CN101450320B - Hydrocracking catalyst containing Y molecular sieve and preparation method thereof - Google Patents
Hydrocracking catalyst containing Y molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrocracking catalyst for producing heavy naphtha in great abundance and a preparation method thereof. The catalyst contains hydrogenation active metals and a carrier which consists of modified Y molecular sieves and alumina, wherein the Y molecular sieves are obtained by using a mixed aqueous solution of aluminum salts and an acid to perform hydro-thermal treatment. The properties of the modified Y molecular sieves are as follows: the specific surface area is between 750 m<2>/g and 850 m<2>/g; the total pore volume is between 0.35 and 0.48 ml/g; the relative crystallinity is between 90 and 130 percent; the cell parameter is between 2.437 and 2.445 nanometers; the silicon-aluminum mol ratio is between 15 and 70; the infrared acid amount is between 0.5 and 1.0 mmol/g; the B acid/L acid is more than 7.0; and the content of sodium oxide is less than or equal to 0.05 weight percent. The hydrocracking catalyst has the characteristics of good catalytic activity, high heavy naphtha selectivity, high yield, high latent content of heavy naphtha arene, and so on.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, hydrocracking catalyst of particularly voluminous catalytic reforming raw material (heavy naphtha) and preparation method thereof.
Background technology
Along with developing rapidly of Chinese national economy, the present and the future in long one period market to the demand of all kinds of industrial chemicals especially aromatic hydrocarbons raw material with sustainable growth, catalytic reforming technical development as production aromatic hydrocarbons raw material is rapid, and this makes it possible to also significantly increase as the demand of the heavy naphtha of catalytic reforming raw material.As one of main means of heavy oil lighting, hydrocracking technology be rationally utilize limited petroleum resources, the optimum oil Refining Technologies of the heavy naphtha that raises productivity and improves the quality.Hydrocracking catalyst is the core of hydrocracking technology, and this just requires to develop the stronger hydrocracking catalyst of specific aim to adapt to the demand in market.
Hydrocracking catalyst is a kind of bifunctional catalyst, promptly has cracking activity and hydrogenation activity simultaneously.Cracking activity is mainly provided by various molecular sieves, and hydrogenation activity is mainly provided by the metal of group vib in the periodic table of elements and VIII family.For the heavy naphtha that raises productivity and improves the quality, require hydrocracking catalyst to have the strong cracking activity and the hydrogenation activity of moderate strength, its key is the performance as the molecular sieve of cracking activity component.
US5670590 discloses a kind of hydrocracking catalyst, and purpose is voluminous naphtha cut, is characterized in having used a kind of USY molecular sieve.This USY molecular sieve is by the exchange of the former powder process of NaY ammonium nitrate, roasting, and then obtains through ammonium nitrate exchange, a roasting, cell parameter 2.438～2.442nm, and sodium content is higher, generally about 1wt%.This catalyst activity is low, and the selectivity of heavy naphtha is not very high, and the hydrogen consumption is also bigger.
US4672048 discloses a kind of light oil type hydrogen cracking catalyst, adopts Y zeolite, is characterized in that silica alumina ratio is 11～15.The Y zeolite preparation method handles ammonia type Y molecular sieve with ammonium hexafluorosilicate in acidic buffer solution, generally about 0.5wt%, catalyst activity is low for gained molecular sieve sodium content.
Hydrocracking catalyst in the above-mentioned patent adopts the modified Y molecular sieve of different performance, and this is because method of modifying has nothing in common with each other, and has therefore also just caused the difference on the catalyst performance.
The method of modified Y molecular sieve is used the chemical dealuminization method always, wherein sour dealuminzation is the most frequently used method, acid-treated condition is generally relatively gentleer, can control it removes non-framework aluminum in the molecular sieve and does not slough framework aluminum, promptly the structure of saboteur sieve not will further be filtered after the acid treatment, be washed to remove remaining acid and acid ion etc.But for the difficult non-framework aluminum that removes of part, if adopt the general acid treatment then can not be effectively, remove equably with it, if by improving the concentration of acid, then can cause removing of part framework aluminum, make that structural deterioration, the degree of crystallinity of molecular sieve descends after the modification, sour irrational distribution, thereby directly cause the reduction of cracking performance.Another kind of chemical dealuminization method is the solution-treated molecular sieve with aluminium salt, has provided a kind of independent method with the Y zeolite after the solution-treated hydrothermal treatment consists of aluminium salt as CN1178721A.Use aluminium salt also can partly remove the non-framework aluminum that forms after the hydrothermal treatment consists separately, but because the pH value of aluminum saline solution is generally between 2～3, also be not enough to remove in large quantities non-framework aluminum, make the non-framework aluminum that part is difficult to remove in micropore also be retained in the molecular sieve, cause the part acid centre of molecular sieve masked, also can influence the distribution of B acid and L acid, be difficult to bring into play to greatest extent the cracking performance of molecular sieve.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of hydrocracking catalyst and preparation method thereof.This hydrocracking catalyst has high catalytic activity, and the heavy naphtha that can raise productivity and improve the quality.
Hydrocracking catalyst of the present invention comprises hydrogenation active metals and the carrier of being made up of modified Y molecular sieve and aluminium oxide, and wherein said modified molecular screen character is as follows: specific surface 750m
2/ g～850m
2/ g, total pore volume 0.35ml/g～0.48ml/g, relative crystallinity 90%～130%, cell parameter 2.437～2.445nm, silica alumina ratio 15～70, be preferably 30～70, meleic acid amount 0.5～1.0mmol/g, B acid/L acid is preferably more than 8.0 greater than 7.0, sodium oxide content≤0.05wt% is preferably≤0.01wt%.
In the hydrocracking catalyst of the present invention, modified Y molecular sieve is to use aluminium salt and inorganic acid or the processing of the organic acid mixed aqueous solution NH through dealumination complement silicon and hydrothermal treatment consists
4The NaY molecular sieve obtains.
Hydrocracking catalyst character of the present invention is as follows: the BET specific area is 330～480m
2/ g, pore volume are 0.32～0.50ml/g.
Described hydrogenation active metals is the metal of group vib and/or group VIII, and the group vib metal is preferably molybdenum and/or tungsten, and the metal of group VIII is preferably and bores and/or nickel.In the weight of catalyst, the content of group vib metal (in oxide) is 15.0%～30.0%, and the content of group VIII metal (in oxide) is 4.0%～8.0%.
The described carrier that contains modified Y molecular sieve, in the weight of carrier, 30%～70% modified Y molecular sieve and 30%～70% aluminium oxide.
The specific area of carrier of hydrocracking catalyst of the present invention is 450～650m
2/ g, pore volume are 0.45～0.70ml/g.
The preparation method of hydrocracking catalyst of the present invention comprises the steps:
With modified Y molecular sieve, aluminium oxide and adhesive mechanical mixture, moulding, catalyst carrier is made in drying and roasting then; Adopt conventional method supported active metal on the catalyst carrier of gained;
Wherein said modified Y molecular sieve comprises being prepared as follows step:
(1) with NH
4The NaY molecular sieve is a raw material, carries out dealumination complement silicon with the hexafluorosilicic acid aqueous ammonium, molecular sieve that obtains and separation of by-products,
(2) Y zeolite that step (1) is obtained carries out hydrothermal treatment consists;
(3) with the Y zeolite of aluminium salt and inorganic acid or organic acid mixed aqueous solution treatment step (2) gained, filter then, wash and drying, obtain Y zeolite of the present invention.
Hydrothermal treatment consists condition described in the step (2) is as follows: gauge pressure 0.05～0.4MPa is preferably 0.1～0.2MPa, 500～600 ℃ of temperature, 0.5～5 hour processing time, preferred 1～3 hour;
In the step (3), in described aluminium salt and inorganic acid or the organic acid mixed aqueous solution, the aluminium salinity is (with Al
3+Meter) 0.2～4.0mol/L, preferred 1.0～2.0mol/L, inorganic acid or organic acid concentration are (with H
+Meter) 0.2～2.0mol/L, preferred 0.4～1.0mol/L.Aluminium salt is (with Al
3+Meter) with inorganic acid or organic acid (with H
+Meter) mol ratio is 0.2～20, preferred 2～5.The weight ratio of aluminium salt and inorganic acid or organic acid mixed solution and molecular sieve is 3: 1～20: 1.Described treatment conditions: 40～120 ℃ of temperature, be preferably 70～100 ℃, the time is 0.5～8 hour, preferred 1～3 hour.Described washing till cleaning solution pH value is near neutrality, under 100～120 ℃ condition dry 3～6 hours then.
Hydrocracking catalyst of the present invention can be used in the conventional hydrocracking process, be specially adapted to the hydrocracking process of voluminous reformer feed, its hydrocracking operating condition is as follows: reaction temperature is 340～420 ℃, stagnation pressure 8～17MPa, hydrogen to oil volume ratio 600～1500, volume space velocity 0.6～2.5h during liquid
-1
Modified Y molecular sieve of the present invention is the Y zeolite that adopts after aluminium salt and sour mixed aqueous solution are handled hydrothermal treatment consists, under the situation that does not remove framework aluminum, not only can remove the non-framework aluminum fragment that almost all is deposited in the secondary pore, and can also remove the non-framework aluminum fragment that is filled in a large number in the micropore, under the situation that keeps the molecular sieve high-crystallinity, improved after the hydrothermal treatment consists amount of removing of non-framework aluminum in the molecular sieve, improved the silica alumina ratio of molecular sieve, increased the specific surface of molecular sieve, adopt suitable hydrothermal treatment consists condition simultaneously, the acidity and the acid that have improved molecular sieve distribute, especially the distribution of B acid and L acid, and make the secondary pore duct that forms after the hydrothermal treatment consists become very " unobstructed ".The formation of secondary pore, to macromolecular reaction is favourable, and the big easier crystals that enters of molecule makes it can touch more activated centre, makes simultaneously that product is easier to be diffused out, and the acid centre of the Y molecular sieve after handling is evenly distributed, and can reduce second pyrolysis.In addition, the sodium oxide content in this modified Y molecular sieve can drop to below 0.01%, and can make by this molecular sieve is the activity increase of the hydrocracking catalyst of active component, can promote the performance of catalyst hydrogenation performance simultaneously better.Catalyst of the present invention adopts this Modified Zeolite Y as acidic components, and is suitable to light oil type hydrogen cracking catalyst, improves activity of such catalysts and heavy naphtha selectivity.
The specific embodiment
Aluminium oxide can comprise macroporous aluminium oxide and little porous aluminum oxide in the carrier of hydrocracking catalyst of the present invention, and wherein little porous aluminum oxide is partly or entirely made adhesive and used.Percentage by weight with carrier is a benchmark: macroporous aluminium oxide content is 5%～50%, is preferably 15%～40%, and the aperture alumina content is 5%～25%, is preferably 10%～25%.
The macroporous aluminium oxide that the present invention is used, its pore volume is 0.6～1.3ml/g, is preferably 0.7～1.1ml/g, specific area is 300～450m
2/ g.
Adhesive therefor of the present invention is to be made by little porous aluminum oxide and inorganic acid and/or organic acid.Used aperture aluminium oxide pore volume is 0.3～0.5ml/g, and specific area is 200～400m
2/ g.
The Y molecular sieve of modification in the hydrocracking catalyst of the present invention, concrete preparation method is as follows:
(1) with NH
4NaY is a raw material, handles with the hexafluorosilicic acid aqueous ammonium.
In aqueous medium, add raw material NH
4NaY stirs and is warmed up to 80～150 ℃, is preferably 90～120 ℃, is added dropwise to the hexafluorosilicic acid aqueous ammonium then, is dropwising back constant temperature stirring 0.1～4 hour, and preferred 1～2 hour, isolated molecule sieve and accessory substance, and washing molecular sieve, filtration, drying.Wherein, raw material NH
4The silica alumina ratio of NaY is 3～6, is preferably 4.5～5.5, cell parameter 2.465～2.470nm, Na
2O content≤5wt%, preferred≤3wt%.The silica alumina ratio of the molecular sieve of step (1) gained is 8～15, and is preferred 9～12, and the meleic acid amount is 1.1～1.5mmol/g, and relative crystallinity is 95%～110%, cell parameter 2.448～2.452nm, Na
2O content is at 0.1wt%～1.0wt%, preferred 0.1wt%～0.3wt%.
(2) with the molecular sieve that obtains in the saturated steam treatment step (1).
Add the molecular sieve that obtains in the step (1) in tubular type hydrothermal treatment consists stove, treatment conditions: gauge pressure 0.05～0.4MPa is preferably 0.1～0.2MPa, 500～600 ℃ of temperature, 0.5～5 hour processing time, preferred 1～3 hour;
(3) molecular sieve that obtains in the mixed aqueous solution treatment step (2) with aluminium salt and acid.
Add the mixed solution of aluminium salt and acid in having the also airtight container of return-flow system, wherein the aluminium salinity is (with Al
3+Meter) 0.2～4.0mol/L, preferred 1.0～2.0mol/L, inorganic acid or organic acid concentration are (with H
+Meter) 0.2～2.0mol/L, preferred 0.4～1.0mol/L stirs and is warmed up to 40～120 ℃, is preferably 70～100 ℃, be 3: 1～20: 1 by aluminium salt with the mixed solution of acid and the weight ratio of molecular sieve then, add the molecular sieve that step (2) obtains, constant temperature stirred 0.5～4 hour, preferred 1～2.5 hour, filter, wash, washing and under 100～120 ℃ condition dry 3～6 hours, obtains Y zeolite of the present invention till cleaning solution pH value is near neutrality.Wherein aluminium salt can be in alchlor, aluminum nitrate, the aluminum sulfate one or more in the mixed aqueous solution of aluminium salt and acid; Inorganic acid or organic acid can be one or more in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, the citric acid.
The detailed process of catalyst carrier for hydrgenating preparation of the present invention is:
Modified Y molecular sieve, aluminium oxide and adhesive are mixed, extruded moulding, drying and roasting are prepared into carrier; Described drying can be carried out under 80 ℃ to 150 ℃ temperature 3～6 hours, and roasting is 500 ℃～600 ℃ roastings 2.5～6 hours.
The load of catalyst activity metal of the present invention, the content of tungsten (in oxide) is 15.0%～30.0%, the content of metallic nickel (in oxide) is 4.0%～8.0%; Can adopt carrying method conventional in the prior art, preferred infusion process, can be saturatedly soak, excessive soak or complexing is soaked, promptly with the solution impregnated catalyst carrier that contains required active component, soaked carrier was 100 ℃～150 ℃ dryings 1～12 hour, 450 ℃～550 ℃ roastings 2.5～6.0 hours, make final catalyst then.
The following examples are used to illustrate in greater detail the present invention, but scope of the present invention is not only limited to the scope of these embodiment.
Analytical method of the present invention: specific surface and pore volume adopt the low temperature liquid nitrogen physisorphtion, relative crystallinity and cell parameter adopt x-ray diffraction method, silica alumina ratio adopts chemical method, meleic acid amount, B acid amount and L acid amount adopt the pyridine adsorption infra-red sepectrometry, wherein the summation of B acid amount and L acid amount is the meleic acid amount, and sodium content adopts plasma emission spectrometry.
Embodiment 1
Get 3000gNa
2O content is the raw material NH of 2.8wt% (butt 70.3wt%)
4NaY, put into and have the flask that reflux also can be airtight, pull an oar with the 11700ml deionized water, and under stirring condition, be warmed up to 95 ℃ rapidly, in 2 hours, drip the aqueous solution with even velocity then, add rear slurry constant temperature 2 hours under 95 ℃ of stirring conditions by 680 gram ammonium hexafluorosilicate and 4500ml deionized water configurations.Stop to stir, left standstill 10 minutes, isolate the molecular sieve on flask top with decantation, filter through 3 washing backs, filter cake in 120 ℃ of baking ovens dry 5 hours is numbered SSY-1.Resulting SSY-1 molecular sieve records its cell parameter 2.450nm, relative crystallinity 98%, Na through X-ray diffraction (XRD) and plasmatron spectrographic analysis
2O content is 0.1wt%.
Embodiment 2
Take by weighing the 300gSSY-1 molecular sieve and put into tubular type hydrothermal treatment consists stove, temperature programming to 550 ℃, under gauge pressure 0.1MPa, handled 1.5 hours, put into then and have the flask that reflux also can be airtight, add the mixed aqueous solution 1500ml that contains concentration 0.9mol/L aluminum sulfate and 0.3mol/L sulfuric acid, stirred 2 hours, filter at 95 ℃ of following constant temperature, and use the hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 ℃ of dryings 5 hours in baking oven.Numbering LSY-1, molecular sieve character sees Table 1.
Embodiment 3
Take by weighing the 300gSSY-1 molecular sieve and put into tubular type hydrothermal treatment consists stove, temperature programming to 570 ℃, under gauge pressure 0.2MPa, handled 2 hours, put into then and have the flask that reflux also can be airtight, add the mixed aqueous solution 6000ml that contains concentration 0.6mol/L aluminum sulfate and 0.2mol/L citric acid, stirred 1 hour, filter at 100 ℃ of following constant temperature, and use the hot deionized water washing leaching cake, after 7, stop washing with the pH value of washing liquid.Filter cake 120 ℃ of dryings 5 hours in baking oven.Numbering LSY-2, molecular sieve character sees Table 1.
Comparative Examples 1
Take by weighing the 200gSSY-1 molecular sieve and put into tubular type hydrothermal treatment consists stove, temperature programming to 550 ℃, under gauge pressure 0.1MPa, handled 1.5 hours, put into then and have the flask that reflux also can be airtight, add and contain concentration 0.9mol/L aluminum sulfate solution 1000ml, stirred 2 hours, filter at 95 ℃ of following constant temperature, and use the hot deionized water washing leaching cake, after 7, stop washing with the pH value of cleaning solution.Filter cake 120 ℃ of dryings 5 hours in baking oven.Numbering DSY-1, molecular sieve character sees Table 1.
Embodiment 4
With 105.3 gram LSY-1 molecular sieves (butt 95wt%), 85.7 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, carrier.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roastings of temperature programming 4 hours, catalyst FHC-1, carrier and corresponding catalyst character see Table 2.
Embodiment 5
With 136.8 gram LSY-1 molecular sieves (butt 95wt%), 42.86 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, carrier.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roastings of temperature programming 4 hours, catalyst FHC-2, carrier and corresponding catalyst character see Table 2.
Embodiment 6
With 94.7 gram LSY-2 molecular sieves (butt 95wt%), 100 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, carrier.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roastings of temperature programming 4 hours, catalyst FHC-3, carrier and corresponding catalyst character see Table 2.
Embodiment 7
With 84.2 gram LSY-2 molecular sieves (butt 95wt%), 114.2 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, carrier.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roastings of temperature programming 4 hours, catalyst FHC-4, carrier and corresponding catalyst character see Table 2.
Comparative Examples 2
With 105.3 gram DSY-1 molecular sieves (butt 95wt%), 85.7 gram macroporous aluminium oxide (pore volume 1.0ml/g, specific area 400m
2/ g, butt 70wt%), 133.3 gram adhesives (butt 30wt%, the mol ratio of nitric acid and little porous aluminum oxide is 0.3) are put into the roller mixed grind, add water, be rolled into paste, extrusion, extrude bar 110 ℃ of dryings 4 hours, then 550 ℃ of roastings 4 hours, carrier.
Carrier is with the maceration extract room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roastings of temperature programming 4 hours, catalyst DHC-1, carrier and corresponding catalyst character see Table 2.
Embodiment 8
Present embodiment has been introduced the catalyst activity evaluation result.Estimate on the fixed bed hydrogenation experimental rig, appreciation condition is: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200: 1, volume space velocity 1.60h
-1Feedstock oil is vacuum distillate (VGO), and character is listed in table 3.Catalyst FHC-1, FHC-3, DHC-1 are estimated under identical process conditions, and the evaluation result that obtains is listed in table 4.
By evaluation result as can be seen, under identical process conditions, the yield of catalyst heavy naphtha of the present invention, quality etc. all are better than reference catalyst.Therefore hydrocracking catalyst of the present invention has very high activity, and the heavy naphtha that can raise productivity and improve the quality.
The physico-chemical property of table 1 embodiment and Comparative Examples gained molecular sieve
| ? | Embodiment 2 | Embodiment 3 | Comparative Examples 1 |
| Numbering | LSY-1? | LSY-2? | DSY-1? |
| The hydrothermal treatment consists condition | ? | ? | ? |
| Temperature, ℃ | 550? | 570? | 550? |
| Pressure, MPa | 0.1? | 0.2? | 0.1? |
| Time, h | 1.5? | 2.0? | 1.5? |
| Washing dealuminzation condition | ? | ? | ? |
| Aluminium salt and/or acid | Aluminum sulfate+sulfuric acid | Aluminum sulfate+citric acid | Aluminum sulfate |
| Treatment temperature, ℃ | 95? | 100? | 95? |
| Aluminum sulfate concentration/sulfuric acid concentration, mol/L | 0.9/0.3? | 0.6/0.2? | 0.9? |
| The mixed solution of aluminium salt and/or acid and the weight ratio of molecular sieve | 5∶1? | 20∶1? | 5∶1? |
| Time, h | 2.0? | 1.0? | 2.0? |
| The character of Y zeolite product | ? | ? | ? |
| Cell parameter, nm | 2.439? | 2.437? | 2.435? |
| Silica alumina ratio | 40.4? | 35.1? | 23.2? |
| Relative crystallinity, % | 110? | 106? | 101? |
| Specific surface, m 2/g? | 830? | 826? | 742? |
| Total pore volume, ml/g | 0.438? | 0.436? | 0.396? |
| Infrared acidity, mmol/g | 0.766? | 0.731? | 0.640? |
| B acid/L acid | 8.32? | 8.07? | 5.31? |
| Na 2O，wt％? | ＜0.01? | ＜0.01? | 0.06? |
The physico-chemical property of table 2 catalyst carrier and catalyst
| ? | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Comparative Examples 2 |
| Carrier is formed and character | ? | ? | ? | ? | ? |
| Modified Y molecular sieve, wt% | 50.0? | 65.0? | 45.0? | 40.0? | 50.0? |
| Macroporous aluminium oxide, wt% | 30.0? | 15.0? | 35.0? | 40.0? | 30.0? |
| Adhesive, wt% | 20.0? | 20.0? | 20.0? | 20.0? | 20.0? |
| Pore volume, ml/g | 0.54? | 0.46? | 0.57? | 0.60? | 0.50? |
| Specific area, m 2/g? | 589? | 649? | 563? | 539? | 540? |
| Catalyst is formed and character | ? | ? | ? | ? | ? |
| Numbering | FHC-1? | FHC-2? | FHC-3? | FHC-4? | DHC-1? |
| ?WO 3，wt％? | 22.46? | 23.40? | 21.30? | 24.62? | 22.12? |
| ?NiO，wt％? | 5.96? | 6.80? | 5.69? | 6.39? | 6.12? |
| Pore volume, ml/g | 0.39? | 0.33? | 0.42? | 0.41? | 0.36? |
| Specific area, m 2/g? | 422? | 453? | 417? | 381? | 385? |
Table 3 feedstock oil main character
| Feedstock oil | Vacuum distillate |
| Density (20 ℃), kg/m 3 | 920.6? |
| Boiling range, ℃ | ? |
| IBP/10％? | 328/413? |
| 30％/50％? | 450/471? |
| 70％/90％? | 493/522? |
| 95％/EBP? | 534/545? |
| Nitrogen, μ g/g | 1575? |
| Carbon, wt% | 85.25? |
| Hydrogen, wt% | 11.96? |
| Carbon residue, wt% | 0.35? |
Table 4 catalyst comparative evaluation result
| Catalyst | FHC-1? | FHC-3? | DHC-1? |
| Feedstock oil | Vacuum distillate | Vacuum distillate | Vacuum distillate |
| Volume space velocity during liquid, h -1 | 1.60? | 1.60? | 1.60? |
| The reaction stagnation pressure, MPa | 14.7? | 14.7? | 14.7? |
| Hydrogen to oil volume ratio | 1200∶1? | 1200∶1? | 1200∶1? |
| Reaction temperature, ℃ | 356? | 358? | 360? |
| Product yield and character | ? | ? | ? |
| Heavy naphtha | ? | ? | ? |
| Yield, wt% | 42.0? | 41.9? | 40.3? |
| Virtue is dived, wt% | 58.1? | 57.5? | 56.2? |
| Jet fuel | ? | ? | ? |
| Yield, wt% | 20.1? | 19.8? | 19.2? |
| Smoke point, mm | 28? | 27? | 27? |
| Aromatic hydrocarbons, v% | 5.1? | 5.3? | 6.2? |
| Diesel oil | ? | ? | ? |
| Yield, wt% | 10.3? | 10.1? | 9.6? |
| Cetane number | 64.6? | 63.6? | 62.8? |
| Tail oil | ? | ? | ? |
| Yield, wt% | 18.2? | 18.3? | 18.6? |
| The BMCI value | 9.1? | 9.3? | 11.8? |
| Chemistry hydrogen consumption, wt% | 2.68? | 2.70? | 2.76? |
| Liquid is received, wt% | 95.2? | 94.9? | 94.1? |
Claims (18)
1. a hydrocracking catalyst comprises hydrogenation active metals and the carrier of being made up of modified Y molecular sieve and aluminium oxide, and wherein said modified Y molecular sieve character is as follows: specific surface 750m
2/ g～850m
2/ g, total pore volume 0.35ml/g～0.48ml/g, relative crystallinity 90%～130%, cell parameter 2.437～2.445nm, silica alumina ratio 30～70, meleic acid amount 0.5～1.0mmol/g, B acid/L acid is greater than 7.0, sodium oxide content≤0.05wt%.
2. according to the described hydrocracking catalyst of claim 1, it is characterized in that described modified Y molecular sieve silica alumina ratio is 30～70, B acid/L acid is greater than 8.0.
3. according to claim 1 or 2 described hydrocracking catalysts, it is characterized in that sodium oxide content≤0.01wt% in the described modified Y molecular sieve.
4. according to the described hydrocracking catalyst of claim 1, it is characterized in that described modified Y molecular sieve is to use aluminium salt and inorganic acid or the processing of the organic acid mixed aqueous solution NH through dealumination complement silicon and hydrothermal treatment consists
4The NaY molecular sieve obtains.
5. according to the described hydrocracking catalyst of claim 1, it is characterized in that in the described carrier of hydrocracking catalyst, in the weight of carrier, comprise 30%～70% modified Y molecular sieve, 30%～70% aluminium oxide.
6. according to claim 1 or 5 described hydrocracking catalysts, it is characterized in that described hydrocracking catalyst character is as follows: specific area is 330～480m
2/ g, pore volume are 0.32～0.50ml/g.
7. according to the described hydrocracking catalyst of claim 1, it is characterized in that described hydrogenation active metals is the metal of group vib and group VIII, the group vib metal is molybdenum and/or tungsten, the metal of group VIII is cobalt and/or nickel, weight in catalyst, the group vib metal is 15.0%～30.0% in the content of oxide, and the group VIII metal is 4.0%～8.0% in the content of oxide.
8. the preparation method of the arbitrary described hydrocracking catalyst of claim 1～7 comprises the steps:
With modified Y molecular sieve, aluminium oxide, adhesive mechanical mixture, moulding, catalyst carrier is made in drying and roasting then; Adopt conventional method supported active metal on the catalyst carrier of gained, drying and roasting make hydrocracking catalyst then;
Wherein said modified Y molecular sieve comprises being prepared as follows step:
(1) with NH
4The NaY molecular sieve is a raw material, carries out dealumination complement silicon with the hexafluorosilicic acid aqueous ammonium, molecular sieve that obtains and separation of by-products,
(2) Y zeolite that step (1) is obtained carries out hydrothermal treatment consists;
(3) with the Y zeolite of aluminium salt and inorganic acid or organic acid mixed aqueous solution treatment step (2) gained, filter then, wash and drying, obtain modified Y molecular sieve of the present invention;
Step (2) hydrothermal treatment consists condition: gauge pressure 0.05～0.4MPa, 500～600 ℃ of temperature, 0.5～5 hour processing time;
In the step (3), in described aluminium salt and inorganic acid or the organic acid mixed aqueous solution, the aluminium salinity is with Al
3+Count 0.2～4.0mol/L, inorganic acid or organic acid concentration are with H
+Count 0.2～2.0mol/L; Aluminium salt is with Al
3+Meter and inorganic acid or organic acid are with H
+The mol ratio of meter is 0.2～20; The weight ratio of aluminium salt and inorganic acid or organic acid mixed solution and molecular sieve is 3: 1～20: 1; Described treatment conditions: 40～120 ℃ of temperature, the time is 0.5～8 hour.
9. according to the described preparation method of claim 8, it is characterized in that in the step (3), in described aluminium salt and inorganic acid or the organic acid mixed aqueous solution, the aluminium salinity is with Al
3+Count 1.0～2.0mol/L, inorganic acid or organic acid concentration are with H
+Count 0.4～1.0mol/L.
10. according to the described preparation method of claim 8, it is characterized in that aluminium salt is with Al in the step (3)
3+Meter and inorganic acid or organic acid are with H
+The mol ratio of meter is 2～5.
11. according to the described preparation method of claim 8, it is characterized in that the described treatment conditions of step (3): temperature is 70～100 ℃, the time is 1～3 hour.
12. according to the described preparation method of claim 8, it is characterized in that in the step (3), described washing till cleaning solution pH value is near neutrality, under 100～120 ℃ condition dry 3～6 hours then.
13., it is characterized in that in the step (3) that described aluminium salt is one or more in alchlor, aluminum nitrate, the aluminum sulfate according to the described preparation method of claim 8; Inorganic acid or organic acid are one or more in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, the citric acid.
14., it is characterized in that the detailed process of step (1) is as follows: in aqueous medium, add raw material NH according to the described preparation method of claim 8
4NaY stirs and is warmed up to 80～150 ℃, is added dropwise to the hexafluorosilicic acid aqueous ammonium then, is dropwising back constant temperature stirring 0.1～4 hour, isolated molecule sieve and accessory substance, and washing molecular sieve, filtration, drying; Wherein, raw material NH
4The silica alumina ratio of NaY is 3～6, cell parameter 2.465～2.470nm, Na
2O content≤5wt%; The silica alumina ratio of the molecular sieve of step (1) gained is 8～15, and the meleic acid amount is 1.1～1.5mmol/g, and relative crystallinity is 95%～110%, cell parameter 2.448～2.452nm, Na
2O content is at 0.1wt%～1.0wt%.
15., it is characterized in that the hydrothermal treatment consists condition of step (2): gauge pressure 0.1～0.2MPa, 500～600 ℃ of temperature, 1～3 hour processing time according to the described preparation method of claim 8.
16. according to the described preparation method of claim 8, it is characterized in that described carrier drying condition is as follows: carried out under 80 ℃ to 150 ℃ temperature 3～6 hours, roasting condition was as follows: 500 ℃～600 ℃ roastings 2.5～6 hours; Described catalyst drying condition is as follows: 100 ℃～150 ℃ dryings 1～12 hour, roasting condition was as follows: 450 ℃～550 ℃ roastings 2.5～6.0 hours.
17. the arbitrary described hydrocracking catalyst of claim 1～7 is used in hydrocracking process, its hydrocracking operating condition is as follows: reaction temperature is 340～420 ℃, stagnation pressure 8～17MPa, hydrogen to oil volume ratio 600～1500, volume space velocity 0.6～2.5h during liquid
-1
18. according to the described application of claim 17, hydrocracking process wherein is the hydrocracking process of voluminous reformer feed.
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