CN101322938B - Ruthenium-based ammonia synthetic catalyst and preparation thereof - Google Patents
Ruthenium-based ammonia synthetic catalyst and preparation thereof Download PDFInfo
- Publication number
- CN101322938B CN101322938B CN2008100714805A CN200810071480A CN101322938B CN 101322938 B CN101322938 B CN 101322938B CN 2008100714805 A CN2008100714805 A CN 2008100714805A CN 200810071480 A CN200810071480 A CN 200810071480A CN 101322938 B CN101322938 B CN 101322938B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ruthenium
- sintering
- preparation
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a Ru-based ammonia synthesis catalyst and a preparation method thereof. The catalyst takes magnesium oxide as a carrier, metal ruthenium as an active constituent and at least one of alkali metal, alkaline earth metal or rare earth metal as an assistant; the composition is Ru-M1/MgO, Ru-M2/MgO, Ru-M1-M2/MgO or Ru-(M1+M2)/MgO and the preparation method is as follows: the precursor, Ru-magnesium hydroxide catalyst, is prepared by a coprecipitation and dipping method: magnesium nitrate and ruthenium chloride are dissolved in water; the mixed solution is added into an alkaline solution to generate a precipitation; the precipitation is centrifugally washed, dried, sintered by reduction or soaked by equivoluminal soaking auxiliary after sintering, thus obtaining the catalyst that is required. The catalyst prepared by the synthesis method of the invention has good performance, relatively cheap raw material that is required, low energy consumption as well as simple devices and flow; besides, the catalyst is beneficial to reducing the cost and realizing mass production.
Description
Technical field
The invention belongs to the ammonia synthesis catalyst preparing technical field, more specifically relate to a kind of ruthenium-based ammonia synthetic catalyst and preparation method thereof.
Background technology
Ammonia synthesis catalyst is a most important catalyst in the ammonia synthesizing industry.The 80s and 90s in last century, people just after deliberation the application of various oxides in ruthenium-based ammonia synthetic catalyst, some early stage documents have been introduced the achievement in research of this part: i.e. the ammonia synthesis of ruthenium catalyst is active general relevant with the alkalescence (electronegativity) of support oxide, the alkalescence of carrier big more (electronegativity is more little), activity of such catalysts is good more, during as 673K, 80kPa, with Ru
3(CO)
12The active order of ruthenium catalyst ammonia synthesis for preparing for presoma is as follows: Ru/MgO>Ru/CaO>Ru/Al
2O
3>Ru/Nb
2O
5=Ru/TiO
2But also found some problems, less as the MgO specific area that alkalescence is the strongest; And for fear of the adverse effect of chlorion to catalyst activity, the ruthenium presoma generally all uses expensive ruthenium presoma such as ruthenium, use the nonaqueous solvents oxolane to handle ruthenium simultaneously, the carrier of low specific surface, expensive ruthenium presoma and complicated load program have had a strong impact on the application of ruthenium/magnesia catalyst in ammonia synthesis.In recent years, Chinese scholars had been carried out a large amount of research to ruthenium/magnesia catalyst.People have proposed the method for multiple raising ammonia synthesis activity from the selection of ruthenium presoma, the preparation of magnesium oxide carrier, the approach such as improvement of load program, as the ruthenium sol-gel process, and magnesium sol-gel process, method such as magnesium oxide modified.Nearest Catalysis Communication (Catal.Commun.2006,7,148-152) with Chemical communications (Chem Commun, 2003,2488-2489) all reported the ruthenium/magnesia catalyst that utilizes the ruthenium sol-gel process to prepare low temperature high activity, this method is reduced the ruthenium spent glycol in ruthenic chloride and the magnesium nitrate mixed solution earlier, directly hydro-oxidation sodium precipitation magnesium nitrate makes ruthenium/magnesia catalyst then, this method adopts relatively cheap ruthenic chloride and magnesium nitrate to make presoma, easy, economical, efficiently, but this method is in order to remove chlorion, need be before magnesium deposition the ruthenic chloride of spent glycol reduction in advance, and ruthenium also wants part to need to reclaim in solution after the magnesium deposition, preliminary treatment in the catalyst preparation process must cause the preparation procedure relative complex, and the recovery post processing of ruthenium also can cause the raising of preparation cost.Recently, and Catalysis Communication (Catal.Commun.2007,8,941-944) reported that a kind of magnesium sol-gel process prepares the method for ruthenium/magnesia catalyst.This method adopts Mg (OEt)
2Prepare the magnesium gel with ammoniacal liquor, utilize infusion process load ruthenium on gel then, make the catalyst of high-ratio surface, specific surface is up to 290~359m
2/ g is 4~7 times of commercial oxidation magnesium, but because Mg (OEt)
2And Ru
3(CO)
12Presoma all is relatively costly presoma, is unfavorable for using and promoting of catalyst.Directly the method for ruthenic chloride and magnesium nitrate prepared by co-precipitation ruthenium/magnesia catalyst is not appeared in the newspapers.
Summary of the invention
Purpose of the present invention provides a kind of preparation method of ruthenium-base ammonia synthetic catalyst, and the catalyst performance of this synthetic method preparation is good, and the raw material that needs is relatively cheap, and power consumption is few, and equipment, flow process are simple, help reducing cost, and accomplish scale production.
Ruthenium-based ammonia synthetic catalyst of the present invention is carrier with magnesia, and metal Ru is an active component, is auxiliary agent with in alkali metal, alkaline-earth metal or the rare earth metal one or more; Described catalyst consist of Ru-M1/MgO, Ru-M2/MgO or Ru-M1-M2/MgO; Wherein M1 is a barium nitrate, and M2 is one or more in alkali metallic sodium, potassium, rubidium, caesium, rare earth nitrades or the hydroxide.
The preparation method of ruthenium-based ammonia synthetic catalyst of the present invention is: described method for preparing catalyst is: adopt coprecipitation-immersion process for preparing catalyst, use coprecipitation to prepare ruthenium-magnesium hydroxide catalyst precursor, adopt infusion process load auxiliary agent: metal nitrate and ruthenic chloride is soluble in water, be made into mixed solution; Certain density precipitant solution is joined in the described mixed solution precipitation ageing a period of time of generation; After the repeatedly centrifugal washing of precipitate with deionized water after the ageing, oven dry, the incipient impregnation auxiliary agent promptly makes required catalyst behind reduction sintering or the sintering.
The present invention compared with prior art has following remarkable advantage:
A) to prepare ruthenium-oxide catalyst be coprecipitation in the present invention, and compared with prior art, technology of the present invention is simple, preparation efficiency height, less energy consumption.
B) it is ruthenic chloride that the present invention adopts the active component presoma, and solvent is a water, and the raw material relative price is cheap, helps reducing production costs significantly.
C) equipment required for the present invention is simple, and operation is easily gone, and realizes large-scale production easily.
D) performance of the catalyst of the present invention's preparation is good, and catalytic activity is strong.
The specific embodiment
Preparation process is:
1) solution preparation: by the chemical composition solution of the ruthenium that will prepare-magnesium hydroxide catalyst precursor, taking by weighing corresponding ruthenic chloride and metal nitrate respectively is dissolved in the deionized water, be made into metallic ion mixed liquor, the concentration of ruthenium ion is 0.03~0.12mol/L in the described metallic ion mixed liquor; The concentration of metal nitrate is 1~2mol/L in the described metallic ion mixed liquor; The preparation precipitant solution, described precipitant solution concentration is 0.1~4mol/L;
2) precipitation: precipitant solution is added in the metallic ion mixed liquor, stir simultaneously, intensification stops to stir and heating after boiling 0~10min, and centrifugal dewatering gets sediment;
3) washing: with step 2) sediment spends deionised water, and centrifugal dehydration is then so operated 6~10 times, till wash water is with the no chlorion of silver nitrate aqueous solution check;
4) oven dry: wet sediment dewaters 50-120 ℃ of drying with infrared lamp or with baking oven, obtains blocks of solid;
5) moulding: oven dry back powder sample extruded moulding, specification 3mm * 5mm;
6) sintering: the body sintering of in tube furnace, ventilating of the blocks of solid after will drying, sintering again behind the solid incipient impregnation auxiliary agent after maybe will drying, behind the described dipping auxiliary agent again the product sintering of sintering do not need to flood again auxiliary agent after intact, sintering temperature is 450~550 ℃, sintering time is 2 hours;
7) dipping auxiliary agent: the sintering afterproduct is plated auxiliary agent with the method for incipient impregnation, and used auxiliary agent is one or both in barium nitrate, potassium nitrate, potassium hydroxide, the cesium nitrate, and pickup is 1%~10% of a total catalyst weight;
8) drying: the product behind the dipping is dried down at 50-120 ℃ and is prepared into catalyst.
Described sintering gas is hydrogen-nitrogen mixture, and the volume ratio of described hydrogen and nitrogen is 3: 1, and perhaps sintering gas is hydrogen-argon gas gaseous mixture, and the volume ratio of described hydrogen and argon gas is 0.4~1: 1.
Metal nitrate is a magnesium nitrate.
Precipitating reagent is a kind of in potassium hydroxide, NaOH or the ammoniacal liquor, and the amount ratio of described precipitant solution and mixed solution is: the mol ratio of precipitating reagent potassium hydroxide, NaOH or ammoniacal liquor and magnesium nitrate is 0.5~3.Dry infrared lamp or the baking oven of adopting of product behind the dipping dried.
Ruthenic chloride generates chloride by precipitating, and chloride is by centrifugal deionized water washing and reduction, and middle chloride ion content has been reduced to 2% in the catalyst, and silver nitrate reagent detects does not have precipitation, and chlorine ion concentration is lower than 0.01% on x-ray photoelectron spectrometer device surface.
Embodiment 1
25.6g magnesium nitrate and 0.43g ruthenic chloride (with the magnesium oxide carrier quality is benchmark, contains ruthenium amount 4%, does not have to specify that percentage of the present invention is percetage by weight) are mixed with the 100ml mixed solution, behind the stirring 10min, add 100ml 2molL fast
-1In the potassium hydroxide solution, add the back that finishes and stir 5min, spend deionised water then to there not being chlorion, dried 24 hours for 120 ℃, 450~550 ℃ of sintering 2 hours in hydrogen-argon gas gaseous mixture atmosphere again, auxiliary agent adopts the equi-volume impregnating dipping, earlier dipping barium nitrate (M1), and then dipping cesium nitrate (M2), make the Ru-M1-M2/MgO catalyst after the drying.
Change the addition of ruthenium trichloride and the addition and the impregnation sequence of auxiliary agent, the sintering and reducing temperature, the mixed solution that can make ammonia synthesis catalyst Ru-M1/MgO, Ru-M2/MgO, Ru-M1-M2/MgO or the dipping M1 and the M2 of different series obtains Ru-(M1+M2)/MgO catalyst; Wherein M1 is a barium nitrate, and M2 is one or more in alkali metallic sodium, potassium, rubidium, caesium, rare earth nitrades or the hydroxide.
Embodiment 2
The catalyst activity evaluation is carried out in high pressure active testing device.Reactor inside diameter is the fixed bed of 14mm.Catalyst granules is 12~16 orders, and the heap volume is 2ml, and catalyst is seated in the isothermal region of reactor.Reaction gas is nitrogen and hydrogen mixed gas, and hydrogen nitrogen ratio is 3: 1.
Embodiment 3
To the Ru-Ba/MgO catalyst, be 550 ℃ in sintering temperature, sintering time is 2 hours, the reacting gas air speed is 10000h
-1, reaction pressure is under the 10MPa condition, has investigated the influence of reaction temperature to catalyst activity, the results are shown in Table 1.
Table 1 reaction temperature is to the influence (vol%) of outlet ammonia concentration
Annotate: it is containing metal ruthenium 4% on the ruthenium catalyst of carrier that mark Ru4-Ba3/MgO refers to magnesia, barium metal 3%, and the implication of following mark is identical therewith.
Embodiment 4
To the Ru4-Ba3/MgO sintering of catalyst time be 2 hours, be 10000h in the reacting gas air speed
-1, reaction pressure is under the 10MPa condition, has investigated the influence of sintering temperature to catalyst activity, the results are shown in Table 2.
Table 2 reaction temperature is to the influence (v%) of outlet ammonia concentration
The result shows that sintering temperature influences catalyst ammonia synthesis activity, the catalyst low-temperature activity height of 500 ℃ of sintering.The catalyst high temperature active of 550 ℃ of sintering is good.
Embodiment 5
The Ru-Ba/MgO catalyst different to Ba content, 500 ℃ of sintering 2 hours are 10000h in the reacting gas air speed
-1,
Reaction pressure is under the 10MPa condition, has investigated the influence of Ba auxiliary agent content to catalyst activity, the results are shown in Table 3.
Table 3 reaction temperature is to the influence (vol%) of outlet ammonia concentration
Embodiment 6
The catalyst identical to ruthenium content adopts different precipitating reagents to prepare the Ru4-Ba6/MgO catalyst, and 500 ℃ of sintering 2 hours are 10000h in the reacting gas air speed
-1, reaction pressure is under the 10MPa condition, has investigated the influence of different precipitating reagents to catalyst activity, the results are shown in Table 4.
Table 4 reaction temperature is to the influence (v%) of outlet ammonia concentration
Embodiment 7
The catalyst identical to ruthenium content adopts KOH to prepare the Ru4-Ba6-M2/MgO catalyst as precipitating reagent, and M2 content is 1wt%, and 500 ℃ of sintering 2 hours are 10000h in the reacting gas air speed
-1, reaction pressure is under the 10MPa condition, has investigated the influence of different precipitating reagents to catalyst activity, the results are shown in Table 5.
Table 5 reaction temperature is to the influence (v%) of outlet ammonia concentration
Claims (5)
1. the preparation method of a ruthenium-based ammonia synthetic catalyst, it is characterized in that: described catalyst is carrier with magnesia, and metal Ru is an active component, is auxiliary agent with in alkali metal, alkaline-earth metal or the rare earth metal one or more; Described catalyst consist of Ru-M1/MgO, Ru-M2/MgO or Ru-M1-M2/MgO; Wherein M1 is a barium nitrate, and M2 is one or more in alkali metallic sodium, potassium, rubidium, caesium and rare earth nitrades or the hydroxide;
Described Preparation of catalysts step is:
1) solution preparation: by the chemical composition solution of the ruthenium that will prepare-magnesium hydroxide catalyst precursor, taking by weighing corresponding ruthenic chloride and metal nitrate respectively is dissolved in the deionized water, be made into metallic ion mixed liquor, the concentration of ruthenium ion is 0.03~0.12mol/L in the described metallic ion mixed liquor; The concentration of metal nitrate is 1~2mol/L in the described metallic ion mixed liquor; The preparation precipitant solution, described precipitant solution concentration is 0.1~4mol/L;
2) precipitation: precipitant solution is added in the metallic ion mixed liquor, stir simultaneously, intensification stops to stir and heating after boiling 0~10min, and centrifugal dewatering gets sediment;
3) washing: with step 2) sediment spends deionised water, and centrifugal dehydration is then so operated 6~10 times, till wash water is with the no chlorion of silver nitrate aqueous solution check;
4) oven dry: wet sediment dewaters 50-120 ℃ of drying with infrared lamp or with baking oven, obtains blocks of solid;
5) moulding: oven dry back powder sample extruded moulding, specification 3mm * 5mm;
6) sintering: the body sintering of in tube furnace, ventilating of the blocks of solid after will drying, sintering again behind the solid incipient impregnation auxiliary agent after maybe will drying, behind the described dipping auxiliary agent again the product sintering of sintering do not need to flood again auxiliary agent after intact, sintering temperature is 450~550 ℃, sintering time is 2 hours;
7) dipping auxiliary agent: the sintering afterproduct is plated auxiliary agent with the method for incipient impregnation, and used auxiliary agent is one or both in barium nitrate, potassium nitrate, potassium hydroxide, the cesium nitrate, and pickup is 1%~10% of a total catalyst weight;
8) drying: the product behind the dipping is dried down at 50-120 ℃ and is prepared into catalyst;
Metal nitrate in the described step 1) is a magnesium nitrate.
2. the preparation method of ruthenium-based ammonia synthetic catalyst according to claim 1, it is characterized in that: described sintering gas is hydrogen-nitrogen mixture, the volume ratio of described hydrogen and nitrogen is 3: 1, perhaps sintering gas is hydrogen-argon gas gaseous mixture, and the volume ratio of described hydrogen and argon gas is 0.4~1: 1.
3. the preparation method of ruthenium-based ammonia synthetic catalyst according to claim 1, it is characterized in that: described precipitating reagent is a kind of in potassium hydroxide, NaOH or the ammoniacal liquor, and the amount ratio of described precipitant solution and mixed solution is: the mol ratio of precipitating reagent potassium hydroxide, NaOH or ammoniacal liquor and magnesium nitrate is 0.5~3.
4. the preparation method of ruthenium-based ammonia synthetic catalyst according to claim 1 is characterized in that: dry infrared lamp or the baking oven of adopting of the product behind the described dipping dried.
5. the preparation method of ruthenium-based ammonia synthetic catalyst according to claim 1, it is characterized in that: ruthenic chloride generates chloride by precipitation, chloride is by centrifugal deionized water washing and reduction, chloride ion content has been reduced to 2% silver nitrate reagent and has been detected the nothing precipitation in the catalyst, and chlorine ion concentration is lower than 0.01% on x-ray photoelectron spectrometer device surface.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008100714805A CN101322938B (en) | 2008-07-29 | 2008-07-29 | Ruthenium-based ammonia synthetic catalyst and preparation thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2008100714805A CN101322938B (en) | 2008-07-29 | 2008-07-29 | Ruthenium-based ammonia synthetic catalyst and preparation thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101322938A CN101322938A (en) | 2008-12-17 |
CN101322938B true CN101322938B (en) | 2010-09-08 |
Family
ID=40186735
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2008100714805A Expired - Fee Related CN101322938B (en) | 2008-07-29 | 2008-07-29 | Ruthenium-based ammonia synthetic catalyst and preparation thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101322938B (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102380420B (en) * | 2011-09-02 | 2013-04-17 | 福州大学 | Ammonia synthesis catalyst and preparation method thereof |
CN103316674B (en) * | 2013-06-22 | 2014-12-03 | 福州大学 | Ruthenium series ammonia synthesis catalyst taking magnesium oxide-graphite composite as carrier |
CN107686120B (en) * | 2016-08-05 | 2020-04-21 | 华中师范大学 | Method for catalytically synthesizing ammonia by gathering solar energy and catalyst thereof |
CN106881085A (en) * | 2017-03-16 | 2017-06-23 | 兰州理工大学 | The catalyst and preparation method and process for selective hydrogenation of hydroquinones hydrogenation |
CN107185534B (en) * | 2017-05-10 | 2019-09-03 | 福州大学化肥催化剂国家工程研究中心 | A kind of ruthenium system ammonia synthesis catalyst and preparation method thereof |
CN107413341B (en) * | 2017-06-09 | 2019-08-20 | 武汉大学 | A kind of ruthenium-based catalyst and its preparation method and application being carried on SrNb2 O6 surface |
CN109126787B (en) * | 2017-06-16 | 2021-08-03 | 中国科学院大连化学物理研究所 | Rare earth metal oxide supported ruthenium catalyst for ammonia synthesis and application thereof |
CN108435166A (en) * | 2018-03-22 | 2018-08-24 | 福州大学 | A kind of preparation method of free from chloride active carbon loading ruthenium ammonia synthesis catalyst |
CN108970610A (en) * | 2018-07-23 | 2018-12-11 | 福州大学 | A kind of preparation method of active carbon loading ruthenium ammonia synthesis catalyst |
CN110280268B (en) * | 2019-07-03 | 2023-04-07 | 北京氦舶科技有限责任公司 | Synthetic ammonia catalyst and preparation method thereof |
CN112774674A (en) * | 2019-11-08 | 2021-05-11 | 中国科学院大连化学物理研究所 | Supported ruthenium cluster catalyst for ammonia synthesis, and preparation method and application thereof |
CN110694626B (en) * | 2019-11-14 | 2022-12-02 | 太原学院 | Composite catalyst for synthesizing 2-pentanone from ethanol and preparation method thereof |
CN111054331B (en) * | 2020-01-09 | 2021-11-23 | 吉林大学 | High-dispersion ruthenium-loaded full-spectrum response semiconductor photocatalyst, and preparation method and application thereof |
CN115487798B (en) * | 2022-09-14 | 2024-04-05 | 福州大学 | Preparation method and application of Ru-based nanocluster catalyst promoted by aid |
CN116651447B (en) * | 2023-06-21 | 2024-05-10 | 安徽工程大学 | Flower-shaped atomic-level Ru/MgO efficient ammonia synthesis catalyst and preparation method thereof |
-
2008
- 2008-07-29 CN CN2008100714805A patent/CN101322938B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN101322938A (en) | 2008-12-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101322938B (en) | Ruthenium-based ammonia synthetic catalyst and preparation thereof | |
CN107365286B (en) | Method for synthesizing 2, 5-furandicarboxylic acid | |
CN102258998B (en) | Ammonia synthesis catalyst and preparation method thereof | |
CN101362080B (en) | Active carbon loading ruthenium ammonia synthesis catalyst and preparation method thereof | |
CN113058595A (en) | Ru-based ammonia decomposition hydrogen production catalyst and preparation method thereof | |
CN101982236A (en) | Hydrogenation catalyst and preparation method of 1,4-cyclohexanedimethanol | |
CN104258864A (en) | Nanocomposite catalyst and preparation method and application thereof | |
CN109529821B (en) | Palladium-based catalyst for thermal catalysis of formaldehyde degradation | |
CN102921413A (en) | Ruthenium-based ammonia synthesis catalyst and its preparation method | |
CN113634257A (en) | Application of bifunctional catalyst to CO in flue gas2Integration of capture and methanation | |
CN103785470A (en) | Preparation method of catalyst for synthesis of acrylic acid | |
CN102302931A (en) | Catalytic combustion deoxidation catalyst for oxygen-containing methane mixed gas, as well as preparation method and application thereof | |
CN102698749B (en) | Ruthenium ammonia synthesis catalyst taking ruthenium ammonia complex as precursor | |
CN102380420B (en) | Ammonia synthesis catalyst and preparation method thereof | |
CN110465279A (en) | Catalyst without mercury carrier active carbon and preparation method thereof for PVC production | |
CN111569869B (en) | Preparation method and application of high-dispersion supported palladium-based catalyst | |
CN113751012A (en) | Preparation method and application of catalyst | |
CN115608375B (en) | Catalyst for ammonia borane hydrolysis hydrogen evolution and preparation method thereof | |
CN109433199B (en) | Ruthenium-based catalyst for carbon dioxide reduction and preparation method and application thereof | |
CN1190357C (en) | Catalyst for low-temp. selective oxidation of CO in hydrogen gas and its preparation method | |
CN105642290B (en) | A kind of preparation method of synthesizing gas by reforming methane with co 2 catalyst | |
CN102580779B (en) | Ammonia synthesis catalyst with ruthenium nitrosyl nitrate as precursor and preparation method thereof | |
CN102580778B (en) | Ruthenium-based ammonia synthesis catalyst with polyhydroxy ruthenium complex as precursor | |
CN112441884B (en) | Method for preparing ethylene glycol through tantalum-based semiconductor photocatalytic methanol coupling | |
CN103480368A (en) | Catalytic combustion deoxygenation catalyst for low-carbon gas mixture and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100908 Termination date: 20130729 |