CN108404999A - A kind of restoring method of ruthenium system ammonia synthesis catalyst - Google Patents

A kind of restoring method of ruthenium system ammonia synthesis catalyst Download PDF

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CN108404999A
CN108404999A CN201810105874.1A CN201810105874A CN108404999A CN 108404999 A CN108404999 A CN 108404999A CN 201810105874 A CN201810105874 A CN 201810105874A CN 108404999 A CN108404999 A CN 108404999A
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reduction
catalyst
ammonia synthesis
temperature
synthesis catalyst
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CN108404999B (en
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倪军
涂子龙
林建新
林炳裕
江莉龙
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FUJIAN SANJU FUDA FERTILIZER CATALYST NATIONAL ENGINEERING RESEARCH CENTER Co Ltd
Fuzhou University
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FUJIAN SANJU FUDA FERTILIZER CATALYST NATIONAL ENGINEERING RESEARCH CENTER Co Ltd
Fuzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to Reduction of Ammonia Synthesis Catalyst technical fields, and in particular to a kind of restoring method of ruthenium system ammonia synthesis catalyst.The restoring method of ruthenium system provided by the invention ammonia synthesis catalyst, it is 0.1~0.4MPa to control entire heating reduction process reduction pressure, and initial stage is restored using low hydrogen reduction according to the reduction feature of catalyst, restore hydrogen reduction during mid-term uses, latter stage is restored using high hydrogen reduction, processing is passivated after reduction, catalyst reduction process is steady, vapour concentration is low, reduction is more thorough, activity, strength and stability after catalyst reduction is all fine, and reduction is of high quality, and catalyst activity is reduced directly high by 1% or more than factory.

Description

A kind of restoring method of ruthenium system ammonia synthesis catalyst
Technical field
The invention belongs to Reduction of Ammonia Synthesis Catalyst technical fields, and in particular to a kind of reduction of ruthenium system ammonia synthesis catalyst Method.
Background technology
From BP companies of Britain in 1992 and Kellogg companies of the U.S. successfully develop activated carbon supported ruthenium ammonia synthesis catalyst with Come, since the catalyst can efficiently synthesize ammonia under the conditions ofs lower reaction temperature, pressure etc., it is considered to be after ferrum-based catalyst Later second generation ammonia synthesis catalyst.
As traditional iron ammonia synthesis catalyst, industrial ruthenium system ammonia synthesis catalyst also must just have after carrying out reduction Activity.The patent document of the prereduction in relation to Fe-series catalyst and passivation is more in the prior art, such as Chinese patent literature The specific aim side that CN104785305B, CN105435861A etc. make both for the reduction feature of iron ammonia synthesis catalyst Case, but since Fe-series catalyst is different from ruthenium catalyst physicochemical properties, such as grain size, carrier, main reduction temperature etc. There are larger differences, therefore can not directly convert.
Currently, the large-scale industrial application time of ruthenium system ammonia synthesis catalyst is shorter, the reduction of catalyst typically exists Ammonia factory is synthesized to carry out.For example, Chinese patent literature CN106540715A discloses the ruthenium system ammino that a kind of activated carbon is carrier At the restoring method of catalyst, concrete operation step is：Catalyst is placed in reactor at normal temperatures, enables reaction system also Former air speed is 3000~30000h-1, reduction pressure be 0.5~4MPa and to be passed through under conditions of reducing gas, make system temperature by Step rises to 500 DEG C, wherein at 200 DEG C, 300 DEG C, 400 DEG C, heats up again after carrying out 0.5~10h of constant temperature, temperature reaches 500 DEG C When, after reduction pressure is adjusted to 10MPa and continues 8~40h of constant temperature, complete the reduction of catalyst.But this patent document Disclosed catalyst prereduction method, reduction pressure is high, and reduction rate is fast, causes reduction system water vapor concentration higher, causes The activity of catalyst reduces；In addition, this method does not include passivation step, therefore it is only applicable to synthesizing the scene of ammonia factory also Original by the production for influencing factory and makes so if design requirement is not achieved in catalyst reduction misoperation, activity level With.Therefore, it is necessary to develop a kind of just progress prereduction and can before the use of synthesis ammonia factory of ruthenium system ammonia synthesis catalyst The performance for playing ruthenium system ammonia synthesis catalyst to greatest extent improves catalyst and uses active method.
Invention content
Therefore, when the technical problem to be solved in the present invention is to overcome ruthenium system Reduction of Ammonia Synthesis Catalyst in the prior art Since reduction pressure height, reduction system water vapor concentration height etc. lead to the defect that catalyst activity cannot play very well, to There is provided a kind of can play catalyst performance, restoring method suitable for ruthenium system ammonia synthesis catalyst to greatest extent.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：
A kind of restoring method of ruthenium system ammonia synthesis catalyst, including,
It it is 60~500 DEG C in reaction temperature, under conditions of reaction pressure is 0.1~0.4MPa, using hydrogen and nitrogen Mixed gas carries out reduction treatment to ruthenium system ammonia synthesis catalyst；
At reduction initial stage, volume content of the hydrogen in mixed gas is 0.1-5%, will with the heating rate of 2-3 DEG C/h The temperature of catalyst is increased to 200 DEG C by 60 DEG C, the recovery time >=30h；
In reduction mid-term, volume content of the hydrogen in mixed gas is 5-20%, will with the heating rate of 5-10 DEG C/h The temperature of catalyst is increased to 400 DEG C by 200 DEG C, recovery time ＞ 30h；
In reduction latter stage, volume content of the hydrogen in mixed gas is 20-70%, will with the heating rate of 5-10 DEG C/h The temperature of catalyst is increased to 500 DEG C by 400 DEG C, recovery time ＞ 30h.
Further, further include after reduction, under nitrogen protection, catalyst temperature being down to 50 DEG C hereinafter, then Nitrogen and air are passed through in reaction system and are passivated, reaction system pressure is controlled in 0.05-0.1MPa, waits for catalyst temperature It is down to 35 DEG C hereinafter, being passivated to terminate, obtains ruthenium system ammonia synthesis catalyst pre-reduction.
Further, vapour concentration is controlled in the reduction step be not more than 1.0g/m3。
Further, vapour concentration is more than 1.0g/m in the reduction step3When, pause heating.
Further, the air speed of hydrogen and nitrogen mixed gas is controlled in 5000h in the reduction step-1More than.
Further, reduction initial stage and reduction mid-term described in gaseous mixture with continous way or it is intermittent be passed through reaction system, Gaseous mixture is passed through reaction system with continous way described in reduction latter stage.
Further, add up water yield in the reduction step and reach theoretical 90% or more water yield, measure vapour concentration 0.1g/m3When following, reduction terminates.
Further, 300~1000h of nitrogen air speed is first kept in the passivation step-1, air is then passed to, air Air speed is raised to 100h from 0-1Afterwards, stop being passed through nitrogen.
Further, passivation step control catalyst temperature is no more than 60 DEG C, catalyst temperature rise rate be less than 5 DEG C/ h。
Further, it is passivated initial stage O2Volume content is controlled 0.1%~0.5%, with the carry out O of process2Volume content Gradually increase to 0.5%~2%；Mid-term oxygen content is passivated 2~10%；It is passivated later stage oxygen content 10~21%, is passivated later stage O2 Content, which is gradually increased until, finally all switches to air.
Further, the residence time at passivation initial stage, passivation mid-term and passivation later stage is 4~6h, it is preferred that is stopped 5h。
Technical solution of the present invention has the following advantages that：
The restoring method of 1 ruthenium system provided by the invention ammonia synthesis catalyst, entire heating reduction process reduction pressure is 0.1 ~0.4MPa, and initial stage is restored using low hydrogen reduction according to the reduction feature of catalyst, hydrogen reduction during reduction mid-term uses restores Latter stage uses high hydrogen reduction, and catalyst reduction process is steady, and vapour concentration is very low, and reduction is more thorough, after catalyst reduction Activity, strength and stability are all fine, and reduction is of high quality, and catalyst activity is reduced directly high by 1% or more than factory.
The restoring method of 2 ruthenium system provided by the invention ammonia synthesis catalysts, hydrogen in reduction phase Discrete control reduction system Gas content, hydrogen usage is reduced, energy-saving.
The restoring method of 3 ruthenium system provided by the invention ammonia synthesis catalysts reduces catalyst using preceding in ammonia synthesis work The stability of the recovery time of factory, catalyst are controllable, reduce the influence to ammonia synthesis factory.
Specific implementation mode
For convenience of description, the catalyst composition used in the embodiment of the present invention and comparative example is as follows：
It is the 5% of catalyst quality that ruthenium system ammonia synthesis catalyst measures ruthenium content by micro-wave digestion-ICP in embodiment, Potassium content is the 4.0% of catalyst quality, and barium content is the 8.30% of catalyst quality.
Embodiment 1
A kind of restoring method of ruthenium system ammonia synthesis catalyst, concrete operation step are as follows：
1) initial stage is restored：Reduction initial stage is a large amount of water outlet stages of ruthenium catalyst, and reduction rate is very fast.The ammonia synthesis of ruthenium system is urged Agent is placed in reactor, is passed through hydrogen nitrogen mixed gas, and the volume ratio of hydrogen exists in reduction initial stage control in the hydrogen nitrogen mixed gas 0.1% or so, and heating rate is controlled, reduction reaction is proceeded by when ruthenium system ammonia synthesis catalyst temperature rises to 60 DEG C, is restored Reaction pressure is 0.4MPa, and the heating rate when reduction initial stage is 3 DEG C/h, and temperature is 60~200 DEG C, and the recovery time is 30h, control vapour concentration is not more than 1.0g/m in reduction process3, vapour concentration is exceeded, pause heating, air speed in reduction process Control is in 5000h-1More than, if heating rate is exceeded, pause is passed through hydrogen.
2) mid-term is restored：Ruthenium catalyst restores that water yield relative reduction initial stage is few, and reduction rate is more steady, when reduction Hydrogen content is higher.When catalyst reduction mid-term, for hydrogen volume content 5% or so, control vapour concentration does not exceed 1.0g/m3, Catalyst layer temperature is 200~400 DEG C, and heating rate is 10 DEG C/h, recovery time 30h.
3) latter stage is restored：When restoring latter stage, reduction temperature is stepped up to 400~500 DEG C, and heating rate is 10 DEG C/h, The recovery time is 20h at 500 DEG C, and reduction latter stage uses continuous tonifying Qi, hydrogen content to improve to 70%, when accumulative water yield reaches reason By 90% or more water yield, vapour concentration 0.1g/Nm is continuously measured three times3Determine that reduction is completed when following.
4) it is passivated the stage：Control system pressure 0.05-0.1MPa or so in passivating process is controlled using air flow meter and is mended Enter air capacity, oxygen content ＜ 0.1% in control loop gas.Sampling analysis oxygen content is imported and exported in tower, keeps a close eye on bed temperature Variation finds that temperature has apparent rise to stop being added air, and temperature does not change interruption supplying air successively, until being added into tower Oxygen content is 0.1% in circulating air.The control of passivating process catalyst bed hot(test)-spot temperature is no more than 60 DEG C, catalyst temperature rise rate Less than 5 DEG C/h, when tower inlet and outlet oxygen content is not much different, and bed temperature stablize relatively after continuous short covering gas again.It is passivated Per half an hour, analysis single sintering tower imports and exports oxygen content to journey.O in passivation initial stage inlet tower gas2Content control is lower, control early period 0.1%~0.5% (volume fraction) is made, it is total to stop as the progress of process gradually increases to 0.5%~2.0% (volume fraction) Time is 4h, and 2%~10%, residence time 6h, the later stage subtracts passivation mid-term Control for Oxygen Content due to catalyst oxidation rate Slowly, O2Content, which can be gradually increased until, finally all switches to air, residence time 4h.
5) discharging stage：When tower is worked off one's feeling vent one's spleen middle O2Bed temperature no longer rises when content reaches about 20% (volume fraction), Bed temperature begins to decline i.e. mark passivation and is over after a period of time, and bed temperature is down to 30 DEG C or less stopping gases Cycle.Analysis is sampled to each equipment and pipeline in system before discharging, it is ensured that ammonia content≤10ppm, hydrogen content in pipeline ≤ 100ppm, oxygen content >=20% reach shutdown standard.
6) catalyst activity is tested：Active testing procatalyst first restores, and heating rate is 1 DEG C/min, and pressure control exists 1MPa, air speed 10000h-1, from room temperature to 400 DEG C, constant temperature is forced into 10MPa after 4 hours constant temperature starts after 4 hours again Survey activity.In 10000h-1, 10MPa, 400 DEG C, H2/N2=3:Under the conditions of 1, the Viability ammino of catalyst is 20.3%, 10000h-1, 10MPa, 500 DEG C, H2/N2=3:Under the conditions of 1 after heat-resisting 40 hours, catalyst activity 20.6%.
Embodiment 2
A kind of restoring method of ruthenium system ammonia synthesis catalyst, concrete operation step are as follows：
1) initial stage is restored：Reduction initial stage is a large amount of water outlet stages of ruthenium catalyst, and reduction rate is very fast.The ammonia synthesis of ruthenium system is urged Agent is placed in reactor, is passed through hydrogen nitrogen mixed gas, and the volume ratio of hydrogen exists in reduction initial stage control in the hydrogen nitrogen mixed gas 1%, and heating rate is controlled, proceed by reduction reaction, reduction reaction pressure when ruthenium system ammonia synthesis catalyst temperature rises to 60 DEG C Power is 0.4MPa, and the heating rate when reduction initial stage is 3 DEG C/h, and temperature is 60~200 DEG C, recovery time 70h, reduction Control vapour concentration is not more than 1.0g/m in the process3, vapour concentration is exceeded, pause heating, and air speed, which controls, in reduction process exists 5000h-1More than, if heating rate is exceeded, pause is passed through hydrogen.
2) mid-term is restored：Ruthenium catalyst restores that water yield relative reduction initial stage is few, and reduction rate is more steady, when reduction Hydrogen content is higher.When catalyst reduction mid-term, for hydrogen volume content 10% or so, control vapour concentration does not exceed 1.0g/m3, Catalyst layer temperature is 200~400 DEG C, and heating rate is 10 DEG C/h, recovery time 30h.
3) latter stage is restored：When restoring latter stage, reduction temperature is stepped up to 400~500 DEG C, and heating rate is 5 DEG C/h, The recovery time is 20h at 500 DEG C, and continuous tonifying Qi may be used in former latter stage, and hydrogen content is improved to 65%, when accumulative water yield reaches 90% or more theoretical water yield continuously measures vapour concentration 0.1g/Nm three times3Determine that reduction is completed when following.
4) it is passivated the stage：Control system pressure 0.05-0.1MPa or so in passivating process is controlled using air flow meter and is mended Enter air capacity, oxygen content ＜ 0.1% in control loop gas.Sampling analysis oxygen content is imported and exported in tower, keeps a close eye on bed temperature Variation finds that temperature has apparent rise that should stop being added air, and temperature does not change can be interrupted supplying air successively, until being added to Enter oxygen content 0.1% in tower circulating air.The control of passivating process catalyst bed hot(test)-spot temperature is no more than 60 DEG C, bed temperature rise rate Less than 5 DEG C/h, when tower inlet and outlet oxygen content is not much different, and bed temperature stablize relatively after continuous short covering gas again.It is passivated Per half an hour, analysis single sintering tower imports and exports oxygen content to journey.O in passivation initial stage inlet tower gas2Content control is lower, control early period 0.1%~0.5% (volume fraction) is made, it is total to stop as the progress of process gradually increases to 0.5%~2.0% (volume fraction) Time is 6h, and 2%~10%, residence time 4h, the later stage subtracts passivation mid-term Control for Oxygen Content due to catalyst oxidation rate Slowly, O2Content, which can be gradually increased until, finally all switches to air, residence time 6h.
5) discharging stage：When tower is worked off one's feeling vent one's spleen middle O2Bed temperature no longer rises when content reaches about 20% (volume fraction), Bed temperature begins to decline i.e. mark passivation and is over after a period of time, and bed temperature is down to 30 DEG C or less stopping gases Cycle.Analysis is sampled to each equipment and pipeline in system before discharging, it is ensured that ammonia content≤10ppm, hydrogen content in pipeline ≤ 100ppm, oxygen content >=20% reach shutdown standard.
6) catalyst activity is tested：Active testing procatalyst first restores, and heating rate is 1 DEG C/min, and pressure control exists 1MPa, air speed 10000h-1, from room temperature to 400 DEG C, constant temperature is forced into 10MPa after 4 hours constant temperature starts after 4 hours again Survey activity.In 10000h-1, 10MPa, 400 DEG C, H2/N2=3:Under the conditions of 1, the Viability ammino of catalyst is 20.1%, 10000h-1, 10MPa, 500 DEG C, H2/N2=3:Under the conditions of 1 after heat-resisting 40 hours, catalyst activity 20.9%.
Embodiment 3
A kind of restoring method of ruthenium system ammonia synthesis catalyst, concrete operation step are as follows：
1) initial stage is restored：Reduction initial stage is a large amount of water outlet stages of ruthenium catalyst, and reduction rate is very fast.The ammonia synthesis of ruthenium system is urged Agent is placed in reactor, is passed through hydrogen nitrogen mixed gas, and the volume ratio of hydrogen exists in reduction initial stage control in the hydrogen nitrogen mixed gas 5%, and heating rate is controlled, proceed by reduction reaction, reduction reaction pressure when ruthenium system ammonia synthesis catalyst temperature rises to 60 DEG C Power is 0.1MPa, and the heating rate when reduction initial stage is 2 DEG C/h, and temperature is 60~200 DEG C, recovery time 50h, reduction Control vapour concentration is not more than 1.0g/m in the process3, vapour concentration is exceeded, pause heating, and air speed should control in reduction process 5000h-1More than, if heating rate is exceeded, pause is passed through hydrogen.
2) mid-term is restored：Ruthenium catalyst restores that water yield relative reduction initial stage is few, and reduction rate is more steady, when reduction Hydrogen content is higher.When catalyst reduction mid-term, hydrogen volume content, with the raising of reduction temperature, is stepped up 20% or so Hydrogen content in reducing gas, control vapour concentration do not exceed 1.0g/m3, catalyst layer temperature is 200~400 DEG C, heating Rate is 5 DEG C/h, recovery time 40h.
3) latter stage is restored：When restoring latter stage, reduction temperature is stepped up to 400~500 DEG C, and heating rate is 8 DEG C/h, The recovery time is 20h at 500 DEG C, and continuous tonifying Qi may be used in former latter stage, and hydrogen content is improved to 50%, when accumulative water yield reaches 90% or more theoretical water yield continuously measures vapour concentration 0.1g/Nm three times3Determine that reduction is completed when following.
4) it is passivated the stage：Control system pressure 0.05-0.1MPa or so in passivating process is controlled using air flow meter and is mended Enter air capacity, oxygen content ＜ 0.1% in control loop gas.Sampling analysis oxygen content is imported and exported in tower, keeps a close eye on bed temperature Variation finds that temperature has apparent rise that should stop being added air, and temperature does not change can be interrupted supplying air successively, until being added to Enter oxygen content 0.1% in tower circulating air.The control of passivating process catalyst bed hot(test)-spot temperature is no more than 60 DEG C, bed temperature rise rate Less than 5 DEG C/h, when tower inlet and outlet oxygen content is not much different, and bed temperature stablize relatively after continuous short covering gas again.It is passivated Per half an hour, analysis single sintering tower imports and exports oxygen content to journey.O in passivation initial stage inlet tower gas2Content control is lower, control early period 0.1%~0.5% (volume fraction) is made, it is total to stop as the progress of process gradually increases to 0.5%~2.0% (volume fraction) Time is 5h, and 2%~10%, residence time 5h, the later stage subtracts passivation mid-term Control for Oxygen Content due to catalyst oxidation rate Slowly, O2Content, which can be gradually increased until, finally all switches to air, residence time 5h.
5) discharging stage：When tower is worked off one's feeling vent one's spleen middle O2Bed temperature no longer rises when content reaches about 20% (volume fraction), Bed temperature begins to decline i.e. mark passivation and is over after a period of time, and bed temperature is down to 30 DEG C or less stopping gases Cycle.Analysis is sampled to each equipment and pipeline in system before discharging, it is ensured that ammonia content≤10ppm, hydrogen content in pipeline ≤ 100ppm, oxygen content >=20% reach shutdown standard.
6) catalyst activity is tested：Active testing procatalyst first restores, and heating rate is 1 DEG C/min, and pressure control exists 1MPa, air speed 10000h-1, from room temperature to 400 DEG C, constant temperature is forced into 10MPa after 4 hours constant temperature starts after 4 hours again Survey activity.In 10000h-1, 10MPa, 400 DEG C, H2/N2=3:Under the conditions of 1, the Viability ammino of catalyst is 20.5%, 10000h-1, 10MPa, 500 DEG C, H2/N2=3:Under the conditions of 1 after heat-resisting 40 hours, catalyst activity 20.7%.
Embodiment 4
A kind of restoring method of ruthenium system ammonia synthesis catalyst, concrete operation step are as follows：
1) initial stage is restored：Reduction initial stage is a large amount of water outlet stages of ruthenium catalyst, and reduction rate is very fast.The ammonia synthesis of ruthenium system is urged Agent is placed in reactor, is passed through hydrogen nitrogen mixed gas, and the volume ratio of hydrogen exists in reduction initial stage control in the hydrogen nitrogen mixed gas 2%, and heating rate is controlled, proceed by reduction reaction, reduction reaction pressure when ruthenium system ammonia synthesis catalyst temperature rises to 60 DEG C Power is 0.2MPa, and the heating rate when reduction initial stage is 3 DEG C/h, and temperature is 60~200 DEG C, recovery time 35h, reduction Control vapour concentration is not more than 1.0g/m in the process3, vapour concentration is exceeded, pause heating, and air speed should control in reduction process 5000h-1More than, if heating rate is exceeded, pause is passed through hydrogen.
2) mid-term is restored：Ruthenium catalyst restores that water yield relative reduction initial stage is few, and reduction rate is more steady, when reduction Hydrogen content is higher.When catalyst reduction mid-term, for hydrogen volume content 12% or so, control vapour concentration does not exceed 1.0g/m3, Catalyst layer temperature is 200~400 DEG C, and heating rate is 10 DEG C/h, recovery time 30h.
3) latter stage is restored：When restoring latter stage, reduction temperature is stepped up to 400~500 DEG C, and heating rate is 5 DEG C/h, The recovery time is 20h at 500 DEG C, and continuous tonifying Qi may be used in former latter stage, and hydrogen content is improved to 65%, when accumulative water yield reaches 90% or more theoretical water yield continuously measures vapour concentration 0.1g/Nm three times3Determine that reduction is completed when following.
4) it is passivated the stage：Control system pressure 0.05-0.1MPa or so in passivating process is controlled using air flow meter and is mended Enter air capacity, oxygen content ＜ 0.1% in control loop gas.Sampling analysis oxygen content is imported and exported in tower, keeps a close eye on bed temperature Variation finds that temperature has apparent rise that should stop being added air, and temperature does not change can be interrupted supplying air successively, until being added to Enter oxygen content 0.1% in tower circulating air.The control of passivating process catalyst bed hot(test)-spot temperature is no more than 60 DEG C, bed temperature rise rate Less than 5 DEG C/h, when tower inlet and outlet oxygen content is not much different, and bed temperature stablize relatively after continuous short covering gas again.It is passivated Per half an hour, analysis single sintering tower imports and exports oxygen content to journey.O in passivation initial stage inlet tower gas2Content control is lower, control early period 0.1%~0.5% (volume fraction) is made, it is total to stop as the progress of process gradually increases to 0.5%~2.0% (volume fraction) Time is 5h, and 2%~10%, residence time 5h, the later stage subtracts passivation mid-term Control for Oxygen Content due to catalyst oxidation rate Slowly, O2Content, which is gradually increased until, finally all switches to air, residence time 5h.
5) discharging stage：When tower is worked off one's feeling vent one's spleen middle O2Bed temperature no longer rises when content reaches about 20% (volume fraction), Bed temperature begins to decline i.e. mark passivation and is over after a period of time, and bed temperature is down to 30 DEG C or less stopping gases Cycle.Analysis is sampled to each equipment and pipeline in system before discharging, it is ensured that ammonia content≤10ppm, hydrogen content in pipeline ≤ 100ppm, oxygen content >=20% reach shutdown standard.
6) catalyst activity is tested：Active testing procatalyst first restores, and heating rate is 1 DEG C/min, and pressure control exists 1MPa, air speed 10000h-1, from room temperature to 400 DEG C, constant temperature is forced into 10MPa after 4 hours constant temperature starts after 4 hours again Survey activity.In 10000h-1, 10MPa, 400 DEG C, H2/N2=3:Under the conditions of 1, the Viability ammino of catalyst is 20.4%, 10000h-1, 10MPa, 500 DEG C, H2/N2=3:Under the conditions of 1 after heat-resisting 40 hours, catalyst activity 20.8%.
Embodiment 5
A kind of restoring method of ruthenium system ammonia synthesis catalyst, concrete operation step are as follows：
1) initial stage is restored：Reduction initial stage is a large amount of water outlet stages of ruthenium catalyst, and reduction rate is very fast.The ammonia synthesis of ruthenium system is urged Agent is placed in reactor, is passed through hydrogen nitrogen mixed gas, and the volume ratio of hydrogen exists in reduction initial stage control in the hydrogen nitrogen mixed gas 3%, and heating rate is controlled, proceed by reduction reaction, reduction reaction pressure when ruthenium system ammonia synthesis catalyst temperature rises to 60 DEG C Power is 0.3MPa, and the heating rate when reduction initial stage is 3 DEG C/h, and temperature is 60~200 DEG C, recovery time 40h, reduction Control vapour concentration is not more than 1.0g/m in the process3, vapour concentration is exceeded, pause heating, and air speed should control in reduction process 5000h-1More than, if heating rate is exceeded, pause is passed through hydrogen.
2) mid-term is restored：Ruthenium catalyst restores that water yield relative reduction initial stage is few, and reduction rate is more steady, when reduction Hydrogen content is higher.When catalyst reduction mid-term, for hydrogen volume content 16% or so, control vapour concentration does not exceed 1.0g/m3, Catalyst layer temperature is 200~400 DEG C, and heating rate is 10 DEG C/h, recovery time 35h.
3) latter stage is restored：When restoring latter stage, reduction temperature is stepped up to 400~500 DEG C, and heating rate is 5 DEG C/h, The recovery time is 20h at 500 DEG C, and continuous tonifying Qi may be used in former latter stage, and hydrogen content is improved to 45%, when accumulative water yield reaches 90% or more theoretical water yield continuously measures vapour concentration 0.1g/Nm three times3Determine that reduction is completed when following.
4) it is passivated the stage：Control system pressure 0.05-0.1MPa or so in passivating process is controlled using air flow meter and is mended Enter air capacity, oxygen content ＜ 0.1% in control loop gas.Sampling analysis oxygen content is imported and exported in tower, keeps a close eye on bed temperature Variation finds that temperature has apparent rise that should stop being added air, and temperature does not change can be interrupted supplying air successively, until being added to Enter oxygen content 0.1% in tower circulating air.The control of passivating process catalyst bed hot(test)-spot temperature is no more than 60 DEG C, bed temperature rise rate Less than 5 DEG C/h, when tower inlet and outlet oxygen content is not much different, and bed temperature stablize relatively after continuous short covering gas again.It is passivated Per half an hour, analysis single sintering tower imports and exports oxygen content to journey.O in passivation initial stage inlet tower gas2Content control is lower, control early period 0.1%~0.5% (volume fraction) is made, it is total to stop as the progress of process gradually increases to 0.5%~2.0% (volume fraction) Time is 5h, and 2%~10%, residence time 5h, the later stage subtracts passivation mid-term Control for Oxygen Content due to catalyst oxidation rate Slowly, O2Content, which is gradually increased until, finally all switches to air, residence time 5h.
5) discharging stage：When tower is worked off one's feeling vent one's spleen middle O2Bed temperature no longer rises when content reaches about 20% (volume fraction), Bed temperature begins to decline i.e. mark passivation and is over after a period of time, and bed temperature is down to 30 DEG C or less stopping gases Cycle.Analysis is sampled to each equipment and pipeline in system before discharging, it is ensured that ammonia content≤10ppm, hydrogen content in pipeline ≤ 100ppm, oxygen content >=20% reach shutdown standard.
6) catalyst activity is tested：Active testing procatalyst first restores, and heating rate is 1 DEG C/min, and pressure control exists 1MPa, air speed 10000h-1, from room temperature to 400 DEG C, constant temperature is forced into 10MPa after 4 hours constant temperature starts after 4 hours again Survey activity.In 10000h-1, 10MPa, 400 DEG C, H2/N2=3:Under the conditions of 1, the Viability ammino of catalyst is 20.5%, 10000h-1, 10MPa, 500 DEG C, H2/N2=3:Under the conditions of 1 after heat-resisting 40 hours, catalyst activity 20.6%.
Comparative example 1
A kind of restoring method of ruthenium system ammonia synthesis catalyst, concrete operation step are as follows：
1) reduction phase：It it is 60-500 DEG C in reaction temperature, under conditions of reaction pressure is 0.1-0.4MPa, using hydrogen Reduction treatment carried out to ruthenium system ammonia synthesis catalyst with the mixed gas of nitrogen, the volume ratio control of hydrogen in the hydrogen nitrogen mixed gas System is 5%, and it is 30 DEG C/h to control heating rate, and reduction is proceeded by instead when ruthenium system ammonia synthesis catalyst temperature rises to 60 DEG C It answers, reduction reaction pressure is 0.1MPa, recovery time 15h, and air speed should be controlled in 5000h in reduction process-1More than.
2) it is passivated the stage：After reduction reaction, hydrogen and nitrogen gas is replaced into pure nitrogen gas, and temperature in reduction tower is down to 50 DEG C Below, pressure control after 0.05~0.1MPa, by air gradually be passed through reduction tower in be passivated, be passivated the stage air and Nitrogen mixture pressure maintains 0.05~0.1MPa, and air content steps up, and reduction tower outlet oxygen highest content is Stop passivation when 20%；Temperature is down to 35 DEG C and is terminated hereinafter, being passivated in tower to be restored, obtains the ammonia synthesis prereduction catalysis of ruthenium system Agent；
3) discharging stage：When tower is worked off one's feeling vent one's spleen middle O2Bed temperature no longer rises when content reaches about 20% (volume fraction), Bed temperature begins to decline i.e. mark passivation and is over after a period of time, and bed temperature is down to 30 DEG C or less stopping gases Cycle.Analysis is sampled to each equipment and pipeline in system before discharging, it is ensured that ammonia content≤10ppm, hydrogen content in pipeline ≤ 100ppm, oxygen content >=20% reach shutdown standard.
4) catalyst activity is tested：Active testing procatalyst first restores, and heating rate is 1 DEG C/min, and pressure control exists 1MPa, air speed 10000h-1, from room temperature to 400 DEG C, constant temperature is forced into 10MPa after 4 hours constant temperature starts after 4 hours again Survey activity.In 10000h-1, 10MPa, 400 DEG C, H2/N2=3:Under the conditions of 1, the Viability ammino of catalyst is 17.5%, 10000h-1, 10MPa, 500 DEG C, H2/N2=3:Under the conditions of 1 after heat-resisting 40 hours, catalyst activity 17.7%.
Comparative example 2
Ruthenium system ammonia synthesis catalyst is placed in reactor by a kind of restoring method of ruthenium system ammonia synthesis catalyst, enables reaction System is 10000h in reduction air speed-1, reduction pressure be 4MPa and be passed through the mixing of hydrogen and nitrogen that hydrogen content is 75% Gas be reducing gas under conditions of, so that system temperature is risen to 200 DEG C with the temperature rise speed of 20 DEG C/h, be warming up in reaction system During 200 DEG C, if the Wen Sheng of catalyst bed is more than 30 DEG C/h, by the hydrogen content control in reducing gas 2%, System temperature carries out constant temperature 5h when rising to 200 DEG C, then system temperature is risen to 300 DEG C and constant temperature 5h with the temperature rise speed of 30 DEG C/h Afterwards, after then system temperature being risen to 400 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 body It is after temperature rises to 500 DEG C, after reduction pressure is adjusted to 10MPa and continues constant temperature 20h, you can the reduction of catalyst is completed, Activated carbon after reduction is the outlet moisture content of the ruthenium system ammonia synthesis catalyst reactor of carrier<0.1g/m3。
Catalyst activity is tested：In 10000h-1, 10MPa, 400 DEG C, H2/N2=3:Under the conditions of 1, the ammonia synthesis of catalyst Activity is 18.6%, in 10000h-1, 10MPa, 500 DEG C, H2/N2=3:Under the conditions of 1 after heat-resisting 40 hours, catalyst activity is 19.0%.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And thus amplify out it is obvious variation or It changes still within the protection scope of the invention.

Claims (10)

1. a kind of restoring method of ruthenium system ammonia synthesis catalyst, which is characterized in that including,
It it is 60~500 DEG C in reaction temperature, under conditions of reaction pressure is 0.1~0.4MPa, using the mixing of hydrogen and nitrogen Gas carries out reduction treatment to ruthenium system ammonia synthesis catalyst；
At reduction initial stage, volume content of the hydrogen in mixed gas is 0.1-5%, will be catalyzed with the heating rate of 2-3 DEG C/h The temperature of agent is increased to 200 DEG C by 60 DEG C, the recovery time >=30h；
In reduction mid-term, volume content of the hydrogen in mixed gas is 5-20%, will be catalyzed with the heating rate of 5-10 DEG C/h The temperature of agent is increased to 400 DEG C by 200 DEG C, recovery time ＞ 30h；
In reduction latter stage, volume content of the hydrogen in mixed gas is 20-70%, will be catalyzed with the heating rate of 5-10 DEG C/h The temperature of agent is increased to 500 DEG C by 400 DEG C, recovery time ＞ 30h.
2. the restoring method of ruthenium system according to claim 1 ammonia synthesis catalyst, which is characterized in that further include reduction knot Catalyst temperature is down to 50 DEG C and is carried out hereinafter, then nitrogen and air are passed through in reaction system by Shu Hou under nitrogen protection Passivation, the control of reaction system pressure are down to 35 DEG C hereinafter, to the end of passivation in 0.05-0.1MPa, when catalyst temperature, obtain ruthenium system Ammonia synthesis catalyst pre-reduction.
3. the restoring method of ruthenium system according to claim 1 ammonia synthesis catalyst, which is characterized in that in the reduction step It controls vapour concentration and is not more than 1.0g/m3。
4. the restoring method of ruthenium system according to claim 3 ammonia synthesis catalyst, which is characterized in that in the reduction step Vapour concentration is more than 1.0g/m3When, pause heating.
5. the restoring method of ruthenium system according to claim 1 ammonia synthesis catalyst, which is characterized in that in the reduction step The air speed of hydrogen and nitrogen mixed gas is controlled in 5000h-1More than.
6. the restoring method of ruthenium system according to claim 1 ammonia synthesis catalyst, which is characterized in that at reduction initial stage and also Gaseous mixture described in former mid-term with continous way or it is intermittent be passed through reaction system, reduction latter stage described in gaseous mixture be passed through with continous way Reaction system.
7. the restoring method of ruthenium system according to claim 1 ammonia synthesis catalyst, which is characterized in that in the reduction step Accumulative water yield reaches theoretical 90% or more water yield, measures vapour concentration 0.1g/m3When following, reduction terminates.
8. the restoring method of ruthenium system according to claim 7 ammonia synthesis catalyst, which is characterized in that the passivation step control Catalyst temperature processed is no more than 60 DEG C, and catalyst temperature rise rate is less than 5 DEG C/h.
9. the restoring method of ruthenium system according to claim 7 ammonia synthesis catalyst, which is characterized in that passivation initial stage O2Volume Content is controlled 0.1%~2%；Mid-term oxygen content is passivated 2~10%；It is passivated later stage oxygen content 10~21%, is passivated the later stage O2Content, which is gradually increased until, finally all switches to air.
10. the restoring method of ruthenium system according to claim 9 ammonia synthesis catalyst, which is characterized in that passivation initial stage, passivation The residence time in mid-term and passivation later stage is 4~6h.
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