CN102451704B - Method for preparing hydrocracking catalyst - Google Patents
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- CN102451704B CN102451704B CN 201010514108 CN201010514108A CN102451704B CN 102451704 B CN102451704 B CN 102451704B CN 201010514108 CN201010514108 CN 201010514108 CN 201010514108 A CN201010514108 A CN 201010514108A CN 102451704 B CN102451704 B CN 102451704B
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Abstract
The invention discloses a method for preparing a hydrocracking catalyst. In the catalyst, amorphous silicon aluminum and aluminum oxide are taken as a carrier, group VIII and VIB metal is taken as a hydrogenation active ingredient, and the catalyst contains an active substance B2O3 preferably. The catalyst is prepared by mixing and forming the amorphous silicon aluminum and the aluminum oxide, drying, loading active metal by an impregnation method, drying and roasting. Compared with the conventional impregnation method, the method has the advantages that: the formed catalyst is not roasted, so that the preparation process is simplified, time and energy are saved, strong interaction between the active metal and the carrier is reduced, the metal is uniformly distributed, the activity of the metal is more easily exerted, and the specific surface area is prevented from being lost due to multi-step roasting. The catalyst prepared by the method is particularly suitable for the processes of hydrocracking distillate oil and hydrogenating productive middle distillate oil, and has high activity and middle distillate oil selectivity.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, particularly a kind of middle oil type hydrocracking catalyst that contains amorphous aluminum silicide and preparation method thereof.
Background technology
The main feature of hydrocracking technology is that adaptability to raw material is strong, product solution flexibly, purpose product selectivity height, good product quality and added value be high, can directly produce multiple high-quality oil product (as gasoline, jet fuel, diesel oil, the lube base wet goods) and high-quality industrial chemicals (as the raw materials for production of benzene,toluene,xylene, ethene etc.).Therefore, along with crude quality year by year variation and market to the sustainable growth of high-quality oil product and high-quality chemical industry raw materials requirement amount and the appearance in succession of new environmental regulation, show the importance day of hydrocracking technology outstanding, use also increasingly extensive, having become and rationally utilized limited petroleum resources, the oil product of production cleaning to greatest extent and the optimum oil Refining Technologies of high-quality industrial chemicals, is the core of oil, change, fine combination in modern oil refining and the petrochemical enterprise.
Comprise many countries of China, diesel and gasoline ratio is on the low side always, and jet fuel and low-coagulation diesel oil have become one of oil product the wellst sold and in short supply on the market.In addition, because the appearance of new environmental regulation, market also improves constantly the requirement of diesel quality, and this just needs the refinery can produce pledge to measure many midbarrel oil products well.
The activity of hydrocracking catalyst and middle distillates oil selectivity are normally conflicting, and higher activity generally causes the decline of middle distillates oil selectivity.Such as with amorphous Si O
2-Al
2O
3Be the catalyst of cracking component, middle distillates oil selectivity is higher, and also quite stable of oily yield in whole use, but activity is lower.
USP5609750 has introduced a kind of hydrotreating catalyst of boracic.This catalyst is by aluminium oxide, amorphous Si O
2-Al
2O
3(or decentralized SiO
2-Al
2O
3), B
2O
3, metal M o and Ni/Co form, B wherein
2O
3Content is 1wt%～20wt%.This Preparation of catalysts method is: with alumina precursor, SiO
2-Al
2O
3, MoO
3And H
3BO
3Add nitric acid behind the mixing and make it to become and can squeeze paste, extrusion, drying and roasting support Co or Ni with infusion process then, drying, roasting makes catalyst.CN 97121663.0 has introduced a kind of hydrocracking catalyst for the production of intermediate oil, be after amorphous aluminum silicide and aperture alumina adhesive are mixed, extruded moulding, drying and roasting then, make catalyst carrier, and then with infusion process load hydrogenation metal active component.Above-mentioned catalyst all is to carry out roasting after the carrier moulding, impregnating metal then, and metal and carrier interact by force like this, influences the even distribution of reactive metal, and specific surface area of catalyst loses greatlyyer, have influenced the performance of catalyst activity.
CN97122139.1 introduced a kind of in oil type hydrocracking catalyst, be with behind amorphous aluminum silicide, macroporous aluminium oxide and the aperture aluminium oxide kneading and compacting, drying, then through hydrothermal treatment consists, dip loading active metal component again.CN00110021.1 introduced a kind of in oil type hydrocracking catalyst, be with behind amorphous aluminum silicide, boron-containing compound, macroporous aluminium oxide and the aperture aluminium oxide kneading and compacting, drying, then through hydrothermal treatment consists, dip loading active metal component again.The hydrothermal treatment consists of above-mentioned catalyst is at 500～700 ℃, handles under 0.05～0.3MPa condition 0.3～2.0 hour.Although this catalyst has carried out being of value to the processing that improves catalytic activity to amorphous aluminum silicide in preparation process, high-temperature water heat treatment makes the catalyst loss exhibiting high surface long-pending, and catalyst activity still is not very high.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of preparation method of hydrocracking catalyst.The catalyst activity metal component decentralization height of this method preparation, the specific area loss is little, catalyst activity is high, purpose product selectivity height.
Preparation of catalysts method of the present invention comprises as follows:
(1) with amorphous aluminum silicide, macroporous aluminium oxide, mixed by the adhesive of little porous aluminum oxide and peptization acid preparation, rolls moulding;
(2) with the article shaped of step (1) gained 100～280 ℃ of dryings 4～24 hours, be preferably in 150～250 ℃ of dryings 4～24 hours;
(3) carrier that makes with the aqueous solution impregnation steps (2) that contains VI B family and group VIII metal after 1～10 hour, through 430～550 ℃ of roastings 1～10 hour, obtains hydrocracking catalyst of the present invention 90～150 ℃ of dryings again.
The described amorphous aluminum silicide of step (1) can be by coprecipitation method, grafting copolymerization process preparation.The character of preferred amorphous aluminum silicide is as follows among the present invention: SiO
2Content is 10wt%～90wt%, Al
2O
3Content is 10wt%～90wt%, and pore volume is 0.5～0.9ml/g, and specific area is 200～450m
2/ g.
The used aluminium oxide of step (1) is boehmite, and wherein, the character of preferred macroporous aluminium oxide is as follows among the present invention: pore volume is 0.8～1.2ml/g, and specific area is 300～500m
2/ g; The preferred character of little porous aluminum oxide that the preparation adhesive is used is as follows: pore volume is 0.4～0.6ml/g, and specific area is 200～450m
2/ g.
Peptization acid used in the step (1) is organic acid and/or inorganic acid, and described organic acid is preferably acetic acid; Inorganic acid is preferably nitric acid.
In step (1) mixed process, preferably add boron-containing compound, wherein said boron-containing compound is B
2O
3, H
3BO
3And B (OC
2H
5)
3In one or more, its addition makes in the final catalyst boracic with B
2O
3Count 2wt%～13wt%.
The described group vib metal of step (3) is preferably molybdenum and/or tungsten, and the metal of group VIII is preferably cobalt and/or nickel.Weight with catalyst is benchmark, and the content of group vib metal (in oxide) is 17.0%～24.0%, and the content of group VIII metal (in oxide) is 4.0%～7.0%.Described dipping method can adopt the method for spraying, saturated infusion process or supersaturation infusion process.Described maceration extract can adopt the maceration extract that contains leaching agent, leaching agent wherein is that organic acid is or/and acylate, organic acid can be one or more in citric acid, ethanedioic acid, acetic acid, the malonic acid etc., and acylate can be one or more in ammonium citrate, ethanedioic acid ammonium, ammonium acetate, the malonic acid ammonium etc.Described maceration extract is prepared according to conventional methods, and it is soluble in water formulated generally solubility to be contained active metallic compound.
The composition of step (3) gained catalyst is preferably as follows: the weight with catalyst is benchmark, the content of group vib metal (in oxide) is 17%～24%, the content of group VIII metal (in oxide) is 4%～7%, and the content of amorphous aluminum silicide is 17wt%～66wt%, Al
2O
3Content be 10wt%～42.0wt%, B
2O
3Content be 0～13wt%.B wherein
2O
3Content is preferably 2wt%～13wt%.The pore volume of this catalyst is 0.2～0.5ml/g, and specific area is 140～360m
2/ g.This catalyst can be used for the distillate hydrocracking process, is particularly useful for the hydrogenation process of voluminous intermediate oil, has activity and middle distillates oil selectivity preferably.
The inventive method has following advantage:
(1) reduces the calcination steps of shaping carrier, simplified preparation process, saved time and the energy;
(2) since carrier without roasting, but the dipping reactive metal after roasting again, strengthened the synergy between auxiliary agent boron, aluminium oxide and the reactive metal, be conducive to the performance of metal active;
(3) because the omission of carrier calcination steps has been avoided handling the specific area loss that causes because multisteps such as roasting or hydrothermal treatment consists are rapid, provide how available specific area, more activated centre namely is provided;
(4) catalyst of the inventive method preparation, can make by amorphous aluminum silicide is the lytic activity increase of the hydrocracking catalyst of active component, also makes the hydrogenation performance of catalyst improve, the product quality after the hydrocracking is improved significantly.
(5) owing to not increasing additional step, simple and easy to do, grasp easily, and can reduce production costs.
The specific embodiment
Further specify technical solution of the present invention below by embodiment, but these embodiment can not limit the present invention.
Comparative example 1
This comparative example prepares catalyst by CN 97122139.1 methods.
The amorphous aluminum silicide, 55.6 of 150.7 gram grafting copolymerization process preparations is restrained macroporous aluminium oxides, puts into roller by adhesive 148.4 grams of rare nitric acid and the preparation of aperture aluminium oxide, rolled 30 minutes, and added suitable quantity of water afterwards, grind to squeezing paste, extrusion is extruded bar 110 ℃ of dryings 4 hours.Above-mentioned dried strip is put into 600 ℃ in hydrothermal treatment consists stove, and hydrothermal treatment consists is 1 hour under the 0.1MPa, makes carrier.With containing WO
3The maceration extract of 56g/100ml, NiO12g/100ml at room temperature flooded above-mentioned carrier 2 hours, and mother liquor separates, 110 ℃ of dryings 4 hours, and 500 ℃ of roastings 4 hours make catalyst DC-1.
Embodiment 1
The amorphous aluminum silicide, 55.6 of 150.7 gram grafting copolymerization process preparations is restrained macroporous aluminium oxides, puts into roller by adhesive 148.4 grams of rare nitric acid and the preparation of aperture aluminium oxide, rolled 30 minutes, add suitable quantity of water afterwards, grind to squeezing paste, extrusion, extrude bar 180 ℃ of dryings 4 hours, make carrier.With containing WO
3The maceration extract of 56g/100ml, NiO12g/100ml at room temperature flooded above-mentioned carrier 2 hours, and mother liquor separates, 110 ℃ of dryings 4 hours, and 500 ℃ of roastings 4 hours make catalyst C1.
Comparative example 2
This comparative example prepares catalyst by the CN00110021.1 method.
Amorphous aluminum silicide, the 28.5 gram boric acid, 46.6 of 150.7 gram grafting copolymerization process preparations are restrained macroporous aluminium oxides, put into roller by adhesive 133.4 grams of rare nitric acid and the preparation of aperture aluminium oxide, rolled 30 minutes, add suitable quantity of water afterwards, grind to squeezing paste, extrusion is extruded bar 110 ℃ of dryings 4 hours.Above-mentioned dried strip is put into 600 ℃ in hydrothermal treatment consists stove, and hydrothermal treatment consists is 1 hour under the 0.1MPa, makes carrier.With containing WO
3The maceration extract of 56g/100ml, NiO12g/100ml at room temperature flooded above-mentioned carrier 2 hours, and mother liquor separates, 110 ℃ of dryings 4 hours, and 500 ℃ of roastings 4 hours make catalyst DC-2.
Embodiment 2
Amorphous aluminum silicide, the 28.5 gram boric acid, 46.6 of 150.7 gram grafting copolymerization process preparations are restrained macroporous aluminium oxides, put into roller by adhesive 133.4 grams of rare nitric acid and the preparation of aperture aluminium oxide, rolled 30 minutes, add suitable quantity of water afterwards, grind to squeezing paste, extrusion, extrude bar 150 ℃ of dryings 8 hours, make carrier.With containing WO
3The maceration extract of 56g/100ml, NiO12g/100ml at room temperature flooded above-mentioned carrier 2 hours, and mother liquor separates, 110 ℃ of dryings 4 hours, and 500 ℃ of roastings 4 hours make catalyst C2.
Embodiment 3
Amorphous aluminum silicide, the 14.3 gram boric acid, 46.6 of 150.7 gram grafting copolymerization process preparations are restrained macroporous aluminium oxides, put into roller by adhesive 133.4 grams of rare nitric acid and the preparation of aperture aluminium oxide, rolled 30 minutes, add suitable quantity of water afterwards, grind to squeezing paste, extrusion, extrude bar 200 ℃ of dryings 6 hours, make carrier.With containing WO
3The maceration extract of 56g/100ml, NiO12g/100ml at room temperature flooded above-mentioned carrier 2 hours, and mother liquor separates, 110 ℃ of dryings 4 hours, and 500 ℃ of roastings 4 hours make catalyst C3.
Embodiment 4
Amorphous aluminum silicide, the 42.8 gram boric acid, 23.3 of 174.9 gram grafting copolymerization process preparations are restrained macroporous aluminium oxides, put into roller by adhesive 133.4 grams of rare nitric acid and the preparation of aperture aluminium oxide, rolled 30 minutes, add suitable quantity of water afterwards, grind to squeezing paste, extrusion, extrude bar 230 ℃ of dryings 5 hours, make carrier.With containing WO
3The maceration extract of 56g/100ml, NiO12g/100ml at room temperature flooded above-mentioned carrier 2 hours, and mother liquor separates, 110 ℃ of dryings 4 hours, and 500 ℃ of roastings 4 hours make catalyst C4.The results are shown in Table 1.
The main character of table 1 catalyst
Embodiment 5
On small-sized evaluating apparatus, adopt single hop once by flow process, be raw material with the vacuum distillate, to estimate at the fixed bed hydrogenation experimental rig, appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.30h during liquid
-1, C-1, C-2, C-3, C-4, DC-1 and DC-2 catalyst are carried out performance evaluation.
Raw materials used oil nature sees Table 2, and evaluation result sees Table 3.
Table 2 feedstock oil main character
| Density (20 ℃), g/cm 3 | 0.9049 |
| Sulphur, wt% | 1.50 |
| Nitrogen, wt% | 0.17 |
| Boiling range, ℃ | 277～548 |
Evaluating catalyst result under table 3 the same terms
| Numbering | C-1 | C-2 | C-3 | C-4 | DC-1 | DC-2 |
| Reaction temperature, ℃ | 381 | 375 | 378 | 378 | 389 | 387 |
| Middle distillates oil selectivity, wt% | 89.3 | 89.6 | 89.0 | 89.1 | 84.3 | 88.9 |
| The jet fuel smoke point, mm | 24 | 27 | 26 | 25 | 25 | 22 |
By table 3 result as seen, catalyst of the present invention very high activity is arranged, and product property improves when keeping high middle distillates oil selectivity.
Claims (7)
1. the preparation method of a hydrocracking catalyst comprises:
(1) with amorphous aluminum silicide, macroporous aluminium oxide, mixed by the adhesive of little porous aluminum oxide and peptization acid preparation, rolls moulding;
(2) with the article shaped of step (1) gained 150～280 ℃ of dryings 4～24 hours;
(3) carrier that makes with the aqueous solution impregnation steps (2) that contains group vib and group VIII metal after 1～10 hour, through 430～550 ℃ of roastings 1～10 hour, obtains hydrocracking catalyst 90～150 ℃ of dryings again; Described hydrocracking catalyst composed as follows: the weight with catalyst is benchmark, the group vib metal is 17%～24% in the content of oxide, the group VIII metal is 4%～7% in the content of oxide, and the content of amorphous aluminum silicide is 17wt%～66wt%, Al
2O
3Content be 10wt%～42.0wt%, B
2O
3Content be 0～13wt%, described group vib metal is molybdenum and/or tungsten, the metal of group VIII is cobalt and/or nickel;
B in described hydrocracking catalyst
2O
3Content when non-vanishing, following manner is adopted in the introducing of boron: in step (1) mixed process, add boron-containing compound, wherein said boron-containing compound is B
2O
3, H
3BO
3And B (OC
2H
5)
3In one or more.
2. in accordance with the method for claim 1, it is characterized in that the described drying condition of step (2) is as follows: 150～250 ℃ of dryings 4～24 hours.
3. in accordance with the method for claim 1, it is characterized in that the character of the described amorphous aluminum silicide of step (1) is as follows: SiO
2Content is 10wt%～90wt%, Al
2O
3Content is 10wt%～90wt%, and pore volume is 0.5～0.9ml/g, and specific area is 200～450m
2/ g.
4. in accordance with the method for claim 1, it is characterized in that the used aluminium oxide of step (1) is boehmite, wherein, the character of macroporous aluminium oxide is as follows: pore volume is 0.8～1.2ml/g, and specific area is 300～500m
2/ g; The character of the little porous aluminum oxide that the preparation adhesive is used is as follows: pore volume is 0.4～0.6ml/g, and specific area is 200～450m
2/ g.
5. in accordance with the method for claim 1, it is characterized in that the described dipping method employing of step (3) sprays method, saturated infusion process or supersaturation infusion process.
6. in accordance with the method for claim 1, it is characterized in that containing leaching agent in the described aqueous solution that contains group vib and group VIII metal of step (3), wherein leaching agent is that organic acid is or/and acylate, organic acid is one or more in citric acid, ethanedioic acid, acetic acid, the malonic acid, and acylate is one or more in ammonium citrate, ethanedioic acid ammonium, ammonium acetate, the malonic acid ammonium.
7. in accordance with the method for claim 1, it is characterized in that in step (3) the gained catalyst B
2O
3Content is 2wt%～13wt%.
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|---|---|---|---|
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| CN104549328B (en) * | 2013-10-22 | 2016-11-16 | 中国石油化工股份有限公司 | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst |
| CN104549333B (en) * | 2013-10-23 | 2017-02-22 | 中国石油化工股份有限公司 | Preparation method for residual oil hydrogenation and demetalization catalyst |
| CN105080556B (en) * | 2014-05-14 | 2018-02-13 | 中国石油化工股份有限公司 | Hydrobon catalyst and catalytic cracking light cycle oil process for purification |
| CN105709764B (en) * | 2014-12-04 | 2018-01-16 | 中国石油化工股份有限公司 | One kind hydrogenation nickel removal catalyst and preparation method thereof |
| CN111375419B (en) * | 2018-12-29 | 2022-07-12 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN112138642A (en) * | 2020-09-27 | 2020-12-29 | 福州大学 | Preparation method and application of cracking catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302851A (en) * | 2000-01-04 | 2001-07-11 | 中国石油化工集团公司 | Medium oil type hydrocracking catalyst and its preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302851A (en) * | 2000-01-04 | 2001-07-11 | 中国石油化工集团公司 | Medium oil type hydrocracking catalyst and its preparing process |
Non-Patent Citations (2)
| Title |
|---|
| 《水热改性对氧化铝载体织构和表面性质的影响》;李俊诚等;《无机化学学报》;20050228;第21卷(第2期);212 * |
| 李俊诚等.《水热改性对氧化铝载体织构和表面性质的影响》.《无机化学学报》.2005,第21卷(第2期),212. |
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