermal region of reactor；Reaction gas is nitrogen With the gaseous mixture of hydrogen, H-N ratio 3:1.
The following table 1 lists catalyst made from above-described embodiment and comparative example at 400 DEG C, 10MPa, 10000h-1Under the conditions of Ammonia synthesis the performance test results.
The ammonia synthesis reaction rate of 1 ruthenium catalyst of table
As shown in Table 1, under the conditions of identical high-area carbon, the ammonia synthesis rate of ruthenium catalyst produced by the present invention can be than not Thermally treated ruthenium catalyst is high by 50% or more；In 5MPa, 500 DEG C and 30000h-1Under the conditions of after heat-resisting 14h, the ammonia of catalyst Synthesis rate is demonstrated by good heat-resistant stability there is no declining, and has preferable industrial prospect.

Claims (10)

1. a kind of preparation method of charcoal loading ruthenium ammonia synthesis catalyst, comprising the following steps:
(1) Carbon Materials are impregnated in metal nitrate saline solution, then Carbon Materials drying after dipping is placed in tube furnace, It is warming up to 600~1000 DEG C of 5~30min of roasting under inert atmosphere, the modified Carbon Materials of metal nitrate are made；
(2) the modification Carbon Materials that step (1) obtains are impregnated in ruthenium trichloride aqueous solution, precipitating reagent are added, then will be after dipping Modified Carbon Materials are washed, are dried, and the charcoal loading ruthenium ammonia synthesis catalyst is obtained.
2. the preparation method of charcoal loading ruthenium ammonia synthesis catalyst according to claim 1, which is characterized in that step (1) In, the Carbon Materials first pass through pretreatment, pre-process actual conditions are as follows: Carbon Materials are washed with deionized, are warming up to 80 ~140 DEG C of dryings, then be placed in atmosphere of hydrogen and carry out high-temperature process.
3. the preparation method of charcoal loading ruthenium ammonia synthesis catalyst according to claim 1, which is characterized in that step (1) In, the Carbon Materials are cocoanut active charcoal, carbon nanotube or high-specific surface area graphite.
4. the preparation method of charcoal loading ruthenium ammonia synthesis catalyst according to claim 1, which is characterized in that step (1) In, the metal nitrate is IA or Group IIA metal nitrate.
5. the preparation method of charcoal loading ruthenium ammonia synthesis catalyst according to claim 1, which is characterized in that step (1) In, it is warming up to 600~850 DEG C of 10~15min of roasting under an inert atmosphere.
6. the preparation method of charcoal loading ruthenium ammonia synthesis catalyst according to claim 1, which is characterized in that step (2) In, the precipitating reagent is the dilute ammonia solution that volumetric concentration is 5~20%.
7. the preparation method of charcoal loading ruthenium ammonia synthesis catalyst according to claim 6, which is characterized in that with Carbon Materials Quality meter, the volumetric usage of the precipitating reagent is 10~20mL/g, and the sedimentation time is 6~14h.
8. the preparation method of charcoal loading ruthenium ammonia synthesis catalyst according to claim 1, which is characterized in that step (1) In step (2), the temperature of the dipping is 20~50 DEG C, and dip time is 8~14h.
9. the preparation method of charcoal loading ruthenium ammonia synthesis catalyst according to claim 1, which is characterized in that the gold The mass ratio of genus nitrobacter, ruthenium trichloride and Carbon Materials is 4~30:5~10:100.
10. a kind of charcoal loading ruthenium ammonia synthesis catalyst, which is characterized in that by preparation side according to any one of claims 1 to 9 Method is made.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115532256A (en) * 2022-09-13 2022-12-30 福州大学 Ruthenium-based ammonia synthesis catalyst and preparation method and application thereof

Citations (1)

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Publication number Priority date Publication date Assignee Title
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Publication number Priority date Publication date Assignee Title
US4142993A (en) * 1977-12-07 1979-03-06 The Research Council Of Alberta Transition metal catalyst

Non-Patent Citations (1)

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Title
王晓南等: "活性炭负载钌基氨合成催化剂的制备和催化活性", 《催化学报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115532256A (en) * 2022-09-13 2022-12-30 福州大学 Ruthenium-based ammonia synthesis catalyst and preparation method and application thereof
CN115532256B (en) * 2022-09-13 2024-04-30 福州大学 Ruthenium-based ammonia synthesis catalyst and preparation method and application thereof

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