CN104226323A - Heavy oil hydrotreating catalyst and preparation and application - Google Patents
Heavy oil hydrotreating catalyst and preparation and application Download PDFInfo
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Abstract
A heavy oil hydrotreating catalyst and its preparation and application. The catalyst contains a carrier and a hydrogenation active metal component loaded on the carrier, wherein the carrier contains aluminium oxide and alkaline-earth metal components. Represented by a mercury intrusion method, pore volume of the carrier is 0.95-1.2 ml/g, specific surface area is 50-300 m<2>/g, and the carrier presents bimodal pore size distribution at the diameter of 10-30nm and at the diameter of 300-500nm. Pore volume of pores with the diameter of 10-30nm accounts for 55-80% of the total pore volume, and pore volume of pores with the diameter of 300-500nm accounts for 10-35% of the total pore volume. The hydrogenation active metal component is selected from at least a VIB group metal component and at least a VB group metal component. Metered based on oxides and with the catalyst as the standard, content of the VIB group metal component is 0.2-15 wt%, and content of the VB group metal component is 0.2-12 wt%. In comparison with catalysts provided in the prior art, the catalyst provided by the invention has the advantage as follows: hydrodemetallization and diasphaltene activities are raised obviously.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst, preparation and application thereof, particularly a kind of be suitable for processing of heavy oil hydrogenation catalyst, preparation and application thereof.
Background technology
Along with the contradiction of worldwide crude oil heaviness, in poor quality and the petrochemicals diversification of demand, lighting is becoming increasingly acute, the main task of petroleum chemical industry will concentrate in heavy oil lighting.Residual oil is cut the heaviest in crude oil, crude oil through distillation after large, the baroque ampholyte species of molecular weight in residual oil, these impurity have material impact to follow-up process and product property, thus must first by hydrotreatment by these impurity removals.Compared with distillate, in heavy oil except there is the impurity such as sulphur, nitrogen, the metal impurities such as Ni, V also containing higher proportion, and asphalt content is high, carbon residue is higher.If wherein the metal impurities such as Ni, V can not get effectively removing, can downstream catalyst be had a negative impact, clog downstream catalyst duct, thus the inactivation causing downstream catalyst.Therefore, the Hydrodemetalation catalyst that exploitation metal removal activity is high effectively can extend the service life of downstream catalyst, thus plays the effect of protection downstream catalyst and prolong operating period.Due to the These characteristics of residual oil, in commercial Application, the activity stability of residual oil hydrocatalyst is very important, and many patent business release multiple residuum hydrogenating and metal-eliminating agent both at home and abroad.
CN1054393C discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, and its feature is to adopt Physical and chemical method two kinds of means to improve the pore structure of residuum hydrogenating and metal-eliminating agent.
CN1267537C discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, its feature is in used carrier containing a kind of alkaline-earth metal, the ratio of alkaline-earth metal accounts for the 0.1-5 % by weight of carrier, the acidity of its carrier is less than 0.2 mM/gram (carrier acid amount is lower), while the HDM activity making catalyst keep higher, coke content is low.
CN1946831A and US7608558 discloses a kind of hydrotreating catalyst comprising VB race metal, it is characterized in that metal component (calculating with oxide) is formed at least 50 % by weight of catalyst, the mol ratio wherein between metal component meets following formula: (group vib+VB race): (VIII)=0.5-2:1.
US5275994 describes the hydrotreating catalyst being applicable to hydrocarbon charging, and it comprises group VIII metal component, group vib metal component and VB race metal component.This trimetallic catalyst must load on silica or aluminium oxide and preferably with comprise be less than 28 % by weight metal component (with oxide basis) for feature.In catalyst preparing, VB race metal component must add as alkoxide in water-less environment, and preferably by monolith at least 500 DEG C of roastings.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of newly, the catalyst with high HDM, diasphaltene isoreactivity and stability, the preparation of this catalyst and application thereof.
The present invention relates to following invention:
1, a heavy oil hydrogenating treatment catalyst, containing carrier and load hydrogenation active metals component on this carrier, wherein, described carrier contains aluminium oxide and alkaline earth metal component, characterize with mercury injection method, the pore volume of described carrier is 0.95-1.2 ml/g, and specific area is 50-300 rice
2/ gram, described carrier be 10-30nm and diameter is 300-500nm at diameter is bimodal pore distribution, wherein, 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, described hydrogenation active metals component is selected from least one group vib metal component and at least one VB race metal component, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is 0.2-15 % by weight, and the content of VB race metal component is 0.2-12 % by weight.
2, the catalyst according to 1, is characterized in that, the pore volume of described aluminium oxide 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, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume; The metal component of described group vib is selected from molybdenum and/or tungsten, VB race metal component is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is 0.5-12 % by weight, and the content of VB race metal component is 0.5-9 % by weight.
3, the catalyst according to 1, is characterized in that, described alkaline earth metal component is selected from one or more in beryllium, magnesium, calcium, strontium and barium, and with described carrier for benchmark and with oxide basis, in described carrier, the content of alkaline-earth metal is 0.1-6 % by weight.
4, the catalyst according to 3, is characterized in that, described alkaline earth metal component is magnesium, and with described carrier for benchmark and with oxide basis, in described carrier, the content of alkaline-earth metal is 0.3-4 % by weight.
5, the catalyst according to 4, is characterized in that, with described carrier for benchmark and with oxide basis, in described carrier, the content of alkaline-earth metal is 0.5-2.5 % by weight.
6, the catalyst according to 1 or 2, it is characterized in that, the metal component of described group vib is molybdenum or tungsten, VB race metal component is vanadium, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is 5-12 % by weight, and the content of VB race metal component is 1-9 % by weight.
7, the preparation method of catalyst according to 1, comprises the steps:
(1) carrier is prepared, comprise and the modifier P2 of hydrated alumina P1 and P1 containing boehmite is mixed the compound also introducing alkaline including earth metal in the mixture, aftershaping, dry and roasting, the Mixing ratio by weight 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 containing boehmite, DI
2for the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite;
(2) carrier adopting infusion process to obtain in step (1) introduces hydrogenation active metals component, comprise preparation contain the dipping solution of the compound of hydrogenation active metals and use this solution impregnating carrier, carry out drying 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 VB race, be benchmark with oxide basis and with catalyst, the concentration of described dipping solution and consumption make the content of the metal component of the group VIB in final catalyst be 0.2-15 % by weight, the content 0.2-12 % by weight of the metal component of described VB race,
Wherein, the drying condition of described step (1) comprising: temperature is 40-350 DEG C, and the time is 1-24 hour, and roasting condition comprises: temperature is for being greater than 500 to being less than or equal to 1200 DEG C, and the time is 1-8 hour; The drying condition of described step (2) comprising: temperature is 100-250 DEG C, and the time is 1-10 hour; Roasting condition comprises: temperature is 360-500 DEG C, and the time is 1-10 hour.
8, the method according to 7, is characterized in that, the Mixing ratio by weight of described P1 and P2 is 70-95:5-25; The k value of described P2 is 0 to being less than or equal to 0.6; The drying condition of described step (1) comprising: temperature is 100-200 DEG C, and the time is 2-12 hour, and roasting condition comprises: temperature is for being greater than 800 to being less than or equal to 1000 DEG C, and roasting time is for being 2-6 hour; The drying condition of described step (2) comprising: temperature is 100-140 DEG C.
9, the method according to 7, it is characterized in that, described alkaline earth metal component is selected from one or more in beryllium, magnesium, calcium, strontium and barium, with oxide basis and with described carrier for benchmark, the introduction volume of described alkaline earth metal compound to make in final carrier with the content of the alkaline earth metal component of oxide basis as 0.1-6 % by weight.
10, the method according to 9, it is characterized in that, described alkaline earth metal component is magnesium, and with oxide basis and with described carrier for benchmark, the introduction volume of described alkaline earth metal compound to make in final carrier with the content of the alkaline earth metal component of oxide basis as 0.3-4 % by weight.
11, the method according to 7 or 8, is characterized in that, the pore volume of the described hydrated alumina P1 containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, can and bore dia 8-30nm.
12, the method according to 11, is characterized in that, the pore volume of the described hydrated alumina P1 containing boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, can and bore dia 10-25nm.
13, the method according to 7 or 8 any one, is characterized in that, described P2 is 80-300 object particle.
14, the method according to 13, is characterized in that, described P2 is 100-200 object particle.
15, the method according to 7, it is characterized in that, by shaping, dry for the described hydrated alumina P1 containing boehmite by one of P1 method being modified as P2, afterwards its all or part of carrying out is ground, sieves, obtaining powder thing is P2, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour; Two of method is article shaped roastings method one obtained, and sintering temperature is for being greater than 350 to being less than or equal to 1400 DEG C, and roasting time is 1-8 hour, and afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2; Three of method is dodged by the hydrated alumina P1 containing boehmite to do, and dodge dry temperature for being greater than 150 to being less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour, and obtaining powder thing is P2; Four of method is mixed to get one or more in two and the modifier that obtains with three of method of one of method, method.
16, the method according to 15, is characterized in that, the condition of the drying in described method one comprises: temperature is 100-200 DEG C, and the time is 2-12 hour; Method two in sintering temperature be 500-1200 DEG C, roasting time is 0.1-6 hour; Method three in sudden strain of a muscle to do temperature be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.
17, the method according to 15 or 16, is characterized in that, described P2 is 80-300 object particle in P1 modifier.
18, the method according to 17, is characterized in that, described P2 is 100-200 object particle in P1 modifier.
19, the method according to 7, it is characterized in that, be benchmark with oxide basis and with catalyst, the concentration of described dipping solution and consumption make the content of the metal component of the group VIB in final catalyst be 0.5-12 % by weight, and the content of VB race metal component is 0.5-9 % by weight.
20, the method according to 19, it is characterized in that, be benchmark with oxide basis and with catalyst, the concentration of described dipping solution and consumption make the content of the metal component of the group VIB in final catalyst be 5-12 % by weight, and the content of VB race metal component is 1-9 % by weight.
21, the application of the hydrotreating catalyst in claim 1-6 described in any one in heavy-oil hydrogenation process.
Depending on different requirement, the carrier in catalyst described in the present invention can be made into the various article shaped being easy to operate, such as spherical, cellular, nest like, tablet or bar shaped (clover, butterfly, cylindrical etc.).Wherein, the method mixed by the modifier P2 of described hydrated alumina P1 and P1 containing boehmite is conventional method, such as, is dropped in stirring-type batch mixer by P1 and P2 of powder mix according to ingredient proportion.The method introducing alkaline earth metal compound in described P1 and P2 mixture is conventional method, such as, can be directly be mixed in aforesaid P1 and P2 mixed process by the alkaline earth metal compound of aequum.
Concrete prepare in the embodiment of carrier at one, the method introducing alkaline earth metal compound in the mixture of the modifier P2 of described hydrated alumina P1 and P1 containing boehmite is that alkaline earth metal compound is mixed with the aqueous solution, this aqueous solution is mixed into while the modifier P2 of described P1 and P1 mixes or again this aqueous solution is mixed into after the modifier P2 of described P1 and P1 mixes, aftershaping, dry and roasting.Described alkaline earth metal compound can be one or more in the water soluble compound of arbitrary alkaline-earth metal.Such as, one or more in the water-soluble inorganic salt of alkaline-earth metal.
In the present invention, describedly shapingly can to carry out according to a conventional method, such as, a kind of method in spin, compressing tablet and extruded moulding or the combination of several method.When shaping, such as extruded moulding, for ensureing described shapingly to carry out smoothly, can add in described mixture water, extrusion aid and/or adhesive, containing or not containing expanding agent, then extrusion molding, carry out drying also roasting afterwards.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, such as 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, one or more in the propenyl copolymer that surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight is 200-10000 and maleic acid copolymer.
After sour peptization index D I in the preparation of described carrier refers to that the hydrated alumina containing boehmite adds nitric acid by certain sour aluminum ratio, within certain reaction time by the hydrated alumina containing 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: the (1) calcination base content (calcination base content refers to by quantitative boehmite in 600 DEG C of roastings 4 hours, its ratio burning rear weight and burn front weight) of the hydrated alumina of mensuration containing boehmite, counts a; (2) take the hydrated alumina W containing boehmite with assay balance
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 containing boehmite taken and deionized water are added in beaker and mix; With 20mL pipette pipette 20mL, concentration is the dilute nitric acid solution of 0.74N, is joined by this acid solution in the beaker of step (2), stirs lower reaction 8 minutes; (4) step (3) reacted slurries are carried out centrifugation in centrifuges, inserted by sediment in the crucible of having weighed, afterwards, by it in 125 DEG C of dryings 4 hours, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh and obtain calcination sample size W
2gram; (5) according to formula DI=(1-W
2/ W
1) × 100% calculates.
Under being enough to make final carrier meet the prerequisite of application claims, the present invention does not specially require the described hydrated alumina P1 containing boehmite, it can be boehmite prepared by any prior art, also can be the mixture of boehmite and other hydrated alumina, other hydrated alumina described be selected from one or more in a Water oxidize aluminium, gibbsite and amorphous hydrated aluminium oxide.Such as, pore volume is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, can and bore dia 8-30nm; Preferred pore volume is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, can and the hydrated alumina containing boehmite of bore dia 10-25nm be just particularly suitable for the present invention.In the present invention, the pore volume of the hydrated alumina containing boehmite, specific area and can and aperture, be that the described hydrated alumina containing boehmite after 4 hours in 600 DEG C of roastings, is characterized by BET N2 adsorption and obtains.
In further preferred embodiment, characterize with X diffraction, in the described hydrated alumina containing boehmite, boehmite content is not less than 50%, is more preferably not less than 60%.
The present inventor is surprised to find, hydrated alumina P1 containing boehmite is heat-treated modified, the peptization index of its modifier changes, by this modifier with without heat treated P1 mixed-forming, dry and after roasting, the carrier obtained has obvious bimodal pore distribution.Particularly by 80-300 object particle wherein, preferred 100-200 object particle with without heat treated part mixed-forming, dry and after roasting, the carrier obtained bimodal in each unimodal pore size distribution concentrated especially.Here, described 80-300 object particle, preferred 100-200 object particle refers to that described modifier is through sieve (step comprising fragmentation or grinding if desired), 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 preferably not less than 70% further.
In concrete enforcement, described P2 conveniently can be obtained by following method:
(1) obtain P2 based on drying, comprise and prepare in regular oxidation alumina supporter process by the hydrated alumina P1 containing boehmite is shaping according to a conventional method, the tailing of drying by-product, such as: in extruded moulding, bar shaped article shaped is at tailing (being called dry waste material traditionally) that is dry, integer process by-product, this tailing is milled, sieves and obtain P2.
(2) obtain based on roasting, comprise and prepare in regular oxidation alumina supporter process by the hydrated alumina P1 containing boehmite is shaping according to a conventional method, through the tailing (being called roasting waste material traditionally) of roasting by-product, such as, in roller forming, the tailing of spheric granules by-product in roasting process, mills this tailing, sieves and obtain P2; Or directly P1 is dodged dry obtaining, when directly dodging dry by P1, flash-off time is preferably 0.05-1 hour, more preferably 0.1-0.5 hour.
(3) two or more be mixed to get in the modifier P2 obtained based on preceding method.When adopting mixed method to obtain P2, the mixed proportion of the modifier P2 that aforementioned several method obtains respectively is not limited.
Described group vib metal component is preferably molybdenum and/or tungsten, more preferably molybdenum or tungsten, and VB race metal component is preferably vanadium and/or niobium, more preferably vanadium.Be benchmark with oxide basis and with catalyst, the content of described group vib metal component is preferably 0.2-15 % by weight, more preferably 0.5-12 % by weight, is more preferably 5-12 % by weight; The content of VB race metal component is preferably 0.2-12 % by weight, more preferably 0.5-9 % by weight, is more preferably 1-9 % by weight.
Be enough under the prerequisite that described hydrogenation active metals component is carried on described alumina support, the present invention is not particularly limited described carrying method, preferred method is infusion process, comprise the dipping solution of preparation containing the compound of described metal, afterwards with the alumina support described in this solution impregnation.Described dipping method is conventional method, such as, can be excessive immersion stain, hole saturation infusion process.
Wherein, one or more (are included in cosolvent and there is lower water-soluble compound) in their water soluble compound are selected from containing the compound of described metal.For the molybdenum of group vib, can be selected from as one or more in molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; For the tungsten of group vib, can be selected from as one or more in tungstates, metatungstate, ethyl metatungstate, preferably ammonium metatungstate, ethyl ammonium metatungstate wherein; For the vanadium of VB race, can be selected from as one or more in vanadic anhydride, ammonium vanadate, ammonium metavanadate, vanadic sulfate, vanadium heteropoly acid, preferably ammonium metavanadate, ammonium vanadate wherein.
According to catalyst provided by the invention, can also the invention provides containing any impact the material that catalyst performance maybe can improve the catalytic performance of catalyst provided by the invention.As contained the components such as phosphorus, be benchmark with oxide basis and with catalyst, the content of said components is no more than 10 % by weight, is preferably 0.5-5 % by weight.
When in described catalyst also containing the component such as phosphorus time, the introducing method of the components such as described phosphorus can be arbitrary method, as can be by containing as described in the component such as phosphorus compound directly with as described in boehmite mix, shaping and roasting; Can be by the compound containing components such as described phosphorus be mixed with containing the compound of hydrogenation active metals component after mixed solution with described carrier contact; Can also be by after independent for the compound containing components such as phosphorus obtain solution with described carrier contact and roasting.When the components such as phosphorus and hydrogenation active metals introduce described carrier respectively, preferably first use containing auxiliary compound solution and described carrier contact and roasting, contact with the solution of the compound containing hydrogenation active metals component more afterwards, such as by the method for dipping, described sintering temperature is 400-600 DEG C, be preferably 420-500 DEG C, roasting time is 2-6 hour, is preferably 3-6 hour.
According to heavy oil hydrogenation treatment method provided by the present invention, the reaction condition of described heavy-oil hydrogenation process is not particularly limited, in a preferred embodiment, described HDM reaction condition is: reaction temperature 300-550 DEG C, preferred 330-480 DEG C further, hydrogen dividing potential drop 4-20 MPa, further preferred 6-18 MPa, volume space velocity 0.1-3.0 hour
-1, preferred 0.15-2 hour further
-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.
The device of described hydrogenation reaction can carry out in the reactor that described feedstock oil is reacted with described catalyst exposure at hydrotreating reaction conditions in any being enough to, and such as, at described fixed bed reactors, carries out in moving-burden bed reactor or fluidized bed reactor.
According to the conventional method in this area, described hydrotreating catalyst before the use, usually can be in presence of hydrogen, presulfurization is carried out with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 DEG C, this presulfurization can be carried out outside device also can be In-situ sulphiding in device, and the active metal component of its load is converted into metal sulfide component.
Compared with the catalyst provided with prior art, the bimodal of carrier that catalyst provided by the invention adopts concentrates on 10nm-30nm and 300nm-500nm.When using it for processing of heavy oil, this catalyst shows good hydrogenation diasphaltene performance.Catalyst provided by the invention can be used alone, and 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).
Detailed description of the invention
The present invention will be further described for the following examples, but therefore should not be interpreted as limitation of the invention.
Agents useful for same in example, except as expressly described, is chemically pure reagent.
The boehmite used below in an example 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).
Embodiment 1-5 illustrates modifier P2 of the described P1 of preparation carrier of the present invention and preparation method thereof.
Embodiment 1
Take 1000 grams of P1-1, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and obtain dried strip, by dried strip shaping, sieve, the dried strip material (being commonly referred to as industrially drying bar waste material) length being less than 2mm is milled, and sieves, gets wherein 100 ~ 200 mesh sieves and divide, obtain the modifier P2A of P1-1.The k value of P2A is in table 1.
Embodiment 2
Take 1000 grams of P1-1, dodge dry 6 minutes in 240 DEG C, obtain the modifier P2B of P1-1.The k value of P2B is in table 1.
Embodiment 3
The each 200 grams of Homogeneous phase mixing of the P2B that the P2A obtain embodiment 1 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 the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and 1200 DEG C of roastings 4 hours, obtain carrier, by carrier strip shaping, sieve, the carrier strip material (being commonly referred to as industrial carrier waste material) length being less than 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 dry 10 minutes in 650 DEG C, 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 |
Embodiment 6-13 illustrates the preparation method of preparation catalyst alkaline-earth metal Bimodal-pore alumina support of the present invention.Comparative example 1-3 illustrates the preparation method of conventional catalyst carrier.
Embodiment 6
Take 800 grams of P1-1, after 200 grams of raw material P2A Homogeneous phase mixing that embodiment 1 is obtained, add containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), containing the aqueous solution 1440 milliliters counting the magnesium nitrate of 3.87 grams with magnesia, double screw banded extruder be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier Z1.The character of carrier Z1 lists in table 2.
Embodiment 7
Take 200 grams of P1-1, after 800 grams of raw material P2B Homogeneous phase mixing that embodiment 2 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, containing the aqueous solution 1440 milliliters counting the calcium nitrate of 3.87 grams with calcium oxide, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier Z2.The character of carrier Z2 lists in table 2.
Embodiment 8
Take 500 grams of P1-1, after 500 grams of raw material P2C Homogeneous phase mixing that embodiment 3 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, containing the aqueous solution 1440 milliliters counting the magnesium nitrate of 3.87 grams with magnesia, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 950 DEG C of roastings 3 hours, obtains carrier Z3.The character of carrier Z3 lists in table 2.
Comparative example 1
Take 1000 grams of P1-1, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing magnesium nitrate 14.7g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier DZ1.The character of carrier DZ1 lists in table 2.
Embodiment 9
Take 800 grams of P1-2, after 200 grams of raw material P2D Homogeneous phase mixing that embodiment 4 is obtained, add containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), containing the aqueous solution 1440 milliliters counting the magnesium nitrate of 3.87 grams with magnesia, double screw banded extruder be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier Z4.The character of carrier Z4 lists in table 2.
Embodiment 10
Take 900 grams of P1-1, after 100 grams of raw material P2E Homogeneous phase mixing that embodiment 5 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, containing the aqueous solution 1440 milliliters counting the magnesium nitrate of 14.29 grams with magnesia, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier Z5.The character of carrier Z5 lists in table 2.
Embodiment 11
Take 850 grams of P1-2, after 150 grams of raw material P2C Homogeneous phase mixing that embodiment 3 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, containing the aqueous solution 1440 milliliters counting the calcium nitrate of 14.29 grams with calcium oxide, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 850 DEG C of roastings 3 hours, obtains carrier Z6.The character of carrier Z6 lists in table 2.
Comparative example 2
Take 1000 grams of P1-2, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, containing the magnesium nitrate aqueous solution 1440 milliliters counting 14.29 grams with magnesia, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier DZ2.The character of carrier DZ2 lists in table 2.
Embodiment 12
Take 900 grams of P1-2, after 100 grams of raw material P2D Homogeneous phase mixing that embodiment 4 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, containing the magnesium nitrate aqueous solution 1440 milliliters counting 14.29 grams with magnesia, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier Z7.The character of carrier Z7 lists in table 2.
Embodiment 13
Take 850 grams of P1-2, after 150 grams of raw material P2E Homogeneous phase mixing that embodiment 5 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, containing the magnesium nitrate aqueous solution 1440 milliliters counting 14.29 grams with magnesia, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier Z8.The character of carrier Z8 lists in table 2.
Comparative example 3
According to the method that patent CN1782031A embodiment 7 provides, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier DZ3.The character of carrier DZ3 lists in table 2.
Table 2
Can be seen by the result of table 2, compared with conventional method, the alumina support prepared by the method for the invention provides has obvious structure of double peak holes.
Embodiment 14 ~ 21 is for illustration of the invention provides heavy oil hydrogenating treatment catalyst and preparation method thereof.
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 spectrometer, and concrete grammar is shown in Petrochemical Engineering Analysis method RIPP133-90).
Embodiment 14
Get 200 grams of carrier Z1, with 220 milliliters containing MoO
380 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 16 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C1, the composition of C1 is listed in table 3.
Embodiment 15
Get 200 grams of carrier Z2, with 220 milliliters containing MoO
380 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 16 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C2, the composition of C2 is listed in table 3.
Embodiment 16
Get 200 grams of carrier Z3, with 220 milliliters containing MoO
380 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 16 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst CZ3, the composition of C3 is listed in table 3.
Comparative example 4
Get 200 grams of carrier Z1, with 220 milliliters containing MoO
380 grams per liters, ammonium heptamolybdate and the nickel nitrate mixed solution of NiO16 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 2 hours, obtain Hydrodemetalation catalyst DC1, the composition of DC1 is listed in table 3.
Comparative example 4
Get 200 grams of DZ1, with 220 milliliters containing MoO
380 grams per liters, ammonium heptamolybdate and the nickel nitrate mixed solution of NiO16 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 2 hours, obtain Hydrodemetalation catalyst DC2, the composition of DC2 is listed in table 3.
Comparative example 5
Get 200 grams of carrier DZ2, with 500 milliliters containing MoO
380 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 16 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst DC3, the composition of DC3 is listed in table 3.
Embodiment 17
Get 200 grams of carrier Z4, with 220 milliliters containing MoO
390 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 20 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C4.The composition of Hydrodemetalation catalyst C4 is listed in table 3.
Embodiment 18
Get 200 grams of Z5, with 220 milliliters containing WO
390 grams per liters, V
2o
5ammonium tungstate and the ammonium metavanadate mixed solution of 20 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C5.The composition of Hydrodemetalation catalyst C5 is listed in table 2.
Embodiment 19
Get 200 grams of Z6, with 220 milliliters containing WO
3100 grams per liters, V
2o
5ammonium tungstate and the ammonium metavanadate mixed solution of 30 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C6.The composition of Hydrodemetalation catalyst C6 is listed in table 2.
Embodiment 20
Get 200 grams of Z7, with 220 milliliters containing MoO
360 grams per liters, V
2o
5ammonium tungstate and the ammonium metavanadate mixed solution of 60 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C7.The composition of Hydrodemetalation catalyst C7 is listed in table 2.
Embodiment 21
Get 200 grams of Z8, with 220 milliliters containing WO
360 grams per liters, V
2o
5ammonium tungstate and the ammonium metavanadate mixed solution of 60 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C8.The composition of Hydrodemetalation catalyst C8 is listed in table 2.
Table 3
Embodiment 22-29
Embodiment 22-29 illustrates the demetallization per, diasphaltene rate, de-carbon yield and the desulfurization degree that the invention provides catalyst.
With the normal slag of Kuwait for raw material, 100 milliliters of small fixed reactors evaluate protective agent.
Catalyst C1, C2, C3, C4, C5 are broken into the particle of diameter 2-3 millimeter, catalyst loading amount is 100 milliliters.Reaction condition is: reaction temperature 380 DEG C, hydrogen dividing potential drop 14 MPa, liquid hourly space velocity (LHSV) are 0.7 hour
-1, hydrogen to oil volume ratio is 1000, reacts after 200 hours and samples.
The circular of demetallization per, diasphaltene rate, de-carbon yield and desulfurization degree is as follows:
Feedstock oil character lists in table 4, and evaluation result is listed in table 5.
Comparative example 7-9
According to the demetallization per of method evaluation catalyst DC1, DC2, DC3 of embodiment 22, diasphaltene rate, de-carbon yield and desulfurization degree, the results are shown in Table 5.
Table 4
| Feedstock oil title | The normal slag of Kuwait |
| Density (20 DEG C), kg/m 3 | 0.998 |
| Mean molecule quantity | 804 |
| Carbon residue, % (m) | 15.9 |
| Four composition, % (m) | ? |
| Saturated point | 20 |
| Fragrance point | 49.3 |
| Colloid | 23 |
| Asphalitine | 7.7 |
| S，m% | 5.0 |
| N，m% | 0.21 |
| Ni，ppm | 26.5 |
| V，ppm | 80 |
Table 5
The result that table 5 provides is the result that evaluation response carries out after 200 hours, relatively can find out, relative to reference catalyst, the HDM of hydrotreating catalyst provided by the invention is active, diasphaltene and de-carbon residue active in reference agent.
Claims (21)
1. a heavy oil hydrogenating treatment catalyst, containing carrier and load hydrogenation active metals component on this carrier, wherein, described carrier contains aluminium oxide and alkaline earth metal component, characterize with mercury injection method, the pore volume of described carrier is 0.95-1.2 ml/g, and specific area is 50-300 rice
2/ gram, described carrier be 10-30nm and diameter is 300-500nm at diameter is bimodal pore distribution, wherein, 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, described hydrogenation active metals component is selected from least one group vib metal component and at least one VB race metal component, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is 0.2-15 % by weight, and the content of VB race metal component is 0.2-12 % by weight.
2. the catalyst according to 1, is characterized in that, the pore volume of described aluminium oxide 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, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume; The metal component of described group vib is selected from molybdenum and/or tungsten, VB race metal component is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is 0.5-12 % by weight, and the content of VB race metal component is 0.5-9 % by weight.
3. the catalyst according to 1, is characterized in that, described alkaline earth metal component is selected from one or more in beryllium, magnesium, calcium, strontium and barium, and with described carrier for benchmark and with oxide basis, in described carrier, the content of alkaline-earth metal is 0.1-6 % by weight.
4. the catalyst according to 3, is characterized in that, described alkaline earth metal component is magnesium, and with described carrier for benchmark and with oxide basis, in described carrier, the content of alkaline-earth metal is 0.3-4 % by weight.
5. the catalyst according to 4, is characterized in that, with described carrier for benchmark and with oxide basis, in described carrier, the content of alkaline-earth metal is 0.5-2.5 % by weight.
6. the catalyst according to 1 or 2, is characterized in that, the metal component of described group vib is molybdenum or tungsten, VB race metal component is vanadium, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is 5-12 % by weight, and the content of VB race metal component is 1-9 % by weight.
7. the preparation method of catalyst according to 1, comprises the steps:
(1) carrier is prepared, comprise and the modifier P2 of hydrated alumina P1 and P1 containing boehmite is mixed the compound also introducing alkaline including earth metal in the mixture, aftershaping, dry and roasting, the Mixing ratio by weight 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 containing boehmite, DI
2for the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite;
(2) carrier adopting infusion process to obtain in step (1) introduces hydrogenation active metals component, comprise preparation contain the dipping solution of the compound of hydrogenation active metals and use this solution impregnating carrier, carry out drying 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 VB race, be benchmark with oxide basis and with catalyst, the concentration of described dipping solution and consumption make the content of the metal component of the group VIB in final catalyst be 0.2-15 % by weight, the content 0.2-12 % by weight of the metal component of described VB race,
Wherein, the drying condition of described step (1) comprising: temperature is 40-350 DEG C, and the time is 1-24 hour, and roasting condition comprises: temperature is for being greater than 500 to being less than or equal to 1200 DEG C, and the time is 1-8 hour; The drying condition of described step (2) comprising: temperature is 100-250 DEG C, and the time is 1-10 hour; Roasting condition comprises: temperature is 360-500 DEG C, and the time is 1-10 hour.
8. the method according to 7, is characterized in that, the Mixing ratio by weight of described P1 and P2 is 70-95:5-25; The k value of described P2 is 0 to being less than or equal to 0.6; The drying condition of described step (1) comprising: temperature is 100-200 DEG C, and the time is 2-12 hour, and roasting condition comprises: temperature is for being greater than 800 to being less than or equal to 1000 DEG C, and roasting time is for being 2-6 hour; The drying condition of described step (2) comprising: temperature is 100-140 DEG C.
9. the method according to 7, it is characterized in that, described alkaline earth metal component is selected from one or more in beryllium, magnesium, calcium, strontium and barium, with oxide basis and with described carrier for benchmark, the introduction volume of described alkaline earth metal compound to make in final carrier with the content of the alkaline earth metal component of oxide basis as 0.1-6 % by weight.
10. the method according to 9, it is characterized in that, described alkaline earth metal component is magnesium, and with oxide basis and with described carrier for benchmark, the introduction volume of described alkaline earth metal compound to make in final carrier with the content of the alkaline earth metal component of oxide basis as 0.3-4 % by weight.
11. methods according to 7 or 8, is characterized in that, the pore volume of the described hydrated alumina P1 containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, can and bore dia 8-30nm.
12. methods according to 11, is characterized in that, the pore volume of the described hydrated alumina P1 containing boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, can and bore dia 10-25nm.
13. methods according to 7 or 8 any one, it is characterized in that, described P2 is 80-300 object particle.
14. methods according to 13, it is characterized in that, described P2 is 100-200 object particle.
15. methods according to 7, it is characterized in that, by shaping, dry for the described hydrated alumina P1 containing boehmite by one of P1 method being modified as P2, afterwards its all or part of carrying out is ground, sieves, obtaining powder thing is P2, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour; Two of method is article shaped roastings method one obtained, and sintering temperature is for being greater than 350 to being less than or equal to 1400 DEG C, and roasting time is 1-8 hour, and afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2; Three of method is dodged by the hydrated alumina P1 containing boehmite to do, and dodge dry temperature for being greater than 150 to being less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour, and obtaining powder thing is P2; Four of method is mixed to get one or more in two and the modifier that obtains with three of method of one of method, method.
16. methods according to 15, it is characterized in that, the condition of the drying in described method one comprises: temperature is 100-200 DEG C, and the time is 2-12 hour; Method two in sintering temperature be 500-1200 DEG C, roasting time is 0.1-6 hour; Method three in sudden strain of a muscle to do temperature be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.
17. methods according to 15 or 16, it is characterized in that, described P2 is 80-300 object particle in P1 modifier.
18. methods according to 17, it is characterized in that, described P2 is 100-200 object particle in P1 modifier.
19. methods according to 7, it is characterized in that, be benchmark with oxide basis and with catalyst, the concentration of described dipping solution and consumption make the content of the metal component of the group VIB in final catalyst be 0.5-12 % by weight, and the content of VB race metal component is 0.5-9 % by weight.
20. methods according to 19, it is characterized in that, be benchmark with oxide basis and with catalyst, the concentration of described dipping solution and consumption make the content of the metal component of the group VIB in final catalyst be 5-12 % by weight, and the content of VB race metal component is 1-9 % by weight.
The application of hydrotreating catalyst in 21. claim 1-6 described in any one in heavy-oil hydrogenation process.
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| CN109569560A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalyst effect and its preparation method and application and heavy-oil hydrogenation depitching matter method |
| CN109894112A (en) * | 2017-12-08 | 2019-06-18 | 中国石油化工股份有限公司 | A kind of preparation method of anthraquinone hydrogenation catalyst |
| CN110773190A (en) * | 2018-07-31 | 2020-02-11 | 中国石油化工股份有限公司 | Heavy oil hydrogenation deasphaltened catalyst and preparation and application thereof |
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| CN102652918A (en) * | 2011-03-03 | 2012-09-05 | 中国石油化工股份有限公司 | Hydrodemetalation catalyst using alkaline-earth-metal-containing alumina as support, and preparation and application thereof |
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| CN107511178A (en) * | 2016-06-15 | 2017-12-26 | 中国石油化工股份有限公司 | A kind of modified aluminium oxide supports and preparation method and a kind of hydrogenation catalyst and preparation method and application |
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| CN109569560A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalyst effect and its preparation method and application and heavy-oil hydrogenation depitching matter method |
| CN109569560B (en) * | 2017-09-29 | 2022-01-04 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalysis effect, preparation method and application thereof, and heavy oil hydrogenation asphaltene removal method |
| CN109894112A (en) * | 2017-12-08 | 2019-06-18 | 中国石油化工股份有限公司 | A kind of preparation method of anthraquinone hydrogenation catalyst |
| CN110773190A (en) * | 2018-07-31 | 2020-02-11 | 中国石油化工股份有限公司 | Heavy oil hydrogenation deasphaltened catalyst and preparation and application thereof |
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