CN104588086A - Preparation method of hydrocracking catalyst - Google Patents
Preparation method of hydrocracking catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a hydrocracking catalyst. According to the method, a nickel and aluminum precipitate is prepared with a straight addition method; a tungsten, silicon and aluminum precipitate is prepared with a parallel flow precipitation method; the two precipitates are mixed, and a suspension liquid of Y-type molecular sieve is added; and the catalyst is prepared. With the method, the pore structure of the catalyst can be optimized. The distributions of different hydrogenation active metals can be controlled; high-activity phase can be formed among active metals tungsten and nickel; and the interaction between active metals and a carrier can be improved. Therefore, the hydrogenation activity and the cracking activity of the obtained hydrocracking catalyst can cooperate well, and the application performance of the hydrocracking catalyst can be improved.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocracking catalyst for the treatment of of heavy hydrocarbon class.
Background technology
At present, worldwide petroleum resources are not enough, and crude quality is deteriorated year by year, intermediate oil demand increases, petroleum chemicals upgrading and environmental regulation are more and more strict, all greatly facilitate heavy oil lighting, and form the very strong driving force of accelerated development hydrogen addition technology.The main feature of hydrocracking technology is that adaptability to raw material is strong, products scheme, object product selectivity are high, good product quality and added value is high, directly can produce multiple high-quality oil product (as gasoline, jet fuel, diesel oil, lube base wet goods) and high-quality industrial chemicals (as the production such as benzene,toluene,xylene, ethene raw material).
Hydrocracking is carried out at elevated pressures, and hydrocarbon molecules and hydrogen carry out at catalyst surface the conversion process that cracking and hydrogenation reaction generate lighter molecule, and the hydrogenation reaction of hydrodesulfurization, denitrogenation and unsaturated hydrocarbons also occurs simultaneously.The cracking reaction of hydro carbons in hydrocracking process is carried out on the acid centre of catalyst, follows carbon ion reaction mechanism, with the generation of hydro carbons isomerization reaction while hydrogenation, cracking reaction.Hydrocracking catalyst is made up of hydrogenation component and acidic components, and both add as required by a certain percentage, makes hydrogenation and cracking performance reach balance, and its effect is the abundant hydrogenation of hydrocarbon mixture, cracking and isomerization orientation reaction.Therefore, the catalyst of distillate hydrocracking process need should possess stronger hydrogenation sites and have moderate acid centre again.
In general, hydrocracking catalyst can make to prepare with the following method, as: infusion process, kneading method, beating method, coprecipitation, may use ion-exchange for noble metal.Infusion process and kneading method are all add metal again after first carrier and acidic components being made, and coprecipitated rule is acidic components and metal coprecipitation gets off, and metal loading is unrestricted.
US6299760, US6156695, US6537442, US6440888, US6652738 disclose containing the bulk phase catalyst and preparation method thereof of group VIII/VI B race active metal component for hydrotreatment.Catalyst metal content can reach 50wt% ~ 100wt%.Active metal component can be Ni-Mo or Ni-Mo-W.Above-mentioned catalyst adopts coprecipitation method to prepare.Hydrocracking catalyst disclosed in US 3954671, hydrogenation conversion catalyst disclosed in US 4313817, the hydrocracking catalyst of nitrogen-resistant type fecund intermediate oil disclosed in CN1253988A, heavy hydrocarbons hydrocraking catalyst disclosed in CN1253989A, these catalyst adopt coprecipitation method to prepare, because the deposition condition of different hydrogenation active metals is different, the distribution of different hydrogenation active metals is caused to be not easy to control, thus the interaction relationship affected between the distribution of different hydrogenation active metals and different activities metal and between active metal and carrier, thus hydrogenation activity can not well be coordinated with cracking activity, the final hydrocracking performance affecting catalyst.Disclosed in CN101239324A, high activity, medium oil type hydrocracking catalyst are that the slurries be made into amorphous aluminum silicide, auxiliary agent and active metal add precipitating reagent alkalescent ammoniac compounds, carry out precipitation reaction, then add molecular sieve suspension and make.The method also adopts coprecipitation method to prepare, still exist different hydrogenation active metals distribution, hydrogenation active metals and and carrier between act on the bad problem of harmonious relations.
CN103055923A discloses a kind of preparation method of hydrocracking catalyst.Adopt containing hydrogenation active metals acid solution, sodium metaaluminate alkaline solution and gas CO
2and stream add water purification is housed retort in plastic; Then the suspension adding Y zeolite mixes, and after filtration, dry, shaping, then obtains hydrocracking catalyst through washing, dry, roasting.The method utilizes the releasing of gas in roasting process, improves the pore structure of catalyst and the dispersion of active metal, but the active metal distribution produced when fundamentally solving precipitation is not easy the problem of regulation and control.
Coprecipitation method Kaolinite Preparation of Catalyst technology, adopts different coprecipitation mode, Gelation Conditions etc., all can have a great impact the interaction relationship between the distribution of different hydrogenation active metals and different hydrogenation active metals and between hydrogenation active metals and carrier.The coprecipitation method of above-mentioned employing can make the distribution of different hydrogenation active metals be not easy to control, thus the interaction relationship affected between the distribution of different hydrogenation active metals and different hydrogenation active metals and between active metal and carrier, thus hydrogenation activity can not well be coordinated with cracking performance, finally affect the hydrocracking performance of catalyst.Therefore, how to regulate and control the distribution of hydrogenation active metals, making to have suitable mating reaction between hydrogenation active metals component and between hydrogenation active metals component and carrier, improve the utilization rate of hydrogenation active metals component, is the key that raising coprecipitation method prepares hydrocracking catalyst Hydrogenation.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of hydrocracking catalyst.The method improves the distribution of hydrogenation active metals in catalyst, improves the utilization rate of hydrogenation active metals, to improve between hydrogenation active metals and and carrier between cooperation effect, make catalyst have higher serviceability.
The preparation method of hydrocracking catalyst of the present invention, comprising:
(1), prepare the solution A containing Ni, Al component and organic compound, precipitating reagent is added dropwise to solution A and carries out plastic reaction, generate nickeliferous, aluminum precipitation thing slurries I; Wherein organic compound is organic formwork agent and surfactant;
(2), preparation containing the mixed solution B of W, Si, Al component, by precipitating reagent and solution B and stream carries out plastic reaction, generate tungstenic, silicon, aluminum precipitation thing slurries II;
(3), by the slurries II of the slurries I of step (1) gained and step (2) gained mix, add the suspension of Y zeolite, then aging under agitation;
(4), step (3) obtain material drying, shaping, washing,
(5), drying and the roasting again of step (4) gained material, obtained hydrocracking catalyst.
In the inventive method, Y zeolite is generally add with the form of molecular sieve suspension, is ground to 80 order ~ 140 orders by molecular sieve, and preferably 100 order ~ 120 orders, then add water and make suspension.Described Y zeolite is conventional hydrocracking catalyst Y zeolite used.
Step (1) or the precipitating reagent described in step (2) are one or more in sodium carbonate, sodium acid carbonate, ammoniacal liquor, NaOH, potassium hydroxide, potash, saleratus, are preferably ammoniacal liquor.
In step (1) mixed solution A, Ni is in the weight concentration of NiO for 20 ~ 80g/L, and preferably 30 ~ 60g/L, Al are with Al
2o
3the weight concentration of meter is 60 ~ 200g/L, preferably 90 ~ 150g/L.Organic compound in solution A is organic formwork agent and surfactant.Wherein organic formwork agent is one or more in tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, TPAOH, TBAB, TBAH, softex kw, DTAC.Surfactant is one or more in the condensation product of alkyl phenol and oxirane, polyoxyethylene sorbitol acid anhydride list olein, AEO, polyoxyethylene stearic acid ester.Organic compound consumption accounts in step (1) introduces Al with Al
2o
31wt% ~ the 35wt% of meter weight, is preferably 5wt% ~ 25wt%; Wherein organic formwork agent occupies the 30wt% ~ 80wt% of organic compounds consumption, preferred 40wt% ~ 70wt%.
In step (2) mixed solution B, W is with WO
3the weight concentration of meter is 50 ~ 120g/L, and preferably 70 ~ 100g/L, Si are with SiO
2weight concentration is 80 ~ 250g/L, and preferably 100 ~ 180g/L, Al are with Al
2o
3the weight concentration of meter is 60 ~ 200g/L, preferably 90 ~ 150g/L.When preparing mixed solution A, the general nickel source adopted can be one or more in nickelous sulfate, nickel nitrate, basic nickel carbonate, nickel chloride, and aluminium source can be one or more in aluminum nitrate, aluminum sulfate, aluminium chloride or aluminium acetate etc.When preparing mixed solution B, the general tungsten source adopted can be one or more in ethyl ammonium metatungstate, ammonium metatungstate; Silicon source can be in Ludox, sodium metasilicate one or more; Aluminium source can be one or more in aluminum nitrate, aluminum sulfate, aluminium chloride or aluminium acetate etc.
In step (1), reaction temperature is 20 ~ 90 DEG C, is preferably 30 ~ 70 DEG C.During cemented into bundles, pH value controls is 6.0 ~ 11.0, is preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, is preferably 0.5 ~ 3.0 hour.
Si, Al of introducing in step (2) with oxide basis weight content in the catalyst for 10wt% ~ 80wt%, preferably 20wt% ~ 60wt%, wherein Si accounts for Si, Al with the 10wt% ~ 90wt% of the gross weight of oxide basis, preferably 30wt% ~ 80wt% in silica; The Al introduced in step (1) with oxide basis weight content in the catalyst for 5wt% ~ 45wt%, preferably 10wt% ~ 30wt%.
In step (2), reaction temperature is 30 ~ 90 DEG C, is preferably 40 ~ 80 DEG C.And when flowing plastic, pH value control is 6.0 ~ 11.0, is preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, is preferably 0.5 ~ 3.0 hour.
In step (1) and step (2), gelling temperature and time can be the same or different.Step (1) and step (2) can carry out also can not simultaneously carrying out simultaneously.
In step (3), aging temperature is 40 ~ 90 DEG C, is preferably 50 ~ 80 DEG C.Time aging, pH value controls is 6.0 ~ 10.0, is preferably 6.5 ~ 9.0.Ageing time is 0.5 ~ 6.0 hour, is preferably 1.0 ~ 4.0 hours.
Drying described in step (4), shaping this area conventional method that can adopt is carried out.Described drying is generally 50 ~ 200 DEG C of dryings 1 ~ 48 hour.In forming process, conventional shaping assistant can be added as required, one or more in such as peptizing agent, adhesive, extrusion aid etc.Described extrusion aid refers to and is conducive to extruded material, and as one or more in sesbania powder, carbon black, graphite powder, citric acid etc., the consumption of extrusion aid accounts for the 1wt% ~ 10wt% of total material butt.
Shaping rear preferably through washing in step (4), washing is generally adopt deionized water or containing decomposable asymmetric choice net salt (as ammonium acetate, ammonium chloride, ammonium nitrate etc.) solution washing, be washed till neutrality.
Drying described in step (5) and roasting can adopt this area normal condition, as 50 ~ 200 DEG C of dryings 1 ~ 48 hour, 450 ~ 600 DEG C of roastings 1 ~ 24 hour, are preferably 2 ~ 8 hours.
In hydrocracking catalyst of the present invention, composition comprises hydrogenation active metals component W and Ni, carrier component aluminium oxide and amorphous aluminum silicide, can also contain molecular sieve.With the weight of catalyst for benchmark, WO
3content be 10wt% ~ 50wt%, preferably the content of 15wt% ~ 30wt%, NiO is 1wt% ~ 30wt%, preferably 5wt% ~ 20wt%, W/Ni atomic ratio is 0.05 ~ 1.0, preferably 0.1 ~ 0.7, the content of amorphous aluminum silicide is 10wt% ~ 80wt%, preferably 20wt% ~ 60wt%, the content of molecular sieve is 0wt% ~ 40wt%, preferably 5wt% ~ 30wt%, alumina content is 5wt% ~ 45wt%, preferably 10wt% ~ 30wt%.In amorphous aluminum silicide, the content of silica is 10wt% ~ 90wt%, preferably 30wt% ~ 80wt%, and the content of aluminium oxide is 10wt% ~ 90wt%, preferably 30wt% ~ 80wt%.
The character of catalyst prepared by the inventive method is as follows: specific area 250 ~ 500m
2/ g, pore volume 0.35 ~ 0.70mL/g.
In hydrocracking catalyst of the present invention, also can contain adjuvant component, described adjuvant component is the IVth B race metal, and the content of the IVth B family metal oxide in hydrocracking catalyst is 1wt% ~ 10wt%.Described IVth B race metal is preferably Ti and/or Zr.In hydrocracking catalyst preparation process of the present invention, in preparation mixed solution A process, add the compound containing adjuvant component, i.e. titanium source and/or zirconium source.Titanium source can adopt in Titanium Nitrate, titanium sulfate, titanium chloride etc. one or more, zirconium source can adopt in zirconium nitrate, zirconium chloride, zirconium oxychloride etc. one or more.
In hydrocracking catalyst of the present invention, Y zeolite used can adopt all Y zeolites that can be used in hydrocracking catalyst in prior art, such as: Y zeolite disclosed in CN102441411A, CN1508228A, CN101450319A, CN96119840.0.Y zeolite disclosed in preferred CN102441411A in the present invention, the molecular sieve reported with CN 96119840.0 is for raw material, it is 650 ~ 800 DEG C in temperature, pressure is that normal pressure is to 0.3MPa, time is that to carry out hydrothermal treatment consists in the condition and range of 20 ~ 30 hours deep sealumination modified, a small amount of ammonia can be contained in water vapour during hydrothermal treatment consists, ammonia dividing potential drop is 50 ~ 3000Pa(absolute pressure), then be 0.5 ~ 10.0mol/L in acid concentration, time is 0.5 ~ 20.0 hour, temperature is 30 ~ 80 DEG C, acid consumption and the ratio of molecular sieve be 1:1 ~ 20:1 condition and range in carry out acid treatment, use inorganic acid is hydrochloric acid, sulfuric acid or nitric acid etc., the Y zeolite being applicable to the present invention's use is obtained after hydrothermal treatment consists and acid treatment, its character is as follows: the pore volume that bore dia is greater than 1.7nm accounts for more than 45% of total pore volume, specific area is 750 ~ 900m
2/ g, cell parameter at 2.423nm ~ 2.545nm, relative crystallinity 95% ~ 110%, SiO
2/ Al
2o
3mol ratio is 7 ~ 60.The existing high degree of crystallinity of this molecular sieve, have again low cell parameter, the secondary pore of molecular sieve is many, is conducive to the diffusion velocity improving raw material and product, reduces the second pyrolysis of product; Large specific area, less acid site number, the intermediate oil being also more conducive to improving hydrocracking catalyst is selective; High silica alumina ratio, major part is the acid centre of moderate strength, and the acid site degree that is evenly distributed is high, makes this molecular sieve have very strong nitrogen resistance and broken ring ability preferably.The above-mentioned characteristic of this molecular sieve can make catalyst have the poisoning ability of good anti-nitride when the raw material that directly contact impurity content is high, the stability that good hydrocracking activity is become reconciled.This catalyst is suitable for single hop once by hydrocracking process, and hydrocracking operation condition is as follows: reaction temperature is 300 ~ 500 DEG C, is more preferably 350 ~ 450 DEG C; Pressure is 6 ~ 20MPa, is more preferably 13 ~ 17MPa; During liquid, volume space velocity is 0.5 ~ 3 h
-1, preferably 0.8 ~ 1.5 h
-1; Hydrogen to oil volume ratio is 400 ~ 2000:1, preferably 800 ~ 1500:1.
The heavy charge scope that catalyst prepared by the inventive method is suitable for is very wide, they comprise vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, the various hydrocarbon ils of catalytic cracking circulation wet goods, also can combinationally use, raw material is the hydro carbons of 250 ~ 550 DEG C usually containing boiling point, and nitrogen content can at 50 ~ 2500 μ g/g.
Catalyst prepared by the inventive method can be used in conventional hydrocracking process, and reaction temperature is 300 ~ 500 DEG C, is more preferably 350 ~ 450 DEG C; Pressure is 6 ~ 20MPa, is more preferably 13 ~ 17MPa; During liquid, volume space velocity is 0.5 ~ 3 h
-1, preferably 0.8 ~ 1.5 h
-1; Hydrogen to oil volume ratio is 400:1 ~ 2000:1, preferably 800:1 ~ 1500:1.
The inventive method adopts positive addition (the acid precipitation method and alkaline precipitating agent are added in acid metal salt solution and precipitate) to prepare nickel aluminium mixed sediment under organic compound exists, parallel flow precipitation is adopted to prepare tungsten, Silicified breccias mixed sediment, after again both being mixed, add molecular sieve suspension, then carry out aging, make hydrocracking catalyst.The present invention prepares the relatively large nickel of crystal grain by adopting positive addition, aluminum precipitation thing, prepare nickel, organic compound is added during aluminum precipitation thing, make the nickel obtained, aluminum precipitation thing crystal grain is relatively large and evenly have good pore structure simultaneously, cocurrent process prepares the relatively little tungsten of crystal grain, Silicified breccias sediment, by above-mentioned two kinds of sediments mixing, the distribution of different hydrogenation active metals can be controlled, be conducive to active metal tungsten, high activity phase is formed between nickel, and the interaction improved between active metal and carrier, and the pore structure of optimization of catalysts, the hydrogenation activity of the hydrocracking catalyst of gained and cracking activity is made to obtain good coordinating, improve the serviceability of hydrocracking catalyst.
The hydrocracking catalyst that the present invention adopts preferred Y zeolite to make is particularly suitable as medium oil type hydrocracking catalyst, both there is high hydrogenation cracking activity, there is again high middle distillates oil selectivity, also there is the serviceability that stronger resistance to nitrogen ability etc. is good simultaneously.This catalyst is used for, in single-stage hydrocracking technical process, having liquid yield high, the advantages such as good product quality.
Detailed description of the invention
In 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 adopts chemical method, sodium content adopts plasma emission spectrometry, and catalyst surface active metal concentration adopts chemical analysis electron spectrum (ESCA) to measure.Transmissioning electric mirror determining catalyst surface WS
2density.In the present invention, wt% is mass fraction, and v% is volume fraction.
Embodiment 1
By being the nickel chloride solution 500 milliliters of 60g/L containing NiO, containing Al
2o
3the liquor alumini chloridi of 118g/L 450 milliliters, containing ZrO
2130g/L zirconyl chloride solution 125 milliliters, be mixed in NaOH solution tank NaOH 1, add 800 milliliters of water purification dilutions, after tetraethyl ammonium hydroxide and polyoxyethylene (20) sorbitan monooleate (Tween 80) mixing, add in NaOH solution tank NaOH 1, organic compound consumption accounts for Al in nickeliferous, the aluminum precipitation thing of synthesis
2o
3the 25.0wt% of weight, tetraethyl ammonium hydroxide accounts for the 55wt% of the consumption being mixed with organic compounds, is configured to solution A after stirring.Will containing WO
3the ammonium metatungstate 1000 milliliters of 110g/L and containing Al
2o
3the liquor alumini chloridi of 118g/L 450 milliliters, is mixed in NaOH solution tank NaOH 2, adds 800 milliliters of water purification dilutions, add 550 milliliters under agitation containing SiO
2rare water glass solution of 120g/L, configuration solution B.Ammoniacal liquor is under agitation added solution A, and gelling temperature remains on 45 DEG C, at the end of pH value control 7.8, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing slurries I.Add in retort by 1000mL water purification, by ammoniacal liquor and solution B and stream adds in retort, gelling temperature remains on 45 DEG C, and flows pH value in plastic course of reaction and control 7.8, and gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing slurries II.Above-mentioned two kinds are mixed containing sediment slurry, when constantly stirring, add containing the mixing of sediment slurries the Y zeolite suspension (preparing by CN102441411A embodiment 3) accounting for total catalyst weight 12wt% through hydrothermal treatment consists modification to two kinds, Y zeolite character is in table 6, in make it be dispersed in mixed serum that plastic obtains, aging 2.0 hours at 72 DEG C, filter, 80 DEG C of dryings 10 hours, roll, extruded moulding.Wash with water purification under room temperature.Then 100 DEG C of dryings 8 hours, 530 DEG C of roastings 4 hours, obtain catalyst A.Catalyst composition and main character are in table 1.
Embodiment 2
According to the method for embodiment 1, by the constituent content proportioning of the catalyst B in table 1, nickel nitrate, titanium chloride, aluminum nitrate solution is added in dissolving tank 1, after softex kw and the mixing of isomery ten alcohol polyoxyethylene (8) ether, add in NaOH solution tank NaOH 1, be mixed with organic compounds consumption and account for Al in nickeliferous, the aluminum precipitation thing of synthesis
2o
3the 20.0wt% of weight, softex kw accounts for the 45wt% of the consumption being mixed with organic compounds, prepare working solution A after stirring, in dissolving tank 2, add aluminum nitrate, ammonium metatungstate and rare waterglass preparation working solution B, wherein rare waterglass is for containing SiO
2rare water glass solution of 100g/L 520 milliliters.Ammoniacal liquor is under agitation added solution A, and gelling temperature remains on 50 DEG C, at the end of pH value control 7.6, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing slurries I.Add in retort by 1000mL water purification, by ammoniacal liquor and solution B and stream adds in retort, gelling temperature remains on 50 DEG C, and flows pH value in plastic course of reaction and control 7.8, and gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing slurries II.Above-mentioned two kinds are mixed containing sediment slurry, when constantly stirring, add containing the mixing of sediment slurries the Y zeolite suspension (preparing by CN102441411A embodiment 3) accounting for total catalyst weight 12wt% through hydrothermal treatment consists modification to two kinds, Y zeolite character in table 6, in make it be dispersed in mixed serum that plastic obtains, aging 2 hours at 75 DEG C, filter, 70 DEG C of dryings 8 hours, roll, extruded moulding, washs with water purification under room temperature.Then 120 DEG C of dryings 10 hours, 600 DEG C of roastings 3.5 hours, obtain catalyst B.Catalyst composition and main character are in table 1.
Embodiment 3
According to the method for embodiment 1, by the constituent content proportioning of the catalyst C in table 1, nickel chloride, liquor alumini chloridi is added in dissolving tank 1, after TBAH and the mixing of stearic acid polyoxyethylene (12) fat, add in NaOH solution tank NaOH 1, be mixed with organic compounds consumption and account for Al in nickeliferous, the aluminum precipitation thing of synthesis
2o
3the 18wt% of weight, TBAH accounts for the 60wt% of the consumption being mixed with organic compounds, prepares working solution A after stirring, and in dissolving tank 2, add aluminium chloride, ammonium molybdate, rare waterglass preparation working solution B, wherein rare waterglass is for containing SiO
2rare water glass solution of 122g/L 380 milliliters.Ammoniacal liquor is under agitation added solution A, and gelling temperature remains on 55 DEG C, at the end of pH value control 8.0, gelation time control, at 50 minutes, generates nickeliferous, aluminum precipitation thing slurries I.Add in retort and 1200mL water purification is housed, by ammoniacal liquor and solution B and stream adds in retort, gelling temperature remains on 40 DEG C, and flows pH value in plastic course of reaction and control 7.8, and gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing slurries II.Above-mentioned two kinds are mixed containing sediment slurry.When constantly stirring, add containing the mixing of sediment slurries the Y zeolite suspension (preparing by CN102441411A embodiment 3) accounting for total catalyst weight 18wt% through hydrothermal treatment consists modification to two kinds, Y zeolite character is in table 6, in make it be dispersed in mixed serum that plastic obtains, aging 3 hours at 70 DEG C, filter, 120 DEG C of dryings 8 hours, roll, extruded moulding.Wash with water purification under room temperature.Then 80 DEG C of dryings 10 hours, 550 DEG C of roastings 4 hours, obtain catalyst C.Catalyst composition and main character are in table 1.
Embodiment 4
According to the method for embodiment 1, by the constituent content proportioning of the catalyst D in table 1, nickel chloride, zirconium oxychloride, liquor alumini chloridi is added in dissolving tank 1, after TPAOH and polyoxyethylene (20) sorbitan monooleate (Tween 80) mixing, add in NaOH solution tank NaOH 1, be mixed with organic compounds consumption and account for Al in nickeliferous, the aluminum precipitation thing of synthesis
2o
3weight 10wt%, TPAOH accounts for the 40wt% of the consumption being mixed with organic compounds, prepares working solution A after stirring, and adds aluminium chloride, ammonium molybdate, rare waterglass preparating acid sex work solution B in dissolving tank 2, and wherein rare waterglass is for containing SiO
2rare water glass solution of 115g/L 420 milliliters.Ammoniacal liquor is under agitation added solution A, and gelling temperature remains on 60 DEG C, at the end of pH value control 8.0, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing slurries I.Add in retort and 1200mL water purification is housed, by ammoniacal liquor and solution B and stream adds in retort, gelling temperature remains on 60 DEG C, and flows pH value in plastic course of reaction and control 7.8, and gelation time control, at 50 minutes, generates tungstenic, silicon, aluminum precipitation thing slurries II.Above-mentioned two kinds are mixed containing sediment slurry.When constantly stirring, add containing the mixing of sediment slurries the Y zeolite suspension (preparing by CN102441411A embodiment 3) accounting for total catalyst weight 10wt% through hydrothermal treatment consists modification to two kinds, Y zeolite character is in table 6, in make it be dispersed in mixed serum that plastic obtains, aging 2.5 hours at 75 DEG C, filter, 80 DEG C of dryings 10 hours, roll, extruded moulding.With water purification washing under room temperature, then 70 DEG C of dryings 12 hours, 550 DEG C of roastings 4 hours, obtain catalyst D.Catalyst composition and main character are in table 1.
Comparative example 1
According to method preparation disclosed in CN101239324A, catalyst composition forms identical with embodiment 1, and concrete steps are as follows:
(1) preparation is containing Al
2o
3concentration is the liquor alumini chloridi 900 milliliters of 118g/L, is the nickel chloride solution 500 milliliters of 60g/L, containing ZrO containing NiO
2130g/L zirconyl chloride solution 125 milliliters, and be mixed in the container of 5 liters, add 2000 milliliters of water purification dilutions.
(2) rare water glass solution is prepared, containing SiO
2(2) are added in (1) by the waterglass of 120g/L molten 550 milliliters under agitation;
(3) ammoniacal liquor is added under agitation the mixture of (1) and (2) until pH value 5.2;
(4) sodium tungstate solution 1000 milliliters is prepared, containing WO
3for 110g/L, and join in the mixture of (1)+(2)+(3) under agitation;
(5) continue to add ammoniacal liquor until pH value is 7.8;
(6) whole plastic process should be carried out at 45 DEG C;
(7) mixture leaves standstill aging 2.0 hours at 72 DEG C; Add the Y zeolite suspension prepared with CN102441411A embodiment 3 before aging, Y zeolite accounts for 12% of total catalyst weight, and character is in table 6.
(8) filter, 80 DEG C of oven dryings 10 hours, roll, with the orifice plate extruded moulding of diameter 3 millimeters; Wash with the ammonium acetate solution of pH=8.8 under room temperature; Then 100 DEG C of oven dryings 8 hours, 530 DEG C of roastings 4 hours, obtain reference agent E, composition and main character are in table 1.
Comparative example 2
Adopt two steps to be cocurrent process plastic in comparative example 2 preparation process and prepare hydrocracking catalyst.Catalyst composition forms identical with embodiment 1, and concrete steps are as follows:
In dissolving tank 1, add chloric acid nickel, zirconium oxychloride, chlorine aluminum solutions, preparation working solution A, in dissolving tank 2, add aluminium chloride, ammonium metatungstate and rare waterglass preparation working solution B, wherein rare waterglass is for containing SiO
2rare water glass solution of 120g/L 550 milliliters.Just 1000mL water purification adds in retort, and by ammoniacal liquor and solution A and stream adds in retort, gelling temperature remains on 45 DEG C, and flows pH value in plastic course of reaction and control 7.8, and gelation time control, at 60 minutes, generates nickel-and aluminum-containing sediment slurries I.Add in retort by 1000mL water purification, by ammoniacal liquor and solution B and stream adds in retort, gelling temperature remains on 45 DEG C, and flows pH value in plastic course of reaction and control 7.8, and gelation time control, at 60 minutes, generates tungstenic, silicon, aluminum precipitation thing slurries II.Above-mentioned two kinds are mixed containing sediment slurry, when constantly stirring, add containing the mixing of sediment slurries the Y zeolite suspension (preparing by CN102441411A embodiment 3) accounting for total catalyst weight 12wt% through hydrothermal treatment consists modification to two kinds, Y zeolite character is in table 6, in make it be dispersed in mixed serum that plastic obtains, aging 2.0 hours at 72 DEG C, filter, 80 DEG C of dryings 10 hours, roll, extruded moulding.Wash with water purification under room temperature.Then 100 DEG C of dryings 8 hours, 530 DEG C of roastings 4 hours, obtain catalyst F.Catalyst composition and main character are in table 1.
Comparative example 3
Adopt two steps to be positive addition plastic in comparative example 3 preparation process and prepare hydrocracking catalyst.Catalyst composition forms identical with embodiment 1, and concrete steps are as follows:
In dissolving tank 1, add chloric acid nickel, zirconium oxychloride, chlorine aluminum solutions, preparation working solution A, in dissolving tank 2, add aluminium chloride, ammonium metatungstate and rare waterglass preparation working solution B, wherein rare waterglass is for containing SiO
2rare water glass solution of 120g/L 550 milliliters.Ammoniacal liquor is under agitation added solution A, and gelling temperature remains on 45 DEG C, at the end of pH value control 7.8, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing slurries I.Ammoniacal liquor is under agitation added solution B, and gelling temperature remains on 45 DEG C, at the end of pH value control 7.8, gelation time control at 60 minutes, tungsten, silicon, aluminum precipitation thing slurries II.Above-mentioned two kinds are mixed containing sediment slurry, when constantly stirring, add containing the mixing of sediment slurries the Y zeolite suspension (preparing by CN102441411A embodiment 3) accounting for total catalyst weight 12wt% through hydrothermal treatment consists modification to two kinds, Y zeolite character is in table 6, in make it be dispersed in mixed serum that plastic obtains, aging 2.0 hours at 72 DEG C, filter, 80 DEG C of dryings 10 hours, roll, extruded moulding.Wash with water purification under room temperature.Then 100 DEG C of dryings 8 hours, 530 DEG C of roastings 4 hours, obtain catalyst G.Catalyst composition and main character are in table 1.
Comparative example 4
Prepare hydrocracking catalyst according to the method for comparative example 2, catalyst composition forms identical with embodiment 1, adds and is mixed with organic compounds, obtain catalyst H when obtain solution A.Catalyst composition and main character are in table 1.
Comparative example 5
Prepare hydrocracking catalyst according to the method for comparative example 3, catalyst composition forms identical with embodiment 1, adds and is mixed with organic compounds, obtain catalyst I when obtain solution A.Catalyst composition and main character are in table 1.
Embodiment 5
Middle oil type hydrocracking catalyst A, B, D of the present invention and reference catalyst E, F and G, H evaluation result on midget plant are compared.Appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.5h
-1, evaluation raw material is Iranian VGO heavy distillate, and its main character is in table 4, and table 5 lists evaluation result.
As can be seen from table 2 and table 3, there is not the reunion of tungsten and nickel particles in catalyst prepared by the inventive method, active metal is uniformly dispersed, and can fully contact.Can find out that catalyst A, catalyst B, the activity of catalyst D and the middle distillates oil selectivity adopting the present invention to prepare all is better than reference agent from the data of table 5, illustrate that active metal is uniformly dispersed, improve the active metal utilization rate of catalyst.
Table 1 catalyst composition and character
| Catalyst is numbered | A | B | C | D | E |
| Catalyst forms | |||||
| NiO， wt% | 13 | 18 | 10 | 12 | 13 |
| WO 3，wt% | 16 | 22 | 20 | 18 | 16 |
| SiO 2，wt% | 30 | 25 | 35 | 31 | 30 |
| Al 2O 3，wt% | 33 | 27 | 35 | 34 | 33 |
| Other/wt% | ZrO 2/8.0 | TiO 2/8.0 | - | ZrO 2/5.0 | ZrO 2/8.0 |
| The content of Y molecular sieve in catalyst, wt% | 12 | 10 | 15 | 18 | 12 |
| Catalyst property | |||||
| Specific area, m 2/g | 417 | 405 | 399 | 435 | 285 |
| Pore volume, mL/g | 0.405 | 0.399 | 0.401 | 0.441 | 0.345 |
| Intensity, N/mm | 21.8 | 21.4 | 22.3 | 20.7 | 18.7 |
Table 1 continues
| Catalyst is numbered | F | G | H | I |
| Catalyst forms | ||||
| NiO， wt% | 13 | 13 | 13 | 13 |
| WO 3，wt% | 16 | 16 | 16 | 16 |
| SiO 2，wt% | 30 | 30 | 30 | 30 |
| Al 2O 3，wt% | 33 | 33 | 33 | 33 |
| Other/wt% | ZrO 2/8.0 | ZrO 2/8.0 | ZrO 2/8.0 | ZrO 2/8.0 |
| The content of Y molecular sieve in catalyst, wt% | 12 | 12 | 12 | 12 |
| Catalyst property | ||||
| Specific area, m 2/g | 291 | 305 | 301 | 308 |
| Pore volume, mL/g | 0.299 | 0.311 | 0.305 | 0.309 |
| Intensity, N/mm | 20.5 | 18.4 | 20.1 | 19.6 |
Table 2 ESCA measures catalyst surface metal relative atomic concentration (mol ratio)
| Catalyst is numbered | A | B | C | D | E | F | G | H | I |
| I W/I Al | 0.17 | 0.18 | 0.19 | 0.19 | 0.12 | 0.11 | 0.11 | 011 | 0.12 |
| I Ni/I Al | 0.49 | 0.47 | 0.48 | 0.48 | 0.41 | 0.41 | 0.42 | 0.41 | 0.42 |
Table 3 transmissioning electric mirror determining catalyst surface WS
2density
| Catalyst is numbered | A | B | C | D | E | F | G | H | I |
| WS 2Density, grain/100nm | 46 | 46 | 47 | 45 | 37 | 36 | 37 | 38 | 37 |
Table 4 feedstock oil main character
| Project | Analysis result |
| Density (20 DEG C), g/cm 3 | 0.9113 |
| Boiling range scope, DEG C | 314-539 |
| S，μg/g | 9800 |
| N，μg/g | 1710 |
| Carbon residue, wt% | 0.14 |
| Condensation point, DEG C | 34 |
| Cetane number | 43.9 |
Table 5 evaluating catalyst result
| Catalyst is numbered | A | B | D | E | F | G | H | I |
| Reaction temperature, DEG C | 388 | 389 | 387 | 397 | 398 | 398 | 397 | 398 |
| Product slates, wt% | ||||||||
| Light naphthar (C 5~82℃） | 5.3 | 5.6 | 5.4 | 5.6 | 5.5 | 5.3 | 5.7 | 5.5 |
| Heavy naphtha (82 ~ 138 DEG C) | 9.1 | 8.9 | 9.1 | 9.9 | 9.8 | 10.1 | 9.5 | 9.3 |
| Jet fuel (138 DEG C ~ 249 DEG C) | 26.2 | 26.5 | 26.2 | 23.5 | 24.2 | 24.0 | 24.3 | 24.0 |
| Diesel oil (249 DEG C ~ 371 DEG C) | 26.8 | 26.1 | 26.5 | 24.6 | 23.8 | 24.1 | 24.0 | 24.1 |
| Tail oil (> 371 DEG C) | 34.2 | 33.9 | 34.5 | 36.1 | 36.7 | 36.4 | 36.2 | 36.2 |
| C 5 +Liquid is received, wt% | 99.2 | 99.5 | 99.4 | 98.7 | 98.1 | 98.8 | 98.7 | 98.8 |
| Chemical hydrogen consumption, wt% | 2.40 | 2.39 | 2.41 | 2.43 | 2.44 | 2.44 | 2.44 | 2.43 |
| Middle distillates oil selectivity, wt% | 80.2 | 79.8 | 80.4 | 75.2 | 75.8 | 75.6 | 75.7 | 75.3 |
The character of the modified molecular screen that table 6 the present invention relates to
| Molecular sieve character | Y |
| Relative crystallinity, % | 95 |
| Cell parameter, nm | 2.439 |
| SiO 2/Al 2O 3，mol/mol | 12.05 |
| Specific area, m 2/g | 839 |
| Pore volume, mL/g | 0.506 |
| 1.7 ~ 10nm secondary pore accounts for total pore volume, % | 48.0 |
| Infrared total acid, mmol/g | 0.999 |
| Na 2O，wt% | 0.093 |
Claims (20)
1. a preparation method for hydrocracking catalyst, comprising:
(1), prepare the solution A containing Ni, Al component and organic compound, precipitating reagent is added dropwise to solution A and carries out plastic reaction, generate nickeliferous, aluminum precipitation thing slurries I; Wherein organic compound is organic formwork agent and surfactant;
(2), preparation containing the mixed solution B of W, Si, Al component, by precipitating reagent and solution B and stream carries out plastic reaction, generate tungstenic, silicon, aluminum precipitation thing slurries II;
(3), by the slurries II of the slurries I of step (1) gained and step (2) gained mix, add Y zeolite suspension, more aging under agitation;
(4), step (3) obtain material drying, shaping, washing,
(5), drying and the roasting again of step (4) gained material, obtained hydrocracking catalyst.
2. in accordance with the method for claim 1, it is characterized in that: described Y zeolite adds with the form of molecular sieve suspension, is ground to 80 order ~ 140 orders, then adds water and make suspension by molecular sieve.
3. in accordance with the method for claim 1, it is characterized in that: the character of described Y zeolite is as follows: the pore volume that bore dia is greater than 1.7nm accounts for more than 45% of total pore volume, specific area is 750 ~ 900m
2/ g, cell parameter at 2.423nm ~ 2.545nm, relative crystallinity 95% ~ 110%, SiO
2/ Al
2o
3mol ratio is 7 ~ 60.
4. in accordance with the method for claim 1, it is characterized in that: in described hydrocracking catalyst, with the weight of catalyst for benchmark, WO
3content be the content of 10wt% ~ 50wt%, NiO be 1wt% ~ 30wt%, W/Ni atomic ratio be 0.05 ~ 1.0.
5. in accordance with the method for claim 1, it is characterized in that: in described hydrocracking catalyst, with the weight of catalyst for benchmark, WO
3content be the content of 15wt% ~ 30wt%, NiO be 5wt% ~ 20wt%, W/Ni atomic ratio be 0.1 ~ 0.7.
6. in accordance with the method for claim 1, it is characterized in that: Si, Al of introducing in step (2) are with oxide basis weight content in the catalyst for 20wt% ~ 60wt%, and wherein Si accounts for Si, Al with the 30wt% ~ 80wt% of the gross weight of oxide basis in silica; The Al introduced in step (1) with oxide basis weight content in the catalyst for 10wt% ~ 30wt%.
7. in accordance with the method for claim 1, it is characterized in that: in described hydrocracking catalyst, the content of Y zeolite is 5wt% ~ 30wt%.
8. in accordance with the method for claim 1, it is characterized in that: in step (1), organic formwork agent is one or more in tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, TPAOH, TBAB, TBAH, softex kw, DTAC; Surfactant is one or more in the condensation product of alkyl phenol and oxirane, polyoxyethylene sorbitol acid anhydride list olein, AEO, polyoxyethylene stearic acid ester; Organic compound consumption accounts in step (1) introduces Al with Al
2o
31wt% ~ the 35wt% of meter weight; Wherein organic formwork agent occupies the 30wt% ~ 80wt% of organic compounds consumption.
9. in accordance with the method for claim 1, it is characterized in that: in step (1), organic compound consumption accounts in step (1) introduces Al with Al
2o
35wt% ~ the 25wt% of meter weight; Wherein organic formwork agent occupies the 40wt% ~ 70wt% of organic compounds consumption.
10. in accordance with the method for claim 1, it is characterized in that: step (1) or the precipitating reagent described in step (2) are one or more in sodium carbonate, sodium acid carbonate, ammoniacal liquor, NaOH, potassium hydroxide, potash, saleratus.
11. in accordance with the method for claim 1, it is characterized in that: step (1) or the precipitating reagent described in step (2) are ammoniacal liquor.
12. in accordance with the method for claim 1, it is characterized in that: in step (1) mixed solution A, and Ni is that 20 ~ 80g/L, Al are with Al in the weight concentration of NiO
2o
3the weight concentration of meter is 60 ~ 200g/L; In step (2) mixed solution B, W is with WO
3the weight concentration of meter is that 50 ~ 120g/L, Si are with SiO
2weight concentration is that 80 ~ 250g/L, Al are with Al
2o
3the weight concentration of meter is 60 ~ 200g/L.
13. in accordance with the method for claim 1, it is characterized in that: in step (1) mixed solution A, and Ni is that 30 ~ 60g/L, Al are with Al in the weight concentration of NiO
2o
3the weight concentration of meter is 90 ~ 150g/L; In step (2) mixed solution B, W is with WO
3the weight concentration of meter is that 70 ~ 100g/L, Si are with SiO
2weight concentration is that 100 ~ 180g/L, Al are with Al
2o
3the weight concentration of meter is 90 ~ 150g/L.
14. in accordance with the method for claim 1, it is characterized in that: when preparing mixed solution A, the nickel source adopted is one or more in nickelous sulfate, nickel nitrate, basic nickel carbonate, nickel chloride, and aluminium source is one or more in aluminum nitrate, aluminum sulfate, aluminium chloride or aluminium acetate etc.; When preparing mixed solution B, the tungsten source of employing is one or more in ethyl ammonium metatungstate, ammonium metatungstate; Silicon source is one or more in Ludox, sodium metasilicate; Aluminium source is one or more in aluminum nitrate, aluminum sulfate, aluminium chloride or aluminium acetate etc.
15. in accordance with the method for claim 1, it is characterized in that: in step (1), reaction temperature is 20 ~ 90 DEG C, and during cemented into bundles, pH value controls is 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour; In step (2), reaction temperature is 30 ~ 90 DEG C, and when flowing plastic, pH value control is 6.0 ~ 11.0, and gelation time is 0.2 ~ 4.0 hour.
16. in accordance with the method for claim 1, it is characterized in that: in step (1), reaction temperature is 30 ~ 70 DEG C, and during cemented into bundles, pH value controls is 7.0 ~ 9.0, and gelation time is 0.5 ~ 3.0 hour; In step (2), reaction temperature is 40 ~ 80 DEG C, and when flowing plastic, pH value control is 7.0 ~ 9.0, and gelation time is 0.5 ~ 3.0 hour.
17. in accordance with the method for claim 1, it is characterized in that: in step (3), aging temperature is 40 ~ 90 DEG C, and time aging, pH value controls is 6.0 ~ 10.0, and ageing time is 0.5 ~ 6.0 hour.
18. in accordance with the method for claim 1, it is characterized in that: the drying condition described in step (4): 50 ~ 200 DEG C of dryings 1 ~ 48 hour; Drying described in step (5) and roasting condition as follows: 50 ~ 200 DEG C of dryings 1 ~ 48 hour, 450 ~ 600 DEG C of roastings 1 ~ 24 hour.
19. in accordance with the method for claim 1, it is characterized in that: containing adjuvant component in described hydrocracking catalyst, described adjuvant component is Ti and/or Zr, with the content of oxide basis in hydrocracking catalyst for 1wt% ~ 10wt%.
20. in accordance with the method for claim 19, it is characterized in that: in hydrocracking catalyst preparation process, adds the compound containing adjuvant component, i.e. titanium source and/or zirconium source in preparation mixed solution A process; Titanium source adopts Titanium Nitrate, titanium sulfate, one or more in titanium chloride, zirconium source adopt in zirconium nitrate, zirconium chloride, zirconium oxychloride one or more.
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