CN103191774B - Method for preparing hydrocracking catalyst - Google Patents
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- CN103191774B CN103191774B CN201210442999.6A CN201210442999A CN103191774B CN 103191774 B CN103191774 B CN 103191774B CN 201210442999 A CN201210442999 A CN 201210442999A CN 103191774 B CN103191774 B CN 103191774B
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Abstract
The invention discloses a method for preparing a hydrocracking catalyst. The method comprises the following steps of carrying out hydrothermal treatment on alumina dry gel powder, uniformly mixing the treated alumina dry gel powder and at least one acidic cracking material powder, dipping the mixture into a hydrogenation active ingredient-containing metal salt solution, carrying out filtration, drying and crushing, adding a peptizing agent or a binder into the crushed product, and carrying out molding, drying and calcination to obtain the hydrocracking catalyst. The hydrocracking catalyst has high hydrogenation active ingredient content, a large pore volume, a large aperture size and a large specific surface area, and is suitable for hydrocracking of a heavy vacuum distillate having a higher boiling point.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocracking catalyst, particularly can process heavy distillate and have the preparation method of highly active hydrocracking catalyst.
Background technology
The features such as hydrocracking technology has that adaptability to raw material is strong, production operation and product solution flexibility is large, good product quality, various heavy inferior chargings can be converted into high-quality jet fuel, diesel oil, lube basestocks and chemical industry naphtha and the tail oil preparing ethylene by steam cracking raw material of market in urgent need, 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.
But due to crude quality variation year by year, the sour crude of import 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.
Along with material quality becomes heavy, variation, and the demand of product quality upgrading and device capacity expansion revamping promotes increasingly, refinery has proposed more and more higher requirement to the performance of hydrocracking catalyst, and the performance of the hydrocracking catalyst of common metal content (in oxide hydrogenation metal total content generally lower than 30%) can not meet current actual user demand completely.Hydrocracking catalyst is the core of hydrocracking technology.Hydrocracking catalyst is the bifunctional catalyst by hydrogenating function and cracking function composition, wherein hydrogenating function is to be provided by hydrogenation active metals, improve the Hydrogenation of hydrocracking catalyst, be conducive to the saturated of aromatic hydrocarbons, can make further open loop conversion of polycyclic aromatic hydrocarbon, this is not only conducive to process the more Hydrocracking Raw Oil of heavy, poor quality, improve liquid product yield and produce high-quality hydrocracking product, can also further improve the poisoning ability of anti-organic nitrogen of catalyst, reduce green coke, carbon deposit, the service life of extending catalyst.Therefore, the Hydrogenation of raising hydrocracking catalyst is to meet to process inferior feedstock oil and produce the most important approach of high quality of products.
Conventionally the method that improves the Hydrogenation of hydrocracking catalyst mainly contains to be improved catalyst interpolation auxiliary agent and improves hydrogenation metal content etc.The method of adding auxiliary agent is mainly to improve the active force of carrier and hydrogenation metal by adding auxiliary agent, to improve the dispersion of hydrogenation metal on catalyst surface, and then the Hydrogenation of raising catalyst.CN01123767.8 has provided 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, makes 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.But the method for adding auxiliary agent has just maximally utilised a limited number of hydrogenation sites, can not make the Hydrogenation of hydrocracking catalyst be significantly improved, improve hydrocracking catalyst hydrogenation metal content and can significantly improve hydrogenation sites number, aspect hydrotreating catalyst, obtained extraordinary application.As patent Introductions such as US5086032, US4820677 and CN200410050730.9 employing coprecipitation method prepare 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 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.US 5,565,088 has introduced a kind of ZSM molecular sieve hydrocracking catalyst that contains, adopt preparation catalyst, the catalyst that the catalyst of its high metal content is lower than tenor can be produced boat coal and the diesel product of better quality, do not exceed 40% but its tenor is the highest, product quality improves limited.
By above analysis, adopt preparation catalyst, can give full play to the performance of hydrogenation metal, but the tenor of Kaolinite Preparation of Catalyst is very restricted; Although coprecipitation method can be prepared the hydrotreating catalyst of high tenor, the utilization rate of metal is not high, and catalyst pores structure is also subject to certain restrictions.Therefore, adopt infusion process to prepare high metal, and there is large pore volume, bigger serface hydrocracking catalyst, will there is very important Practical significance.
Summary of the invention
For deficiency and the hydrocracking catalyst preparation method's that metal dispersion is bad and utilization ratio is low of existing common metal content hydrocracking catalyst performance restriction, the invention provides the preparation method of a kind of large pore volume, bigger serface, hydrocracking catalyst that hydrogenation activity is high.
The preparation method of hydrocracking catalyst of the present invention, comprising:
(1) 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, and gauge pressure is 0.01～0.1MPa, adopts water vapour closed processes, and the processing time is 1～3 hour;
(2) acid to the aluminum oxide dry glue powder after hydrothermal treatment consists and at least one cracking material powder is mixed;
(3) preparation is containing the metal salt solution of hydrogenation activity component, hydrogenation activity component is generally one or more in W, Mo, Ni and Co, with the mixture of this metal salt solution impregnation steps (2) gained, then to filter, be dried, pulverize, hydrogenation activity component is dispersed in carrier material powder;
(4) in the mixture of step (3) gained, add peptizing agent or binding agent, fully roll aftershaping, then dry, roasting obtains hydrocracking catalyst.
Acid cracking material of the present invention comprises molecular sieve and/or amorphous acidic components, 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., and required molecular sieve can require to carry out suitable modification according to serviceability.Amorphous acidic components are generally one or more in amorphous aluminum silicide, amorphous silicon magnesium and clay etc.
While containing amorphous acidic components in acid cracking material in hydrocracking catalyst of the present invention, preferably amorphous acidic components are 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, the processing time is 1～3 hour.Amorphous acidic components hydrothermal treatment consists together after can mixing with aluminum oxide dry glue powder, also can carry out respectively hydrothermal treatment consists with aluminum oxide dry glue powder.
In hydrocracking catalyst of the present invention, the water content of the aluminum oxide dry glue powder that generally adopted or contained amorphous silica-alumina dry glue powder is 20wt%～30wt%, there is the ability of very strong adsorption activity metal component, while making to adopt the method load hydrogenation component of hydrogenation active metals component solution impregnated alumina dry glue powder or contained amorphous silica-alumina dry glue powder, easily cause intermetallic overlapping, reduce the utilization ratio of active metal, catalyst of the present invention adopts low-temperature hydrothermal to process aluminum oxide dry glue powder for this reason, preferred process contained amorphous silica-alumina dry glue powder, make aluminum oxide dry glue powder or contained amorphous silica-alumina dry glue powder there is the water content of 30wt%～50wt%, can improve again the pore passage structure of aluminium oxide and amorphous aluminum silicide simultaneously, hydrogenation component can be dispersed in carrier simultaneously, avoid the impact of hydrogenation component on cracking component surface property, being conducive to hydrogenation component coordinates with the function of cracking component.
The raw material with large pore volume, bigger serface in the preferred this area of amorphous acidic components and aluminium oxide.By weight content in final catalyst, the general content of acid carrier material is 1% ~ 65%, and in oxide, the weight content in catalyst is generally 25% ~ 50% to hydrogenation activity component, is preferably 30% ~ 45%, and alumina content is 10%～50%.
In step (3) containing in the metal salt solution of hydrogenation activity component, can add as required suitable adjuvant component, as contained one or more the compound in P, F, B, Zr, Ti etc. in dipping solution.
Peptizing agent is generally organic acid and/or inorganic acid in step (4), and as rare nitric acid etc., binding agent is generally the little porous aluminum oxide through peptization.Moulding can be determined according to the shape of final catalyst, as extrusion etc.The sintering temperature of catalyst is generally 300 ~ 600 DEG C, and roasting time is generally 2 ~ 10 hours.
Hydrocracking catalyst prepared by the inventive method has following character, and specific area is 150m
2/ g ~ 400m
2/ g, is preferably 160m
2/ g ~ 350m
2/ g; Pore volume is 0.20cm
3/ g ~ 0.60cm
3/ g, is preferably 0.30cm
3/ g ~ 0.5cm
3/ g.
The inventive method adopts the method for carrier of hydrocracking catalyst material powder dipping hydrogenation activity component, compared with carrier impregnation after conventional moulding, carrier material powder dipping can absorb more maceration extract, pick up than moulding after carrier pick up improve several times.Therefore maceration extract does not need higher metal concentration just can prepare the final catalyst prod that active metallic content is higher.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, metal component has higher 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 in the time that active metallic content is higher, after conventional method carrier impregnation hydrogenation component, when particularly hydrogenation component load capacity is larger, the pore volume of catalyst, aperture and specific area all obviously reduce, even and when a large amount of hydrogenation component of the inventive method load, to the pore volume of final catalyst, aperture and specific area impact are less, can obtain hydrogenation component content high, large pore volume, bigger serface and wide-aperture hydrocracking catalyst.
In the preparation process of hydrocracking catalyst of the present invention, maceration extract can recycle.Therefore the method has that preparation technology is simple, cost is low, pollute the features such as little, and applicable commercial scale is promoted the use of.The catalyst of preparation, owing to having higher hydrogenation metal content and larger pore volume and aperture, goes for the more hydrocracking process of heavy, inferior raw material.
Detailed description of the invention
A kind of detailed process of hydrocracking catalyst of the present invention is as follows:
(1) first aluminum oxide dry glue powder is carried out to low-temperature hydrothermal processing, low-temperature hydrothermal treatment conditions 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, and the aluminum oxide dry glue powder being obtained after hydrothermal treatment consists mixes with acid cracking material powder.After hydrothermal treatment consists, obtain water content in aluminum oxide dry glue powder and be preferably 30wt%～50wt%, low-temperature hydrothermal product after treatment has good macropore structure simultaneously, this pore passage structure can have very large reservation degree in shaping of catalyst process, has ensured that final catalyst has suitable macropore structure;
Wherein, in the time that acid cracking material step (1) Suo Shu comprises amorphous acidic components, especially amorphous aluminum silicide, preferably amorphous acidic components are carried out to hydrothermal treatment consists, hydrothermal treatment consists condition is: 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, wherein amorphous acidic components hydrothermal treatment consists process can be carried out respectively with aluminum oxide dry glue powder, also together with after can mixing with alumina dry glue, carry out, in the aluminum oxide dry glue powder obtaining and amorphous acidic components, water content is preferably 30wt%～50wt%,
(2) taking tungsten nickel as example, non-your hydrogenation metal salting liquid preparation: get a certain amount of deionized water under stirring, add gradually nickel nitrate and ammonium metatungstate crystal, after all dissolving, static, filter, obtain metal impregnation solution, wherein WO
3content 10.0 ~ 50.0gWO
3/ 100ml, NiO content 2.0 ~ 15.0gNiO/100ml.The preparation of molybdenum nickel, molybdenum cobalt and three constituent element metal component solution belongs to content well known to those skilled in the art;
(3) mensuration hydrogenation splits the contents on dry basis of catalyst carrier material, as the contents on dry basis of the materials such as molecular sieve, aluminum hydroxide solid elastomer and contained amorphous silica-alumina dry glue.Take a certain amount of said components in the required ratio of hydrocracking catalyst, be placed in and stir metal impregnation solution, solid-to-liquid ratio is 1:5 ~ 1:20, and beating time is 30 ~ 120min.Mixed serum carries out suction filtration, and filter cake butt is controlled at 15wt% ~ 30wt%, under 100 ~ 150 DEG C of conditions, is dried 2 ~ 6 hours, is 40% ~ 80% containing the powder butt (weight) of hydrogenation metal component, then pulverizes granularity control 100 ~ 200 orders;
(4) powder of the dispersion hydrogenation metal component (3) step being obtained rolls, and after 20 ~ 60min, adding concentration is 2 ~ 10gHNO
3/ 100ml dilute nitric acid solution, continues to roll formation and can squeeze paste shape, then extruded moulding, and catalyst shape can be column, clover, bunge bedstraw herb and other different in nature bar etc., length control 3 ~ 8mm;
(5) carrier strip step (4) being obtained is first dried 2 ~ 6 hours under 100 ~ 150 DEG C of conditions, then carries out roasting, 300 ~ 600 DEG C of sintering temperatures, and the time is 2 ~ 10 hours, prepares catalyst finished product.
Modified molecular screen used in carrier of hydrocracking catalyst of the present invention, can Modified Zeolite Y, one or more compound uses of beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve.The method of modifying of molecular sieve can be hydrothermal treatment consists or EDTA, SiCl
4, (NH
4)
2siF
6, the chemical dealuminization modification method such as phosgene or oxalic acid, and the molecular sieve of the hydro-thermal that uses acid, alkali, salt formula complexing agent and the method for modifying processing such as chemical dealuminization combines.The character of molecular sieve used is preferably: silica and alumina molar ratio are 3 ~ 100, are preferably 10 ~ 60, Na
2o content≤0.5wt%, meleic acid amount is 0.1 ~ 1.0mmol/g, preferably 0.2 ~ 0.6mmol/g.
Aluminium oxide or amorphous aluminum silicide that the present invention uses are generally selected super big hole modified aluminas and macropore amorphous aluminum silicide, can select existing goods, also can prepare according to prior art.The high-silicon amorphous silica aluminum that amorphous aluminum silicide is prepared as CN200810010246.1, pore volume is 1.0mL/g ~ 2.0mL/g, specific area is 400m
2/ g ~ 650m
2/ g.
The present invention selects metal salt solution, is generally group vib and group VIII metallic salt, and as the salting liquid of the metals such as W, Mo, Ni, Co one or more, metallic solution concentration is generally 5.0 ~ 50g metal/100mL, and wherein metal is in oxide.
The following examples are for illustrating in greater detail the preparation method of carrier of the present invention, but scope of the present invention is not only limited to the scope of these embodiment.In the present invention, 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.
Aluminium oxide or amorphous aluminum silicide that the present invention uses are generally selected super big hole modified aluminas and macropore amorphous aluminum silicide, can select existing goods, also can prepare according to prior art.
The physico-chemical property of the aluminum oxide dry glue powder that embodiment uses is: its 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.The high-silicon amorphous silica aluminum that amorphous aluminum silicide is prepared as CN200810010246.1, pore volume is up to 1.0mL/g ~ 2.0mL/g, and specific area is 400m
2/ g ~ 650m
2/ g, the butt of amorphous aluminum silicide is 75wt%.
Embodiment 1
Get respectively aluminum oxide dry glue powder and the each 1000g of amorphous silicon aluminium powder carries out steam treatment, at gauge pressure 0.05MPa, hydrothermal treatment consists temperature is 45 DEG C, processing time is 1.5 hours, aluminum oxide dry glue powder after the hydrothermal treatment consists obtaining and the water content of amorphous aluminum silicide are respectively 35wt% and 36wt%, are numbered LA-1 and LSA-1.
Embodiment 2
Get respectively aluminum oxide dry glue powder and the each 1000g of contained amorphous silica-alumina dry glue powder carries out steam treatment, at gauge pressure 0.08MPa, hydrothermal treatment consists temperature is 75 DEG C, processing time is 2 hours, aluminum oxide dry glue powder after the hydrothermal treatment consists obtaining and the water content of amorphous aluminum silicide are respectively 43wt% and 42wt%, are numbered LA-2 and LSA-2.
Embodiment 3
Get respectively aluminum oxide dry glue powder and the each 1000g of contained amorphous silica-alumina dry glue powder carries out steam treatment, at gauge pressure 0.1MPa, hydrothermal treatment consists temperature is 90 DEG C, processing time is 3 hours, the hydrothermal treatment consists rear oxidation aluminium dry glue powder obtaining and the water content of amorphous aluminum silicide are respectively 50wt% and 49wt%, are numbered LA-3 and LSA-3.
Embodiment 4
By final hydrocracking catalyst weighing scale, containing Y molecular sieve 15%, containing amorphous aluminum silicide 25%, containing nickel oxide 12%, containing tungsten oxide 35%, surplus is aluminium oxide.Select aforementioned catalyst raw materials: modified Y molecular sieve 1, aluminum oxide dry glue powder LA-1 and contained amorphous silica-alumina dry glue powder LSA-1.
Catalyst preparation process is as follows: Y-1 molecular sieve, LA-1 aluminum oxide dry glue powder and LSA-1 contained amorphous silica-alumina dry glue powder are fully mixed, the making beating of the solution hybrid infusion containing hydrogenation component nickel and tungsten compound with preparation, dip time 120min, suction filtration, at 120 DEG C, be dried 4 hours, then pulverize, with the 180 orders powder that sieves to obtain.Powder is mixed with appropriate extrusion aid sesbania powder, and adding concentration is 4gHNO
3rare nitric acid of/100ml carries out peptization, and being extruded into diameter is 1.5mm clover strip.Then at 120 DEG C, be dried 4 hours, roasting 3 hours at 480 DEG C, catalyst numbering is respectively HC-1.
Embodiment 5
By final hydrocracking catalyst weighing scale, containing Y molecular sieve 25%, containing amorphous aluminum silicide 10%, containing nickel oxide 10%, containing tungsten oxide 30%, surplus is aluminium oxide.Select aforementioned catalyst raw materials: modified Y molecular sieve 1, LA-2 aluminum oxide dry glue powder and LSA-2 contained amorphous silica-alumina dry glue powder.
Preparation method, with embodiment 4, obtains catalyst and is numbered HC-2.
Embodiment 6
By final hydrocracking catalyst weighing scale, containing Y molecular sieve 30%, containing amorphous aluminum silicide 10%, containing nickel oxide 10%, containing tungsten oxide 30%, surplus is aluminium oxide.Select aforementioned catalyst raw materials: modified Y molecular sieve 1, LA-3 aluminum oxide dry glue powder and LSA-3 contained amorphous silica-alumina dry glue powder.
Preparation method, with embodiment 4, obtains catalyst and is numbered HC-3.
Embodiment 7
Contain Modified Zeolite Y 5% by final hydrocracking catalyst weighing scale, amorphous aluminum silicide 38%, containing nickel oxide 7%, select aforementioned catalyst raw materials containing tungsten oxide 23%: modified Y molecular sieve 2, LA-1 aluminum oxide dry glue powder and LSA-1 contained amorphous silica-alumina dry glue powder, in dipping solution, contain phosphoric acid, in final catalyst, contain 2wt% phosphorous oxides.
Preparation method, with embodiment 4, obtains catalyst and is numbered HC-4.
Embodiment 8
Contain Y molecular sieve 20% by final hydrocracking catalyst weighing scale, containing amorphous aluminum silicide 18%, containing nickel oxide 10%, containing tungsten oxide 25%, surplus is that aluminium oxide is selected aforementioned catalyst raw materials: modified Y molecular sieve 1, LA-2 aluminum oxide dry glue powder and the contained amorphous silica-alumina dry glue powder without hydrothermal treatment consists.
Preparation method, with embodiment 4, obtains catalyst and is numbered HC-5.
Comparative example 1
According to catalyst composition and the raw material of embodiment 4, wherein aluminium oxide and amorphous aluminum silicide do not carry out hydrothermal treatment consists, support material is made to catalyst carrier, then adopt infusion process load hydrogenation activity component, need carry out twice active metal component dipping and just must obtain required active metallic content, be numbered HC-B1 to catalyst.
Comparative example 2
According to catalyst composition and the raw material of embodiment 7, wherein aluminium oxide and amorphous aluminum silicide do not carry out hydrothermal treatment consists, support material is made to catalyst carrier, after base, adopt infusion process load hydrogenation activity component, need carry out twice active metal component dipping and just must obtain required active metallic content, be numbered HC-B2 to catalyst.
Comparative example 3
According to catalyst composition and the raw material of embodiment 8, wherein aluminium oxide and amorphous aluminum silicide do not carry out hydrothermal treatment consists, support material is made to catalyst carrier, after base, adopt infusion process load hydrogenation activity component, need carry out twice active metal component dipping and just must obtain required active metallic content, be numbered HC-B3 to catalyst.
table 1 Modified Zeolite Y physico-chemical property
| 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 surface, m 2/g | 872 | 846 |
| Total pore volume, ml/g | 0.457 | 0.461 |
| Infrared acidity, mmol/g | 0.75 | 0.58 |
In the present embodiment, above each routine catalyst is carried out to instrumental analysis and activity rating.Each routine catalyst physico-chemical property is shown in Table 1.
Table 2. catalyst physico-chemical property
| Numbering | HC-1 | HC-2 | HC-3 | HC-4 | HC-5 | HC-B1 | HC-B2 | HC-B3 |
| WO 3，wt% | 35 | 30 | 30 | 23 | 25 | 35 | 23 | 25 |
| NiO，wt% | 12 | 10 | 10 | 7 | 10 | 12 | 7 | 10 |
| Specific area, m 2/g | 198 | 265 | 207 | 257 | 267 | 147 | 178 | 195 |
| Pore volume, ml/g | 0.33 | 0.40 | 0.35 | 0.43 | 0.40 | 0.25 | 0.22 | 0.28 |
| Average pore diameter, nm | 7.7 | 9.1 | 8.0 | 9.3 | 9.1 | 6.2 | 7.2 | 8.0 |
Evaluating apparatus adopts on 200ml small hydrogenation device and carries out, and before activity rating, catalyst is carried out to presulfurization.The raw materials used oil nature of evaluation of catalyst activity and reaction process condition are in table 2 and table 3, and catalyst reaction performance comparison the results are shown in Table 4.While evaluating HC-1, HC-5 and HC-B1, HC-B3, then feedstock oil first directly enter hydrocracking catalyst bed through Hydrobon catalyst bed, controls organic nitrogen content in feedstock oil lower than 20 μ g/g during through Hydrobon catalyst bed.While evaluating HC-4 and HC-B2, do not use Hydrobon catalyst bed, feedstock oil is directly by hydrocracking catalyst bed.
Table 3. feedstock oil character
| Density (20 DEG C), g/cm 3 | 0.9159 |
| Boiling range/DEG C | ? |
| ? IBP/10% | 328/376 |
| ? 30%/50% | 400/430 |
| ? 70%/90% | 455/499 |
| ? 95%/FBP | 514/536 |
| Condensation point/DEG C | 32 |
| Refractive power/n D 70 | 1.4899 |
| Carbon residue, wt% | 0.32 |
| S，wt% | 1.60 |
| N，wt% | 0.1575 |
Table 4. evaluating catalyst process conditions
| Catalyst | HC-1, HC-5 and HC-B1, HC-B3 | HC-4 and HC-B2 |
| Reaction pressure, MPa | 14.7 | 14.7 |
| Volume space velocity when liquid, h -1 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio | 900：1 | 900：1 |
| Control conversion ratio, wt% | 60 | 60 |
Table 5. catalyst reaction performance comparison result
| Catalyst | HC-1 | HC-5 | HC-B1 | HC-B3 | HC-4 | HC-B2 |
| Reaction temperature, DEG C | 379 | 380 | 383 | 389 | 385 | 390 |
| Intermediate oil is selective, wt% | 84 | 83 | 81 | 83 | 88 | 84 |
| Kerosene product smoke point, mm | 28 | 27 | 22 | 22 | 23 | 22 |
| Tail oil BMCI value | 8 | 8.5 | 12 | 14 | 10 | 15 |
Claims (9)
1. a preparation method for hydrocracking catalyst, comprising:
(1) 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, and gauge pressure is 0.01～0.1MPa, adopts water vapour closed processes, processing time is 1～3 hour, and in the aluminum oxide dry glue powder after hydrothermal treatment consists, water content is 30wt%～50wt%;
(2) acid to the aluminum oxide dry glue powder after hydrothermal treatment consists and at least one cracking material powder is mixed;
(3) preparation is containing the metal salt solution of hydrogenation activity component, and hydrogenation activity component is one or more in W, Mo, Ni and Co, with the mixture of this metal salt solution impregnation steps (2) gained, then filters, is dried, pulverizes;
(4) in the mixture of step (3) gained, add peptizing agent or binding agent, fully roll aftershaping, then dry, roasting obtains hydrocracking catalyst;
Described hydrocracking catalyst, taking the weight of hydrocracking catalyst as benchmark, acid cracking material content is 1%～65%, and hydrogenation activity component is taking the content of oxide as 25%～50%, and alumina content is 10%～50%; The concentration of the described metal salt solution containing hydrogenation activity component is 5.0～50g metal/100mL, and wherein metal is in oxide.
2. in accordance with the method for claim 1, it is characterized in that described acid cracking material comprises molecular sieve and/or amorphous acidic components, molecular sieve comprises one or more in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve; Amorphous acidic components are one or more in amorphous aluminum silicide, amorphous silicon magnesium and clay.
3. in accordance with the method for claim 2,, while it is characterized in that described acid cracking material comprises molecular sieve, the character of described molecular sieve is: silica and alumina molar ratio are 3～100, Na
2o content≤0.5wt%, meleic acid amount is 0.1～1.0mmol/g.
4. in accordance with the method for claim 2, it is characterized in that described amorphous acidic components are amorphous aluminum silicide, character is as follows: pore volume is 1.0mL/g～2.0mL/g, and specific area is 400m
2/ g～650m
2/ g.
5. in accordance with the method for claim 1, while containing amorphous acidic components in acid cracking material described in it is characterized in that, amorphous acidic components are 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, the processing time is 1～3 hour; The independent hydrothermal treatment consists of amorphous acidic components, or hydrothermal treatment consists together after mixing with aluminum oxide dry glue powder.
6. in accordance with the method for claim 5, it is characterized in that, amorphous acidic components are after hydrothermal treatment consists, and water content is 30wt%～50wt%.
7. in accordance with the method for claim 1, it is characterized in that in step (3) containing in the metal salt solution of hydrogenation activity component, contain one or more the compound in P, F, B, Zr, Ti.
8. in accordance with the method for claim 1, it is characterized in that the described drying condition of step (3) is as follows: under 100～150 DEG C of conditions, be dried 2～6 hours, the butt of dry rear material is 40wt%～80wt%.
9. in accordance with the method for claim 1, it is characterized in that the described drying condition of step (4) is as follows: under 100～150 DEG C of conditions, be dried 2～6 hours, roasting condition is as follows: 300～600 DEG C of sintering temperatures, the time is 2～10 hours.
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|---|---|---|---|
| CN201210442999.6A CN103191774B (en) | 2012-01-06 | 2012-11-08 | Method for preparing hydrocracking catalyst |
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| CN103191774B true CN103191774B (en) | 2014-08-20 |
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| CN105709805B (en) * | 2014-12-04 | 2018-07-06 | 中国石油化工股份有限公司 | A kind of chemical industry type hydrocracking catalyst and preparation method thereof |
| CN105709803B (en) * | 2014-12-04 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of preparation process of hydrocracking catalyst |
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| CN1096296C (en) * | 1998-11-13 | 2002-12-18 | 中国石油化工集团公司 | Hydrocracking catalyst for producing middle distillate and its preparation method |
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