CN1172858C - Process for preparing molybdenum nitride and use thereof as hydrogenation and desulfurizing catalyst - Google Patents

Process for preparing molybdenum nitride and use thereof as hydrogenation and desulfurizing catalyst Download PDF

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CN1172858C
CN1172858C CNB021300585A CN02130058A CN1172858C CN 1172858 C CN1172858 C CN 1172858C CN B021300585 A CNB021300585 A CN B021300585A CN 02130058 A CN02130058 A CN 02130058A CN 1172858 C CN1172858 C CN 1172858C
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molybdenum nitride
nitrogen
preparation
temperature
gas
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CN1401580A (en
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陈皓侃
龚树文
李文
李保庆
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The present invention relates to a preparation method for molybdenum nitride. A multi-stage temperature programming reaction is carried out to molybdenum trioxide in the atmosphere of a mixture gas of nitrogen and hydrogen with certain purity on the basis of suitable proportion; then, the molybdenum trioxide is cooled in atmosphere inert gas and passivated in a certain oxygen concentration. The prepared molybdenum nitride used as a hydrodesulfurization catalyst is applied to hydrodesulfurization at the temperature of 250 to 450 DEG C under the pressure of 0.2 to 20MPa. The present invention has the advantages of simple preparation process, production cost reduction and easy industrialization application.

Description

The preparation method of molybdenum nitride and as the application of Hydrobon catalyst
Affiliated field:
The present invention relates to a kind of preparation method of molybdenum nitride, and this molybdenum nitride is as Hydrobon catalyst, the particularly application of liquid fuel Hydrobon catalyst.
Background technology:
The environmental legislation of increasingly stringent is more and more lower to the content that requires sulphur in the liquid fuel, and therefore suitable gasoline, diesel deep desulfurization catalyzer of exploitation, and heavy crude and coal-based liquid fuel hydrofining utilize the research of catalyzer constantly to increase.At present, the liquid fuel Hydrobon catalyst of industrial widespread usage mostly is moly-sulfide class catalyzer load or that add auxiliary agents such as nickel, cobalt.Yet, the difficult fragrant thiophene sulfocompounds of many cyclophanes that remove alkyl replacement in the liquid fuel of moly-sulfide class catalyzer, as 4, the 6-dimethyl Dibenzothiophene.In addition, in the mink cell focus hydrogenation process, moly-sulfide class catalyzer is easy to poisoning and deactivation.In order to adapt to the accurately machined trend of liquid fuel deep desulfuration and mink cell focus, require to seek and develop new catalyst system selecting low-cost raw material and simplifying on preparation technology's the basis.
Recently discover, molybdenum nitride has stronger hydrodesulfurization activity, strong desulphurizing activated of the fragrant thiophene sulfocompounds of many cyclophanes that the selectivity of high carbon-sulfide linkage fracture especially arranged and alkyl is replaced, so molybdenum nitride is the catalyzer that is hopeful very much with the liquid fuel hydrogenating desulfurization of potentiality.Yet, the desulphurizing activated molybdenum nitride that has of preparation is a γ crystal formation molybdenum nitride at present, its XRD crystal phase structure feature d value is: 2.404,2.081,1.472,1.255,1.202,1.041, and preparation process is loaded down with trivial details, condition is harsh, cost is higher, be difficult to realize the large-scale industrialization preparation, restricted its practical application.
Summary of the invention:
Order of the present invention provides that a kind of operating process is easy, cost is lower, be easy to the molybdenum nitride preparation method of suitability for industrialized production and as the application of Hydrobon catalyst
The object of the present invention is achieved like this: the molybdic oxide (MoO that gets certain mass 3), under the gas mixture atmosphere of nitrogen suitable proportion, certain purity and hydrogen, carry out the multi-stage procedure temperature reaction, in inert atmosphere, cool off passivation under certain oxygen concentration then.
Concrete preparation process of the present invention may further comprise the steps:
(1) with molybdic oxide (MoO 3) wear into Powdered less than 150 μ m, put into reactor;
(2) with nitrogen and hydrogen by nitrogen: the hydrogen volume ratio is 1: 1-4 mixes, and with MoO 3: gas mixture=1g: (200-500) flow velocity of ml/min feeds reactor;
(3) be that 5-20 ℃/min rises to 300 ℃ from room temperature with molybdic oxide with warm speed, with warm speed is that 0.5-1 ℃/min rises to 500 ℃ from 300 ℃, being 2-10 ℃/min with the temperature rise rate rises to 650-750 ℃ of nitrogenize temperature eventually from 500 ℃, carries out constant temperature 1-5 hour in the whole temperature of nitrogenize;
(4) after temperature reaction finishes, (3) material is chilled to room temperature in inert atmosphere;
(5) at room temperature, be that the 0.5-2% passivating gas carries out passivation to (4) material with the oxygen concentration, get the molybdenum nitride of the present invention's preparation.
Aforesaid molybdic oxide (MoO 3) also can add thermal bake-out from ammonium molybdate and produce, be about to ammonium molybdate at 500 ℃ of roasting certain hours, be used further to this Preparation of Catalyst.
Nitrogen oxygen level in (2) step will be lower than 0.1% as mentioned above, and hydrogen purity is greater than 99%.
Inert atmosphere in (4) step is nitrogen, argon gas or helium as mentioned above, and wherein oxygen level will be lower than 0.1%.
Passivating gas in (5) step can be prepared with air and nitrogen or argon gas, helium as mentioned above, and gas flow is during passivation: MoO 3: passivating gas=1g: (50-150) ml/min.
The XRD crystal phase structure feature d value of the molybdenum nitride of the present invention's preparation is: 2.385,2.094,2.012,1.481,1.451,1.258,1.222,1.193.
The molybdenum nitride of the present invention's preparation is at 250-450 ℃ as the application conditions of Hydrobon catalyst, carries out hydrogenating desulfurization under the 0.2-20MPa.
The present invention has following advantage:
(1) the present invention has simplified preparation process, has reduced the harsh degree of preparation condition, has reduced production cost, is easy to industrial applications.
(2) molybdenum nitride of the present invention's preparation has the crystalline phase of homogeneous, and main XRD crystal phase structure feature d value is: 2.385,2.094,2.012,1.481,1.451,1.258,1.222,1.193.
(3) molybdenum nitride with this crystal phase structure is a catalyzer, has high desulfurization activity and high chemo-selective in the hydrodesulfurization reaction to thiophenes.Having now found that, at temperature 250-450 ℃, is suitable in the wide region of pressure 0.2-20MPa.
Embodiment:
Embodiment 1
(1) takes by weighing molybdic oxide (MoO3) 1 gram of Chinese Shanghai gelatinizing plant produced, wear into less than 150 μ m powder.
(2) with the flow velocity of 140ml/min, feed 99.9% nitrogen, with the flow velocity of 260ml/min, feed 99% hydrogen, in mixing tank, make it thorough mixing.
(3) adopt following temperature program(me) to react: room temperature-300 ℃, temperature rise rate is 10 ℃/min; 300-500 ℃, temperature rise rate is 0.6 ℃/min; 500-700 ℃, temperature rise rate is 2 ℃/min; 700 ℃ of constant temperature 2 hours.
(4) the temperature programming reaction finishes, and with the flow velocity of 60ml/min, the nitrogen of feeding 99.9% is chilled to room temperature.
(5) with the flow velocity of 100ml/min, aerating oxygen/nitrogen volume ratio is 1/99 passivating gas, passivation 2 hours.Be prepared into product A.
(6) on the microreactor of laboratory, carry out catalytic test.Fill 0.1 gram product A in reactor, temperature of reaction is 360 ℃, system pressure 0.5MPa, hydrogen flowing quantity is 20ml/min, and the sample size of thiophene is 0.02ml/min, and data were taken from stopping reaction after 1 hour, the amount that transforms thiophene with every gram catalyzer per minute is come the active size of comparison, with the C that generates 4In the compound alkene class and alkyl compound than value representation hydrogenation selectivity, evaluation result sees Table 1.
Embodiment 2
(1) takes by weighing with molybdic oxide identical among the embodiment 1 (MoO3) 1 gram, wear into less than 150 μ m powder.
(2) with the flow velocity of 200ml/min, feed 99.9% nitrogen, with the flow velocity of 200ml/min, feed 99% hydrogen, thorough mixing in mixing tank.
(3) adopt following temperature program(me) to react: room temperature-300 ℃, temperature rise rate is 10 ℃/min; 300-500 ℃, temperature rise rate is 0.6 ℃/min; 500-700 ℃, temperature rise rate is 2 ℃/min; 700 ℃ of constant temperature 2 hours.
(4) the temperature programming reaction finishes, and with the flow velocity of 60ml/min, the nitrogen of feeding 99.9% is chilled to room temperature.
(5) with the flow velocity of 100ml/min, aerating oxygen/nitrogen volume ratio is 1/99 passivating gas, passivation 2 hours.Be prepared into product B.
(6) on the microreactor of laboratory, carry out catalytic test.Fill 0.1 gram product B in reactor, temperature of reaction is 360 ℃, system pressure 1MPa, hydrogen flowing quantity is 20ml/min, and the sample size of thiophene is 0.02ml/min, and data were taken from stopping reaction after 1 hour, the amount that transforms thiophene with every gram catalyzer per minute is come the active size of comparison, with the C that generates 4In the compound alkene class and alkyl compound than value representation hydrogenation selectivity, evaluation result sees Table 1.
Embodiment 3
(1) takes by weighing with molybdic oxide identical among the embodiment 1 (MoO3) 1 gram, wear into 150 μ m powder.
(2) with the flow velocity of 80ml/min, feed 99.9% nitrogen, with the flow velocity of 320ml/min, feed 99% hydrogen, thorough mixing in mixing tank.
(3) adopt following temperature program(me) to react: room temperature-300 ℃, temperature rise rate is 10 ℃/min; 300-500 ℃, temperature rise rate is 0.6 ℃/min; 500-700 ℃, temperature rise rate is 2 ℃/min; 700 ℃ of constant temperature 2 hours.
(4) the temperature programming reaction finishes, and with the flow velocity of 60ml/min, the nitrogen of feeding 99.9% is chilled to room temperature.
(5) with the flow velocity of 100ml/min, aerating oxygen/nitrogen volume ratio is 1/99 passivating gas, passivation 2 hours.Be prepared into product C.
(6) on the microreactor of laboratory, carry out catalytic test.Fill 0.1 gram product C in reactor, temperature of reaction is 300 ℃, system pressure 0.2MPa, hydrogen flowing quantity is 20ml/min, and the sample size of thiophene is 0.02ml/min, and data were taken from stopping reaction after 1 hour, the amount that transforms thiophene with every gram catalyzer per minute is come the active size of comparison, with the C that generates 4In the compound alkene class and alkyl compound than value representation hydrogenation selectivity, evaluation result sees Table 1.
Embodiment 4
(1) takes by weighing with molybdic oxide identical among the embodiment 1 (MoO3) 1 gram, clay into power.
(2) with the flow velocity of 80ml/min, feed 99.9% nitrogen, with the flow velocity of 320ml/min, feed 99% hydrogen, thorough mixing in mixing tank.
(3) adopt following temperature program(me) to react: room temperature-300 ℃, temperature rise rate is 10 ℃/min; 300-500 ℃, temperature rise rate is 0.6 ℃/min; 500-700 ℃, temperature rise rate is 2 ℃/min; 700 ℃ of constant temperature 2 hours.
(4) the temperature programming reaction finishes, and with the flow velocity of 60ml/min, the nitrogen of feeding 99.9% is chilled to room temperature.
(5) with the flow velocity of 100ml/min, aerating oxygen/nitrogen volume ratio is 1/99 passivating gas, passivation 4 hours.Be prepared into product D.
(6) on the microreactor of laboratory, carry out catalytic test.Fill 0.1 gram product D in reactor, temperature of reaction is 280 ℃, system pressure 0.2MPa, hydrogen flowing quantity is 20ml/min, and the sample size of thiophene is 0.02ml/min, and data were taken from stopping reaction after 1 hour, the amount that transforms thiophene with every gram catalyzer per minute is come the active size of comparison, with the C that generates 4In the compound alkene class and alkyl compound than value representation hydrogenation selectivity, evaluation result sees Table 1.
Product A, B, C, D are the molybdenum nitride of crystalline phase homogeneous, all have identical characteristic peak and d value in the spectrogram of XRD analysis, and their main crystal phase structure feature d value is: 2.385,2.094,2.012,1.481,1.451,1.258,1.222,1.193.
Comparative example 1
This routine product is the moly-sulfide by the traditional method preparation.
(1) get with embodiment 1 in identical molybdic oxide (MoO3) 0.1 gram, put into crystal reaction tube.
(2) preparation contains the cyclohexane solution of 3% (weight) dithiocarbonic anhydride (CS2), as strong vulcanizing agent.
(3) with hydrogen as carrier gas, Bubbling method is vulcanized molybdic oxide by force, hydrogen flowing quantity is 20ml/min.
(4) strong curing temperature is 350 ℃, and the reaction times is 4h.Must compare product E.
(5) on the microreactor of laboratory, carry out catalytic test.Fill 0.1 gram product E in reactor, temperature of reaction is 360 ℃, system pressure 0.2MPa, hydrogen flowing quantity is 20ml/min, and the sample size of thiophene is 0.02ml/min, and data were taken from stopping reaction after 1 hour, the amount that transforms thiophene with every gram catalyzer per minute is come the active size of comparison, with the C that generates 4In the compound alkene class and alkyl compound than value representation hydrogenation selectivity, evaluation result sees Table 1.
Table 1 evaluating catalyst result
Catalyzer A B C D E
Desulphurizing activated (μ mol/min -1g -1) 223 247 122 103 194
Hydrogenation selectivity 4.23 2.35 4.1 2.07 2.51
As can be seen from Table 1, the molybdenum nitride of present method preparation has significantly desulphurizing activated as catalyzer, the desulphurizing activated reference catalyst E that is better than of A, B wherein, and the hydrogenation selectivity of A, C is better than reference catalyst E simultaneously.

Claims (5)

1. the preparation method of a molybdenum nitride is characterized in that comprising the steps:
(1) with molybdic oxide MoO 3Wear into Powdered less than 150 μ m, put into reactor;
(2) with nitrogen and hydrogen by nitrogen: the hydrogen volume ratio is 1: 1-4 mixes, and with MoO 3: gas mixture=1g: (200-500) flow velocity of ml/min feeds reactor;
(3) be that 5-20 ℃/min rises to 300 ℃ from room temperature with molybdic oxide with warm speed, with warm speed is that 0.5-1 ℃/min rises to 500 ℃ from 300 ℃, being 2-10 ℃/min with the temperature rise rate rises to 650-750 ℃ of nitrogenize temperature eventually from 500 ℃, carries out constant temperature 1-5 hour in the whole temperature of nitrogenize;
(4) after reaction finishes, (3) material is chilled to room temperature in inert atmosphere;
(5) under the room temperature, be that the 0.5-2% passivating gas carries out passivation to (4) material, get molybdenum nitride with the oxygen concentration.
2. the preparation method of a kind of molybdenum nitride as claimed in claim 1 is characterized in that described molybdic oxide is to produce 500 ℃ of roastings from ammonium molybdate.
3. the preparation method of a kind of molybdenum nitride as claimed in claim 1, it is characterized in that described as (2) step in the nitrogen oxygen level to be lower than 0.1%, hydrogen purity is greater than 99%.
4. the preparation method of a kind of molybdenum nitride as claimed in claim 1 is characterized in that the inert atmosphere in described (4) step is nitrogen, argon gas or helium, and wherein oxygen level will be lower than 0.1%.
5. the preparation method of a kind of molybdenum nitride as claimed in claim 1 is characterized in that the passivating gas in described (5) step is prepared with air and nitrogen or argon gas, helium, and gas flow is during passivation: MoO 3: passivating gas=1g: (50-150) ml/min.
CNB021300585A 2002-08-19 2002-08-19 Process for preparing molybdenum nitride and use thereof as hydrogenation and desulfurizing catalyst Expired - Fee Related CN1172858C (en)

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CN100391606C (en) * 2005-06-29 2008-06-04 中国科学院金属研究所 Process and apparatus for preparing metal nitride catalyst material
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
TWI496735B (en) * 2011-03-23 2015-08-21 Nat Univ Tsing Hua Method for preparing nanocrystalline nitride materials
CN103846425B (en) * 2012-12-03 2016-02-17 安徽港铭新材料科技有限公司 A kind of preparation method of molybdenum nitrogen alloy
CN107456988B (en) * 2017-08-15 2019-11-12 常州大学 A kind of molybdenum nitride hydrogenation deoxidation catalyst and its preparation method and application
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
CN109772422A (en) * 2019-03-22 2019-05-21 湘潭大学 A kind of preparation method and catalyst of hetero-junctions catalyst

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