CN104437518A - Selective hydrodesulfurization catalyst, and preparation and application thereof - Google Patents
Selective hydrodesulfurization catalyst, and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a selective hydrodesulfurization catalyst, and preparation and application thereof. The catalyst comprises a carrier, at least one non-noble metal composition selected from group VIII and supported on the carrier, at least one metal composition selected from group VI B, and one or more of organics selected from alcohols, organic acids and organic amines. Based on the catalyst in terms of oxides, the mass fraction of the group VIII metal composition is 0.1-6%, the mass fraction of the group VI B metal composition is 1-25%, and the molar ratio of the organic to the group VIII metal composition is 0.5-2.5. The carrier is double-peak porous aluminium oxide, and characterized by mercury intrusion porosimetry, the carrier has the pore volume of 0.9-1.2 mL/g and the specific surface area of 50-300 m<2>/g, the pore volume of pores with the diameter of 10-30 nm accounts for 55-80% of the total pore volume, and the pore volume of pores with the diameter of 300-500 nm accounts for 10-35% of the total pore volume. Compared with the prior art, the provided catalyst is especially applied to hydrofining processes of coked gasoline and catalytically-cracked gasoline.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst and Synthesis and applications thereof, more specifically to a kind of catalyst for selectively hydrodesulfurizing and Synthesis and applications thereof.
Background technology
As everyone knows, air pollution brings serious environmental problem.A large amount of engine discharges causes air-polluting one of the main reasons.In recent years, for adapting to the requirement of protection of the environment, the composition of countries in the world to engine fuel proposes stricter restriction, to reducing the discharge of harmful substance.The comburant SOx of sulfide in petrol mainly contains one of harmful substances, and it is also one of main matter of poisoning automotive exhaust catalysis reforming unit catalyst simultaneously.
Generally speaking, relative to heavy distillate, Sulfur capacity contained in gasoline fraction is easily removed by hydrofinishing.But, due to the lower alkene of collateralization degree in the process very easily hydrotreated lube base oil become low-octane alkane.This not only can make declining to a great extent of octane number, causes hydrogen consumption meaningless in a large number simultaneously.Therefore, the subject matter adopting method of hydrotreating to carry out desulfurization to gasoline fraction oil how ensureing desulfurization while, to reduce olefins hydrogenation, improves the selective of hydrogenation reaction.
CN1133723 discloses a kind of catalyst for hydrorefining distillate oil and preparation method thereof, with the alumina globule containing silica 5 ~ 15w% for carrier, containing MoO
321 ~ 28w%, NiO2 ~ 8w%, CoO0.03 ~ 2.0w%, adopts two sections and sprays.Described catalyst has higher hydrodesulfurization and hydrodenitrogenationactivity activity simultaneously, is applicable to the inferior distillate oil hydrofinishing that sulfur-bearing nitrogen is more simultaneously.
CN1101454 discloses a kind of catalyst for hydrodesulfurizationfraction fraction oil and preparation method, and catalyst for carrier, take Mo-Ni as active component with aluminium oxide or silicon-containing alumina, adds phosphate builder.By adopting the Mo-Ni-P co-impregnated solution segmentation total immersion carrier of alkalescence, make Metal Distribution on catalyst evenly, the activity of catalyst, particularly fraction oil hydrodesulfurizing activity is improved.
CN1472283 discloses a kind of Catalysts and its preparation method for olefinic naphtha selective hydrodesulfurization.Described catalyst is prepared from mainly through adopting Monolayer Dispersion method, and its composition proportion is: CoO+MoO
3: 6 ~ 20wt%; MgO:8 ~ 20wt%.
U.S.Pat.No.5,525,211 disclose a kind of catalyst for selectively hydrodesulfurizing, and this catalyst contains the molybdenum being selected from group vib and/or the tungsten of 0.1-40 % by weight, the nickel being selected from the VIIIth race of 0.1-15 weight and cobalt, 0.01-20 % by weight is selected from IA race alkali metal, alkaline-earth metal, Sc, Y, and lanthanide series, carrier is the MgAl with spinel structure
2o
4, ZnAl
2o
4, CaAl
2o
4, NiAl
2o
4, CoAl
2o
4or BaAl
2o
4.
WO2007084438 discloses a kind of catalyst for selectively hydrodesulfurizing, and this catalyst contains the molybdenum being selected from group vib of 8-30 % by weight, the cobalt being selected from the VIIIth race of 2-8 weight, and the organic matter of appropriate amount as complexing agent load on silicon carrier.Use this catalyst treatment catalytically cracked gasoline raw material, olefin saturated rate is low.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of newly, be more suitable for for olefin containing gasoline distillate catalyst for selectively hydrodesulfurizing and methods for making and using same thereof.
The content that the present invention relates to comprises:
1. a catalyst for selectively hydrodesulfurizing, containing carrier, load at least one is on this carrier selected from the non-noble metal components of the VIIIth race, at least one is selected from the metal component of group vib and is selected from alcohol, one or more organic matter in organic acid and organic amine, be benchmark with oxide basis and with catalyst, the mass fraction of described metal component of group VIII is 0.1-6%, the mass fraction of group vib metal component is 1-25 % by weight, wherein, the mol ratio of described organic matter and metal component of group VIII is 0.5-2.5, described carrier is a kind of bimodal porous aluminum oxide, characterize with mercury injection method, the pore volume of described carrier is 0.9-1.2 ml/g, specific area is 50-300 rice
2/ gram, diameter is the 55-80% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume.
2. the catalyst according to 1, it is characterized in that, be benchmark with oxide basis and with catalyst, and the mass fraction of described metal component of group VIII is 1-5%, the mass fraction of group vib metal component is 5-20%, and the mol ratio of organic matter and metal component of group VIII is 1-2.
3. the catalyst according to 1, 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, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.
4. catalyst according to claim 1 and 2, is characterized in that, described alcohol is selected from ethylene glycol, glycerine, molecular weight are one or more in 200-1500 polyethylene glycol, diethylene glycol, butanediol; Described organic acid is selected from one or more in acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-CDTA, citric acid, tartaric acid, malic acid; Described organic amine is selected from ethylenediamine or EDTA and ammonium salt thereof.
5. catalyst according to claim 1 and 2, is characterized in that, the non-noble metal components of described VIII race is selected from cobalt and/or nickel, and described group vib metal component is selected from molybdenum and/or tungsten.
6. catalyst according to claim 5, is characterized in that, the non-noble metal components of described VIII race is cobalt, and the metal component of described group vib is molybdenum.
7. a preparation method for catalyst for selectively hydrodesulfurizing, comprises the steps:
(1) prepare carrier, comprise and the modifier P2 of hydrated alumina P1 and P1 containing boehmite is mixed, aftershaping, dry and roasting, to be the κ value of 20-95:5-80, P2 be for the Mixing ratio by weight of described P1 and P2 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 obtained in step (1) is introduced at least one is selected from the non-noble metal components of VIII race, at least one is selected from group vib metal component and to be selected from alcohol, organic acid and organic amine the organic matter of one or more, dry afterwards, with oxide basis and with described catalyst for benchmark, the consumption of each component makes the mass fraction of metal component of group VIII in described catalyst be 0.1-6 % by weight, the mass fraction of group vib metal component is 1-25 % by weight, the mol ratio of described organic matter and metal component of group VIII is 0.5-2.5
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 100-210 DEG C, and the time is 1-15 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 70-95:5-30, 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; Be benchmark with oxide basis and with catalyst, the consumption of each component makes the mass fraction of metal component of group VIII in described catalyst be 1-5%, the mass fraction of group vib metal component is 5-20%, and the mol ratio of described organic matter and metal component of group VIII is 0.5-2.5; The drying condition of described step (2) comprising: temperature 120-190 DEG C, and drying time is 2-4 hour.
9. the method according to 7 or 8, 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.
10. the method according to 9, 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.
11. methods according to 7 or 8, 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.
12. methods according to 11, 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.
13. methods according to 7 or 8, it is characterized in that, the non-noble metal metal component of described VIII race is selected from cobalt and/or nickel, and the metal component of described group vib is selected from molybdenum and/or tungsten.
14. methods according to 13, it is characterized in that, the non-noble metal metal component of described VIII race is cobalt, and the metal component of described group vib is molybdenum.
15. methods according to 7 or 8, it is characterized in that, the described method introducing hydrogenation active metals component on carrier is infusion process.
16. methods according to 7 or 8, it is characterized in that, described P2 is 80-300 object particle.
17. methods according to 16, it is characterized in that, described P2 is 100-200 object particle.
18. methods according to 7 or 8, is characterized in that, described alcohol is selected from ethylene glycol, glycerine, molecular weight are one or more in 200-1500 polyethylene glycol, diethylene glycol, butanediol; Described organic acid is selected from one or more in acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-CDTA, citric acid, tartaric acid, malic acid; Described organic amine is selected from ethylenediamine or EDTA and ammonium salt thereof.
19. 1 kinds of selective hydrodesulfurization methods, under being included in selective hydrodesulfurization reaction condition, reacting sulfur-bearing feedstock oil and catalyst exposure, it is characterized in that, described catalyst is the catalyst described in claim 1-6 any one
Depending on different requirement, the carrier in catalyst of the present invention can be made into the various article shaped being easy to operate, such as, and 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.
Describedly shapingly 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, for 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.The example of described extrusion aid is as one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, 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.
In the present invention, after sour peptization index D I in the preparation of described carrier refers to that the hydrated alumina (comprising its modifier) 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 (also referred to as butt) 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.
In the present invention, described at least one of introducing on carrier is selected from the non-noble metal metal component of VIII race and at least one and is selected from the metal component of group vib and the organic method of one or more in alcohol, organic acid and organic amine that is selected from is preferably the method for dipping, described dipping method is conventional method, such as hole saturation dipping, excessive immersion stain and spray impregnating.Wherein, described VIIIth race, group vib and be selected from the organic matter of one or more in alcohol, organic acid and organic amine and can be introduced separately into, also can between two or three kinds introduce simultaneously.When adopting infusion process to introduce, comprise preparation dipping solution, such as, be selected from described in containing the compound of the metal component of at least one group vib, containing the metal component of at least one the VIIIth race compound or be selected from the organic matter of one or more in alcohol, organic acid and organic amine and prepare dipping solution respectively, and with these dipping solutions impregnated carrier respectively; Or be selected from described in containing at least one group vib metal component, containing the compound of the metal component of at least one the VIIIth race and two or three preparation hybrid infusion solution in being selected from alcohol, organic acid and organic amine one or more organic matter, and by the method for these dipping solutions impregnated carrier respectively.When described dipping is step impregnation, the order of described dipping solution impregnated carrier is not limited.Although optional, after each dipping, preferably include dry step.Described drying condition comprises: baking temperature 100-210 DEG C, preferred 120-190 DEG C, and drying time, 1-6 hour, was preferably 2-4 hour.
The described compound containing the non-noble metal components of VIII race is selected from one or more in their soluble-salt and complex compound, such as, one or more in the nitrate of VIII race's metal, chloride, acetate, subcarbonate, are selected from one or more in the solubility of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt for cobalt salt.
The described compound containing group vib metal component is selected from one or more in their soluble compound, such as, molybdenum oxide, molybdate are (such as, ammonium molybdate, ammonium paramolybdate, ammonium phosphomolybdate), one or more in tungstates (such as, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, ethyl metatungstate).
The described organic matter being selected from alcohol, organic acid and organic amine one or more, wherein said alcohol can be selected from one or more in ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, described acid is selected from acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartaric acid, malic acid, described organic amine is selected from ethylenediamine or EDTA and ammonium salt thereof.Wherein, the mol ratio that the introduction volume being selected from alcohol, organic acid and organic amine described in meets described organic matter and metal component of group VIII is preferably 0.5-2.5, more preferably 1-2.
According to catalyst provided by the invention, the material of the catalytic performance of catalyst provided by the invention wherein maybe can be improved containing any material not affecting the catalytic performance that the invention provides catalyst.As contained phosphorus, be benchmark in element and with catalyst, the content of above-mentioned auxiliary agent is no more than 10 % by weight, is preferably 0.5-5 % by weight.
When in described catalyst also containing when being selected from the components such as phosphorus, the preparation method of described catalyst comprises the step introducing the adjuvant components such as phosphorus, introducing method can be arbitrary method, as can be by containing as described in auxiliary agent compound be selected from VIII race non-noble metal slaine and be selected from group vib slaine be mixed with mixed solution after flood as described in the method for carrier introduce.
Catalyst provided by the invention before the use, usually preferably in presence of hydrogen, 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 outside device also can be In-situ sulphiding in device, is translated into sulfide type.
Described selective hydrodesulfurization reaction can realize in arbitrary fraction oil hydrogenation refining reaction unit, is not particularly limited this present invention.Such as, described selective hydrodesulfurization reaction adopts one stage hydrofining, and its operating condition can adjust in following ranges according to feedstock oil character with to the requirement of oil quality: reaction temperature 200 ~ 400 DEG C, volume space velocity 3 ~ 15h
-1, hydrogen dividing potential drop 0.8 ~ 6.0MPa, hydrogen-oil ratio 50 ~ 800:1(volume is (v)).
Compared with prior art, catalyst provided by the invention is when the hydrodesulfurization for high-sulfur catalytically cracked gasoline, gasoline antiknock figure penalties is little, be particularly suitable for the raw material being rich in sulphur and alkene, comprise the unifining process of coker gasoline, catalytically cracked gasoline whole or the different fractions after cutting.
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).
P1-3: (pore volume is 0.85 ml/g to the dry glue powder that Shandong Aluminium Industrial Corp produces, and specific surface is 180 meters
2/ gram, can and bore dia 7nm.Butt is 72%, and wherein boehmite content is 67%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 19.5).
Embodiment 1-4 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.
Table 1
| Embodiment | Raw material | k |
| 1 | P2A | 0.5 |
| 2 | P2B | 0.4 |
| 3 | P2C | 0.4 |
| 4 | P2D | 0 |
Embodiment 5-10 illustrates the preparation method of preparation carriers for catalysts of the present invention.Comparative example 1-4 illustrates the preparation method of conventional catalyst carrier.
Embodiment 5
Take 800 grams of P1-1, after 200 grams of raw material P2A Homogeneous phase mixing that embodiment 1 is obtained, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), 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 Z1.The character of carrier Z1 lists in table 2.
Embodiment 6
Take 950 grams of P1-1, after 50 grams of raw material P2B Homogeneous phase mixing that embodiment 2 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, 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 7
Take 850 grams of P1-1, 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) aqueous solution 1440 milliliters of 10 milliliters, 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) aqueous solution 1440 milliliters of 10 milliliters, 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 8
Take 800 grams of P1-2, after 200 grams of raw material P2A Homogeneous phase mixing that embodiment 1 is obtained, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), 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 Z4.The character of carrier Z4 lists in table 2.
Embodiment 9
Take 850 grams of P1-2, after 150 grams of raw material P2C Homogeneous phase mixing that embodiment 3 is obtained, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), 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 Z5.The character of carrier Z5 lists in table 2.
Comparative example 2
Take 1000 grams of P1-2, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), 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.
Comparative example 3
Take 1000 grams of P1-3, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), 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 DZ3.The character of carrier DZ3 lists in table 2.
Embodiment 10
Take 900 grams of P1-3, after 100 grams of raw material P2B Homogeneous phase mixing that embodiment 2 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, 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 Z6.The character of carrier Z6 lists in table 2.
Comparative example 4
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 DZ4.The character of carrier DZ4 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 11-14 and comparative example 5 illustrate catalyst provided by the invention and reference catalyst and preparation thereof respectively.
Embodiment 11
Get 100 grams of carrier Z1.
The method of total immersion stain is adopted to introduce molybdenum, cobalt and organic matter at carrier Z1.First, take citric acid 12.0 grams, after being dissolved to clear in deionized water, continuous heating is to solution temperature 50 DEG C, slowly adds molybdenum trioxide 12.9 grams, basic cobaltous carbonate 7.6 grams, continues to be dissolved to total liquid 94 milliliters.Course of dissolution heats, and temperature remains on 50 DEG C, with this solution impregnation 100g carrier Z1, in 170 DEG C of dryings 4 hours, obtains catalyst C1.In catalyst C1, the molar ratio of citric acid and group VIII metal component is cobalt in 1.0, C1, molybdenum oxide content lists in table 3.
Embodiment 12
Get 100 grams of carrier Z1.
The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier Z1.First, take ammonium paramolybdate 12.8 grams, take cobalt nitrate 13.6 grams, citric acid 15.4 grams, dissolves ammonium paramolybdate, citric acid and cobalt nitrate to total liquid 94 milliliters successively by deionized water, heating, solution temperature remains on 50 DEG C, with this solution impregnating carrier Z1, in 170 DEG C of dryings 4 hours, obtain catalyst C2.In catalyst C2, the molar ratio of citric acid and group VIII metal component is cobalt in 1.6, C2, molybdenum oxide content lists in table 3.
Embodiment 13
Get 100 grams of carrier Z1.
The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier Z1.First, take ammonium paramolybdate 18.0 grams, after being dissolved to clear with ammonia solvent to 70 ml soln that concentration is 18 % by weight, take basic cobaltous carbonate 8.4 grams, EDTA22.2 gram, add above-mentioned solution and continue to be dissolved to total liquid 94 milliliters.Course of dissolution heats, and temperature remains on 50 DEG C, with this solution impregnation 100g carrier Z3, in 170 DEG C of dryings 4 hours, obtains catalyst C3.In catalyst C3, the molar ratio of EDTA and group VIII metal component is cobalt in 1.0, C3, molybdenum oxide content lists in table 3.
Embodiment 14
Get 100 grams of carrier Z1.
The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier Z1.First, take ammonium paramolybdate 8.9 grams, after being dissolved to clear with ammonia solvent to 90 ml soln that concentration is 18 % by weight, take basic cobaltous carbonate 3.9 grams, EDTA10.8 gram, add above-mentioned solution and continue to be dissolved to total liquid 94 milliliters.Course of dissolution heats, and temperature remains on 50 DEG C, with this solution impregnation 100g carrier Z1, in 170 DEG C of dryings 4 hours, obtains catalyst C4.In catalyst C4, the molar ratio of EDTA and group VIII metal component is cobalt in 1.2, C4, molybdenum oxide content lists in table 3.
Comparative example 5
Get 100 grams of carrier DZ4.
The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier DZ4.First, take ammonium paramolybdate 18.6 grams, after being dissolved to clear with ammonia solvent to 90 ml soln that concentration is 18 % by weight, take basic cobaltous carbonate 8.8 grams, EDTA24.1 gram, add above-mentioned solution and continue to be dissolved to total liquid 95 milliliters.Course of dissolution heats, and temperature remains on 50 DEG C, with this solution impregnation 100g carrier DZ4, in 170 DEG C of dryings 4 hours, obtains catalyst DB1.In catalyst DB1, the molar ratio of EDTA and group VIII metal component is cobalt in 1.2, DB1, molybdenum oxide content lists in table 3.
Comparative example 6
Get 100 grams of carrier DZ4.
The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier DZ4.First, take ammonium paramolybdate 12.7 grams, after being dissolved to clear with ammonia solvent to 80 ml soln that concentration is 18 % by weight, take cobalt nitrate 11.3 grams, add above-mentioned solution and continue to be dissolved to total liquid 95 milliliters.The micro-heating of course of dissolution, temperature remains on 30 DEG C, and with this solution impregnation 100g carrier DZ4, in 170 DEG C of dryings 4 hours, 350 DEG C of roastings 3 hours, obtain catalyst DB2.In DB2, cobalt, molybdenum oxide content are listed in table 3.
Table 3
| Example | Catalyst | Carrier | CoO, % by weight | MoO3, % by weight |
| 11 | C1 | Z1 | 3.8 | 11.0 |
| 12 | C2 | Z1 | 3.0 | 9.0 |
| 13 | C3 | Z1 | 4.3 | 12.4 |
| 14 | C4 | Z1 | 2.1 | 6.5 |
| Comparative example 5 | DB1 | DZ4 | 4.3 | 12.4 |
| Comparative example 6 | DB2 | DZ4 | 2.5 | 9.0 |
Remarks: on metal, amount is for catalyst is through 550 DEG C of roastings XRF analysis result after 4 hours.
Embodiment 15-18
The model compound containing 10% thiophene, 20% n-hexylene and 70% normal heptane is adopted to carry out activity rating to catalyst C1-C4.Evaluating apparatus is fixed bed hydrogenation microreactor, and hydrogen adopts and once passes through.First carry out presulfurization before evaluating catalyst, sulfurized oil is for containing 6%CS
2cyclohexane.Conditions of vulcanization is: pressure 1.6MPa, hydrogen to oil volume ratio 3600:1, weight space velocity 6.0h
-1, temperature 320 DEG C, time 2 h.
Change model compound into after sulfuration terminates, reaction temperature 230 ~ 320 DEG C of changes, on-line chromatograph analysis, and draw thiophene conversion ratio-hydrotreated lube base oil rate curve, when being 80% according to response curve reading thiophene conversion ratio afterwards, the hydrotreated lube base oil rate HYD of n-hexylene, the results are shown in Table 4.
Comparative example 7-8
Evaluate comparative catalyst DB1, DB2 according to embodiment 15-18 same procedure, the results are shown in Table 4.
Table 4
| Embodiment | Catalyst | HYD，％ |
| 15 | C1 | 44 |
| 16 | C2 | 48 |
| 17 | C3 | 42 |
| 18 | C4 | 47 |
| Comparative example 7 | DB1 | 58 |
| Comparative example 8 | DB2 | 61 |
Embodiment 19
This example high-sulfur catalytically cracked gasoline carries out activity rating to catalyst C3.Feedstock oil character is in table 5.
Evaluating apparatus is fixed bed hydrogenation reactor, and hydrogen adopts and once passes through.Before reaction, first catalyst carries out presulfurization, and sulfurized oil is for containing 2%CS
2grand celebration direct steaming gasoline.Conditions of vulcanization is: pressure 1.6MPa, hydrogen to oil volume ratio 400:1, volume space velocity 2.0h
-1, temperature is 320 DEG C, 3 hours time.Charging is switched to grand celebration direct steaming gasoline, after stablizing 30 hours, charging is switched to the reaction of high-sulfur catalytically cracked gasoline, reaction condition and the results are shown in Table 6.
Anti-knock index is (RON+MON)/2.Anti-knock index change refers to the anti-knock index of desulfurization product and the difference of feedstock oil anti-knock index.If the anti-knock index of desulfurization product refers to lower than feedstock oil antiknock
Number, then anti-knock index is changed to negative value, otherwise be on the occasion of.
Table 5
| Test number | Raw material |
| Sulphur, microgram/g | 1500 |
| Group composition, v% | |
| Saturated hydrocarbons | 38.0 |
| Alkene | 22.9 |
| Aromatic hydrocarbons | 39.1 |
Table 6
| Embodiment | 14 |
| Reaction temperature, DEG C | 270 |
| LHSV，h -1 | 4 |
| Reaction pressure, kg/cm 2 | 16 |
| Hydrogen-oil ratio, v/v | 400：1 |
| Sulphur, microgram/g | 41 |
| Desulfurization degree, m% | 97.27 |
| Olefin saturated rate, v% | 33.01 |
Table 6 result shows, has high desulfurization activity and lower olefin saturated activity, be more suitable for the selective hydrodesulfurization for olefin containing gasoline distillate according to catalyst provided by the invention.
Claims (19)
1. a catalyst for selectively hydrodesulfurizing, containing carrier, load at least one is on this carrier selected from the non-noble metal components of the VIIIth race, at least one is selected from the metal component of group vib and is selected from alcohol, one or more organic matter in organic acid and organic amine, be benchmark with oxide basis and with catalyst, the mass fraction of described metal component of group VIII is 0.1-6%, the mass fraction of group vib metal component is 1-25 % by weight, the mol ratio of described organic matter and metal component of group VIII is 0.5-2.5, described carrier is a kind of bimodal porous aluminum oxide, characterize with mercury injection method, the pore volume of described carrier is 0.9-1.2 ml/g, specific area is 50-300 rice
2/ gram, diameter is the 55-80% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume.
2. the catalyst according to 1, it is characterized in that, be benchmark with oxide basis and with catalyst, and the mass fraction of described metal component of group VIII is 1-5%, the mass fraction of group vib metal component is 5-20%, and the mol ratio of organic matter and metal component of group VIII is 1-2.
3. the catalyst according to 1, 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, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume.
4. catalyst according to claim 1 and 2, is characterized in that, described alcohol is selected from ethylene glycol, glycerine, molecular weight are one or more in 200-1500 polyethylene glycol, diethylene glycol, butanediol; Described organic acid is selected from one or more in acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-CDTA, citric acid, tartaric acid, malic acid; Described organic amine is selected from ethylenediamine or EDTA and ammonium salt thereof.
5. catalyst according to claim 1 and 2, is characterized in that, the non-noble metal components of described VIII race is selected from cobalt and/or nickel, and described group vib metal component is selected from molybdenum and/or tungsten.
6. catalyst according to claim 5, is characterized in that, the non-noble metal components of described VIII race is cobalt, and the metal component of described group vib is molybdenum.
7. a preparation method for catalyst for selectively hydrodesulfurizing, comprises the steps:
(1) prepare carrier, comprise and the modifier P2 of hydrated alumina P1 and P1 containing boehmite is mixed, aftershaping, dry and roasting, to be the κ value of 20-95:5-80, P2 be for the Mixing ratio by weight of described P1 and P2 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 obtained in step (1) is introduced at least one is selected from the non-noble metal components of VIII race, at least one is selected from group vib metal component and to be selected from alcohol, organic acid and organic amine the organic matter of one or more, dry afterwards, with oxide basis and with described catalyst for benchmark, the consumption of each component makes the mass fraction of metal component of group VIII in described catalyst be 0.1-6 % by weight, the mass fraction of group vib metal component is 1-25 % by weight, the mol ratio of described organic matter and metal component of group VIII is 0.5-2.5
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 100-210 DEG C, and the time is 1-15 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 70-95:5-30, 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; Be benchmark with oxide basis and with catalyst, the consumption of each component makes the mass fraction of metal component of group VIII in described catalyst be 1-5%, the mass fraction of group vib metal component is 5-20%, and the mol ratio of described organic matter and metal component of group VIII is 0.5-2.5; The drying condition of described step (2) comprising: temperature 120-190 DEG C, and drying time is 2-4 hour.
9. the method according to 7 or 8, 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.
10. the method according to 9, 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.
11. methods according to 7 or 8, 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.
12. methods according to 11, 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.
13. methods according to 7 or 8, it is characterized in that, the non-noble metal metal component of described VIII race is selected from cobalt and/or nickel, and the metal component of described group vib is selected from molybdenum and/or tungsten.
14. methods according to 13, it is characterized in that, the non-noble metal metal component of described VIII race is cobalt, and the metal component of described group vib is molybdenum.
15. methods according to 7 or 8, it is characterized in that, the described method introducing hydrogenation active metals component on carrier is infusion process.
16. methods according to 7 or 8, it is characterized in that, described P2 is 80-300 object particle.
17. methods according to 16, it is characterized in that, described P2 is 100-200 object particle.
18. methods according to 7 or 8, is characterized in that, described alcohol is selected from ethylene glycol, glycerine, molecular weight are one or more in 200-1500 polyethylene glycol, diethylene glycol, butanediol; Described organic acid is selected from one or more in acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-CDTA, citric acid, tartaric acid, malic acid; Described organic amine is selected from ethylenediamine or EDTA and ammonium salt thereof.
19. 1 kinds of selective hydrodesulfurization methods, under being included in selective hydrodesulfurization reaction condition, reacting sulfur-bearing feedstock oil and catalyst exposure, it is characterized in that, described catalyst is the catalyst described in claim 1-6 any one.
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Cited By (11)
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| CN106140308A (en) * | 2015-03-30 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils |
| CN106362757A (en) * | 2015-07-21 | 2017-02-01 | 中国石油化工股份有限公司 | Selective hydrodesulfurization catalyst and applications thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101757931A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method thereof and hydrocracking method |
-
2013
- 2013-09-22 CN CN201310432504.6A patent/CN104437518B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101757931A (en) * | 2008-12-25 | 2010-06-30 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method thereof and hydrocracking method |
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