CN1382527A - Pore-enlarging process for activated carbonate as carrier of carried ruthenium catalyst - Google Patents
Pore-enlarging process for activated carbonate as carrier of carried ruthenium catalyst Download PDFInfo
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- CN1382527A CN1382527A CN 02106362 CN02106362A CN1382527A CN 1382527 A CN1382527 A CN 1382527A CN 02106362 CN02106362 CN 02106362 CN 02106362 A CN02106362 A CN 02106362A CN 1382527 A CN1382527 A CN 1382527A
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- active carbon
- reaming
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- ruthenium catalyst
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Abstract
A pore-enlarging process for the carrier of the carried Ru catalyst used for synthesizing ammonia includes high-temp treating of the activated carbon from marcket under the protection of inertial gas for graphitizing it, and enlarging the pores of graphitized activated carbon. The resultant activated carbon used as said carrier features high stability and high specific surface area.
Description
Affiliated technical field
The present invention relates to be used in the ammonia synthesizing industry prepare the preparing carriers technology of new ammonia synthesis catalyst, the reaming that specifically a kind of activated carbon supported ruthenium is an absorbent charcoal carrier in the ammonia synthesis catalyst is handled.
Technical background
At present, domestic in ammonia synthesizing industry the ammonia synthesis catalytic reaction mostly use traditional iron catalyst, advantages such as that iron catalyst has is cheap, good stability.But, iron catalyst light-off temperature height, the ammonia synthesis catalytic reaction must be carried out under the condition of high temperature, high pressure, and production process is harsh to the equipment requirement, energy consumption is big.
Develop a kind of novel ammonia synthesis catalyst in recent years abroad, promptly supported ruthenium is an ammonia synthesis catalyst, can be under conditions such as lower temperature, pressure the catalysis ammonia synthesis reaction.The carrier that is used to prepare load ruthenium catalyst has varied, and active carbon is wherein very important a kind of.Because active carbon has high-ratio surface, the large pore volume that can hold active component and promoter, is easy to the surface group of modulation, special aspect characteristics such as Electronic Performance, can recycling for noble ruthenium in the discarded catalyst.Therefore, absorbent charcoal carrier is used to prepare load ruthenium catalyst and not only has higher service efficiency, and helps the sustainable use of resource.
The production technology of absorbent charcoal carrier influences specific surface, pore volume, pore size distribution, chemical property and the stability of absorbent charcoal carrier to a great extent, thereby influences the preparation and the ammonia synthesis catalytic efficiency of ruthenium catalyst.Common commercial active carbon is not suitable for directly as the preparing carriers ruthenium catalyst.Be on the one hand because common commercial active carbon all contains a certain amount of non-carbon component; On the other hand, untreated active carbon in the presence of high temperature, high pressure and hydrogen, character instability, and the methanation phenomenon may occur.If, active carbon is carried out high-temperature heat treatment, can remove the non-carbon component in the charcoal carrier, simultaneously heat endurance that also can enhanced activity charcoal carrier is avoided the generation of methanation phenomenon in certain temperature range.But simple high-temperature heat treatment sharply descends the specific surface of absorbent charcoal carrier, pore volume, and obvious variation also takes place in pore size distribution, and this is very unfavorable to the preparation load type metal catalyst.For example, reactive metal and promoter can not fully be disperseed on carrier, and catalyst can not effectively contact or the like with reacting gas.
According to China Chemical Information Center to World Patent Index 1980-2001; " Chinese patent database " 1985-2001; " chemical science and technology achievement compilation " 1978-1987; The retrieval of relevant reference books such as " chemical science and technology achievement in research communique " 1987-1996, database, the result shows: have not yet to see absorbent charcoal carrier and carry out the relevant report that reaming is handled.
Summary of the invention
For at supported ruthenium be ammonia synthesis catalyst in the presence of high temperature, high pressure and hydrogen, carried by active carbon volume property instability, and problems such as methanation phenomenon may occur.The present invention will provide a kind of stable absorbent charcoal carrier, being used to prepare supported ruthenium is ammonia synthesis catalyst, ruthenium catalyst with this absorbent charcoal carrier preparation not only has high ammonia synthesis catalytic efficiency, and, under certain temperature, pressure condition, have stability preferably.
The object of the present invention is achieved like this: the reaming of absorbent charcoal carrier is handled and be it is characterized in that in a kind of novel load ruthenium catalyst: with common commercial active carbon under the protection of inert gas; carry out high-temperature heat treatment; after heat treatment become the graphitization active carbon; again the graphitization active carbon is carried out reaming and handle, promptly formed absorbent charcoal carrier with high stability, high-ratio surface.Described active carbon heat treatment process must be carried out under the inert gas shielding of anaerobic, and its temperature requirement is between 1600-2500 ℃, and heat treatment time is 0.5-5 hour; Described reaming is handled and must be fed mist, and mist has two kinds: (1) oxygen is 2-25%, and nitrogen is 75-98%; (2) water vapour 5-25%, nitrogen 75-95%; Its treatment temperature is 200-700 ℃, and the processing time is 3-40 hour.Thereby the reaming active carbon of the high stability that obtains promptly can substitute the general commercial active carbon, uses as carrier, and the preparation supported ruthenium is an ammonia synthesis catalyst.
The present invention has used modern instrument and equipment and scientific method, after common commercial active carbon heat-treated again reaming handle, use as carrier with the reaming charcoal after the final processing, load active component ruthenium and multiple promoter, promptly can prepare highly active novel ruthenium is ammonia synthesis catalyst, its ammonia synthesis efficient can improve 1 times combined coefficient than the ruthenium catalyst of original undressed general commercial active carbon as preparing carriers; Carry out the ruthenium catalyst of the heat treated active carbon of the first step than only, can improve 6 times combined coefficient as preparing carriers.Because, if active carbon is only carried out the heat treatment of the first step, and handle as carrier without further reaming, though the active carbon of this moment stability obviously improves, but, be that the carrier of ammonia synthesis catalyst is worthless as the preparation supported ruthenium because specific surface, pore volume sharply reduces and the influence factor of aspect such as pore size distribution structure division destruction.So the present invention can reach the purpose of drafting.
The specific embodiment
Embodiment 1:
Commercial granular activated carbon with 200 grams is placed in the resistant to elevated temperatures black-fead crucible, and black-fead crucible is put into the Medium frequency induction graphitizing furnace carry out high-temperature heat treatment.Before the processing, vacuumize earlier, make the vacuum of system reach 10
-2Pa begins then to heat up, and continues to vacuumize, when system temperature reaches 1500 ℃, stop to vacuumize, feed the inert gas of anaerobic, gas pressure reaches 100Pa, continue to be warmed up to outlet temperature (between 1600-2500 ℃), and in outlet temperature after constant 2 hours, cooling naturally is when temperature drops to room temperature, take out goods, obtain the graphitization active carbon.
Reaming is handled and is adopted following two kinds of methods to carry out.
Method one: hot graphitization active carbon is placed in the tube furnace, feed mist, gas componant: oxygen 15%, nitrogen 85%.Behind the system stability, carry out temperature programming, 5 ℃/min of heating rate, and 400-550 ℃ constant 20 hours, in above-mentioned atmosphere, drop to room temperature, take out goods, and spend deionised water, promptly can be used as carrier after the oven dry and use.
Method two: the graphitization active carbon is placed in the tube furnace, feed mist, gas componant: water vapour 20%, nitrogen 80%.Behind the system stability, carry out temperature programming, 5 ℃/min of heating rate, and, in above-mentioned atmosphere, drop to room temperature 500-550 ℃ of processing 25 hours, and take out goods, and spend deionised water, promptly can be used as carrier after the oven dry and use.
Claims (3)
1. the reaming of absorbent charcoal carrier is handled in the novel load ruthenium catalyst; it is characterized in that: with common commercial active carbon under inert gas shielding; carry out high-temperature heat treatment; after heat treatment become the graphitization active carbon; again the graphitization active carbon is carried out reaming and handle, promptly formed novel absorbent charcoal carrier.
2. the reaming of absorbent charcoal carrier is handled in the load ruthenium catalyst according to claim 1; it is characterized in that: described active carbon heat treatment process; must carry out under the inert gas shielding of anaerobic, its temperature requirement is between 1600-2500 ℃, and heat treatment time is 0.5-5 hour.
3. the reaming of absorbent charcoal carrier is handled in the load ruthenium catalyst according to claim 1, it is characterized in that: described reaming is handled and must be fed mist, and mist has two kinds: (1) oxygen is 2-25%, and nitrogen is 75-98%; (2) water vapour 5-25%, nitrogen 75-95%; Its treatment temperature is 200-700 ℃, and the processing time is 3-40 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02106362 CN1128016C (en) | 2002-03-01 | 2002-03-01 | Pore-enlarging process for activated carbonate as carrier of carried ruthenium catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02106362 CN1128016C (en) | 2002-03-01 | 2002-03-01 | Pore-enlarging process for activated carbonate as carrier of carried ruthenium catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1382527A true CN1382527A (en) | 2002-12-04 |
| CN1128016C CN1128016C (en) | 2003-11-19 |
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| CN 02106362 Expired - Fee Related CN1128016C (en) | 2002-03-01 | 2002-03-01 | Pore-enlarging process for activated carbonate as carrier of carried ruthenium catalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299823C (en) * | 2004-10-10 | 2007-02-14 | 福州开发区科盛催化材料有限公司 | Methanation resisting active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity |
| CN101362080B (en) * | 2008-10-06 | 2013-07-24 | 福州开发区科盛催化材料有限公司 | Active carbon loading ruthenium ammonia synthesis catalyst and preparation method thereof |
| CN107096560A (en) * | 2017-05-19 | 2017-08-29 | 福州大学化肥催化剂国家工程研究中心 | A kind of ruthenium-based ammonia synthetic catalyst and preparation method thereof |
| CN112730726A (en) * | 2020-12-29 | 2021-04-30 | 中冶建筑研究总院有限公司 | Method for measuring content of metal loaded in catalyst |
| CN114950415A (en) * | 2022-06-08 | 2022-08-30 | 福州大学 | Preparation method of Ru-based catalyst with stable size and application of Ru-based catalyst in ammonia synthesis |
| CN115364851A (en) * | 2021-10-27 | 2022-11-22 | 福州大学 | Size-controllable Ru-based nanocluster catalyst, preparation method thereof and application thereof in low-temperature and low-pressure ammonia synthesis |
-
2002
- 2002-03-01 CN CN 02106362 patent/CN1128016C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299823C (en) * | 2004-10-10 | 2007-02-14 | 福州开发区科盛催化材料有限公司 | Methanation resisting active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity |
| CN101362080B (en) * | 2008-10-06 | 2013-07-24 | 福州开发区科盛催化材料有限公司 | Active carbon loading ruthenium ammonia synthesis catalyst and preparation method thereof |
| CN107096560A (en) * | 2017-05-19 | 2017-08-29 | 福州大学化肥催化剂国家工程研究中心 | A kind of ruthenium-based ammonia synthetic catalyst and preparation method thereof |
| CN107096560B (en) * | 2017-05-19 | 2019-09-03 | 福州大学化肥催化剂国家工程研究中心 | A kind of ruthenium-based ammonia synthetic catalyst and preparation method thereof |
| CN112730726A (en) * | 2020-12-29 | 2021-04-30 | 中冶建筑研究总院有限公司 | Method for measuring content of metal loaded in catalyst |
| CN112730726B (en) * | 2020-12-29 | 2023-10-24 | 中冶建筑研究总院有限公司 | Method for measuring content of metal loaded in catalyst |
| CN115364851A (en) * | 2021-10-27 | 2022-11-22 | 福州大学 | Size-controllable Ru-based nanocluster catalyst, preparation method thereof and application thereof in low-temperature and low-pressure ammonia synthesis |
| CN114950415A (en) * | 2022-06-08 | 2022-08-30 | 福州大学 | Preparation method of Ru-based catalyst with stable size and application of Ru-based catalyst in ammonia synthesis |
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| Publication number | Publication date |
|---|---|
| CN1128016C (en) | 2003-11-19 |
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