CN106540715B - A kind of active carbon is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier - Google Patents
A kind of active carbon is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier Download PDFInfo
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- CN106540715B CN106540715B CN201610931108.1A CN201610931108A CN106540715B CN 106540715 B CN106540715 B CN 106540715B CN 201610931108 A CN201610931108 A CN 201610931108A CN 106540715 B CN106540715 B CN 106540715B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
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Abstract
The invention discloses a kind of restoring method for the ruthenium system ammonia synthesis catalyst that active carbon is carrier, it is ruthenium system ammonia synthesis catalyst made of carrier that the catalyst, which is by active component, reaming graphitization active carbon of metal Ru, restoring method of the present invention passes through control reduction temperature and heating rate, catalyst is subjected to reduction under the reducing gas containing hydrogen and makes it have catalytic activity, restoring method of the invention has easy to operate, easy implement, so that catalyst reduction is abundant, catalyst activity is increased substantially, the features such as energy-saving effect is significant.
Description
Technical field
The invention belongs to ammonia synthesis catalyst treatment process fields, and in particular to a kind of active carbon is the ruthenium system ammino of carrier
At the restoring method of catalyst.
Background technique
The exploration of ammonia synthesis catalyst has been carried out more than 100 years in researcher, traditional industrial ammonia synthesis catalysis
Agent is with Fe3O4For parent, develop highly developed.In ferrum-based catalyst (Fe3O4) under effect, synthesized by nitrogen, hydrogen
Ammonia is still under high-temperature and high-pressure conditions and carries out, and temperature requirement is at 400~500 DEG C, and pressure is in 150~300 bar.Ammonia synthesis
It is the industry of highly energy-consuming, and ammonia synthesis industry is the chemical industry pillar industry in China, therefore energy-saving and emission-reduction are imperative.Catalyst
Continuous development is the important channel that ammonia synthesis industry reduces energy consumption.
Ruthenium system ammonia synthesis catalyst is known as second generation ammonia synthesis catalyst, has low-temp low-pressure high activity, not by product
The influence of ammonia density, to water, carbon monoxide is insensitive the advantages that.Industrial ammonia synthesis catalyst must just have work after carrying out reduction
Property.In recent years, the ruthenium system ammonia synthesis catalyst developed, although it has the advantages that activity is high under low-temp low-pressure.But it is same,
Activity is low-down in unreduced situation, by H2After reduction, catalytic activity is greatly improved.Auxiliary agent
Oxide or hydroxide form are the most effective promotion forms of ruthenium-based ammonia synthetic catalyst, so the reduction activation of catalyst walks
Suddenly it is highly desirable.The compound of ruthenium is not only reduced to active metal ruthenium by reduction activation, but also can be by auxiliary agent by its forerunner
Body is reduced to effectively facilitate agent.
The light-off temperature of traditional ferrum-based catalyst is relatively high, usually starts to restore at 350 DEG C, and main phase reduction temperature is 400
~430 DEG C, a large amount of leaving water temperatures are at 410~440 DEG C, and final reduction temperature is at 490~500 DEG C.The required recovery time is longer, and one
As be 3~7 days.Theoretical water yield is 292.8kg/t.Meanwhile to pressure requirements height, usually in 20.0~30.0MPa.In ammonia
In the production process of synthesis, the requirement to equipment is harsh.Chinese patent CN1091997A discloses one kind with Fe1-XO(wustite)
For the catalyst of parent.Fe1-XThe initial reduction temperature and traditional catalyst of O base catalyst are essentially identical, and most fast reduction temperature exists
434 DEG C, final reduction temperature is 490 DEG C.Theoretical water yield is 231.2kg/t.Fe1-XO base catalyst reaches iron-based urges with tradition
When the same ammonia density of agent, pressure is reduced in 3.5MPa or more.And for ruthenium catalyst, initial reduction temperature is 70
DEG C or so, main reduction temperature is between 100~200 DEG C, and final reduction temperature is at 500 DEG C.In terms of initial reduction temperature, ruthenium
The unrivaled advantage of series catalysts.Generally in 3 MPa, the later period can be improved to 10 MPa heating reduction pressure.
It can be seen that traditional ferrum-based catalyst, Fe1-XO base catalyst and ruthenium catalyst, in reduction use process
There are biggish differences for required temperature, pressure etc..The reducing program of present Ru/AC ammonia synthesis catalyst mainly uses for reference iron
The characteristics of being the reducing program of ammonia synthesis catalyst, ruthenium catalyst cannot be embodied completely, it is active and steady after catalyst reduction
It is qualitative that optimum state has not been reached yet.Chinese patent CN104785305A also describes a kind of reduction for synthetic ammonia catalyst
Passivating method, the reduction passivating method of description are to be reduced to the iron oxide of ammonia synthesis catalyst in reduction furnace by hydrogen
Iron atom, then with air, by reduction-state, oh catalyst is passivated.Such reduction passivating method only makes catalyst
Surface forms passivating film, convenient for storage.But it is still Fe that the active component of catalyst, which is,3O4, and with water-soluble no chlorine ruthenium complex
It is quite different for the ammonia synthesis catalyst of presoma.The present invention studies temperature, pressure by adjusting Ru/AC ammonia synthesis reducing program
Power, time, air speed etc. change the influence to ruthenium system ammonia synthesis catalyst, change the reducing condition of intrinsic Fe-series catalyst, find
It is suitble to the best restoring method of ruthenium catalyst.
Summary of the invention
In order to solve the deficiencies in the prior art, that the purpose of the present invention is to provide a kind of reduction effects is good, step is simple
Active carbon is the ruthenium system Reduction of Ammonia Synthesis Catalyst method of carrier.
In order to realize above-mentioned technical purpose, the technical solution of the present invention is as follows:
A kind of active carbon is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier, and catalyst is placed in reaction at normal temperature
In device, reaction system is enabled to restore air speed as 3000~30000h-1, reduction pressure be 0.5~4MPa and to be passed through reducing gas
Under the conditions of, so that system temperature is gradually risen to 500 DEG C, wherein at 200 DEG C, 300 DEG C, 400 DEG C, after carrying out 0.5~10h of constant temperature
It heats up again, when temperature reaches 500 DEG C, after being adjusted to 10MPa by reduction pressure and continue 8~40h of constant temperature, catalyst can be completed
Reduction.
The active carbon is that the ruthenium presoma in the ruthenium system ammonia synthesis catalyst of carrier is water solubility without chlorine ruthenium complex.
The active carbon is the ruthenium content in the ruthenium system ammonia synthesis catalyst of carrier 4%~10%.
The reaction system is 4~25 DEG C/h in the heating rate for being warming up to 200 DEG C of processes, is heated up at 200 DEG C~500 DEG C
The heating rate of process is 10~40 DEG C/h.
The active carbon is that the active carbon in the ruthenium system ammonia synthesis catalyst of carrier is the graphitization active carbon through reaming.
The active carbon is that the ruthenium system ammonia synthesis catalyst of carrier is not higher than in the outlet moisture content of reduction post-reactor
2g/m3。
The reducing gas is that hydrogen is mixed with the one of which in nitrogen, argon gas, helium, Krypton, xenon.
Preferably, the content of hydrogen is 5%~75% in the reducing gas.
Further, the restoring method further includes, during reaction system is warming up to 200 DEG C, if catalyst bed
Temperature rise when being more than 25 DEG C/h, the hydrogen content in reducing gas is controlled 1%~4%.
Through the above technical solution, the invention has the benefit that
(1) present invention in it is low for equipment requirements as the restoring method of the ruthenium system ammonia synthesis catalyst of carrier using active carbon, when
Between it is short, energy-saving effect is significant, there is preferable prospects for commercial application；
(2) restoring method of the invention, it is easy to operate, easy to implement, so that catalyst reduction is abundant, increases substantially and urge
Agent activity；
(3) active carbon prepared in the present invention is that the catalyst low-temperature activity of the ruthenium system ammonia synthesis of carrier is good, light-off temperature
Low, hydrazine yield is high.
Specific embodiment
A kind of active carbon is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier, and catalyst is placed in reaction at normal temperature
In device, reaction system is enabled to restore air speed as 3000~30000h-1, reduction pressure be 0.5~4MPa and to be passed through reducing gas
Under the conditions of, so that system temperature is gradually risen to 500 DEG C, wherein at 200 DEG C, 300 DEG C, 400 DEG C, after carrying out 0.5~10h of constant temperature
It heats up again, when temperature reaches 500 DEG C, after being adjusted to 10MPa by reduction pressure and continue 8~40h of constant temperature, catalyst can be completed
Reduction.
The active carbon is that the ruthenium presoma in the ruthenium system ammonia synthesis catalyst of carrier is water solubility without chlorine ruthenium complex.
The active carbon is the ruthenium content in the ruthenium system ammonia synthesis catalyst of carrier 4%~10%.
The reaction system is 4~25 DEG C/h in the heating rate for being warming up to 200 DEG C of processes, is heated up at 200 DEG C~500 DEG C
The heating rate of process is 10~40 DEG C/h.
The active carbon is that the active carbon in the ruthenium system ammonia synthesis catalyst of carrier is the graphitization active carbon through reaming.
The active carbon is that the ruthenium system ammonia synthesis catalyst of carrier is not higher than in the outlet moisture content of reduction post-reactor
2g/m3。
The reducing gas is that hydrogen is mixed with the one of which in nitrogen, argon gas, helium, Krypton, xenon.
Preferably, the content of hydrogen is 5%~75% in the reducing gas.
Further, the restoring method further includes, during reaction system is warming up to 200 DEG C, if catalyst bed
Temperature rise when being more than 25 DEG C/h, the hydrogen content in reducing gas is controlled 1%~4%.
Embodiment 1
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.94%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.63%.
Embodiment 2
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 50% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 18.96%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.13%.
Embodiment 3
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 5% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 18.56%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 19.98%.
Embodiment 4
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and helium that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.95%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.46%.
Embodiment 5
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and argon gas that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.97%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.61%.
Embodiment 6
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through the hydrogen content hydrogen for being 75% and Krypton are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.89%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.63%.
Embodiment 7
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through the hydrogen content hydrogen for being 75% and xenon are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.98%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.62%.
Embodiment 8
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 4% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 16.67%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 17.03%.
Embodiment 9
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 8% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 18.56%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 19.03%.
Embodiment 10
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 3000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.14%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 19.66%.
Embodiment 11
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 20000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 20.26%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.66%.
Embodiment 12
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 30000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 20.43%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.71%.
Embodiment 13
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 10
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 20 DEG C/h, then with the temperature rise speed of 20 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 20 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.63%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.12%.
Embodiment 14
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 4
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.33%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 19.98%.
Embodiment 15
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 25
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.98%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.67%.
Embodiment 16
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 10 DEG C/h, then with the temperature rise speed of 10 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 10 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.82%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 19.89%.
Embodiment 17
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 40 DEG C/h, then with the temperature rise speed of 40 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 40 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 20.04%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.67%.
Embodiment 18
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 3h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 3h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 3h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 18.94%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 19.77%.
Embodiment 19
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, constant temperature 0.5h is carried out when system temperature rises to 200 DEG C, then
After system temperature is risen to 300 DEG C and constant temperature 0.5h with the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system
It, will reduction pressure after temperature rises to 400 DEG C and constant temperature 0.5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h
After power is adjusted to 10MPa and continues constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system of carrier
The outlet moisture content of ammonia synthesis catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 18.50%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 19.66%.
Embodiment 20
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 10h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 10h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 10h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 20.03%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.93%.
Embodiment 21
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 8h, the reduction of catalyst can be completed, the active carbon after reduction is that the ruthenium system ammonia synthesis of carrier is urged
The outlet moisture content of agent reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.76%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 19.99%.
Embodiment 22
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 40h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 20.06%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.97%.
Embodiment 23
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 0.5MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with
The temperature rise speed of 20 DEG C/h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is super
When crossing 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, constant temperature 5h is carried out when system temperature rises to 200 DEG C, then
After system temperature is risen to 300 DEG C and constant temperature 5h with the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After degree rises to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, pressure tune will be restored
After section is 10MPa and continues constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammino of carrier
Outlet moisture content at catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.53%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 19.88%.
Embodiment 24
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be 2
Under conditions of MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.76%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.01%.
Embodiment 25
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 1%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.83%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.51%.
Embodiment 26
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 4%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 1g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.98%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.77%.
Embodiment 27
It is at normal temperature carrier by the graphitization active carbon through reaming and presoma is that no chlorine ruthenium complex synthesizes ruthenium content
It is placed in reactor for 10% ruthenium system ammonia synthesis catalyst, reaction system is enabled to restore air speed as 10000h-1, reduction pressure be
Under conditions of 4MPa and the gaseous mixture for being passed through hydrogen and nitrogen that hydrogen content is 75% are reducing gas, make system temperature with 20
DEG C/temperature rise speed of h rises to 200 DEG C, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 2%, the progress constant temperature 5h when system temperature rises to 200 DEG C, then with
After system temperature is risen to 300 DEG C and constant temperature 5h by the temperature rise speed of 30 DEG C/h, then with the temperature rise speed of 30 DEG C/h by system temperature
After rising to 400 DEG C and constant temperature 5h, then after system temperature is risen to 500 DEG C with the temperature rise speed of 30 DEG C/h, reduction pressure is adjusted
For 10MPa and after continuing constant temperature 20h, the reduction of catalyst can be completed, the active carbon after reduction is the ruthenium system ammonia synthesis of carrier
The outlet moisture content of catalyst reactor is 2g/m3。
Performance test
The ruthenium system ammonia synthesis catalyst that active carbon obtained is carrier is placed in reactors for synthesis of ammonia and is used as catalyst,
H2: N2=3:1, reaction temperature be 400 DEG C, air speed 10000h-1, pressure be 10MPa under conditions of carry out ammonia synthesis, detect
The ammonia density of reactor outlet reaches 19.57%, then by reaction temperature be promoted to 500 DEG C, pressure be inspection after 10MPa synthesizes 20h
The ammonia density for measuring reactor outlet reaches 20.43%.
The above is the embodiment of the present invention, for the ordinary skill in the art, religion according to the present invention
Lead, without departing from the principles and spirit of the present invention all equivalent changes done according to scope of the present invention patent, repair
Change, replacement and variant, is all covered by the present invention.
Claims (8)
1. the restoring method that a kind of active carbon is the ruthenium system ammonia synthesis catalyst of carrier, it is characterised in that: at normal temperature will catalysis
Agent is placed in reactor, and reaction system is enabled to restore air speed as 3000~30000h-1, reduction pressure be 0.5~4MPa and to be passed through
Under conditions of reducing gas, system temperature is made gradually to rise to 500 DEG C, wherein at 200 DEG C, 300 DEG C, 400 DEG C, to carry out constant temperature
It heats up again after 0.5~10h, when temperature reaches 500 DEG C, after being adjusted to 10MPa by reduction pressure and continue 8~40h of constant temperature
Complete the reduction of catalyst；The active carbon is that the ruthenium presoma in the ruthenium system ammonia synthesis catalyst of carrier is water solubility without chlorine ruthenium
Complex compound.
2. a kind of active carbon according to claim 1 is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier, feature
Be: the active carbon is the ruthenium content in the ruthenium system ammonia synthesis catalyst of carrier 4%~10%.
3. a kind of active carbon according to claim 1 is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier, feature
Be: the reaction system is 4~25 DEG C/h in the heating rate for being warming up to 200 DEG C of processes, is heated up at 200 DEG C~500 DEG C
The heating rate of journey is 10~40 DEG C/h.
4. a kind of active carbon according to claim 1 is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier, feature
Be: the active carbon is that the active carbon in the ruthenium system ammonia synthesis catalyst of carrier is the graphitization active carbon through reaming.
5. a kind of active carbon according to claim 1 is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier, feature
Be: the active carbon is that the ruthenium system ammonia synthesis catalyst of carrier is not higher than 2g/ in the outlet moisture content of reduction post-reactor
m3。
6. a kind of active carbon according to claim 1 is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier, feature
Be: the reducing gas is that hydrogen is mixed with the one of which in nitrogen, argon gas, helium, Krypton, xenon.
7. a kind of active carbon according to claim 6 is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier, feature
Be: the content of hydrogen is 5%~75% in the reducing gas.
8. a kind of active carbon according to claim 1 is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier, feature
Be: the restoring method further includes, during reaction system is warming up to 200 DEG C, if the temperature rise of catalyst bed is more than
When 25 DEG C/h, the hydrogen content in reducing gas is controlled 1%~4%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610931108.1A CN106540715B (en) | 2016-10-31 | 2016-10-31 | A kind of active carbon is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier |
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| CN201610931108.1A CN106540715B (en) | 2016-10-31 | 2016-10-31 | A kind of active carbon is the restoring method of the ruthenium system ammonia synthesis catalyst of carrier |
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| CN1401426A (en) * | 2001-08-15 | 2003-03-12 | 中国石油化工股份有限公司 | Ammonia synthesis ruthenium based catalyst and preparing process thereof |
| CN101053834A (en) * | 2006-04-14 | 2007-10-17 | 中国石油化工股份有限公司 | Ruthenium-based ammonia synthesis catalyst and its preparation method |
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| CN1401426A (en) * | 2001-08-15 | 2003-03-12 | 中国石油化工股份有限公司 | Ammonia synthesis ruthenium based catalyst and preparing process thereof |
| CN101053834A (en) * | 2006-04-14 | 2007-10-17 | 中国石油化工股份有限公司 | Ruthenium-based ammonia synthesis catalyst and its preparation method |
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| Title |
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| "The Effect of Hydrogen Treatment of Active Carbon on Ru Catalysts for Ammonia Synthesis";Zhi-hua Zhong等;《JOURNAL OF CATALYSIS》;19981231;第173卷;第535页右栏第4段-536页左栏第6段 |
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