CN103100400B - Preparation method of hydrocracking catalyst - Google Patents
Preparation method of hydrocracking catalyst Download PDFInfo
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- CN103100400B CN103100400B CN201110350776.2A CN201110350776A CN103100400B CN 103100400 B CN103100400 B CN 103100400B CN 201110350776 A CN201110350776 A CN 201110350776A CN 103100400 B CN103100400 B CN 103100400B
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Abstract
The invention discloses a preparation method of a hydrocracking catalyst. The method comprises: first selecting a solution containing a hydrogenation active metal and an organic reagent to dip mixed powder of a molecular sieve and alumina, conducting drying, then subjecting the obtained material and a peptizing agent or a binder together to rolling, molding, drying and roasting, thus obtaining the catalyst. Only through one time high temperature roasting can the catalyst product be obtained. The preparation method is simple, and the preparation cost is obviously reduced. In addition, the hydrogenation activity center and the cracking activity center of the catalyst coordinate, so that the catalyst has very high catalytic activity. Also with a large specific surface area and pore volume, the hydrocracking catalyst is more suitable for a catalytic process of treating high dry point inferior vacuum distillate oil by hydrocracking for high production of naphtha.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocracking catalyst, be particularly applicable to process inferior raw material and there is the preparation method of hydrocracking catalyst of high activity fecund naphtha.
Background technology
Hydrocracking technology has that adaptability to raw material is strong, products scheme flexibility large, object product selectivity is high, good product quality, added value high, various heavy, inferior raw material can be converted into the industrial chemicals of clean fuel oil and high-quality, become one of modern oil refining and petro chemical industry most important heavy oil deep processing technique, and obtain increasingly extensive application.Because crude quality is deteriorated year by year, sour crude import volume significantly increases, and environmental protection requires increasingly strict to oil refining process itself and petroleum product-quality, market constantly increases clean fuel oil and industrial chemicals demand.Therefore, hydrocracking technology also will obtain applying more widely, also itself proposes higher requirement to hydrocracking technology simultaneously.
Along with developing rapidly of World Economics, the demand of market to chemical products sharply increases, and wherein more vigorous with the demand of the basic chemical industry such as triolefin, triphen raw material, this also drives its production capacity to expand rapidly.Along with the operation of the large-scale reformation of many covers and ethylene unit is gone into operation, only can not meet the requirement of market to industrial chemicals by atmospheric and vacuum distillation unit, the breach of chemical raw material is increasing, and the supply of the chemical industry light oil raw materials for production wherein based on naphtha is more urgent.Hydrocracking technology can produce sulphur and the high heavy naphtha product of extremely low, the fragrant potential content of nitrogen content, can directly for the catalytic reforming unit producing aromatic hydrocarbons or high-knock rating gasoline provides quality raw materials; The products such as hydrocracking tail oil, light naphthar and liquefied gas are rich in alkane, when doing the charging of preparing ethylene by steam cracking device, have the features such as triolefin yield is high, pyrolysis furnace coke cleaning period is long, energy and material consumption is low, good in economic efficiency.Therefore, further raising is very necessary to produce the hydrocracking technology level of product for the purpose of industrial chemicals (i.e. light oil type hydrogen cracking, to produce the light oil such as naphtha for major product), the industrial chemicals that raises productivity and improves the quality to meet the growing market demand.
Because crude oil constantly becomes bad, becomes heavy, imported high sulfur crude oil increases considerably, and refinery is for increasing economic efficiency, start generally to adopt crude oil deep vacuum distillation technology, doing of vacuum distillate is made to have brought up to about 600 DEG C by original 520 DEG C, the impurity contents such as its density is increasing, boiling range is more and more higher, the molecular weight of contained hydrocarbon molecule is increasing, structure also becomes increasingly complex, sulphur nitrogen also get more and more, considerably increase the difficulty of hydrocracking, these are proposed higher requirement to hydrocracking technology and hydrocracking catalyst.
Hydrocracking catalyst is a kind of bifunctional catalyst, namely has cracking activity and hydrogenation activity simultaneously.Cracking activity provides primarily of various molecular sieve, and hydrogenation activity supplies primarily of the metal carrying of group vib and VIII in the periodic table of elements.In order to the heavy naphtha that raises productivity and improves the quality, General Requirements hydrocracking catalyst has strong cracking activity and the hydrogenation activity of moderate strength, and its key is as the Optimized Matching between the molecular sieve of cracking active component and hydrogenation component.
US6174429 discloses a kind of hydrocracking catalyst, this catalyst contain at least one acidifying of 1 ~ 99wt% containing aluminium [amorphous, a kind of cell parameter of 0.1 ~ 80wt% is 2.438nm, SiO
2/ Al
2o
3chemistry mol ratio is about 8, SiO
2/ Al
2o
3framework mole ratio is the Y zeolite of about 20, at least one group VIII metal component of 0.1 ~ 30wt%, at least one group vib metal component of 1 ~ 40wt%, the auxiliary agent of 0.1 ~ 20wt% and at least one VIIA race element of 0 ~ 20wt%.This catalyst adopts first prepares carrier, after support the preparation method of hydrogenation metal, catalyst has active and stability preferably, but heavy naphtha and boat yield of coal not high.
CN98114489.6 discloses a kind of hydrocracking catalyst, adopts coprecipitation method preparation.Wherein amorphous aluminum silicide accounts for 10 ~ 60wt% of catalyst, Modified Zeolite Y 1 ~ 40wt%, group vib metal oxide accounts for 10 ~ 40wt%, group VIII metal oxide accounts for 1 ~ 10wt%, IVB family metal oxide accounts for 1 ~ 10wt%, produce intermediate oil for one-stage serial hydrocracking, the N content of cracking zone charging can reach 100 μ g/g.This catalyst has good catalytic activity, and catalyst also has very high anti-nitrogen, but its preparation method is more complicated, and preparation cost is also higher, and naphtha product yield is lower.
The patents such as US5086032 and US4820677 also describe and adopt coprecipitation method to prepare high tenor hydrotreating catalyst, prepare tenor up to 50% ~ 95% hydrotreating catalyst, the Hydrogenation of catalyst obtains great raising, and product quality obtains great improvement.Although this type of catalyst has higher Hydrogenation, but the pore volume of catalyst and specific area are relatively little, generally can only process the cut of below diesel oil compared with lightweight, and because coprecipitation method Kaolinite Preparation of Catalyst using rate of metal is low, metal dispersion performance is bad, and complicated process of preparation, product stability is poor, so catalyst cost performance is not high.
The method of the Hydrogenation of usual raising hydrocracking catalyst mainly contains adds auxiliary agent and improves hydrogenation metal content etc.The method of adding auxiliary agent mainly improves the active force of carrier and hydrogenation metal by adding auxiliary agent, to improve the dispersion of hydrogenation metal on catalyst surface, and then improve the Hydrogenation of catalyst.CN01123767.8 discloses a kind of hydrocracking catalyst preparation method containing rare earth, and the method, by adding rare-earth additive, is improved the dispersity of carrier and hydrogenation metal, made the Hydrogenation of catalyst obtain certain improvement.US 6,527,945, CN00110016.5 and CN00109747.4, by adding the auxiliary agents such as boron, phosphorus and halogen (F, Cl), make the performance of hydrocracking catalyst obtain further raising.
By above analysis, adopt preparation catalyst, the performance of hydrogenation metal can be given full play to, but the tenor of Kaolinite Preparation of Catalyst is very restricted; Although coprecipitation method can prepare the hydrotreating catalyst of high tenor, the utilization rate of metal is not high, and catalyst pore structure is also subject to certain restrictions.Kneading method also can prepare the catalyst of various active metallic content, but catalyst performance prepared by kneading method is relatively poor, and active metal effective rate of utilization is low, the less employing kneading method preparation of hydrogenation catalyst in industrial production.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of hydrocracking catalyst.The method is coordinated with the optimization of Cracking Component by hydrogenation component, can the hydrogenation of optimization of catalysts and cracking function, gives full play to the performance of the two, improves the ability of process inferior raw material, meet the object of the heavy naphtha that raises productivity and improves the quality.
The preparation method of hydrocracking catalyst of the present invention, comprises following process:
(1) preparation contains the dipping solution of hydrogenation active metals and organic reagent,
(2) by molecular sieve with alumina powder jointedly to mix,
(3) mixed powder of dipping solution impregnation steps (2) gained prepared by step (1), after filtration, dry, pulverize;
(4) material that step (3) obtains is put into roller together with peptizing agent or adhesive to roll, obtain final catalyst through overmolding, drying and roasting.
Hydrocracking catalyst of the present invention, comprise molecular sieve, aluminium oxide, hydrogenation active metals component, hydrogenation active metals component is group vib metal component and/or group VIII is hydrogenation component, with the weight of hydrocracking catalyst catalyst for benchmark, the content of molecular sieve is 20% ~ 70%, the content of aluminium oxide is 10% ~ 40%, hydrogenation active metals component with the content of oxide basis for 15% ~ 38%.
In method for preparing catalyst of the present invention, described organic reagent can be one or more in acetic acid, malonic acid, citric acid, ammonium nitrate, ammonium citrate.In dipping solution described in step (1), the concentration of organic reagent is 1g/100mL ~ 20g/100mL, and the consumption of hydrogenation active metals is 5.0 ~ 50.0g hydrogenation active metals/100mL.
In method for preparing catalyst of the present invention, during the mixed powder of dipping solution impregnation steps (2) gained prepared by step (1), the liquid-solid ratio of employing is 2 ~ 10 mL solution/g powders.Dipping temperature is generally 10 ~ 50 DEG C, preferably 15 ~ 40 DEG C.
In the inventive method, molecular sieve used can commonly use molecular sieve for hydrocracking catalyst, comprises one or more in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve, is preferably Y zeolite.The Y zeolite that hydrocracking catalyst of the present invention adopts is preferably successively through hydrothermal treatment consists and acid-treated molecular sieve, wherein hydrothermal conditions is: gauge pressure 0.05 ~ 0.4MPa, is preferably 0.1 ~ 0.2MPa, temperature 500 ~ 600 DEG C, 0.5 ~ 5 hour processing time, preferably 1 ~ 3 hour.Acid treatment generally adopts inorganic acid and/or organic acid to carry out acidification.The character of described Y zeolite is preferably as follows: specific area is 600m
2/ g ~ 900m
2/ g, total pore volume is 0.30mL/g ~ 0.5mL/g, and relative crystallinity is 90% ~ 130%, and cell parameter is 2.435 ~ 2.445nm, and silica alumina ratio is 5 ~ 40, and meleic acid amount is 0.3 ~ 0.8mmol/g.
In the inventive method, aluminium oxide used can be conventional macroporous aluminium oxide, and preferably Si modification aluminium oxide, as macropore Si modification aluminium oxide prepared by CN200510047483.1, its character is as follows: pore volume is 1.4 mL/g ~ 1.8mL/g, and specific area is 500m2/g ~ 550m
2/ g, silica content is 10wt% ~ 15wt%.
In hydrocracking catalyst of the present invention, hydrogenation active metals component is the metal component of group vib and/or group VIII, and group vib metal component is preferably molybdenum and/or tungsten, and the metal of group VIII is preferably Gu He ∕ or nickel.With the weight of catalyst for benchmark, the content of group vib metal (with oxide basis) is 10.0% ~ 30.0%, and the content of group VIII metal (with oxide basis) is 3.0% ~ 8.0%.Catalyst carries out sulfuration before use, and metal component is sulphided state under reactiveness, to improve Hydrogenation.
In method for preparing catalyst of the present invention, adhesive is made up of little porous aluminum oxide and inorganic acid and/or organic acid.Aperture aluminium oxide pore volume used is 0.3 ~ 0.5mL/g, and specific area is 200 ~ 400m
2/ g.Peptization acid is inorganic acid and/or organic acid, such as nitric acid, acetic acid etc.
Drying condition described in step (3) is as follows: baking temperature is 100 ~ 150 DEG C, and drying time is 5 ~ 10 hours, controls filter cake butt 60% ~ 80%, then pulverizes, granularity control 100 ~ 200 order.
Mixed powder after dipping mixes with peptizing agent or adhesive by step (4), and then extruded moulding, catalyst shape can be column, clover, bunge bedstraw herb and other irregular strip etc., and length can be 3 ~ 8mm.Described drying can carry out 3 ~ 6 hours at the temperature of 80 DEG C ~ 150 DEG C, and roasting is 400 DEG C ~ 600 DEG C roastings 2 ~ 6 hours.
In hydrocracking catalyst of the present invention, hydrogenation active metals component is distributed in carrier powder equably, adopt containing hydrogenation active metals component and the dipping solution impregnated alumina of organic reagent and the method load hydrogenation active metals component of molecular sieve mixed powder, because the mixed powder conjunction of aluminium oxide and molecular sieve has stronger solution absorbability, less carrier can be adopted to bear more hydrogenation active metals components, hydrogenation active metals can be made to be distributed to equably in aluminium oxide and molecular sieve, to be conducive to hydrogenation component and to coordinate with the function of Cracking Component.Hydrocracking catalyst of the present invention can make metal disperse well on a catalyst support, hydrogenating function and cracking function can Proper Matchs, and under the strong cracking functional conditions of guarantee, appropriateness reduces Hydrogenation, add the cracking probability of heavy distillate, reach the object of the heavy naphtha that raises productivity and improves the quality.Adopt catalyst pore passage structure opening more prepared by the inventive method in addition, larger molecule can be made to react in the catalyst, be conducive to the diffusion of reactant and product, improve the ability of catalyst treatment more heavy and inferior raw material, improve the severity of hydrocracking technology.
In hydrocracking catalyst preparation process of the present invention, adopt containing hydrogenation active metals component and the dipping solution impregnated alumina of organic reagent and the mixed powder of molecular sieve, metal component can be made to load to equably in carrier, and maceration extract does not need higher metal concentration just can prepare the higher final catalyst prod of active metallic content.Add organic reagent in maceration extract, the high hydrocracking catalyst of active metallic content can be prepared under lower metallic solution concentration, and solution preparation is simple, stable in properties, be applicable to commercial scale and use.Dilute metal salt maceration extract containing organic reagent can reduce the viscosity of solution, reduce solution surface tension, the impact of capillary drag phenomena in dipping process can be weakened like this, hydrogenation metal is enable to be distributed in aluminium oxide and molecular sieve equably, not only can ensure that in catalyst, hydrogenation metal component has higher content, the decentralization of metal at carrier surface can also be improved further.Hydrocracking catalyst preparation method of the present invention is compared with the preparation method of other hydrocracking catalyst, in hydrogenation metal solution containing organic reagent, hydrogenation metal and organic reagent can form a kind of complex system, be conducive to the dispersion of metal, also help the aperture of improving final catalyst when active metallic content is higher, during conventional method Kaolinite Preparation of Catalyst, when particularly hydrogenation component load capacity is larger, the pore volume of catalyst, aperture and specific area all obviously reduce, even and if during a large amount of hydrogenation component of the inventive method load, to the pore volume of final catalyst, aperture and specific area affect less, hydrogenation component content can be obtained high, large pore volume, the wide-aperture hydrocracking catalyst of Large ratio surface sum.
Catalyst of the present invention adopts bakes to burn the article technique just can prepare catalyst prod; than conventional first Kaolinite Preparation of Catalyst carrier; the method for preparing catalyst step supporting hydrogenation metal again simplifies, and industrial preparation cost significantly declines, and is conducive to environmental protection and improves social benefit.In the preparation process of hydrocracking catalyst of the present invention, dipping solution can recycle.
Catalyst prepared by the present invention is owing to having larger pore volume and aperture, and preparation cost is lower, goes for the hydrocracking process of more heavy, inferior raw material.
When being used for heavy oil hydrocracking by hydrocracking catalyst of the present invention, particularly at condition of high voltage (10 ~ 20MPa) and the various inferior raw material of process (VGO, CGO and DAO), there is very high catalytic activity and naphtha selective, and the fragrant potential content of gained heavy naphtha is high, it is the catalytic reforming feed stock of extremely high-quality, under the prerequisite of producing naphtha to greatest extent, also can hold concurrently and produce high-quality hydrogenation tail oil, can preparing ethylene by steam cracking raw material the most.
Detailed description of the invention
Analytical method of the present invention: specific surface and pore volume adopt low temperature liquid nitrogen physisorphtion, relative crystallinity and cell parameter adopt x-ray diffraction method, silica alumina ratio (silica and alumina molar ratio) adopts chemical method, and meleic acid amount adopts Pyridine adsorption IR spectra method.In the present invention, wt% is mass fraction.
The following examples are used for illustrating in greater detail the present invention, but scope of the present invention is not only limited to the scope of these embodiments.
The physico-chemical property of the Y zeolite that hydrocracking catalyst of the present invention adopts is in table 1.
The physico-chemical property of the Si modification aluminium oxide that embodiment uses is: its pore volume is 0.95mL/g, and specific area is 400m
2/ g, the weight contents on dry basis of powder is 68%, SiO
2content be 12wt%.
Embodiment 1
For tungsten-nickel system, carry out the preparation of catalyst.
Preparing metal dipping solution, wherein the concentration of metal is 25.6g metal (with oxide basis)/100mL solution, ammonium citrate concentration is 4g/100mL solution, dipping temperature is 30 DEG C, and liquid-solid ratio is 6mL solution/g powder, floods the mixed powder of 66 grams of Si modification aluminium oxide and 200 grams of Y-1 molecular sieves, dip time is 2.5 hours, and 120 DEG C of dryings 8 hours, and be ground into 180 orders, obtain the mixed material (butt is 76.6wt%) of metallic components.
Get above-mentioned metallic components mixed material 370 grams and 259 grams of adhesives (butt 5.8wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.5) put into roller mixed grind, be rolled into paste, being extruded into diameter is 1.8mm cylinder.At 120 DEG C dry 5 hours, catalyst was cut into the length of 3 ~ 8mm, after pelletizing through temperature programming 510 DEG C of roastings 4 hours, obtain final catalyst, numbering HC-1 character is in table 2.
Embodiment 2
For tungsten-nickel system, carry out the preparation of catalyst.
Preparing metal dipping solution, wherein the concentration of metal is 25.6g metal (with oxide basis)/100mL solution, ammonium citrate concentration is 6g/100mL solution, dipping temperature is 30 DEG C, and liquid-solid ratio is 6mL solution/g powder, floods the mixed powder of 66 grams of Si modification aluminium oxide and 200 grams of Y-2 molecular sieves, dip time is 2.5 hours, and 120 DEG C of dryings 8 hours, and be ground into 180 orders, obtain the mixed material (butt is 76.6wt%) of metallic components.
Get above-mentioned metallic components mixed material 370 grams and 259 grams of adhesives (butt 5.8wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.5) put into roller mixed grind, be rolled into paste, being extruded into diameter is 1.8mm cylinder.At 120 DEG C dry 5 hours, catalyst was cut into the length of 3 ~ 8mm, after pelletizing through temperature programming 510 DEG C of roastings 4 hours, obtain final catalyst, numbering HC-2 character is in table 2.
Embodiment 3
For tungsten-nickel system, carry out the preparation of catalyst.
Preparing metal dipping solution, wherein the concentration of metal is 27.2g metal (with oxide basis)/100mL solution, ammonium citrate concentration is 8g/100mL solution, dipping temperature is 40 DEG C, and liquid-solid ratio is 8mL solution/g powder, floods the mixed powder of 133 grams of Si modification aluminium oxide and 134 grams of Y-1 molecular sieves, dip time is 4 hours, and 120 DEG C of dryings 8 hours, and be ground into 180 orders, obtain the mixed material (butt is 75.1wt%) of metallic components.
Get above-mentioned metallic components mixed material 380 grams and 259 grams of adhesives (butt 5.8wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.5) put into roller mixed grind, be rolled into paste, being extruded into diameter is 1.8mm cylinder.At 120 DEG C dry 5 hours, catalyst was cut into the length of 3 ~ 8mm, after pelletizing through temperature programming 510 DEG C of roastings 4 hours, obtain final catalyst, numbering HC-3 character is in table 2.
Embodiment 4
For tungsten-nickel system, carry out the preparation of catalyst.
Preparing metal dipping solution, wherein the concentration of metal is 28.9g metal (with oxide basis)/100mL solution, malonic acid concentration is 6g/100mL solution, dipping temperature is 20 DEG C, and liquid-solid ratio is 8 mL solution/g powders, floods the mixed powder of 133 grams of Si modification aluminium oxide and 100 grams of Y-1 molecular sieves, dip time is 2 hours, and 120 DEG C of dryings 8 hours, and be ground into 180 orders, obtain metallic components mixed material (butt is 70.2wt%).
Get above-mentioned metallic components mixed material 406 grams and 218 grams of adhesives (butt 5.8wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.5) put into roller mixed grind, be rolled into paste, being extruded into diameter is 1.8mm cylinder.At 120 DEG C dry 5 hours, catalyst was cut into the length of 3 ~ 8mm, after pelletizing through temperature programming 510 DEG C of roastings 4 hours, obtain final catalyst, numbering HC-4 character is in table 2.
Embodiment 5
For tungsten-nickel system, carry out the preparation of catalyst.
Preparing metal dipping solution, wherein the concentration of metal is 19.5g metal (with oxide basis)/100mL solution, acetic acid concentration is 2g/100mL solution, dipping temperature is 40 DEG C, and liquid-solid ratio is 8mL solution/g powder, floods the mixed powder of 66 grams of Si modification aluminium oxide and 200 grams of Y-2 molecular sieves, dip time is 3 hours, and 120 DEG C of dryings 8 hours, and be ground into 180 orders, obtain metallic components mixed material (butt is 79.2wt%).
Get above-mentioned metallic components mixed material 360 grams and 270 grams of adhesives (butt 5.8wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.5) put into roller mixed grind, be rolled into paste, being extruded into diameter is 1.8mm cylinder.At 120 DEG C dry 5 hours, catalyst was cut into the length of 3 ~ 8mm, after pelletizing through temperature programming 510 DEG C of roastings 4 hours, obtain final catalyst, numbering HC-5 character is in table 2.
Embodiment 6
For tungsten-nickel system, carry out the preparation of catalyst.
Preparing metal dipping solution, wherein the concentration of metal is 36.3g metal (with oxide basis)/100mL solution, malonic acid and acetic acid concentration are altogether for being 3g/100mL solution, dipping temperature is 25 DEG C, and liquid-solid ratio is 3mL solution/g powder, floods the mixed powder of 88 grams of Si modification aluminium oxide and 134 grams of Y-1 molecular sieves, dip time is 2 hours, and 120 DEG C of dryings 8 hours, and be ground into 180 orders, obtain the mixed material (butt is 76.3wt%) of metallic components.
Get above-mentioned metallic components mixed material 375 grams and 345 grams of adhesives (butt 5.8wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.5) put into roller mixed grind, be rolled into paste, being extruded into diameter is 1.8mm cylinder.At 120 DEG C dry 5 hours, catalyst was cut into the length of 3 ~ 8mm, after pelletizing through temperature programming 510 DEG C of roastings 4 hours, obtain final catalyst, numbering HC-6 character is in table 2.
Comparative example 1
Prepare the catalyst identical with HC-1 pulp furnish, adopt conventional first Kaolinite Preparation of Catalyst carrier, by the hydrocracking catalyst preparation method of supersaturation dipping hydrogenation metal.Get 66 grams of Si modification aluminium oxide and 200 grams of Y-1 molecular sieves and 260 grams of adhesive (butt 5.8wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.5) put into roller mixed grind, be rolled into paste, being extruded into diameter is 1.8mm cylinder, catalyst carrier is obtained through super-dry and roasting (540 DEG C, 3 hours).Then use tungsten nickel solution impregnated carrier, and obtain finished catalyst through super-dry and roasting (510 DEG C, 4 hours), be numbered DHC-1, character is in table 2.
Comparative example 2
Prepare the catalyst identical with HC-1 pulp furnish, adopt conventional first Kaolinite Preparation of Catalyst carrier, by the hydrocracking catalyst preparation method of supersaturation dipping hydrogenation metal.Get 66 grams of Si modification aluminium oxide and 200 grams of Y-1 molecular sieves and 260 grams of adhesive (butt 5.8wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.5) put into roller mixed grind, be rolled into paste, being extruded into diameter is 1.8mm cylinder, catalyst carrier is obtained through super-dry and roasting (540 DEG C, 3 hours).Then with the solution impregnating carrier containing tungsten nickel and ammonium citrate, containing tungsten nickel in mixed solution is 48.2 g/100mL solution, and the amount of ammonium citrate is 4g/100mL solution, and through super-dry and roasting (510 DEG C, 4 hours) obtain finished catalyst, be numbered DHC-2, character is in table 2.
Comparative example 3
Prepare the catalyst identical with HC-5 pulp furnish, adopt conventional first Kaolinite Preparation of Catalyst carrier, by the hydrocracking catalyst preparation method of supersaturation dipping hydrogenation metal (containing acetic acid, concentration is 2g/100mL).Get 66 grams of Si modification aluminium oxide and 200 grams of Y-2 molecular sieves and 260 grams of adhesive (butt 5.8wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.5) put into roller mixed grind, add water, be rolled into paste, being extruded into diameter is 1.8mm cylinder, catalyst carrier is obtained through super-dry and roasting (540 DEG C, 3 hours).Then use the solution impregnating carrier of tungsten nickel and organic reagent, containing tungsten nickel in mixed solution is 46.5 g/100mL solution, and acetic acid concentration is 2g/100mL solution, and through super-dry and roasting (510 DEG C, 4 hours) obtain finished catalyst, be numbered DHC-3, character is in table 2.
Embodiment 5
This embodiment describes catalyst activity evaluation result.Fixed bed hydrogenation experimental rig is evaluated, and appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200:1, volume space velocity 1.5h
-1; Feedstock oil is vacuum distillate (VGO), and character lists in table 3.Catalyst HC-1 with DHC-1, DHC-2 are evaluated under identical process conditions, the evaluation result obtained lists in table 4.
As can be seen from evaluation result, under identical process conditions, the yield, quality etc. of catalyst heavy naphtha of the present invention are all better than reference catalyst.Therefore hydrocracking catalyst of the present invention process more inferior raw material time there is very high activity, and the heavy naphtha that can raise productivity and improve the quality.The hydrogenation tail oil simultaneously produced has very high paraffinicity and low BMCI value, is the preparing ethylene by steam cracking raw material of very high-quality.
table 1 Y zeolite physico-chemical property
| Numbering | Y-1 | Y-2 |
| Hydrothermal conditions | ||
| Temperature, DEG C | 550 | 580 |
| Pressure, MPa | 0.1 | 0.2 |
| Time, h | 1.5 | 2.0 |
| Acid reaction variables | Hydrochloric acid | Nitric acid |
| Treatment temperature, DEG C | 95 | 100 |
| Acid concentration, mol/L | 0.3 | 0.4 |
| Cell parameter, nm | 2.439 | 2.436 |
| Silica alumina ratio | 28.5 | 39.6 |
| Relative crystallinity, % | 115 | 118 |
| Specific area, m 2/g | 768 | 789 |
| Total pore volume, ml/g | 0.436 | 0.451 |
| Infrared acidity, mmol/g | 0.649 | 0.535 |
the physico-chemical property of table 2 catalyst
| Numbering | HC-1 | HC-2 | HC-3 | HC-4 | HC-5 | HC-6 | DHC-1 | DHC-2 | DHC-3 |
| Al 2O 3，wt% | 21.62 | 20.66 | 33.68 | 28.11 | 20.63 | 24.88 | 21.54 | 21.39 | 20.55 |
| SiO 2，wt% | 58.38 | 59.34 | 41.32 | 31.89 | 59.37 | 40.12 | 58.67 | 58.43 | 58.98 |
| WO 3，wt% | 15.10 | 15.05 | 20.30 | 24.50 | 15.06 | 26.87 | 14.89 | 15.33 | 15.23 |
| NiO，wt% | 4.90 | 4.95 | 4.70 | 10.50 | 4.94 | 8.13 | 4.90 | 4.85 | 5.24 |
| Pore volume, mL/g | 0.456 | 0.432 | 0.389 | 0.367 | 0.441 | 0.358 | 0.365 | 0.360 | 0.347 |
| Specific area, m 2/g | 385 | 379 | 342 | 316 | 395 | 295 | 311 | 306 | 268 |
table 3 feedstock oil main character
| Feedstock oil | Vacuum distillate |
| Density (20 DEG C), kg/m 3 | 940.5 |
| Boiling range, DEG C | |
| IBP/10% | 328/417 |
| 30%/50% | 456/469 |
| 70%/90% | 500/521 |
| 95%/EBP | 547/575 |
| Nitrogen, μ g/g | 1575 |
| Carbon, wt% | 85.25 |
| Hydrogen, wt% | 11.96 |
| Carbon residue, wt% | 0.35 |
table 4 catalyst performance evaluation result
| Catalyst | HC-1 | DHC-1 | DHC-2 |
| Feedstock oil | Vacuum distillate | Vacuum distillate | Vacuum distillate |
| Volume space velocity during liquid, h -1 | 1.5 | 1.5 | 1.5 |
| Reaction stagnation pressure, MPa | 14.7 | 14.7 | 14.7 |
| Hydrogen to oil volume ratio | 1200:1 | 1200:1 | 1200:1 |
| Reaction temperature, DEG C | 356 | 360 | 359 |
| Product yield and character | |||
| Heavy naphtha | |||
| Yield, wt% | 42.0 | 40.3 | 40.6 |
| Virtue is dived, wt% | 59.9 | 56.2 | 57.0 |
| Heavy naphtha is selective ＊，% | 81.71 | 76.91 | 77.48 |
| Jet fuel | |||
| Yield, wt% | 20.1 | 19.2 | 19.4 |
| Smoke point, mm | 30 | 25 | 26 |
| Aromatic hydrocarbons, v% | 4.2 | 6.1 | 5.9 |
| Diesel oil | |||
| Yield, wt% | 10.3 | 9.6 | 9.7 |
| Cetane number | 67.6 | 61.8 | 63.5 |
| Tail oil | |||
| Yield, wt% | 18.2 | 18.6 | 18.5 |
| BMCI value | 7.1 | 10.5 | 9.3 |
*: heavy naphtha is selective=heavy naphtha yield/(in 1-oily yield-tail oil yield) × 100%
Claims (11)
1. a preparation method for hydrocracking catalyst, comprises following process:
(1) dipping solution of preparation containing hydrogenation active metals and organic reagent, described organic reagent is one or more in acetic acid, malonic acid, citric acid, ammonium citrate; In described dipping solution, the concentration of organic reagent is 1g/100mL ~ 20g/100mL, and the consumption of hydrogenation active metals is 5.0g ~ 50.0g hydrogenation active metals/100mL;
(2) by molecular sieve with alumina powder jointedly to mix,
(3) mixed powder of dipping solution impregnation steps (2) gained prepared by step (1), after filtration, dry, pulverize; During the mixed powder of dipping solution impregnation steps (2) gained prepared by step (1), the liquid-solid ratio of employing is 2 ~ 10mL solution/g powder;
(4) material that step (3) obtains is put into roller together with peptizing agent or adhesive to roll, obtain final catalyst through overmolding, drying and roasting; Described hydrocracking catalyst, comprise molecular sieve, aluminium oxide, hydrogenation active metals component, hydrogenation active metals component is group vib metal component and/or group VIII is hydrogenation component, with the weight of hydrocracking catalyst for benchmark, the content of molecular sieve is 20% ~ 70%, the content of aluminium oxide is 10% ~ 40%, hydrogenation active metals component with the content of oxide basis for 15% ~ 38%.
2. in accordance with the method for claim 1, it is characterized in that in described hydrocracking catalyst, group vib metal component with the content of oxide basis for 10.0% ~ 30.0%, group VIII metal with the content of oxide basis for 3.0% ~ 8.0%.
3. in accordance with the method for claim 1, it is characterized in that, the temperature of step (3) described dipping is 10 ~ 50 DEG C.
4. in accordance with the method for claim 1, it is characterized in that one or more that described molecular sieve comprises in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve.
5. in accordance with the method for claim 1, it is characterized in that described molecular sieve is that wherein hydrothermal conditions is: gauge pressure 0.05 ~ 0.4MPa, temperature 500 ~ 600 DEG C, 0.5 ~ 5 hour processing time successively through hydrothermal treatment consists and acid-treated Y zeolite.
6. in accordance with the method for claim 5, it is characterized in that the character of described Y zeolite is as follows: specific area is 600m
2/ g ~ 900m
2/ g, total pore volume is 0.30mL/g ~ 0.5mL/g, and relative crystallinity is 90% ~ 130%, and cell parameter is 2.435 ~ 2.445nm, and silica alumina ratio is 5 ~ 40, and meleic acid amount is 0.3 ~ 0.8mmol/g.
7. in accordance with the method for claim 1, it is characterized in that aluminium oxide used is Si modification aluminium oxide, its character is as follows: pore volume is 1.4mL/g ~ 1.8mL/g, and specific area is 500m
2/ g ~ 550m
2/ g, silica content is 10wt% ~ 15wt%.
8. in accordance with the method for claim 1, it is characterized in that, group vib metal component is molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel.
9. in accordance with the method for claim 1, it is characterized in that, adhesive is made up of little porous aluminum oxide and inorganic acid and/or organic acid; Aperture aluminium oxide pore volume used is 0.3 ~ 0.5mL/g, and specific area is 200 ~ 400m
2/ g; Peptization acid is inorganic acid and/or organic acid.
10. in accordance with the method for claim 1, it is characterized in that the drying condition described in step (3) is as follows: baking temperature is 100 ~ 150 DEG C, drying time is 5 ~ 10 hours, and control filter cake butt at 60wt% ~ 80wt%, then pulverize, granularity control 100 ~ 200 order.
11. in accordance with the method for claim 1, and it is characterized in that the drying described in step (4) carries out 3 ~ 6 hours at the temperature of 80 DEG C ~ 150 DEG C, roasting is 400 DEG C ~ 600 DEG C roastings 2 ~ 6 hours.
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| CN103394368B (en) * | 2013-07-22 | 2015-06-17 | 中国海洋石油总公司 | Light oil type hydrocracking catalyst with composite molecular sieve as well as preparation method and application thereof |
| CN104549345B (en) * | 2013-10-23 | 2017-01-25 | 中国石油化工股份有限公司 | Active hydrocracking proppant and preparation method thereof |
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| CN107344102B (en) * | 2016-05-05 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation method |
| CN108262076A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | Catalyst carrier for hydrgenating 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 |
| CN112717984A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrocracking catalyst, and preparation method and application thereof |
| CN114471670B (en) * | 2020-10-27 | 2023-08-01 | 中国石油化工股份有限公司 | Catalyst for hydrocracking and preparation method and application thereof |
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