CN101099934A - Aromatic saturated hydrogenation catalyst and its preparing process - Google Patents
Aromatic saturated hydrogenation catalyst and its preparing process Download PDFInfo
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- CN101099934A CN101099934A CNA2006100911594A CN200610091159A CN101099934A CN 101099934 A CN101099934 A CN 101099934A CN A2006100911594 A CNA2006100911594 A CN A2006100911594A CN 200610091159 A CN200610091159 A CN 200610091159A CN 101099934 A CN101099934 A CN 101099934A
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Abstract
The present invention relates to one kind of arene saturation hydrogenating metal nitride catalyst, which consists of gamma-Al2O3 carrier and supported bimetal Ni-Mo nitride. Of the active components, Ni accounts for 2.5-10 wt%, Mo accounts for 6-25 wt%, and Ni and Mo co-exist as Ni2Mo3N, Ni, Mo2N and small amount of oxides. The catalyst is prepared through the following steps: roasting gamma-Al2O3 powder at 500-550 deg.c for 4-5 hr; dissolving nickel acetate, ammonium molybdenum and HMT in the molar ratio of 14 to 3 to 17.2-27 in 13 % ammonia water solution to form immersion solution; soaking the gamma-Al2O3 powder in the solution via stirring for 2-4 hr, filtering, air drying, vacuum drying at 60-100 deg.c for 5-8 hr, tabletting and sieving; roasting first in Ar flow to 650-680 deg.c for 2 hr and then in H2 flow for 2 hr, and cooling to room temperature in H2; and final deactivating in N2 containing O2 in 1 % for 4 hr. It has high catalytic activity and other features.
Description
Technical field
The present invention relates to a kind of metal nitride catalyst agent that is applied to aromatic saturated hydrogenation, the two transition metal nitride Catalysts and its preparation methods of particularly a kind of support type.
Background technology
Transition metal nitride is the compounds that is generated in the transition metal lattice that incorporates of nitrogen-atoms calking, and it has unique physics and chemical property, especially receives much concern because of having the catalytic activity that is similar to noble metal.Recent research shows, the introducing of second metal can improve the catalytic activity of nitride greatly, especially Ni introduces the resulting bimetallic nitride in back, have outstanding hydrodenitrogeneration, hydrodesulfurization and aromatic saturated hydrogenation performance, in oil hydrogenation is handled, shown good application prospects.Usually, the bimetallic nitride catalyst all is that oxide precursor makes by the temperature programmed nitridation method, and this method needs the ammonia of high-speed, heating rate and higher preparation temperature etc. slowly, and its harsh preparation condition has limited this class Application of Catalyst.In the recent period, a kind of new method for preparing the bimetallic nitride catalyst is suggested, this method prepares nitride catalyst by the formed mixture of complex compound of roasting slaine and hexa (HMT) in inert gas atmosphere, this method has simply, characteristics such as energy-conservation and environmental protection might become the preparation method of the nitride catalyst that is suitable for commercial Application.
In the research both at home and abroad, be used for the nitride catalyst of hydrotreatment at present, the overwhelming majority adopts γ-Al
2O
3As carrier, the use of this carrier can make active component be disperseed preferably, simultaneously can better control table area and pore size distribution, and make this catalyst be more suitable in commercial Application.
Along with the more and more high requirement of needs and environmental protection aspect of heavy oil and residual oil deep processing, aromatic hydrogenation is saturated in the oil product becomes active demand.Oil hydrogenation commonly used is handled in the catalyst, traditional sulfide catalyst since thermodynamic limitation to be difficult to the aromatic hydrocarbons that reaches than the degree of depth saturated; And the noble metal catalyst with excellent hydrogenation performance, again because of cost an arm and a leg and easily effects limit such as poisoning its extensive use in industry.Developing a kind of novel common metal catalyst with outstanding aromatic hydrogenation performance is a very significant job.
Summary of the invention
The objective of the invention is to adopt equi-volume impregnating and complexing roasting method provide a kind of be applied to monocycle and double ring arene saturated hydrogenation show load type metal nitride catalyst of high catalytic activity and preparation method thereof.
Load type double-metal nitride catalyst provided by the invention, it is at industrial macropore γ-Al
2O
3Nickel-loaded molybdenum bimetallic nitride on the carrier, the weight percentage of its active component Ni is 2.5%～10%, the weight percentage of Mo is 6%～25%.Wherein Ni, Mo are mainly with Ni
2Mo
3N, Ni, Mo
2The form of N and the coexistence of small amounts thing exists.
The concrete preparation method of described load-type nickel molybdenum bimetallic nitride catalyst comprises the steps:
Under 500 ℃～550 ℃ to powder γ-Al
2O
3Carrier roasting 4h～5h takes by weighing γ-Al after the roasting by metering
2O
3Powder, nickel acetate, ammonium molybdate and HMT.Nickel acetate, ammonium molybdate and HM are dissolved into the maceration extract of clarification by equi-volume impregnating, carrier is joined in the maceration extract, stirring at room dipping 2h～4h, filter, fully dry, in 60 ℃～100 ℃ vacuum drying 5h～8h, compression molding sieves, directly intensification roasting in certain air-flow.
Contain nickel acetate, ammonium molybdate and HMT in the described maceration extract, three's mol ratio is 14: 3: 17.2 to 14: 3: 27.
The above-mentioned precursor detailed process of described direct intensification roasting is: in the Ar air-flow, rise to 650 ℃～680 ℃ with the speed of 10 ℃/min from room temperature, keep 2h, Ar gas air speed is 500h
-1～1500h
-1Switch H
2Air-flow continues to keep 2h, then at H
2In be cooled to room temperature, H
2Air speed is 500
-1～1500h
-1Containing 1%O at last
2N
2Middle passivation 4h.
Load-type nickel molybdenum bimetallic nitride catalyst provided by the invention has higher hydrogenation saturated activity to monocycle and double ring arene, and its catalytic performance is tested by following method:
Adopt fixed bed continuous-flow pressurized reactor, with the 50wt% n-dodecane, the mixed solution of 40wt% paraxylene and 10wt% naphthalene is done reaction raw materials.Experiment condition is as follows: measure the 1ml catalyst, be diluted in the flat-temperature zone that 5ml places reactor with quartz sand; In temperature is 400 ℃, and system pressure is 0.3Mpa, H
2Flow velocity is prereduction 3h under the condition of 20ml/min; In temperature is 250 ℃, H
2Flow velocity is 100ml/min, and system pressure is 3.0MPa, and the charging air speed is 5h
-1Condition under carry out activity rating.After the stable reaction, get the 5th, the mix products of 6h carries out gas chromatographic analysis, activity of such catalysts is in the conversion ratio of paraxylene in the raw material and naphthalene.
Catalyst provided by the invention is used for the reaction of monocycle and double ring arene saturated hydrogenation and has advantages of high catalytic activity, and characteristics such as simple, energy-conservation and environmental protection that its preparation method has have bigger commercial Application meaning.
The specific embodiment
Embodiment 1
550 ℃ of following powders calcined γ-Al
2O
3Carrier 4h.Take by weighing the γ-Al after the 6.0g roasting
2O
3Dust carrier is 6.5wt% by the weight percentage of Ni in the catalyst, and the weight percentage of Mo is 15.8wt%, nickel acetate (Ni (CH
3COO)
24H
2O), ammonium molybdate ((NH
4)
6Mo
7O
246H
2O) and the molar ratio of HMT be 14: 3: 27.Take by weighing nickel acetate, ammonium molybdate and HMT, nickel acetate, ammonium molybdate and HM are dissolved in are mixed with the clarification maceration extract in 13% ammonia spirit successively, alleged γ-Al
2O
3Carrier joins in the maceration extract, and stirring at room dipping 3h filters, and fully dries, successively at 60 ℃ of following and 120 ℃ of each 3h of following vacuum drying.With this precursor compression molding, fragmentation is screened to 20 orders～40 orders.
Measuring the above-mentioned precursor of 2ml, place quartz tube reactor, is in the 40ml/min Ar air-flow at flow velocity earlier, rises to 650 ℃ with the speed of 10 ℃/min from room temperature, keeps 2h; Switching flow velocity is 40ml/min H
2Air-flow continues to keep 2h, then at H
2In be cooled to room temperature; Containing 1%O at last
2N
2Middle passivation 4h.
Investigated the aromatic saturated hydrogenation performance of prepared catalyst, reaction condition as mentioned above, experimental result is as shown in table 1.
Embodiment 2
Change the molar ratio of nickel acetate, ammonium molybdate and HMT among the embodiment 1 into 14: 3: 22.8, other are all with embodiment 1.Experimental result sees Table 1.
Embodiment 3
Change the molar ratio of nickel acetate, ammonium molybdate and HMT among the embodiment 1 into 14: 3: 20, other are all with embodiment 1.Experimental result sees Table 1.
Embodiment 4
Change precursor final calcination temperature among the embodiment 1 into 680 ℃, other are all with embodiment 1.Experimental result sees Table 2.
Embodiment 5
Change precursor final calcination temperature among the embodiment 2 into 680 ℃, other are all with embodiment 2.Experimental result sees Table 2.
Embodiment 6
Change precursor final calcination temperature among the embodiment 3 into 680 ℃, other are all with embodiment 3.Experimental result sees Table 2.
Embodiment 7
Change the molar ratio of nickel acetate, ammonium molybdate and HMT among the embodiment 6 into 14: 3: 17.2, other are all with embodiment 6.Experimental result sees Table 2.
Embodiment 8
Change the weight percentage of Ni in the catalyst among the embodiment 6 into 2.5wt%, the weight percentage of Mo is 6.2wt%, and other are all with embodiment 6.Experimental result sees Table 3.
Embodiment 9
Change the weight percentage of Ni in the catalyst among the embodiment 6 into 4.8wt%, the weight percentage of Mo is 12.4wt%, and other are all with embodiment 6.Experimental result sees Table 3.
Embodiment 10
Change the weight percentage of Ni in the catalyst among the embodiment 6 into 5.6wt%, the weight percentage of Mo is 13.8wt%, and other are all with embodiment 6.Experimental result sees Table 3.
Different HMT content gained catalyst activities comparisons in precursor when table 1 preparation temperature is 650 ℃
| Embodiment | Three kinds of component mol ratios in the catalyst precarsor * | Paraxylene conversion ratio (%) | Naphthalene conversion ratio (%) | Naphthane yield (%) |
| 1 2 3 | 14∶3∶27 14∶3∶22.8 14∶3∶20 | 7.35 14.8 33.7 | 100.0 100.0 100.0 | 54.4 32.8 32.8 |
*Three kinds of components of catalyst precarsor are nickel acetate, ammonium molybdate and HMT.
Different HMT content gained catalyst activities comparisons in precursor when table 2 preparation temperature is 680 ℃
| Embodiment | Three kinds of component mol ratios in the catalyst precarsor * | Paraxylene conversion ratio (%) | Naphthalene conversion ratio (%) | Naphthane yield (%) |
| 4 5 6 | 14∶3∶27 14∶3∶22.8 14∶3∶20 | 18.3 99.3 98.6 | 100.0 100.0 100.0 | 33.5 0.0 0.0 |
| 7 | 14∶3∶17.2 | 73.5 | 100.0 | 0.0 |
*Three kinds of components of catalyst precarsor are nickel acetate, ammonium molybdate and HMT.
Table 3 different loads amount activity of such catalysts relatively
| Embodiment | Ni in the catalyst, Mo quality percentage composition (wt%) | Paraxylene conversion ratio (%) | Naphthalene conversion ratio (%) | Naphthane yield (%) |
| 8 9 10 6 | Ni 2.5，Mo 6.2 Ni 4.8，Mo 12.4 Ni 5.6，Mo 13.8 Ni 6.5，Mo 15.8 | 11.5 82.0 99.4 98.6 | 82.3 100.0 100.0 100.0 | 41.4 0.0 0.0 0.0 |
Claims (2)
1. aromatic saturated hydrogenation catalyst, it is characterized in that: it is at industrial macropore γ-Al
2O
3Nickel-loaded molybdenum bimetallic nitride on the carrier, the weight percentage of its active component Ni is 2.5%～10% of a gross weight, and the weight percentage of Mo is 6%～25% of a gross weight, and wherein Ni, Mo are with Ni
2Mo
3N, Ni, Mo
2The form of N and the coexistence of small amounts thing exists.
2. the preparation method of aromatic saturated hydrogenation catalyst according to claim 1 is characterized in that: comprise the steps:
Under 500 ℃～550 ℃ to powder γ-Al
2O
3Carrier roasting 4h～5h; With nickel acetate, ammonium molybdate and HMT is to be dissolved in 14: 3: 17.2～14: 3: 27 to be mixed with the clarification maceration extract in 13% ammonia spirit in molar ratio; With carrier γ-Al
2O
3Powder joins in the maceration extract in the ratio of claim 1, stirring at room dipping 2h～4h, filter, fully dry, in 60 ℃～100 ℃ vacuum drying 5h～8h, compression molding, sieve, directly intensification roasting in the Ar air-flow, the Ar air-flow rises to 650 ℃～680 ℃ with the speed of 10 ℃/min from room temperature, keep 2h, Ar gas air speed is 500h
-1～1500h
-1Switch H
2Air-flow continues to keep 2h, then at H
2In be cooled to room temperature, H
2Air speed is 500h
-1～1500h
-1Containing 1%O at last
2N
2Middle passivation 4h.
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|---|---|---|---|
| CNB2006100911594A CN100548483C (en) | 2006-07-04 | 2006-07-04 | A kind of application of aromatic saturated hydrogenation catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100911594A CN100548483C (en) | 2006-07-04 | 2006-07-04 | A kind of application of aromatic saturated hydrogenation catalyst |
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| CN100548483C CN100548483C (en) | 2009-10-14 |
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| CN101837294A (en) * | 2010-03-03 | 2010-09-22 | 巴州东辰工贸有限公司 | Preparation method for solid acid catalyst r-AI203 |
| CN103785433A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrotreatment catalyst and preparation method thereof |
| CN103785402A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of hydrotreatment catalyst with long service life |
| CN103785432A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Distillate oil hydrogenation catalyst and preparation method thereof |
| CN103785446A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | High-activity hydrocracking catalyst and preparation method thereof |
| CN103785443A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| RU2653494C1 (en) * | 2017-12-22 | 2018-05-10 | Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук (ИК СО РАН) | Catalyst of protective layer |
| CN108404952A (en) * | 2017-02-10 | 2018-08-17 | 中国石油化工股份有限公司 | The method of ordered structure desulphurization catalyst and preparation method thereof and sulfur-bearing hydrocarbon desulfurization |
| CN109092347A (en) * | 2017-06-21 | 2018-12-28 | 神华集团有限责任公司 | Hydrogenation catalyst and its preparation method and application |
| CN109692699A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | Alloy with high activity type aromatic hydrocarbon hydrogenation catalyst and preparation method thereof |
| CN112295581A (en) * | 2019-07-24 | 2021-02-02 | 中国科学院宁波材料技术与工程研究所 | Electrocatalyst material and application thereof |
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| CN103785432B (en) * | 2012-11-01 | 2016-05-18 | 中国石油化工股份有限公司 | A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof |
| CN103785432A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Distillate oil hydrogenation catalyst and preparation method thereof |
| CN103785446A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | High-activity hydrocracking catalyst and preparation method thereof |
| CN103785443A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN103785402B (en) * | 2012-11-01 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of preparation method of long-life hydrotreating catalyst |
| CN103785446B (en) * | 2012-11-01 | 2016-02-03 | 中国石油化工股份有限公司 | A kind of high-activity hydrocracking catalyst and preparation method thereof |
| CN103785443B (en) * | 2012-11-01 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation method and application |
| CN103785433A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Hydrotreatment catalyst and preparation method thereof |
| CN103785402A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of hydrotreatment catalyst with long service life |
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| CN109692699A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | Alloy with high activity type aromatic hydrocarbon hydrogenation catalyst and preparation method thereof |
| CN109692699B (en) * | 2017-10-20 | 2022-04-01 | 中国石油化工股份有限公司 | High-activity alloy type aromatic hydrogenation catalyst and preparation method thereof |
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| RU2653494C1 (en) * | 2017-12-22 | 2018-05-10 | Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук (ИК СО РАН) | Catalyst of protective layer |
| CN112295581A (en) * | 2019-07-24 | 2021-02-02 | 中国科学院宁波材料技术与工程研究所 | Electrocatalyst material and application thereof |
| CN112295581B (en) * | 2019-07-24 | 2022-10-14 | 中国科学院宁波材料技术与工程研究所 | Electrocatalyst material and application thereof |
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