CN104162438A - Hydrogenation protection catalyst, preparation and application thereof - Google Patents
Hydrogenation protection catalyst, preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a hydrogenation protection catalyst, preparation and an application thereof. The hydrogenation protection catalyst contains a carrier and a hydrogenation active metal component loaded on the carrier, wherein the carrier contains alumina and an alkaline-earth metal component. According to the mercury intrusion method, the pore volume of the carrier is 0.95-1.2 ml/g; the specific surface area of the carrier is 50-300 m<2>/g; the carrier presents the bimodal pore distribution at the diameter of 10-30 nm and the diameter of 300-500 nm; the volume of the holes with the diameter of 10-30 nm accounts for 55-80% of the total pore volume, and the volume of the holes with the diameter of 300-500 nm accounts for 10-35% of the total pore volume. The hydrogenation active metal component is selected from at least a group VIII metal component and at least a group VB metal component, wherein the group VIII metal component content (calculated as the oxide) is more than 0 and is less than or equal to 0.8 wt% by adopting the catalyst as the reference, and the group VB metal component content (calculated as the oxide) is more than 0 and is less than or equal to 5 wt% by adopting the catalyst as the reference. Compared with hydrogenation protection catalysts in the prior art, the hydrogenation protection catalyst of the present invention concurrently has good hydrogenation and metal removal activity.
Description
Technical field
The present invention relates to a kind of hydrogenation protecting catalyst and preparation thereof and application.
Background technology
Along with the aggravation of crude oil heaviness, in poor quality trend, crude oil difficulty of processing strengthen, light oil yield reduce, and market to the demand of high grade light-end products in continuous increase, it is strict that environmental regulation is also more and more tending towards.At present, the heavy oil especially processing and making full use of of residual oil just becomes the staple of conversation that global Oil Refining Industry is paid close attention to, and residual hydrogenation technology is a kind of widely used processing technology in processing of heavy oil technique, is the economic environment-friendly type deep process technology of generally acknowledging.In residual oil, contain metal impurities and the solid impurities such as a large amount of Ni, V, Fe, Ca, if this part impurity can not effectively be removed, can downstream hydrogenation catalyst be had a negative impact, be easy to make downstream catalyst inactivation.One of effective way addressing this problem is the protective agent in hydrogenation catalyst top filling with hydrogenation activity, therefore develops that metal removal activity is high, to hold the strong protective agent of metal ability be one of key technology of heavy-oil hydrogenation processing.In prior art, the disclosed example about hydrogenation protecting catalyst and preparation method thereof comprises:
CN101890381A discloses a kind of hydrotreating guard catalyst for residual oil and application thereof.This catalyst pore volume is large, and aperture is large, and porosity is high, reasonable pore distribution, and outer surface orifice is larger, and duct penetrability is good, and 1000nm contains more than 36% in above duct.
CN00124903.7 discloses a kind of hydrogenation protecting catalyst; this catalyst contains a kind of alumina support and loads on molybdenum and/or tungsten and nickel and/or the cobalt on alumina support; wherein; total ammonia integral heat of adsorption of described alumina support is not more than 25 joule/gram, and the percentage that the ammonia integral heat of adsorption that ammonia differential heat of adsorption is greater than 100 kj/mol accounts for total ammonia integral heat of adsorption is not more than 10%.
Patent CN98111379.6 discloses a kind of hydrogenation protecting catalyst and preparation method thereof, and catalyst carrier is ultra-large aperture, and aperture is the bimodal hole of 0.1-30 μ m, and catalyst pore volume is 0.1-0.8ml/g, specific surface 0.1-20m
2/ g, containing the metallic element 6.65m%-20.0m% of VI B family and/or the metallic element 8.7m1% of VIII family ,-26.13m%.Preparation method adopts particle to pile up legal system for alumina support, then adopts containing molybdenum solution and solution containing nickel equivalent impregnation, and the catalyst after dipping is at 100-120 DEG C of dry 2-5h, at 500-550 DEG C of configuration roast 2-5h.
Summary of the invention
The technical problem to be solved in the present invention is to provide preparation method and the application thereof of a kind of new hydrogenation protecting catalyst, this hydrogenation protecting catalyst.
Content of the present invention comprises:
1, a hydrogenation protecting catalyst, contains carrier and loads on the 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 is that 10-30nm and diameter are that 300-500nm is bimodal pore distribution at diameter, 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 metal component of group VIII and at least one VB family metal component, in oxide and taking catalyst as benchmark, the content of described metal component of group VIII is for being greater than 0 to being less than or equal to 0.8 % by weight, and the content of VB family metal component is for being greater than 0 to being less than or equal to 5 % by weight.
2, according to the hydrogenation protecting 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; Described metal component of group VIII is selected from nickel and/or cobalt, VB family metal component is selected from vanadium and/or niobium, in oxide and taking catalyst as benchmark, the content of described metal component of group VIII is 0.1-0.7 % by weight, and the content of VB family metal component is 1-4 % by weight.
3, according to the hydrogenation protecting catalyst described in 2, it is characterized in that, in oxide and taking catalyst as benchmark, the content of described metal component of group VIII is 0.2-0.6 % by weight, and the content of VB family metal component is 1.5-3.5 % by weight.
4, according to the hydrogenation protecting catalyst described in 1; it is characterized in that; described alkaline earth metal component is selected from one or more in beryllium, magnesium, calcium, strontium and barium, and taking described carrier as benchmark and with oxide, in described carrier, the content of alkaline-earth metal is 0.1-6 % by weight.
5, according to the hydrogenation protecting catalyst described in 4, it is characterized in that, described alkaline earth metal component is magnesium, and taking described carrier as benchmark and with oxide, in described carrier, the content of alkaline earth metal component is 0.3-4 % by weight.
6, according to the hydrogenation protecting catalyst described in 5, it is characterized in that, taking described carrier as benchmark and with oxide, in described carrier, the content of alkaline earth metal component is 0.5-2.5 % by weight.
7, according to the preparation method of the hydrogenation protecting catalyst described in 1, comprise the steps:
(1) prepare carrier, comprise mixed the modifier P2 of the hydrated alumina P1 that contains boehmite and the P1 compound of introducing alkaline including earth metal in this mixture that is incorporated in, moulding afterwards, dry and roasting, 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;
(2) on the carrier obtaining in step (1), introduce hydrogenation active metals component, described hydrogenation active metals component is selected from least one metal component of group VIII and at least one VB family metal component, in oxide and taking catalyst as benchmark, the introduction volume of described metal component of group VIII makes the content of the metal component of group VIII in final catalyst for being greater than 0 to being less than or equal to 0.8 % by weight, the introduction volume of described VB family metal component makes the content of the VB family metal component in final catalyst for being greater than 0 to being less than or equal to 5 % by weight, afterwards dry and roasting;
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, according to the method described in 7, it is characterized in that, the weight mixing ratio of described P1 and P2 is 70-95:5-25, and 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, according to the method described in 7, it is characterized in that, in oxide and taking described carrier as benchmark, it is 0.1-6 % by weight that the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline components in final carrier.
10, according to the method described in 9, it is characterized in that, in oxide and taking described carrier as benchmark, it is 0.3-4 % by weight that the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline components in final carrier.
11, according to the method described in 10, it is characterized in that, in oxide and taking described carrier as benchmark, it is 0.5-2.5 % by weight that the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline components in final carrier.
12, according to the method described in 7 or 8, it is characterized in that, the pore volume of described P1 is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, can and bore dia 8-30nm; Described P2 is 80-300 object particle.
13, according to the method described in 12, it is characterized in that, the pore volume of described P1 is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, can and bore dia 10-25nm; Described P2 is 100-200 object particle.
14, according to the method described in 7, 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 DEG C, 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 DEG C, 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 DEG C, 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.
15, according to the method described in 14, it is characterized in that, the dry condition 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 the dry temperature of sudden strain of a muscle be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.
16, according to the method described in 7, it is characterized in that, the metal component of described VIII family is selected from nickel and/or cobalt, the metal component of VB family is selected from vanadium and/or niobium, in oxide and taking catalyst as benchmark, it is 0.1-0.7 % by weight that the introduction volume of described metal component of group VIII makes the content of the metal component of group VIII in final catalyst, and it is 1-4 % by weight that the introduction volume of described VB family metal component makes the content of the VB family metal component in final catalyst.
17, according to the method described in 16, it is characterized in that, it is 0.2-0.6 % by weight that the introduction volume of described metal component of group VIII makes the content of the metal component of group VIII in final catalyst, and it is 1.5-3.5 % by weight that the introduction volume of described VB family metal component makes the content of the VB family metal component in final catalyst.
18, according to the method described in 7, it is characterized in that, the described method of introducing hydrogenation active metals component on carrier is infusion process.
19, the application of the hydrogenation protecting catalyst described in any one in hydrocarbon oil hydrogenation is processed in claim 1-6.
Depending on different requirements, the carrier described in the present invention in catalyst can be made into the article shaped of 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.Being conventional method to the method for introducing the compound of alkaline including earth metal in described P1 and P2 mixture, for example, can be directly the compound of the alkaline including earth metal of aequum to be sneaked in aforesaid P1 and P2 mixed process.
In a concrete embodiment of preparing carrier, to the method for introducing the compound of alkaline including earth metal in the mixture of the modifier P2 of the described hydrated alumina P1 that contains boehmite and P1 be, alkaline including earth metal compound is mixed with to the aqueous solution, 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.The compound of described alkaline including earth metal can be one or more in the water soluble compound of alkaline-earth metal arbitrarily.For example, one or more in the water-soluble inorganic salt of alkaline-earth metal.
In the present invention, described moulding is 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, taking extruded moulding as example, for ensureing 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 acid, 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 DEG C 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 DEG C dry 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.
Be enough to that final carrier is met under the prerequisite of requirement of the present invention, the present invention does not have special requirement to the described hydrated alumina P1 that contains boehmite, it 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.For example, pore volume is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, can and bore dia 8-30nm; Preferably pore volume is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, can and the hydrated alumina that contains 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 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 DEG C of roastings.
In further 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 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 hydrogenation protecting catalyst provided by the invention; wherein; the preferred metal component of group VIII of described hydrogenation active metals component is cobalt and/or nickel; the metal component of VB family is vanadium and/or niobium; in oxide and taking catalyst as benchmark; the content of described metal component of group VIII is for being greater than 0 to being less than or equal to 0.8 % by weight; preferably 0.1-0.7 % by weight; more preferably 0.2-0.6 % by weight; the content of described VB family metal component is for being greater than 0 to being less than or equal to 5 % by weight; preferably 1-4 % by weight, more preferably 1.5-3.5 % 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 the carrying method of described hydrogenation active metals component, preferred method is infusion process, comprise the dipping solution of preparation containing the compound of described metal, use 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.The described metal component compound containing being selected from V B family is selected from one or more in the soluble compound in them, for example, 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.One or more in the described soluble compound that is selected from them containing the compound that is selected from metal component of group VIII, 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 taking 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 DEG C, is preferably 420-500 DEG C, 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 DEG C, further preferred 330-480 DEG C, 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 DEG C, 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.
The employing providing with prior art has compared with hydrogenation protecting catalyst prepared by bimodal hole carrier, bimodal 10nm-30nm and the 300nm-500nm of concentrating on of the carrier that hydrogenation activity guard catalyst provided by the invention adopts.This catalyst has good HDM activity in having GPF (General Protection False agent function.This catalyst be particularly suitable as hydrogenation activity guard catalyst for heavy oil particularly poor residuum carry out hydrotreatment.
Detailed description of the invention
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 DEG C 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 DEG C, 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 DEG C dry 4 hours, 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) 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 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 |
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, 1440 milliliters of the aqueous solution that add and contain 10 milliliters, nitric acid (Tianjin chemical reagent three factory's products), contains magnesium nitrate 14.7g are extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm on plunger type bar extruder.Wet bar in 120 DEG C dry 4 hours, obtain article shaped, by 900 DEG C 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 aqueous solution of magnesium nitrate 14.7g, on plunger type bar extruder, be extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar in 120 DEG C dry 4 hours, obtain article shaped, by 900 DEG C 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 aqueous solution of calcium nitrate 11.4g, on double screw banded extruder, be extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar in 120 DEG C dry 4 hours, obtain article shaped, by 950 DEG C 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 aqueous solution of magnesium nitrate 14.7g, on plunger type bar extruder, be extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar in 120 DEG C dry 4 hours, obtain article shaped, by 900 DEG C 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, 1440 milliliters of the aqueous solution that add and contain 10 milliliters, nitric acid (Tianjin chemical reagent three factory's products), contains magnesium nitrate 15.4g are extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm on plunger type bar extruder.Wet bar in 120 DEG C dry 4 hours, obtain article shaped, by 1000 DEG C 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 aqueous solution of magnesium nitrate 51.5g, on plunger type bar extruder, be extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar in 120 DEG C dry 4 hours, obtain article shaped, by 1000 DEG C 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 aqueous solution of calcium nitrate 39.9g, on plunger type bar extruder, be extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar in 120 DEG C dry 4 hours, obtain article shaped, by 850 DEG C 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 aqueous solution of magnesium nitrate 51.5g, on plunger type bar extruder, be extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar in 120 DEG C dry 4 hours, obtain article shaped, by 1000 DEG C 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 aqueous solution of magnesium nitrate 53.72g, on plunger type bar extruder, be extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar in 120 DEG C dry 4 hours, obtain article shaped, by 1000 DEG C 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 aqueous solution of magnesium nitrate 51.5g, on plunger type bar extruder, be extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar in 120 DEG C dry 4 hours, obtain article shaped, by 900 DEG C 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 7 is extruded into external diameter 2.5mm on plunger type bar extruder, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar in 120 DEG C dry 4 hours, obtain article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ3.The character of carrier DZ3 is listed in table 2.
Table 2
Embodiment 14-19 illustrates guard catalyst provided by the invention and preparation method thereof.
Embodiment 14
Get 200 grams of carrier Z1, with 220 milliliters containing V
2o
528.6 grams per liters, the ammonium metavanadate of NiO5 grams per liter and nickel nitrate mixed solution dipping 1 hour, dries 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C1.The composition of C1 is listed in table 3.
Embodiment 15
Get 200 grams of carrier Z2, with 220 milliliters containing V
2o
528.6 grams per liters, the ammonium metavanadate of CoO5 grams per liter and cobalt nitrate mixed solution dipping 1 hour, dries 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C2.The composition of C2 is listed in table 3.
Embodiment 16
Get 200 carrier Z3, with 220 milliliters containing V
2o
525 grams per liters, the ammonium metavanadate of NiO3 grams per liter and nickel nitrate mixed solution dipping 1 hour, dries 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C3.The composition of C3 is listed in table 3.
Embodiment 17
Get 200 grams of carrier Z4, with 220 milliliters containing V
2o
525 grams per liters, the ammonium metavanadate of CoO3 grams per liter and cobalt nitrate mixed solution dipping 1 hour, dries 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C4.The composition of C4 is listed in table 3.
Embodiment 18
Get 200 grams of carrier Z5, with 220 milliliters containing V
2o
519.0 grams per liters, the ammonium metavanadate of NiO2 grams per liter and nickel nitrate mixed solution dipping 1 hour, dries 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C5.The composition of C5 is listed in table 3.
Embodiment 19
Get 200 grams of carrier Z8, with 220 milliliters containing V
2o
519.0 grams per liters, the ammonium metavanadate of NiO2 grams per liter and nickel nitrate mixed solution dipping 1 hour, dries 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C6.The composition of C6 is listed in table 3.
Contrast row 4
Get 200 grams of carrier DZ1, with 220 milliliters containing V
2o
528.6 grams per liters, the ammonium metavanadate of NiO5 grams per liter and nickel nitrate mixed solution dipping 1 hour, dries 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC1.The composition of DC1 is listed in table 3.
Contrast row 5
Get 200 grams of carrier DZ1, with 220 milliliters containing WO
328.6 grams per liters, the ammonium metatungstate of NiO5 grams per liter and nickel nitrate mixed solution dipping 1 hour, dries 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC2.The composition of DC2 is listed in table 3.
Comparative example 6
Get 200 grams of carrier DZ2, with 220 milliliters containing V
2o
525 grams per liters, the ammonium metavanadate of NiO3 grams per liter and nickel nitrate mixed solution dipping 1 hour, dries 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC3.The composition of DC3 is listed in table 3.
Comparative example 7
Get 200 grams of carrier DZ3, with 220 milliliters containing MoO
325 grams per liters, the ammonium molybdate of CoO3 grams per liter and cobalt nitrate mixed solution dipping 1 hour, dries 4 hours for 120 DEG C, and 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC4.The composition of DC4 is listed in table 3.
Table 3
In catalyst, the content of each metal component is calculated value.
Embodiment 20-25
Embodiment 20-25 illustrates the demetallization per of hydrogenation protecting catalyst provided by the invention.
Taking the normal slag of Yi Chong as raw material (feedstock oil character is in table 4), on 100 milliliters of small fixed reactors, evaluate protective agent.
Catalyst C1, C2, C3, C4, C5 and C6 are broken into the particle of diameter 2-3 millimeter, catalyst loading amount is 100 milliliters.Reaction condition is: 380 DEG C of reaction temperatures, hydrogen dividing potential drop 14 MPas, liquid hourly space velocity (LHSV) are 0.7 hour
-1, hydrogen to oil volume ratio is 1000, reacts sample analysis after 200 hours.Adopt inductive coupling plasma emission spectrograph (ICP-AES) to measure 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 metal in the oil of hydrotreatment front and back.Calculate according to the following formula metal removal rate:
Feedstock oil character is listed in table 4, and evaluation result is listed in table 5.
Comparative example 8-11
According to the demetallization per of method evaluation catalyst DC1, DC2, DC3 and the DC4 of embodiment 20-25, the results are shown in Table 5.
Table 4
| Feedstock oil title | The normal slag of Yi Chong |
| Density (20 DEG C), kg/m 3 | 0.966 |
| Mean molecule quantity | 452 |
| Ni，μg/g | 47.7 |
| V，μg/g | 133 |
| Fe，μg/g | 8.4 |
| Ca，μg/g | 29.5 |
Table 5 protective agent evaluation result
Can be found out compared with existing catalyst by the data of table 5, hydrogenation protecting agent provided by the invention has higher demetallization per.
Claims (19)
1. a hydrogenation protecting catalyst, contains carrier and loads on the 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 is that 10-30nm and diameter are that 300-500nm is bimodal pore distribution at diameter, 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 metal component of group VIII and at least one VB family metal component, in oxide and taking catalyst as benchmark, the content of described metal component of group VIII is for being greater than 0 to being less than or equal to 0.8 % by weight, and the content of VB family metal component is for being greater than 0 to being less than or equal to 5 % by weight.
2. according to the hydrogenation protecting 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; Described metal component of group VIII is selected from nickel and/or cobalt, VB family metal component is selected from vanadium and/or niobium, in oxide and taking catalyst as benchmark, the content of described metal component of group VIII is 0.1-0.7 % by weight, and the content of VB family metal component is 1-4 % by weight.
3. according to the hydrogenation protecting catalyst described in 2, it is characterized in that, in oxide and taking catalyst as benchmark, the content of described metal component of group VIII is 0.2-0.6 % by weight, and the content of VB family metal component is 1.5-3.5 % by weight.
4. according to the hydrogenation protecting catalyst described in 1, it is characterized in that, described alkaline earth metal component is selected from one or more in beryllium, magnesium, calcium, strontium and barium, and taking described carrier as benchmark and with oxide, in described carrier, the content of alkaline-earth metal is 0.1-6 % by weight.
5. according to the hydrogenation protecting catalyst described in 4, it is characterized in that, described alkaline earth metal component is magnesium, and taking described carrier as benchmark and with oxide, in described carrier, the content of alkaline earth metal component is 0.3-4 % by weight.
6. according to the hydrogenation protecting catalyst described in 5, it is characterized in that, taking described carrier as benchmark and with oxide, in described carrier, the content of alkaline earth metal component is 0.5-2.5 % by weight.
7. according to the preparation method of the hydrogenation protecting catalyst described in 1, comprise the steps:
(1) prepare carrier, comprise mixed the modifier P2 of the hydrated alumina P1 that contains boehmite and the P1 compound of introducing alkaline including earth metal in this mixture that is incorporated in, moulding afterwards, dry and roasting, 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;
(2) on the carrier obtaining in step (1), introduce hydrogenation active metals component, described hydrogenation active metals component is selected from least one metal component of group VIII and at least one VB family metal component, in oxide and taking catalyst as benchmark, the introduction volume of described metal component of group VIII makes the content of the metal component of group VIII in final catalyst for being greater than 0 to being less than or equal to 0.8 % by weight, the introduction volume of described VB family metal component makes the content of the VB family metal component in final catalyst for being greater than 0 to being less than or equal to 5 % by weight, afterwards dry and roasting;
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. according to the method described in 7, it is characterized in that, the weight mixing ratio of described P1 and P2 is 70-95:5-25, and 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. according to the method described in 7, it is characterized in that, in oxide and taking described carrier as benchmark, it is 0.1-6 % by weight that the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline components in final carrier.
10. according to the method described in 9, it is characterized in that, in oxide and taking described carrier as benchmark, it is 0.3-4 % by weight that the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline components in final carrier.
11. according to the method described in 10, it is characterized in that, in oxide and taking described carrier as benchmark, it is 0.5-2.5 % by weight that the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline components in final carrier.
12. according to the method described in 7 or 8, it is characterized in that, the pore volume of described P1 is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, can and bore dia 8-30nm; Described P2 is 80-300 object particle.
13. according to the method described in 12, it is characterized in that, the pore volume of described P1 is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, can and bore dia 10-25nm; Described P2 is 100-200 object particle.
14. according to the method described in 7, 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 DEG C, 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 DEG C, 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 DEG C, 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.
15. according to the method described in 14, it is characterized in that, the dry condition 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 the dry temperature of sudden strain of a muscle be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.
16. according to the method described in 7, it is characterized in that, the metal component of described VIII family is selected from nickel and/or cobalt, the metal component of VB family is selected from vanadium and/or niobium, in oxide and taking catalyst as benchmark, it is 0.1-0.7 % by weight that the introduction volume of described metal component of group VIII makes the content of the metal component of group VIII in final catalyst, and it is 1-4 % by weight that the introduction volume of described VB family metal component makes the content of the VB family metal component in final catalyst.
17. according to the method described in 16, it is characterized in that, it is 0.2-0.6 % by weight that the introduction volume of described metal component of group VIII makes the content of the metal component of group VIII in final catalyst, and it is 1.5-3.5 % by weight that the introduction volume of described VB family metal component makes the content of the VB family metal component in final catalyst.
18. according to the method described in 7, it is characterized in that, the described method of introducing hydrogenation active metals component on carrier is infusion process.
The application of hydrogenation protecting catalyst in 19. claim 1-6 described in any one in hydrocarbon oil hydrogenation is processed.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105749924A (en) * | 2014-12-17 | 2016-07-13 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst and use thereof |
| CN110773189A (en) * | 2018-07-31 | 2020-02-11 | 中国石油化工股份有限公司 | Hydrogenation activity protection catalyst and preparation and application thereof |
| CN110773184A (en) * | 2018-07-31 | 2020-02-11 | 中国石油化工股份有限公司 | Hydrogenation activity protection catalyst and preparation and application thereof |
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| CN102649068A (en) * | 2011-02-24 | 2012-08-29 | 中国石油化工股份有限公司 | Hydrogenation active protective agent with boron-containing aluminum oxide as carrier and preparation as well as application thereof |
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| 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 |
| CN102649070A (en) * | 2011-02-24 | 2012-08-29 | 中国石油化工股份有限公司 | Hydrogenated active protective agent taking alumina containing alkali earth metals as carrier, as well as preparation and application of hydrogenated active protective agent |
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| CN105749924A (en) * | 2014-12-17 | 2016-07-13 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst and use thereof |
| CN105749924B (en) * | 2014-12-17 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of heavy oil hydrogenating treatment catalyst and its application |
| CN110773189A (en) * | 2018-07-31 | 2020-02-11 | 中国石油化工股份有限公司 | Hydrogenation activity protection catalyst and preparation and application thereof |
| CN110773184A (en) * | 2018-07-31 | 2020-02-11 | 中国石油化工股份有限公司 | Hydrogenation activity protection catalyst and preparation and application thereof |
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