CN101757929A - Hydrocracking catalyst and preparation method thereof - Google Patents
Hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN101757929A CN101757929A CN 200810240866 CN200810240866A CN101757929A CN 101757929 A CN101757929 A CN 101757929A CN 200810240866 CN200810240866 CN 200810240866 CN 200810240866 A CN200810240866 A CN 200810240866A CN 101757929 A CN101757929 A CN 101757929A
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Abstract
The invention relates to a hydrocracking catalyst and a preparation method thereof. The catalyst contains a carrier, a hydrogenering active component loaded on the carrier, and IVB group metal components in the periodic table of elements, wherein the pore diameter of the most probable pore of the carrier is 6-12 nanometers, the concentration degree of the pore diameter is more than 7, and the concentration degree of the pore diameter is the ratio of the height of a peak and the half-height width of the peak in a distribution curve of the differentiation of specific pore volume to the pore diameter with the pore diameter. Compared with the existing hydrocracking catalyst, the hydrocracking catalyst provided by the invention has smaller pore diameter of the carrier (the pore diameter of the most probable pore is small), the distribution is concentrated (the concentration degree of the pore diameter is high), and the hydrodesulfurization and hydrogenation carbon residue removal of the catalyst are obviously improved.
Description
Technical field
The invention relates to a kind of hydrocracking catalyst and preparation method thereof.
Background technology
In recent years, crude oil heavy and poor qualityization tendency are obvious day by day in the world wide, meanwhile, and to the but constantly increase of demand of middle distillate and reformation, steam crack material.This impels the heavy distillate process technology to be developed rapidly, and hydrogenation catalyst comprises that hydrofinishing, hydrotreatment and hydrocracking catalyst are wherein important and The key factor.
For residual oil hydrocatalyst, catalysqt deactivation is the problem of the right maximum of demand side often, has bigger aperture and the enough pore volume except requiring catalyst, also needs necessary reactive metal with activation hydrogen, make the reactant hydrogenation on the one hand, slow down the inactivation of catalyst on the other hand.The hydrogenation activity component generally is metal, metal oxide and/or the metal sulfide that is selected from group vib and VIII family in the periodic table of elements.
CN1803995A discloses a kind of fluorine-containing hydrogenization catalyst preparation method, this method is included in and introduces fluorine and hydrogenation active metals component in the carrier, wherein, it is under 60-250 ℃ and the airtight condition that the method for introducing fluorine is included in temperature, carrier is contacted 0.5-5 hour with a kind of solution of fluorochemical, and described fluorochemical is selected from HF, NH
4F, (NH
4)
2SiF
6, (NH
4)
2ZrF
6, (NH
4)
2TiF
6, (NH
4)
2AlF
6, C
6H
5IF, fluoroacetic acid.The hydrogenation catalyst that adopts this method to make can improve the hydrogenation activity of catalyst, and still, it is still lower that the hydrodesulfurization of this hydrogenation catalyst and hydrogenation take off the carbon residue performance.
Summary of the invention
The hydrodesulfurization and the hydrogenation that the objective of the invention is to overcome the hydrocracking catalyst of prior art take off the lower defective of carbon residue performance, provide a kind of hydrodesulfurization and hydrogenation to take off higher hydrocracking catalyst of carbon residue performance and preparation method thereof.
The present inventor finds that the hydrodesulfurization of existing hydrocracking catalyst and hydrogenation take off aperture big (being generally the 8-14 nanometer) or the wider distribution (the aperture concentration degree is below 6) that the lower main cause of carbon residue performance is carrier.
The invention provides a kind of hydrocracking catalyst, this catalyst contains carrier and loads on hydrogenation activity component on this carrier and the IVB family metal component in the periodic table of elements, wherein, described carrier has pore structure, the aperture, most probable hole of this pore structure is the 6-12 nanometer, the aperture concentration degree is more than 7, and described aperture concentration degree is meant in the long-pending distribution curve of differential with the aperture to the aperture of specific pore volume, the ratio of the height at peak and the halfwidth at this peak.
The present invention also provides the preparation method of described hydrocracking catalyst, wherein, this method comprises respectively the IVB family metal component in the hydrogenation activity component and the periodic table of elements is loaded on the carrier, wherein, described carrier has pore structure, and the aperture, most probable hole of this pore structure is the 6-14 nanometer, and the aperture concentration degree is more than 7, described aperture concentration degree is meant in the long-pending distribution curve of differential with the aperture to the aperture of specific pore volume, the ratio of the height at peak and the halfwidth at this peak.
Compare with existing hydrocracking catalyst, the aperture of the carrier of hydrocracking catalyst provided by the invention less (aperture, most probable hole is little) and distribute concentrated (aperture concentration degree height), the hydrodesulfurization of catalyst and hydrogenation take off the carbon residue performance and have obtained significant raising.
Description of drawings
Fig. 1 is the distribution curve schematic diagram of the long-pending differential to the aperture of the specific pore volume of carrier of embodiment 1 with the aperture.
The specific embodiment
Hydrocracking catalyst provided by the invention contains carrier and loads on hydrogenation activity component on this carrier and the IVB family metal component in the periodic table of elements, wherein, described carrier has pore structure, the aperture, most probable hole of this pore structure is the 6-14 nanometer, the aperture concentration degree is more than 7, described aperture concentration degree is meant in the long-pending distribution curve of differential with the aperture to the aperture of specific pore volume, the ratio of the height at peak and the halfwidth at this peak.
Aperture, described most probable hole is meant: adopt the BET method to measure the pore structure of sample, can obtain the distribution curve of the long-pending differential (dV/dr) to the aperture of specific pore volume with the aperture, the long-pending differential (dV/dr) to the aperture of the pairing specific pore volume in certain aperture is illustrated near the pairing pore volume in hole this aperture, and wherein aperture, the pairing hole of Zui Da dV/dr is called aperture, most probable hole.Wherein, the long-pending assay method of BET method and specific pore volume has been as well known to those skilled in the art, for example can adopt " industrial catalyst analytical test sign " (Sinopec publishing house, nineteen ninety front page, volumes such as Liu Xiyao, the structure determination of chapter 2 catalyst pores) the middle method of putting down in writing.
The aperture concentration degree is meant in the long-pending distribution curve of differential with the aperture to the aperture of specific pore volume, the ratio of the height at peak and the halfwidth at this peak.The ratio of the height at peak and the halfwidth at this peak is big more, shows that the intensity in aperture is high more.For the single hole pattern, can calculate an aperture concentration degree according to this method, this aperture concentration degree is more than 7; For the porous pattern, can be according to this method to a plurality of holes difference calculated hole diameters concentration degree, wherein, at least one aperture concentration degree is more than 7.
Fig. 1 is the distribution curve schematic diagram of the long-pending differential to the aperture of the specific pore volume of carrier of embodiment 1 with the aperture.Abscissa is the aperture of carrier, and unit is
Ordinate is the long-pending differential to the aperture of specific pore volume.M represents peak height (i.e. Zui Da dV/dr) among Fig. 1, and N represents halfwidth, promptly on the abscissa corresponding to the distance between two points of 1/2M.When the calculated hole diameters concentration degree, the unit of halfwidth and peak height adopts fundamental length unit.
The aperture, most probable hole of described pore structure is preferably the 6-10 nanometer, and the aperture concentration degree is preferably 7-50.
IVB family metal component in described hydrogenation activity component and the periodic table of elements preferably aqueous solution of the compound by will containing IVB family metal respectively and the aqueous solution that contains the compound of hydrogenation activity component contacts with described carrier, dry and roasting and loading on the carrier.
Total amount with catalyst is a benchmark, and the content of described carrier can be 5-90 weight %, is preferably 40-80 weight %; In oxide, described hydrogenation activity components contents can be 5-60 weight %, is preferably 10-50 weight %, and the content of described IVB family metal component can be 0.5-40 weight %, is preferably 1-30 weight %.
Described IVB family metal component is preferably titanium and/or zirconium, more preferably titanium and zirconium, and in oxide, the weight ratio of titanium and zirconium can be 1: 0.1-10 is preferably 1: 0.2-5.When IVB family metal component is titanium and zirconium, can further improve the hydrogenation activity of catalyst.The existence form of described IVB family metal component is preferably the oxide of IVB family metal.
Described hydrogenation activity component can be the hydrogenation activity component of routine, for example can comprise the oxide of VIII family metal and the oxide of group vib metal.The oxide of described VIII family metal is preferably the oxide of nickel, and the oxide of described group vib metal is preferably the oxide of molybdenum and the oxide of tungsten, and the weight ratio of the oxide of the oxide of nickel, the oxide of molybdenum and tungsten can be 1: 0.1-10: 1-50.
Described carrier can be the conventional carrier as the preparation hydrocracking catalyst.Described carrier can comprise heat-resistant inorganic oxide.Described heat-resistingization thing can be selected from aluminium oxide, silica, zirconia, titanium oxide, magnesia, thorium oxide, beryllium oxide, aluminium oxide-silicon oxide, aluminium oxide-titanium oxide, aluminium oxide-magnesia, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, the oxidation titania-zirconia, silica-alumina-zirconia, silica-alumina-thorium oxide, in silica-alumina-titanium oxide and the silica-alumina-magnesia one or more
Described carrier can also comprise molecular sieve, and the weight ratio of heat-resistant inorganic oxide and molecular sieve can be 1: 0.1-5.Described molecular sieve can be to be selected from the zeolite-type molecular sieves that is commonly used for active component of cracking catalyst in the prior art, in the non-zeolite molecular sieve one or more.For example, be selected from ZRP, Y zeolite, β zeolite, modenite, ZSM-5, MCM-41, Ω, ZSM-12, the MCM-22 zeolite molecular sieve one or more.Among preferred Y zeolite, β zeolite, modenite, the ZSM-5 one or more.Described molecular sieve can be commercially available commodity, also can adopt the routine techniques preparation.
Described carrier is looked different the article shaped that require can be made into various easy operatings, for example microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, for example, for the complex carrier of a kind of molecular sieve and inorganic refractory oxides, can be with described heat-resistant inorganic oxide or its precursor is mixed, the preparation of the method for extruded moulding and roasting with described molecular sieve.Wherein, the precursor of described heat-resistant inorganic oxide refers to can form after the roasting compound of described heat-resistant inorganic oxide, typically refers to hydroxide, hydrous oxide, contains the gel of its oxide, hydroxide and in the colloidal sol one or more.For example, the precursor of aluminium oxide can be selected from one or more in various hydrated aluminas, the aluminium colloidal sol.When extrusion molding, can add an amount of extrusion aid and/or adhesive, extrusion molding then.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not give unnecessary details at this.The temperature of described roasting is 350-800 ℃, is preferably 450-650 ℃, and roasting time is 1-10 hour, is preferably 2-8 hour.
The preparation method of described hydrocracking catalyst provided by the invention comprises respectively the IVB family metal component in the hydrogenation activity component and the periodic table of elements is loaded on the carrier, wherein, described carrier has pore structure, the aperture, most probable hole of this pore structure is the 6-14 nanometer, the aperture concentration degree is more than 7, described aperture concentration degree is meant in the long-pending distribution curve of differential with the aperture to the aperture of specific pore volume, the ratio of peak height and halfwidth.
The step of described drying and roasting can be carried out after contacting at every turn, also can all carry out after the contact.
Wherein, the pore size distribution of carrier and kind have been done detailed description hereinbefore, do not repeat them here.
In the process of the described hydrocracking catalyst of preparation, it is benchmark that the consumption of each material makes the total amount with catalyst, and the content of described carrier can be 5-90 weight %, is preferably 40-80 weight %; In oxide, described hydrogenation activity components contents can be 5-60 weight %, is preferably 10-50 weight %, and the content of described IVB family metal can be 0.5-40 weight %, is preferably 1-30 weight %.
The aqueous solution that hydrogenation activity component and IVB family metal component in the periodic table of elements the method on the carrier of loading to is preferably included the aqueous solution of the compound that contains IVB family metal and contain the compound of hydrogenation activity component contacts dry and roasting with described carrier.
Wherein, will contain the aqueous solution that method that the aqueous solution of the compound of IVB family metal contacts with described carrier is preferably with the compound that contains IVB family metal and flood described catalyst carrier.According to the preparation method of hydrocracking catalyst provided by the invention, the temperature of described dipping is not particularly limited, can be all temps that maceration extract can reach.Time to dipping is not particularly limited, as long as can make the compound that contains IVB family metal of aequum in the catalyst carrier load, for example, the temperature of dipping can be 5-150 ℃, and dip time can be 0.5-12 hour.
The temperature of described drying can be 100-300 ℃, is preferably 105-250 ℃; The dry time can be 1-24 hour, is preferably 2-12 hour.
The temperature of roasting can be 350-600 ℃, is preferably 400-550 ℃; The time of roasting can be 1-10 hour, is preferably 2-8 hour.
The described compound that contains IVB family metal can be the water soluble compound of IVB family metal, be preferably water-soluble titanium compound and/or water-soluble zirconium compound, more preferably water-soluble titanium compound and water-soluble zirconium compound, in oxide, the weight ratio of water-soluble titanium compound and water-soluble zirconium compound can be 1: 0.1-10 is preferably 1: 0.2-5.When the compound that contains IVB family metal is water-soluble titanium compound and water-soluble zirconium compound, can further improve the hydrogenation activity of catalyst.
Described water-soluble titanium compound is preferably (NH
4)
2TiF
6, H
2TiF
6, TiCl
4, TiCl
3, TiO (SO
4)
2, in positive metatitanic acid and the metatitanic acid one or more; Described water-soluble zirconium compound is preferably (NH
4)
2ZrF
6, H
2ZrF
6, ZrCl
4, ZrCl
3And ZrO (SO
4)
2In one or more.
According to method provided by the invention, the method that the hydrogenation activity component is loaded on the catalyst carrier comprises that the aqueous solution that will contain the compound of hydrogenation activity component contacts with catalyst carrier, dry and roasting.
To contain the aqueous solution that method that the aqueous solution of the compound of hydrogenation activity component contacts with catalyst carrier is preferably with the compound that contains the hydrogenation activity component and flood described catalyst carrier.According to the preparation method of hydrocracking catalyst provided by the invention, the temperature of described dipping is not particularly limited, can be all temps that maceration extract can reach.Time to dipping is not particularly limited, as long as can make the compound that contains the hydrogenation activity component of aequum in the catalyst carrier load, for example, the temperature of dipping can be 5-150 ℃, and dip time can be 0.5-12 hour.
There is no particular limitation to the condition of described drying and roasting, can be this area various dryings and roasting condition commonly used, and for example, the temperature of described drying can be 80-350 ℃, is preferably 100-300 ℃; The dry time can be 0.5-24 hour, is preferably 1-12 hour; The temperature of roasting can be 360-700 ℃, is preferably 400-650 ℃; The time of roasting can be 0.2-12 hour, is preferably 1-10 hour.
The described compound that contains the hydrogenation activity component can for example can comprise the soluble metal compound of at least a group VIII metal and the soluble metal compound of at least a group vib metal for the compound that contains the hydrogenation activity component that is used to prepare hydrocracking catalyst of routine.
The kind of the soluble metal compound of described group VIII metal is conventionally known to one of skill in the art, as, can be selected from nitrate, acetate, soluble carbon hydrochlorate, chloride and the soluble complexes of VIII family metal one or more.Under the preferable case, the soluble metal compound of described group VIII metal is one or more in nitrate, acetate, soluble carbon hydrochlorate, chloride and the soluble complexes of nickel.
The kind of the soluble compound of described group vib metal is conventionally known to one of skill in the art, under the preferable case, the soluble compound of described group vib metal comprises one or more in one or more and wolframic acid, metatungstic acid, ethyl metatungstic acid, tungstates, metatungstate and the ethyl metatungstic acid in molybdic acid, para-molybdic acid, molybdate and the paramolybdate.
The consumption of hydrogenation activity component predecessor makes the oxide of molybdenum and the oxide of tungsten, and the weight ratio of the oxide of the oxide of nickel, the oxide of molybdenum and tungsten is 1: 0.1-10: 1-50.
According to the conventional method in this area, the preparation method of hydrocracking catalyst provided by the invention preferably also is included in before the use, in the presence of hydrogen, under 140-370 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
The hydrocracking catalyst that adopts the preparation method of hydrocracking catalyst provided by the invention to make is applicable to hydrocarbon raw material carried out hydrocracking, has hydrocarbon fraction than low boiling and lower molecular weight with production.Described hydrocarbon raw material can be various heavy mineral oils or artificial oil or their mixed fraction oil, as vacuum gas oil (VGO), metal removal oil, reduced crude, depitching decompression residuum, decompression residuum, coker distillate, shale oil, asphalt sand oil, liquefied coal coil.
When the hydrocracking catalyst that adopts the preparation method of hydrocracking catalyst provided by the invention to make is used for the hydrocarbon raw material hydrocracking, can under the hydrocracking process condition of routine, use, as reaction temperature 200-650 ℃, preferred 300-510 ℃, reaction pressure 3-24 MPa, preferred 4-15 MPa, liquid hourly space velocity (LHSV) 0.1-30 hour
-1, hydrogen/oil mol ratio is 15-35.
The following examples will the present invention is described further.Agents useful for same among the embodiment except that specifying, is chemically pure reagent.
Carrier used in following examples makes as follows:
Embodiment 1
This embodiment illustrates the preparation of hydrocracking catalyst provided by the invention.
Take by weighing 150 gram SD-2 powder and (, produced alumina content 64.4%, specific area 268m in 2004 available from the Chang Ling catalyst plant
2/ g can a few hole aperture 9.7nm, hole concentration degree 4.1), being extruded into circumscribed circle diameter with banded extruder is 1.4 millimeters butterfly bar, 120 ℃ of dryings 6 hours.Then, at blowing air, under 600 ℃ of conditions, calcination process 3 hours, air mass flow are 1.6 cubic metres/kilogram hours, make carrier.Adopt the BET method to measure the pore structure of carrier, obtain the distribution curve of the long-pending differential (dV/dr) to the aperture of specific pore volume, as shown in Figure 1 with the aperture.
Load capacity 12 weight % according to titanium oxide take by weighing ammonium titanium fluoride, add water 65ml, stir dissolving down, this solution is mixed with 100 gram carriers, kept 3 hours under sealing, 25 ℃ of conditions, the unnecessary water that inclines was dried 12 hours down in 120 ℃, carrier after the oven dry 450 ℃ of following roastings 5 hours, is promptly obtained containing titanium carrier.
Be respectively 14 weight % and 2.6 weight % according to molybdenum oxide and nickel oxide loaded amount, adopt ammonium molybdate and nickel nitrate configuration mixed aqueous solution respectively, saturated infusion process dipping is above-mentioned to be contained behind the titanium carrier in 110 ℃ of oven dry 2 hours down, promptly makes catalyst in 1 hour in 450 ℃ of following roastings, is designated as catalyst A.
Embodiment 2
This embodiment illustrates the preparation of hydrocracking catalyst provided by the invention.
Take by weighing 150 gram CL powder (available from the Chang Ling catalyst plant, produced in 2007 the 147th batch, alumina content 72.8%, specific area 299m
2/ g can a few hole aperture 14.5nm, hole concentration degree 3.6), being extruded into circumscribed circle diameter with banded extruder is 1.1 millimeters cylindrical bar, 150 ℃ of dryings 4 hours.Then, at blowing air, under 580 ℃ of conditions, calcination process 4 hours, air mass flow are 1.1 cubic metres/kilogram hours, make carrier.Adopt the BET method to measure the aperture, most probable hole and the aperture concentration degree of carrier, the result is as shown in table 1.
8 weight % take by weighing ammonium fluozirconate according to the zirconia load capacity, add water 85ml, stir dissolving down, this solution is mixed with 100 gram carriers, kept 7 hours under uncovered, 60 ℃ of conditions, the unnecessary water that inclines is in 140 ℃ of oven dry 6 hours down, carrier after the oven dry 550 ℃ of following roastings 3 hours, is promptly made and contains the zirconium carrier.
Be respectively 16 weight % and 2.5 weight % according to molybdenum oxide and nickel oxide loaded amount, adopt ammonium molybdate and nickel nitrate configuration mixed aqueous solution respectively, saturated infusion process dipping is above-mentioned to be contained behind the zirconium carrier in 110 ℃ of oven dry 2 hours down, promptly make catalyst in 0.5 hour in 500 ℃ of following roastings, be designated as catalyst B.
Embodiment 3
This embodiment illustrates the preparation of hydrocracking catalyst provided by the invention.
Prepare catalyst according to the method identical with embodiment 1, note is catalyst C, and different is that carrier prepares by following process.
Take by weighing 150 gram SX-101 powder (available from the Chang Ling catalyst plant, 2002 the 34th batch, alumina content 71.3%, specific area 311m
2/ g can a few hole aperture 19.3nm, hole concentration degree 4.6), being extruded into circumscribed circle diameter with banded extruder is 1.4 millimeters cloverleaf pattern bar, 110 ℃ of dryings 10 hours.Then, at blowing air, under 560 ℃ of conditions, calcination process 3 hours, air mass flow are 1.8 cubic metres/kilogram hours, make carrier.Adopt the BET method to measure the aperture, most probable hole and the aperture concentration degree of carrier, the result is as shown in table 1.
Embodiment 4
This embodiment illustrates the preparation of hydrocracking catalyst provided by the invention.
Take by weighing 150 gram ASA powder (available from the Chang Ling catalyst plant, aluminum silicon powder, silicon oxide-containing 20%, specific area 474m
2/ g can a few hole aperture 16.4nm, hole concentration degree 5.2), being extruded into circumscribed circle diameter with banded extruder is 1.4 millimeters butterfly bar, 150 ℃ of dryings 7 hours.Then, at blowing air, under 570 ℃ of conditions, calcination process 2.5 hours, air mass flow are 1.0 cubic metres/kilogram hours, make carrier.Adopt the BET method to measure the aperture, most probable hole and the aperture concentration degree of carrier, the result is as shown in table 1.
Be respectively 3 weight % and 7.5 weight % take by weighing ammonium fluozirconate and metatitanic acid according to zirconia and titania oxide supported amount, add water 180ml, stir dissolving down, this solution is mixed with carrier, kept 1 hour under sealing, 140 ℃ of conditions, the unnecessary water that inclines was dried 2 hours down in 110 ℃, carrier after the oven dry 750 ℃ of following roastings 0.5 hour, is promptly made and contains zirconium and titanium carrier.
Be respectively 18 weight % and 3.2 weight % according to molybdenum oxide and nickel oxide loaded amount, adopt ammonium molybdate and nickel nitrate configuration mixed aqueous solution respectively, saturated infusion process dipping is above-mentioned to be contained behind zirconium and the titanium carrier in 110 ℃ of oven dry 2 hours down, promptly make catalyst in 2 hours in 400 ℃ of following roastings, be designated as catalyst D.
Embodiment 5
This embodiment illustrates the preparation of hydrocracking catalyst provided by the invention.
Take by weighing 75 gram CL powder and 75 gram SD-2 powder (available from the Chang Ling catalyst plant, batch the same), being extruded into circumscribed circle diameter with banded extruder is 1.4 millimeters cloverleaf pattern bar, 120 ℃ of dryings 8 hours.Then, at blowing air, under 580 ℃ of conditions, calcination process 3 hours, air mass flow are 1.3 cubic metres/kilogram hours, make carrier.Adopt the BET method to measure the aperture, most probable hole and the aperture concentration degree of carrier, the result is as shown in table 1.
Be respectively 5 weight % and 1.5 weight % take by weighing ammonium fluozirconate and metatitanic acid according to zirconia and titania oxide supported amount, add water 83ml, stir dissolving down, this solution is mixed with carrier, kept 4 hours under sealing, 40 ℃ of conditions, the unnecessary water that inclines was dried 4 hours down in 150 ℃, carrier after the oven dry 550 ℃ of following roastings 4 hours, is promptly made and contains zirconium and titanium carrier.
Be respectively 20 weight % and 1.6 weight % according to tungsten oxide and nickel oxide loaded amount, adopt ammonium metatungstate and nickel nitrate configuration mixed aqueous solution respectively, saturated infusion process dipping is above-mentioned to be contained behind zirconium and the titanium carrier in 110 ℃ of oven dry 2 hours down, promptly make catalyst in 3 hours in 350 ℃ of following roastings, be designated as catalyst E.
Embodiment 6
This embodiment illustrates the preparation of hydrocracking catalyst provided by the invention.
Take by weighing 50 gram SX-101 powder and 100 gram SD-2 powder (available from the Chang Ling catalyst plant, batch the same), being extruded into circumscribed circle diameter with banded extruder is 0.8 millimeter cylindrical bar, 130 ℃ of dryings 12 hours.Then, at blowing air, under 580 ℃ of conditions, calcination process 3 hours, air mass flow are 1.2 cubic metres/kilogram hours, make carrier.Adopt the BET method to measure the aperture, most probable hole and the aperture concentration degree of carrier, the result is as shown in table 1.
7 weight % take by weighing ammonium fluozirconate according to the zirconia load capacity, add water 80ml, stir dissolving down, this solution is mixed with carrier, kept 6 hours under uncovered, 105 ℃ of conditions, the unnecessary water that inclines is in 105 ℃ of oven dry 8 hours down, carrier after the oven dry 650 ℃ of following roastings 2 hours, is promptly made and contains the zirconium carrier.
Be respectively 12 weight % and 2 weight % according to molybdenum oxide and nickel oxide loaded amount, adopt ammonium molybdate and nickel nitrate configuration mixed aqueous solution respectively, saturated infusion process dipping is above-mentioned to be contained behind the zirconium carrier in 110 ℃ of oven dry 2 hours down, promptly makes catalyst in 2.5 hours in 450 ℃ of following roastings, is designated as catalyst F.
Comparative Examples 1
Prepare catalyst according to the method identical with embodiment 1, note is catalyst C1, and different is that carrier prepares by following process.
The CL powder (available from the Chang Ling catalyst plant, 2000 13 batches, alumina content 74.4%, specific area 287m
2/ g can a few hole aperture 26nm, hole concentration degree 2.2) 251.0g, the SD powder (available from the Chang Ling catalyst plant, 2000 19 batches, alumina content 73.8%, specific area 274m
2/ g can a few hole aperture 9nm, hole concentration degree 3.8) 107.8g, mix, add the peptizing agent moulding, in 650 ℃ of following roastings 3 hours, make catalyst carrier.Ammonium fluosilicate 17.8g is dissolved in the 150ml water, gets the 110.5g carrier and immerses, and handles 3 hours down in 180 ℃, and the cooling back is with the water rinse of 1000ml 2 times, 105 ℃ down the oven dry back in 400 ℃ of following roastings 3 hours.
Adopt the BET method to measure the aperture, most probable hole and the aperture concentration degree of carrier, the result is as shown in table 1.
Embodiment 7-12
Embodiment 7-12 explanation embodiment of the invention 1-6 provides the performance of catalyst.
Raw material oil properties: husky light VRDS.Density (20 ℃): 0.9687g/cm
3, viscosity (100 ℃), 62.37mm
2/ s; MCR, 12.4 quality %; S, 3.18 quality %; N, 0.34 quality %; C, 85.3 quality %; H, 11.03 quality %; Tenor Ni, 23.2ppm; V, 64.7ppm; Fe, 8.3ppm; Ca, 2.1ppm; Na, 0.9ppm, four components, saturated hydrocarbons, 32.2 quality %, aromatic hydrocarbons, 41.5 quality %, colloid, 22.3 quality %, asphalitine (C7 insoluble matter), 4.0 quality %.
Evaluating catalyst method: the particle that catalyst breakage is become diameter 0.5-1.0 millimeter, in 200 milliliters of fixed bed reactors, pack into 200 milliliters of this catalyst, before the logical oil, catalyst is at first at hydrogen dividing potential drop 15.0MPa, sulfuration is 28 hours under 300 ℃ of conditions, afterwards at hydrogen dividing potential drop 15.0MPa, volume space velocity 0.50h
-1, hydrogen-oil ratio 700v/v, reaction temperature is 380 ℃ and feeds feedstock oil down, reacts sampling after 400 hours.
Calculate conversion ratio according to following formula, the result is as shown in table 1.
Conversion ratio=[(in the raw material＞350 ℃ of yield-products in＞350 ℃ of yields)/raw material in＞350 ℃ of yields] * 100%
Calculate desulfurization degree according to following formula, the result is as shown in table 1.
Desulfurization degree=[sulfur content in (in the raw material in sulfur content-product sulfur content)/raw material] * 100%
Take off the carbon residue rate according to following formula calculating, the result is as shown in table 1.
Take off carbon residue rate=[carbon residue content in (in the raw material in carbon residue content-product carbon residue content)/raw material] * 100%
Comparative Examples 3 explanations Comparative Examples 1 of the present invention provides the performance of catalyst.
According to the method identical with embodiment 7-12, measure Comparative Examples 1 and the performance that catalyst is provided respectively, the result is as shown in table 1.
Table 1
| The embodiment numbering | The catalyst numbering | Aperture, most probable hole (nm) | The aperture concentration degree | Conversion ratio (%) | Desulfurization degree (%) | Take off carbon residue rate (%) |
| Embodiment 7 | ??A | ??6.6 | ??16.4 | ??38.23 | ??80.9 | ??46.3 |
| Embodiment 8 | ??B | ??8.1 | ??17.4 | ??38.75 | ??83.8 | ??48.9 |
| The embodiment numbering | The catalyst numbering | Aperture, most probable hole (nm) | The aperture concentration degree | Conversion ratio (%) | Desulfurization degree (%) | Take off carbon residue rate (%) |
| Embodiment 9 | ??C | ??8.9 | ??17.4 | ??38.36 | ??80.7 | ??46.2 |
| Embodiment 10 | ??D | ??7.7 | ??20.2 | ??39.50 | ??83.9 | ??49.1 |
| Embodiment 11 | ??E | ??7.8 | ??12.3 | ??39.41 | ??83.5 | ??48.8 |
| Embodiment 12 | ??F | ??7.5 | ??21.4 | ??38.20 | ??84.3 | ??49.3 |
| Comparative Examples 3 | ??C1 | ??10.5 | ??5.7 | ??38.25 | ??76.5 | ??41.4 |
From the result shown in the table 1 as can be seen, compare with Comparative Examples 1 catalyst, catalyst A-F of embodiment 1-6 has significantly improved the desulfurization degree of feedstock oil and has taken off the carbon residue rate.
Claims (18)
1. hydrocracking catalyst, this catalyst contains carrier and loads on hydrogenation activity component on this carrier and the IVB family metal component in the periodic table of elements, wherein, the aperture, most probable hole of described carrier is the 6-14 nanometer, the aperture concentration degree is more than 7, described aperture concentration degree is meant in the long-pending distribution curve of differential with the aperture to the aperture of specific pore volume, the ratio of the height at peak and the halfwidth at this peak.
2. catalyst according to claim 1, wherein, aperture, described most probable hole is the 6-10 nanometer, the aperture concentration degree is 7-50.
3. catalyst according to claim 1, wherein, the aqueous solution of the compound of the IVB family metal component in described hydrogenation activity component and the periodic table of elements by will containing IVB family metal respectively and the aqueous solution that contains the compound of hydrogenation activity component contact with described carrier, dry and roasting loads on the carrier.
4. catalyst according to claim 1 wherein, is a benchmark with the total amount of catalyst, the content of described carrier is 5-90 weight %, in oxide, described hydrogenation activity components contents is 5-60 weight %, and the content of described IVB family metal component is 0.5-40 weight %.
5. according to claim 1,3 or 4 described catalyst, wherein, described IVB family metal component is titanium and/or zirconium.
6. catalyst according to claim 5, wherein, described IVB family metal component is titanium and zirconium, in oxide, the weight ratio of titanium and zirconium is 1: 0.1-10.
7. according to claim 1,3 or 4 described catalyst, wherein, described hydrogenation activity component is VIII family metal and group vib metal.
8. according to any described catalyst among the claim 1-4, wherein, described carrier comprises heat-resistant inorganic oxide, and described heat-resistant inorganic oxide is aluminium oxide and/or aluminium oxide-silicon oxide.
9. catalyst according to claim 8, wherein, described carrier also comprises molecular sieve, the weight ratio of heat-resistant inorganic oxide and molecular sieve is 1: 0.1-5.
10. the preparation method of the described hydrocracking catalyst of claim 1, it is characterized in that, this method comprises respectively the IVB family metal component in the hydrogenation activity component and the periodic table of elements is loaded on the carrier, wherein, the aperture, most probable hole of described carrier is the 6-14 nanometer, the aperture concentration degree is more than 7, and described aperture concentration degree is meant in the long-pending distribution curve of differential with the aperture to the aperture of specific pore volume, the ratio of the height at peak and the halfwidth at this peak.
11. method according to claim 10, wherein, aperture, described most probable hole is the 6-10 nanometer, and the aperture concentration degree is 7-50.
12. method according to claim 10, wherein, method on the carrier that hydrogenation activity component and IVB family metal component in the periodic table of elements the are loaded to aqueous solution that comprises the aqueous solution of the compound that contains IVB family metal and contain the compound of hydrogenation activity component contact with described carrier, dry and roasting.
13. method according to claim 12, wherein, it is benchmark that the consumption of each material makes the total amount with catalyst, the content of described carrier is 5-90 weight %, in oxide, described hydrogenation activity components contents is 5-60 weight %, and the content of described IVB family metal component is 0.5-40 weight %.
14. method according to claim 12, wherein, the compound of the described IVB of containing family metal is water-soluble titanium compound and/or water-soluble zirconium compound.
15. method according to claim 14, wherein, the compound of the described IVB of containing family metal is water-soluble titanium compound and water-soluble zirconium compound, and in oxide, the weight ratio of water-soluble titanium compound and water-soluble zirconium compound is 1: 0.1-10; Described water-soluble titanium compound is selected from (NH
4)
2TiF
6, H
2TiF
6, TiCl
4, TiCl
3, TiO (SO
4)
2, in positive metatitanic acid and the metatitanic acid one or more; Described water-soluble zirconium compound is selected from (NH
4)
2ZrF
6, H
2ZrF
6, ZrCl
4, ZrCl
3And ZrO (SO
4)
2In one or more.
16. method according to claim 12, wherein, the described compound that contains the hydrogenation activity component is the soluble metal compound of at least a group VIII metal and the soluble metal compound of at least a group vib metal.
17. according to any described method among the claim 10-13, wherein, described carrier comprises heat-resistant inorganic oxide, described heat-resistant inorganic oxide is aluminium oxide and/or aluminium oxide-silicon oxide.
18. method according to claim 17, wherein, described carrier also comprises molecular sieve, and the weight ratio of heat-resistant inorganic oxide and molecular sieve is 1: 0.1-5.
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Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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-
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- 2008-12-24 CN CN2008102408664A patent/CN101757929B/en active Active
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