CN104368370A - Preparation method of supported molybdenum carbide catalyst - Google Patents
Preparation method of supported molybdenum carbide catalyst Download PDFInfo
- Publication number
- CN104368370A CN104368370A CN201410520202.9A CN201410520202A CN104368370A CN 104368370 A CN104368370 A CN 104368370A CN 201410520202 A CN201410520202 A CN 201410520202A CN 104368370 A CN104368370 A CN 104368370A
- Authority
- CN
- China
- Prior art keywords
- molybdenum carbide
- carbide catalyst
- ammonium molybdate
- preparation
- load type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a supported molybdenum carbide catalyst. The preparation method comprises the following steps of 1, mixing molybdenum trioxide and deionized water to obtain uniform slurry, and dropwisely adding ammonia water into the slurry until slurry pH value is in a range of 7.5-8 and an ammonium molybdate solution is obtained, 2, adding a surfactant into the ammonium molybdate solution obtained by the step 1 and carrying out stirring to obtain a uniform mixture, 3, carrying out vacuum drying treatment on carriers, dropwisely adding the ammonium molybdate solution into the carriers for dipping adsorption under the ultrasonic vibration conditions, then carrying out filtering treatment, and carrying out drying to obtain the carriers adsorbed with ammonium molybdate, and 4, orderly carrying out air removal, roasting and passivation treatment to obtain the supported molybdenum carbide catalyst. The supported molybdenum carbide catalyst has a large specific surface area, high strength and good poisoning resistance.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of preparation method of load type molybdenum carbide catalyst.
Background technology
Transition metal carbide is that carbon atom enters the lattice of transition metal and the class produced has between metalline and fills compound, they combine three kinds of different materials: the characteristic of covalency solid, ionic crystals and transition metal, thus have special physics and chemistry character.They show the hardness the same with covalency solid and brittleness, and the same with typical ionic crystals have simple crystal structure and high fusing point, has the advantages such as hardness is large, fusing point is high, anticorrosive.After within 1973, Levy and Boudart finds that WC has class Pt character in a series of catalytic reaction, transition metal carbide causes the very big concern of people in catalytic science as a class new catalytic material.Research shows widely subsequently, in many reactions of precious metal catalyst, carbide all shows good catalytic performance, in the reaction even participated at some hydrogen close to or exceeded noble metal catalyst, fully shown the significance of its theoretical research and wide application prospect thereof.
Adopt electron microscopic observation, at MoO
3and CH
4/ H
2in gaseous mixture course of reaction, pass through MoO
3the minimizing of platelet transmitance carrys out observing response process, and result shows MoO
3change to lower valency and occur in about 630K, at below 620K MoO
3substantially do not change.Along with MoO
3and CH
4/ H
2the rising Mo of reaction temperature
2first C is being parallel to MoO
3(120) crystal face generate and extend, but the surface topography of gained solid does not change, end product Mo
2the pattern of C and MoO
3similar.In end product, Mo
2(100) face of C and MoO
3(010) direction of platelet is parallel, i.e. (100) Mo
2c//(010) MoO
3, therefore, by MoO
3to Mo
2c is through topotactic reaction.
Therefore, a kind of preparation method that can overcome the load type molybdenum carbide catalyst of conventional precious metal catalyst high cost and body molybdenum carbide catalyst specific area low technical defect of research and development is needed badly.
Summary of the invention
Technical problem to be solved by this invention is, for above-mentioned the deficiencies in the prior art, to provide a kind of preparation method of load type molybdenum carbide catalyst.Adopt the load type molybdenum carbide catalyst prepared of the method to overcome conventional precious metal catalyst high cost and the low technological deficiency of body molybdenum carbide catalyst specific area, specific area is large, and intensity is high, and anti-poisoning performance is good.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of load type molybdenum carbide catalyst, is characterized in that, the method comprises the following steps:
Step one, by molybdenum trioxide and deionized water by volume 1: (20 ~ 30) mix, obtain slurries, be then under the condition of 40 DEG C ~ 50 DEG C in temperature, in slurries, drip ammoniacal liquor, be till 7.5 ~ 8 until the pH value of slurries, obtain ammonium molybdate solution;
Step 2, to be joined in ammonium molybdate solution described in step one by surfactant and stir, the addition of described surfactant adds 2g ~ 4g surfactant in often liter of ammonium molybdate solution;
Step 3, vacuum drying treatment is carried out to carrier, then the carrier after vacuum drying treatment is placed in comes, under the condition of ultrasonic wave vibration, the ammonium molybdate solution being added with surfactant in step 2 is dripped dipping absorption 2h ~ 4h on carrier, carry out filtration treatment afterwards, after drying, obtain the carrier being adsorbed with ammonium molybdate; The volume ratio of the described ammonium molybdate solution and carrier that are added with surfactant is 1: 1, and described carrier is active carbon, silica or active alchlor;
Step 4, the carrier being adsorbed with ammonium molybdate is placed in tube furnace carries out deaeration, roasting and Passivation Treatment successively described in step 3, detailed process is:
Step 401, deaeration: in tube furnace, pass into nitrogen or argon gas, till by the air emptying in tube furnace;
Step 402, roasting: the mist passing into methane and hydrogen in the tube furnace in step 401 after deaeration, under the flow velocity of the mist of methane and hydrogen is the condition of 40mm/min ~ 50mm/min, first be incubated 150min ~ 250min with after the ramp to 150 of 8 DEG C/min ~ 20 DEG C/min DEG C ~ 250 DEG C, then 100min ~ 150min is incubated with after the ramp to 550 of 0.5 DEG C/min ~ 3 DEG C/min DEG C ~ 640 DEG C, stop the mist passing into methane and hydrogen afterwards, adopt nitrogen or argon gas to be cooled to 25 DEG C of room temperatures;
Step 403, passivation: the mist passing into oxygen and nitrogen in tube furnace, under the flow velocity of the mist of oxygen and nitrogen is the condition of 40mm/min ~ 50mm/min, Passivation Treatment is carried out to the carrier after calcination process in step 402, obtain load type molybdenum carbide catalyst.
The preparation method of above-mentioned a kind of load type molybdenum carbide catalyst, is characterized in that, the quality purity of molybdenum trioxide described in step one is not less than 99.99%.
The preparation method of above-mentioned a kind of load type molybdenum carbide catalyst, it is characterized in that, ammoniacal liquor described in step one is by deionized water and industrial ammonia by volume 1: (0.5 ~ 0.9) mixes and forms, and wherein the mass percent concentration of industrial ammonia is 25% ~ 28%.
The preparation method of above-mentioned a kind of load type molybdenum carbide catalyst, is characterized in that, surfactant described in step 2 is neopelex, softex kw or AEO.
The preparation method of above-mentioned a kind of load type molybdenum carbide catalyst, is characterized in that, active carbon described in step 3 is wood activated charcoal or cocoanut active charcoal.
The preparation method of above-mentioned a kind of load type molybdenum carbide catalyst, it is characterized in that, the temperature of vacuum drying treatment described in step 3 is 80 DEG C ~ 100 DEG C, and the time of described vacuum drying treatment is 30min ~ 40min, and the vacuum of described vacuum drying treatment is not more than 0.08MPa.
The preparation method of above-mentioned a kind of load type molybdenum carbide catalyst, is characterized in that, the speed dripped described in step one and step 3 is 3mL/min ~ 10mL/min.
The preparation method of above-mentioned a kind of load type molybdenum carbide catalyst, is characterized in that, the mist of methane described in step 402 and hydrogen is by methane and hydrogen 1:(30 ~ 70 by volume) mix and form.
The preparation method of above-mentioned a kind of load type molybdenum carbide catalyst, is characterized in that, the mist of oxygen described in step 403 and nitrogen is by oxygen and nitrogen 1:(10 ~ 30 by volume) mix and form.
The preparation method of above-mentioned a kind of load type molybdenum carbide catalyst, is characterized in that, the time of passivation described in step 403 is 20h ~ 30h.
The present invention compared with prior art has the following advantages:
1, the present invention adopts the mist of oxygen and nitrogen to carry out Passivation Treatment, and a small amount of oxygen not only can improve chemistry and heat endurance, and change catalyst acid position due to a small amount of oxygen, thus remote-effects catalyst performance, improve catalyst activity;
2, the present invention carries out vacuum drying to carrier before dipping process, can more contribute to molybdate and be distributed in carrier inside equably;
3, the dipping process of carrier of the present invention and ammonium molybdate solution is incipient impregnation, and adopts ultrasonic wave to vibrate assistant soakage, and in dipping process, first ammonium molybdate is dissociated into molybdenum acid ion and ammonium radical ion, enters carrier afterwards, can ensure maximum saturation degree of impregnation;
4, the present invention adopts high-purity molybdenum trioxide to prepare ammonium molybdate solution, and adds proper ammonia, ensures that the pH value of final ammonium molybdate solution is 7.5 ~ 8, avoids the introducing of impurity in other ammonium molybdate product;
5, instant invention overcomes conventional precious metal catalyst high cost and the low technological deficiency of body molybdenum carbide catalyst specific area, adopt load type molybdenum carbide catalyst prepared by the present invention, its catalytic efficiency is high, and anti-poisoning performance is good, and the life-span is long.
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is the X-ray crystallographic analysis figure of load type molybdenum carbide catalyst prepared by the embodiment of the present invention 1.
Fig. 2 is the XPS atomic valence analysis chart of load type molybdenum carbide catalyst prepared by the embodiment of the present invention 1.
Fig. 3 is the electron scanning Electronic Speculum figure of load type molybdenum carbide catalyst under multiplication factor is 1200 times of conditions prepared by the embodiment of the present invention 1.
Fig. 4 is the electron scanning Electronic Speculum figure of load type molybdenum carbide catalyst under multiplication factor is 14000 times of conditions prepared by the embodiment of the present invention 1.
Detailed description of the invention
Embodiment 1
The preparation method of the present embodiment load type molybdenum carbide catalyst comprises the following steps:
Step one, molybdenum trioxide quality purity being not less than 99.99% mix by volume with deionized water at 1: 25, obtain slurries, be then under the condition of 45 DEG C in temperature, in slurries, drip ammoniacal liquor, be till 7.5 until the pH value of slurries, obtain ammonium molybdate solution; The industrial ammonia that described ammoniacal liquor is 26% by deionized water and mass percent concentration mixes forms by volume at 1: 0.7;
Step 2, to be joined in ammonium molybdate solution described in step one by surfactant and stir, the addition of described surfactant adds 3g surfactant in often liter of ammonium molybdate solution; Described surfactant is neopelex, softex kw or AEO; That the present embodiment adopts is neopelex (SDBS);
Step 3, carrier is carried out vacuum drying treatment, the temperature of described vacuum drying treatment is 100 DEG C, the time of described vacuum drying treatment is 35min, the vacuum of described vacuum drying treatment is not more than 0.08MPa, then be placed in comes, under the condition of ultrasonic wave vibration, the ammonium molybdate solution being added with surfactant dripped dipping absorption 3h on carrier in step 2, carry out filtration treatment afterwards, after drying, obtain the carrier being adsorbed with ammonium molybdate; The volume ratio of the described ammonium molybdate solution and carrier that are added with surfactant is 1: 1, and described carrier is active carbon, silica or active alchlor; The carrier that the present embodiment adopts is cocoanut active charcoal, column, intensity >95%, and average pore size is 1nm ~ 5nm, and moisture is 5% ~ 10%, and aqueous fusion thing is 0.1% ~ 0.5%, and molysite content is 0.001% ~ 0.05%;
Step 4, the carrier being adsorbed with ammonium molybdate is placed in tube furnace carries out deaeration, roasting and Passivation Treatment successively described in step 3, detailed process is:
Step 401, deaeration: in tube furnace, pass into nitrogen or argon gas, till by the air emptying in tube furnace;
Step 402, roasting: the mist passing into methane and hydrogen in the tube furnace in step 401 after deaeration, the mist of described methane and hydrogen by volume by methane and hydrogen is mixed forms at 1: 50, under the flow velocity of the mist of methane and hydrogen is the condition of 45mm/min, first be incubated 200min with after the ramp to 200 of 12 DEG C/min DEG C, then 120min is incubated with after the ramp to 590 of 1.5 DEG C/min DEG C, stop the mist passing into methane and hydrogen afterwards, adopt nitrogen or argon gas to be cooled to 25 DEG C of room temperatures;
Step 403, passivation: the mist passing into oxygen and nitrogen in tube furnace, the mist of described oxygen and nitrogen by volume by oxygen and nitrogen is mixed forms at 1: 20, under the flow velocity of the mist of oxygen and nitrogen is the condition of 45mm/min, Passivation Treatment 20h is carried out to the carrier after calcination process in step 402, obtain load type molybdenum carbide catalyst.
Fig. 1 is the X-ray crystallographic analysis figure of load type molybdenum carbide catalyst prepared by the present embodiment.The catalyst that as shown in Figure 1 prepared by the present embodiment is really molybdenum carbide catalyst.Fig. 2 is the XPS atomic valence analysis chart of load type molybdenum carbide catalyst prepared by the present embodiment.In the catalyst prepared of the present embodiment, the valence state of molybdenum is reduced to+4 valencys by+6 valencys as shown in Figure 2, and also this catalyst of susceptible of proof is molybdenum carbide catalyst thus.Fig. 3 is the electron scanning Electronic Speculum figure of load type molybdenum carbide catalyst under multiplication factor is 1200 times of conditions prepared by the present embodiment.Fig. 4 is the electron scanning Electronic Speculum figure of load type molybdenum carbide catalyst under multiplication factor is 14000 times of conditions prepared by the present embodiment.From Fig. 3 and Fig. 4, in catalyst prepared by the present embodiment, molybdenum carbide is carried on carrier really, and is evenly distributed.
Embodiment 2
The preparation method of the present embodiment load type molybdenum carbide catalyst comprises the following steps:
Step one, molybdenum trioxide quality purity being not less than 99.99% mix by volume with deionized water at 1: 20, obtain slurries, be then under the condition of 50 DEG C in temperature, in slurries, drip ammoniacal liquor, be till 7.5 until the pH value of slurries, obtain ammonium molybdate solution; The industrial ammonia that described ammoniacal liquor is 28% by deionized water and mass percent concentration mixes forms by volume at 1: 0.9;
Step 2, to be joined in ammonium molybdate solution described in step one by surfactant and stir, the addition of described surfactant adds 2g surfactant in often liter of ammonium molybdate solution; Described surfactant is neopelex, softex kw or AEO; The surfactant that the present embodiment adopts is softex kw (CTMAB);
Step 3, carrier is carried out vacuum drying treatment, the temperature of described vacuum drying treatment is 90 DEG C, the time of described vacuum drying treatment is 40min, the vacuum of described vacuum drying treatment is not more than 0.08MPa, then be placed in comes, under the condition of ultrasonic wave vibration, the ammonium molybdate solution being added with surfactant dripped dipping absorption 3h on carrier in step 2, carry out filtration treatment afterwards, after drying, obtain the carrier being adsorbed with ammonium molybdate; The volume ratio of the described ammonium molybdate solution and carrier that are added with surfactant is 1: 1, described carrier is active carbon, silica or active alchlor, what the present embodiment adopted is silica, and its average pore size is 10nm ~ 30nm, and average pore volume is 0.1mL/g ~ 1.0mL/g;
Step 4, the carrier being adsorbed with ammonium molybdate is placed in tube furnace carries out deaeration, roasting and Passivation Treatment successively described in step 3, detailed process is:
Step 401, deaeration: in tube furnace, pass into nitrogen or argon gas, till by the air emptying in tube furnace;
Step 402, roasting: the mist passing into methane and hydrogen in the tube furnace in step 401 after deaeration, the mist of described methane and hydrogen by volume by methane and hydrogen is mixed forms at 1: 40, under the flow velocity of the mist of methane and hydrogen is the condition of 40mm/min, first be incubated 250min with after the ramp to 150 of 20 DEG C/min DEG C, then 150min is incubated with after the ramp to 550 of 0.5 DEG C/min DEG C, stop the mist passing into methane and hydrogen afterwards, adopt nitrogen or argon gas to be cooled to 25 DEG C of room temperatures;
Step 403, passivation: the mist passing into oxygen and nitrogen in tube furnace, the mist of described oxygen and nitrogen by volume by oxygen and nitrogen is mixed forms at 1: 10, under the flow velocity of the mist of oxygen and nitrogen is the condition of 40mm/min, Passivation Treatment 20h is carried out to the carrier after calcination process in step 402, obtain load type molybdenum carbide catalyst.
X-ray crystallographic analysis, the analysis of XPS atomic valence and electron scanning electronic microscope photos is carried out respectively known by the load type molybdenum carbide catalyst prepared the present embodiment, catalyst prepared by the present embodiment is really load type molybdenum carbide catalyst, and the molybdenum carbide be carried on carrier is in being evenly distributed.
Embodiment 3
The preparation method of the present embodiment load type molybdenum carbide catalyst comprises the following steps:
Step one, molybdenum trioxide quality purity being not less than 99.99% mix by volume with deionized water at 1: 20, obtain slurries, be then under the condition of 40 DEG C in temperature, in slurries, drip ammoniacal liquor, be till 8 until the pH value of slurries, obtain ammonium molybdate solution; The industrial ammonia that described ammoniacal liquor is 25% by deionized water and mass percent concentration mixes forms by volume at 1: 0.9;
Step 2, to be joined in ammonium molybdate solution described in step one by surfactant and stir, the addition of described surfactant adds 4g surfactant in often liter of ammonium molybdate solution; Described surfactant is neopelex, softex kw or AEO, and that the present embodiment adopts is AEO (AE);
Step 3, carrier is carried out vacuum drying treatment, the temperature of described vacuum drying treatment is 100 DEG C, the time of described vacuum drying treatment is 30min, the vacuum of described vacuum drying treatment is not more than 0.08MPa, then be placed in comes, under the condition of ultrasonic wave vibration, the ammonium molybdate solution being added with surfactant dripped dipping absorption 4h on carrier in step 2, carry out filtration treatment afterwards, after drying, obtain the carrier being adsorbed with ammonium molybdate; The volume ratio of the described ammonium molybdate solution and carrier that are added with surfactant is 1: 1, described carrier is active carbon, silica or active alchlor, what the present embodiment adopted is activated alumina, and its average pore size is 20nm ~ 30nm, and average pore volume is 0.5mL/g ~ 1.0mL/g;
Step 4, the carrier being adsorbed with ammonium molybdate is placed in tube furnace carries out deaeration, roasting and Passivation Treatment successively described in step 3, detailed process is:
Step 401, deaeration: in tube furnace, pass into nitrogen or argon gas, till by the air emptying in tube furnace;
Step 402, roasting: the mist passing into methane and hydrogen in the tube furnace in step 401 after deaeration, the mist of described methane and hydrogen by volume by methane and hydrogen is mixed forms at 1: 30, under the flow velocity of the mist of methane and hydrogen is the condition of 40mm/min, first be incubated 250min with after the ramp to 150 of 20 DEG C/min DEG C, then 150min is incubated with after the ramp to 550 of 3 DEG C/min DEG C, stop the mist passing into methane and hydrogen afterwards, adopt nitrogen or argon gas to be cooled to 25 DEG C of room temperatures;
Step 403, passivation: the mist passing into oxygen and nitrogen in tube furnace, the mist of described oxygen and nitrogen by volume by oxygen and nitrogen is mixed forms at 1: 30, under the flow velocity of the mist of oxygen and nitrogen is the condition of 40mm/min, Passivation Treatment 30h is carried out to the carrier after calcination process in step 402, obtain load type molybdenum carbide catalyst.
X-ray crystallographic analysis, the analysis of XPS atomic valence and electron scanning electronic microscope photos is carried out respectively known by the load type molybdenum carbide catalyst prepared the present embodiment, catalyst prepared by the present embodiment is really load type molybdenum carbide catalyst, and the molybdenum carbide be carried on carrier is in being evenly distributed.
Embodiment 4
The preparation method of the present embodiment load type molybdenum carbide catalyst comprises the following steps:
Step one, molybdenum trioxide quality purity being not less than 99.99% mix by volume with deionized water at 1: 30, obtain slurries, be then under the condition of 50 DEG C in temperature, in slurries, drip ammoniacal liquor, be till 7.5 until the pH value of slurries, obtain ammonium molybdate solution; The industrial ammonia that described ammoniacal liquor is 28% by deionized water and mass percent concentration mixes forms by volume at 1: 0.5;
Step 2, to be joined in ammonium molybdate solution described in step one by surfactant and stir, the addition of described surfactant adds 2g surfactant in often liter of ammonium molybdate solution; Described surfactant is neopelex, softex kw or AEO, and that the present embodiment adopts is neopelex (SDBS);
Step 3, carrier is carried out vacuum drying treatment, the temperature of described vacuum drying treatment is 80 DEG C, the time of described vacuum drying treatment is 40min, the vacuum of described vacuum drying treatment is not more than 0.08MPa, then be placed in comes, under the condition of ultrasonic wave vibration, the ammonium molybdate solution being added with surfactant dripped dipping absorption 2h on carrier in step 2, carry out filtration treatment afterwards, after drying, obtain the carrier being adsorbed with ammonium molybdate; The volume ratio of the described ammonium molybdate solution and carrier that are added with surfactant is 1: 1, described carrier is active carbon, silica or active alchlor, what the present embodiment adopted is wood activated charcoal, column, intensity >95%, average pore size is 1nm ~ 5nm, and moisture is 5% ~ 10%, aqueous fusion thing is 0.1% ~ 0.5%, and molysite content is 0.001% ~ 0.05%;
Step 4, the carrier being adsorbed with ammonium molybdate is placed in tube furnace carries out deaeration, roasting and Passivation Treatment successively described in step 3, detailed process is:
Step 401, deaeration: in tube furnace, pass into nitrogen or argon gas, till by the air emptying in tube furnace;
Step 402, roasting: the mist passing into methane and hydrogen in the tube furnace in step 401 after deaeration, the mist of described methane and hydrogen by volume by methane and hydrogen is mixed forms at 1: 70, under the flow velocity of the mist of methane and hydrogen is the condition of 50mm/min, first be incubated 150min with after the ramp to 250 of 8 DEG C/min DEG C, then 100min is incubated with after the ramp to 640 of 0.5 DEG C/min DEG C, stop the mist passing into methane and hydrogen afterwards, adopt nitrogen or argon gas to be cooled to 25 DEG C of room temperatures;
Step 403, passivation: the mist passing into oxygen and nitrogen in tube furnace, the mist of described oxygen and nitrogen by volume by oxygen and nitrogen is mixed forms at 1: 10, under the flow velocity of the mist of oxygen and nitrogen is the condition of 50mm/min, Passivation Treatment 20h is carried out to the carrier after calcination process in step 402, obtain load type molybdenum carbide catalyst.
X-ray crystallographic analysis, the analysis of XPS atomic valence and electron scanning electronic microscope photos is carried out respectively known by the load type molybdenum carbide catalyst prepared the present embodiment, catalyst prepared by the present embodiment is really load type molybdenum carbide catalyst, and the molybdenum carbide be carried on carrier is in being evenly distributed.
Embodiment 5
The preparation method of the present embodiment load type molybdenum carbide catalyst comprises the following steps:
Step one, molybdenum trioxide quality purity being not less than 99.99% mix by volume with deionized water at 1: 30, obtain slurries, be then under the condition of 50 DEG C in temperature, in slurries, drip ammoniacal liquor, be till 7.5 until the pH value of slurries, obtain ammonium molybdate solution; The industrial ammonia that described ammoniacal liquor is 28% by deionized water and mass percent concentration mixes forms by volume at 1: 0.7;
Step 2, to be joined in ammonium molybdate solution described in step one by surfactant and stir, the addition of described surfactant adds 4g surfactant in often liter of ammonium molybdate solution; Described surfactant is neopelex, softex kw or AEO, and that the present embodiment adopts is AEO (AE);
Step 3, carrier is carried out vacuum drying treatment, the temperature of described vacuum drying treatment is 80 DEG C, the time of described vacuum drying treatment is 40min, the vacuum of described vacuum drying treatment is not more than 0.08MPa, then be placed in comes, under the condition of ultrasonic wave vibration, the ammonium molybdate solution being added with surfactant dripped dipping absorption 2h on carrier in step 2, carry out filtration treatment afterwards, after drying, obtain the carrier being adsorbed with ammonium molybdate; The volume ratio of the described ammonium molybdate solution and carrier that are added with surfactant is 1: 1, described carrier is active carbon, silica or active alchlor, what the present embodiment adopted is wood activated charcoal, 6 ~ 8 order graininess, its intensity is 70% ~ 80%, and average pore size is 1nm ~ 4nm, and moisture is 5% ~ 10%, aqueous fusion thing is 0.2% ~ 0.4%, and molysite content is 0.001% ~ 0.01%;
Step 4, the carrier being adsorbed with ammonium molybdate is placed in tube furnace carries out deaeration, roasting and Passivation Treatment successively described in step 3, detailed process is:
Step 401, deaeration: in tube furnace, pass into nitrogen or argon gas, till by the air emptying in tube furnace;
Step 402, roasting: the mist passing into methane and hydrogen in the tube furnace in step 401 after deaeration, the mist of described methane and hydrogen by volume by methane and hydrogen is mixed forms at 1: 70, under the flow velocity of the mist of methane and hydrogen is the condition of 50mm/min, first be incubated 150min with after the ramp to 250 of 8 DEG C/min DEG C, then 100min is incubated with after the ramp to 640 of 0.5 DEG C/min DEG C, stop the mist passing into methane and hydrogen afterwards, adopt nitrogen or argon gas to be cooled to 25 DEG C of room temperatures;
Step 403, passivation: the mist passing into oxygen and nitrogen in tube furnace, the mist of described oxygen and nitrogen by volume by oxygen and nitrogen is mixed forms at 1: 10, under the flow velocity of the mist of oxygen and nitrogen is the condition of 50mm/min, Passivation Treatment 20h is carried out to the carrier after calcination process in step 402, obtain load type molybdenum carbide catalyst.
X-ray crystallographic analysis, the analysis of XPS atomic valence and electron scanning electronic microscope photos is carried out respectively known by the load type molybdenum carbide catalyst prepared the present embodiment, catalyst prepared by the present embodiment is really load type molybdenum carbide catalyst, and the molybdenum carbide be carried on carrier is in being evenly distributed.
The above is only preferred embodiment of the present invention, not imposes any restrictions the present invention.Every above embodiment is done according to invention technical spirit any simple modification, change and equivalence change, all still belong in the protection domain of technical solution of the present invention.
Claims (10)
1. a preparation method for load type molybdenum carbide catalyst, is characterized in that, the method comprises the following steps:
Step one, by molybdenum trioxide and deionized water by volume 1: (20 ~ 30) mix, obtain slurries, be then under the condition of 40 DEG C ~ 50 DEG C in temperature, in slurries, drip ammoniacal liquor, be till 7.5 ~ 8 until the pH value of slurries, obtain ammonium molybdate solution;
Step 2, to be joined in ammonium molybdate solution described in step one by surfactant and stir, the addition of described surfactant adds 2g ~ 4g surfactant in often liter of ammonium molybdate solution;
Step 3, vacuum drying treatment is carried out to carrier, then the carrier after vacuum drying treatment is placed in comes, under the condition of ultrasonic wave vibration, the ammonium molybdate solution being added with surfactant in step 2 is dripped dipping absorption 2h ~ 4h on carrier, carry out filtration treatment afterwards, after drying, obtain the carrier being adsorbed with ammonium molybdate; The volume ratio of the described ammonium molybdate solution and carrier that are added with surfactant is 1: 1, and described carrier is active carbon, silica or active alchlor;
Step 4, the carrier being adsorbed with ammonium molybdate is placed in tube furnace carries out deaeration, roasting and Passivation Treatment successively described in step 3, detailed process is:
Step 401, deaeration: in tube furnace, pass into nitrogen or argon gas, till by the air emptying in tube furnace;
Step 402, roasting: the mist passing into methane and hydrogen in the tube furnace in step 401 after deaeration, under the flow velocity of the mist of methane and hydrogen is the condition of 40mm/min ~ 50mm/min, first be incubated 150min ~ 250min with after the ramp to 150 of 8 DEG C/min ~ 20 DEG C/min DEG C ~ 250 DEG C, then 100min ~ 150min is incubated with after the ramp to 550 of 0.5 DEG C/min ~ 3 DEG C/min DEG C ~ 640 DEG C, stop the mist passing into methane and hydrogen afterwards, adopt nitrogen or argon gas to be cooled to 25 DEG C of room temperatures;
Step 403, passivation: the mist passing into oxygen and nitrogen in tube furnace, under the flow velocity of the mist of oxygen and nitrogen is the condition of 40mm/min ~ 50mm/min, Passivation Treatment is carried out to the carrier after calcination process in step 402, obtain load type molybdenum carbide catalyst.
2. the preparation method of a kind of load type molybdenum carbide catalyst according to claim 1, is characterized in that, the quality purity of molybdenum trioxide described in step one is not less than 99.99%.
3. the preparation method of a kind of load type molybdenum carbide catalyst according to claim 1, it is characterized in that, ammoniacal liquor described in step one is by deionized water and industrial ammonia by volume 1: (0.5 ~ 0.9) mixes and forms, and wherein the mass percent concentration of industrial ammonia is 25% ~ 28%.
4. the preparation method of a kind of load type molybdenum carbide catalyst according to claim 1, is characterized in that, surfactant described in step 2 is neopelex, softex kw or AEO.
5. the preparation method of a kind of load type molybdenum carbide catalyst according to claim 1, is characterized in that, active carbon described in step 3 is wood activated charcoal or cocoanut active charcoal.
6. the preparation method of a kind of load type molybdenum carbide catalyst according to claim 1, it is characterized in that, the temperature of vacuum drying treatment described in step 3 is 80 DEG C ~ 100 DEG C, the time of described vacuum drying treatment is 30min ~ 40min, and the vacuum of described vacuum drying treatment is not more than 0.08MPa.
7. the preparation method of a kind of load type molybdenum carbide catalyst according to claim 1, is characterized in that, the speed dripped described in step one and step 3 is 3mL/min ~ 10mL/min.
8. the preparation method of a kind of load type molybdenum carbide catalyst according to claim 1, is characterized in that, the mist of methane described in step 402 and hydrogen is by methane and hydrogen 1:(30 ~ 70 by volume) mix and form.
9. the preparation method of a kind of load type molybdenum carbide catalyst according to claim 1, is characterized in that, the mist of oxygen described in step 403 and nitrogen is by oxygen and nitrogen 1:(10 ~ 30 by volume) mix and form.
10. the preparation method of a kind of load type molybdenum carbide catalyst according to claim 1, is characterized in that, the time of passivation described in step 403 is 20h ~ 30h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410520202.9A CN104368370A (en) | 2014-09-30 | 2014-09-30 | Preparation method of supported molybdenum carbide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410520202.9A CN104368370A (en) | 2014-09-30 | 2014-09-30 | Preparation method of supported molybdenum carbide catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104368370A true CN104368370A (en) | 2015-02-25 |
Family
ID=52547716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410520202.9A Pending CN104368370A (en) | 2014-09-30 | 2014-09-30 | Preparation method of supported molybdenum carbide catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104368370A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836702A (en) * | 2016-04-27 | 2016-08-10 | 清华大学 | Method for preparing hydrogen through hydrogen iodide catalysis and decomposition |
| CN106563480A (en) * | 2016-11-16 | 2017-04-19 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesis of methyl acetate and ethanol through hydrogenation of dimethyl oxalate, and preparation method and application thereof |
| CN108745398A (en) * | 2018-05-23 | 2018-11-06 | 中国林业科学研究院林产化学工业研究所 | A kind of Mo2C/NMC catalyst and preparation method thereof and the application in the reaction of oleic acid hydrogenation deoxidation |
| CN108946725A (en) * | 2018-07-19 | 2018-12-07 | 深圳市环球绿地新材料有限公司 | Spherical activated charcoal, the preparation method and use of loading cation surfactant |
| CN110652991A (en) * | 2019-10-28 | 2020-01-07 | 福州大学 | Molybdenum carbide/cerium oxide catalyst for ammonia synthesis and preparation method thereof |
| CN110980640A (en) * | 2019-12-31 | 2020-04-10 | 湘潭大学 | Method for preparing hydrogen by catalyzing direct conversion of methane |
| CN111135844A (en) * | 2019-12-19 | 2020-05-12 | 浙江师范大学 | Application of organic soluble molybdenum salt in preparation of molybdenum carbide catalyst, preparation method and application of molybdenum carbide catalyst |
| CN113235106A (en) * | 2021-04-07 | 2021-08-10 | 中南林业科技大学 | Preparation method of molybdenum carbide-loaded wood-based electrocatalyst and catalyst for hydrogen production by water electrolysis |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61192345A (en) * | 1985-02-22 | 1986-08-26 | Hitachi Ltd | Preparation of carbide catalyst |
| CN101829588A (en) * | 2010-05-27 | 2010-09-15 | 复旦大学 | Synthetic method of load type molybdenum carbide catalyst |
| CN102600877A (en) * | 2012-01-11 | 2012-07-25 | 大连理工大学 | High-selectivity catalyst for naphthalene hydrogenation reaction for preparing tetrahydronaphthalene and preparation method thereof |
-
2014
- 2014-09-30 CN CN201410520202.9A patent/CN104368370A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61192345A (en) * | 1985-02-22 | 1986-08-26 | Hitachi Ltd | Preparation of carbide catalyst |
| CN101829588A (en) * | 2010-05-27 | 2010-09-15 | 复旦大学 | Synthetic method of load type molybdenum carbide catalyst |
| CN102600877A (en) * | 2012-01-11 | 2012-07-25 | 大连理工大学 | High-selectivity catalyst for naphthalene hydrogenation reaction for preparing tetrahydronaphthalene and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 刘燕等: "高活性PtMo2C/Al2O3催化剂的研究进展", 《中国钼业》 * |
| 朱洪法等: "《催化剂制备及应用技术》", 30 June 2011, 中国石化出版社 * |
| 李凤生著: "《特种超细粉体制备技术及应用》", 31 January 2002, 国防工业出版社 * |
| 金谷著: "《表面活性剂化学第2版》", 31 August 2013, 中国科学技术大学出版社 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836702A (en) * | 2016-04-27 | 2016-08-10 | 清华大学 | Method for preparing hydrogen through hydrogen iodide catalysis and decomposition |
| CN106563480A (en) * | 2016-11-16 | 2017-04-19 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesis of methyl acetate and ethanol through hydrogenation of dimethyl oxalate, and preparation method and application thereof |
| CN108745398A (en) * | 2018-05-23 | 2018-11-06 | 中国林业科学研究院林产化学工业研究所 | A kind of Mo2C/NMC catalyst and preparation method thereof and the application in the reaction of oleic acid hydrogenation deoxidation |
| CN108946725A (en) * | 2018-07-19 | 2018-12-07 | 深圳市环球绿地新材料有限公司 | Spherical activated charcoal, the preparation method and use of loading cation surfactant |
| CN110652991A (en) * | 2019-10-28 | 2020-01-07 | 福州大学 | Molybdenum carbide/cerium oxide catalyst for ammonia synthesis and preparation method thereof |
| CN111135844A (en) * | 2019-12-19 | 2020-05-12 | 浙江师范大学 | Application of organic soluble molybdenum salt in preparation of molybdenum carbide catalyst, preparation method and application of molybdenum carbide catalyst |
| CN111135844B (en) * | 2019-12-19 | 2023-01-31 | 浙江师范大学 | Application of organic soluble molybdenum salt in preparation of molybdenum carbide catalyst, preparation method and application of molybdenum carbide catalyst |
| CN110980640A (en) * | 2019-12-31 | 2020-04-10 | 湘潭大学 | Method for preparing hydrogen by catalyzing direct conversion of methane |
| CN113235106A (en) * | 2021-04-07 | 2021-08-10 | 中南林业科技大学 | Preparation method of molybdenum carbide-loaded wood-based electrocatalyst and catalyst for hydrogen production by water electrolysis |
| CN113235106B (en) * | 2021-04-07 | 2022-07-15 | 中南林业科技大学 | Preparation method of molybdenum carbide-loaded wood-based electrocatalyst and catalyst for hydrogen production by electrolyzing water |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104368370A (en) | Preparation method of supported molybdenum carbide catalyst | |
| US20190381487A1 (en) | Carbon nitride membrane composite material modified by black phosphorus/ metal organic framework, and preparation method thereof and application in waste gas treatment | |
| CN105597777B (en) | A kind of ordered mesopore carbon loaded Cu-Mn bimetallic denitration catalysts and preparation method thereof | |
| CN104627960B (en) | A kind of method of changed red mud catalytic methane cracking hydrogen production | |
| CN104211040B (en) | The preparation method of high specific surface area porous carbon nano rod | |
| CN102698785B (en) | A kind of tripolite loading nitrogen-doped nanometer TiO 2the preparation method of catalysis material | |
| CN109626670A (en) | A kind of porous Fe/C/N composite material and preparation method | |
| CN105478120A (en) | Preparation method for red mud-based iron-series catalyst and application of red mud-based iron-series catalyst in hydrogen production through cracking of methane | |
| CN103506146B (en) | Catalyst for decomposing hydrogen phosphide gas as well as preparation method and application thereof | |
| CN109174148A (en) | A kind of catalyst and preparation method thereof of catalysis oxidation toluene synthesizing benzaldehyde | |
| CN102600878A (en) | Method for preparing TiC-TiO2 core-shell type nanometer material | |
| CN113117722A (en) | For normal temperature NH3Preparation method of-SCR denitration atomic-level active site catalyst | |
| CN108355701A (en) | Ag supports two-dimentional graphite phase carbon nitride nanosheet photocatalyst and its preparation method and application | |
| CN105381812B (en) | A kind of method for preparing the composite semiconductor material with meso-hole structure | |
| CN110479350A (en) | A kind of preparation method of thin layer nitride porous carbon photochemical catalyst | |
| CN109179446A (en) | A kind of hollow nano H-type ZSM-5 molecular sieve and preparation method thereof | |
| CN102583437A (en) | Preparation method for CNT (carbon nano tube)-SAPO (silicoaluminophosphate)-5 molecular-sieve composite membrane | |
| CN106587166A (en) | Ferric oxide mesocrystal nano particle as well as synthesis method and application method thereof | |
| CN107824172A (en) | A kind of preparation method of nano oxidized alumina supporter of the surface rich in defective bit | |
| CN108097262B (en) | Catalyst, preparation method and application thereof | |
| CN103657641B (en) | A kind of preparation method of the catalyst for removing phenolic compound in water | |
| CN112076757A (en) | Porous LaCoO prepared by acetic acid etching3Process for perovskite catalysts | |
| CN106902890A (en) | A kind of Cu BTC/ pucherites/SWCNTs ternary heterojunction structure photochemical catalysts and preparation method and application | |
| CN108636410A (en) | A kind of preparation method and applications of the Fe2O3 doping aluminium oxide hollow microsphere with porous structure | |
| Li et al. | Mechanism and DFT study of degradation of organic pollutants on rare earth ions doped TiO2 photocatalysts prepared by sol-hydrothermal synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150225 |
|
| RJ01 | Rejection of invention patent application after publication |