CN1401426A - Ammonia synthesis ruthenium based catalyst and preparing process thereof - Google Patents
Ammonia synthesis ruthenium based catalyst and preparing process thereof Download PDFInfo
- Publication number
- CN1401426A CN1401426A CN 01125634 CN01125634A CN1401426A CN 1401426 A CN1401426 A CN 1401426A CN 01125634 CN01125634 CN 01125634 CN 01125634 A CN01125634 A CN 01125634A CN 1401426 A CN1401426 A CN 1401426A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- ruthenium
- alkaline
- earth metal
- alkali metal
- 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.)
- Granted
Links
Abstract
A Ru-base catalyst for synthesizing ammonia is composed of activated carbon as carrier. Ru as active component, and alkali metal or alkali-earth metal as cocatalyst. Its preparing process includes pretreating the carrier, impregnating in solution of alkali-earth metal solt, impregnating in solution of Ru compound, reducing in hydrogen or nitrogen-hydrogen gas at 100-450 deg.C for 1-24 hr, and impregnation in the solution of alkali metal and/or alkali-earth metal salt.
Description
The present invention relates to a kind of is active component with the noble ruthenium, is co-catalyst with alkali metal and alkaline-earth metal, is the new and effective ammonia synthesis catalyst and preparation method thereof and the application in ammonia synthesizing industry of carrier with the activated carbon.
Traditional ammonia synthesis catalyst is a fused iron catalyst, with aluminium oxide, potassium oxide etc. as co-catalyst.Its operating pressure (10～30MPa) and operating temperature (450 ℃～550 ℃) all higher, the energy consumption height requires harshly to equipment material, can't realize waiting novel energy-conserving technology such as being pressed into.Therefore, a kind of to have highly active ammonia synthesis catalyst under low-temp low-pressure imperative in exploitation.The Preparation of Catalyst route that CN1 270 081A patents are described is: earlier with containing ruthenium compound solution impregnation charcoal carrier, reduce and the dipping of co-catalyst again.This patent adopts two step infusion processes, and wherein the at first dipping of ruthenium parent is the necessary condition that obtains active better catalyst.All in all, its catalyst activity that makes is still lower.DE2 748 972, and GB2 034 194, and it is carrier that the patent of WO84-3 642 ruthenium-based ammonia synthetic catalysts such as grade all adopts graphited active carbon, and the catalyst cost is higher.Though it is carrier that US4 142 993 patents adopt activated carbon, need repeatedly adopt vacuum baking in its preparation process, preparation facilities is rare, more difficult industrialization.In the described method for preparing catalyst of US3 830753 patents, its catalyst promoter adopts the alkali metal vacuum moulding machine to catalyst, and this method is industrial also infeasible.It is precursor by ruthenium trichloride that US4 600 571 has narrated a kind of, and the graphitization active carbon of high temperature specially treated is the ruthenium-based catalyst of carrier, and wherein the graphitization active carbon needs through specially treated, and specific (special) requirements is arranged, preparation method's complexity, condition harshness.In the prior art, what have industrial value is a kind of ruthenium-based catalyst of British Petroleum Company (BP) exploitation, and this catalyst is a carrier with the graphitization active carbon of high temperature specially treated, with ruthenium (Ru
3(CO)
12) be the parent compound of ruthenium, obviously its preparation technology is quite complicated, catalyst cost height.
The purpose of this invention is to provide a kind of new and effective ammonia synthesis catalyst and preparation method thereof, it has under lower temperature and pressure, the catalytic activity height, is suitable for commercial Application, characteristics such as especially uses in the novel energy-conserving process unit.
Catalyst of the present invention is made up of active component, co-catalyst and carrier, it is characterized in that: be active component with the ruthenium, loading is 1～12wt% (wherein wt% is weight percentage), with alkali metal and alkaline-earth metal is co-catalyst, the mol ratio of alkali metal and ruthenium is 4～16, and the mol ratio of alkaline-earth metal and ruthenium is 0.1～6; Carrier is an activated carbon.The best loading of ruthenium is 1～9wt% among the present invention.The specific area of absorbent charcoal carrier is 100～1300m
2/ g.Its co-catalyst is made up of alkali metal and alkaline-earth metal bi-component, and wherein alkali metal comprises sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), and alkaline-earth metal comprises calcium (Ca), magnesium (Mg), strontium (Sr), barium (Ba).Its preparation method is: activated carbon is handled through diluted acid, washs to neutrality, floods with alkaline-earth metal salt solution earlier; Dipping contains ruthenium compound solution again, and reduces 1～24 hour under 100～450 ℃ of nitrogen atmosphere or nitrogen and hydrogen mixture atmosphere; Final impregnating alkali metal and/or alkaline-earth metal salt solution.The used ruthenium compound that contains is ruthenium trichloride (RuCl
3), immersion solvent is a water.The co-catalyst precursor is alkali metal and/or alkali metal, the nitrate of alkaline-earth metal, hydroxide, carbonate.
Carrier material of the present invention is an activated carbon.Because activated carbon surface contains impurity and some harmful groups, therefore need (for example use rare HNO with diluted acid
3) in 〉=80 ℃ water bath with thermostatic control, handle.Support active component and co-catalyst with the active carbon after handling, can obtain effect preferably.
The ruthenium compound that contains that the present invention adopts is a ruthenium trichloride, need not to use expensive Ru
3(CO)
12Or other ruthenium compound.Flood the catalyst of ruthenium parent, needed fully reduction in 100～450 ℃ of hydrogen or nitrogen and hydrogen mixture atmosphere.
The co-catalyst precursor that the present invention adopts is selected from nitrate, hydroxide and the carbonate of alkali metal and/or alkali metal, alkaline-earth metal.The at first dipping of alkaline-earth metal (the especially compound of baric) wherein, the secondly dipping of ruthenium and alkali metal catalyst helps the acquisition of high activity ruthenium-based ammonia synthetic catalyst.
Preparation method of the present invention handles with diluted acid activated carbon earlier in 〉=80 ℃ water bath with thermostatic control, washing is dry to neutral back.Flood with alkaline-earth metal salt solution earlier; After the drying again dipping contain ruthenium compound solution, and under 100～450 ℃ of hydrogen or nitrogen and hydrogen mixture atmosphere, reduced 1～24 hour; Final impregnating alkali metal and/or alkaline-earth metal salt solution.Immersion solvent in the preparation process all adopts water.
Preparation of catalysts condition (as loading, co-catalyst kind and content, impregnation sequence etc.) and reaction condition (as reaction temperature, reaction pressure and air speed etc.) have remarkable influence to activity of such catalysts.
The loading of active component is the key factor that influences catalyst performance.Catalyst of the present invention is along with the increase of ruthenium loading, and its catalytic activity increases, and reaches maximum at the ruthenium loading during for 8wt%; Continue to increase the loading of ruthenium, activity of such catalysts descends thereupon.Therefore, the loading of active component has an optimum range, and the optimum range under this experiment condition is 1～9wt%.
Co-catalyst kind and content are the another key factors that influences catalyst performance.Concerning single auxiliary agent, facilitation effect the best of barium; Concerning two/many auxiliary agents, the effect of uniting promotion with alkaline-earth metal and alkali metal is good.The present invention adopts alkali metal and alkaline-earth metal bi-component as co-catalyst, and wherein alkali metal comprises sodium (Na), potassium (K), rubidium (Rb), caesium (Cs) etc., and alkaline-earth metal comprises calcium (Ca), magnesium (Mg), strontium (Sr), barium (Ba) etc.Different catalyst is formed, and its suitable cocatalyst content is different.Usually, the mol ratio of alkali metal and ruthenium is 4～16, and the mol ratio of alkaline-earth metal and ruthenium is 0.1～6.
Impregnation sequence in the catalyst preparation process of the present invention also is one of factor that influences catalytic performance.Wherein, at first being impregnated with of base earth metal promoter is beneficial to the highly active ruthenium-based ammonia synthetic catalyst of acquisition.
Reaction condition such as reaction temperature, reaction pressure and air speed etc. all have remarkable influence to activity of such catalysts.
Different catalyst is formed, the catalyst serviceability temperature scope difference that it is best.The operating temperature of catalyst of the present invention is the best with 325～450 ℃, but exceeds this scope, also can obtain catalytic activity preferably.That is to say the suitable operating temperature range broad of catalyst of the present invention.
Along with the increase of reaction pressure, catalyst activity of the present invention increases thereupon.
Catalyst of the present invention is being lower than 30 000h
-1The air speed scope then can obtain higher catalytic activity.
Compared with the prior art, catalyst of the present invention has high activity under low-temp low-pressure.The specific activity that table 1 has provided catalyst of the present invention and prior art.
The comparison of table 1 catalyst of the present invention and prior art activity
Reaction pressure reaction temperature air speed outlet ammonia concentration-response speed project catalyst
MPa ℃ of h
-1V% mmol.g
-1.h
-1Prior art Ru-
7.0 400 3000 8.30 20.53(CN1270081A) Ba/AC
Ba-Ru-the present invention
7.0 400 20620 15.49 205.78
K/AC
As known from Table 1, under same reaction pressure and temperature conditions, catalyst of the present invention is at air speed 20 620h
-1Under outlet ammonia concentration ratio prior art at 3 000 h
-1Taller 7.19% under (according to the ammonia synthesis reaction theory, under similarity condition, air speed is lower, and outlet ammonia concentration is higher) improves 86.6% relatively, and reaction rate then improves 10 times.Therefore, use this catalyst, can significantly improve the ammonia synthesis rate, improve synthetic ammonia output significantly, and can reduce operating temperature and pressure, establish technical foundation for realizing the novel energy-conserving ammonia synthesis process.Therefore, catalyst of the present invention has the industrial applications value of reality.Compare with industrialized prior art (BP), catalyst of the present invention is formed and preparation technology etc. has notable attribute at the ruthenium compound of selecting for use, carrier material, co-catalyst.Table 2 has provided the present invention and has compared with typical prior art.
Table 2 the present invention compares with typical prior art
The parent preparation technology of ruthenium inventor alive
The carrier co-catalyst
Compound (impregnation sequence) property
Two promoter three step infusion processes RuCl of the present invention
3Common active carbon
High
(Ba-K) (Ba→Ru→K)
Single promoter (IA, two step infusion process (Ru → BP Ru
3(CO)
12The graphitization active carbon
High
IIA, La system) the CN1270 RuCl of Rb or Rb → Ru)
3Or two step of charcoal fiber, carbon molecular sieve, single promoter infusion process
Low-081A Ru
3(CO)
12Many empty graphite carbon nanotubes (K or Ba) (Ru → K (Ba))
As shown in Table 2, catalyst of the present invention is that raw material is the most cheap and easy to get, and the preparation method is the simplest, catalyst cost the highest minimum, active new ammonia synthesis catalyst.
Be explained in more detail below by embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
With alkali salt (M1) Ba (NO
3)
2Be mixed with the aqueous solution, add the activated carbon of handling well through diluted acid (AC), after the stirred for several hour, evaporate to dryness on Rotary Evaporators was in 110 ℃ of oven dry 10～24 hours.Stir with ruthenium trichloride aqueous solution dipping then, evaporate to dryness on Rotary Evaporators, and in 110 ℃ of oven dry 10～24 hours, under 100～450 ℃ of hydrogen or nitrogen and hydrogen mixture atmosphere, reduced 1～24 hour.Final impregnating alkali/alkaline earth metal co-catalyst (M2) KNO
3(KOH, CsNO
3Or Ba (NO
3)
2), make the M1-Ru-M2/AC catalyst after the drying.
Change the pickup and the impregnation sequence of co-catalyst and ruthenium trichloride, can make the ruthenium-based ammonia synthetic catalyst M1-Ru-M2/AC or Ru-(the M1+M2)/AC catalyst of different series.
Embodiment 2
The catalyst activity evaluation in high pressure active testing device, carry out (≤20.0MPa).Reactor is the fixed bed of internal diameter 14mm.Catalyst granules is 1.0～1.4mm, and stacking volume is 2ml, and catalyst is seated in the isothermal region of reactor.Reaction gas is nitrogen and hydrogen gaseous mixture, and hydrogen nitrogen ratio is 3: 1.Table 3 has been listed catalyst at 425 ℃, the test result under the different air speeds of 5MPa.
The different air speeds of table 3 are to the influence (v%) of outlet ammonia concentration
Reacting gas air speed (h
-1)
Catalyst
5,000 10,000 20000 30000Ba-Ru (2wt%)-K 8.79 7.76 6.57Ba-Ru (8wt%)-K 11.90 (balance ammonia concentration) 11.09 10.87 fused iron catalysts 11.79
The result shows that catalyst ammonia synthesis activity of the present invention is high.
Embodiment 3
To the Ba-Ru-K/AC catalyst, at reacting gas air speed 30000h
-1, under the reaction pressure 5.0MPa condition, investigated the influence of reaction temperature to catalyst activity, the results are shown in table 4.
Table 4 reaction temperature is to the influence (v%) of catalyst outlet ammonia concentration
The reacting gas temperature (℃) catalyst
375 400 425 450Ba-Ru(2wt％)-K 2.01 4.18 6.57 7.87Ba-Ru(8wt％)-K 9.28 11.34 10.87 9.17
As can be seen from the above table, different catalyst, its optimum operating temperature difference.
Embodiment 4
To the Ba-Ru-K/AC catalyst, at reacting gas air speed 30000h
-1, under 425 ℃ of conditions of reaction temperature, investigated the influence of reaction pressure to catalyst activity, the results are shown in table 5.
Table 5 reaction pressure is to the influence (v%) of catalyst outlet ammonia concentration
Reaction gas pressure (MPa) catalyst
5.0 7.0 10.0 15.0Ba-Ru(2wt％)-K 6.57 8.30 12.28 17.82Ba-Ru(8wt％)-K 10.87 13.21 18.82 22.87
As can be seen from the above table, along with the increase of reaction pressure, outlet ammonia is dense to be increased thereupon.
Embodiment 5
To the Ba-Ru-K/AC catalyst, be 30000h in the reacting gas air speed
-1, reaction pressure is respectively 5.0MPa, 10.0MPa and 15.0MPa, and reaction temperature is under the condition of 400 ℃ and 425 ℃, has investigated the influence of ruthenium content to catalyst activity, the results are shown in table 6.
Table 6 ruthenium content to influence (v%) the reaction pressure reaction temperature ruthenium content (wt%) of catalyst outlet ammonia concentration (MPa) (℃) 248 10 12
400 4.18 8.13 11.34 11.03 10.885.0
425 6.57 9.34 10.87 10.58 10.32
400 5.31 10.18 17.67 18.19 17.1510.0
425 10.50 12.20 18.82 18.21 17.98
400 17.74 18.49 21.56 22.48 20.5415.0
425 17.82 19.11 22.87 23.19 20.67
As can be seen from the above table, along with the increase of ruthenium content, its outlet ammonia concentration is fallen after rising, and an optimum value is arranged.Under test condition, the suitable content of ruthenium content is about 4～10wt%, and the higher meeting of content causes the catalyst cost too high.
Embodiment 6
At reacting gas air speed 20000h
-1, reaction pressure 7.0MPa has investigated the co-catalyst kind to the active influence of single auxiliary agent catalyst (Ru-B/AC), the results are shown in table 7.
Table 7 co-catalyst kind is to the influence (v%) of catalyst outlet ammonia concentration
The reacting gas temperature (℃) co-catalyst
375 400 425 450Sr(NO
3)
2 0.54 1.30 2.51 5.03KNO
3 1.75 3.52 8.02 11.01K
2SO
4 - 0.11 0.23 0.32Ba(NO
3)
2 3.01 5.13 9.26 11.07
As can be seen from the above table, the facilitation effect of barium is preferable, and the facilitation effect of the potassium promoter of sulfur-bearing acid group is the poorest.
Embodiment 7
At reacting gas air speed 30000h
-1, reaction pressure 5.0MPa under the condition that reaction temperature is 425 ℃, is an example with K and Cs, has investigated cocatalyst content to the active influence of catalyst Ru-(Ba+B2)/AC (ruthenium content is 4wt%), the results are shown in table 8.
Table 8 cocatalyst content is to the influence (v%) of catalyst outlet ammonia concentration
B2/Ru mol ratio co-catalyst
5 10 15 20K 8.60 9.34 9.03 9.01Cs 8.98 9.95 7.66 7.24
The result shows in the table, and the optimum mole ratio of sylvite and cesium salt and ruthenium is 10, and mol ratio less than 10 situation under, the facilitation effect of cesium salt is better than sylvite.
Embodiment 8
At reacting gas air speed 30000h
-1, under the condition of reaction pressure 5.0MPa, investigated the influence of impregnation sequence to catalyst activity.The results are shown in table 9.
Table 9 impregnation sequence to the reaction temperature of the different impregnation sequences of catalyst outlet ammonia concentration as influencing factor (v%) (℃) catalyst 400 425 450 475 (Ba+K)-Ru/AC 3.27 5.12 6.62 6.52Ba-Ru-K/AC 8.13 9.34 8.69 reach balance ammonia concentration Ba-K-Ru/AC 0.29 0.60 1.16 1.98Ru-Ba-K/AC 5.25 7.91 8.18 7.2Ru-(Ba+K)/AC 4.06 6.38 7.86 7.08Ru-K-Ba/AC 6.68 8.59 8.64 and reach balance ammonia concentration K-Ba-Ru/AC 0.84 1.75 2.93 4.48K-Ru-Ba/AC 3.29 5.92 7.56 7.16
By data in the table as can be seen, the impregnation sequence of ruthenium and co-catalyst is bigger to the influence of catalyst activity.Under experiment condition, be good with the Ba-Ru-K order, especially to the influence of low temperature active.
Claims (7)
1. ruthenium-based ammonia synthetic catalyst, form by active component, co-catalyst and carrier, it is characterized in that: be active component with the ruthenium, loading is 1～12wt%, with alkali metal and alkaline-earth metal is co-catalyst, the mol ratio of alkali metal and ruthenium is 4～16, and the mol ratio of alkaline-earth metal and ruthenium is 0.1～6; Carrier is an activated carbon.
2. according to the described ruthenium-based ammonia synthetic catalyst of claim 1, it is characterized in that: the best loading of ruthenium is 1～9wt%.
3. according to the described ruthenium-based ammonia synthetic catalyst of claim 1, it is characterized in that: described carrier is an active carbon, and its specific area is 100～1300m
2/ g.
4. according to the described ruthenium-based ammonia synthetic catalyst of claim 1, it is characterized in that: described co-catalyst is made up of alkali metal and alkaline-earth metal bi-component, and wherein alkali metal comprises sodium, potassium, rubidium, caesium, and alkaline-earth metal comprises calcium, magnesium, strontium, barium.
5. the preparation method of the described ruthenium-based ammonia synthetic catalyst of claim 1, it is characterized in that: activated carbon is handled through diluted acid, washs to neutrality, floods with alkaline-earth metal salt solution earlier; Dipping contains ruthenium compound solution again, and reduces 1～24 hour under 100～450 ℃ of nitrogen atmosphere or nitrogen and hydrogen mixture atmosphere; Final impregnating alkali metal and/or alkaline-earth metal salt solution.
6. according to the preparation method of the described ruthenium-based ammonia synthetic catalyst of claim 5, it is characterized in that: it is ruthenium trichloride that indication contains ruthenium compound, and immersion solvent is a water.
7. according to the preparation method of the described ruthenium-based ammonia synthetic catalyst of claim 5, it is characterized in that: the co-catalyst precursor is alkali metal and/or alkali metal, the nitrate of alkaline-earth metal, hydroxide, carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011256346A CN1162219C (en) | 2001-08-15 | 2001-08-15 | Ammonia synthesis ruthenium based catalyst and preparing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011256346A CN1162219C (en) | 2001-08-15 | 2001-08-15 | Ammonia synthesis ruthenium based catalyst and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1401426A true CN1401426A (en) | 2003-03-12 |
| CN1162219C CN1162219C (en) | 2004-08-18 |
Family
ID=4666022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011256346A Expired - Fee Related CN1162219C (en) | 2001-08-15 | 2001-08-15 | Ammonia synthesis ruthenium based catalyst and preparing process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1162219C (en) |
Cited By (10)
| 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 |
| CN100448529C (en) * | 2006-04-14 | 2009-01-07 | 中国石油化工股份有限公司 | Ruthenium-based ammonia synthesis catalyst and its preparation method |
| CN101579627B (en) * | 2008-05-15 | 2011-02-09 | 中国石油天然气股份有限公司 | Catalyst for synthesizing ammonia through activated-carbon-loading ruthenium, and preparation method thereof |
| 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 |
| CN103736487A (en) * | 2013-12-29 | 2014-04-23 | 浙江工业大学 | Method for preparing supported metal catalyst through solvent-free mechanical mixing |
| CN103801300A (en) * | 2013-09-28 | 2014-05-21 | 西北大学 | Ammonia catalyst synthesized by methane and nitrogen under normal pressure and preparation method of ammonia catalyst |
| CN104289217A (en) * | 2014-11-13 | 2015-01-21 | 浙江工业大学 | Biomorphic-composite-oxide loaded ruthenium catalyst for ammonia synthesis and preparation method thereof |
| CN106540715A (en) * | 2016-10-31 | 2017-03-29 | 福州大学 | A kind of method of reducing of activated carbon for the ruthenium system ammonia synthesis catalyst of carrier |
| 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 |
| CN108816221A (en) * | 2018-06-11 | 2018-11-16 | 福州大学 | A kind of aluminium oxide is the preparation method of the ruthenium-based ammonia synthetic catalyst of carrier |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100493700C (en) * | 2005-10-28 | 2009-06-03 | 厦门大学 | Preparation method of ruthenium-base ammonia synthetic catalyst |
-
2001
- 2001-08-15 CN CNB011256346A patent/CN1162219C/en not_active Expired - Fee Related
Cited By (13)
| 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 |
| CN100448529C (en) * | 2006-04-14 | 2009-01-07 | 中国石油化工股份有限公司 | Ruthenium-based ammonia synthesis catalyst and its preparation method |
| CN101579627B (en) * | 2008-05-15 | 2011-02-09 | 中国石油天然气股份有限公司 | Catalyst for synthesizing ammonia through activated-carbon-loading ruthenium, and preparation method thereof |
| 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 |
| CN103801300A (en) * | 2013-09-28 | 2014-05-21 | 西北大学 | Ammonia catalyst synthesized by methane and nitrogen under normal pressure and preparation method of ammonia catalyst |
| CN103736487B (en) * | 2013-12-29 | 2016-02-24 | 浙江工业大学 | A kind of solvent-free mechanical mixture prepares the method for load type metal catalyst |
| CN103736487A (en) * | 2013-12-29 | 2014-04-23 | 浙江工业大学 | Method for preparing supported metal catalyst through solvent-free mechanical mixing |
| CN104289217A (en) * | 2014-11-13 | 2015-01-21 | 浙江工业大学 | Biomorphic-composite-oxide loaded ruthenium catalyst for ammonia synthesis and preparation method thereof |
| CN106540715A (en) * | 2016-10-31 | 2017-03-29 | 福州大学 | A kind of method of reducing of activated carbon for the ruthenium system ammonia synthesis catalyst of carrier |
| CN106540715B (en) * | 2016-10-31 | 2019-06-11 | 福州大学 | A kind of active carbon is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier |
| 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 |
| CN108816221A (en) * | 2018-06-11 | 2018-11-16 | 福州大学 | A kind of aluminium oxide is the preparation method of the ruthenium-based ammonia synthetic catalyst of carrier |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1162219C (en) | 2004-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1179788C (en) | Unsaturated hydrocarbon selective hydrogenation catalyst, its preparation process and use thereof | |
| CN1784269A (en) | Silver-containing catalysts, the manufacture method and use thereof | |
| CN1301791C (en) | Silver catalyst carrier for epoxyethane production, preparation method and application thereof | |
| CN1401426A (en) | Ammonia synthesis ruthenium based catalyst and preparing process thereof | |
| CN1232349C (en) | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use | |
| CN1035254A (en) | Make a kind of method of desulfurizing agent | |
| CN1164363C (en) | Catalyst in oxychlorination reaction as well as its preparation method and application | |
| CN1100124C (en) | Aromatizing catalyst for light hydrocarbon and its preparing process | |
| CN1133493C (en) | Efficient catalyst for synthesizing ammonia and its preparing process | |
| CN1007130B (en) | Prepn. of ethyene oxide and catalyst therefor | |
| CN1511633A (en) | Carrier for producing silver catalyst for epoxy ethane production, its preparing method and use | |
| CN1141915A (en) | Process for preparation of methanethiol | |
| CN1310703C (en) | Ethylene oxide catalyst carrier preparation | |
| CN1506300A (en) | Ruthenium-based catalyst for decomposing ammonia to prepare mixed H2-N2 gas and its prepn | |
| CN1176746C (en) | Fischer-Tropsch catalyst and its preparing process | |
| CN1044094C (en) | Catalyst and process for changing methone intor high-level hydrocarbon | |
| CN1131101C (en) | Ru-based ammonia synthesizing catalyst carried by nano carbon fiber and its prepn. | |
| CN1218915C (en) | Solid acid catalyst for preparing ethylene glycol by ethylene oxide hydration | |
| CN1384176A (en) | Reforming catalyst containing molecular sieve | |
| CN1313423C (en) | Method for preparing difluoromethane by stage continuous fluorination | |
| CN1218917C (en) | Process for preparing ethylene glycol by ethylene oxide catalytic hydration | |
| CN1481935A (en) | Accelerating agent and its application in synthesizing carbolic acid using benzene and hydrogen dioxide | |
| CN1162416C (en) | Silver catalyst for epoxyethane production, its preparation method and application | |
| CN1171672C (en) | Silver catalyst for epoxyethane production, its preparation method and application | |
| CN1084219C (en) | Catalyzer for producing unsaturated ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |