CN103191775B - Preparation method of hydrocracking catalyst - Google Patents
Preparation method of hydrocracking catalyst Download PDFInfo
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- CN103191775B CN103191775B CN201210443121.4A CN201210443121A CN103191775B CN 103191775 B CN103191775 B CN 103191775B CN 201210443121 A CN201210443121 A CN 201210443121A CN 103191775 B CN103191775 B CN 103191775B
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Abstract
The invention discloses a preparation method of a hydrocracking catalyst. The preparation method comprises carrying out low-temperature hydro-thermal treatment on alumina dry gel powder, dipping the alumina dry gel powder into a hydrogenation active metal-containing solution, carrying out drying, and carrying out full grinding, molding, drying and calcination of the dipped material with a molecular sieve in the presence of a peptizing agent or a binder. The preparation method improves a catalyst pore structure. The hydrocracking catalyst has a large specific surface area and a large pore volume, is conducive to optimization cooperation of a hydrogenation ingredient and a cracking ingredient, has high catalytic activity, and is suitable for hydrocracking yield-increasing of high-quality heavy naphtha from vacuum distillate having a high dry point and poor quality and for improvement of tail oil product quality.
Description
Technical field
The present invention relates to the preparation method of a kind of preparation method's of hydrocracking catalyst, particularly heavy distillate hydrocracking catalyst.
Background technology
Hydrocracking technology has that adaptability to raw material is strong, product solution flexibility large, object product selectivity is high, good product quality, added value high, various heavys, inferior raw material directly can be transformed to the industrial chemicals of clean fuel oil and high-quality, become one of modern oil refining and the most important heavy oil deep processing of petro chemical industry technique, obtained increasingly extensive application at home and abroad.Although the existing hydrocracking unit working ability of China has exceeded 50.0Mt/a, but due to domestic crude quality variation year by year, sour crude import volume significantly increases, environmental protection is increasingly strict to oil refining process itself and petroleum product-quality requirement, and market constantly increases clean fuel oil and industrial chemicals demand.Therefore, hydrocracking technology also will obtain applying more widely, also hydrocracking technology itself be had higher requirement simultaneously.
Along with developing rapidly of China's economy, market sharply increases the demand of chemical products, 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 depend on atmospheric and vacuum distillation unit can not meet the requirement of market to industrial chemicals, the breach of chemical raw material is increasing, wherein taking naphtha as the supply of main chemical industry light oil raw materials for production more urgent.Hydrocracking technology can be produced sulphur and the high heavy naphtha product of extremely low, the fragrant potential content of nitrogen content, can be directly for the catalytic reforming unit of 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, while 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 improving taking production industrial chemicals as the hydrocracking technology level of object product (being light oil type hydrogen cracking, to produce the light oil such as naphtha as major product), the industrial chemicals that raises productivity and improves the quality is very necessary 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 decompression deep drawing technology, make doing by original 520 DEG C of vacuum distillate bring up to 600 DEG C of left and right, 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 are also more and more, greatly increased the difficulty of hydrocracking, these are all had higher requirement to hydrocracking technology and hydrocracking catalyst.
Hydrocracking catalyst is a kind of bifunctional catalyst, has cracking activity and hydrogenation activity simultaneously.Cracking activity is mainly provided by various molecular sieves, and hydrogenation activity is mainly supplied by the metal carrying of periodic table of elements ZhongⅥ B family and VIII family.For 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 molecular sieve and the hydrogenation component of cracking activity component.
US6174429 discloses a kind of hydrocracking catalyst, at least one acidifying that this catalyst contains 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 8 left and right, SiO
2/ Al
2o
3skeleton mol ratio is the Y zeolite of 20 left and right, at least one group VIII metal component of 0.1~30wt%, at least one of 1~40wt% group vib metal component, at least one VIIA family element of the auxiliary agent of 0.1~20wt% and 0~20wt%.This catalyst adopts first prepares carrier, after support the preparation method of hydrogenation metal, catalyst has good activity and stability, but heavy naphtha and boat yield of coal are 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 patent such as US5086032 and US4820677 has also been introduced employing coprecipitation method and has been prepared high tenor hydrotreating catalyst, prepare tenor up to 50% ~ 95% hydrotreating catalyst, the Hydrogenation of catalyst has obtained great raising, and product quality has obtained great improvement.Although this type of catalyst has higher Hydrogenation, but catalyst pore volume and specific area are relatively little, generally can only process diesel oil following compared with the cut of lightweight, and because coprecipitation method Kaolinite Preparation of Catalyst using rate of metal is low, metal dispersion can be bad, and complicated process of preparation, product stability is poor, so catalyst cost performance is not high.
Kneading method also can be prepared the catalyst of various active metallic contents, 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, coordinate with the optimization of cracking component by hydrogenation component, increase the cracking probability of heavy distillate, meet raise productivity and improve the quality heavy naphtha and the object of improving tail oil product quality.
The preparation method of hydrocracking catalyst of the present invention, comprise: aluminum oxide dry glue powder is carried out to hydrothermal treatment consists, hydrothermal treatment consists condition is as follows: temperature is 30~90 DEG C, gauge pressure is 0.01~0.1MPa, adopt water vapour closed processes, processing time is 1~3 hour, then adopt the aluminum oxide dry glue powder after the solution impregnation hydrothermal treatment consists that contains hydrogenation active metals component composition, after drying, again with molecular sieve under the effect of peptizing agent or binding agent, through rolling, moulding, dry and roasting, obtain hydrocracking catalyst.
In the preparation method of hydrocracking catalyst of the present invention, the water content of the aluminum oxide dry glue powder after hydrothermal treatment consists is controlled at 30wt%~50wt%.
Hydrocracking catalyst preparation process particular content of the present invention is as follows:
(1) select suitable hydrothermal treatment consists condition to process aluminum oxide dry glue powder, make aluminium oxide there is the ability of good pore passage structure and suitable supported active metal;
(2) kind of selective hydrocracking catalyst hydrogenation metal component used, selects suitable compound, is mixed with dipping solution;
(3) select Kaolinite Preparation of Catalyst modified molecular screen used;
(4) with the aluminum oxide dry glue powder after the dipping solution dipping modification preparing, make hydrogenation active metals component dispersed, and through press filtration, dry and pulverizing, stand-by; Wherein baking temperature is 100~150 DEG C, and be 5~10 hours drying time, and the butt of dry rear material is 60wt%~80wt%;
(5) aluminum oxide dry glue powder of the carried metal component in step (4) is put into roller with molecular sieve together with peptizing agent or adhesive and roll, obtain final hydrocracking catalyst through overmolding, dry and roasting.Described dry can carrying 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.
In hydrocracking catalyst of the present invention, molecular sieve can adopt molecular sieve conventional in hydrocracking catalyst, molecular sieve generally comprises one or more in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve etc., required molecular sieve can require to carry out suitable modification according to serviceability, preferably Y zeolite, hydrogenation active metals component is group vib and/or group VIII metal, group vib metal is preferably Mu with ∕ or tungsten, and the metal of group VIII is preferably Gu with ∕ or nickel.Taking the weight of hydrocracking catalyst as benchmark, the content of molecular sieve is 30%~70%, and the content of aluminium oxide is 10%~40%, and hydrogenation active metals component counts 19%~35% with oxide.Hydrocracking catalyst preferably composed as follows: taking the weight of hydrocracking catalyst as benchmark, the content of Y zeolite is 30%~70%, the content of aluminium oxide is 10%~40%, group vib metal component is taking the content of oxide as 15.0%~30.0%, and group VIII metal is taking the content of oxide as 4.0%~8.0%.
The character of the hydrocracking catalyst that the inventive method obtains is as follows: specific area is 250~550m
2/ g, pore volume is 0.30~0.60mL/g.
In hydrocracking catalyst of the present invention, Y zeolite preferred property is as follows: specific area is 600m
2/ g~900m
2/ g, total pore volume 0.30mL/g~0.5mL/g, relative crystallinity 90%~130%, cell parameter 2.435~2.445nm, sial (silica and aluminium oxide) mol ratio 15~70, is preferably 30~70, meleic acid amount 0.5~1.0mmol/g.
In hydrocracking catalyst of the present invention, the character of aluminum oxide dry glue powder used is as follows: pore volume is 0.6~1.3mL/g, is preferably 0.7~1.1mL/g, and specific area is 300~600m
2/ g.
Hydrocracking catalyst of the present invention vulcanizes before use, and active metal component is sulphided state under reactiveness, to improve Hydrogenation.
In hydrocracking catalyst of the present invention, hydrogenation active metals component loads on aluminium oxide, does not contain hydrogenation active metals component in molecular sieve component duct.
In method for preparing catalyst of the present invention, aluminum oxide dry glue powder, molecular sieve etc. can adopt commercial goods, also can prepare by this area conventional method.
In method for preparing catalyst of the present invention, peptizing agent can adopt conventional inorganic acid and/or organic acid.Adhesive is to be 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.
In hydrocracking catalyst of the present invention, hydrogenation active metals component is mainly distributed in aluminium oxide, the water content of the aluminum oxide dry glue powder that generally adopted is 20wt%~30wt%, there is the ability of very strong carried metal, make to adopt the method load hydrogenation component of hydrogenation active metals component solution impregnated alumina dry glue powder, because aluminum hydroxide solid elastomer powder has stronger solution absorbability, in aluminium oxide load a large amount of metals, cause intermetallic overlapping, reduce the utilization ratio of metal, catalyst of the present invention adopts low-temperature hydrothermal to process aluminum oxide dry glue powder for this reason, make aluminum oxide dry glue powder there is the water content of 30wt%~50wt%, can improve again the pore passage structure of aluminium oxide simultaneously, hydrogenation active metals component can be dispersed in aluminium oxide simultaneously, avoid the impact of hydrogenation active metals component on cracking component surface property, being conducive to hydrogenation component coordinates with the function of cracking component.The inventive method can make active metal be dispersed in well in catalyst carrier, after overactivation, match with cracking function, ensureing under the condition of strong cracking function, appropriateness reduces Hydrogenation, increase the cracking probability of heavy distillate, reached raise productivity and improve the quality heavy naphtha and the object of improving hydrogenation tail oil product quality.
In hydrocracking catalyst preparation process of the present invention, adopt active metal component solution impregnation aluminum oxide dry glue powder, metal component is loaded in aluminium oxide equably, and maceration extract does not need higher metal concentration just can prepare the suitable final catalyst prod of active metallic content.Owing to not needing the dipping solution of high concentration, solution preparation is simple, and stable in properties is applicable to commercial scale and uses.Rarer slaine maceration extract can reduce the viscosity of solution, reduces solution surface tension, can weaken like this impact of capillary resistance phenomenon in dipping process.Not only can ensure that in catalyst, active metal component has suitable content, can also further improve the decentralization of metal at carrier surface.Hydrocracking catalyst preparation method of the present invention is compared with flooding the method for hydrogenation component after carrier moulding, also help the aperture of improving final catalyst, after conventional method carrier impregnation hydrogenation component, when particularly hydrogenation component load capacity is larger, pore volume, aperture and the specific area of catalyst all obviously reduces, even and when a large amount of hydrogenation activity component of the inventive method load, pore volume on final catalyst, aperture and specific area impact are less, can obtain that hydrogenation component content is high, large pore volume, bigger serface and wide-aperture hydrocracking catalyst.
In the preparation process of hydrocracking catalyst of the present invention, dipping solution can recycle.High-temperature calcination process once only in catalyst preparation process, therefore the method has that preparation technology is simple, cost is low, energy consumption is low, pollute the features such as little, and applicable commercial scale is promoted the use of.The catalyst of preparation is owing to having larger pore volume and aperture, and preparation cost is lower, goes for the more hydrocracking process of heavy, inferior raw material.
Detailed description of the invention
Hydrocracking catalyst of the present invention is to adopt hydrogenation metal to be first impregnated on aluminum oxide dry glue powder, then with molecular sieve under the effect of peptizing agent or binding agent, through fully rolling, moulding, dry and roasting and the catalyst that obtains;
Wherein said metal is taking tungsten-nickel system as example.The low-temperature hydrothermal treatment conditions of aluminum oxide dry glue powder are: treatment temperature is 30~90 DEG C, gauge pressure is 0.01~0.1MPa, adopt water vapour closed processes, processing time is 1~3 hour, the water content of the alumina dry glue after hydrothermal treatment consists is preferably 30wt%~50wt%, have good macroporous structure, this pore passage structure can have very large reservation degree in shaping of catalyst process, has ensured that final catalyst has suitable macropore structure.At 10~50 DEG C of temperature, preferably 15~40 DEG C, be that 2:1~10:1(liquid-solid ratio unit is mL solution/g solid in liquid-solid ratio), aluminum oxide dry glue powder after the solution impregnation hydrothermal treatment consists that employing contains hydrogenation active metals component composition, be uniformly mixed slurry with certain stir speed (S.S.), mixing time is 1~5 hour, then mixed slurry is carried out to press filtration, after press filtration, filter cake is dried, baking temperature is 100~150 DEG C, be 5~10 hours drying time, after dry, material butt is 60wt%~80wt%, then pulverize, granularity control 100~200 orders.
The solution that what the present invention selected contain hydrogenation active metals component composition, be generally group vib and/or group VIII metallic salt, as one or more of the saline solution of the metals such as W, Mo, Ni, Co, active metal solution concentration is generally 10~50g metal/100mL, and wherein metal is in oxide.
The Y zeolite that hydrocracking catalyst of the present invention adopts is preferably the Modified Zeolite Y after hydrothermal treatment consists and acid treatment, hydrothermal treatment consists condition is: gauge pressure 0.05~0.4MPa, is preferably 0.1~0.2MPa, 500~600 DEG C of temperature, 0.5~5.0 hour processing time, preferably 1~3 hour.Molecular sieve after hydrothermal treatment consists, again through peracid treatment, generally adopts finite concentration inorganic acid and/or organic acid to carry out acidification.
By the aluminum oxide dry glue powder of Modified Zeolite Y, supported active metal and peptizing agent or adhesive mixing, then extruded moulding, catalyst shape can be column, clover, bunge bedstraw herb and other irregular strip etc., length is controlled at 3~8mm.Described dry can carrying 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.
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 embodiment.In the inventive method, wt% is mass fraction.
Analytical method of the present invention: specific area 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 infra-red sepectrometry.
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 aluminum oxide dry glue powder that embodiment uses is as follows: pore volume is 1.0mL/g, and specific area is 450m
2/ g, the weight contents on dry basis of aluminium oxide is 75%.The percentage composition not relating in embodiment is weight percentage.
Embodiment 1
Get aluminum oxide dry glue powder 1000g and carry out steam treatment, at gauge pressure 0.05MPa, hydrothermal treatment consists temperature is 45 DEG C, and the processing time is 1.5 hours, and the water content of the aluminum oxide dry glue powder after the hydrothermal treatment consists obtaining is 35wt%, and pore volume is 1.1mL/g, and specific area is 440m
2/ g, is numbered LA-1.
Embodiment 2
Get aluminum oxide dry glue powder 1000g and carry out steam treatment, at gauge pressure 0.08MPa, hydrothermal treatment consists temperature is 75 DEG C, and the processing time is 2 hours, and the water content of the aluminum oxide dry glue powder after the hydrothermal treatment consists obtaining is 43wt%, and pore volume is 1.15mL/g, and specific area is 420m
2/ g, is numbered LA-2.
Embodiment 3
Get aluminum oxide dry glue powder 1000g and carry out steam treatment, at gauge pressure 0.1MPa, hydrothermal treatment consists temperature is 90 DEG C, and the processing time is 3 hours, and the water content of the aluminum oxide dry glue powder after the hydrothermal treatment consists obtaining is 50wt%, and pore volume is 1.17mL/g, and specific area is 415m
2/ g, is numbered LA-3.
Embodiment 4
Taking tungsten-nickel system as example, carry out the preparation of catalyst.
The dipping solution concentration of preparation tungstenic, nickel is 26.5g metal (in oxide)/100mL solution, dipping temperature is 30 DEG C, be that 4:1(liquid-solid ratio unit is mL solution/g solid in liquid-solid ratio, following examples are same), dipping 200g LA-1 aluminum oxide dry glue powder, dip time is 2.5 hours, is then dried 8 hours at 120 DEG C, be ground into 180 orders, must be containing the alumina dry glue powder mixture (butt is 74.3wt%) of active metal component.
Getting above-mentioned alumina dry glue powder mixture, Y-1 molecular sieve 509g(butt containing active metal component is 85wt%) and 144.5 grams of adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, being extruded into diameter is 1.8mm cylinder.At 120 DEG C, be dried 5 hours, catalyst is cut into the length of 3~8mm, and at 510 DEG C, roasting 4 hours, obtains final catalyst, and numbering HC-1 character is in table 2.
Embodiment 5
Taking tungsten-nickel system as example, carry out the preparation of catalyst.
The solution concentration of preparation tungstenic, nickel is 21g metal (in oxide)/100mL solution, dipping temperature is 20 DEG C, liquid-solid ratio is 6:1, dipping 200g LA-2 aluminum oxide dry glue powder, dip time is 4 hours, then be dried 8 hours at 120 DEG C, and be ground into 180 orders, must be containing the aluminum hydroxide solid elastomer powder mixture (butt is 70.5wt%) of active metal component.
Getting above-mentioned alumina dry glue powder mixture, Y-1 molecular sieve 203g(butt containing active metal component is 85wt%) and 72.2 grams of adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, being extruded into diameter is 1.8mm cylinder.At 120 DEG C, be dried 5 hours, catalyst is cut into the length of 3~8mm, and at 510 DEG C, roasting 4 hours, obtains final catalyst, and numbering HC-2 character is in table 2.
Embodiment 6
Taking tungsten-nickel system as example, carry out the preparation of catalyst.
The solution concentration of preparation tungstenic, nickel is 17.6g metal (in oxide)/100mL solution, dipping temperature is 20 DEG C, liquid-solid ratio is 4:1, dipping 200g LA-1 aluminum oxide dry glue powder, dip time is 3 hours, then be dried 8 hours at 120 DEG C, and be ground into 180 orders, must be containing the alumina dry glue powder mixture (butt is 72.5wt%) of active metal component.
Getting above-mentioned alumina dry glue powder mixture, Y-1 molecular sieve 306g(butt containing active metal component is 85wt%) and 86.7 grams of adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, being extruded into diameter is 1.8mm cylinder.At 120 DEG C, be dried 5 hours, catalyst is cut into the length of 3~8mm, and at 510 DEG C, roasting 4 hours, obtains final catalyst, and numbering HC-3 character is in table 2.
Embodiment 7
Taking tungsten-nickel system as example, carry out the preparation of catalyst.
The solution concentration of preparation tungstenic, nickel is 39.8g metal (in oxide)/100mL solution, dipping temperature is 20 DEG C, liquid-solid ratio is 5:1, dipping 200g LA-3 aluminum oxide dry glue powder, dip time is 3 hours, and be dried 8 hours at 120 DEG C, and be ground into 180 orders, must be containing the mixed powder compound (butt is 69.1wt%) of the alumina dry glue of active metal component.
Getting above-mentioned alumina dry glue powder mixture, Y-2 molecular sieve 153g(butt containing active metal component is 85wt%) and 72.2 grams of adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, being extruded into diameter is 1.8mm cylinder.At 120 DEG C, be dried 5 hours, catalyst is cut into the length of 3~8mm, and at 510 DEG C, roasting 4 hours, obtains final catalyst, and numbering HC-4 character is in table 2.
Comparative example 1
Prepare the catalyst identical with HC-3 raw material proportioning, adopt conventional first Kaolinite Preparation of Catalyst carrier (aluminum oxide dry glue powder is without hydrothermal treatment consists), by the hydrocracking catalyst preparation method of supersaturation dipping hydrogenation active metals.Get 200 g aluminum oxide dry glue powders, Y-1 molecular sieve 306g(butt is 85wt%) and 86.7 grams of adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, being extruded into diameter is 1.8mm cylinder, within 3 hours, obtains catalyst carrier through super-dry and 540 DEG C of roastings.Then use the solution impregnating carrier of tungstenic, nickel, and within 4 hours, obtain catalyst finished product through super-dry and 510 DEG C of roastings, be numbered DHC-1, character is in table 2.
Comparative example 2
Prepare the catalyst identical with HC-4 raw material proportioning, adopt conventional first Kaolinite Preparation of Catalyst carrier, by the hydrocracking catalyst preparation method of supersaturation dipping hydrogenation metal.Get 200 g aluminum oxide dry glue powders, Y-2 molecular sieve 153g(butt is 85wt%) and 72.2 grams of adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, being extruded into diameter is 1.8mm cylinder, within 3 hours, obtains catalyst carrier through super-dry and 540 DEG C of roastings.Then use the solution impregnating carrier of tungstenic, nickel, and within 4 hours, obtain catalyst finished product through super-dry and 510 DEG C of roastings, be numbered DHC-2, character is in table 2.
Comparative example 3
The dipping solution concentration of preparation tungstenic, nickel is 23.7g metal (in oxide)/100mL solution, dipping temperature is 30 DEG C, be that 4:1(liquid-solid ratio unit is mL solution/g solid in liquid-solid ratio), dipping 200g is without the aluminum oxide dry glue powder of hydrothermal treatment consists, dip time is 2.5 hours, then be dried 8 hours at 120 DEG C, be ground into 180 orders, must be containing the alumina dry glue powder mixture (butt is 73.3wt%) of active metal component.
Getting above-mentioned alumina dry glue powder mixture, Y-1 molecular sieve 395g(butt containing active metal component is 85wt%) and 144.5 grams of adhesive (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) put into roller mixed grind, add water, be rolled into paste, being extruded into diameter is 1.8mm cylinder.At 120 DEG C, be dried 5 hours, catalyst is cut into the length of 3~8mm, and at 510 DEG C, roasting 4 hours, obtains final catalyst, and numbering DHC-3 character is in table 2.
Embodiment 8
The present embodiment has been introduced catalyst activity evaluation result.On fixed bed hydrogenation experimental rig, evaluate, appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200:1, volume space velocity 1.5h when liquid
-1; Feedstock oil is vacuum distillate (VGO), and character is listed in table 3.Catalyst HC-3 and DHC-1, DHC-3 are evaluated under identical process conditions, and the evaluation result obtaining is listed in table 4.
Can be found out by evaluation result, under identical process conditions, yield, the quality etc. of catalyst heavy naphtha of the present invention is all better than reference catalyst.Therefore hydrocracking catalyst of the present invention has very high activity, and the heavy naphtha and improve the advantages such as tail oil product quality of can raising productivity and improving the quality.
the physico-chemical property of table 1 Modified Zeolite Y
Numbering | Y-1 | Y-2 |
Hydrothermal treatment consists condition | ? | ? |
Temperature, DEG C | 540 | 580 |
Pressure, MPa | 0.1 | 0.2 |
Time, h | 1 | 1.5 |
Acid treatment condition | ? | ? |
Acid | Hydrochloric acid | Hydrochloric acid |
Treatment temperature, DEG C | 95 | 100 |
Acid concentration, mol/L | 0.4 | 0.5 |
Modified Zeolite Y character | ? | ? |
Cell parameter, nm | 2.440 | 2.435 |
Silica alumina ratio | 31.9 | 50.2 |
Relative crystallinity, % | 110 | 111 |
Specific area, m 2/g | 872 | 846 |
Total pore volume, ml/g | 0.457 | 0.461 |
Infrared acidity, mmol/g | 0.75 | 0.58 |
the physico-chemical property of table 2 catalyst
Numbering | HC-1 | HC-2 | HC-3 | HC-4 | DHC-1 | DHC-2 | DHC-3 |
Al 2O 3,wt% | 22.7 | 34.1 | 32.1 | 37.0 | 32.1 | 36.9 | 27.9 |
SiO 2,wt% | 47.4 | 39.9 | 47.9 | 32.0 | 47.8 | 31.8 | 37.8 |
WO 3,wt% | 23.8 | 20.5 | 15.3 | 24.2 | 15.4 | 24.0 | 23.7 |
NiO,wt% | 6.1 | 5.5 | 4.7 | 6.8 | 4.7 | 7.3 | 6.2 |
Pore volume, mL/g | 0.42 | 0.37 | 0.48 | 0.37 | 0.37 | 0.28 | 0.36 |
Specific area, m 2/g | 320 | 339 | 380 | 342 | 259 | 235 | 278 |
table 3 feedstock oil main character
Feedstock oil | Vacuum distillate |
Density (20 DEG C), kg/m 3 | 920.7 |
Boiling range, DEG C | ? |
? IBP/10% | 329/412 |
? 30%/50% | 451/472 |
? 70%/90% | 491/524 |
? 95%/EBP | 533/547 |
Nitrogen, μ g/g | 1518 |
Carbon, wt% | 85.27 |
Hydrogen, wt% | 11.92 |
Carbon residue, wt% | 0.28 |
table 4 catalyst performance evaluation result
Catalyst | HC-3 | DHC-1 | DHC-3 |
Feedstock oil | Vacuum distillate | Vacuum distillate | Vacuum distillate |
Volume space velocity when 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 | 357 | 363 | 361 |
Product yield and character | ? | ? | ? |
Heavy naphtha | ? | ? | ? |
Yield, wt% | 42.5 | 40.1 | 40.9 |
Virtue is dived, wt% | 58.9 | 56.0 | 57.1 |
Heavy naphtha is selective *,% | 82.7 | 78.9 | 80.2 |
Jet fuel | ? | ? | ? |
Yield, wt% | 20.0 | 19.5 | 19.8 |
Smoke point, mm | 28 | 27 | 27 |
Aromatic hydrocarbons, v%(volume) | 5.0 | 6.1 | 5.5 |
Diesel oil | ? | ? | ? |
Yield, wt% | 10.5 | 11.3 | 11.0 |
Cetane number | 64.6 | 62.8 | 63.4 |
Tail oil | ? | ? | ? |
Yield, wt% | 18.1 | 18.4 | 18.2 |
BMCI value | 7.1 | 11.8 | 8.9 |
*: heavy naphtha is selective=heavy naphtha yield/(oily yield-tail oil yield in 1-) × 100%
Claims (9)
1. the preparation method of a hydrocracking catalyst, comprise following process: aluminum oxide dry glue powder is carried out to hydrothermal treatment consists, hydrothermal treatment consists condition is as follows: temperature is 30~90 DEG C, gauge pressure is 0.01~0.1MPa, adopt water vapour closed processes, processing time is 1~3 hour, then adopt the aluminum oxide dry glue powder after the solution impregnation hydrothermal treatment consists that contains hydrogenation active metals component composition, after drying, again with molecular sieve under the effect of peptizing agent or binding agent, through rolling, moulding, dry and roasting, obtain hydrocracking catalyst; The water content of the aluminum oxide dry glue powder after hydrothermal treatment consists is 30wt%~50wt%; Described hydrocracking catalyst, taking the weight of hydrocracking catalyst as benchmark, the content of molecular sieve is 30%~70%, the content of aluminium oxide is 10%~40%, hydrogenation active metals component counts 19%~35% with oxide, and the character of described hydrocracking catalyst is as follows: specific area is 250~550m
2/ g, pore volume is 0.30~0.60mL/g; The solution concentration that contains hydrogenation active metals component composition is 10~50g metal/100mL, and wherein metal is in oxide.
2. in accordance with the method for claim 1, it is characterized in that described molecular sieve is Y zeolite, hydrogenation active metals is group vib metal and/or group VIII metal, and wherein group vib metal is Mu with ∕ or tungsten, and the metal of group VIII is that Gu is with ∕ or nickel.
3. in accordance with the method for claim 2, 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 0.30mL/g~0.5mL/g, relative crystallinity 90%~130%, cell parameter 2.435~2.445nm, silica alumina ratio 15~70, meleic acid amount is 0.5~1.0mmol/g.
4. in accordance with the method for claim 3, it is characterized in that described hydrocracking catalyst, taking the weight of hydrocracking catalyst as benchmark, the content of Y zeolite is 30%~70%, the content of aluminium oxide is 10%~40%, group vib metal component is taking the content of oxide as 15.0%~30.0%, and group VIII metal is taking the content of oxide as 4.0%~8.0%.
5. in accordance with the method for claim 1, it is characterized in that the character of described aluminum oxide dry glue powder is as follows: pore volume is 0.6~1.3mL/g, and specific area is 300~600m
2/ g.
6. in accordance with the method for claim 1, it is characterized in that described peptizing agent adopts inorganic acid and/or organic acid, described binding agent is to be made up of little porous aluminum oxide and inorganic acid and/or organic acid, and aperture aluminium oxide pore volume used is 0.3~0.5mL/g, and specific area is 200~400m
2/ g.
7. in accordance with the method for claim 1, it is characterized in that, after aluminum oxide dry glue powder after the solution impregnation hydrothermal treatment consists that employing contains hydrogenation active metals component composition, carry out dry condition as follows: baking temperature is 100~150 DEG C, be 5~10 hours drying time, and the butt of dry rear material is 60wt%~80wt%.
8. according to the method described in claim 2 or 3, it is characterized in that described Y zeolite is the Modified Zeolite Y after hydrothermal treatment consists and acid treatment, hydrothermal treatment consists condition is: gauge pressure 0.05~0.4MPa, 500~600 DEG C of temperature, 0.5~5 hour processing time, molecular sieve after hydrothermal treatment consists, again through peracid treatment, adopts inorganic acid and/or organic acid to process.
9. in accordance with the method for claim 1, it is characterized in that, after shaping of catalyst, carry out dry condition as follows: at the temperature of 80 DEG C~150 DEG C dry 3~6 hours, roasting condition was: roasting is 400 DEG C~600 DEG C roastings 2~6 hours.
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