CN103182310B - Method for preparing distillate oil hydrotreatment catalyst - Google Patents
Method for preparing distillate oil hydrotreatment catalyst Download PDFInfo
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- CN103182310B CN103182310B CN201110446040.5A CN201110446040A CN103182310B CN 103182310 B CN103182310 B CN 103182310B CN 201110446040 A CN201110446040 A CN 201110446040A CN 103182310 B CN103182310 B CN 103182310B
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Abstract
The invention relates to a method for preparing a distillate oil hydrotreatment catalyst. Ni, Co, W/Mo active components are loaded by gamma-Al2O3 or silicon-containing gamma-Al2O3, P element is included as a cocatalyst component, and any element selected from the group consisting of Mg, Zn, Fe and Ca may also be included as a cocatalyst component. The method for preparing the distillate oil hydrotreatment catalyst comprises the following steps: (1) firstly preparing gamma-Al2O3 or a silicon-containing gamma-Al2O3 carrier; (2) loading the gamma-Al2O3 or the silicon-containing gamma-Al2O3 with a Ni metal component and a P auxiliary component, then drying and calcining; (3) soaking the carrier obtained in step (2) into a solution of Co-containing compound, and W and/or Mo-containing compound, drying and calcining to obtain a finished catalyst. The catalyst can be used for hydrotreatment of light distillate oils such as a reforming raw material, gasoline fraction and kerosene fraction, and has a high hydrodesulfurization activity.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogenation catalyst, more particularly, is a kind of preparation method about the distillate particularly Hydrobon catalyst of light ends oil.
Background technology
No. 3 jet fuel national standards (GB 6537-2006) propose nearly 30 index requests from aspects such as outward appearance, color, composition, volatility, density, mobility, flammability, corrosivity, stability, cleanliness, electric conductivity, water separation index and lubricities to jet fuel.Jet fuel is one of product that in oil product, Con trolling index at most, quality requirement is the tightest.
From world wide, jet fuel is mainly produced for raw material passes through to refine with the straight run component that the boiling range cut from atmospheric distillation device is suitable, and refining link is wherein divided into again Non-adding hydrogen and hydroprocessing technique.
Non-adding hydrogen, owing to there is pollution in various degree, produces the more waste material not easily disposed, and simultaneously along with the variation of crude quality, simple Non-adding hydrogen is difficult to meet jet fuel and produces refining requirement.Non-adding hydrogen be hydroprocessed gradually technique to replace be development trend from now on.
The Main Function of hydroprocessing technique removes mercaptan, colloid and a small amount of polarity thing and pollutes impurity, reduces acid number (as removing aphthenic acids etc.).After hydrogenation, the target improvement such as smell, color, thermal oxidation stability of oil product is obvious.Because hydroconversion condition relaxes, the natural sulfide isopolarity material major part in raw material with the wear-resistant effect of antioxygen is retained, therefore the anti-oxidative stability of oil product and lubricity better.
In jet fuel unifining process, in order to retain in raw material the natural sulfide isopolarity material with antioxygen, wear-resistant effect, ensureing anti-oxidative stability and the lubricity of oil product, simultaneously in order to reduce hydrogen consumption, generally all adopting the process conditions of low temperature, low pressure, low hydrogen/gasoline ratio.On the other hand, need again to be realized mercaptan, colloid and a small amount of polarity thing in deep removal raw material and pollution impurity by hydrogenation, reduce acid number.This just requires developed catalyst, under low temperature, low pressure, low hydrogen/gasoline ratio process conditions, still have very high hydrogenation activity and activity stability, especially has very strong removal of mercaptans, depickling, improves oil product color activity.
At present, normally the light ends oil Hydrobon catalysts such as the reformed pre-hydrogenated catalyst of commercial Application or diesel oil hydrofining catalyst are directly used in jet fuel hydrogenation.Although product quality also can reach No. 3 jet fuel national standards, because the design specific aim of catalyst is not strong, there is reaction condition and relax not, the problems such as plant energy consumption is higher.
Summary of the invention
The object of this invention is to provide one and be suitable for the hydrofinishing of light ends oil, be especially suitable for the preparation method that the hydrogenation catalyst of jet fuel is produced in straight run kerosene fraction hydrofinishing.When using this catalyst treatment inferior raw material, have the advantages that operating condition relaxes.
Light ends oil Hydrobon catalyst of the present invention is with γ-Al
2o
3or siliceous γ-Al
2o
3for carrier, with Ni, Co and W and/or Mo for active component, also containing P auxiliary agent, be that absolutely nickel oxide is 1.5% ~ 5.5%, and cobalt oxide is 0.5% ~ 3.5%, and tungstic acid and/or molybdenum trioxide are 12.0% ~ 22.0%, P in catalyst weight
2o
5be 0.5% ~ 3.5%, γ-Al
2o
3or siliceous γ-Al
2o
3for surplus.
The specific area of catalyst is 120m
2/ g ~ 190m
2/ g, pore volume 0.30ml/g ~ 0.55ml/g.Can one or more conven-tional adjuvants be contained, as Mg, Zn, Fe, Ca etc. in catalyst.
The concrete preparation process of light ends oil Hydrobon catalyst of the present invention is:
(1) siliceous or not siliceous boehmite powder is got, add field mountain valley with clumps of trees and bamboo powder to mix, add peptizing agent, deionized water kneading again until become plastic shape, at 100 DEG C ~ 120 DEG C dry 2h ~ 14h, in high temperature furnace at 500 DEG C ~ 800 DEG C roasting 3h ~ 8h, the programming rate of roasting is 1 DEG C/min ~ 3 DEG C/min.
(2) Ni compound is contained with equi-volume impregnating dipping, containing the maceration extract that P-compound and other auxiliary agent are prepared, carrier after dipping is at 100 DEG C ~ 120 DEG C dry 2h ~ 4h, in high temperature furnace at 450 DEG C ~ 700 DEG C roasting 3h ~ 8h, the programming rate of roasting is 1 DEG C/min ~ 3 DEG C/min, and obtained catalyst semi-finished product.
(3) C o compound is contained with equi-volume impregnating dipping, containing the maceration extract that W and/or Mo compound and other auxiliary agent are prepared, carrier after dipping is at 100 DEG C ~ 120 DEG C dry 2h ~ 4h, in high temperature furnace at 450 DEG C ~ 700 DEG C roasting 3h ~ 16h, the programming rate of roasting is 1 DEG C/min ~ 3 DEG C/min, and obtained finished catalyst.
Described in above-mentioned steps (2) is one or both in nickel nitrate, basic nickel carbonate containing Ni compound; Phosphorus-containing compound is one or more in ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, phosphoric acid, calcium phosphate, calcium monohydrogen phosphate, fatty alcohol ether phosphate, PAPE.
Described in above-mentioned steps (3) is one or both in basic cobaltous carbonate, cobalt nitrate containing Co compound; Be ammonium metatungstate containing W compound; Be one or both in ammonium molybdate, molybdenum trioxide containing Mo compound.
The feature of the catalyst prepared by the present invention is: be first mixed with impregnation fluid carrier with Ni element and the compound of P element and the auxiliary agent of necessity, after drying and roasting, nickle atom with the phosphide form load of nickel on carrier.With the nickel of the existence of phosphide form, be easy to form Monolayer Dispersion at carrier surface, improve the decentralization of nickel.The formation of phosphide, changes the electronic structure of nickel, is formed and acts synergistically, play the effect as adjuvant component better, improve the catalytic activity of tungsten and/or molybdenum with the cobalt element of load in subsequent step.
Detailed description of the invention
Content of the present invention is set forth further below in conjunction with embodiment.
Embodiment 1
(1) γ-Al
2o
3the preparation of carrier
Take 1000g without silicon boehmite powder, 30g field mountain valley with clumps of trees and bamboo powder, 30g citric acid, 3 ~ 5% dust technology 700ml mix, extruded with banded extruder, 110 DEG C of dry 10h, in air atmosphere after 650 DEG C of calcination process, obtain γ-Al
2o
3carrier.
(2) Ni-P/ γ-Al
2o
3preparation
Preparation 1000ml dipping solution: weigh 107.6g tartaric acid and join in 600ml deionized water, to stir and after being heated to 50 DEG C, weighing 83.6g nickel nitrate (technical grade) and 26.3g ammonium dihydrogen phosphate (ADP) (technical grade) join in this solution, boil 0.5 hour, add weak aqua ammonia and solution p H value is adjusted to 4.0.After being cooled to room temperature, transferred to by solution in volumetric flask, the constant volume that adds water, to 1000ml, obtains nickeliferous and dipping solution that is phosphorus.
Take the γ-Al prepared by 500g step (1)
2o
3carrier, measures the dipping solution of above-mentioned the prepared nickeliferous and phosphorus of 375ml, incipient impregnation 30 minutes, and 110 DEG C of dryings 2 hours, 460 DEG C of roastings, obtain catalyst semi-finished product.
(3) Co-Mo-Ni-P/ γ-Al
2o
3the preparation of catalyst
Preparation 1000m l dipping solution: weigh 105.0g citric acid and join in 700ml water, after stirring and dissolving, weighing 49.3g basic cobaltous carbonate (technical grade) and 266.0g ammonium molybdate (technical grade) join in this solution, boil 0.5 hour, be cooled to room temperature, transferred to by solution in volumetric flask, the constant volume that adds water, to 1000ml, obtains the dipping solution containing cobalt and molybdenum.
Take the Ni-P/ γ-Al prepared by 500g step (2)
2o
3catalyst semi-finished product, measure the dipping solution containing cobalt and molybdenum that 347ml is above-mentioned prepared, incipient impregnation 30 minutes, and 110 DEG C of dryings 2 hours, 460 roastings, obtain finished catalyst.
Embodiment 2
(1) siliceous γ-Al
2o
3the preparation of carrier
Take the siliceous boehmite of 1000g, 45g field mountain valley with clumps of trees and bamboo powder, 35g oxalic acid, 3 ~ 5% dust technology 680m l mix, extruded with banded extruder, 110 DEG C of oven dry, after the lower 550 DEG C of calcination process of air atmosphere, obtain siliceous γ-Al
2o
3carrier.
(2) the siliceous γ of Ni-P/-Al
2o
3preparation
Preparation 1000ml dipping solution: weigh 140.0g oxalic acid and join in 600ml water, to stir and after being heated to 50 DEG C, weighing 45.5g basic nickel carbonate nickel (technical grade) and 31.3g calcium monohydrogen phosphate (technical grade) join in this solution, boil 0.5 hour, be cooled to room temperature, transferred to by solution in volumetric flask, the constant volume that adds water, to 1000ml, obtains nickeliferous and dipping solution that is phosphorus.
Take the siliceous γ-Al prepared by 500g step (1)
2o
3carrier, measures the dipping solution of the nickeliferous and phosphorus that 366m l prepares, incipient impregnation 30 minutes, and 110 DEG C of dryings 2 hours, 500 roastings, obtain catalyst semi-finished product.
(3) the siliceous γ of Co-Mo-Ni-P/-Al
2o
3the preparation of catalyst
Maceration extract preparation is with embodiment 1 (3).
Take the siliceous γ of the Ni-P/-Al prepared by 500g step (2)
2o
3catalyst semi-finished product, measure the dipping solution containing cobalt and molybdenum that 340ml is above-mentioned prepared, incipient impregnation 30 minutes, and 110 DEG C of dryings 2 hours, 460 roastings, obtain finished catalyst.
Embodiment 3
(1) γ-Al
2o
3the preparation of carrier
With embodiment 1 (1).
(2) Ni-P/ γ-Al
2o
3preparation
Maceration extract preparation is with embodiment 2 (2).
Take 500g γ-Al
2o
3carrier, measures the dipping solution of the nickeliferous and phosphorus that 375ml prepares, incipient impregnation 30 minutes, and 110 DEG C of dryings 2 hours, 460 DEG C of roastings, obtain catalyst semi-finished product.
(3) Co-Mo-Ni-P/ γ-Al
2o
3the preparation of catalyst
Maceration extract preparation is with embodiment 1 (3).
Take the Ni-P/ γ-Al prepared by 500g step (2)
2o
3catalyst semi-finished product, the dipping solution containing cobalt and molybdenum measuring that 347ml prepares, incipient impregnation 30 minutes, 110 DEG C of dryings 2 hours, 460 DEG C of roastings, obtain finished catalyst.
Comparative example 1
(1) γ-Al
2o
3the preparation of carrier
With embodiment 1 (1).
(2) Co-Mo-Ni/ γ-Al
2o
3the preparation of catalyst
Configuration 1000ml dipping solution: weigh 144.0g citric acid and join in 600ml water, after stirring and dissolving, weighing 44.0g basic cobaltous carbonate (technical grade) and 119.0g nickel nitrate (technical grade) join in this solution, boil 1.0 hours, again 272.0g ammonium molybdate (technical grade) is joined in this solution, with concentrated ammonia liquor by solution dilution to 1000ml.Obtain the dipping solution containing cobalt, molybdenum, nickel.
Take the γ-Al prepared by 500g step (1)
2o
3carrier, measures the dipping solution containing cobalt, molybdenum, nickel that 375ml prepares, incipient impregnation 30 minutes, and 110 DEG C of dryings 2 hours, 460 DEG C of roastings, obtain finished catalyst.
Comparative example 2
(1) siliceous γ-Al
2o
3the preparation of carrier
With embodiment 2 (1).
(2) the siliceous γ of Co-Mo-Ni/-Al
2o
3the preparation of catalyst
Maceration extract preparation is with comparative example 1 (2).
Take the siliceous γ-Al prepared by 500g step (1)
2o
3carrier, measures the dipping solution containing cobalt, molybdenum, nickel that 366ml prepares, incipient impregnation 30 minutes, and 110 DEG C of dryings 2 hours, 460 DEG C of roastings, obtain finished catalyst.
The physico-chemical property of the catalyst above obtained by each example lists in table 1.
The composition of each routine catalyst of table 1
The evaluation of 100m l hydrogenation activity is carried out with the catalyst prepared by above each example.Evaluation result is in table 2.
The each routine catalyst activity evaluation result of table 2
| Project | Feedstock oil | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Sulphur, g/g | 4071 | 742 | 683 | 699 | 1035 | 1131 |
| Mercaptan sulfur, g/g | 83 | 4.7 | 5.3 | 6.1 | 28.4 | 31.2 |
| Color, number | 13 | 30 | 30 | 30 | 25 | 25 |
| Arene content, Φ % | 20.7 | 19.1 | 19.0 | 18.9 | 20.4 | 20.3 |
Note: (1) conditions of vulcanization: first catalyst uses the kerosene containing carbon disulfide 2% under 290 hydrogen atmospheres, under 7.0MPa pressure, carries out presulfurization 25h, then enters raw material; (2) reaction condition: reaction temperature 230, pressure 2.0MPa, air speed (volume) 3.0h
-1, hydrogen oil (volume) is than 150.
Claims (1)
1. a preparation method for catalyst for hydrogenation of fraction oil, is characterized in that: with γ-Al
2o
3or siliceous γ-Al
2o
3for carrier, with Ni and Co and W and/or Mo for active component, containing P auxiliary agent, in catalyst weight percent, nickel oxide is 1.5% ~ 5.5%, and cobalt oxide is 0.5% ~ 3.5%, and tungstic acid and/or molybdenum trioxide are 12.0% ~ 22.0%, P
2o
5content be 0.5% ~ 3.5%, γ-Al
2o
3or siliceous γ-Al
2o
3for surplus;
(1) boehmite powder and field mountain valley with clumps of trees and bamboo powder are mixed, then add peptizing agent, deionized water kneading, then extrusion, drying, roasting, obtained γ-Al
2o
3or siliceous γ-Al
2o
3carrier;
Described dry run is at 100 DEG C ~ 120 DEG C dry 2h ~ 14h, and roasting process is at high temperature furnace roasting 3h ~ 8h at 500 DEG C ~ 800 DEG C;
(2) Ni compound is contained with infusion process load, containing the maceration extract that P-compound and other auxiliary agent are prepared, then dry, roasting, obtained catalyst semi-finished product;
Described is one or both in nickel nitrate, basic nickel carbonate containing Ni compound; Phosphorus-containing compound is one or more in ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, phosphoric acid, calcium phosphate, calcium monohydrogen phosphate, fatty alcohol ether phosphate, PAPE;
Described dry run is at 100 DEG C ~ 120 DEG C dry 2h ~ 4h, and roasting process is at high temperature furnace roasting 3h ~ 8h at 450 DEG C ~ 700 DEG C;
(3) Co compound is contained with infusion process load, containing the maceration extract that W and/or Mo compound and other auxiliary agent are prepared, then dry, roasting, obtained finished catalyst; Described dry run is at 100 DEG C ~ 120 DEG C dry 2h ~ 4h, and roasting process is at high temperature furnace roasting 3h ~ 16h at 450 DEG C ~ 700 DEG C.
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| CN201110446040.5A CN103182310B (en) | 2011-12-28 | 2011-12-28 | Method for preparing distillate oil hydrotreatment catalyst |
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| CN201110446040.5A CN103182310B (en) | 2011-12-28 | 2011-12-28 | Method for preparing distillate oil hydrotreatment catalyst |
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| CN103182310B true CN103182310B (en) | 2015-07-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2926759C (en) | 2013-11-07 | 2021-11-30 | Shell Internationale Research Maatschappij B.V. | Process for preparing a hydrotreating catalyst |
| CN104624215A (en) * | 2013-11-15 | 2015-05-20 | 中国石油天然气股份有限公司 | Distillate oil hydrofining catalyst and preparation method and application ofdistillate oil hydrofining catalyst |
| CN103638987B (en) * | 2013-12-02 | 2016-08-17 | 煤炭科学技术研究院有限公司 | Liquefied coal coil catalyst carrier for hydrgenating, catalyst and preparation method and application |
| CN105478129B (en) * | 2014-09-17 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and its application |
| CN105478156B (en) * | 2014-09-17 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and its application |
| CN106540697A (en) * | 2015-09-22 | 2017-03-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN106914260A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Oil hydrogenation catalyst for refining, its preparation method and application |
| CN107597137A (en) * | 2016-07-11 | 2018-01-19 | 中国石油天然气股份有限公司 | The preparation method of catalyst for hydrorefining distillate oil |
| CN109647452B (en) * | 2017-10-10 | 2022-04-05 | 中国石油化工股份有限公司 | Hydrogenation catalyst for preparing cyclohexylamine |
| CN111318293B (en) * | 2018-12-13 | 2023-09-01 | 中国石油化工股份有限公司 | Hydrotreating catalyst for rapidly increasing content of monocyclic aromatic hydrocarbon and preparation method thereof |
| CN115069253A (en) * | 2022-07-14 | 2022-09-20 | 西安交通大学 | Antioxidant organic coated nickel-based catalyst and preparation method and application thereof |
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|---|---|---|---|---|
| US5484756A (en) * | 1992-05-15 | 1996-01-16 | Nikki-Universal Co., Ltd. | Hydrodesulfurization catalyst and preparation thereof |
| CN101089132A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Fraction oil hydrodesulfurizing catalyst and its prepn process |
Non-Patent Citations (1)
| Title |
|---|
| 磷化镍调变MoS2/γ-Al2O3催化剂的加氢脱硫性能;刘理华 等;《化工学报》;20110531;第62卷(第5期);第1297页左栏第1、3段，第1298页左栏第1段，右栏第2、4段 * |
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