CN103357445A - Heavy-petroleum hydrogenating deasphaltenizing catalyst and preparation and application thereof - Google Patents
Heavy-petroleum hydrogenating deasphaltenizing catalyst and preparation and application thereof Download PDFInfo
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Abstract
The invention provides a hydrogenating deasphaltenizing catalyst and preparation and application thereof. The hydrogenating deasphaltenizing catalyst comprises a supporter and a hydrogenating active metallic compound, wherein the supporter is a doublet-hole alumina supporter which has the pore volume of 0.9 to 1.2ml/g and specific surface area of 50 to 300m<2>/g under the representation in a mercury intrusion method, and the pore volume of a hole being 10 to 30nm in diameter accounts for 55 to 80% of the total pore volume, and the pore volume of a hole being 300 to 500nm in diameter accounts for 10 to 35% of the total pore volume. The preparation method of the supporter comprises the following steps of: mixing, molding, drying and roasting hydrated alumina P1 containing pseudo-boehmite and a modifying substance P2 of the P1, wherein the mixing ratio in weight of the P1 to P2 is (20-95): (5-80; ); the k value of P2 ranges from 0 to 0.9, and the k is DI2/DI1, wherein DI1 represents the acid peptizing index of the hydrated alumina P1 containing the pseudo-boehmite; and DI2 represents the acid peptizing index of the modifying substance P2 of the P1. Compared with the prior art, the catalyst provided by the invention shows greater performance on hydrogenating deasphaltenizing and demetalizing after being applied to hydroprocessing of residual oil.
Description
Technical field
The present invention relates to a kind of hydrogenation diasphaltene catalyst and preparation and application thereof.
Background technology
The mink cell focus that comprises residual oil is carried out the utilization rate that deep processing not only is conducive to improve crude oil, alleviate the nervous trend of energy supply, simultaneously can also environmental contamination reduction, reach the clean utilization of the energy.Compare with distillate, contain the macromolecular reaction things such as a large amount of asphalitines, colloid in the mink cell focus, and the heavy metal such as the heteroatomic compound such as the sulphur in the mink cell focus, nitrogen, oxygen and nickel and vanadium and condensed-nuclei aromatics major part concentrate in the asphalitine, these impurity and heavy metal can pollute corresponding catalyst in follow-up process, thereby bitum hydro-conversion is a critical step in the residual hydrogenation process.And in bitum conversion and subtractive process, need to be according to bitum characteristic, select the catalyst of the function admirable of active high and good stability.
For the hydrogenation catalyst of diasphaltene, its pore-size distribution is of great significance the catalyst performance tool.Bitum molecular size is about tens of to hundreds of nanometers, if the spacing of catalyst active center is less than asphaltene molecules, then asphaltene molecules is difficult to contact with the activated centre of catalyst by diffusion, and mainly be outer surface or the aperture that is adsorbed on catalyst, along with the carrying out that reacts can only form coke because of thermal condensation, cause catalysqt deactivation.Macroporous catalyst is conducive to bitum removing, but the aperture of catalyst and specific surface negative correlation each other, i.e. the large catalyst of average pore size, and its specific area is just little.Therefore in order to take into account this character, catalyst need to have rational pore size distribution.
The weak point of existing mink cell focus hydrogenation catalyst is can not reach good coupling between its S, N removal efficiency, heavy metal removing rate and the asphaltene removal, for example, often S, N removal efficiency and asphaltene removal are not high to remove the high catalyst of metal active.The reason that produces problems is very complicated.At first be raw material, the characteristics of each component are that molecular weight is large in the residual oil, complex structure, and saturation degree low (armaticity is high), S, N content are high.And beyond the sulphur removal, the overwhelming majority of impurity is be present in the asphalitine again more, therefore want to remove this type of S, N, must carry out to asphaltene molecules the conversion (comprising saturated, open loop and hydrogenolysis etc.) of appropriateness.Next is catalyst.In the prior art, having the catalyst that is suitable for carrying out this type of reaction aperture is guard catalyst and catalyst for demetalation, for example:
Disclosed a kind of Hydrodemetalation catalyst with lower carbon deposition quantity and greater activity of CN1267537C and preparation method thereof.
The disclosed a kind of residuum hydrogenating and metal-eliminating catalyst of CN1796500A, this catalyst is by a kind of carrier with double-hole and load on molybdenum on this carrier and/or tungsten and cobalt and/or nickel metal component form.The preparation method of the carrier that catalyst uses comprise with a kind of precursor of aluminium oxide mix with a kind of deacidification nitrogen-containing compound in addition, moulding and roasting.
The disclosed catalyst for heavy oil fixed bed hydrogenating treatment of CN1233795C and preparation method etc.
But the asphaltene removal of these catalyst is generally lower.
Summary of the invention
The technical problem to be solved in the present invention provide a kind of new, have the catalyst of better hydrogenation diasphaltene performance, preparation method and an application of this catalyst.
The present invention relates to following content:
1. a hydrogenation diasphaltene catalyst contains carrier and hydrogenation active metals component, and wherein, described carrier is a kind of bimodal porous aluminum oxide carrier, characterizes with mercury injection method, and the pore volume of described carrier is 0.9-1.2 ml/g, and specific area is 50-300 rice
2/ gram, diameter is the 55-80% that the pore volume in 10-30nm hole accounts for total pore volume, diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume.
2. according to 1 described catalyst, it is characterized in that, the pore volume of described carrier is 0.95-1.15 ml/g, and specific area is 80-200 rice
2/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.
3. according to 1 described catalyst, it is characterized in that, described hydrogenation active metals component is selected from least a group VIII metal component and at least a group vib metal component, in oxide and take catalyst as benchmark, the content of described VIII family metal component is greater than 0.8 to less than or equal to 3 % by weight, the content of group vib metal component greater than 3 to less than or equal to 10 % by weight.
4. according to 3 described catalyst, it is characterized in that, described group VIII metal component is selected from cobalt and/or nickel, the group vib metal component is selected from molybdenum and/or tungsten, in oxide and take catalyst as benchmark, the content of described VIII family metal component is the 1-2 % by weight, the content of group vib metal component greater than 4 to less than or equal to 8 % by weight.
5. according to the preparation method of 1 described catalyst, comprise the preparation carrier and load hydrogenation active metals component on this carrier, wherein, the preparation of described carrier comprises and will contain modifier P2 mixing, moulding, the dry and roasting of hydrated alumina P1 and the P1 of boehmite, wherein, the weight mixing ratio of described P1 and P2 is 20-95: 5-80, and the κ value of P2 is 0 to less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1Be the sour peptization index of the hydrated alumina P1 that contains boehmite, DI
2Sour peptization index for the modifier P2 of the hydrated alumina P1 that contains boehmite.
6. according to 5 described methods, it is characterized in that, the weight mixing ratio of described P1 and P2 is 70-95: 5-25.
7. according to 5 described methods, it is characterized in that, the k value of described P2 is 0 to less than or equal to 0.6.
8. according to 5 or 6 described methods, it is characterized in that, the described pore volume that contains the hydrated alumina P1 of boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram can reach bore dia 8-30nm.
9. according to 8 described methods, it is characterized in that, the described pore volume that contains the hydrated alumina P1 of boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram can reach bore dia 10-25nm.
10. according to the described method of 5,6 or 7 any one, it is characterized in that, described P2 is 80-300 purpose particle.
11. according to 10 described methods, it is characterized in that, described P2 is 100-200 purpose particle.
12. according to 5 described methods, it is characterized in that, the condition of described drying comprises: temperature is 40-350 ℃, and the time is 1-24 hour, and the condition of described roasting comprises: temperature is for greater than 500 to less than or equal to 1200 ℃, and the time is 1-8 hour.
13. according to 12 described methods, it is characterized in that, the condition of described drying comprises: temperature is 100-200 ℃, and the time is 2-12 hour, and the condition of described roasting comprises: temperature is for greater than 800 to less than or equal to 1000 ℃, and roasting time is for being 2-6 hour.
14. according to 5 described methods, it is characterized in that, one of method that P1 is modified as P2 is hydrated alumina P1 moulding, the drying that contains boehmite with described, afterwards it is all or part ofly ground, sieves, obtaining the powder thing is P2, the condition of described drying comprises: temperature is 40-350 ℃, and the time is 1-24 hour; Two of method is article shaped roastings that method one is obtained, and sintering temperature is greater than 350 to less than or equal to 1400 ℃, and roasting time is 1-8 hour, afterwards it is all or part ofly ground, sieves, and obtaining the powder thing is P2; Three of method be will contain the hydrated alumina P1 of boehmite dodge and do, dodge that to do temperature be greater than 150 to less than or equal to 1400 ℃, flash-off time is 0.05-1 hour, obtaining the powder thing is P2; Four of method is that in two and the modifier that obtains with three of method of one of method, method one or more are mixed to get.
15. according to 14 described methods, it is characterized in that, the condition of the drying in the described method one comprises: temperature is 100-200 ℃, the time is 2-12 hour; Method two in sintering temperature be 500-1200 ℃, roasting time is 0.1-6 hour; Method three in sudden strain of a muscle to do temperature be 200-1000 ℃, flash-off time is 0.1-0.5 hour.
16. according to 14 or 15 described methods, it is characterized in that, described P2 is 80-300 purpose particle in the P1 modifier.
17. according to 16 described methods, it is characterized in that, described P2 is 100-200 purpose particle in the P1 modifier.
18. according to 5 described methods, it is characterized in that, described on carrier the method for load hydrogenation active metals component be infusion process, comprise the solution of preparing the compound that contains hydrogenation active metals and use this solution impregnating carrier, carry out afterwards drying, roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least a group vib and the metal component of at least a group VIII, in oxide and take catalyst as benchmark, the content of metal component that the described compound that contains hydrogenation active metals makes the group vib in the final catalyst at the consumption of the concentration of described solution and described solution is greater than 3 to less than or equal to 10 % by weight, the content of the metal component of described group VIII greater than 0.8 to less than or equal to 3 % by weight; Described drying condition comprises: temperature is 100-250 ℃, and the time is 1-10 hour; Described roasting condition comprises: temperature is 360-500 ℃, and the time is 1-10 hour.
19. according to 18 described methods, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, the metal component of group VIII is selected from cobalt and/or nickel, in oxide and take catalyst as benchmark, the content of metal component that the described compound that contains hydrogenation active metals makes the group vib in the final catalyst at the consumption of the concentration of described solution and described solution is greater than 4 to less than or equal to 8 % by weight, and the content of the metal component of group VIII is the 1-2 % by weight; Described drying condition comprises: temperature is 100-140 ℃, and the time is 1-6 hour; Described roasting condition comprises: temperature is 360-450 ℃, and the time is 2-6 hour.
20. the application of the described catalyst of any one in hydrocarbon oil hydrogenation is processed among the claim 1-4.
According to catalyst provided by the invention, depending on the different article shaped that require wherein carrier to can be made into various easy operatings, such as spherical, cellular, nest like, tablet or bar shaped (clover, butterfly, cylindrical etc.).Moulding can be carried out according to a conventional method, for example, and a kind of method in spin, compressing tablet and the extruded moulding or the combination of several method.When moulding, for example extruded moulding carries out smoothly for guaranteeing described moulding, can add entry, extrusion aid and/or adhesive, contains or not contain expanding agent in described mixture, and drying and roasting are carried out in then extrusion molding afterwards.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, for example common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, the PVOH, described peptizing agent can be inorganic acid and/or organic acid, and described expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and the surfactant.Synthetic cellulose wherein is preferably one or more in CMC, methylcellulose, ethyl cellulose, the hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in polyethylene glycol, poly-propyl alcohol, the polyvinyl alcohol, and surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight is the propenyl copolymer of 200-10000 and one or more in the maleic acid copolymer.
Wherein, after the hydrated alumina that the sour peptization index D I in the preparation of described carrier refers to contain boehmite adds nitric acid by certain sour aluminum ratio, within certain reaction time by the hydrated alumina that contains boehmite of peptization with Al
2O
3The percentage of meter, DI=(1-W
2/ W
1) * 100%, W
1And W
2Be respectively intend thin water aluminium with acid reaction front and with acid reaction after with Al
2O
3The weight of meter.
The mensuration of DI comprises: (1) measure the hydrated alumina contain boehmite calcination base content (calcination base content refers to quantitative boehmite in 600 ℃ of roastings 4 hours, after it burns weight and burn before the ratio of weight), count a; (2) take by weighing the hydrated alumina W that contains boehmite with assay balance
0Gram, W
0Amount satisfy with Al
2O
3The W of meter
1Be 6 gram (W
1/ a=W
0), take by weighing deionized water W gram, W=40.0-W
0, stir in the lower hydrated alumina that contains boehmite that will take by weighing and the deionized water adding beaker and mix; (3) with the 20mL pipette pipette 20mL, concentration is the dilute nitric acid solution of 0.74N, this acid solution is joined in the beaker of step (2), stirs lower reaction 8 minutes; (4) the reacted slurries of step (3) are carried out centrifugation in centrifuge, sediment is inserted in the crucible of having weighed, afterwards, in 125 ℃ of dryings 4 hours, 850 ℃ of roastings were 3 hours in Muffle furnace with it, and weighing obtains calcination sample size W
2Gram; (5) according to formula DI=(1-W
2/ W
1) * 100% calculates.
The described hydrated alumina that contains boehmite can be the boehmite of any prior art preparation, also can be the mixture of boehmite and other hydrated alumina, described other hydrated alumina be selected from one or more in a water aluminium oxide, gibbsite and the amorphous hydrated aluminium oxide.In preferred embodiment, characterize with the X diffraction, boehmite content is not less than 50% in the described hydrated alumina that contains boehmite, more preferably is not less than 60%.
In the present invention, containing pore volume, the specific area of the hydrated alumina of boehmite and can reach the aperture, is that the described hydrated alumina that contains boehmite, is obtained by BET nitrogen absorption representation after 4 hours in 600 ℃ of roastings.
The present inventor is surprised to find, after the hydrated alumina P1 that will contain boehmite heat-treats modification, the peptization index of its modifier changes, with this modifier with without heat treated P1 mixed-forming, dry and roasting after, resulting carrier has obvious bimodal pore distribution.Particularly at 80-300 purpose particle that will be wherein, preferred 100-200 purpose particle with without after heat treated partially mixed moulding, the dry and roasting, each the unimodal pore size distribution in resulting carrier bimodal is concentrated especially.Here, described 80-300 purpose particle, preferred 100-200 purpose particle refers to that described modifier is through sieve (step that comprises in case of necessity fragmentation or grinding), its screening thing (screenings) satisfies 80-300 purpose particle, the percentage (by weight) that preferred 100-200 purpose particle accounts for total amount is not less than 60%, further preferably is not less than 70%.
In implementation, described P2 can conveniently be obtained by following method:
(1) obtains P2 based on drying, comprise by the hydrated alumina P1 that contains boehmite according to a conventional method moulding prepare in the conventional alumina support process, the tailing of drying by-product, for example: in extruded moulding, the bar shaped article shaped is at tailing (being called traditionally dry waste material) dry, integer process by-product, this tailing is milled, and sieving obtains P2.
(2) obtain based on roasting, comprise by the hydrated alumina P1 that contains boehmite according to a conventional method moulding prepare in the conventional alumina support process, tailing (being called traditionally the roasting waste material) through the roasting by-product, for example, in roller forming, the tailing of spheric granules by-product in roasting process is milled this tailing, and sieving obtains P2; Or directly P1 is dodged dried obtaining, when directly the P1 sudden strain of a muscle being done, flash-off time is preferably 0.05-1 hour, more preferably 0.1-0.5 hour.
(3) being mixed to get of two or more among the modifier P2 that obtains based on preceding method.When adopting mixed method to obtain P2, the not restriction of mixed proportion of the modifier P2 that aforementioned several method is obtained respectively.
According to catalyst provided by the invention, wherein, described hydrogenation active metals component is kind known in those skilled in the art and content thereof, preferred VIII family metal component is cobalt and/or nickel, the group vib metal component is molybdenum and/or tungsten, in oxide and take catalyst as benchmark, the content of described VIII family metal component is preferably greater than 0.8 to less than or equal to 3 % by weight, 1-2 % by weight more preferably, the content of described group vib metal component is preferably greater than 3 to less than or equal to 10 % by weight, further is preferably greater than 4 to less than or equal to 8 % by weight.
Under the prerequisite that is enough to described hydrogenation active metals component is carried on the described carrier, the present invention is not particularly limited described carrying method, preferred method is infusion process, comprises that preparation contains the dipping solution of the compound of described metal, uses the described carrier of this solution impregnation afterwards.Described dipping method is conventional method, for example, can be excessive liquid dipping, hole saturation infusion process.The described metal component compound that is selected from group vib that contains is selected from the soluble compound in them one or more, such as in molybdenum oxide, molybdate, the paramolybdate one or more, and preferred molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; In tungstates, metatungstate, the ethyl metatungstate one or more, preferred ammonium metatungstate, ethyl ammonium metatungstate wherein.Described one or more that contain in the soluble compound that the compound that is selected from VIII family metal component is selected from them, such as in the soluble complexes of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt one or more, be preferably cobalt nitrate, basic cobaltous carbonate; In the soluble complexes of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel one or more are preferably nickel nitrate, basic nickel carbonate.
According to catalyst provided by the invention, can also contain any impact and the invention provides the interpolation component that catalyst performance maybe can improve the catalytic performance of catalyst provided by the invention.Add component as containing phosphorus etc., in oxide and take catalyst as benchmark, the content of described interpolation component is no more than 10 % by weight, is preferably the 0.1-4 % by weight.
When also containing phosphorus etc. in the described catalyst and add component, the introducing method of described interpolation component can be method arbitrarily, as can be with the compound of the components such as phosphorus as described in containing directly with as described in boehmite mix, moulding and roasting; Can be that the compound that will contain the component such as described phosphorus and the compound that contains the hydrogenation active metals component are mixed with the described carrier of dipping behind the mixed solution; Can also be to contain the described carrier of dipping and roasting behind the independent obtain solution of compound of the component such as phosphorus.When the interpolation component such as phosphorus and hydrogenation active metals are introduced described carrier respectively, preferred at first with the described carrier of solution impregnation and the roasting that contain described interpolation component composition, afterwards again with the solution impregnation that contains the hydrogenation active metals component composition.Wherein, described sintering temperature is 400-600 ℃, is preferably 420-500 ℃, and roasting time is 2-6 hour, is preferably 3-6 hour.
According to hydrocarbon ils provided by the present invention (comprising residual oil) hydrotreating method, reaction condition to the hydrotreatment of described hydrocarbon ils is not particularly limited, in preferred embodiment, described hydrotreatment reaction condition is: reaction temperature 300-550 ℃, further preferred 330-480 ℃, hydrogen dividing potential drop 4-20 MPa, further preferred 6-18 MPa, volume space velocity 0.1-3.0 hour
-1, further preferred 0.15-2 hour
-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.
The device of described hydrogenation reaction can be enough to make described feedstock oil to carry out under the hydrotreatment reaction condition with in the catalytic reactor of described catalyst any, for example, at described fixed bed reactors, carries out in moving-burden bed reactor or the fluidized bed reactor.
According to the conventional method in this area, described hydrotreating catalyst is before using, usually can be 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 outside device also can original position sulfuration in device, and the active metal component of its load is converted into the metal sulfide component.
Catalyst provided by the invention can use separately, also can use with other catalyst combination, this catalyst be particularly suitable for heavy oil particularly poor residuum carry out hydrotreatment, in order to provide qualified feedstock oil for subsequent technique (such as catalytic cracking process).Compared with prior art, catalyst provided by the invention has better hydrogenation diasphaltene and demetalization performance when being used for residual hydrocracking.
The specific embodiment
The present invention will be further described for the following examples, but should therefore not be interpreted as limitation of the invention.
Agents useful for same in the example except specifying, is chemically pure reagent.
Embodiment 1-13 illustrates bimodal hole provided by the invention carrier and preparation method thereof.Comparative Examples 1-2 explanation conventional catalyst carrier and preparation method thereof.
The boehmite that uses in following embodiment comprises:
P1-1: (pore volume is 1.2 ml/gs to the dry glue powder that catalyst branch company in Chang Ling produces, and specific surface is 280 meters
2/ gram can reach bore dia 15.8nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 15.8).
P1-2: (pore volume is 1.1 ml/gs to the dry glue powder that the permanent brightness chemical industry in Yantai Co., Ltd produces, and specific surface is 260 meters
2/ gram can reach bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 17.2).
Modifier P2 of the described P1 that embodiment 1-5 explanation preparation carrier of the present invention is used and preparation method thereof.
Embodiment 1
Take by weighing 1000 gram P1-1, add afterwards 1440 milliliters of the aqueous solution containing 10 milliliters in nitric acid (Tianjin chemical reagent three factory's products), be extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar obtains dried strip, with the dried strip shaping in 120 ℃ of dryings 4 hours, sieve, length is milled less than the dried strip material (being commonly referred to as industrially drying bar waste material) of 2mm, sieve, get wherein that 100～200 mesh sieves divide, obtain the modifier P2A of P1-1.The k value of P2A sees Table 1.
Embodiment 2
Take by weighing 1000 gram P1-1, dodge in 240 ℃ and did 6 minutes, obtain the modifier P2B of P1-1.The k value of P2B sees Table 1.
Embodiment 3
Each 200 gram of the P2B that the P2A that embodiment 1 is obtained and embodiment 2 obtain evenly mix, and obtain the modifier P2C of P1-1.The k value of P2C sees Table 1.
Embodiment 4
Take by weighing 1000 gram P1-2, add afterwards 1440 milliliters of the aqueous solution containing 10 milliliters in nitric acid (Tianjin chemical reagent three factory's products), be extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar is in 120 ℃ of dryings 4 hours, and 1200 ℃ of roastings 4 hours obtain carrier, with the carrier strip shaping, sieve, length is milled less than the carrier strip material (being commonly referred to as industrial carrier waste material) of 2mm, sieve, get wherein that 100～200 mesh sieves divide, namely get the modifier P2D of P1-2.The k value of P2D sees Table 1.
Embodiment 5
Take by weighing 1000 gram P1-2, dodge in 650 ℃ and did 10 minutes, obtain the modifier P2E of P1-2.The k value of P2E sees Table 1.
Table 1
| Embodiment | Raw material | k |
| 1 | P2A | 0.5 |
| 2 | P2B | 0.4 |
| 3 | P2C | 0.4 |
| 4 | P2D | 0 |
| 5 | P2E | 0.3 |
The embodiment 6-13 explanation preparation catalyst of the present invention preparation method of carrier.The preparation method of Comparative Examples 1-2 explanation conventional catalyst carrier.
Embodiment 6
Take by weighing 800 gram P1-1, after 200 gram raw material P2A that embodiment 1 makes evenly mixed, adding contained 1440 milliliters of the aqueous solution of 10 milliliters in nitric acid (Tianjin chemical reagent three factory's products), was extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar obtains article shaped in 120 ℃ of dryings 4 hours, with 900 ℃ of roastings of this article shaped 3 hours, obtains carrier Z1.The character of carrier Z1 is listed in table 2.
Embodiment 7
Take by weighing 200 gram P1-1, after 800 gram raw material P2B that embodiment 2 makes evenly mixed, adding contained nitric acid Tianjin chemical reagent three factory's products) 1440 milliliters of 10 milliliters the aqueous solution, be extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar obtains article shaped in 120 ℃ of dryings 4 hours, with 900 ℃ of roastings of this article shaped 3 hours, obtains carrier Z2.The character of carrier Z2 is listed in table 2.
Embodiment 8
Take by weighing 500 gram P1-1, after 500 gram raw material P2C that embodiment 3 makes evenly mixed, adding contained nitric acid Tianjin chemical reagent three factory's products) 1440 milliliters of 10 milliliters the aqueous solution, be extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar obtains article shaped in 120 ℃ of dryings 4 hours, with 950 ℃ of roastings of this article shaped 3 hours, obtains carrier Z3.The character of carrier Z3 is listed in table 2.
Comparative Examples 1
Take by weighing 1000 gram P1-1, add and to contain nitric acid Tianjin chemical reagent three factory's products) 1440 milliliters of 10 milliliters the aqueous solution, be extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar obtains article shaped in 120 ℃ of dryings 4 hours, with 900 ℃ of roastings of this article shaped 3 hours, obtains carrier DZ1.The character of carrier DZ1 is listed in table 2.
Embodiment 9
Take by weighing 800 gram P1-2, after 200 gram raw material P2D that embodiment 4 makes evenly mixed, adding contained 1440 milliliters of the aqueous solution of 10 milliliters in nitric acid (Tianjin chemical reagent three factory's products), was extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar obtains article shaped in 120 ℃ of dryings 4 hours, with 1000 ℃ of roastings of this article shaped 3 hours, obtains carrier Z4.The character of carrier Z4 is listed in table 2.
Embodiment 10
Take by weighing 900 gram P1-1, after 100 gram raw material P2E that embodiment 5 makes evenly mixed, adding contained nitric acid Tianjin chemical reagent three factory's products) 1440 milliliters of 10 milliliters the aqueous solution, be extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar obtains article shaped in 120 ℃ of dryings 4 hours, with 1000 ℃ of roastings of this article shaped 3 hours, obtains carrier Z5.The character of carrier Z5 is listed in table 2.
Embodiment 11
Take by weighing 850 gram P1-2, after 150 gram raw material P2C that embodiment 3 makes evenly mixed, adding contained nitric acid Tianjin chemical reagent three factory's products) 1440 milliliters of 10 milliliters the aqueous solution, be extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar obtains article shaped in 120 ℃ of dryings 4 hours, with 850 ℃ of roastings of this article shaped 3 hours, obtains carrier Z6.The character of carrier Z6 is listed in table 2.
Comparative Examples 2
Take by weighing 1000 gram P1-2, add and to contain nitric acid Tianjin chemical reagent three factory's products) 1440 milliliters of 10 milliliters the aqueous solution, be extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar obtains article shaped in 120 ℃ of dryings 4 hours, with 1000 ℃ of roastings of this article shaped 3 hours, obtains carrier DZ2.The character of carrier DZ2 is listed in table 2.
Embodiment 12
Take by weighing 900 gram P1-2, after 100 gram raw material P2D that embodiment 4 makes evenly mixed, adding contained nitric acid Tianjin chemical reagent three factory's products) 1440 milliliters of 10 milliliters the aqueous solution, be extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar obtains article shaped in 120 ℃ of dryings 4 hours, with 1000 ℃ of roastings of this article shaped 3 hours, obtains carrier Z7.The character of carrier Z7 is listed in table 2.
Embodiment 13
Take by weighing 850 gram P1-2, after 150 gram raw material P2E that embodiment 5 makes evenly mixed, adding contained nitric acid Tianjin chemical reagent three factory's products) 1440 milliliters of 10 milliliters the aqueous solution, be extruded into the butterfly bar of external diameter φ 1.4mm at double screw banded extruder.Wet bar obtains article shaped in 120 ℃ of dryings 4 hours, with 900 ℃ of roastings of this article shaped 3 hours, obtains carrier Z8.The character of carrier Z8 is listed in table 2.
Table 2
Result by table 2 can see, compares with conventional method, has obvious structure of double peak holes by the alumina support that the invention provides the method preparation.
Embodiment 14-16 illustrates Catalysts and its preparation method provided by the invention.
Wherein, the content of active metal component adopts Xray fluorescence spectrometer to measure (all appts is Rigaku electric machine industry Co., Ltd. 3271 type Xray fluorescence spectrometers, and concrete grammar is seen Petrochemical Engineering Analysis method RIPP133-90) in the catalyst.
Embodiment 14
Get 200 gram carrier Z1, contain MoO with 210 milliliters
367.9 grams per liter, the molybdenum oxide of CoO 11.3 grams per liters and basic cobaltous carbonate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst C1.Molybdenum oxide among the catalyst C1 and the content of cobalt oxide are listed in table 3.
Comparative Examples 3
Get 200 gram carrier DZ1, contain MoO with 180 milliliters
379.2 grams per liter, the molybdenum oxide of CoO 13.2 grams per liters and basic cobaltous carbonate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst DC1.Molybdenum oxide among the catalyst DC1 and the content of cobalt oxide are listed in table 3.
Embodiment 15
Get 200 carrier Z2, contain MoO with 200 milliliters
353.1 grams per liter, the molybdenum oxide of NiO 10.6 grams per liters and basic nickel carbonate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst C2.Molybdenum oxide among the catalyst C2 and the content of nickel oxide are listed in table 3.
Comparative Examples 4
Get 200 carrier DZ1, contain MoO with 180 milliliters
359.0 grams per liter, the molybdenum oxide of NiO 11.8 grams per liters and basic nickel carbonate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst DC2.Molybdenum oxide among the catalyst DC2 and the content of nickel oxide are listed in table 3.
Embodiment 16
Get 200 gram carrier Z3, contain MoO with 205 milliliters
378.5 grams per liter, the ammonium molybdate of NiO 15.7 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst C3.Molybdenum oxide among the catalyst C3 and the content of nickel oxide are listed in table 3.
Comparative Examples 5
Get 200 gram carrier DZ2, contain MoO with 180 milliliters
387.2 grams per liter, the molybdenum oxide of NiO 17.4 grams per liters and basic nickel carbonate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst DC3.Molybdenum oxide among the catalyst DC3 and the content of nickel oxide are listed in table 3.
Embodiment 17
Get 200 gram carrier Z4, contain MoO with 210 milliliters
367.9 grams per liter, the molybdenum oxide of NiO 11.3 grams per liters and basic nickel carbonate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst C4.Molybdenum oxide among the catalyst C4 and the content of nickel oxide are listed in table 3.
Embodiment 18
Get 200 gram carrier Z8, contain MoO with 200 milliliters
382.8 grams per liter, the molybdenum oxide of CoO 19.1 grams per liters and basic cobaltous carbonate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst C5.Molybdenum oxide among the catalyst C5 and the content of cobalt oxide are listed in table 3.
Table 3
Embodiment 19-23
Embodiment 19-23 illustrates the residuum hydrogenating and metal-eliminating performance of catalyst provided by the invention.
The particle that respectively catalyst C1, C2, C3, C4 and C5 the is broken into diameter 2-3 millimeter reactor of packing into.Reaction condition is: 380 ℃ of reaction temperatures, hydrogen dividing potential drop 14 MPas, the content (instrument is the U.S. PE-5300 of PE company type plasma quantometer, and concrete grammar is seen Petrochemical Engineering Analysis method RIPP124-90) of nickel and vanadium in the oil of employing inductive coupling plasma emission spectrograph (ICP-AES) mensuration hydrotreatment front and back.Adopt asphalt compound mensuration method to analyze hydrotreatment front and back oily studies on asphaltene mass fraction (concrete grammar is referring to SH/T 0509-92).Calculate asphalitine and metal removal rate according to following formula:
Feedstock oil is that nickel content is that 29.3ppm, content of vanadium are that 83ppm, sulfur content are 4.7%, nitrogen content is 0.3%, carbon residue is 15.1% the normal slag of Kuwait.
The activity data of each catalyst sees Table 4.
Comparative Examples 6-8
Demetallization per and diasphaltene rate according to method evaluation catalyst DC1, DC2 and the DC3 of embodiment 19-23 the results are shown in Table 4.
Table 4
| Embodiment | The catalyst numbering | Diasphaltene rate/% | Demetallization per/% |
| 19 | C1 | 88 | 73.4 |
| Comparative Examples 6 | DC1 | 65 | 68.5 |
| 20 | C2 | 90 | 70.1 |
| Comparative Examples 7 | DC2 | 63 | 65.1 |
| 21 | C3 | 95 | 72.3 |
| Comparative Examples 8 | DC3 | 75 | 70.1 |
| 22 | C4 | 90 | 80 |
| 23 | C5 | 94 | 83 |
Can be seen by table 4 result, in poor residuum hydrotreatment process, will obviously be better than existing catalyst by the diasphaltene that the invention provides catalyst and metal removal activity, illustrate that present technique invention catalyst is more suitable for processing in the processing of poor residuum.
Claims (20)
1. a hydrogenation diasphaltene catalyst contains carrier and hydrogenation active metals component, and wherein, described carrier is a kind of bimodal porous aluminum oxide carrier, characterizes with mercury injection method, and the pore volume of described carrier is 0.9-1.2 ml/g, and specific area is 50-300 rice
2/ gram, diameter is the 55-80% that the pore volume in 10-30nm hole accounts for total pore volume, diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume.
2. according to 1 described catalyst, it is characterized in that, the pore volume of described carrier is 0.95-1.15 ml/g, and specific area is 80-200 rice
2/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.
3. according to 1 described catalyst, it is characterized in that, described hydrogenation active metals component is selected from least a group VIII metal component and at least a group vib metal component, in oxide and take catalyst as benchmark, the content of described VIII family metal component is greater than 0.8 to less than or equal to 3 % by weight, the content of group vib metal component greater than 3 to less than or equal to 10 % by weight.
4. according to 3 described catalyst, it is characterized in that, described group VIII metal component is selected from cobalt and/or nickel, the group vib metal component is selected from molybdenum and/or tungsten, in oxide and take catalyst as benchmark, the content of described VIII family metal component is the 1-2 % by weight, the content of group vib metal component greater than 4 to less than or equal to 8 % by weight.
5. according to the preparation method of 1 described catalyst, comprise the preparation carrier and load hydrogenation active metals component on this carrier, wherein, the preparation of described carrier comprises and will contain modifier P2 mixing, moulding, the dry and roasting of hydrated alumina P1 and the P1 of boehmite, wherein, the weight mixing ratio of described P1 and P2 is 20-95: 5-80, and the κ value of P2 is 0 to less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1Be the sour peptization index of the hydrated alumina P1 that contains boehmite, DI
2Sour peptization index for the modifier P2 of the hydrated alumina P1 that contains boehmite.
6. according to 5 described methods, it is characterized in that, the weight mixing ratio of described P1 and P2 is 70-95: 5-25.
7. according to 5 described methods, it is characterized in that, the k value of described P2 is 0 to less than or equal to 0.6.
8. according to 5 or 6 described methods, it is characterized in that, the described pore volume that contains the hydrated alumina P1 of boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram can reach bore dia 8-30nm.
9. according to 8 described methods, it is characterized in that, the described pore volume that contains the hydrated alumina P1 of boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram can reach bore dia 10-25nm.
10. according to the described method of 5,6 or 7 any one, it is characterized in that, described P2 is 80-300 purpose particle.
11. according to 10 described methods, it is characterized in that, described P2 is 100-200 purpose particle.
12. according to 5 described methods, it is characterized in that, the condition of described drying comprises: temperature is 40-350 ℃, and the time is 1-24 hour, and the condition of described roasting comprises: temperature is for greater than 500 to less than or equal to 1200 ℃, and the time is 1-8 hour.
13. according to 12 described methods, it is characterized in that, the condition of described drying comprises: temperature is 100-200 ℃, and the time is 2-12 hour, and the condition of described roasting comprises: temperature is for greater than 800 to less than or equal to 1000 ℃, and roasting time is for being 2-6 hour.
14. according to 5 described methods, it is characterized in that, one of method that P1 is modified as P2 is hydrated alumina P1 moulding, the drying that contains boehmite with described, afterwards it is all or part ofly ground, sieves, obtaining the powder thing is P2, the condition of described drying comprises: temperature is 40-350 ℃, and the time is 1-24 hour; Two of method is article shaped roastings that method one is obtained, and sintering temperature is greater than 350 to less than or equal to 1400 ℃, and roasting time is 1-8 hour, afterwards it is all or part ofly ground, sieves, and obtaining the powder thing is P2; Three of method be will contain the hydrated alumina P1 of boehmite dodge and do, dodge that to do temperature be greater than 150 to less than or equal to 1400 ℃, flash-off time is 0.05-1 hour, obtaining the powder thing is P2; Four of method is that in two and the modifier that obtains with three of method of one of method, method one or more are mixed to get.
15. according to 14 described methods, it is characterized in that, the condition of the drying in the described method one comprises: temperature is 100-200 ℃, the time is 2-12 hour; Method two in sintering temperature be 500-1200 ℃, roasting time is 0.1-6 hour; Method three in sudden strain of a muscle to do temperature be 200-1000 ℃, flash-off time is 0.1-0.5 hour.
16. according to 14 or 15 described methods, it is characterized in that, described P2 is 80-300 purpose particle in the P1 modifier.
17. according to 16 described methods, it is characterized in that, described P2 is 100-200 purpose particle in the P1 modifier.
18. according to 5 described methods, it is characterized in that, described on carrier the method for load hydrogenation active metals component be infusion process, comprise the solution of preparing the compound that contains hydrogenation active metals and use this solution impregnating carrier, carry out afterwards drying, roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least a group vib and the metal component of at least a group VIII, in oxide and take catalyst as benchmark, the content of metal component that the described compound that contains hydrogenation active metals makes the group vib in the final catalyst at the consumption of the concentration of described solution and described solution is greater than 3 to less than or equal to 10 % by weight, the content of the metal component of described group VIII greater than 0.8 to less than or equal to 3 % by weight; Described drying condition comprises: temperature is 100-250 ℃, and the time is 1-10 hour; Described roasting condition comprises: temperature is 360-500 ℃, and the time is 1-10 hour.
19. according to 18 described methods, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, the metal component of group VIII is selected from cobalt and/or nickel, in oxide and take catalyst as benchmark, the content of metal component that the described compound that contains hydrogenation active metals makes the group vib in the final catalyst at the consumption of the concentration of described solution and described solution is greater than 4 to less than or equal to 8 % by weight, and the content of the metal component of group VIII is the 1-2 % by weight; Described drying condition comprises: temperature is 100-140 ℃, and the time is 1-6 hour; Described roasting condition comprises: temperature is 360-450 ℃, and the time is 2-6 hour.
20. the application of the described catalyst of any one in hydrocarbon oil hydrogenation is processed among the claim 1-4.
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| US13/853,195 US9657236B2 (en) | 2012-03-31 | 2013-03-29 | Process for hydrotreating heavy raw oils |
| TW102111777A TWI537373B (en) | 2012-03-31 | 2013-04-01 | A hydrogenation method for heavy feedstock oil |
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