CN104437520A - Heavy-oil hydrotreatment catalyst, and preparation and application thereof - Google Patents
Heavy-oil hydrotreatment catalyst, and preparation and application thereof Download PDFInfo
- Publication number
- CN104437520A CN104437520A CN201310432227.9A CN201310432227A CN104437520A CN 104437520 A CN104437520 A CN 104437520A CN 201310432227 A CN201310432227 A CN 201310432227A CN 104437520 A CN104437520 A CN 104437520A
- Authority
- CN
- China
- Prior art keywords
- weight
- catalyst
- metal component
- pore volume
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a heavy-oil hydrotreatment catalyst, and preparation and application thereof. The catalyst comprises an aluminium oxide carrier with a double-peak pore structure, and the carrier contains one or more auxiliary agent compositions selected from boron, silicon and fluorine. Characterized by mercury intrusion porosimetry, the carrier has the pore volume of 0.8-1.2 mL/g and the specific surface area of 120-400 m<2>/g, the pore volume of pores with the diameter of 6-30 nm accounts for 58-80% of the total volume, the pore volume of pores with the diameter of 10-30 nm is less than 55% of the total volume, and the pore volume of pores with the diameter of 300-500 nm accounts for 10-35% of the total volume. Based on the total weight of the catalyst in terms of oxides, the content of auxiliary boron and silicon is 8 wt% or less, and the content of fluorine in terms of an element is 8 wt% or less. Compared with hydrotreatment catalysts provided in the prior art, the provided catalyst simultaneously possesses relatively good hydrogenation metal removal activity and desulphurization activity.
Description
Technical field
The present invention relates to a kind of heavy oil hydrogenating treatment catalyst and Synthesis and applications thereof.
Background technology
(heavy oil is called for short for heavy raw oil, typically refer to the feedstock oil of boiling point more than 350 DEG C), the yield that secondary operations not only can improve light-end products is carried out by hydrogenation technique, the content of the pollutant such as sulphur, nitrogen in oil product can also be reduced simultaneously, therefore in market, light-end products demand is constantly increased, environmental regulation is also tending towards strict today, is subject to the generally favor of oil refining manufacturer.Compared with light-end products, containing metal impurities such as a large amount of Ni, V, Fe, Ca, if this part impurity can not effectively be removed, downstream hydrogenation catalyst can be had a negative impact, is easy to make downstream catalyst inactivation in heavy distillate.And the subtractive process of metal and the impurity removal such as sulphur, nitrogen different, require that catalyst not only has good reactivity, also need to have excellent diffusion simultaneously, catalyst carrier pore structure has material impact to catalyst performance for this reason.The carrier with bimodal distribution of pores not only can provide diffusion path for macromolecular reaction thing, and carries out providing maximum specific surface for reacting, and thus in inferior heavy oil hydroprocessing processes, has good activity and stability.In prior art, disclosed in have bimodal distribution of pores catalyst patented technology as follows.
CN1084224C discloses a kind of catalyst for dehydrogenation of saturated hydrocarbon and preparation method thereof, and this catalyst used carrier is a kind of large aperture γ-Al with double-hole distribution
2o
3, the pore volume that its diplopore is distributed as 5-100 nano-pore accounts for the 20-35% of total pore volume, and the pore volume of 100-1000 nano-pore accounts for the 44-58% of total pore volume.A certain amount of alchlor is first at high temperature used ammonia neutralization by the preparation method of this carrier, and forming oil column, drying after the aluminium hydroxide acidifying of generation, be no less than 2 hours 600 ~ 800 DEG C of Water Under steam treatment afterwards and obtain.
US Patent No. 4,448,896 catalyst disclosing a kind of hydrodesulfurization and heavy metal, the specific surface of the carrier that this catalyst adopts is 100-350 rice
2/ gram, pore radius
pore volume be 0.5-1.5 ml/g, the ratio of this pore volume and total pore volume is at least 90%, and its pore size distribution is less than at pore radius
with
there is characteristic peak in two places, pore radius
pore volume be at least 0.2 ml/g, pore radius
pore volume be at least 0.1 ml/g, the preparation method of this carrier be activated alumina or activated alumina precursor are mixed with carbon black, shaping and roasting.With described aluminium oxide for benchmark, the consumption of carbon black is 10-120 % by weight.
CN1089039A discloses a kind of preparation method with the alumina support of double-hole, the method is by aluminium oxide different for two kinds of pore-size distributions or its precursor and carbon powder, surfactant, peptizing agent and water mixed-forming, drying, roasting, obtaining bore dia is that the hole of 10-20 nanometer accounts for total pore volume is greater than 50%, bore dia is greater than 100 nanometers hole to account for total pore volume be 5-30%.
CN1690172A discloses a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method, by adding nitrogenous expanding agent in carrier preparation process, obtains the carrier with bimodal distribution of pores.Wherein the pore volume of 10-20 nanometer accounts for the 35-80% of total pore volume, bore dia is the 15-60% that the pore volume of 500-1200 nanometer accounts for total pore volume, and the pore volume sum of bore dia < 10 nanometer, > 20-< 500 nanometer and > 1200 nanometer accounts for the 5-40% of total pore volume.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new catalyst of heavy-oil hydrogenation process and the preparation method of this catalyst and application.
The content that the present invention relates to comprises:
1, a kind of heavy oil hydrogenating treatment catalyst, containing a kind of alumina support with structure of double peak holes of one or more adjuvant components containing being selected from boron, silicon and fluorine, characterize with mercury injection method, the pore volume of described carrier is 0.8-1.2 ml/g, and specific area is 120-400 rice
2/ gram, diameter is the 58-80% that the pore volume in 6-30nm hole accounts for total pore volume, wherein diameter is that the pore volume in 10-30nm hole is lower than 55% of total pore volume, diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume, with oxide basis and with described carrier total amount for benchmark, the content of described auxiliary agent boron, silicon is 0.5-8 % by weight, in the Oil repellent of element for 0.5-8 % by weight.
2, the catalyst according to 1, is characterized in that, the pore volume of described carrier is 0.9-1.15 ml/g, and specific area is 150-300 rice
2/ gram, diameter is the 60-75% that the pore volume in 6-30nm hole accounts for total pore volume, diameter is that the pore volume in 10-30nm hole is lower than 54% of total pore volume, diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume, with oxide basis and with described carrier total amount for benchmark, the content of described auxiliary agent boron, silicon is 1-6 % by weight, in the Oil repellent of element for 1-6 % by weight.
3, the catalyst according to 2, is characterized in that, with oxide basis and with described carrier total amount for benchmark, the content of described auxiliary agent boron, silicon is 1-4 % by weight, in the Oil repellent of element for 1-4 % by weight.
4, the catalyst according to 1, it is characterized in that, hydrogenation active metals component in described catalyst is selected from least one metal component of group VIII and at least one metal component of group VIB, be benchmark with oxide basis and with catalyst, the content of described metal component of group VIII is 0.5-10 % by weight, and the content of metal component of group VIB is 0.5-15 % by weight.
5, the catalyst according to 4, it is characterized in that, described metal component of group VIII is selected from nickel and/or cobalt, metal component of group VIB is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyst, the content of described metal component of group VIII is 0.8-8 % by weight, and the content of metal component of group VIB is 1-12 % by weight.
6, the catalyst according to 5, is characterized in that, is benchmark with oxide basis and with catalyst, and the content of described metal component of group VIII is 1-6 % by weight, and the content of metal component of group VIB is 2-10 % by weight.
7, the preparation method of catalyst according to 1, comprise and prepare carrier, the preparation method of described carrier comprises the modifier P2 of hydrated alumina P1 and P1 containing boehmite mixing and introducing is selected from boron in the mixture, one or more adjuvant components of silicon and fluorine, aftershaping, dry also roasting, wherein, with oxide basis and with described carrier total amount for benchmark, described boron, the introduction volume of silicon is 0.5-8 % by weight, in element and with described carrier total amount for benchmark, the introduction volume of described fluorine is 0.5-8 % by weight, the condition of described drying comprises: temperature is 40-350 DEG C, time is 1-24 hour, the condition of described roasting comprises: temperature is for being greater than 500 to being less than 850 DEG C, time is 1-8 hour, the Mixing ratio by weight of described P1 and P2 is 20-95:5-80, the κ value of P2 is 0 to being less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1for the sour peptization index of the hydrated alumina P1 containing boehmite, DI
2for the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite.
8, the method according to 7, is characterized in that, with oxide basis and with described carrier total amount for benchmark, the introduction volume of described boron, silicon is 1-6 % by weight, and in element and with described carrier total amount for benchmark, the introduction volume of described fluorine is 1-6 % by weight; The Mixing ratio by weight of described P1 and P2 is 70-95:5-30; The k value of described P2 is 0 to being less than or equal to 0.6; The pore volume of described P1 is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, most probable bore dia 8-30nm.
9, the method according to 8, is characterized in that, with oxide basis and with described carrier total amount for benchmark, the introduction volume of described boron, silicon is 1-4 % by weight, and in element and with described carrier total amount for benchmark, the introduction volume of described fluorine is 1-4 % by weight; The pore volume of described P1 is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, most probable bore dia 10-25nm.
10, the method according to 7 or 8 any one, is characterized in that, described P2 is 80-300 object particle.
11, the method according to 10, is characterized in that, described P2 is 100-200 object particle.
12, the method according to 7, is characterized in that, the condition of described drying comprises: temperature is 100-200 DEG C, and the time is 2-12 hour, and the condition of described roasting comprises: temperature is 600-800 DEG C, and roasting time is 2-6 hour.
13, the method according to 7, it is characterized in that, by shaping, dry for the described hydrated alumina P1 containing boehmite by one of P1 method being modified as P2, afterwards its all or part of carrying out is ground, sieves, obtaining powder thing is P2, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour; Two of method is article shaped roastings method one obtained, and sintering temperature is for being greater than 350 to being less than or equal to 1400 DEG C, and roasting time is 1-8 hour, and afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2; Three of method is dodged by the hydrated alumina P1 containing boehmite to do, and dodge dry temperature for being greater than 150 to being less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour, and obtaining powder thing is P2; Four of method is mixed to get one or more in two and the modifier that obtains with three of method of one of method, method.
14, the method according to 13, 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.
15, the method according to 13 or 14, is characterized in that, described P2 is 80-300 object particle in P1 modifier.
16, the method according to 15, is characterized in that, described P2 is 100-200 object particle in P1 modifier.
17, method according to 7, it is characterized in that, comprise and adopt the method for dipping on carrier, introduce hydrogenation active metals component, carry out drying afterwards, the step of roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least one the VIIIth race and the metal component of at least one group VIB, be benchmark with oxide basis and with catalyst, the consumption of the concentration of the described compound containing hydrogenation active metals in described dipping solution and described solution makes the content of the metal component of the VIIIth race in final catalyst be 0.5-10 % by weight, the content of the metal component of described group VIB is 0.5-15 % by weight, described drying condition comprises: temperature is 100-250 DEG C, and the time is 1-10 hour, described roasting condition comprises: temperature is 360-500 DEG C, and the time is 1-10 hour.
18, the method according to 17, it is characterized in that, the metal component of described VIIIth race is selected from nickel and/or cobalt, the metal component of group VIB is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyst, the consumption of the concentration of the described compound containing hydrogenation active metals in described dipping solution and described solution makes the content of the metal component of group VIII in final catalyst be 0.8-8 % by weight, and the content of the metal component of group VIB is 1-12 % by weight; Described drying condition comprises: temperature is 100-140 DEG C, and the time is 1-6 hour; Described roasting condition comprises: temperature is 360-450 DEG C, and the time is 2-6 hour.
19, the method according to 18, it is characterized in that, be benchmark with oxide basis and with catalyst, the consumption of the concentration of the described compound containing hydrogenation active metals in described dipping solution and described solution makes the content of the metal component of group VIII in final catalyst be 1-6 % by weight, and the content of the metal component of group VIB is 2-10 % by weight.
20, the application of the hydrotreating catalyst in claim 1-6 described in any one in hydrocarbon oil hydrogenation process.
In the present invention, depending on different, the carrier of described catalyst requires that carrier wherein can be made into the various article shaped being easy to operate, such as spherical, cellular, nest like, tablet or bar shaped (clover, butterfly, cylindrical etc.).Wherein, the method mixed by the modifier P2 of described hydrated alumina P1 and P1 containing boehmite is conventional method, such as, is dropped in stirring-type batch mixer by P1 and P2 of powder mix according to ingredient proportion.The method introducing boron-containing compound in described P1 and P2 mixture is conventional method, such as, can be directly the boron-containing compound of aequum is mixed in aforesaid P1 and P2 mixed process, or boron-containing compound is mixed with the aqueous solution, this aqueous solution is mixed into while described P1 and P1 mixing or again this aqueous solution is mixed into after described P1 and P1 mixing, aftershaping, dry and roasting.Described boron-containing compound can one or more in the water soluble compound of preferred boracic.Such as, one or more in the water-soluble inorganic salt of boracic.
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, such as extruded moulding, for ensureing described shapingly to carry out smoothly, can add in described mixture water, extrusion aid and/or adhesive, containing or not containing expanding agent, then extrusion molding, carry out drying also roasting afterwards.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, such as common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH, described peptizing agent can be inorganic acid and/or organic acid, and described expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and surfactant.Synthetic cellulose is wherein preferably one or more in CMC, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in polyethylene glycol, poly-propyl alcohol, polyvinyl alcohol, one or more in the propenyl copolymer that surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight is 200-10000 and maleic acid copolymer.
In the present invention, after described sour peptization index D I refers to that hydrated alumina containing boehmite and the hydrated alumina modifier containing boehmite add 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
2before being respectively hydrated alumina containing boehmite and acid reaction and with acid reaction after with Al
2o
3the weight of meter.
The mensuration of DI comprises: (calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours calcination base (also referred to as the butt) content of hydrated alumina (1) measuring containing boehmite, its ratio burning rear weight and burn front weight, be expressed as a percentage), count 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.
In the present invention, the pore volume of the hydrated alumina containing boehmite, specific area and most probable pore size are that the described hydrated alumina containing boehmite after 4 hours in 600 DEG C of roastings, is characterized by BET N2 adsorption and obtained.
In further preferred embodiment, characterize with X diffraction, the boehmite content in the described hydrated alumina P1 containing boehmite 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.
The Mixing ratio by weight of described P1 and P2 refers to the ratio of the shared parts by weight of P1 and P2 difference in the mixture of every hundred parts of described P1 and P2.Wherein, the preferred span of 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 5-30.
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, the hydrogenation active metals component in described catalyst and content thereof are the active metal component and the content that are usually used in catalyst for hydrogenating hydrocarbon oil.Such as, described hydrogenation active metals component is selected from the metal component of at least one the VIIIth race and the metal component of at least one group VIB, and preferably the metal component of described VIIIth race is selected from nickel and/or cobalt, and the metal component of group VIB is selected from molybdenum and/or tungsten,
Be enough under the prerequisite that described hydrogenation active metals component is carried on described carrier, the present invention is not particularly limited the described method to carrier introducing hydrogenation active metals component, preferred method is infusion process, comprise the dipping solution of preparation containing the compound of described metal, afterwards with the carrier described in this solution impregnation.Described dipping method is conventional method, such as, can be excessive immersion stain, hole saturation infusion process.One or more in the described soluble compound be selected from containing the metal component compound being selected from VI B race in them, as one or more in molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; One or more in tungstates, metatungstate, ethyl metatungstate, preferably ammonium metatungstate, ethyl ammonium metatungstate wherein.Described containing the compound being selected from VIII race's metal component be selected from their soluble compound one or more, 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 hydrocarbon ils provided by the present invention (comprising residual oil) hydrotreating method, be enough to, under the prerequisite realizing described hydrotreatment reaction object, be not particularly limited the reaction condition of the hydrotreatment of described hydrocarbon ils.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, preferred 0.15-2 hour further
-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.
The device of described hydrogenation reaction can carry out in the reactor that described feedstock oil is reacted with described catalyst exposure at hydrotreating reaction conditions in any being enough to, and such as, at described fixed bed reactors, carries out in moving-burden bed reactor or fluidized bed reactor.
According to the conventional method in this area, described hydrotreating catalyst before the use, usually can be in presence of hydrogen, presulfurization is carried out with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 DEG C, this presulfurization can be carried out outside device also can be In-situ sulphiding in device, and the active metal component of its load is converted into metal sulfide component.
Catalyst provided by the invention can be used alone, and also can use with other catalyst combination, this catalyst be particularly suitable for heavy oil particularly inferior heavy oil carry out hydrotreatment, to provide qualified feedstock oil for subsequent technique (as catalytic cracking process).Compared with the hydrotreating catalyst provided with prior art, catalyst provided by the invention has good HDM and desulphurizing activated simultaneously.
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, most probable 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, most probable bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 17.2).
Embodiment 1-5 illustrates modifier P2 of the described P1 of preparation carrier of the present invention and preparation method thereof.
Embodiment 1
Take 1000 grams of P1-1, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and obtain dried strip, by dried strip shaping, sieve, the dried strip material (being commonly referred to as industrially drying bar waste material) length being less than 2mm is milled, and sieves, gets wherein 100 ~ 200 mesh sieves and divide, obtain the modifier P2A of P1-1.The k value of P2A is in table 1.
Embodiment 2
Take 1000 grams of P1-1, dodge dry 6 minutes in 240 DEG C, obtain the modifier P2B of P1-1.The k value of P2B is in table 1.
Embodiment 3
The each 200 grams of Homogeneous phase mixing of the P2B that the P2A obtain embodiment 1 and embodiment 2 obtain, obtain the modifier P2C of P1-1.The k value of P2C is in table 1.
Embodiment 4
Take 1000 grams of P1-2, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and 1200 DEG C of roastings 4 hours, obtain carrier, by carrier strip shaping, sieve, the carrier strip material (being commonly referred to as industrial carrier waste material) length being less than 2mm is milled, sieve, get wherein 100 ~ 200 mesh sieves and divide, obtain the modifier P2D of P1-2.The k value of P2D is in table 1.
Embodiment 5
Take 1000 grams of P1-2, dodge dry 10 minutes in 650 DEG C, obtain the modifier P2E of P1-2.The k value of P2E is in table 1.
Table 1
| Embodiment | Raw material | k |
| 1 | P2A | 0.5 |
| 2 | P2B | 0.4 |
| 3 | P2C | 0.4 |
| 4 | P2D | 0 |
| 5 | P2E | 0.3 |
Embodiment 6-13 illustrates the preparation method of preparation carriers for catalysts of the present invention.Comparative example 1-2 illustrates the preparation method of conventional catalyst carrier.
Embodiment 6
Take 800 grams of P1-1, after 200 grams of raw material P2A Homogeneous phase mixing that embodiment 1 is obtained, add containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), the aqueous solution 1440 milliliters containing diboron trioxide 2.4g, 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 800 DEG C of roastings 3 hours, obtains carrier Z1.The character of carrier Z1 lists in table 2.
Embodiment 7
Take 200 grams of P1-1, after 800 grams of raw material P2B Homogeneous phase mixing that embodiment 2 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing diboron trioxide 2.4g, 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 840 DEG C of roastings 3 hours, obtains carrier Z2.The character of carrier Z2 lists in table 2.
Embodiment 8
Take 500 grams of P1-1, after 500 grams of raw material P2C Homogeneous phase mixing that embodiment 3 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing diboron trioxide 2.4g, 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 750 DEG C of roastings 3 hours, obtains carrier Z3.The character of carrier Z3 lists in table 2.
Comparative example 1
Take 1000 grams of P1-1, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing diboron trioxide 2.4g, 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 800 DEG C of roastings 3 hours, obtains carrier DZ1.The character of carrier DZ1 lists in table 2.
Embodiment 9
Take 800 grams of P1-2, after 200 grams of raw material P2D Homogeneous phase mixing that embodiment 4 is obtained, add containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), containing diboron trioxide 14g the aqueous solution 1440 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 800 DEG C of roastings 3 hours, obtains carrier Z4.The character of carrier Z4 lists in table 2.
Embodiment 10
Take 900 grams of P1-1, after 100 grams of raw material P2E Homogeneous phase mixing that embodiment 5 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing diboron trioxide 14g, 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 750 DEG C of roastings 3 hours, obtains carrier Z5.The character of carrier Z5 lists in table 2.
Embodiment 11
Take 850 grams of P1-2, after 150 grams of raw material P2C Homogeneous phase mixing that embodiment 3 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing diboron trioxide 14g, 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 800 DEG C of roastings 3 hours, obtains carrier Z6.The character of carrier Z6 lists in table 2.
Comparative example 2
Take 1000 grams of P1-2, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing diboron trioxide 14g, 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 800 DEG C of roastings 3 hours, obtains carrier DZ2.The character of carrier DZ2 lists in table 2.
Embodiment 12
Take 900 grams of P1-2, after 100 grams of raw material P2D Homogeneous phase mixing that embodiment 4 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing diboron trioxide 28g, 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 750 DEG C of roastings 3 hours, obtains carrier Z7.The character of carrier Z7 lists in table 2.
Embodiment 13
Take 850 grams of P1-2, after 150 grams of raw material P2E Homogeneous phase mixing that embodiment 5 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing diboron trioxide 28g, 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 830 DEG C of roastings 3 hours, obtains carrier Z8.The character of carrier Z8 lists in table 2.
Table 2
Embodiment 14-19 illustrates and the invention provides Catalysts and its preparation method.
Embodiment 14
Get 200 grams of carrier Z1, with 220 milliliters containing MoO
320 grams per liters, ammonium molybdate and the nickel nitrate mixed solution of NiO5 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst C1.The composition of C1 is listed in table 3.
Embodiment 15
Get 200 grams of carrier Z2, with 220 milliliters containing MoO
320 grams per liters, ammonium molybdate and the cobalt nitrate mixed solution of CoO 5 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst C2.The composition of C2 is listed in table 3.
Embodiment 16
Get 200 carrier Z3, with 220 milliliters containing WO
322 grams per liters, ammonium metatungstate and the nickel nitrate mixed solution of NiO 6 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst C3.The composition of C3 is listed in table 3.
Embodiment 17
Get 200 grams of carrier Z4, with 220 milliliters containing WO
322 grams per liters, ammonium metatungstate and the cobalt nitrate mixed solution of CoO 6 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst C4.The composition of C4 is listed in table 3.
Embodiment 18
Get 200 grams of carrier Z5, with 220 milliliters containing MoO
316 grams per liters, ammonium molybdate and the nickel nitrate mixed solution of NiO4 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst C5.The composition of C5 is listed in table 3.
Embodiment 19
Get 200 grams of carrier Z8, with 220 milliliters containing MoO
316 grams per liters, ammonium molybdate and the nickel nitrate mixed solution of NiO 4 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst C6.The composition of C6 is listed in table 3.
Contrast row 3
Get 200 grams of carrier DZ1, with 220 milliliters containing MoO
320 grams per liters, ammonium molybdate and the nickel nitrate mixed solution of NiO 5 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst DC1.The composition of DC1 is listed in table 3.
Contrast row 4
Get 200 grams of carrier DZ2, with 220 milliliters containing MoO
320 grams per liters, ammonium molybdate and the cobalt nitrate mixed solution of CoO 5 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst DC2.The composition of DC2 is listed in table 3.
Comparative example 5
Get 200 grams of carrier DZ1, with 220 milliliters containing WO
322 grams per liters, ammonium metatungstate and the nickel nitrate mixed solution of NiO6 grams per liter flood 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrotreating catalyst DC3.The composition of DC3 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 removing impurities matter performance of hydrotreating catalyst provided by the invention.
With a kind of inferior heavy oil for raw material (feedstock oil character is in table 4), evaluate catalysts on 100 milliliters of small fixed reactors.
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: reaction temperature 340 DEG C, hydrogen dividing potential drop 8 MPa, liquid hourly space velocity (LHSV) are 2.0 hours
-1, hydrogen to oil volume ratio is 600, reacts sample analysis after 200 hours.Evaluation result is listed in table 5.
In oil sample, the content of nickel and vanadium adopts inductive coupling plasma emission spectrograph (ICP-AES) to measure (instrument is U.S. PE company PE-5300 type plasma quantometer, and concrete grammar is shown in Petrochemical Engineering Analysis method RIPP124-90)
In oil sample, sulfur content uses coulometry to measure (concrete grammar is shown in Petrochemical Engineering Analysis method RIPP62-90).
In oil sample, carbon residue content uses microdetermination (concrete grammar is shown in Petrochemical Engineering Analysis method RIPP149-90)
Comparative example 6-8
According to the performance of method evaluation catalyst DC1, DC2 and DC3 of embodiment 20-25, the results are shown in Table 5.
Table 4
| Feedstock oil | Inferior heavy oil |
| Density (20 DEG C), kg/m 3 | 0.96 |
| Ni，μg/g | 3.2 |
| V，μg/g | 9.6 |
| S，% | 3.5 |
| CCR，% | 6.6 |
Table 5 evaluating catalyst result
Can find out compared with existing catalyst by the data of table 5, while hydrotreating catalyst provided by the invention has higher desulfurization and de-carbon residue activity, catalyst has good metal removal capacity.
Claims (20)
1. a heavy oil hydrogenating treatment catalyst, containing a kind of alumina support with structure of double peak holes of one or more adjuvant components containing being selected from boron, silicon and fluorine, characterize with mercury injection method, the pore volume of described carrier is 0.8-1.2 ml/g, and specific area is 120-400 rice
2/ gram, diameter is the 58-80% that the pore volume in 6-30nm hole accounts for total pore volume, wherein diameter is that the pore volume in 10-30nm hole is lower than 55% of total pore volume, diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume, with oxide basis and with described carrier total amount for benchmark, the content of described auxiliary agent boron, silicon is 0.5-8 % by weight, in the Oil repellent of element for 0.5-8 % by weight.
2. the catalyst according to 1, is characterized in that, the pore volume of described carrier is 0.9-1.15 ml/g, and specific area is 150-300 rice
2/ gram, diameter is the 60-75% that the pore volume in 6-30nm hole accounts for total pore volume, diameter is that the pore volume in 10-30nm hole is lower than 54% of total pore volume, diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume, with oxide basis and with described carrier total amount for benchmark, the content of described auxiliary agent boron, silicon is 1-6 % by weight, in the Oil repellent of element for 1-6 % by weight.
3. the catalyst according to 2, is characterized in that, with oxide basis and with described carrier total amount for benchmark, the content of described auxiliary agent boron, silicon is 1-4 % by weight, in the Oil repellent of element for 1-4 % by weight.
4. the catalyst according to 1, it is characterized in that, hydrogenation active metals component in described catalyst is selected from least one metal component of group VIII and at least one metal component of group VIB, be benchmark with oxide basis and with catalyst, the content of described metal component of group VIII is 0.5-10 % by weight, and the content of metal component of group VIB is 0.5-15 % by weight.
5. the catalyst according to 4, it is characterized in that, described metal component of group VIII is selected from nickel and/or cobalt, metal component of group VIB is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyst, the content of described metal component of group VIII is 0.8-8 % by weight, and the content of metal component of group VIB is 1-12 % by weight.
6. the catalyst according to 5, is characterized in that, is benchmark with oxide basis and with catalyst, and the content of described metal component of group VIII is 1-6 % by weight, and the content of metal component of group VIB is 2-10 % by weight.
7. the preparation method of catalyst according to 1, comprise and prepare carrier, the preparation method of described carrier comprises the modifier P2 of hydrated alumina P1 and P1 containing boehmite mixing and introducing is selected from boron in the mixture, one or more adjuvant components of silicon and fluorine, aftershaping, dry also roasting, wherein, with oxide basis and with described carrier total amount for benchmark, described boron, the introduction volume of silicon is 0.5-8 % by weight, in element and with described carrier total amount for benchmark, the introduction volume of described fluorine is 0.5-8 % by weight, the condition of described drying comprises: temperature is 40-350 DEG C, time is 1-24 hour, the condition of described roasting comprises: temperature is for being greater than 500 to being less than 850 DEG C, time is 1-8 hour, the Mixing ratio by weight of described P1 and P2 is 20-95:5-80, the κ value of P2 is 0 to being less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1for the sour peptization index of the hydrated alumina P1 containing boehmite, DI
2for the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite.
8. the method according to 7, is characterized in that, with oxide basis and with described carrier total amount for benchmark, the introduction volume of described boron, silicon is 1-6 % by weight, and in element and with described carrier total amount for benchmark, the introduction volume of described fluorine is 1-6 % by weight; The Mixing ratio by weight of described P1 and P2 is 70-95:5-30; The k value of described P2 is 0 to being less than or equal to 0.6; The pore volume of described P1 is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, most probable bore dia 8-30nm.
9. the method according to 8, is characterized in that, with oxide basis and with described carrier total amount for benchmark, the introduction volume of described boron, silicon is 1-4 % by weight, and in element and with described carrier total amount for benchmark, the introduction volume of described fluorine is 1-4 % by weight; The pore volume of described P1 is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, most probable bore dia 10-25nm.
10. the method according to 7 or 8 any one, is characterized in that, described P2 is 80-300 object particle.
11. methods according to 10, it is characterized in that, described P2 is 100-200 object particle.
12. methods according to 7, it is characterized in that, the condition of described drying comprises: temperature is 100-200 DEG C, and the time is 2-12 hour, and the condition of described roasting comprises: temperature is 600-800 DEG C, and roasting time is 2-6 hour.
13. methods according to 7, it is characterized in that, by shaping, dry for the described hydrated alumina P1 containing boehmite by one of P1 method being modified as P2, afterwards its all or part of carrying out is ground, sieves, obtaining powder thing is P2, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour; Two of method is article shaped roastings method one obtained, and sintering temperature is for being greater than 350 to being less than or equal to 1400 DEG C, and roasting time is 1-8 hour, and afterwards its all or part of carrying out is ground, sieved, obtaining powder thing is P2; Three of method is dodged by the hydrated alumina P1 containing boehmite to do, and dodge dry temperature for being greater than 150 to being less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour, and obtaining powder thing is P2; Four of method is mixed to get one or more in two and the modifier that obtains with three of method of one of method, method.
14. methods according to 13, 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.
15. methods according to 13 or 14, it is characterized in that, described P2 is 80-300 object particle in P1 modifier.
16. methods according to 15, it is characterized in that, described P2 is 100-200 object particle in P1 modifier.
17. methods according to 7, it is characterized in that, comprise and adopt the method for dipping on carrier, introduce hydrogenation active metals component, carry out drying afterwards, the step of roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least one the VIIIth race and the metal component of at least one group VIB, be benchmark with oxide basis and with catalyst, the consumption of the concentration of the described compound containing hydrogenation active metals in described dipping solution and described solution makes the content of the metal component of the VIIIth race in final catalyst be 0.5-10 % by weight, the content of the metal component of described group VIB is 0.5-15 % by weight, described drying condition comprises: temperature is 100-250 DEG C, and the time is 1-10 hour, described roasting condition comprises: temperature is 360-500 DEG C, and the time is 1-10 hour.
18. methods according to 17, it is characterized in that, the metal component of described VIIIth race is selected from nickel and/or cobalt, the metal component of group VIB is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyst, the consumption of the concentration of the described compound containing hydrogenation active metals in described dipping solution and described solution makes the content of the metal component of group VIII in final catalyst be 0.8-8 % by weight, and the content of the metal component of group VIB is 1-12 % by weight; Described drying condition comprises: temperature is 100-140 DEG C, and the time is 1-6 hour; Described roasting condition comprises: temperature is 360-450 DEG C, and the time is 2-6 hour.
19. methods according to 18, it is characterized in that, be benchmark with oxide basis and with catalyst, the consumption of the concentration of the described compound containing hydrogenation active metals in described dipping solution and described solution makes the content of the metal component of group VIII in final catalyst be 1-6 % by weight, and the content of the metal component of group VIB is 2-10 % by weight.
The application of hydrotreating catalyst in 20. claim 1-6 described in any one in hydrocarbon oil hydrogenation process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310432227.9A CN104437520B (en) | 2013-09-22 | 2013-09-22 | A kind of heavy oil hydrogenating treatment catalyst and preparation thereof and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310432227.9A CN104437520B (en) | 2013-09-22 | 2013-09-22 | A kind of heavy oil hydrogenating treatment catalyst and preparation thereof and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104437520A true CN104437520A (en) | 2015-03-25 |
| CN104437520B CN104437520B (en) | 2016-08-24 |
Family
ID=52884729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310432227.9A Active CN104437520B (en) | 2013-09-22 | 2013-09-22 | A kind of heavy oil hydrogenating treatment catalyst and preparation thereof and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437520B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433245A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and hydrogenation modification method of heavy distillate oil |
| CN114471632A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
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 |
| 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 |
-
2013
- 2013-09-22 CN CN201310432227.9A patent/CN104437520B/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 |
| CN1782031A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Slag oil hydro-demetallization catalyst and its preparing method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471632A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
| CN114471632B (en) * | 2020-10-23 | 2023-07-14 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
| CN114433245A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and hydrogenation modification method of heavy distillate oil |
| CN114433245B (en) * | 2020-10-30 | 2023-12-12 | 中国石油化工股份有限公司 | Catalyst carrier, hydrogenation catalyst and hydrogenation modification method of heavy distillate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104437520B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104226342A (en) | Heavy oil hydrotreating catalyst and preparation and application | |
| CN104437517A (en) | Heavy-oil hydrotreatment catalyst, and preparation and application thereof | |
| CN103357417A (en) | Guard catalyst with hydrogenation activity as well as preparation and application thereof | |
| CN103865568B (en) | VB metal component-containing hydrogenation catalyst, preparation and application thereof | |
| CN104226297A (en) | Heavy-oil hydrotreatment catalyst and preparation and application thereof | |
| CN104226323A (en) | Heavy oil hydrotreating catalyst and preparation and application | |
| CN104162437A (en) | Hydrogenation activity protection catalyst and preparation and application thereof | |
| CN104162438B (en) | A kind of hydrogenation protecting catalyst and Synthesis and applications thereof | |
| CN104437520A (en) | Heavy-oil hydrotreatment catalyst, and preparation and application thereof | |
| CN104437523A (en) | Dialkene selective hydrogenation catalyst, and preparation and application thereof | |
| CN104293389B (en) | A kind of process for hydrogenating residual oil | |
| CN103923692B (en) | A kind of hydroprocessing process of heavy raw oil | |
| CN104293390B (en) | A kind of process for hydrogenating residual oil | |
| CN104437521A (en) | Hydrocarbon-oil hydrotreatment catalyst, and preparation and application thereof | |
| CN104226298A (en) | Heavy oil hydrotreatment catalyst, and preparation and application thereof | |
| CN104368392A (en) | Hydrogenation activity protection catalyst and preparation and use thereof | |
| CN104449815A (en) | Hydrocarbon-oil hydrotreatment method | |
| CN103861602A (en) | Hydrogenation activity protection catalyst, preparation and application thereof | |
| CN104449832A (en) | Hydrogenation pretreatment method for catalytically-cracked raw oil | |
| CN104162436B (en) | A kind of hydrogenation activity guard catalyst and preparation and application thereof | |
| CN104368348A (en) | Hydrogenation activity protection catalyst and preparation and use thereof | |
| CN103861605A (en) | Hydrogenation activity protection catalyst, preparation and application thereof | |
| CN104162435B (en) | A kind of hydrogenation activity guard catalyst and preparation and application thereof | |
| CN104437579A (en) | Distillate-oil hydrofining catalyst, and preparation and application thereof | |
| CN103923697B (en) | A kind of mink cell focus hydroprocessing process of high metal content |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |