CN2834691Y - An equipment for preparing metal nitride catalytic material - Google Patents
An equipment for preparing metal nitride catalytic material Download PDFInfo
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- CN2834691Y CN2834691Y CN 200520093461 CN200520093461U CN2834691Y CN 2834691 Y CN2834691 Y CN 2834691Y CN 200520093461 CN200520093461 CN 200520093461 CN 200520093461 U CN200520093461 U CN 200520093461U CN 2834691 Y CN2834691 Y CN 2834691Y
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- heat exchanger
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 66
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 230000008929 regeneration Effects 0.000 claims description 9
- 238000011069 regeneration method Methods 0.000 claims description 9
- 239000002912 waste gas Substances 0.000 claims description 5
- 229910015421 Mo2N Inorganic materials 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000007423 decrease Effects 0.000 abstract 1
- 238000010792 warming Methods 0.000 abstract 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 53
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000005121 nitriding Methods 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 239000012495 reaction gas Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 101150001783 fic1 gene Proteins 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000033228 biological regulation Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000004868 gas analysis Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The utility model relates to the technical field of catalysis material, more specifically to a device for preparing metal nitride catalytic material. A mixer enters a fluidized-bed reactor through a pipeline and the outlet of the fluidized-bed reactor enters a heat exchanger through the pipeline. On one hand, the heat exchanger enters the mixer through the pipeline and the pipeline is connected with the gas chromatograph through a plane six-way valve, and on the other hand, the heat exchanger enters a water cooler through the pipeline. A separator enters a compressor from a drying part through the pipelines, the outlet of the compressor is connected with the heat exchanger through the pipeline, and an interstage cooler is respectively connected with the inlet conduit and the outlet conduit of the compressor. The utility model uses the method of warming the fluidized-bed orderly to produce the metal nitride (gamma-Mo2N) and thoroughly avoids the problems that the purity and the quality of the product decline, etc. because of the inherent problems of the filling material and the fixed bed; therefore, the gamma-Mo2N with high ratio surface area can be made.
Description
Technical Field
The utility model relates to the technical field of catalytic materials, in particular to a method for preparing metal nitride (gamma-Mo) by adopting a temperature programming fluidized bed2N) a device for catalyzing a material.
Background
For metal nitrides (gamma-Mo) at home and abroad2N) catalytic materials have been studied for many years. For more than 90 years, the study of NH has been performed by West and Markel3The basic principle and dynamics of synthesis and decomposition and the basis of catalytic performance, the research of NH is emphasized3With MoO3In a quartz tubular reactor, the reaction temperature is related to the reaction product and the surface area. Polycrystalline MoO when the temperature rises to 473K3Fragmentation, slight increase in surface area, presence of unknown phase (804pm) and MoO at 573K3，673K MoO3Disappearance and appearance of MoO2And another unknown phase (621, 307 and 205pm), more than 773K forming Mo2N, MoO, increasing with increasing temperature2The amount of (c) is reduced. The reaction is carried out for 980K +2hr at constant temperature, the reduction nitridation reaction is complete, and the reaction product is completely converted into gamma-Mo2And N is added. But gamma-Mo2The crystal grains of N grow larger, and the surface area is slightly reduced. From this, it was concluded that MoO3And NH3The maximum temperature of the temperature program is 980K, and the temperature should be kept constant for 2 hours to ensure the reaction is complete. In the calculation of the bed temperature of the tubular reactor, the central temperature was found to be 120K lower than the furnace temperature, and the diameter was found to beThe temperature is 80K lower, the surface temperature of the bed is 40K lower than the furnace temperature, even though the inner diameter is 4mm and the length is 1m, the tube furnace MoO3The loading of (a) was only 0.5 grams, actually measured at 35K with a hot well, and both were substantially identical. For a tube furnace with a diameter of 25cm, the temperature gradient can reach hundreds of degrees, so that the conclusion can be drawn that Mo is prepared in large batch2N, the control of bed temperature is a very difficult problem. In the presence of NH3When used as a nitriding reactant, there are two key problems affecting product quality: firstly, reduction of MoO3Water generation ( ) The presence of water vapor promotes Mo as a product2N is hydrothermally sintered, and H2O and H2In MoO3Competitive adsorption of Mo2The surface area of N is reduced; second is NH3Decomposition into endothermic reaction results in very uneven bed temperature distribution in the reactor and large axial and radial temperature gradients.
The institute of metal of Chinese academy of sciences provides a preparation method of metal nitride catalytic material and its special-purpose equipment (application number: 200510046779.1, application date: 2005, 6/29), and uses the mixed gas of nitrogen and hydrogen as reducing and nitriding reactant and MoO added with mixed filler3Reaction for preparing Mo2N, due to NH3The problem of bed temperature gradient caused by heat absorption by decomposition, and Mo caused by steam2N causes a problem of hydrothermal sintering. However, this method still has the problem that the reaction between the nitriding reactant and the mixed filler causes the deterioration of the purity and quality of the product.
SUMMERY OF THE UTILITY MODEL
In order to solve the above problems, the present invention provides an apparatus for preparing a metal nitride catalytic material by a temperature programmed fluidized bed method for preparing a metal nitride (γ -Mo)2N), the problems of product purity and quality reduction caused by the inherent problems of the filler and the fixed bed are thoroughly avoided.
The technical scheme of the utility model is that:
an apparatus for preparing a metal nitride catalytic material includes a mixer, a heat exchanger, a water cooler, a separator, a fluidized bed reactor, a drying part, a compressor, an intersegmental cooler, a gas chromatograph, a planar six-way valve; the mixer enters the fluidized bed reactor from the bottom of the fluidized bed reactor through a pipeline, the outlet of the fluidized bed reactor enters the heat exchanger through a pipeline, on one hand, the heat exchanger enters the mixer through a pipeline, and the pipeline passes through the plane six-way valve to the gas chromatograph; on the other hand, the water-cooled gas enters a water cooler through a pipeline, a separator enters a compressor through a drying part through a pipeline, the outlet of the compressor is connected with a heat exchanger through a pipeline, and an intersegment cooler is respectively connected with an inlet pipeline and an outlet pipeline of the compressor. The drying part is formed by connecting a dryer IA and a dryer IB which are connected in series with a dryer IIA and a dryer IIB which are connected in series in parallel.
The equipment for preparing the metal nitride catalytic material can adopt the following structure: the mixer enters a fluidized bed reactor through a pipeline, the pipeline is provided with a check valve and is connected with a pressure display instrument and a needle valve, the inlet of the fluidized bed reactor is provided with a temperature control display instrument and a temperature display instrument, the outlet of the fluidized bed reactor is divided into two paths, one path enters a heat exchanger through the pipeline, the other path is communicated with the atmosphere through the pipeline, and the pipeline is provided with a stop valve; on one hand, the heat exchanger enters the mixer through a pipeline, the pipeline is connected with a needle valve, and the needle valve are connected in parallel and then are connected to a gas chromatograph through a plane six-way valve; the other side of the heat exchanger enters a water cooler through a pipeline, the pipeline is provided with a temperature display instrument, the water cooler is communicated with the atmosphere through a separator and a pipeline, the pipeline is provided with a stop valve, the separator enters a compressor through a drying part through a pipeline, the pipeline is provided with a temperature control display instrument, the drying part is formed by connecting a dryer IA and a dryer IB which are connected in series in parallel with a dryer IIA and a dryer IIB which are connected in series, the dryer IA, the dryer IB, the dryer IIA and the dryer IIB are respectively connected with the temperature control display instrument, inlet valves and regeneration waste gas outlet valves are respectively arranged at inlets of the dryer IA (6) and the dryer IIA, an outlet valve and a regeneration nitrogen inlet valve are respectively arranged at outlets of the dryer IB and the dryer, and a pressure display instrument, a check valve and a stop valve are arranged; the outlet of the compressor is connected with the heat exchanger through a pipeline, a stop valve and a mass flow meter are arranged on the pipeline, the intersegmental cooler is respectively connected with the inlet pipeline and the outlet pipeline of the compressor, and the pipeline connected with the outlet of the compressor is provided with the stop valve and the check valve.
Method for preparing metal nitride catalytic material by using the device, MoO3/TiO2、MoO3/NiO-TiO2、MoO3/Al2O3-TiO2Or MoO3/Al2O3Putting the mixture into a fluidized bed reactor for N2-H2Reductive replacement of MoO3To prepare Mo2N/TiO2、Mo2N/NiO-TiO2、Mo2N/Al2O3-TiO2Or Mo2N/Al2O3Supported metal nitrogenA compound catalyst; n is a radical of2-H2Volume ratio of mixed gas: h2/N2＝(3-5)/1，N2-H2The space velocity of the mixed gas is 6,000--1The reaction temperature is 933K +/-10K, and the heat preservation time is 0.5-1 hour.
The temperature control process in the fluidized bed reactor is as follows:
1) rapidly heating from room temperature to 673K at a heating rate of 1-50K/min;
2)673 heating at 0.6-1K/min with 933K;
3)933K + -10K keeping the temperature for 0.5-1 hr;
4) cooling to room temperature in the fluidized bed reactor.
Reacting N at room temperature2-H2The volume ratio of the mixed gas is switched to 99% Ar-1% O2Mixing the gases for 12-24 hours.
The utility model has the advantages of it is following:
(1) the utility model adopts N2-H2Mixed gas substituted NH3With MoO3And (3) reacting, wherein when the reaction temperature is about 660 ℃ and the temperature rise speed is 0.6-1K/min, the airspeed is increased, and the surface area of the product is increased. Hydrogen rich N2-H2Mixed gas (H)2/N23-5/1), space velocity of 6,000--1High surface area Mo can be obtained2And N is added. The utility model can be made with a specific surface area as high as 150m2gamma-Mo of/g2N；
(2) The reaction gas of the utility model is recycled through drying treatment, the utilization rate is 100 percent, and the cost is low;
(3) adopt the utility model discloses than use NH3The operation is simplified, and the operation danger and the environmental pollution are eliminated;
(4) the utility model adopts N2-H2The mixed gas fluidizes the reaction bed to eliminate NH3The decomposition endotherm causes the problem of temperature gradient caused by poor heat conduction of the reaction bed. Thereby avoiding the problems of the quality reduction of the product caused by the filler and the like.
Drawings
FIG. 1 is a flow chart of a molybdenum nitride batch synthesis apparatus. In the figure, 1 mixer; 2, a heat exchanger; 3, a water cooler; 4, a separator; 5 a fluidized bed reactor; 6 a dryer IA; 7 a dryer IB; 8, a dryer IIA; 9 a dryer IIB; 10 a compressor; 11-stage intercoolers; 12 gas chromatography; 13 plane six-way valve.
FIG. 2 is a schematic view of the heating system used in the present invention.
Detailed Description
Below is γ -Mo2The preparation technology of N is explained in detail, and the room temperature in the utility model is generally 16-30 ℃.
In view of preparing gamma-Mo with high specific surface area2N, the utility model adopts the approach of temperature programmed gradual reaction and utilizes N2Reduction of MoO as a reducing gas3. The accumulation of the moisture of the product is prevented by controlling the temperature rise speed and increasing the gas flow; in order to reduce gas consumption, a gas circulation device is designed in the system so as to reduce preparation cost.
The reaction device for preparing molybdenum nitride by a fluidized bed is shown in figure 1.
A gas
1, nitrogen-high purity nitrogen (volume concentration is 99.999%), nitriding raw material from a steel cylinder, and removing the nitriding raw material from a mixer;
2, hydrogen-high purity hydrogen (volume concentration is 99.999%), nitriding raw material from a steel cylinder, and removing the nitriding raw material from a mixer;
3, mixed gas, which is formed by mixing nitrogen, hydrogen and circulating gas and is subjected to heat exchange and denitrification in the fluidized bed reactor;
4, cooling the reaction gas, namely the gas discharged from the nitriding fluidized bed reactor, to a dryer;
5, drying gas, namely gas (gas out of the dryer) after being dried and dehydrated, enters the inlet of the compressor;
6, circulating gas, namely gas pressurized by a compressor (gas discharged from the compressor), cooling and then sending to a mixer;
7 regenerating nitrogen, namely high-purity nitrogen (the volume concentration is 99.999 percent), from a steel cylinder and removing the nitrogen from a dryer;
8, directly discharging regenerated waste gas, namely nitrogen containing moisture removed by the regeneration of the drying agent;
9 feedback gas-gas from the compressor outlet directly to the compressor inlet.
Second, equipment
1 mixer-mixing nitrogen, hydrogen, recycle gas, stainless steel;
2, a heat exchanger, namely heat exchange is carried out on reaction gas and circulating gas, the stainless steel shell has the diameter of 108mm, and a spiral corrugated pipe is arranged in the stainless steel shell; tube pass: reaction gas; shell pass: circulating gas;
3 water cooler-cooling the reaction gas after the heat exchanger, stainless steel, shell diameter 108mm, and installing a coiled corrugated pipe;
tube pass: reaction gas; shell pass: cooling water;
4 separator for separating condensed water;
5 fluidized bed reactor-fluidized bed, the catalyst precursor molybdenum oxide is filled in, and equipped with thermocouple, L is 1150mm phi, 42mm x 3mm, and its interior is equipped with thermocouple sleeve, and the heating electric furnace is 4 KW;
6 dryer IA-fluidized bed adsorber, fill silica gel, L ═ 750mm, phi 42mm x 3mm, electric furnace 2 KW;
7 dryer IB-fluidized bed adsorber, built-in molecular sieve, L is 550mm, phi 42mm x 3mm, electric stove 2 KW;
8 dryer IIA-fluidized bed adsorber, silica gel is filled in, L is 750mm, phi 42mm is multiplied by 3mm, electric furnace 2 KW;
9 dryer IIB-fluidized bed adsorber, built-in molecular sieve, L is 550mm, phi 42mm x 3mm, electric stove 2 KW;
10 compressor-reciprocating compressor, discharge pressure not more than 0.55 MPa;
11 interstage coolers for cooling the feedback gas;
12 gas chromatography-model GC9800TP, FID, TCD detector: stationary phase TDX-02, d is 3 mm;
helium is formed by separating circulating gas and mixed gas;
13 plane six-way valve-for gas analysis sampling.
Third, instrument, valve and legend
3.1
A mass flow meter and a mass flow controller;
FIC-1 control shows nitrogen flow;
FIC-2 controls and displays hydrogen flow;
3.2a mass flow meter;
FI-1 shows the circulating gas flow rate;
3.3
a non-return valve;
3.4
a needle valve;
SA-for mixture analysis;
SB-for cycle gas analysis;
3.5
a stop valve;
v1 — for draining condensed water;
v2-for system air defense;
v3 — for adjusting feedback gas flow;
v4 — for adjusting compressor inlet flow;
v5 — for adjusting compressor outlet flow;
i-1 and II-1 are inlet valves (for adsorption) of dryers IA and IIA;
II-4 and I-4 are outlet valves of IB and IIB of the dryer (for adsorption);
i-5 and II-5 are regeneration nitrogen inlet valves (for desorption) of driers IB and IIB;
i-2 and II-2 are regeneration waste gas outlet valves (for desorption) of the dryers IA and IIA;
TIC temperature control display instrument;
a TIC-1 SR53 temperature controller for controlling the temperature of the nitriding fluidized bed reactor (solid state relay);
TIC-2 temperature controller (PID regulation), control dryer IA (solid state relay);
TIC-3 temperature controller (PID regulation), control dryer IB (solid state relay);
TIC-4 temperature controller (PID regulation), control dryer IIA (solid state relay);
a TIC-5 temperature controller (PID regulation) for controlling a dryer IIB (solid state relay);
a TI temperature display instrument;
TI-1 shows the bed temperature of the nitriding fluidized bed reactor;
TI-2 shows the temperature of the reaction gas at the outlet of the heat exchanger;
TI-3 shows the temperature of the reaction gas at the outlet of the water cooler;
a PI pressure display instrument;
PI-1 shows the inlet pressure of the nitriding fluidized bed reactor;
PI-2 shows the dryer outlet pressure;
as shown in fig. 1, the apparatus of the present invention comprises: mixer 1, heat exchanger 2, water cooler 3, separator 4, fluidized bed reactor 5, dryer IA6, dryer IB7, dryer IIA8, dryer IIB9, compressor 10, interstage cooler 11, gas chromatograph 12, planar six-way valveA valve 13. N is a radical of2、H2The device is respectively led to a mixer 1 through a mass flow meter and mass flow controllers FIC-1 and FIC-2, the mixer 1 enters a fluidized bed reactor 5 from the bottom of the fluidized bed reactor 5 through a pipeline, the pipeline is provided with a check valve and is connected with a pressure display instrument PI-1 and a needle valve SA through pipelines, a temperature control display instrument TIC-1 and a temperature display instrument TI-1 are arranged at the inlet of the fluidized bed reactor 5, the outlet of the fluidized bed reactor 5 is divided into two paths, one path enters a heat exchanger 2 through the pipeline, the other path is led to the atmosphere through the pipeline, and the pipeline is provided with a stop valve V2; on one hand, the heat exchanger 2 enters the mixer 1 through a pipeline, the pipeline is connected with a needle valve SB, and the needle valve SA and the needle valve SB are connected in parallel and then are transmitted to a gas chromatograph 12 through a plane six-way valve 13; the heat exchanger 2 on the other hand enters the water cooler 3 through a pipeline, the pipeline is provided with a temperature display instrument TI-2, the water cooler 3 is communicated with the atmosphere through a separator 4 through a pipeline, the pipeline is provided with a stop valve V1, the separator 4 enters a compressor 10 through a pipeline through a drying part, the pipeline is provided with a temperature control display instrument TI-3, the drying part is formed by connecting a dryer IA6 and a dryer IB7 which are connected in series in parallel with a dryer IIA8 and a dryer IIB9 which are connected in series, the dryer IA6, the dryer IB7, the dryer IIA8 and the dryer IIB9 are respectively connected with a temperature control display instrument TIC-2, TIC-3, TIC-4 and TIC-5, inlet valves I-1 and II-1 and regenerated waste gas outlet valves I-2 and II-2 are respectively arranged at inlets of the dryer IA6 and the dryer IIA8, outlet valves II-4 and dryer IB7 and dryer 9 are respectively provided with an outlet valve II-4 and IIB-, I-4 and regeneration nitrogen inlet valves I-5 and II-5, wherein a pressure display instrument PI-2, a check valve and a stop valve V4 are arranged on a pipeline connecting the drying part and the inlet of the compressor 10; the outlet of the compressor 10 is connected with the heat exchanger 2 through a pipeline, a stop valve V5 and a mass flow meter FI-1 are arranged on the pipeline, the inter-segment cooler 11 is respectively connected with the inlet and the outlet of the compressor 10, and a stop valve V3 and a check valve are arranged on the pipeline connecting the inter-segment cooler 11 and the outlet of the compressor 10.
Fourthly, the process flow is as follows:
nitrogen and hydrogen from the steel cylinder enter the mixer 1 through the mass flow controller and are mixed with the circulating gas (unreacted nitrogen and hydrogen) from the compressor 10 to form a certain hydrogen-nitrogen ratio (proportion range H)2/N2And (3-5)/1) enters a fluidized bed reactor 5, the temperature is controlled by an SR53 temperature controller, and molybdenum oxide reacts to generate molybdenum nitride under a certain temperature condition according to a set temperature rise program. Unreacted gas is discharged from an outlet of the nitriding fluidized bed reactor, sequentially enters a heat exchanger 2 and a water cooler 3, is subjected to condensation water separation by a separator 4, then enters a dryer for deep dehydration, and then enters a compressor 10 for pressurization and then returns to the system.
The operation steps are as follows: (for example, dryer IA, IB are used for adsorption and dryer IIA, IIB are regenerated)
1) Open color spectrum
Opening a main valve of the steel cylinder, and adjusting a partial pressure valve to be about 0.15-0.2 MPa;
switching on a main power supply of the gas chromatograph, and adjusting the front pressure of the column to be 0.15 MPa;
opening a chromatographic workstation and connecting a passage B (the workstation is divided into two passages, and can detect two paths of gas simultaneously, because only one passage is used, namely the passage B);
2) temperature rise
Setting and heating to 130 ℃ of a column box, 140 ℃ of a detection chamber TCD and 160 ℃ of a sample injector;
a stable temperature (no less than 0.5 hour with a linear base);
opening a bridge current switch, and adjusting to 120-130 mA;
standby;
3) a control panel power main switch is turned on (a heat exchange/water cooling temperature display instrument is turned on); opening mass flow meters including FIC-1, FIC-2 and FI-1;
airtight test (can be carried out in a whole system or in sections);
closing SA, SB, V1, V2, V3, I-1, II-4, I-2, II-2, I-5, II-5 (right to bottom);
full-open V4, V5, II-1 and I-4;
opening an N2 gas steel cylinder, and adjusting a partial pressure valve to 0.25 MPa;
adjusting FIC-1, and introducing nitrogen into the system at a flow rate of 20-28L/min;
maintaining pressure and testing leakage, after the system pressure is balanced (the system is full of gas), the FIC value falls back and is not more than 2L/min, otherwise, detecting leakage by using leakage liquid, finding a leakage point and processing (screwing) in time;
opening I-1 and II-4 completely, closing II-1 and I-4, and repeating ④⑤;
FIC-1 is turned off (to indicate a value of 0);
4) temperature rise
Connecting TIC-1(SR53), setting the temperature according to a temperature-raising program, and raising the temperature of the nitriding fluidized bed reactor until the bed layer reaches a set first temperature point (TI-1 is shown to meet the first-stage temperature rise); preparing ventilation synchronously;
5) ventilation
Adjusting FIC-1 according to the hydrogen-nitrogen ratio, introducing nitrogen into the system at a flow rate of 20L/min, adjusting FIC-2 to introduce corresponding hydrogen into the system at a corresponding flow rate (adjusting the pressure of a hydrogen steel cylinder to be the same as that of the nitrogen after reducing pressure), and returning the indication values of FIC-1 and FIC-2 to the specified values (less than 2L/min); the pressure of PI-1 and PI-2 is not changed any more, and is close to the pressure of the inlet and outlet of the compressor after the pressure of the steel cylinder is reduced;
6) starting the compressor and establishing a cycle
7) Analysing gas composition
And (3) mixed gas analysis:
starting the SA;
sampling (full displacement) (six-way valve left and right);
sample introduction (six-way valve is towards left and right);
closing the SA;
and (3) circulating gas analysis:
opening the SB;
sampling (full displacement) (six-way valve left and right);
sample introduction (six-way valve is towards left and right);
closing the SB;
8) adjusting composition
The flow entering the system is adjusted by fine tuning the pressure;
9) starting compressor
After the FI-1 flow is normal, under the condition of full opening of V3:
① if the flow is increased, the pressure (N2, H2 are adjusted simultaneously) Pmax after the pressure of the steel cylinder is reduced is less than or equal to 0.38 MPa;
② if the flow is reduced, the V4 valve is closed;
10) normal experiment
The gas composition is analyzed, and the flow is adjusted according to the analyzed gas composition.
Sixthly, normal parking
1) Stopping the compressor;
2) stopping the electric furnace;
3) closing the hydrogen main pressure valve and closing the nitrogen main pressure valve;
4) opening V5, and releasing pressure of the system;
seven, closing the chromatogram
1) Closing the bridge flow;
2) turning off the heating power supply;
3) turning off the detector power supply;
4) turning off the carrier gas when the temperature of the detector is lower than 70 ℃;
eighth, dryer switching
If the dryer I series is changed from adsorption to regeneration, the dryer II series is changed from standby to normal operation;
opening II-1 and I-4 fully, and closing I-1 and II-4;
connecting a dryer IA and a dryer IB, and setting the dryer IA at 140 ℃; a dryer IB 350 ℃;
opening I-2 and I-5;
introducing regenerated nitrogen (only by gas passing);
a gas distribution system:N2-H2the gas is mixed with the mixture of the air and the water,Ar-O2(1％O2volume ratio), attached flow meter, pressure reducing valve, regulating valve, and sampling analysis.
Example 1
The utility model discloses a temperature programming system as shown in figure 2, the best temperature programming system:
1. the temperature is rapidly increased from room temperature to 673K, and the temperature increasing speed is 1-50K/min (25K/min in the embodiment);
2.673-933K is heated at a speed of 0.6-1K/min (O.6K/min in the embodiment);
3.933K is kept constant for 0.5-1hr (1 hr in this example);
4. cooling to room temperature in a fluidized bed reactor;
5. reacting N at room temperature2-H2The volume ratio of the mixed gas is switched to 99% Ar-1% O2The time of the mixed gas (i.e. passivation) is 12-24 hr, in this embodiment 24 hr.
The utility model is gamma-Mo2The N supported catalyst was prepared as follows:
respectively adding MoO according to the above process3/TiO2、MoO3/NiO-TiO2、MoO3/Al2O3-TiO2Or MoO3/Al2O3Put into the fluidized bed reactor of the utility model for N2-H2Reductive replacement of MoO3To prepare Mo2N/TiO2、Mo2N/NiO-TiO2、Mo2N/Al2O3-TiO2Or Mo2N/Al2O3A supported metal nitride catalyst. N is a radical of2-H2Volume ratio of mixed gas: h2/N2＝4/1，N2-H2The space velocity of the mixed gas is 6,000--1(50,000 h in this example)-1) Detection of gamma-Mo by X-ray diffraction2The existence of N, the specific surface area of which is up to 150m2/g。
Example 2
The difference from the embodiment 1 is that:
1. rapidly heating from room temperature to 673K at a heating rate of 1K/min;
2.673-933K is heated up at a speed of 0.8K/min;
3.933K maintaining the temperature for 0.8 hr;
4. cooling to room temperature in a fluidized bed reactor;
5. reacting N at room temperature2-H2The volume ratio of the mixed gas is switched to 99% Ar-1% O2Mixing the gases (i.e. passivation treatment) for 12 hr.
The utility model is gamma-Mo2The N supported catalyst was prepared as follows:
respectively adding MoO according to the above process3/TiO2、MoO3/NiO-TiO2、MoO3/Al2O3-TiO2Or MoO3/Al2O3Put into the fluidized bed reactor of the utility model for N2-H2Reductive replacement of MoO3To prepare Mo2N/TiO2、Mo2N/NiO-TiO2、Mo2N/Al2O3-TiO2Or Mo2N/Al2O3A supported metal nitride catalyst. N is a radical of2-H2Volume ratio of mixed gas: h2/N2＝3/1，N2-H2The space velocity of the mixed gas is 6,000h-1Derived by X-raysgamma-Mo injection detection2The existence of N, the specific surface area of which is up to 130m2/g。
Example 3
The difference from the embodiment 1 is that:
1. rapidly heating from room temperature to 673K at a heating rate of 50K/min;
2.673-933K adopts 1K/min speed to heat up;
3.933K maintaining the temperature for 0.5 hr;
4. cooling to room temperature in a fluidized bed reactor;
5. reacting N at room temperature2-H2The volume ratio of the mixed gas is switched to 99% Ar-1% O2Mixing the gases (i.e. passivation) for 18 hr.
The utility model is gamma-Mo2The N supported catalyst was prepared as follows:
respectively adding MoO according to the above process3/TiO2、MoO3/NiO-TiO2、MoO3/Al2O3-TiO2Or MoO3/Al2O3Put into the fluidized bed reactor of the utility model for N2-H2Reductive replacement of MoO3To prepare Mo2N/TiO2、Mo2N/NiO-TiO2、Mo2N/Al2O3-TiO2Or Mo2N/Al2O3A supported metal nitride catalyst. N is a radical of2-H2Volume ratio of mixed gas: h2/N2＝5/1，N2-H2The space velocity of the mixed gas is 10,000h-1Detection of gamma-Mo by X-ray diffraction2The existence of N, the specific surface area of which is up to 140m2/g。
The utility model discloses well MoO3/TiO2In a weight ratio of MoO3∶TiO2＝1∶5；
The utility model discloses well MoO3/NiO-TiO2In a weight ratio of MoO3∶NiO∶TiO2＝1∶5∶1；
The utility model discloses well MoO3/Al2O3-TiO2In a weight ratio of MoO3∶Al2O3∶TiO2＝1∶5∶1；
The utility model discloses well MoO3/Al2O3In a weight ratio of MoO3∶Al2O3＝1∶5。
Claims (3)
1. An apparatus for preparing a metal nitride catalytic material, characterized by: comprises a mixer (1), a heat exchanger (2), a water cooler (3), a separator (4), a fluidized bed reactor (5), a drying part, a compressor (10), an intersegmental cooler (11), a gas chromatograph (12) and a plane six-way valve (13); the mixer (1) enters the fluidized bed reactor (5) from the bottom of the fluidized bed reactor (5) through a pipeline, the outlet of the fluidized bed reactor (5) enters the heat exchanger (2) through a pipeline, on one hand, the heat exchanger (2) enters the mixer (1) through a pipeline, and the pipeline passes through the plane six-way valve (13) to the gas chromatograph (12); on the other hand, the water-cooled gas enters the water cooler (3) through a pipeline, the separator (4) enters the compressor (10) through a drying part through a pipeline, the outlet of the compressor (10) is connected with the heat exchanger (2) through a pipeline, and the inter-stage cooler (11) is respectively connected with the inlet pipeline and the outlet pipeline of the compressor (10).
2. The apparatus for producing a metal nitride catalytic material as set forth in claim 1, wherein: the drying part is formed by connecting a dryer IA (6) and a dryer IB (7) which are connected in series with a dryer IIA (8) and a dryer IIB (9) which are connected in series in parallel.
3. The apparatus for producing a metal nitride catalytic material as set forth in claim 1, wherein: the mixer (1) enters a fluidized bed reactor (5) through a pipeline, the pipeline is provided with a check valve and is connected with a pressure display instrument (PI-1) and a needle valve (SA), the inlet of the fluidized bed reactor (5) is provided with a temperature control display instrument (TIC-1) and a temperature display instrument (TI-1), the outlet of the fluidized bed reactor (5) is divided into two paths, one path enters a heat exchanger (2) through the pipeline, the other path leads to the atmosphere through the pipeline, and the pipeline is provided with a stop valve (V2); on one hand, the heat exchanger (2) enters the mixer (1) through a pipeline, the pipeline is connected with a needle valve (SB), and the needle valve (SA) and the needle valve (SB) are connected in parallel and then are connected to a gas chromatograph (12) through a plane six-way valve (13); the other side of the heat exchanger (2) enters a water cooler (3) through a pipeline, the pipeline is provided with a temperature display instrument (TI-2), the water cooler (3) is communicated with the atmosphere through a separator (4) through the pipeline, the pipeline is provided with a stop valve (V1), the separator (4) enters a compressor (10) through a drying part through the pipeline, the pipeline is provided with a temperature control display instrument (TI-3), the drying part is formed by connecting a dryer IA (6) and a dryer IB (7) in series in parallel with a dryer IIA (8) and a dryer IIB (9) in series, the dryer IA (6), the dryer IB (7), the dryer IIA (8) and the dryer IIB (9) are respectively connected with the temperature control display instruments (TIC-2, TIC-3, TIC-4 and TIC-5), and the inlets of the dryer IA (6) and the dryer IIA (8) are respectively provided with an inlet valve (I-1, a temperature display instrument, II-1) and regeneration waste gas outlet valves (I-2, II-2), outlet valves (II-4, I-4) and regeneration nitrogen inlet valves (I-5, II-5) are respectively arranged at the outlets of a dryer IB (7) and a dryer IIB (9), and a pressure display instrument (PI-2), a check valve and a stop valve (V4) are arranged on a pipeline connecting the drying part and the inlet of the compressor (10); the outlet of the compressor (10) is connected with the heat exchanger (2) through a pipeline, a stop valve (V5) and a mass flow meter (FI-1) are arranged on the pipeline, the intersegmental cooler (11) is respectively connected with the inlet pipeline and the outlet pipeline of the compressor (10), and the pipeline connecting the intersegmental cooler (11) and the outlet of the compressor (10) is provided with a stop valve (V3) and a check valve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200520093461 CN2834691Y (en) | 2005-11-14 | 2005-11-14 | An equipment for preparing metal nitride catalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200520093461 CN2834691Y (en) | 2005-11-14 | 2005-11-14 | An equipment for preparing metal nitride catalytic material |
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| CN2834691Y true CN2834691Y (en) | 2006-11-08 |
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| CN 200520093461 Expired - Fee Related CN2834691Y (en) | 2005-11-14 | 2005-11-14 | An equipment for preparing metal nitride catalytic material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457270C (en) * | 2005-11-14 | 2009-02-04 | 中国科学院金属研究所 | Apparatus and method for preparing metal nitride catalytic material |
| CN108358178A (en) * | 2018-05-03 | 2018-08-03 | 中国工程物理研究院流体物理研究所 | A kind of Mo2The air atmosphere synthetic method of N |
-
2005
- 2005-11-14 CN CN 200520093461 patent/CN2834691Y/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457270C (en) * | 2005-11-14 | 2009-02-04 | 中国科学院金属研究所 | Apparatus and method for preparing metal nitride catalytic material |
| CN108358178A (en) * | 2018-05-03 | 2018-08-03 | 中国工程物理研究院流体物理研究所 | A kind of Mo2The air atmosphere synthetic method of N |
| CN108358178B (en) * | 2018-05-03 | 2019-10-25 | 中国工程物理研究院流体物理研究所 | A kind of Mo2The air atmosphere synthetic method of N |
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