CN1782031A - Slag oil hydro-demetallization catalyst and its preparing method - Google Patents
Slag oil hydro-demetallization catalyst and its preparing method Download PDFInfo
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Abstract
The slag oil hydrodemetallizing catalyst contains a kind of double-peak hole alumina carrier and supported Mo and/or W and Ni and/or Co metal components. The double-peak hole alumina carrier has pore volume of 0.8-1.6 ml/g, specific surface area 150-350 sq m/g, pore volume fraction of 10-30 nm size holes in 40-90 % and pore volume fraction of 100-2000 nm size holes in 10-60 %, and is prepared through mixing alumina hydrate and ammonium aluminum carbonate, forming and roasting. The slag oil hydrodemetallizing catalyst has simple preparation process and high hydrodemetallizing performance.
Description
Technical field
The invention relates to a kind of Hydrobon Catalyst And Its Preparation Method, more specifically say so about a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof.
Background technology
Residual oil is carried out the utilization ratio that deep processing not only helps improving crude oil, alleviate the nervous trend of power supply, can also reduce environmental pollution simultaneously, reach the clean utilization of the energy.Sulphur in the crude oil, nitrogen, metal impurities major part concentrate among the residual oil, and these impurity can pollute corresponding catalyzer in the follow-up course of processing, thus must be earlier by hydrotreatment with these impurity removals.Compare with distillate, contain macromolecular reaction things such as a large amount of bituminous matters, colloid in the residual oil, their diffusion processes in catalyzer will directly influence the hydrogenation reaction activity of catalyzer.Have catalyzer that double-hole distributes and guaranteeing the macromolecular reaction thing preferably in the diffusion, hydrodemetallation (HDM) is active high, is the normal a kind of catalyzer that adopts of heavy oil upgrading.
The pore distribution of catalyzer is by the carrier decision that constitutes catalyzer, and therefore, the carrier that preparation has double-hole is that this class of preparation has the key of the Hydrodemetalation catalyst of double-hole.
CN1084224C discloses a kind of catalyst for dehydrogenation of saturated hydrocarbon and preparation method thereof, and this catalyzer used carrier is a kind of wide aperture γ-Al that double-hole distributes that has
2O
3, the pore volume that its diplopore is distributed as the 5-100 nanoporous accounts for the 20-35% of total pore volume, and the pore volume of 100-1000 nanoporous accounts for the 44-58% of total pore volume.The preparation method of this carrier be earlier with a certain amount of aluminum chloride at high temperature with the ammoniacal liquor neutralization, forming oil column, drying after the aluminium hydroxide acidifying of generation, steam-treated is no less than 2 hours and obtains under 600～800 ℃ of conditions afterwards.
U.S. Pat 4,448,896 disclose the catalyzer of a kind of hydrogenating desulfurization and heavy metal, and the specific surface of the carrier that this catalyzer adopted is a 100-350 rice
2/ gram, the pore volume of pore radius 37.5-75000 is 0.5-1.5 milliliter/gram, this pore volume is at least 90% with the ratio of total pore volume, its pore distribution occurs characteristic peak at pore radius less than 100 and 100-1000 two places, the pore volume of pore radius 37.5-100 is at least 0.2 milliliter/gram, the pore volume of pore radius 100-1000 is at least 0.1 milliliter/gram, the preparation method of this carrier be with activated alumina or activated alumina precursor mix with carbon black, moulding and roasting.With described aluminum oxide is benchmark, and the sooty consumption is 10120 weight %.
CN 1103009A discloses to plant has the preparation method of double-hole alumina supporter, this method is by two kinds of aluminum oxide or its precursor and carbon black powders that pore size distribution is different, tensio-active agent, peptizing agent and water mixing moulding, drying, roasting is made, wherein, aluminum oxide, carbon powder, the weight ratio of mixture of tensio-active agent and peptizing agent is: 1: 0.05-0.1: 0.05-0.1: 0.02-0.05, drying temperature is 100-300 ℃, be 1-12 hour time of drying, maturing temperature is 550-650 ℃, roasting time is 1-4 hour, bore dia in this carrier is that the hole of 100-200 dust accounts for total pore volume greater than 50%, be preferably 55-90%, bore dia accounts for the 5-30% of total pore volume greater than the hole of 1000 dusts.
CN1047957C discloses a kind of preparation method of alumina supporter, this method is with the pseudo-boehmite dry glue powder of aluminum chloride and ammonia liquor neutralization process preparation and at least a pseudo-boehmite dry glue powder uniform mixing by the preparation of sodium metaaluminate neutralisation, wherein the pseudo-boehmite dry glue powder of aluminum chloride and ammonia liquor neutralization process preparation accounts for 15-80 weight %, pseudo-boehmite dry glue powder by sodium metaaluminate neutralisation preparation accounts for 20-85 weight %, then by peptization, moulding, drying with at 700-1100 ℃ of following roasting 1-5 hour.Used peptizing agent is nitric acid or acetate and adopts the moulding of oil ammonia column forming method in this method.The carrier pore volume that is obtained by this method is 0.7-1.6 milliliter/gram, and specific surface is a 100-200 rice
2/ gram, the pore volume of aperture more than 100 nanometers accounts for the 10-56% of total pore volume.
The existing preparation in the method for Hydrodemetalation catalyst, at the employing carbon powder, when the preparation of organic expanding agent has dual porous aluminum oxide carrier, the existence of temperature runaway phenomenon during because of high-temperature roasting, temperature control is complicated, product stability is poor; When adopting oil ammonia column forming method moulding preparation to have dual porous aluminum oxide carrier, its flow process complexity, yield rate are low.
Summary of the invention
The objective of the invention is shortcoming, a kind of new preparation Hydrodemetalation catalyst method and the catalyzer that is prepared by this method are provided at existing preparation Hydrodemetalation catalyst method.
Method provided by the invention is included in and introduces molybdenum and/or tungsten and nickel and/or cobalt metal component in the alumina supporter, wherein, described carrier by comprise with hydrated aluminum oxide mix with the aluminium carbonate ammonium, the method preparation of moulding and roasting, the weight ratio of mixture of described hydrated aluminum oxide and aluminium carbonate ammonium is: 20-90: 10-80, described maturing temperature is 450-1000 ℃, and roasting time is 1-8 hour.
Catalyzer provided by the invention contains a kind of bimodal porous aluminum oxide carrier and the molybdenum and/or tungsten and cobalt and/or the nickel metal component that load on this carrier, the method preparation that this catalyzer is provided by the invention described above.
The preparation method of Hydrodemetalation catalyst provided by the invention is simple to operate, is easier to implement.Simultaneously, the Hydrodemetalation catalyst performance by this method preparation obviously improves.
For example, the molybdenum oxide 8.2 weight % that contain provided by the invention, the catalyzer of nickel oxide 1.6 weight %, its carrier are by pseudo-boehmite and the aluminium carbonate ammonium mixed according to 1: 1, and a kind of pore volume that obtains after extruded moulding and roasting is 208 meters of 1.3 milliliters/gram, specific surfaces
2/ gram, wherein the pore volume in 10～30nm hole accounts for total pore volume 67.0%, the pore volume in 100～2000nm hole accounts for the carrier of total pore volume 25.6%, and this catalyzer is being that 20ppm, content of vanadium are that the vacuum residuum of 40ppm is raw material during to this evaluating catalyst with nickel content, and its demetallization per is 78%; Contain molybdenum oxide 8.4 weight % and existing method provides, the catalyzer of nickel oxide 1.6 weight %, its carrier are that a kind of to adopt a kind of pore volume of oil ammonia column forming method preparation be 161 meters of 1.1 milliliters/gram, specific surfaces
2/ gram, wherein the hole pore volume of the 10～30nm hole pore volume that accounts for total pore volume 35.1%, 100～2000nm accounts for the carrier of total pore volume 34.2%, and when estimating with identical stock oil and reaction conditions, its demetallization per only is 63%.
Embodiment
According to method provided by the invention, the weight ratio of mixture of wherein said hydrated aluminum oxide and aluminium carbonate ammonium is preferably: 30-80: 20-70, described maturing temperature are preferably 550-950 ℃, and roasting time is preferably 2-4 hour.
Described hydrated aluminum oxide is selected from one or more among hibbsite, boehmite, pseudo-boehmite and the amorphous hydroted alumina, or among hibbsite, monohydrate alumina and the amorphous hydroted alumina of siliceous, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth one or more.Be preferably pseudo-boehmite.They can be that commercially available commodity also can be by any one method preparation in the prior art.As adopting Tai-Ace S 150 method or CO
2One sodium metaaluminate legal system is equipped with pseudo-boehmite.
Described aluminium carbonate ammonium preferred group becomes (NH
4) mAlO (OH) (HCO
3) mnH
2O, 0＜m wherein＜1,0＜n≤5 are preferably 0.2≤m≤0.5,0.5≤n≤4.They can be commercially available commodity, also can be by any one existing method preparation, preferred manufacturing procedure comprises a kind of aqueous solution of aluminum contained compound and ammonium bicarbonate aqueous solution reaction, heavyization, washing and drying, described reaction conditions comprises that pH value is 6.0-9.0, be preferably 6.5-8.5, temperature is 5-45 ℃, is preferably 10-40 ℃; Heavyization condition comprises that temperature is 5-65 ℃, is preferably 10-55 ℃, and the heavyization time is 0.5-12 hour, is preferably 1-6 hour.Wherein, described aluminum contained compound is selected from Tai-Ace S 150, exsiccated ammonium alum, aluminum nitrate and the aluminum chloride a kind of.Described washing is conventional method, and for example, when described aluminum contained compound was Tai-Ace S 150 or aluminum chloride, described washing should finally make (NH
4) mAlO (OH) (HCO
3) mnH
2The content of sulfate radical or chlorion is less than 1 weight % among the O.
Described moulding can adopt customary way to carry out, and all can as methods such as compressing tablet, spin, extrusions.Be preferably extrusion, spin method.When adopting the customary way moulding, for guarantee moulding carry out smoothly in described mixture, introduce auxiliary agent and allow, for example when extrusion, can in mixture, introduce an amount of extrusion aid and water, extrusion moulding afterwards.The kind of described extrusion aid and consumption all can be this area routines, for example can be selected from sesbania powder, citric acid, methylcellulose gum, starch, polyvinyl alcohol, the poly-ethanol one or more.
According to method provided by the invention, before described moulding, also be included in and introduce one or more in the mixture of described hydrated aluminum oxide and aluminium carbonate ammonium and be selected from nitrogenous compound except that the aluminium carbonate ammonium.Water-soluble nitrogenous compound outside the preferred deacidification is as in ammonium citrate, bicarbonate of ammonia, ammonium acetate, ammonium oxalate, the urea one or more.Mixture with hydrated aluminum oxide and aluminium carbonate ammonium is a benchmark, and the consumption of described nitrogenous compound is 2-20 weight %, is preferably 4-15 weight %.
The introducing of described nitrogenous compound can be that the mixture with described hydrated aluminum oxide and aluminium carbonate ammonium directly mixes with it, also can at first it be mixed with the aqueous solution, afterwards the mixture of this solution with described hydrated aluminum oxide and aluminium carbonate ammonium is mixed.
According to the carrier that the invention provides the method preparation, its pore volume is 0.8-1.6 milliliter/gram, and specific surface area is a 150-350 rice
2/ gram, the aperture accounts for total pore volume 40～90% at the pore volume of 10～30 nanometers, and the aperture accounts for total pore volume 10～60% at the pore volume of 100～2000 nanometers.
The content of cobalt in the described catalyzer and/or nickel, molybdenum and/or tungsten is the content of Hydrodemetalation catalyst routine, in general, with the catalyzer is benchmark, in oxide compound, the content of cobalt and/or nickel is 0.3-8 weight %, be preferably 0.5-5 weight %, the content of molybdenum and/or tungsten is 0.5-15 weight %, is preferably 3-15 weight %.
The method of introducing molybdenum and/or tungsten and nickel and/or cobalt metal component is conventionally known to one of skill in the art, in general be under the condition that is enough to molybdenum and/or tungsten and nickel and/or cobalt metal component be deposited on the described bimodal porous aluminum oxide carrier, flood described bimodal porous aluminum oxide carrier with containing molybdenum and/or tungsten and nickel and/or cobalt solution of metal compound.Wherein, in oxide compound, the consumption of each component makes cobalt and/or the nickel of the molybdenum that contains 0.5-15 weight % in the final catalyzer and/or tungsten, 0.3-8 weight %.
Described molybdate compound is selected from one or more in the soluble compound that contains molybdenum, as in molybdenum oxide, molybdate, the paramolybdate one or more, and preferred molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein.
Described Tungstenic compound is selected from one or more in the soluble compound of tungstenic, as in tungstate, metatungstate, the ethyl metatungstate one or more, and preferred ammonium metawolframate, ethyl ammonium metawolframate wherein.
Described cobalt compound is selected from one or more in the soluble compound that contains cobalt, as in the soluble complexes of Xiao Suangu, Cobaltous diacetate, cobaltous dihydroxycarbonate, cobalt chloride and cobalt one or more, is preferably Xiao Suangu, cobaltous dihydroxycarbonate.
Described nickel compound containing is selected from one or more in the nickeliferous soluble compound, as in the soluble complexes of nickelous nitrate, nickel acetate, basic nickel carbonate, nickelous chloride and nickel one or more, is preferably nickelous nitrate, basic nickel carbonate.
Catalyzer provided by the invention is applicable to heavier hydrocarbon feeds is carried out hydrodemetallation (HDM), to produce the low stock oil with high added value of metal content.Described heavier hydrocarbon feeds comprises crude oil, normal pressure or vacuum residuum and normal pressure or vacuum distillate.
Following example will the present invention will be further described.
Agents useful for same in the example except that specifying, is chemically pure reagent.
Sulfate radical, carbonate adopt infrared absorption determining in the example, and chlorion adopts ion selective electrode method to measure, and nitrogen adopts chemiluminescence determination, the calcination gravimetric determination of aluminium, hydromining.
Example 1-5 explanation aluminium carbonate ammonium and preparation method thereof.
Example 1
Take by weighing Tai-Ace S 150 (Beijing Chemical Plant's product) 666 gram, adding deionized water dissolving, to become volumetric molar concentration be 0.3 solution a1, takes by weighing bicarbonate of ammonia (Beijing Chemical Plant's product) 1000 grams, and adding deionized water dissolving, to become volumetric molar concentration be 2.5 solution b1.Solution a1 is joined one 10 liters become in the glue jar with solution b1 simultaneously in the mode that also flows to react, the control pH value is 7.5 in the reaction process, temperature is 40 ℃, the white precipitate that generates was 40 ℃ of heavyization 1.5 hours, filter, filter cake is with the deionized water wash of 10 times (weight) 40 ℃ three times, and 120 ℃ of dryings are 4 hours in loft drier, obtain aluminium carbonate ammonium F1, its chemical formula is (NH
4)
0.2AlO (OH) (HCO
3)
0.24H
2O, sulfate ion content are 0.3 weight %.
Example 2
Take by weighing aluminum chloride (Beijing Chemical Plant's product) 483 gram, adding deionized water dissolving, to become volumetric molar concentration be 1 solution a2, takes by weighing bicarbonate of ammonia (Beijing Chemical Plant's product) 800 grams, and adding deionized water dissolving, to become volumetric molar concentration be 2 solution b2.Solution a2 is joined one 10 liters become in the glue jar with solution b2 simultaneously in the mode that also flows to react, reaction process control pH value is 8.0, temperature is 30 ℃, the white precipitate that generates was 30 ℃ of heavyization 1.5 hours, filter, filter cake with the deionized water wash secondary of 20 times (weight) 30 ℃, in loft drier 120 ℃ of dryings 4 hours, obtain aluminium carbonate ammonium F2, its chemical formula is (NH
4)
0.4AlO (OH) (HCO
3)
0.42H
2O, chloride ion content are 0.4 weight %.
Example 3
Take by weighing aluminum nitrate (Beijing Chemical Plant's product) 750 gram, adding deionized water dissolving, to become volumetric molar concentration be 1 solution a3, takes by weighing bicarbonate of ammonia (Beijing Chemical Plant's product) 800 grams, and adding deionized water dissolving, to become volumetric molar concentration be 2.5 solution b3.Solution a3 is joined one 10 liters become in the glue jar with solution b3 simultaneously in the mode that also flows to react, this control pH value of reaction process is 7.0, temperature is 25 ℃, the white precipitate that generates was 25 ℃ of heavyization 1.5 hours, filter, 120 ℃ of dryings are 4 hours in loft drier, obtain aluminium carbonate ammonium F3, and its chemical formula is (NH
4)
0.5A1O (OH) (HCO
3)
0.53H
2O.
Example 4
Take by weighing Tai-Ace S 150 (Beijing Chemical Plant's product) 666 gram, adding deionized water dissolving, to become volumetric molar concentration be 0.5 solution a4, takes by weighing bicarbonate of ammonia (Beijing Chemical Plant's product) 800 grams, and adding deionized water dissolving, to become volumetric molar concentration be 2.5 solution b4.Solution a4 is joined one 10 liters become in the glue jar with solution b4 simultaneously in the mode that also flows to react, reaction process control pH value is 6.5, temperature is 15 ℃, the white precipitate that generates was 55 ℃ of heavyization 1.5 hours, filter, filter cake is with the deionized water wash of 10 times (weight) 55 ℃ three times, and 120 ℃ of dryings are 4 hours in loft drier, obtain aluminium carbonate ammonium F4, its chemical formula is (NH
4)
0.3AlO (OH) (HCO
3)
0.33H
2O, sulfate ion content are 0.3 weight %.
Example 5
Take by weighing aluminum chloride (Beijing Chemical Plant's product) 483 gram, adding deionized water dissolving, to become volumetric molar concentration be 0.5 solution a5, takes by weighing bicarbonate of ammonia (Beijing Chemical Plant's product) 800 grams, and adding deionized water dissolving, to become volumetric molar concentration be 2 solution b5.Solution a5 is joined one 10 liters become in the glue jar with solution b5 simultaneously in the mode that also flows to react, the control pH value is 7.0 in the reaction process, temperature is 15 ℃, the white precipitate that generates was 55 ℃ of heavyization 1.5 hours, filter, filter cake is with the deionized water wash of 10 times (weight) 55 ℃ three times, and 120 ℃ of dryings are 4 hours in loft drier, obtain aluminium carbonate ammonium F5, its chemical formula is (NH
4)
0.3AlO (OH) (HCO
3)
0.32H
2O, chloride ion content are 0.2 weight %.
Example 6-12 explanation the invention provides alumina supporter in the method and preparation method thereof.
Example 6
Take by weighing pseudo-boehmite dry glue powder (Chang Ling, Hunan refinery company catalyst plant product) 70 grams, mix with 30 gram aluminium carbonate ammonium F1, add 4 gram sesbania powder, add 87 milliliters of solution containing 6 gram ammonium oxalate, being extruded into equivalent diameter on the screw rod banded extruder is the trilobal bar of 1.2mm, in 120 ℃ of dryings 2 hours, and 750 ℃ of roastings 2 hours, obtain carrier Z1, its pore volume, specific surface, pore diameter distribution are listed in the table 1.
Example 7
Take by weighing pseudo-boehmite dry glue powder (Chang Ling, Hunan refinery company catalyst plant product) 50 grams, mix with 50 gram aluminium carbonate ammonium F1, add 4 gram sesbania powder, add 95 milliliters of solution containing 6 gram ammonium oxalate, being extruded into equivalent diameter on the screw rod banded extruder is the trilobal bar of 1.2mm, in 120 ℃ of dryings 2 hours, and 850 ℃ of roastings 2 hours, obtain carrier Z2, its pore volume, specific surface, pore diameter distribution are listed in the table 1.
Example 8
Take by weighing pseudo-boehmite dry glue powder (Chang Ling, Hunan refinery company catalyst plant product) 70 grams, mix with 30 gram aluminium carbonate ammonium F1, add 4 gram sesbania powder, add 100 milliliters of deionized waters, being extruded into equivalent diameter on the screw rod banded extruder is the trilobal bar of 1.2mm, in 120 ℃ of dryings 2 hours, and 750 ℃ of roastings 2 hours, obtain carrier Z3, its pore volume, specific surface, pore diameter distribution are listed in the table 1.
Example 9
Take by weighing pseudo-boehmite dry glue powder (Chang Ling, Hunan refinery company catalyst plant product) 80 grams, mix with 20 gram aluminium carbonate ammonium F2, add 4 gram sesbania powder, add 95 milliliters of solution containing 6 gram ammonium citrates, being extruded into equivalent diameter on the screw rod banded extruder is the trilobal bar of 1.2mm, in 120 ℃ of dryings 2 hours, and 600 ℃ of roastings 2 hours, obtain carrier Z4, its pore volume, specific surface, pore diameter distribution are listed in the table 1.
Example 10
Take by weighing pseudo-boehmite dry glue powder (Chang Ling, Hunan refinery company catalyst plant product) 50 grams, mix with 50 gram aluminium carbonate ammonium F3, add 4 gram sesbania powder, add 95 milliliters of solution containing 10 gram urea, being extruded into equivalent diameter on the screw rod banded extruder is the trilobal bar of 1.2mm, in 120 ℃ of dryings 2 hours, and 750 ℃ of roastings 3 hours, obtain carrier Z5, its pore volume, specific surface, pore diameter distribution are listed in the table 1.
Example 11
Take by weighing pseudo-boehmite dry glue powder (Chang Ling, Hunan refinery company catalyst plant product) 80 grams, mix with 20 gram aluminium carbonate ammonium F4, add 4 gram sesbania powder, add 95 milliliters of solution containing 6 gram ammonium acetates, being extruded into equivalent diameter on the screw rod banded extruder is the trilobal bar of 1.2mm, in 120 ℃ of dryings 2 hours, and 700 ℃ of roastings 4 hours, obtain carrier Z6, its pore volume, specific surface, pore diameter distribution are listed in the table 1.
Example 12
Take by weighing pseudo-boehmite dry glue powder (Chang Ling, Hunan refinery company catalyst plant product) 30 grams, mix with 70 gram aluminium carbonate ammonium F5, add 4 gram sesbania powder, add 100 milliliters of solution containing 6 gram ammonium citrates, being extruded into equivalent diameter on the screw rod banded extruder is the trilobal bar of 1.2mm, in 120 ℃ of dryings 2 hours, and 750 ℃ of roastings 2 hours, obtain carrier Z7, its pore volume, specific surface, pore diameter distribution are listed in the table 1.
Alumina supporter in the existing method of Comparative Examples 1-3 explanation and preparation method thereof.
Comparative Examples 1
According to U.S. Pat 4,448, the method for describing in 896 prepares alumina supporter.
Get 125 gram SB pseudo-boehmite powder, add 135 gram polyvinyl alcohol water solutions, wherein contain polyvinyl alcohol 3.8 grams in the solution, mixed 70 minutes, and then add high wear-resistant carbon black powder 34 grams (the 30 weight % that are equivalent to SB powder amount), 20 gram water mixed 30 minutes, were extruded into diameter and are 1.8 millimeters trilobal bar, drying is 3 hours under 120 ℃, 600 ℃ of following roastings 3 hours, alumina supporter DZ1, its pore volume, specific surface, pore diameter distribution are listed in the table 1.
Comparative Examples 2
Prepare alumina supporter according to the described method of Chinese patent CN1047957C.
Getting Chinese Qilu Petrochemical company restrains with the pseudo-boehmite dry glue powder 340 that pseudo-boehmite dry glue powder 380 grams and the Fushun petrochemical corporation (complex) of carbonic acid gas neutralisation preparation produces with aluminum chloride, ammonia liquor neutralization process, 550 milliliters of salpeter solutions that add 1.5 weight %, stir into slurries, on the oil ammonia column balling head, drip ball, the wet gel ball is following dry 4 hours at 120 ℃, heat-up rate with 200 ℃/hour reaches 1000 ℃ in stoving oven then, constant temperature 2 hours, obtain alumina supporter DZ2, its pore volume, specific surface, pore diameter distribution are listed in the table 1.
Comparative Examples 3
Prepare alumina supporter according to the described method of Chinese patent CN1084224C.
With concentration is that the aluminum chloride of/100 milliliters of 4 grams and the ammoniacal liquor that contains 6 weight % add by calculated amount, mixes control PH7.5-8.5 under 60-80 ℃ in neutralization tank; The aluminium hydroxide gel that generates filters, washing, and filter cake forms slurries with the nitric acid acidifying, and moulding in oil ammonia column, aging is dry in 120 ℃ of baking ovens.The 750 ℃ of roastings 4 hours in activation furnace of the aluminium hydroxide bead of gained were handled 12 hours 750 ℃ of UR with the water vapor of volume ratio 1.0, obtained carrier DZ3, and its pore volume, specific surface, pore diameter distribution are listed in the table 1.
Table 1
| Example | Example 6 | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Carrier | Z1 | Z2 | Z3 | Z4 | Z5 | Z6 | Z7 | DZ1 | DZ2 | DZ3 |
| Specific surface/m 2·g -1 | 196 | 208 | 182 | 258 | 216 | 213 | 224 | 215 | 161 | 140 |
| Pore volume/mlg -1 | 0.93 | 1.30 | 0.89 | 1.16 | 1.45 | 1.08 | 1.48 | 0.65 | 1.10 | 1.10 |
| Pore distribution/% 10-30 nanometer 100-2000 nanometer | 56.2 22.8 | 67.0 25.6 | 57.6 20.5 | 45.7 24.8 | 57.3 33.2 | 50.2 27.1 | 52.2 36.6 | 32.0 7.4 | 25.1 34.2 | 18.2 54.5 |
| Intensity/Nmm -1 | 20.4 | 17.9 | 13.9 | 16.4 | 14.6 | 14.7 | 13.4 | 25.6 | - | - |
Example 13-16 illustrates method provided by the invention and the catalyzer that is prepared by this method.
Example 13
Get carrier Z2 200 grams of example 7 preparations, contain MoO with 500 milliliters
380 grams per liters, the ammonium molybdate of NiO16 grams per liter and nickelous nitrate mixing solutions dipping 1 hour filters the back in 120 ℃ of oven dry 2 hours, and 500 ℃ of roastings 4 hours obtain catalyzer C1.Molybdenum oxide among the catalyzer C1, the content of nickel oxide are listed in the table 2.
Comparative Examples 4-6
Get carrier DZ1, DZ2, each 200 gram of DZ3 of Comparative Examples 1-3 preparation, contain MoO with 500 milliliters respectively
380 grams per liters, the ammonium molybdate of NiO16 grams per liter and nickelous nitrate mixing solutions dipping 1 hour filters the back in 120 ℃ of oven dry 2 hours, and 500 ℃ of roastings 4 hours obtain catalyzer CD1, CD2, CD3.The molybdenum oxide among catalyzer CD1, CD2, the CD3 and the content of nickel oxide are listed in the table 2.
Example 14
Get the carrier Z5200 gram of example 10 preparations, contain MoO with 500 milliliters
3120 grams per liters, the ammonium molybdate of NiO25 grams per liter and nickelous nitrate mixing solutions dipping 1 hour filters the back in 120 ℃ of oven dry 2 hours, and 480 ℃ of roastings 4 hours obtain catalyzer C2.Molybdenum oxide among the catalyzer C2, the content of nickel oxide are listed in the table 2.
Example 15
Get the carrier Z6200 gram of example 11 preparations, contain WO with 500 milliliters
370 grams per liters, the ammonium metawolframate of NiO28 grams per liter and nickelous nitrate mixing solutions dipping 1 hour filters the back in 120 ℃ of oven dry 2 hours, and 450 ℃ of roastings 4 hours obtain catalyzer C3.Tungsten oxide 99.999 among the catalyzer C3, the content of nickel oxide are listed in the table 2.
Example 16
Get the carrier Z7200 gram of example 12 preparations, contain MoO with 500 milliliters
370 grams per liters, the molybdic acid of CoO15 grams per liter acid ammonium and Xiao Suangu mixing solutions dipping 1 hour filter the back in 120 ℃ of oven dry 2 hours, and 480 ℃ of roastings 4 hours obtain catalyzer C4.Molybdenum oxide among the catalyzer C4, the content of cobalt oxide are listed in the table 2.
Table 2
| Example number | Used carrier | The catalyzer numbering | Metal oxide content, heavy % | |||
| MoO 3 | WO 3 | NiO | CoO | |||
| 13 | Z2 | C1 | 8.2 | 1.6 | ||
| Comparative Examples 4 | D1 | CD1 | 8.2 | 1.6 | ||
| Comparative Examples 5 | D2 | CD2 | 8.2 | 1.6 | ||
| Comparative Examples 6 | D3 | CD3 | 8.2 | 1.6 | ||
| 14 | Z5 | C2 | 12.0 | 2.2 | ||
| 15 | Z6 | C3 | 7.0 | 3.0 | ||
| 16 | Z7 | C4 | 7.2 | 1.8 | ||
Example 17-20
Example 17-20 explanation the invention provides the hydrodemetallation (HDM) performance of catalyzer.
With nickel content is that 20ppm, content of vanadium are that the vacuum residuum of 40ppm is raw material, evaluate catalysts on 100 milliliters of small stationary bed bioreactors.Catalyzer C1, C2, C3, C4 are broken into the particle of diameter 2-3 millimeter, and the catalyzer loading amount is 100 milliliters.Reaction conditions is: 390 ℃ of temperature of reaction, hydrogen dividing potential drop 15 MPas, liquid hourly space velocity are 0.5 hour
-1, hydrogen to oil volume ratio is 800, reacts sampling after 200 hours, adopts plasma emission spectrum (AES/ICP) method to measure the content that generates nickel, vanadium in the oil, and calculates demetallization per, the results are shown in table 3.
Comparative Examples 7-9
According to the method evaluate catalysts CD1 of example 17, the hydrodemetallation (HDM) performance of CD2, CD3, the results are shown in Table 3.
Table 3
| Example number | The catalyzer numbering | Demetallization per/% |
| 17 | C1 | 78 |
| Comparative Examples 7 | CD1 | 54 |
| Comparative Examples 8 | CD2 | 63 |
| Comparative Examples 9 | CD3 | 62 |
| 18 | C2 | 80 |
| 19 | C3 | 74 |
| 20 | C4 | 75 |
By table 3 as seen, catalyzer C1 provided by the invention and reference catalyst CD1, CD2, CD3 active ingredient and content suitable (seeing Table 2).But the demetallization per of catalyzer C1 exceeds 24,15 and 16 percentage points than reference catalyst CD1, CD2, CD3.The demetalization performance that shows Hydrodemetalation catalyst provided by the invention is better than the catalyzer that prior art provides.
Claims (11)
1, a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, be included in and introduce molybdenum and/or tungsten and nickel and/or cobalt metal component in the alumina supporter, wherein, described carrier by comprise with hydrated aluminum oxide mix with the aluminium carbonate ammonium, the method preparation of moulding and roasting, the weight ratio of mixture of described hydrated aluminum oxide and aluminium carbonate ammonium is: 20-90: 10-80, described maturing temperature is 450-1000 ℃, and roasting time is 1-8 hour.
2, method according to claim 1 is characterized in that, the weight ratio of mixture of described hydrated aluminum oxide and aluminium carbonate ammonium is: 30-80: 20-70.
3, method according to claim 1 and 2 is characterized in that, described aluminium carbonate ammonium consist of (NH
4) mAlO (OH) (HCO
3) mnH
2O, 0＜m wherein＜1,0＜n≤5.
4, method according to claim 3 is characterized in that, described 0.2≤m≤0.5,0.5≤n≤4.
5, method according to claim 1 and 2 is characterized in that, described hydrated aluminum oxide is selected from one or more in hibbsite, boehmite, pseudo-boehmite and the amorphous hydroted alumina; Or in hibbsite, monohydrate alumina and the amorphous hydroted alumina of siliceous, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth one or more.
6, method according to claim 5 is characterized in that, described hydrated aluminum oxide is a pseudo-boehmite.
7, method according to claim 1 is characterized in that, described maturing temperature is 550-950 ℃, and roasting time is preferably 2-4 hour.
8, method according to claim 1, it is characterized in that, before moulding, also be included in and introduce one or more in the mixture of described hydrated aluminum oxide and aluminium carbonate ammonium and be selected from nitrogenous compound except that the aluminium carbonate ammonium, mixture with hydrated aluminum oxide and aluminium carbonate ammonium is a benchmark, and the consumption of described nitrogenous compound is 2-20 weight %.
9, method according to claim 8, it is characterized in that, described nitrogenous compound is selected from one or more in ammonium citrate, bicarbonate of ammonia, ammonium acetate, ammonium oxalate, the urea, mixture with hydrated aluminum oxide and aluminium carbonate ammonium is a benchmark, and the consumption of described nitrogenous compound is 4-15 weight %.
10, method according to claim 1 is characterized in that, the pore volume of described bimodal porous aluminum oxide carrier is 0.8-1.6 milliliter/gram, and specific surface area is a 150-350 rice
2/ gram, the aperture accounts for total pore volume 40～90% at the pore volume of 10～30 nanometers, and the aperture accounts for total pore volume 10～60% at the pore volume of 100～2000 nanometers.
11, a kind of residuum hydrogenating and metal-eliminating catalyst, this catalyzer contain a kind of macropore alumina supporter and the molybdenum and/or tungsten and cobalt and/or the nickel metal component that load on this carrier, and this catalyzer is according to any described method preparation among the claim 1-10.
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