CN103861651A - Heavy oil hydrogenation and asphaltene-removing catalyst, preparation and application thereof - Google Patents
Heavy oil hydrogenation and asphaltene-removing catalyst, preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a heavy oil hydrogenation and asphaltene-removing catalyst, preparation and an application thereof. The heavy oil hydrogenation and asphaltene-removing catalyst contains a boron-containing alumina carrier and a hydrogenation activity metal component, wherein the carrier has a bimodal pore structure and is characterized through a mercury injection method, the pore volume of the carrier is 0.9-1.2 ml/g, the specific surface area is 50-300 m<2>/g, the pore volume of the pores having a diameter of 10-30 nm accounts for 55-80% of the total pore volume, and the pore volume of the pores having a diameter of 300-500 nm accounts for 10-35% of the total pore volume, wherein the carrier preparation comprises: mixing pseudoboehmite-containing hydrated alumina P1 and a modifier P2 of the P1, introducing a boron-containing compound into the obtained mixture, molding, drying and calcinating, wherein a weight mixing ratio of the P1 to the P2 is 20-95:5-80, the k value of the P2 is more than or equal to 0 and is less than or equal to 0.9, the k is equal to DI2/DI1, the DI1 is the acid dispersion index of the pseudoboehmite-containing hydrated alumina P1, and the DI2 is the acid dispersion index of the modifier P2 of the P1. Compared with the heavy oil hydrogenation and asphaltene-removing catalyst in the prior art, the heavy oil hydrogenation and asphaltene-removing catalyst of the present invention has good hydrogenation and asphaltene-removing and demetallization performance when the catalyst is used for residual oil hydrotreating.
Description
Technical field
The present invention relates to a kind of hydrogenation diasphaltene catalyst and preparation and application thereof.
Background technology
Mink cell focus including residual oil is carried out to the utilization rate that deep processing is not only conducive to improve crude oil, alleviate the nervous trend of energy supply, can also reduce environmental pollution, reach the clean utilization of the energy simultaneously.Compared with distillate, in mink cell focus, contain a large amount of macromolecular reaction such as asphalitine, colloid things, and the heavy metal such as heteroatomic compound and nickel and vanadium such as sulphur in mink cell focus, nitrogen, oxygen and condensed-nuclei aromatics major part concentrate in asphalitine, these impurity and heavy metal can pollute corresponding catalyst in follow-up process, thereby bitum hydro-conversion is a critical step in 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 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, asphaltene molecules is difficult to contact with the activated centre of catalyst by diffusion, and be mainly outer surface or the aperture that is adsorbed on catalyst, along with the carrying out of reaction 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, 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 asphaltene removal, for example, often S, N removal efficiency and asphaltene removal are not high to remove the catalyst that metal active is high.The reason that produces problems is very complicated.First be raw material, in residual oil, the feature of each component is that molecular weight is large, complex structure, and saturation degree low (armaticity is high), S, N content are high.And beyond sulphur removal, the overwhelming majority of impurity be present in asphalitine again, therefore want to remove this type of S, N, must carry out appropriate conversion (comprising saturated, open loop and hydrogenolysis etc.) to asphaltene molecules more.Next is catalyst.In 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 carrier that catalyst uses comprise by a kind of precursor of aluminium oxide mix with a kind of deacidification nitrogen-containing compound in addition, moulding 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 be to provide a kind of new, there is the catalyst of better hydrogenation diasphaltene performance, preparation method and the application of this catalyst.
The present invention relates to following content:
1. a hydrogenation diasphaltene catalyst, the alumina support that contains boracic and hydrogenation active metals component, wherein, described carrier has structure of double peak holes, 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 the catalyst described in 1, 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 the catalyst described in 1, it is characterized in that, in oxide and take carrier as benchmark, the content of described boron is 0.1-8 % by weight.
4. according to the catalyst described in 3, it is characterized in that, in oxide and take carrier as benchmark, the content of described boron is 1-6 % by weight.
5. according to the catalyst described in 4, it is characterized in that, in oxide and take carrier as benchmark, the content of described boron is 2-5 % by weight.
6. according to the catalyst described in 1, it is characterized in that, described hydrogenation active metals component is selected from least one metal component of group VIII and at least one 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 being less than or equal to 3 % by weight, and the content of metal component of group VIB is greater than 3 to being less than or equal to 10 % by weight.
7. according to the catalyst described in 6, it is characterized in that, described metal component of group VIII is selected from cobalt and/or nickel, 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 1-2 % by weight, and the content of metal component of group VIB is greater than 4 to being less than or equal to 8 % by weight.
8. according to the preparation method of catalyst described in 1, comprise and prepare carrier and load hydrogenation active metals component on this carrier, wherein, the preparation of described carrier comprises introduces boron-containing compound by mixed the modifier P2 of the hydrated alumina P1 that contains boehmite and P1 being incorporated in this mixture, moulding afterwards, dry and roasting, wherein, the weight mixing ratio of described P1 and P2 is 20-95:5-80, the κ value of P2 is 0 to being less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1for the sour peptization index of the hydrated alumina P1 that contains boehmite, DI
2for the sour peptization index of the modifier P2 of the hydrated alumina P1 that contains boehmite.
9. according to the method described in 8, it is characterized in that, the weight mixing ratio of described P1 and P2 is 70-95:5-25.
10. according to the method described in 8, it is characterized in that, in oxide and take described carrier as benchmark, it is 0.1-8 % by weight that the introduction volume of described boron-containing compound makes the content of boron in final carrier.
11. according to the method described in 10, it is characterized in that, in oxide and take described carrier as benchmark, it is 1-6 % by weight that the introduction volume of described boron-containing compound makes the content of boron in final carrier.
12. according to the method described in 8, it is characterized in that, the k value of described P2 is 0 to being less than or equal to 0.6.
13. according to the method described in 8 or 9, it is characterized in that, described in contain boehmite the pore volume of hydrated alumina P1 be 0.9-1.4 ml/g, specific surface is 100-350 rice
2/ gram, can and bore dia 8-30nm.
14. according to the method described in 13, it is characterized in that, described in contain boehmite the pore volume of hydrated alumina P1 be 0.95-1.3 ml/g, specific surface is 120-300 rice
2/ gram, can and bore dia 10-25nm.
15. according to the method described in 8,9 or 12 any one, it is characterized in that, described P2 is 80-300 object particle.
16. according to the method described in 15, it is characterized in that, described P2 is 100-200 object particle.
17. according to the method described in 8, it is characterized in that, described dry condition comprises: temperature is 40-350 ℃, and the time is 1-24 hour, and the condition of described roasting comprises: temperature is for being greater than 500 to being less than or equal to 1200 ℃, and the time is 1-8 hour.
18. according to the method described in 17, it is characterized in that, described dry condition comprises: temperature is 100-200 ℃, and the time is 2-12 hour, and the condition of described roasting comprises: temperature is for being greater than 800 to being less than or equal to 1000 ℃, and roasting time is for being 2-6 hour.
19. according to the method described in 8, it is characterized in that, it is by the described hydrated alumina P1 moulding that contains boehmite, dry that P1 is modified as to one of method of P2, afterwards it is all or part ofly ground, sieved, obtaining powder thing is P2, described dry condition 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 for being greater than 350 to being less than or equal to 1400 ℃, and roasting time is 1-8 hour, afterwards it is all or part ofly ground, is sieved, and obtaining powder thing is P2; Three of method is that the hydrated alumina P1 that contains boehmite is dodged and done, and dodges dry temperature for being greater than 150 to being less than or equal to 1400 ℃, and flash-off time is 0.05-1 hour, and obtaining powder thing is P2; Four of method is that one or more in two and the modifier that obtains with three of method of one of method, method are mixed to get.
20. according to the method described in 19, it is characterized in that, the dry condition in described method one comprises: temperature is 100-200 ℃, and the time is 2-12 hour; Method two in sintering temperature be 500-1200 ℃, roasting time is 0.1-6 hour; Method three in the dry temperature of sudden strain of a muscle be 200-1000 ℃, flash-off time is 0.1-0.5 hour.
21. according to the method described in 19 or 20, it is characterized in that, described P2 is 80-300 object particle in P1 modifier.
22. according to the method described in 21, it is characterized in that, described P2 is 100-200 object particle in P1 modifier.
23. according to the method described in 8, it is characterized in that, described on carrier the method for load hydrogenation active metals component be infusion process, comprise preparation containing the solution of the compound of hydrogenation active metals and use this solution impregnating carrier, be dried afterwards, roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least one group vib and the metal component of at least one VIII family, in oxide and take catalyst as benchmark, the described compound containing hydrogenation active metals makes the content of the metal component of the group vib in final catalyst be greater than 3 to being less than or equal to 10 % by weight in the concentration of described solution and the consumption of described solution, the content of the metal component of described VIII family is greater than 0.8 to being 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.
24. according to the method described in 23, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, the metal component of VIII family is selected from cobalt and/or nickel, in oxide and take catalyst as benchmark, the described compound containing hydrogenation active metals makes the content of the metal component of the group vib in final catalyst be greater than 4 to being less than or equal to 8 % by weight in the concentration of described solution and the consumption of described solution, and the content of the metal component of VIII family is 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.
The application of catalyst in 25. aforementioned 1-7 described in any one in hydrocarbon oil hydrogenation is processed
According to catalyst provided by the invention, depending on the different article shaped that require carrier wherein to can be made into various easy operatings, such as spherical, cellular, nest like, tablet or bar shaped (clover, butterfly, cylindrical etc.).Wherein, the method that the modifier P2 of the described hydrated alumina P1 that contains boehmite and P1 is mixed is conventional method, for example, the P1 of powder and P2 is dropped in stirring-type batch mixer and is mixed according to ingredient proportion.Be conventional method to the method for introducing boron-containing compound in described P1 and P2 mixture, in a concrete embodiment of preparing carrier, that boron-containing compound is mixed with to the aqueous solution to the method for introducing boron-containing compound in the mixture of the modifier P2 of the described hydrated alumina P1 that contains boehmite and P1, this aqueous solution is sneaked into when described P1 and P1 mix or after described P1 and P1 mix, again this aqueous solution is sneaked into moulding afterwards, dry and roasting.Described boron-containing compound can be one or more in boron water soluble compound arbitrarily.For example, one in boric acid and Boratex and composition thereof.
Described moulding can be carried out according to a conventional method, for example, and a kind of method in spin, compressing tablet and extruded moulding or the combination of several method.In the time of moulding, for example extruded moulding, for guaranteeing that described moulding carries out smoothly, can to add in described mixture water, extrusion aid and/or adhesive, containing or containing expanding agent, then extrusion molding, be dried also roasting 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, 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 surfactant.Synthetic cellulose is wherein preferably one or more in CMC, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in polyethylene glycol, poly-propyl alcohol, polyvinyl alcohol, and surfactant is preferably one or more in propenyl copolymer and the maleic acid copolymer that fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight are 200-10000.
Sour peptization index D I in the preparation of described carrier refers to that the hydrated alumina that contains boehmite adds after 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 and 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 that contains boehmite calcination base content (calcination base (also referred to as butt) content refers to quantitative boehmite in 600 ℃ of roastings 4 hours, its burn after weight and burn before the ratio of weight), count a; (2) take with assay balance the hydrated alumina W that contains boehmite
0gram, W
0amount meet with Al
2o
3the W of meter
1be 6 grams of (W
1/ a=W
0), take deionized water W gram, W=40.0-W
0, under stirring, the hydrated alumina that contains boehmite taking and deionized water are added in beaker and are mixed; (3) pipette with 20mL pipette the dilute nitric acid solution that 20mL, concentration are 0.74N, this acid solution is joined in the beaker of step (2), stir lower reaction 8 minutes; (4) the reacted slurries of step (3) are carried out to centrifugation in centrifuge, sediment are inserted in the crucible of having weighed, afterwards, by its in 125 ℃ dry 4 hours, in Muffle furnace, 850 ℃ of roastings 3 hours, weigh and obtain calcination sample size W
2gram; (5) according to formula DI=(1-W
2/ W
1) × 100% calculates.
The described hydrated alumina P1 that contains boehmite can be boehmite prepared by any prior art, 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 amorphous hydrated aluminium oxide.In a preferred embodiment, with X diffraction characterize, described in contain boehmite hydrated alumina in boehmite content be not less than 50%, be more preferably not less than 60%.
The pore volume of the hydrated alumina P1 that contains boehmite described in further preferred is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, can and bore dia 8-30nm, the pore volume that contains the hydrated alumina P1 of boehmite described in being more preferably is 0.95-1.3 ml/g, specific surface is 120-300 rice
2/ gram, can and bore dia 10-25nm.
In the present invention, the pore volume of the hydrated alumina that contains boehmite, specific area and can and aperture, be 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, the hydrated alumina P1 that contains boehmite is heat-treated after modification, the peptization index of its modifier changes, by this modifier with without heat treated P1 mixed-forming, dry and roasting after, the carrier obtaining has obvious bimodal pore distribution.Particularly by 80-300 object particle wherein, preferably 100-200 object particle with without after heat treated part mixed-forming, dry and roasting, the each unimodal pore size distribution in the carrier obtaining bimodal is concentrated especially.Here, described 80-300 object particle, preferably 100-200 object particle refers to that described modifier is through sieve (step that comprises if desired fragmentation or grinding), its screening thing (screenings) meets 80-300 object particle, the percentage (by weight) that preferred 100-200 object particle accounts for total amount is not less than 60%, is further preferably not less than 70%.
The weight mixing ratio of described P1 and P2 refers to P1 and the P2 ratio of shared parts by weight respectively in the mixture of every hundred parts of described P1 and P2.Wherein, the preferred span of the parts by weight of P1 is 20-95, more preferably 70-95; The preferred span of parts by weight of P2 is 5-80, more preferably 5-25.
In concrete enforcement, described P2 can conveniently be obtained by following method:
(1) based on the dry P2 that obtains, comprise by the hydrated alumina P1 that contains boehmite according to a conventional method moulding prepare in conventional alumina support process, the tailing of drying by-product, for example: in extruded moulding, bar shaped article shaped is at tailing (being called traditionally dry waste material) dry, integer process by-product, this tailing is milled, sieve and obtain P2.
(2) obtain based on roasting, comprise by the hydrated alumina P1 that contains boehmite according to a conventional method moulding prepare in conventional alumina support process, through the tailing (being called traditionally roasting waste material) of roasting by-product, for example, in roller forming, the tailing of spheric granules by-product in roasting process, mills this tailing, sieves and obtains P2; Or directly P1 is dodged to dry obtaining, in the time directly 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 in the modifier P2 obtaining based on preceding method.In the time adopting mixed method to obtain P2, the mixed proportion of the modifier P2 that aforementioned several method is obtained respectively does not limit.
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, preferably VIII family metal component is cobalt and/or nickel, VI B family 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 being less than or equal to 3 % by weight, more preferably 1-2 % by weight, the content of described VI B family metal component is preferably greater than 3 to being less than or equal to 10 % by weight, is further preferably greater than 4 to being less than or equal to 8 % by weight.
Described hydrogenation active metals component is carried under the prerequisite on described carrier being enough to, the present invention is not particularly limited described carrying method, preferred method is infusion process, comprises the dipping solution of preparation containing the compound of described metal, uses afterwards the carrier described in this solution impregnation.Described dipping method is conventional method, for example, can be excessive immersion stain, hole saturation infusion process.Described be selected from one or more in the soluble compound in them containing the metal component compound that is selected from VI B family, as one or more in molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; One or more in tungstates, metatungstate, ethyl metatungstate, preferred ammonium metatungstate, ethyl ammonium metatungstate wherein.One or more in the described soluble compound that is selected from them containing the compound that is selected from VIII family metal component, as one or more in the soluble complexes of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt, be preferably cobalt nitrate, basic cobaltous carbonate; One or more in the soluble complexes of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel, are preferably nickel nitrate, basic nickel carbonate.
According to catalyst provided by the invention, can also contain any interpolation component that the invention provides catalyst performance and maybe can improve the catalytic performance of catalyst provided by the invention that do not affect.As contained the interpolation components such as phosphorus, in oxide and take catalyst as benchmark, the content of described interpolation component is no more than 10 % by weight, is preferably 0.1-4 % by weight.
In the time also containing phosphorus etc. in described catalyst and add component, the introducing method of described interpolation component can be method arbitrarily, as can be by containing as described in the component such as phosphorus compound directly with as described in boehmite mix, moulding roasting; Can be to flood described carrier after the compound that contains the components such as described phosphorus and the compound that contains hydrogenation active metals component are mixed with to mixed solution; Can also be after independent the compound that contains the components such as phosphorus obtain solution, to flood described carrier roasting.In the time that the interpolation components such as phosphorus and hydrogenation active metals are introduced described carrier respectively, preferably first with carrier roasting described in the solution impregnation that contains described interpolation component composition, afterwards again by the solution impregnation that contains 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, the reaction condition of the hydrotreatment to described hydrocarbon ils is not particularly limited, in a 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 hydrotreatment reaction condition with the catalytic reactor of described catalyst any, for example, at described fixed bed reactors, in moving-burden bed reactor or fluidized bed reactor, carries out.
According to the conventional method in this area, described hydrotreating catalyst is before using, conventionally can be under hydrogen exists, at the temperature of 140-370 ℃, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out outward also can in device, original position vulcanizing at device, and the active metal component of its load is converted into 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, to provide qualified feedstock oil for subsequent technique (as catalytic cracking process).Compared with prior art, catalyst provided by the invention has better hydrogenation diasphaltene and demetalization performance when 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 example, except special instruction, is chemically pure reagent.
The boehmite using in following embodiment comprises:
P1-1: (pore volume is 1.2 mls/g to the dry glue powder that Chang Ling catalyst branch company produces, and specific surface is 280 meters
2/ gram, can and 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 mls/g to the dry glue powder that Yantai Heng Hui Chemical Co., Ltd. produces, and specific surface is 260 meters
2/ gram, can and 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 1000 grams of P1-1, add afterwards containing 1440 milliliters of the aqueous solution of 10 milliliters, nitric acid (Tianjin chemical reagent three factory's products), on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, obtain dried strip, by dried strip shaping, sieve, the dried strip material (being commonly referred to as industrially drying bar waste material) that length is less than to 2mm is milled, and sieves, and gets wherein 100～200 mesh sieves and divides, and obtains the modifier P2A of P1-1.The k value of P2A is in table 1.
Embodiment 2
Take 1000 grams of P1-1, dodge and do 6 minutes in 240 ℃, obtain the modifier P2B of P1-1.The k value of P2B is in table 1.
Embodiment 3
Each 200 grams of even mixing of P2B that the P2A that embodiment 1 is obtained and embodiment 2 obtain, obtain the modifier P2C of P1-1.The k value of P2C is in table 1.
Embodiment 4
Take 1000 grams of P1-2, add afterwards containing 1440 milliliters of the aqueous solution of 10 milliliters, nitric acid (Tianjin chemical reagent three factory's products), on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, 1200 ℃ of roastings 4 hours, obtain carrier, by carrier strip shaping, sieve, the carrier strip material (being commonly referred to as industrial carrier waste material) that length is less than to 2mm is milled, sieve, get wherein 100～200 mesh sieves and divide, obtain the modifier P2D of P1-2.The k value of P2D is in table 1.
Embodiment 5
Take 1000 grams of P1-2, dodge and do 10 minutes in 650 ℃, obtain the modifier P2E of P1-2.The k value of P2E is in 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 preparation method of carrier for embodiment 6-13 explanation preparation catalyst of the present invention.The preparation method of comparative example 1-2 explanation conventional catalyst carrier.
Embodiment 6
Take 800 grams of P1-1, after 200 grams of raw material P2A that make with embodiment 1 evenly mix, add containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory's products), containing 1440 milliliters of the boric acid aqueous solutions of diboron trioxide 2.4g, on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, obtain article shaped, by 900 ℃ of roastings of this article shaped 3 hours, obtain carrier Z1.The character of carrier Z1 is listed in table 2.
Embodiment 7
Take 200 grams of P1-1, after 800 grams of raw material P2B that make with embodiment 2 evenly mix, add containing nitric acid Tianjin chemical reagent three factory's products) 10 milliliters, containing 1440 milliliters of the boric acid aqueous solutions of diboron trioxide 2.4g, on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, obtain article shaped, by 900 ℃ of roastings of this article shaped 3 hours, obtain carrier Z2.The character of carrier Z2 is listed in table 2.
Embodiment 8
Take 500 grams of P1-1, after 500 grams of raw material P2C that make with embodiment 3 evenly mix, add containing nitric acid Tianjin chemical reagent three factory's products) 10 milliliters, containing 1440 milliliters of the boric acid aqueous solutions of diboron trioxide 2.4g, on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, obtain article shaped, by 950 ℃ of roastings of this article shaped 3 hours, obtain carrier Z3.The character of carrier Z3 is listed in table 2.
Comparative example 1
Take 1000 grams of P1-1, add containing nitric acid Tianjin chemical reagent three factory's products) 10 milliliters, containing 1440 milliliters of the boric acid aqueous solutions of diboron trioxide 2.4g, on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, obtain article shaped, by 900 ℃ of roastings of this article shaped 3 hours, obtain carrier DZ1.The character of carrier DZ1 is listed in table 2.
Embodiment 9
Take 800 grams of P1-2, after 200 grams of raw material P2D that make with embodiment 4 evenly mix, add containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory's products), containing 1440 milliliters of the boric acid aqueous solutions of diboron trioxide 14g, on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, obtain article shaped, by 1000 ℃ of roastings of this article shaped 3 hours, obtain carrier Z4.The character of carrier Z4 is listed in table 2.
Embodiment 10
Take 900 grams of P1-1, after 100 grams of raw material P2E that make with embodiment 5 evenly mix, add containing nitric acid Tianjin chemical reagent three factory's products) 10 milliliters, containing 1440 milliliters of the boric acid aqueous solutions of diboron trioxide 14g, on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, obtain article shaped, by 1000 ℃ of roastings of this article shaped 3 hours, obtain carrier Z5.The character of carrier Z5 is listed in table 2.
Embodiment 11
Take 850 grams of P1-2, after 150 grams of raw material P2C that make with embodiment 3 evenly mix, add containing nitric acid Tianjin chemical reagent three factory's products) 10 milliliters, containing 1440 milliliters of the boric acid aqueous solutions of diboron trioxide 14g, on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, obtain article shaped, by 850 ℃ of roastings of this article shaped 3 hours, obtain carrier Z6.The character of carrier Z6 is listed in table 2.
Comparative example 2
Take 1000 grams of P1-2, add containing nitric acid Tianjin chemical reagent three factory's products) 10 milliliters, containing 1440 milliliters of the boric acid aqueous solutions of diboron trioxide 14g, on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, obtain article shaped, by 1000 ℃ of roastings of this article shaped 3 hours, obtain carrier DZ2.The character of carrier DZ2 is listed in table 2.
Embodiment 12
Take 900 grams of P1-2, after 100 grams of raw material P2D that make with embodiment 4 evenly mix, add containing nitric acid Tianjin chemical reagent three factory's products) 10 milliliters, containing 1440 milliliters of the boron aqueous solution of diboron trioxide 28g, on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, obtain article shaped, by 1000 ℃ of roastings of this article shaped 3 hours, obtain carrier Z7.The character of carrier Z7 is listed in table 2.
Embodiment 13
Take 850 grams of P1-2, after 150 grams of raw material P2E that make with embodiment 5 evenly mix, add containing nitric acid Tianjin chemical reagent three factory's products) 10 milliliters, containing 1440 milliliters of the boric acid aqueous solutions of diboron trioxide 28g, on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 ℃ dry 4 hours, obtain article shaped, by 900 ℃ of roastings of this article shaped 3 hours, obtain carrier Z8.The character of carrier Z8 is listed in table 2.
Comparative example 3
The method providing according to patent CN1782031A embodiment 9 is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar in 120 ℃ dry 4 hours, obtain article shaped, by 900 ℃ of roastings of this article shaped 3 hours, obtain carrier DZ3.The character of carrier DZ3 is listed in table 2.
Table 2
Result by table 2 can see, compared with conventional method, the alumina support of being prepared by the method for the invention provides has obvious structure of double peak holes.
Embodiment 14-16 illustrates Catalysts and its preparation method provided by the invention.
Wherein, in catalyst, 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 shown in Petrochemical Engineering Analysis method RIPP133-90).
Embodiment 14
Get 200 grams of carrier Z1, with 210 milliliters containing MoO
367.9 grams per liters, the molybdenum oxide of CoO 11.3 grams per liters and basic cobaltous carbonate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 420 ℃ of roastings 3 hours, obtain catalyst C1.Molybdenum oxide in catalyst C1 and the content of cobalt oxide are listed in table 3.
Comparative example 4
Get 200 grams of carrier DZ1, with 180 milliliters containing MoO
379.2 grams per liters, the molybdenum oxide of CoO 13.2 grams per liters and basic cobaltous carbonate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 420 ℃ of roastings 3 hours, obtain catalyst DC1.Molybdenum oxide in catalyst DC1 and the content of cobalt oxide are listed in table 3.
Embodiment 15
Get 200 carrier Z2, with 200 milliliters containing MoO
353.1 grams per liters, the molybdenum oxide of NiO 10.6 grams per liters and basic nickel carbonate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 420 ℃ of roastings 3 hours, obtain catalyst C2.Molybdenum oxide in catalyst C2 and the content of nickel oxide are listed in table 3.
Comparative example 5
Get 200 carrier DZ1, with 180 milliliters containing MoO
359.0 grams per liters, the molybdenum oxide of NiO 11.8 grams per liters and basic nickel carbonate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 420 ℃ of roastings 3 hours, obtain catalyst DC2.Molybdenum oxide in catalyst DC2 and the content of nickel oxide are listed in table 3.
Embodiment 16
Get 200 grams of carrier Z3, with 205 milliliters containing MoO
378.5 grams per liters, the ammonium molybdate of NiO 15.7 grams per liters and nickel nitrate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 420 ℃ of roastings 3 hours, obtain catalyst C3.Molybdenum oxide in catalyst C3 and the content of nickel oxide are listed in table 3.
Comparative example 6
Get 200 grams of carrier DZ2, with 180 milliliters containing MoO
387.2 grams per liters, the molybdenum oxide of NiO 17.4 grams per liters and basic nickel carbonate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 420 ℃ of roastings 3 hours, obtain catalyst DC3.Molybdenum oxide in catalyst DC3 and the content of nickel oxide are listed in table 3.
Embodiment 17
Get 200 grams of carrier Z4, with 210 milliliters containing MoO
367.9 grams per liters, the molybdenum oxide of NiO 11.3 grams per liters and basic nickel carbonate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 420 ℃ of roastings 3 hours, obtain catalyst C4.Molybdenum oxide in catalyst C4 and the content of nickel oxide are listed in table 3.
Embodiment 18
Get 200 grams of carrier Z8, with 200 milliliters containing MoO
382.8 grams per liters, the molybdenum oxide of CoO 19.1 grams per liters and basic cobaltous carbonate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 420 ℃ of roastings 3 hours, obtain catalyst C5.Molybdenum oxide in catalyst C5 and the content of cobalt oxide are listed in table 3.
Comparative example 7
Get 200 grams of carrier DZ3, with 200 milliliters containing MoO
382.8 grams per liters, the molybdenum oxide of CoO 19.1 grams per liters and basic cobaltous carbonate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 420 ℃ of roastings 3 hours, obtain catalyst DC4.Molybdenum oxide in catalyst DC4 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 is broken into diameter 2-3 millimeter packs reactor 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 shown in 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 the hydrotreatment oily studies on asphaltene mass fractions in front and back (concrete grammar is referring to SH/T 0509-92).Calculate according to the following formula asphalitine and metal removal rate:
The normal slag of Kuwait that 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 activity data of each catalyst is in table 4.
Comparative example 8-11
According to demetallization per and the diasphaltene rate of method evaluation catalyst DC1, DC2, DC3 and the DC4 of embodiment 19-23, the results are shown in Table 4.
Table 4
| Embodiment | Catalyst numbering | Diasphaltene rate/% | Demetallization per/% |
| 19 | C1 | 90 | 74 |
| Comparative example 8 | DC1 | 66 | 70 |
| 20 | C2 | 92 | 72 |
| Comparative example 9 | DC2 | 64 | 64 |
| 21 | C3 | 96 | 74 |
| Comparative example 10 | DC3 | 77 | 71 |
| 22 | C4 | 93 | 82 |
| 23 | C5 | 95 | 86 |
| Comparative example 11 | DC4 | 88 | 80 |
Can be seen by table 4 result, in poor residuum hydrotreatment process, will obviously be better than existing catalyst by the diasphaltene and the metal removal activity that the invention provides catalyst, illustrate that this technological invention catalyst is more suitable for the processing processing in poor residuum.
Claims (25)
1. a hydrogenation diasphaltene catalyst, the alumina support that contains boracic and hydrogenation active metals component, wherein, described carrier has structure of double peak holes, 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 the catalyst described in 1, 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 the catalyst described in 1, it is characterized in that, in oxide and take carrier as benchmark, the content of described boron is 0.1-8 % by weight.
4. according to the catalyst described in 3, it is characterized in that, in oxide and take carrier as benchmark, the content of described boron is 1-6 % by weight.
5. according to the catalyst described in 4, it is characterized in that, in oxide and take carrier as benchmark, the content of described boron is 2-5 % by weight.
6. according to the catalyst described in 1, it is characterized in that, described hydrogenation active metals component is selected from least one metal component of group VIII and at least one 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 being less than or equal to 3 % by weight, and the content of metal component of group VIB is greater than 3 to being less than or equal to 10 % by weight.
7. according to the catalyst described in 6, it is characterized in that, described metal component of group VIII is selected from cobalt and/or nickel, 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 1-2 % by weight, and the content of metal component of group VIB is greater than 4 to being less than or equal to 8 % by weight.
8. according to the preparation method of catalyst described in 1, comprise and prepare carrier and load hydrogenation active metals component on this carrier, wherein, the preparation of described carrier comprises introduces boron-containing compound by mixed the modifier P2 of the hydrated alumina P1 that contains boehmite and P1 being incorporated in this mixture, moulding afterwards, dry and roasting, wherein, the weight mixing ratio of described P1 and P2 is 20-95:5-80, the κ value of P2 is 0 to being less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1for the sour peptization index of the hydrated alumina P1 that contains boehmite, DI
2for the sour peptization index of the modifier P2 of the hydrated alumina P1 that contains boehmite.
9. according to the method described in 8, it is characterized in that, the weight mixing ratio of described P1 and P2 is 70-95:5-25.
10. according to the method described in 8, it is characterized in that, in oxide and take described carrier as benchmark, it is 0.1-8 % by weight that the introduction volume of described boron-containing compound makes the content of boron in final carrier.
11. according to the method described in 10, it is characterized in that, in oxide and take described carrier as benchmark, it is 1-6 % by weight that the introduction volume of described boron-containing compound makes the content of boron in final carrier.
12. according to the method described in 8, it is characterized in that, the k value of described P2 is 0 to being less than or equal to 0.6.
13. according to the method described in 8 or 9, it is characterized in that, described in contain boehmite the pore volume of hydrated alumina P1 be 0.9-1.4 ml/g, specific surface is 100-350 rice
2/ gram, can and bore dia 8-30nm.
14. according to the method described in 13, it is characterized in that, described in contain boehmite the pore volume of hydrated alumina P1 be 0.95-1.3 ml/g, specific surface is 120-300 rice
2/ gram, can and bore dia 10-25nm.
15. according to the method described in 8,9 or 12 any one, it is characterized in that, described P2 is 80-300 object particle.
16. according to the method described in 15, it is characterized in that, described P2 is 100-200 object particle.
17. according to the method described in 8, it is characterized in that, described dry condition comprises: temperature is 40-350 ℃, and the time is 1-24 hour, and the condition of described roasting comprises: temperature is for being greater than 500 to being less than or equal to 1200 ℃, and the time is 1-8 hour.
18. according to the method described in 17, it is characterized in that, described dry condition comprises: temperature is 100-200 ℃, and the time is 2-12 hour, and the condition of described roasting comprises: temperature is for being greater than 800 to being less than or equal to 1000 ℃, and roasting time is for being 2-6 hour.
19. according to the method described in 8, it is characterized in that, it is by the described hydrated alumina P1 moulding that contains boehmite, dry that P1 is modified as to one of method of P2, afterwards it is all or part ofly ground, sieved, obtaining powder thing is P2, described dry condition 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 for being greater than 350 to being less than or equal to 1400 ℃, and roasting time is 1-8 hour, afterwards it is all or part ofly ground, is sieved, and obtaining powder thing is P2; Three of method is that the hydrated alumina P1 that contains boehmite is dodged and done, and dodges dry temperature for being greater than 150 to being less than or equal to 1400 ℃, and flash-off time is 0.05-1 hour, and obtaining powder thing is P2; Four of method is that one or more in two and the modifier that obtains with three of method of one of method, method are mixed to get.
20. according to the method described in 19, it is characterized in that, the dry condition in described method one comprises: temperature is 100-200 ℃, and the time is 2-12 hour; Method two in sintering temperature be 500-1200 ℃, roasting time is 0.1-6 hour; Method three in the dry temperature of sudden strain of a muscle be 200-1000 ℃, flash-off time is 0.1-0.5 hour.
21. according to the method described in 19 or 20, it is characterized in that, described P2 is 80-300 object particle in P1 modifier.
22. according to the method described in 21, it is characterized in that, described P2 is 100-200 object particle in P1 modifier.
23. according to the method described in 8, it is characterized in that, described on carrier the method for load hydrogenation active metals component be infusion process, comprise preparation containing the solution of the compound of hydrogenation active metals and use this solution impregnating carrier, be dried afterwards, roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least one group vib and the metal component of at least one VIII family, in oxide and take catalyst as benchmark, the described compound containing hydrogenation active metals makes the content of the metal component of the group vib in final catalyst be greater than 3 to being less than or equal to 10 % by weight in the concentration of described solution and the consumption of described solution, the content of the metal component of described VIII family is greater than 0.8 to being 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.
24. according to the method described in 23, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, the metal component of VIII family is selected from cobalt and/or nickel, in oxide and take catalyst as benchmark, the described compound containing hydrogenation active metals makes the content of the metal component of the group vib in final catalyst be greater than 4 to being less than or equal to 8 % by weight in the concentration of described solution and the consumption of described solution, and the content of the metal component of VIII family is 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.
25. application in hydrocarbon oil hydrogenation is processed according to the catalyst described in any one in 1-7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107837797A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | The preparation method and alumina globule and catalytic reforming catalyst of alumina globule with bimodal pore distribution |
| CN114522693A (en) * | 2020-10-30 | 2022-05-24 | 中国石油化工股份有限公司 | Boron-containing heavy oil hydrotreating catalyst and heavy oil hydrotreating method |
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|---|---|---|---|---|
| JPH03273092A (en) * | 1990-03-22 | 1991-12-04 | Nippon Oil Co Ltd | Catalyst for hydrogenation of residual oil |
| CN1488441A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
| CN1782031A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Slag oil hydro-demetallization catalyst and its preparing method |
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2012
- 2012-12-12 CN CN201210536835.XA patent/CN103861651B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03273092A (en) * | 1990-03-22 | 1991-12-04 | Nippon Oil Co Ltd | Catalyst for hydrogenation of residual oil |
| CN1488441A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
| CN1782031A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Slag oil hydro-demetallization catalyst and its preparing method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107837797A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | The preparation method and alumina globule and catalytic reforming catalyst of alumina globule with bimodal pore distribution |
| CN107837797B (en) * | 2016-09-21 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of alumina pellets with bimodal pore distribution, alumina pellets and catalytic reforming catalyst |
| CN114522693A (en) * | 2020-10-30 | 2022-05-24 | 中国石油化工股份有限公司 | Boron-containing heavy oil hydrotreating catalyst and heavy oil hydrotreating method |
| CN114522693B (en) * | 2020-10-30 | 2023-07-14 | 中国石油化工股份有限公司 | Boron-containing heavy oil hydrotreating catalyst and heavy oil hydrotreating method |
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