CN104713968A - Online analysis system and method for continuous monitoring of catalysis of ammonia synthesis reaction - Google Patents

Online analysis system and method for continuous monitoring of catalysis of ammonia synthesis reaction Download PDF

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CN104713968A
CN104713968A CN201310689499.7A CN201310689499A CN104713968A CN 104713968 A CN104713968 A CN 104713968A CN 201310689499 A CN201310689499 A CN 201310689499A CN 104713968 A CN104713968 A CN 104713968A
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China
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reaction
catalyzer
temperature
anger
micro
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CN201310689499.7A
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Chinese (zh)
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李海洋
谢园园
花磊
侯可勇
陈平
赵无垛
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中国科学院大连化学物理研究所
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Publication of CN104713968A publication Critical patent/CN104713968A/en

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Abstract

The invention provides an online analysis system for continuous monitoring of catalysis of an ammonia synthesis reaction; the used online analysis system comprises a micro reactor device, a temperature control device, a reaction out-flowing gas transmission part, a gas supply device and a reaction out-flowing gas detection device. An online analysis method comprises that the online analysis device is adopted, nitrogen-hydrogen mixed gas flows into the micro reactor device with a certain flow quantity; at the same time, the temperature control device is utilized to set a certain reaction temperature program; and finally, the nitrogen-hydrogen mixed gas are catalyzed by a catalyst at a certain temperature, then a part of reaction gas directly enters the reaction out-flowing gas detection device for analysis through the reaction out-flowing gas transmission part, and the rest is used as tail gas to be discharged. Synthesized ammonia with different concentrations can be obtained through changing the flow rate of the nitrogen-hydrogen mixed gas, the reactor temperature and the catalyst mass and types, the synthesized ammonia directly enters the reaction out-flowing gas detection device through an inlet of the reaction out-flowing gas transmission part without the need of offline concentration, derivatization and other steps; the operation is simple, the analysis speed is fast, the measuring accuracy is high, and the method detection limit is low.

Description

A kind of continuous monitoring catalyzes and synthesizes on-line analysis system and the method for ammonia react

Technical field

The present invention relates to on-line analysis system and method that a kind of continuous monitoring catalyzes and synthesizes ammonia react, be exactly catalyze and synthesize ammonia in micro-reaction tube of utilizing this on-line analysis system to be passed into by nitrogen and hydrogen mixture a certain amount of catalyzer is housed specifically, catalyzer is made to catalyze and synthesize ammonia at different temperature by temperature control equipment, final reaction effluent gases enters gas-detecting device continuously by quartz capillary, thus realizes the object of continuous on-line monitoring synthetic ammonia.

Background technology

The converted products of ammonia and ammonia has important effect in the fields such as plastics, medicine, explosive, metallurgy, environmental protection.In addition the main source of nitrogen manure in it or agricultural, can increase the output of grain significantly, be related to the stable of society and development.At present, the annual production of global ammonia has reached 16,000,000,000 tons.For a long time, various countries' researcher is researching and developing the ammonia synthesis catalyst of high stability, high activity, low cost always.

At present, the off-line chromatography of ions and online Electron impact mass spectra method (EI-MS) is had for the method for catalytic activity and stability under evaluate catalysts different temperatures.The chromatography of ions utilizes the NH in sulfuric acid solution absorption reaction stove effluent gases 3, the NH produced is obtained by the conductance parameter measuring absorbing liquid 3content.But the method wastes time and energy due to steps such as needs pre-concentration, derivatization, wash-outs, low to the concentration change temporal resolution of the ammonia of synthesis, the NH produced cannot be detected by real-time online 3.Can produce very high background signal during the effluent gases of EI-MS on-line analysis reacting furnace, baseline is high, and sensitivity is low, cannot detect the NH of low concentration 3.For detecting NH in document 3method also have Proton transfer reaction mass spectrometry method (PTR-MS), mainly for detection of the NH of ppbv-pptv magnitude in air 3.PTR-MS is with H based on Proton-Transfer Reactions 3o +for reagent ion analyzes ammonia, primary product ion is NH 4 +.But PTR-MS device produces certain density ammonia owing to employing hollow cathode ion source inner can the ionization of ionization source thus produces higher instrumental background signal.In addition, NH 3target peak NH 4 +h may be subject to 2the interference of O, is difficult to qualitative.Afterwards, researcher improved on the basis of PTR-MS instrument, with O 2 +for reagent ion analysis detects NH 3, end-product is NH mainly 3 +but, PTR-MS and with O 2 +chemical ionization mass spectrometry (CI-MS) for reagent ion is all the synthesis for the ammonia of pptv-ppbv magnitude in analyse atmos environment, and the ammonia for the high concentration catalyzed and synthesized also did not carry out continuous on-line detection.In numerous soft ionization mode, Single-photon ionization (SPI) is convenient to the advantage such as qualitative less with its high sensitivity and fragmention and is more and more obtained widely using of people, and for the organic components etc. of the release such as timber, fossil fuels in the concentration change of fragrance matter in on-line analysis cigarette burning flue gas, baked coffee and thermogravimetric analysis.But due to NH 3ionization energy higher, utilize merely SPI cannot obtain higher detection sensitivity, therefore we combine with O 2 +for chemi-ionization (CI) mode of reagent ion, namely the compound electric of SPI-CI analyzes NH from mode 3, the problem of detection sensitivity difference can be solved, and with NH 3 +for object ion carries out qualitative, quantitative, the ammonia that continuous on-line analysis catalyzes and synthesizes middle generation can well be realized.

Object is herein to provide a kind of new method evaluating synthetic ammonia catalyst activity.The method take microreactor as place, nitrogen and hydrogen mixture synthesizes certain density ammonia under the catalysis of catalyzer, then reaction stream give vent to anger enter near the kapillary one end below supporting screening plate reaction stream give vent to anger pick-up unit and Single-photon ionization and chemi-ionization compound electric from mass spectrometer in carry out ionization detection.The method achieve continuous on line real time, without any need for pre-concentration, derivatization or elution step, in long continuous detecting process, time precision is high, can observe the ammonia concentration change at short notice of synthesis.In addition, this device gas circuit is simple, with low cost, convenient operation.

Summary of the invention

The object of this invention is to provide on-line analysis system and method that a kind of continuous monitoring catalyzes and synthesizes ammonia react.

For achieving the above object, technical scheme of the present invention is as follows:

Continuous monitoring catalyzes and synthesizes an on-line analysis system for ammonia react, it is characterized in that: comprise microreactor device, give vent to anger hop, feeder and reaction stream of temperature control equipment, reaction stream give vent to anger pick-up unit;

Wherein, described feeder comprises mass flow controller on carrier gas steel cylinder, its export pipeline, two-way valve and deoxygenation except water pipe;

Described microreactor device is the airtight cavity of hollow, comprise the outlet of micro-reaction tube, heating jacket and residual gas, cavity wall is provided with the heating jacket be connected with extraneous power supply, one end of cavity is provided with nitrogen and hydrogen mixture injection port, combination gas injection port is connected with one end of stainless-steel tube, the other end away from combination gas injection port is provided with reaction stream exhaust outlets and residual gas outlet, be provided with supporting screening plate in cavity between combination gas injection port and reaction stream exhaust outlets, in cavity, be filled with silica wool and catalyzer;

Described temperature control equipment comprises temperature controller and thermocouple temperature sensitive element; One end of thermocouple temperature sensitive element and the outer wall of micro-reaction tube are closely affixed;

Described reaction stream hop of giving vent to anger is elastic quartz capillary tube; It is inner that micro-reaction tube is directly inserted in one end of kapillary, below supporting screening plate, ensure that zero dead volume and zero-lag time, and the give vent to anger sample feeding mouth of pick-up unit of the other end and reaction stream is connected.

Described reaction stream pick-up unit of giving vent to anger is the analytical equipment of direct gas sampling, is mainly the on-line mass spectroscopy instrument of gas sampling, and intercept the part that reaction stream gives vent to anger and analyze, all the other are discharged as tail gas.

Described supporting screening plate is that pore size is controlled, the dividing plate of variable number, the upper end of dividing plate is filled with silica wool, leak under avoiding catalyzer, the below of dividing plate and reaction stream give vent to anger hop one end near, silica wool is filled in the two ends of micro-reaction tube, catalyzer is then filled between silica wool, to avoid air-flow, catalyzer is blown out micro-reaction tube.

Combination gas is mainly nitrogen hydrogen, and volume ratio is 1:3, is transmitted by stainless-steel tube, and through deoxygenation cleaning except water pipe, two-way valve removes water pipe by stainless-steel tube with micro-reaction tube and deoxygenation and is connected;

Described residual gas outlet is also provided with deoxygenation except water pipe, avoids outside air reflux to enter micro-reaction tube, causes the poisoning of catalyzer and inactivation.

Continuous monitoring catalyzes and synthesizes an on-line analysis for ammonia react, comprises the steps:

A. load catalyzer: take catalyzer, load and insert in micro-reaction tube of silica wool in advance, finally insert upper strata silica wool sealing;

B. setting program Elevated Temperature Conditions: carry out reduction reaction and the test of nitrogen hydrogen catalysis ammonia synthesis reaction according to catalyst type and the suitable temperature programme condition of quality settings;

C. reduction reaction process: at control temperature with constantly pass into high-purity H 2condition under, reduction reaction is carried out to catalyzer, the certain group reduction in catalyzer is removed;

D. ammonia react process is catalyzed and synthesized: at control temperature with constantly pass into high-purity H 2condition under, carry out the reaction catalyzing and synthesizing ammonia, explore catalyzer catalytic activity at different temperatures;

E. utilize reaction stream give vent to anger pick-up unit to given vent to anger by reaction stream hop flow out the continuous on-line sampling of partial reaction gas, and the data gathered for a long time are plotted curve in real time, the concentration obtaining ammonia in effluent gases is in time or the variation tendency of micro-reaction tube temperature.

Described catalyzer is solid catalyst.Described micro-reaction tube is quartz glass material, non-metallic material, has catalytic effect to avoid metal pair nitrogen hydrogen ammonia synthesis reaction.

Microreactor device is the highest is heated to 500 DEG C, and what be suitable for high-temperature pressure catalyzes and synthesizes ammonia react, and regulates highest stabilizing temperature according to the kind of catalyzer.

The ultimate principle of this on-line analysis is:

First, nitrogen and hydrogen mixture catalyzes and synthesizes the principle of ammonia and is:

N 2 + 3 H 2 → catalyst N H 3

Secondly, reaction stream pick-up unit of giving vent to anger adopts the compound electric of Single-photon ionization and chemi-ionization from mode, acquisition NH 3 +ionization approach have:

N H 3 → hv N H 3 + + e - ( SPI )

O 2+e-→O 2 ++2e- (CI)

O 2 ++NH3→NH 3 ++O 2(CI)

Wherein based on CI, SPI is auxiliary, and compare simple SPI mode, ionizing efficiency improves greatly.And key reaction gas H 2and N 2the ionization energy higher due to it and can not being ionized, thus eliminate the interference of blank gas.

Accompanying drawing explanation

Fig. 1 is that monitoring catalyzes and synthesizes the device schematic diagram of the on-line analysis system of ammonia react continuously; 1-microreactor device; 2-reaction stream is given vent to anger pick-up unit; 3-temperature control equipment; 4-reaction stream is given vent to anger hop; 5-silica wool; 6-supporting screening plate; 7-catalyzer; 8-residual gas exports; The micro-reaction tube of 9-; 10-heating jacket; 11-feeder; 12-ionized region; 13-vacuum UV lamp; The air inlet kapillary of 14-reagent gas high purity oxygen; 15-field-free flight district; 16-vacuum plant; 17-MCP detector; 18-data acquisition system (DAS); 19-two-way valve; 20-deoxygenation is except water pipe; 21-precision mass flow controller; 22-carrier gas steel cylinder.

Fig. 2 is be tested object with two kinds of catalyzer (a kind of for catalyst A, another kind of catalyst B), utilizes the concentration change of the ammonia of this on-line analysis system and the continuous on-line monitoring synthesis of analytical approach;

The catalytic activity of catalyst B at different temperature in Fig. 3.

Embodiment

First, Fig. 1 is the on-line analysis system that a kind of continuous monitoring catalyzes and synthesizes ammonia react, it is characterized in that: comprise microreactor device 1, give vent to anger hop 4, feeder 9 and reaction stream of temperature control equipment 3, reaction stream give vent to anger pick-up unit 2;

Wherein, described feeder 9 comprises mass flow controller 21 on carrier gas steel cylinder 22, its export pipeline, two-way valve 19 with deoxygenation except water pipe 20;

Described microreactor device 1 is the airtight cavity of hollow, comprise micro-reaction tube 9, heating jacket 10 and residual gas outlet 8, cavity wall is provided with the heating jacket 10 be connected with extraneous power supply, one end of cavity is provided with nitrogen and hydrogen mixture injection port, combination gas injection port is connected with one end of stainless-steel tube, the other end away from combination gas injection port is provided with reaction stream exhaust outlets and residual gas outlet 8, be provided with supporting screening plate 6 in cavity between combination gas injection port and reaction stream exhaust outlets, in cavity, be filled with silica wool 5 and catalyzer 7;

Described temperature control equipment 3 comprises temperature controller and thermocouple temperature sensitive element; One end of thermocouple temperature sensitive element and the outer wall of micro-reaction tube 9 are closely affixed;

Described reaction stream gives vent to anger hop 4 for elastic quartz capillary tube; It is inner that micro-reaction tube 9 is directly inserted in one end of kapillary, below supporting screening plate 6, ensure that zero dead volume and zero-lag time, and the give vent to anger sample feeding mouth of pick-up unit 2 of the other end and reaction stream is connected.

Described reaction stream pick-up unit 2 of giving vent to anger is the analytical equipment of direct gas sampling, is mainly the on-line mass spectroscopy instrument of gas sampling, and intercept the part that reaction stream gives vent to anger and analyze, all the other are discharged as tail gas.

Described supporting screening plate 6 is that pore size is controlled, the dividing plate of variable number, the upper end of dividing plate is filled with silica wool 5, catalyzer is avoided to leak for 7 times, the below of dividing plate and reaction stream give vent to anger hop 4 one end near, silica wool 5 is filled in the two ends of micro-reaction tube 9, catalyzer 7 is filled between silica wool 5, to avoid air-flow, catalyzer is blown out micro-reaction tube 9.

Combination gas is mainly nitrogen hydrogen, and volume ratio is 1:3, is transmitted by stainless-steel tube, and through deoxygenation cleaning except water pipe 20, two-way valve 19 removes water pipe 20 by stainless-steel tube with micro-reaction tube 9 and deoxygenation and is connected;

Described residual gas outlet 8 is also provided with deoxygenation except water pipe 20, avoids outside air reflux to enter micro-reaction tube 9, causes the poisoning of catalyzer 7 and inactivation.

Continuous monitoring catalyzes and synthesizes an on-line analysis for ammonia react, comprises the steps:

A. load catalyzer 7: take catalyzer, load and insert in micro-reaction tube 9 of silica wool 5 in advance, finally insert upper strata silica wool 5 and seal;

B. setting program Elevated Temperature Conditions: carry out reduction reaction and the test of nitrogen hydrogen catalysis ammonia synthesis reaction according to catalyzer 7 kind and the suitable temperature programme condition of quality settings;

C. reduction reaction process: at control temperature with constantly pass into high-purity H 2condition under, reduction reaction is carried out to catalyzer 7, the certain group reduction in catalyzer 7 is removed;

D. ammonia react process is catalyzed and synthesized: at control temperature with constantly pass into high-purity H 2condition under, carry out the reaction catalyzing and synthesizing ammonia, explore catalyzer 7 catalytic activity at different temperatures;

E. utilize reaction stream give vent to anger pick-up unit 2 to given vent to anger by reaction stream hop 4 flow out the continuous on-line sampling of partial reaction gas, and the data gathered for a long time are plotted curve in real time, the concentration obtaining ammonia in effluent gases is in time or the variation tendency of micro-reaction tube 9 temperature.

Described catalyzer 7 is solid catalyst.Described micro-reaction tube 9 is quartz glass material, non-metallic material, has catalytic effect to avoid metal pair nitrogen hydrogen ammonia synthesis reaction.

Microreactor device 5 is the highest is heated to 500 DEG C, and what be suitable for high-temperature pressure catalyzes and synthesizes ammonia react, and regulates highest stabilizing temperature according to the kind of catalyzer 7.

Wherein, adopt heating mantle heats, around the cavity being distributed in microreactor device.Thermopair is inserted between heating jacket and micro-reaction tube.In order to reduce dead volume and dead time as far as possible, the kapillary one end of the hop that in test, reaction stream is given vent to anger extend into immediately below the silica wool of lower end, can transmit the ammonia that reaction generates in time.In addition, reaction stream pick-up unit of giving vent to anger adopts the time of-flight mass spectrometer of Single-photon ionization-chemi-ionization, this mass spectrometer adopts orthogonal acceleration design, detect with MCP detector, a reaction stream part of giving vent to anger enters mass spectrometer analysis by the kapillary one end directly gone out below reaction tube inner support sieve plate in a subtle way, and all the other are discharged as waste gas.Wherein the air pressure of ionized region can be regulated by the internal diameter and length changing kapillary.The capillary inner diameter adopted in experiment is 200 μm, and length is about 32cm, and the air inlet capillary inner diameter of the about 15ml/min high purity oxygen of gas flow is 250 μm, and length is about 0.5m, and ionized region total gas pressure maintains about 42Pa.

Embodiment 1

The on-line analysis system of ammonia react and the examination of method performance is catalyzed and synthesized for a kind of continuous monitoring of the present invention, test with two kinds of catalyst A as object, quality is 100mg, utilize the concentration change of the ammonia of this on-line analysis system and the continuous on-line monitoring synthesis of analytical approach, the high-purity H of setting reducing gas 2flow be 30mL/min, reduction process does not carry out on-line checkingi.The flow of nitrogen and hydrogen mixture is 50ml/min, the temperature of microreactor starts to heat up with the speed of 2 DEG C/min from room temperature, and stop the regular hours 40 DEG C, 80 DEG C, 120 DEG C, 160 DEG C, 200 DEG C, 240 DEG C, 280 DEG C, 320 DEG C and 360 DEG C respectively, so that the catalytic activity of catalyzer under observing this temperature.In experiment, the ionization mode of ionization source adopts the compound electric of VUV single-photon ionization (VUV-SPI) and chemi-ionization (CI) from mode, wherein reagent ion O 2 +intensity be 300,000 counts, ionized region air pressure maintains about 42Pa.High-purity H was purged before this under room temperature 2enter mass spectrometer with nitrogen and hydrogen mixture to carry out blank and sample, the sampling time is 30s, continuous acquisition number point, by the mean value of its collection signal signal as a setting.Afterwards, open temp control device, make temperature from ambient start to rise, in this process, the air pressure of ionized region there will be and slightly fluctuates, but within 1.5Pa.Fig. 2 is the catalytic activity of catalyst A at different temperature.Can find by shown in little figure, this on-line analysis system and analytical approach can differentiate the concentration quick shift at short notice of ammonia, therefore there is very high temporal resolution, can find that the method has good long-time stability from continuous monitoring time, the task of continuous monitoring can be born.

Embodiment 2

The on-line analysis system of ammonia react and the examination of method performance is catalyzed and synthesized for a kind of continuous monitoring of the present invention, test with two kinds of catalyst B as object, quality is 100mg, utilize the concentration change of the ammonia of this on-line analysis system and the continuous on-line monitoring synthesis of analytical approach, the high-purity H of setting reducing gas 2flow be 30mL/min, reduction process does not carry out on-line checkingi.The flow of nitrogen and hydrogen mixture is 50ml/min, the temperature of microreactor starts to heat up with the speed of 2 DEG C/min from room temperature, and stop the regular hours 40 DEG C, 80 DEG C, 120 DEG C, 160 DEG C, 200 DEG C, 240 DEG C, 280 DEG C, 320 DEG C and 360 DEG C respectively, so that the catalytic activity of catalyzer under observing this temperature.In experiment, the ionization mode of ionization source adopts the compound electric of VUV single-photon ionization (VUV-SPI) and chemi-ionization (CI) from mode, wherein reagent ion O 2 +intensity be 300,000 counts, ionized region air pressure maintains about 42Pa.High-purity H was purged before this under room temperature 2enter mass spectrometer with nitrogen and hydrogen mixture to carry out blank and sample, the sampling time is 30s, continuous acquisition number point, by the mean value of its collection signal signal as a setting.Afterwards, open temp control device, make temperature from ambient start to rise, in this process, the air pressure of ionized region there will be and slightly fluctuates, but within 1.5Pa.The catalytic activity of catalyst B at different temperature in Fig. 3.Therefrom see, the method has good long-time stability, can bear the task of continuous monitoring.

Claims (10)

1. continuously monitoring catalyzes and synthesizes an on-line analysis system for ammonia react, it is characterized in that: comprise microreactor device (1), give vent to anger hop (4), feeder (9) and reaction stream of temperature control equipment (3), reaction stream give vent to anger pick-up unit (2);
Wherein, described feeder (9) comprises mass flow controller (21) on carrier gas steel cylinder (22), its export pipeline, two-way valve (19) with deoxygenation except water pipe (20);
The airtight cavity that described microreactor device (1) is hollow, comprise micro-reaction tube (9), heating jacket (10) and residual gas outlet (8), cavity wall is provided with the heating jacket (10) be connected with extraneous power supply, one end of cavity is provided with nitrogen and hydrogen mixture injection port, combination gas injection port is connected with one end of stainless-steel tube, the other end away from combination gas injection port is provided with reaction stream exhaust outlets and residual gas outlet (8), supporting screening plate (6) is provided with in cavity between combination gas injection port and reaction stream exhaust outlets, silica wool (5) and catalyzer (7) is filled with in cavity,
Described temperature control equipment (3) comprises temperature controller and thermocouple temperature sensitive element; One end of thermocouple temperature sensitive element and the outer wall of micro-reaction tube (9) are closely affixed;
Described reaction stream hop (4) of giving vent to anger is elastic quartz capillary tube; It is inner that micro-reaction tube (9) is directly inserted in one end of kapillary, near supporting screening plate (6) below, ensure that zero dead volume and zero-lag time, and the give vent to anger sample feeding mouth of pick-up unit (2) of the other end and reaction stream is connected.
2. device according to claim 1, is characterized in that:
Described reaction stream is given vent to anger the analytical equipment that pick-up unit (2) is direct gas sampling, is mainly the on-line mass spectroscopy instrument of gas sampling, and intercept the part that reaction stream gives vent to anger and analyze, all the other are discharged as tail gas.
3. device according to claim 1, is characterized in that:
Described supporting screening plate (6) is for pore size is controlled, the dividing plate of variable number, the upper end of dividing plate is filled with silica wool (5), leak under avoiding catalyzer (7), the below of dividing plate and reaction stream give vent to anger hop (4) one end near, silica wool (5) is filled in the two ends of micro-reaction tube (9), catalyzer (7) is then filled between silica wool (5), to avoid air-flow, catalyzer is blown out micro-reaction tube (9).
4. device according to claim 1, is characterized in that:
Combination gas is mainly nitrogen hydrogen, and volume ratio is 1:3, is transmitted by stainless-steel tube, and through deoxygenation cleaning except water pipe (20), two-way valve (19) removes water pipe (20) by stainless-steel tube with micro-reaction tube (9) and deoxygenation and is connected.
5. device according to claim 1, is characterized in that:
Described residual gas outlet (8) is also provided with deoxygenation except water pipe (20), avoids outside air reflux to enter micro-reaction tube (9), causes the poisoning and inactivation of catalyzer (7).
6. monitoring catalyzes and synthesizes an on-line analysis for ammonia react continuously, it is characterized in that:
Adopt arbitrary described device in claim 1-5 to operate, comprise the steps:
A. load catalyzer (7): take catalyzer, load and insert in advance in micro-reaction tube (9) of silica wool (5), finally insert upper strata silica wool (5) sealing;
B. setting program Elevated Temperature Conditions: carry out reduction reaction and the test of nitrogen hydrogen catalysis ammonia synthesis reaction according to catalyzer (7) kind and the suitable temperature programme condition of quality settings;
C. reduction reaction process: at control temperature with constantly pass into high-purity H 2condition under, reduction reaction is carried out to catalyzer (7), the certain group reduction in catalyzer (7) is removed;
D. ammonia react process is catalyzed and synthesized: at control temperature with constantly pass into high-purity H 2condition under, carry out the reaction catalyzing and synthesizing ammonia, explore catalyzer (7) catalytic activity at different temperatures;
E. utilize reaction stream the to give vent to anger continuous on-line sampling of partial reaction gas that pick-up unit (2) flowed out hop (4) of being given vent to anger by reaction stream, and the data gathered for a long time are plotted curve in real time, the concentration obtaining ammonia in effluent gases is in time or the variation tendency of micro-reaction tube (9) temperature.
7. method according to claim 6, is characterized in that:
Described catalyzer (7) is solid catalyst.
8. the method according to claim 6 or 7, is characterized in that:
Described micro-reaction tube (9) is quartz glass material, non-metallic material, has catalytic effect to avoid metal pair nitrogen hydrogen ammonia synthesis reaction.
9. method according to claim 6, is characterized in that:
Microreactor device (5) is the highest is heated to 500 DEG C, and what be suitable for high-temperature pressure catalyzes and synthesizes ammonia react, and regulates highest stabilizing temperature according to the kind of catalyzer (7).
10. method according to claim 6, is characterized in that:
Reaction stream pick-up unit (2) of giving vent to anger adopts the compound electric of Single-photon ionization and chemi-ionization to give vent to anger from mode (SPI-CI) to reaction stream to ionize, and the method can improve NH 3detection sensitivity.
CN201310689499.7A 2013-12-13 2013-12-13 Online analysis system and method for continuous monitoring of catalysis of ammonia synthesis reaction CN104713968A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018031155A1 (en) * 2016-08-10 2018-02-15 The Arizona Board Of Regents On Behalf Of The University Of Arizona A microscale reactor and methods for small scale synthesis and rapid screening conditions

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