CN105195164A - Catalyst as well as preparation method and application thereof - Google Patents
Catalyst as well as preparation method and application thereof Download PDFInfo
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- CN105195164A CN105195164A CN201510751230.6A CN201510751230A CN105195164A CN 105195164 A CN105195164 A CN 105195164A CN 201510751230 A CN201510751230 A CN 201510751230A CN 105195164 A CN105195164 A CN 105195164A
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Abstract
The invention discloses a catalyst as well as a preparation method and application thereof, and aims at providing the catalyst which has a simple preparation process, a wide raw material source, low cost, and relatively high effect of catalyzing heavy oil to be subjected to hydrogenation desulfurization, and also relatively high hydrogenation saturation activity on polycyclic aromatic hydrocarbon in the heavy oil. The catalyst is technically characterized in that gamma-Al2O3 is used as a carrier; by taking the mass of gamma-Al2O3 as the standard, the catalyst comprises the following components by weight percent: 4-16% of nickel and 2-12% of molybdenum. The preparation method of the catalyst sequentially comprises the following steps: (1) carrying out calcining pre-treatment on the carrier gamma-Al2O3; (2) preparing an impregnation solution containing Ni; adding the carrier gamma-Al2O3 and impregnating; drying and roasting to obtain an oxidized-state Ni-gamma-Al2O3 ball; (3) preparing an impregnation solution containing Mo, and adding the oxidized-state Ni-gamma-Al2O3 ball to be impregnated; drying and roasting to obtain an oxidized-state Ni-Mo/gamma-Al2O3 catalyst; and (4) putting the oxidized-state Ni-Mo/gamma-Al2O3 catalyst into an atmosphere of H2 gas and activating to obtain an activated-state Ni-Mo/gamma-Al2O3 catalyst. The catalyst as well as the preparation method and the application thereof belong to the technical field of treatment of the heavy oil.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof and with application, especially relate to a kind of high-sulfur, high aromatic hydrocarbons heavy oil hydrogenating treatment catalyst and Synthesis and applications thereof.
Background technology
Heavy oil is the residue mink cell focus after crude oil extracts gasoline, diesel oil.Heavy oil generally has that viscosity is high, molecular weight is large, sulfur-bearing, containing the feature such as colloid and asphalitine.Along with Gong the utilization of conventional oil reduces day by day, the particularly rising of crude oil price, the ratio shared in world oil total supply of the output of heavy oil, also in continuous increase, is just becoming the valuable source of the mankind from now on.Develop actively is to the deep processing of heavy oil, and particularly heavy-oil hydrogenation technology, is not only conducive to the utilization rate improving crude oil, alleviates the nervous trend of energy supply, can also reduce environmental pollution simultaneously, realize the efficient clean utilization of the energy.
Sulfur content in oil product evaluates the important parameter of oil quality.Special in heavy oil, general containing a large amount of aromatic hydrocarbons in heavy oil, there is larger value.But due to sulfur in heavy oil content this feature high, seriously hinder the refining further of this oil product, reduce its economic worth.Originally, heavy oil is generally in harmonious proportion by simple or simply directly sold as raw material using reset condition, and price is very low, the sulfide contained in oil product, not only can affect the storage safe of oil product, enter environment in a variety of manners in use, produce atmosphere pollution, cause great harm.
As far back as 2005, clear stipulaties was just made to condensed-nuclei aromatics content in rubber filling oil by European Union: benzene content and 8 kinds of non-compliant rubber filling oils of condensed-nuclei aromatics content can not throw in EU market, can not be used for European Union's tire and associated components production.In the past, the production of this product is monopolized by external producer always, and import price is expensive, and on January 1st, 2010 starts, and the rubber filling oil product not meeting European Union 2005/69/EC standard can not throw in EU market.The execution of this standard proposes severe challenge to Chinese rubber manufacturing enterprise, and the environment-friendly type aromatic hydrocarbon rubber extender oil that Development and Production has independent intellectual property right becomes the task of top priority.If high aromatic hydrocarbons heavy oil feature can be utilized preferably, saturated by catalytic hydrogenation, produce environment-friendly rubber extend oil, so will produce huge economic worth and market prospects, and meet these themes of the times of Green Chemistry.Realize this goal, just will study and how deep desulfuration is carried out to this kind of oil product and height hydrotreated lube base oil is carried out to the aromatic hydrocarbons contained by it.
Sulfur-containing organic compound content in heavy oil is high, and molecular volume is comparatively large, and remove on a catalyst mainly through hydrofining technology, traditional Hydrobon catalyst is load type Co-Mo, Ni-Mo or Ni-W sulfide.Six during the last ten years, although sulfide catalyst is through updating, its activity still cannot meet the requirement of the environmental regulation of increasingly stringent.Therefore, people, while updating sulfide catalyst, are also constantly seeking new deep desulfurization catalyst.Meanwhile, the sulfur-bearing feature of heavy oil requires that catalyst has macroporous structure, and in addition, in heavy-oil hydrogenation process, contaminated catalysts is serious, is difficult to regeneration.Therefore require to reduce catalyst cost, select low-cost raw material and simplify preparation technology.
CN102989491A reports a kind of heavy-oil hydrogenation guard catalyst and Synthesis and applications thereof.The preparation of catalyst is with Al
2o
3or containing SiO
2al
2o
3for carrier, carrier pore volume scope is at 0.98-1.15ml/g, and specific surface scope is at 340-380m
2/ g, pore size distribution is as follows: the pore volume of bore dia < 5nm accounts for the 10%-15% of total pore volume, and the pore volume of bore dia 5-15nm accounts for the 50%-55% of total pore volume, and the pore volume of bore dia > 15nm accounts for the 25%-40% of total pore volume; Nickel-loaded molybdenum sulphur, nickel tungsten sulphur, molybdenum sulfide, tungsten sulfide, cobalt molybdenum sulphur, cobalt tungsten sulphur, nickel cobalt molybdenum sulphur, nickel cobalt tungsten sulphur or the same Ni of cobalt molybdenum nickel tungsten
2p carries out the composite catalyst combined; Catalyst has aperture and is suitable for, melts the feature that metal ability is high, active component yardstick is little, good dispersion degree, catalyst activity are high, and is applicable to heavy-oil hydrogenation protection.
CN102397790A reports a kind of heavy oil hydrogenating treatment catalyst, preparation and application thereof.This catalyst with molybdenum, cobalt and nickel for active metal component.Be 5-20wt% containing molybdenum amount, the content sum of cobalt and nickel is 1-6wt%, and wherein, the atomic ratio of cobalt and nickel is 2-4, and this catalyst, to have heavy oil hydrodesulfurization simultaneously active, also has the performances such as de-carbon residue, demetalization.
CN101249440 reports a kind of for aromatic hydrocarbons or the hydrogenation adsorption desulfurize catalyst containing aroamtic hydrocarbon raw material.Catalyst consists of: reduced state nickel is 5-70wt%, and zinc oxide is 30-95wt%, and aluminium oxide is 0-50wt%.Adopt fixed bed as reactor, range of reaction temperature 200-400 DEG C, reaction pressure at normal pressure-3MPa, hydrogen with raw material ratio be 400-1500, air speed is 1-10h
-1carry out hydrogenation adsorption desulfurize.The catalyst of this invention is applicable to the hydrodesulfurization reaction containing aroamtic hydrocarbon raw material, and aromatic hydrocarbons loss is little.
Dalai, A report a kind of NiMo/Al containing B and P
2o
3catalyst.Catalyst forms: ni content 1.8-3.1wt%, measures 10.6-13.2wt% containing Mo, measures 0.5-1.7wt%, P content 2.7wt% containing B.B, P add the formation facilitating superpower acidity center on catalyst, significantly improve HDN activity.This NiMo/Al
2o
3catalyst can be applicable to hydrodesulfurization and the hydrodenitrogeneration of the heavy gas oil deriving from Athabasca coal tar.
EP.1417282A2 reports a kind of aromatic hydrogenation treatment process.The active component of used catalyst is Pt and Pd, is carried on SiO
2-Al
2o
3on complex carrier, wherein Al
2o
3accounting for carrier quality percentage is 55%.The gas containing hydrocarbon raw material that can be used for containing arene content being 10% carries out aromatic hydrogenation process.
USA.3627672 reports a kind of catalyst of catalyzing aromatic hydrocarbon hydrogenation, and contained component is (a) Al
2o
3(>=20wt%), (b) Ni, Co (NiO or CoO, 1-10wt%), (c) Mo (MoO
3, 5-25wt%) and (d) Ti or Zr (TiO
2or ZrO
2, 5-20wt%), (e) P
2o
3(3-15wt%), catalyst particle density is greater than 1.4g/cc.Organic clay also containing 0.5-20% in catalyst, not containing noble metal and silicon components.The more traditional noble metal catalyst of this catalyst has sulphur, nitrogen adaptability widely, can be used for the aromatic hydrogenation reaction that arene content is 5-95% (particularly 20-80%), sulfur content is greater than the raw material of 200ppm.
US6383975 reports the catalyst preparation process of a kind of hydrodesulfurization for moderate and heavy distillate, hydrodenitrogeneration and HDM.This catalyst adopts a kind of alumina substrate, makes with the oxide of periodic table of elements IVB group element is mixed mutually.The preparation of catalyst carrier adopts coprecipitation or infusion process, and infusion process adopts the organic solution containing aluminium and Ti as maceration extract, through impregnation drying, roasting, obtained catalyst.
Prior art mostly adopts TiO
2, Al
2o
3, SiO
2or be carrier containing the composite oxides such as B, P, with Co, Mo, Ni or noble metal for active metal component, adopt presulfurization process, the hydrodesulfurization of preparation sulphided state, hydrodenitrogeneration, aromatic hydrocarbon hydrogenation catalyst.These catalyst of reporting can be used for hydrodesulfurization, hydrodenitrogeneration or aromatic hydrogenation, but be difficult to meet be directed to high-sulfur, high aroamtic hydrocarbon raw material oil product while hydrodesulfurization and aromatic saturation requirement.The patent such as patent CN1100004, CN1210759 describes Ni-Mo and Co-Mo hydrodesulfurization respectively and refines, and tool aromatic saturation optionally catalyst, but its reaction temperature and pressure higher, and selective more weak to aromatic saturation.Patent CN102423713 describes a kind of Hydrobon catalyst, can keep good hydrodesulfurization under lower pressure and temperature, but urges aromatic saturation selective still more weak.
Summary of the invention
For above-mentioned deficiency, the object of the present invention is to provide a kind of preparation technology simple, raw material sources are extensive, cheap, there is higher catalytic heavy hydrodesulfurization activity, the condensed-nuclei aromatics in heavy oil is had to the catalyst of higher hydrotreated lube base oil activity simultaneously.
Above-mentioned technical problem to be solved by this invention, is achieved by the following technical programs:
Catalyst provided by the invention is with γ-Al
2o
3for carrier, by weight, with γ-Al
2o
3quality is benchmark, nickeliferous 4 ~ 16%, and containing molybdenum 2 ~ 12%.
As a kind of preferred version, described catalyst by weight, with γ-Al
2o
3quality is benchmark, nickeliferous 6 ~ 12%, and containing molybdenum 4 ~ 8%.
For preparing above-mentioned catalyst, another technical scheme of the present invention is to provide the preparation method of this catalyst, and the method comprises the following steps successively:
(1) by carrier γ-Al
2o
3through calcining pretreatment;
(2) configuration is containing the maceration extract of Ni, adds carrier γ-Al
2o
3dipping, obtains oxidation state Ni-γ-Al through super-dry, roasting
2o
3ball;
(3) configuration is containing the maceration extract of Mo, adds oxidation state Ni-γ-Al
2o
3ball floods, and obtains oxidation state Ni-Mo/ γ-Al through super-dry, roasting
2o
3catalyst;
(4) by oxidation state Ni-Mo/ γ-Al
2o
3catalyst need be placed in H
2activate in the atmosphere of gas, obtain activated state Ni-Mo/ γ-Al
2o
3catalyst.
As a kind of preferred version, the preparation method of described catalyst, the calcining pretreatment temperature described in step (1) is 300 ~ 450 DEG C, carrier γ-Al
2o
3saturated water absorption be 0.5 ~ 0.9ml/g; Baking temperature described in step (2) is 100 ~ 120 DEG C, and drying time is 2 ~ 4h, and sintering temperature is 450 ~ 550 DEG C, and roasting time is 4 ~ 8h; Baking temperature in step (3) is 100 ~ 120 DEG C, and drying time is 2 ~ 4h, and sintering temperature is 450 ~ 550 DEG C, and roasting time is 4 ~ 8h; Step (4) activation condition is with the programming rate of 5 ~ 10 DEG C/min, is raised to 400 ~ 450 DEG C from room temperature, at the H of 10 ~ 30ml/min
2in flowing environment, reduction 4 ~ 7h, at the N of flowing after reduction treatment terminates
2naturally cool to room temperature in environment, and use N
2protection, N
2flow velocity is 5 ~ 15ml/min.
The present invention also has a technical scheme to be to provide this catalyst at heavy-oil hydrogenation deep desulfuration or/and purposes in aromatic saturation.
In order to better use this catalyst, last technical scheme of the present invention is to provide the using method of this catalyst, the method is under heavy-oil hydrogenation processing reaction condition, by heavy oil feedstock oil in dirty or upper reaches mode at fixed bed gas-solid catalysis device and catalyst exposure.
As a kind of preferred version, the using method of above-mentioned catalyst, described heavy oil is high-sulfur, high aromatic hydrocarbons heavy oil, 3.3% >=sulfur content >=0.5%, 90% >=arene content >=60%.
As a kind of preferred version, described heavy-oil hydrogenation processing reaction condition is: reaction temperature 250 ~ 400 DEG C, hydrogen dividing potential drop 8 ~ 22MPa, and hydrogen/oil ratio is 1000 ~ 2000, and during liquid, volume space velocity LHSV is 0.1 ~ 1h
-1.
Compared with prior art, technical scheme provided by the invention has following technological merit:
1, the catalyst prepared by technical scheme provided by the invention does not need through presulfurization, but the metallic state catalyst directly prepared through hydrogen reducing pretreatment, nickel, molybdenum high degree of dispersion on carrier.
2, the sulfide type catalyst that the catalyst prepared by technical scheme provided by the invention is more traditional, has better catalytic heavy hydrodesulfurization activity, has higher hydrotreated lube base oil active to the condensed-nuclei aromatics in heavy oil simultaneously.
3, the preparation technology of catalyst provided by the invention is simple, and raw material is easy to get and cheap, and adopting saturated dipping method, take deionized water as raw material, achieves the efficient clean utilization of raw material.
4, the catalyst prepared by technical scheme provided by the invention is used for deep hydrodesulfurizationof to high-sulfur heavy oil, can realize turning waste into wealth, and has important economic worth and application prospect widely.
Detailed description of the invention
Explain the present invention further below in conjunction with specific embodiment, but embodiment does not limit in any form to the present invention.
Wherein, active component Ni and the auxiliary agent Mo constituent content of catalyst are recorded by x ray fluorescence spectrometry, measured the valence state of element, judge the existence form of metallic element in catalyst according to result by X-ray energy spectrum; Sulfur content in oil product is recorded by purple light fluorescence Fix sulfur method; Aromatic saturation rate is recorded by carbon type analysis method.
Embodiment 1
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 3.11g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 16h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 4h through 100 DEG C, calcines 8h after drying in 450 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 14ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.7g/ml), saturated dipping Mo maceration extract, dip time is 14h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 3h through 110 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 5 DEG C/min, is raised to 400 DEG C from room temperature, at the H of 20ml/min
2in flowing environment, reduction 6h, reduction terminates at N
2naturally cold in atmosphere, obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst A).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 4%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 1:1.
With sulfur content for 1.2%, arene content be 80% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) LHSV0.35h
-1, hydrogen/oil (v/v) 1300, hydrogen dividing potential drop 10MPa.Product test data list in table 1.
Embodiment 2
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 6.23g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 16h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb wet bulb dries 4h through 100 DEG C, calcines 8h after drying in 450 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 15ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.72g/ml), saturated dipping Mo maceration extract, dip time is 14h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 3h through 110 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 5 DEG C/min, is raised to 400 DEG C from room temperature, at the H of 20ml/min
2in flowing environment, reduction 6h, reduction terminates at N
2naturally cold in atmosphere, obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst B).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 8%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 2.2%, arene content be 90% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) LHSV0.35h
-1, hydrogen/oil (v/v) 1300, hydrogen dividing potential drop 10MPa.Product test data list in table 1.
Comparative example 1
Based on embodiment 2, the Ni/Mo atomic ratio adopted in this routine Kaolinite Preparation of Catalyst process is 1:2, obtains this routine reference agent 1.The reaction condition of heavy-oil hydrogenation is identical with embodiment 2, and the sulfur content of heavy oil feedstock is 2.0%, and arene content is 82%.Product test data list in table 1.
Comparative example 2
Based on embodiment 2, the Ni/Mo atomic ratio adopted in this routine Kaolinite Preparation of Catalyst process is 1:4, obtains this routine reference agent 2.The reaction condition of heavy-oil hydrogenation is identical with embodiment 2, and the sulfur content of heavy oil feedstock is 2.0%, and arene content is 82%.Product test data list in table 1.
Embodiment 3
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 4.67g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 16h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 4h through 100 DEG C, calcines 8h after drying in 450 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 0.95g
4)
6mo
7o
244H
2o is dissolved in 14.5ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.71g/ml), saturated dipping Mo maceration extract, dip time is 14h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 3h through 110 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 5 DEG C/min, is raised to 400 DEG C from room temperature, at the H of 20ml/min
2in flowing environment, reduction 6h, reduction terminates at N
2naturally cold in atmosphere, obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst C).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 6%, and auxiliary agent Mo mass percentage is 4%, Ni/Mo atomic ratio is 3:1.
With sulfur content for 2.2%, arene content be 60% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) LHSV0.35h
-1, hydrogen/oil (v/v) 1300, hydrogen dividing potential drop 10MPa.Product test data list in table 1.
Embodiment 4
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 7.79g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 16h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 4h through 100 DEG C, calcines 8h after drying in 450 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.18g
4)
6mo
7o
244H
2o is dissolved in 14ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.7g/ml), saturated dipping Mo maceration extract, dip time is 14h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 3h through 110 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 5 DEG C/min, is raised to 400 DEG C from room temperature, at the H of 20ml/min
2in flowing environment, reduction 6h, reduction terminates at N
2naturally cold in atmosphere, obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst D).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 10%, and auxiliary agent Mo mass percentage is 5%, Ni/Mo atomic ratio is 4:1.
With sulfur content for 3.3%, arene content be 78% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) LHSV0.35h
-1, hydrogen/oil (v/v) 1300, hydrogen dividing potential drop 10MPa.Product test data list in table 1.
Embodiment 5
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 9.34g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 16h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 4h through 100 DEG C, calcines 8h after drying in 450 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.34g
4)
6mo
7o
244H
2o is dissolved in 15ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.75g/ml), saturated dipping Mo maceration extract, dip time is 14h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 3h through 110 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 5 DEG C/min, is raised to 400 DEG C from room temperature, at the H of 20ml/min
2in flowing environment, reduction 6h, reduction terminates at N
2naturally cold in atmosphere, obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst E).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 12%, and auxiliary agent Mo mass percentage is 5%, Ni/Mo atomic ratio is 5:1.
With sulfur content for 2.2%, arene content be 87% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) LHSV0.35h
-1, hydrogen/oil (v/v) 1300, hydrogen dividing potential drop 10MPa.Product test data list in table 1.
Embodiment 6
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 12.46g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 16h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 4h through 100 DEG C, calcines 8h after drying in 450 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.26g
4)
6mo
7o
244H
2o is dissolved in 14.7ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.73g/ml), saturated dipping Mo maceration extract, dip time is 14h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 3h through 110 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 5 DEG C/min, is raised to 400 DEG C from room temperature, at the H of 20ml/min
2in flowing environment, reduction 6h, reduction terminates at N
2naturally cold in atmosphere, obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst F).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 16%, and auxiliary agent Mo mass percentage is 5%, Ni/Mo atomic ratio is 6:1.
With sulfur content for 1.5%, arene content be 82% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) LHSV0.35h
-1, hydrogen/oil (v/v) 1300, hydrogen dividing potential drop 10MPa.Product test data list in table 1.
Embodiment 7
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 6.23g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 16h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 4h through 100 DEG C, calcines 8h after drying in 450 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 14ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.7g/ml), saturated dipping Mo maceration extract, dip time is 14h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 3h through 110 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 5 DEG C/min, is raised to 400 DEG C from room temperature, at the H of 20ml/min
2in flowing environment, reduction 6h, reduction terminates at N
2naturally cold in atmosphere, obtain activated state Ni-Mo/ γ-Al
2o
3catalyst (catalyst G).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 8%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 1.5%, arene content be 82% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) LHSV0.4h
-1, hydrogen/oil (v/v) 1200, hydrogen dividing potential drop 15MPa.Product test data list in table 2.
Embodiment 8
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 6.23g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 14h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 2h through 120 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 15ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.72g/ml), saturated dipping Mo maceration extract, dip time is 10h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 2h through 120 DEG C, calcines 4h after drying in 550 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 8 DEG C/min, is raised to 420 DEG C from room temperature, at the H of 10ml/min
2in flowing environment, reduction 7h, reduction terminates at N
2naturally cold in atmosphere, obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst H).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 8%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 1.2%, arene content be 80% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) LHSV0.3h
-1, hydrogen/oil (v/v) 1500, hydrogen dividing potential drop 12MPa.Product test data list in table 2.
Embodiment 9
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 6.23g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 12h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 3h through 110 DEG C, calcines 4h after drying in 550 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 14.5ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.75g/ml), saturated dipping Mo maceration extract, dip time is 8h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 2h through 120 DEG C, calcines 4h after drying in 550 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 5 DEG C/min, is raised to 450 DEG C from room temperature, at the H of 15ml/min
2in flowing environment, reduction 5h, reduction terminates at N
2naturally cold in atmosphere, obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst I).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 8%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 2.2%, arene content be 75% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 280 DEG C, liquid hourly space velocity (LHSV) LHSV0.2h
-1, hydrogen/oil (v/v) 1200, hydrogen dividing potential drop 15MPa.Product test data list in table 2.
Enforcement grins 10
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 6.23g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 12h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 2h through 120 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 15ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.77g/ml), saturated dipping Mo maceration extract, dip time is 10h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 2h through 120 DEG C, calcines 4h after drying in 550 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 10 DEG C/min, is raised to 430 DEG C from room temperature, at the H of 20ml/min
2in flowing environment, reduction 6h, reduction terminates at N
2naturally cold in atmosphere, obtained activated state Ni-Mo/ γ-Al
2o
3catalyst (catalyst J).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 8%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 2.2%, arene content be 90% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) LHSV0.5h
-1, hydrogen/oil (v/v) 1500, hydrogen dividing potential drop 10MPa.Product test data list in table 2.
Embodiment 11
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 6.23g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 10h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 3h through 120 DEG C, calcines 4h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 14.1ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.71g/ml), saturated dipping Ni maceration extract, dip time is 15h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 3h through 110 DEG C, calcines 4h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst precarsor, with the programming rate of 5 DEG C/min, is raised to 450 DEG C from room temperature, at the H of 25ml/min
2in flowing environment, reduction 5h, reduction terminates at N
2naturally cold in atmosphere, obtain activated state Ni-Mo/ γ-Al
2o
3catalyst (catalyst K).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 8%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 0.5%, arene content be 85% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 320 DEG C, liquid hourly space velocity (LHSV) LHSV0.25h
-1, hydrogen/oil (v/v) 1700, hydrogen dividing potential drop 15MPa.Product test data list in table 2.
Embodiment 12
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 6.23g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 16h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 4h through 110 DEG C, calcines 4h after drying in 550 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 14.5ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.75g/ml), saturated dipping Mo maceration extract, dip time is 16h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 2h through 120 DEG C, calcines 4h after drying in 550 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 10 DEG C/min, is raised to 450 DEG C from room temperature, at the H of 30ml/min
2in flowing environment, reduction 7h, reduction terminates at N
2naturally cold in atmosphere, obtain activated state Ni-Mo/ γ-Al
2o
3catalyst (catalyst L).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 8%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 0.5%, arene content be 60% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 330 DEG C, liquid hourly space velocity (LHSV) LHSV0.5h
-1, hydrogen/oil (v/v) 1800, hydrogen dividing potential drop 18MPa.Product test data list in table 2.
Embodiment 13
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 6.23g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 12h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 4h through 100 DEG C, calcines 5h after drying in 530 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 14.3ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.76g/ml), saturated dipping Mo maceration extract, dip time is 12h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 3h through 110 DEG C, calcines 8h after drying in 450 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 10 DEG C/min, is raised to 400 DEG C from room temperature, at the H of 10ml/min
2in flowing environment, reduction 5h, reduction terminates at N
2naturally cold in atmosphere, obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst M).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 8%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 1.5%, arene content be 90% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 280 DEG C, liquid hourly space velocity (LHSV) LHSV0.2h
-1, hydrogen/oil (v/v) 1200, hydrogen dividing potential drop 10MPa.Product test data list in table 2.
Embodiment 14
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 6.23g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 15h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 3h through 105 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 14.1ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.73g/ml), saturated dipping Mo maceration extract, dip time is 10h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 2h through 120 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst precarsor, with the programming rate of 8 DEG C/min, is raised to 420 DEG C from room temperature, at the H of 15ml/min
2in flowing environment, reduction 5h, reduction terminates at N
2naturally cold in atmosphere, obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst n).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 8%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 2.2%, arene content be 85% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) LHSV0.35h
-1, hydrogen/oil (v/v) 1400, hydrogen dividing potential drop 12MPa.Product test data list in table 2.
Embodiment 15
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 6.23g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 8h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 3.5h through 110 DEG C, calcines 6h after drying in 500 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 14.2ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball, water absorption rate is 0.72g/ml, saturated dipping Mo maceration extract, and dip time is 15h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 2.5h through 115 DEG C, calcines 8h after drying in 450 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 8 DEG C/min, is raised to 400 DEG C from room temperature, at the H of 30ml/min
2in flowing environment, reduction 4h, reduction terminates at N
2naturally cold in atmosphere, both obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst O).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 8%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 3.3%, arene content be 82% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) LHSV0.4h
-1, hydrogen/oil (v/v) 1300, hydrogen dividing potential drop 15MPa.Product test data list in table 2.
Embodiment 16
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 6.23g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 10h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 2h through 120 DEG C, calcines 4h after drying in 550 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 1.89g
4)
6mo
7o
244H
2o is dissolved in 14.6ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.75g/ml), saturated dipping Mo maceration extract, dip time is 16h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.By Ni-Mo/ γ-Al
2o
3catalyst wet bulb dries 2h through 120 DEG C, calcines 4h after drying in 550 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 5 DEG C/min, is raised to 450 DEG C from room temperature, at the H of 25ml/min
2in flowing environment, reduction 6h, reduction terminates at N
2naturally cold in atmosphere, obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst P).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 8%, and auxiliary agent Mo mass percentage is 8%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 1.5%, arene content be 75% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 290 DEG C, liquid hourly space velocity (LHSV) LHSV0.5h
-1, hydrogen/oil (v/v) 1500, hydrogen dividing potential drop 13MPa.Product test data list in table 2.
Embodiment 17
By γ-Al
2o
3ball type carrier is for subsequent use after 400 DEG C × 6h roasting.First step dipping Ni, takes the nitric acid nickel (NO of 7.79g
3)
26H
2o is dissolved in 16ml in deionized water, makes Ni maceration extract.Get the γ-Al after above-mentioned roasting
2o
3carrier 20g (water absorption rate is 0.8g/ml), saturated dipping Ni maceration extract, dip time is 16h, obtains Ni-γ-Al
2o
3wet bulb.By Ni-γ-Al
2o
3wet bulb dries 4h through 110 DEG C, calcines 4h after drying in 550 DEG C of Muffle furnaces, naturally cools, obtains oxidation state Ni-γ-Al
2o
3ball.Second step leaching Mo, takes the ammonium molybdate (NH of 2.36g
4)
6mo
7o
244H
2o is dissolved in 14.5ml in deionized water, makes Mo maceration extract, floods above-mentioned oxidation state Ni-γ-Al
2o
3ball (water absorption rate is 0.75g/ml), saturated dipping Mo maceration extract, dip time is 16h, obtains Ni-Mo/ γ-Al
2o
3catalyst wet bulb.Wet bulb is dried 2h through 120 DEG C, after drying, in 550 DEG C of Muffle furnaces, calcines 4h, naturally cool, obtain oxidation state Ni-Mo/ γ-Al
2o
3catalyst.3rd step activating catalyst, by oxidation state Ni-Mo/ γ-Al
2o
3catalyst, with the programming rate of 10 DEG C/min, is raised to 450 DEG C from room temperature, at the H of 30ml/min
2in flowing environment, reduction 7h, reduction terminates at N
2naturally cold in atmosphere, both obtain the Ni-Mo/ γ-Al of activated state
2o
3catalyst (catalyst Q).With γ-Al
2o
3for benchmark, wherein active component Ni mass percentage is 10%, and auxiliary agent Mo mass percentage is 10%, Ni/Mo atomic ratio is 2:1.
With sulfur content for 1.2%, arene content be 80% heavy oil be raw material, evaluate catalysts on fixed bed reactors, reaction condition is: reaction temperature 330 DEG C, liquid hourly space velocity (LHSV) LHSV0.5h
-1, hydrogen/oil (v/v) 1800, hydrogen dividing potential drop 18MPa.Product test data list in table 3.
Comparative example 3
Based on embodiment 17, difference is catalyst that this example adopts before for catalytic reaction without hydrogen pre-reduction treatment, but the direct oxidized catalyst adopting second step to prepare is as this routine reference agent 3, catalytic heavy hydrogenation, the reaction condition of heavy-oil hydrogenation is identical with embodiment 17.The sulfur content of heavy oil feedstock is 1.2%, and arene content is 80%.Product test data list in table 3.
Comparative example 4
Vulcanization type FHUDS-6 (Ni-Mo/ γ-the Al that this example adopts Fushun petrochemical industry research institute to provide
2o
3class) catalyst, as this routine reference agent 4, the reaction condition of heavy-oil hydrogenation is identical with embodiment 17.The sulfur content of heavy oil feedstock is 1.2%, and arene content is 80%.Product test data list in table 3.
The hydrogenation activity measurement result of table 1 catalyst
Evaluation result in table 1 can illustrate, when Ni/Mo atomic ratio is 1 ~ 6:1, catalyst provided by the invention, when the catalytic hydrogenation reaction for high-sulfur, high aromatic hydrocarbons heavy oil, has higher heavy oil desulfurization and aromatic saturation performance simultaneously.The activity of the catalyst B that the catalyst adopting preparation method of the present invention to prepare is 2:1 with Ni/Mo atomic ratio is the highest, and desulphurizing activated and arene saturating activity is all less than two kinds of reference agent of 1 apparently higher than Ni/Mo atomic ratio.
Hydrogenation activity measurement result under table 2 different technology conditions
Evaluation result in table 2 can illustrate, under different process conditions, when the catalyst towards heavy oil catalytic desulfurhydrogenation adopting embodiment 2 to prepare and aromatic saturation, reaction temperature 330 DEG C, hydrogen dividing potential drop 18MPa, hydrogen/oil (v/v) is than 1800, and during liquid, volume space velocity LHSV is 0.5h
-1process conditions under, catalyst activity reaches best, desulfurization degree 99.6%, aromatic saturation rate 96.2%.
Table 3 products measure result
Evaluation result in table 3 can illustrate, during to high-sulfur, high aromatic hydrocarbons heavy-oil catalytic hydrogenation, adopt the pretreated catalyst of hydrogen reducing, desulphurizing activated and arene saturating activity is all apparently higher than oxidation state (reference agent 3) and sulphided state type catalyst (reference agent 4), sulphided state type catalyst also has higher desulphurizing activated, but its arene saturating activity is then lower.
Claims (10)
1. a catalyst, is characterized in that, with γ-Al
2o
3for carrier, by weight, with γ-Al
2o
3quality is benchmark, nickeliferous 4 ~ 16%, and containing molybdenum 2 ~ 12%.
2. according to catalyst according to claim 1, it is characterized in that, by weight, with γ-Al
2o
3quality is benchmark, nickeliferous 6 ~ 12%, and containing molybdenum 4 ~ 8%.
3. the method for the catalyst of preparation described in claim 1 or 2, is characterized in that, comprise the following steps successively:
(1) by carrier γ-Al
2o
3through calcining pretreatment;
(2) configuration is containing the maceration extract of Ni, adds carrier γ-Al
2o
3dipping, obtains oxidation state Ni-γ-Al through super-dry, roasting
2o
3ball;
(3) configuration is containing the maceration extract of Mo, adds oxidation state Ni-γ-Al
2o
3ball floods, and obtains oxidation state Ni-Mo/ γ-Al through super-dry, roasting
2o
3catalyst;
(4) by oxidation state Ni-Mo/ γ-Al
2o
3catalyst need be placed in H
2activate in the atmosphere of gas, obtain activated state Ni-Mo/ γ-Al
2o
3catalyst.
4. the preparation method of catalyst according to claim 3, is characterized in that, the calcining pretreatment temperature described in step (1) is 300 ~ 450 DEG C, carrier γ-Al
2o
3saturated water absorption be 0.5 ~ 0.9ml/g.
5. the preparation method of catalyst according to claim 3, is characterized in that, the baking temperature described in step (2) is 100 ~ 120 DEG C, and drying time is 2 ~ 4h, and sintering temperature is 450 ~ 550 DEG C, and roasting time is 4 ~ 8h; Baking temperature in step (3) is 100 ~ 120 DEG C, and drying time is 2 ~ 4h, and sintering temperature is 450 ~ 550 DEG C, and roasting time is 4 ~ 8h.
6. the preparation method of catalyst according to claim 3, is characterized in that, step (4) activation condition is with the programming rate of 5 ~ 10 DEG C/min, is raised to 400 ~ 450 DEG C from room temperature, at the H of 10 ~ 30ml/min
2in flowing environment, reduction 4 ~ 7h, at the N of flowing after reduction treatment terminates
2naturally cool to room temperature in environment, and use N
2protection, N
2flow velocity is 5 ~ 15ml/min.
7. the catalyst as requested described in 1 or 2 at heavy-oil hydrogenation deep desulfuration or/and purposes in aromatic saturation.
8. the using method of the catalyst described in claim 1 or 2, it is characterized in that, under heavy-oil hydrogenation processing reaction condition, by heavy oil feedstock oil in dirty or upper reaches mode at fixed bed gas-solid catalysis device and catalyst exposure, the catalyst of described catalyst any one of claim 1 ~ 2 described in claim.
9. the using method of catalyst according to claim 8, is characterized in that, described heavy oil is high-sulfur, high aromatic hydrocarbons heavy oil, 3.3% >=sulfur content >=0.5%, 90% >=arene content >=60%.
10. the using method of catalyst according to claim 8, is characterized in that, heavy-oil hydrogenation processing reaction condition is: reaction temperature 250 ~ 400 DEG C, hydrogen dividing potential drop 8 ~ 22MPa, and hydrogen/oil ratio is 1000 ~ 2000, and during liquid, volume space velocity LHSV is 0.1 ~ 1h
-1.
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| CN107913715A (en) * | 2017-11-22 | 2018-04-17 | 河南大学 | A kind of hydrogenation deoxidation catalyst and its preparation method and application |
| CN111318300A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN112973765A (en) * | 2019-12-13 | 2021-06-18 | 中国石油化工股份有限公司 | C5 petroleum resin hydrogenation catalyst and preparation method thereof |
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| CN114768811B (en) * | 2022-03-09 | 2024-03-26 | 太原理工大学 | High-loading nickel-aluminum catalyst and preparation method and application thereof |
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