CN104324723B - A kind of hydrogenation protecting catalyst and preparation method and application - Google Patents
A kind of hydrogenation protecting catalyst and preparation method and application Download PDFInfo
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Abstract
A kind of hydrogenation protecting catalyst and preparation method and application; the catalyst contains the hydrogenation active metals component of carrier and load on this carrier; wherein; the carrier contains aluminum oxide and alkaline earth metal component; characterized with mercury injection method; the pore volume of the carrier is 0.5-1 mls/g, and specific surface area is 30-150 meters2/ gram, most probable pore size is 80-300nm, the carrier is in bimodal pore distribution in a diameter of 12-15nm and a diameter of 100-200nm, the pore volume in a diameter of 12-15nm holes accounts for the 10-22% of total pore volume, the pore volume in a diameter of 100-200nm holes accounts for the 40-70% of total pore volume, the hydrogenation active metals component is selected from least one metal component of group VIII and at least one Group VB metal component, counted by oxide and on the basis of catalyst, the content of the metal component of group VIII is to less than or equal to 0.8 weight % more than 0, the content of Group VB metal component is to less than or equal to 5 weight % more than 0.Compared with prior art, the hydrogenation protecting catalyst that the present invention is provided, which has, preferably holds metallicity.
Description
Technical field
The present invention relates to a kind of hydrogenation protecting catalyst and preparation method and application.
Background technology
As crude quality is deteriorated, the impurity content such as colloid, asphalitine and organo-metallic compound increases in crude oil, and the presence of these impurity easily causes the rapid decrease of catalyst activity so that inactivation.The effective ways for solving this problem are to load the protective agent with hydrogenation activity on hydrogenation catalyst bed top.Hydrogenation protecting catalyst with larger pore volume and bore dia holds metal and holds charcoal ability by force, can play a part of protecting downstream hydrogenation host, extend the service life of host.
In the prior art on hydrogenation protecting catalyst and its example of preparation such as：
CN200610113493.5 discloses a kind of hydrogenation protecting agent and its preparation; the protective agent contains one or more of porous heat-resistant inorganic oxides; it is characterized in that; the total pore volume of the protective agent is 0.3-1.5 millimeter/gram; wherein contain grade macropore; grade macropore bore dia is 0.1~1.5 micron, and grade macropore pore volume is 0.05~0.7 ml/g.The preparation method of the hydrogenation protecting agent; including the precursor of one or more of porous heat-resistant inorganic oxides and/or porous heat-resistant inorganic oxide is mixed, is molded, dried and is calcined with least one organic matter; wherein, the organic compound is fusing point between 30~200 DEG C, 0.3~2.5 millimeter of particle diameter and water insoluble solid particle.
CN201010220850.4 discloses a kind of protectant preparation method of hydrotreating.Alumina support is prepared using two kinds of different boehmite dry glue powder kneading methods in this method, then supported active metals；Wherein the first crystallization degree of pseudo-boehmite is relatively small, pore volume is big, bore dia 30nm~100nm hole can be provided, second of crystallization degree of pseudo-boehmite is of a relatively high, it is possible to provide micron-sized hole, and because its acidity indexes is high, extremely hard bulk is showed after drying, 100% by 50 mesh after being crushed, and can not only increase the quantity of micrometer grade hole, can also improve the intensity of catalyst carrier.By the mixed proportion of adjustment between the two, intensity height, the hydrotreating protective agent that bulk density is big, pore volume is big and wear rate is low can be made.
CN98111379.6 discloses hydrogenation protecting catalyst and preparation method thereof, and the catalyst carrier is ultra-large aperture, and aperture is 0.1-30 μm of bimodal hole, and catalyst pore volume is 0.1-0.8ml/g, than surface 0.1-20m2/ g, the 6.65m%-20.0m of metallic element containing group vib and/or VIII race's metallic element 8.71%, -26.13m%.Preparation method is to prepare alumina support using the particle method of piling up, and is then calcined 2-5h at 500-550 DEG C in 100-120 DEG C of dry 2-5h using the catalyst contained after molybdenum solution and solution containing nickel equivalent impregnation, dipping.
CN00110019.X is disclosed contains the aluminum oxide of γ mono- and δ-aluminum oxide simultaneously in a kind of Hydrogenation active protective agent and preparation method thereof, protective agent used carrier;The 3-22m% of metal oxide containing group vib and VIII family metal oxide 0.5-5m% in protective agent, family metal oxide containing IA 0-2m%, phosphorous 0-3m%, than surface 100-250m2/g.Pore volume 0.4-0.8ml/g.
CN200910206230.2 discloses a kind of hydrotreating guard catalyst for residual oil and its application.The catalyst pore volume is big, and aperture is big, and porosity is high, and reasonable pore distribution, outer surface orifice is larger, and duct penetrability is good, and more than 1000nm contains more than 36% in duct.Whole beds are homogeneously precipitated in particular for metal that abjection in residue fixed-bed hydrogenation method, can be made, impurity vanadium and calcium can be deposited in inside duct, improve the utilization rate of hole, keep long-term operation.
CN100577288C discloses a kind of hydrogenation protecting agent and preparation method thereof; the protective agent contains one or more porous heat-resistant inorganic oxides; it is characterized in that; the total pore volume of the protective agent is 0.3~1.5 millimeter/gram; wherein contain grade macropore; grade macropore bore dia is 0.1~1.5 micron, and grade macropore pore volume is 0.05~0.7 ml/g.The hydrogenation protecting agent contain at least one group ia and（Or）Group iia metal component, is counted by oxide and on the basis of the protective agent, and the introduction volume of the metal component makes the content of metal component described in final protective agent be not more than 5 weight %.
The problem of above-mentioned prior art is directed in hydrogenation protecting catalyst use, gives a variety of solutions.But, when this kind of catalyst is used for into processing of heavy oil, its performance still suffers from the space of significant improvement.
The content of the invention
The technical problem to be solved in the present invention is to provide it is a kind of it is new, hold higher hydrogenation protecting catalyst of metal ability and preparation method and application.
Usually, preparing hydrogenation protecting catalyst carrier has bimodal porous.It was found by the inventors of the present invention that the aluminum oxide article shaped with bimodal porous of prior art offer is the characteristics of universal, the aperture of the aperture portion in bimodal hole or smaller（For example, less than 10nm,）, the aperture of macroperforation or bigger than normal（For example, more than 1000nm disclosed in CN200910206230.2）.When this kind of carrier to be used to prepare hydrogenation protecting catalyst, it holds metallicity and still suffers from very big improved space.
Content of the present invention includes：
1st, a kind of hydrogenation protecting catalyst, the hydrogenation active metals component containing carrier and load on this carrier, wherein; the carrier contains aluminum oxide and alkaline earth metal component; characterized with mercury injection method, the pore volume of the carrier is 0.5-1 mls/g, and specific surface area is 30-150 meters2/ gram, most probable pore size is 80-300nm, the carrier is in bimodal pore distribution in a diameter of 12-15nm and a diameter of 100-200nm, the pore volume in a diameter of 12-15nm holes accounts for the 10-22% of total pore volume, the pore volume in a diameter of 100-200nm holes accounts for the 40-70% of total pore volume, the hydrogenation active metals component is selected from least one metal component of group VIII and at least one Group VB metal component, counted by oxide and on the basis of catalyst, the content of the metal component of group VIII is to less than or equal to 0.8 weight % more than 0, the content of Group VB metal component is to less than or equal to 5 weight % more than 0.
2nd, the catalyst according to 1, it is characterised in that the pore volume of the carrier is 0.5-0.8 mls/g, specific surface area is 50-130 meters2/ gram, most probable pore size is 80-280nm, and the pore volume in a diameter of 12-15nm holes accounts for the 10-20% of total pore volume, and the pore volume in a diameter of 100-2.00nm holes accounts for the 45-70% of total pore volume；The metal component of group VIII is selected from nickel and/or cobalt, and Group VB metal component is selected from vanadium and/or niobium, counted by oxide and on the basis of catalyst, and the content of the metal component of group VIII is 0.1-0.7 weight %, and the content of Group VB metal component is 1-4 weight %.
3. the catalyst according to 2, it is characterised in that counted by oxide and on the basis of catalyst, the content of VIII race metal component is 0.1-0.6 weight %, and the content of the Vth B races metal component is 1.5-3.5 weight %.
4th, the catalyst according to 1, it is characterised in that the alkaline-earth metal is selected from the one or more in beryllium, magnesium, calcium, strontium and barium, on the basis of the carrier and in terms of oxide, the content of alkaline-earth metal is 0.1-6 weight % in the carrier.
5th, the catalyst according to 4, it is characterised in that the alkaline earth metal component is magnesium, on the basis of the carrier and in terms of oxide, the content of alkaline-earth metal is 0.3-4 weight % in the carrier.
6th, the catalyst according to 5, it is characterised in that on the basis of the carrier and in terms of oxide, the content of alkaline-earth metal is 0.5-2.5 weight % in the carrier.
7th, a kind of preparation method of hydrogenation protecting catalyst, comprises the following steps：
（1）Prepare carrier, including a kind of hydrated alumina to be mixed to and introduced in the mixture the compound of alkaline including earth metal component, shaping, drying with a kind of Alpha-alumina and is calcined, wherein, the sintering temperature is 750-1000 DEG C, roasting time is 1-10 hours, and the hydrated alumina counted using butt and the mixing ratio of Alpha-alumina is 20-75:25-80, the pore volume of the hydrated alumina is 0.9-1.4 mls/g, is 100-350 meters than surface2/ gram, most probable bore dia 8-30nm；
（2）In step（1）Hydrogenation active metals component is introduced on obtained carrier, the hydrogenation active metals component is selected from least one metal component of group VIII and at least one Group VB metal component, counted by oxide and on the basis of catalyst, the introduction volume of the metal component of group VIII makes the content of the metal component of group VIII in final catalyst be to less than or equal to 0.8 weight % more than 0, the introduction volume of the Group VB metal component makes the content of the Group VB metal component in final catalyst be to less than or equal to 5 weight % more than 0, dry and be calcined afterwards, described drying condition includes：Temperature is 100-250 DEG C, and the time is 1-10 hours, and roasting condition includes：Temperature is 360-500 DEG C, and the time is 1-10 hours.
8th, the method according to 7, it is characterised in that the step（1）In sintering temperature be 800-950 DEG C, roasting time be 2-8 hours, the hydrated alumina counted using butt and the mixing ratio of Alpha-alumina is 30-70:30-70, the pore volume of the hydrated alumina is 0.95-1.3 mls/g, is 120-300 meters than surface2/ gram, most probable bore dia 10-25nm；The metal component of VIIIth race is selected from nickel and/or cobalt, the metal component of Group VB is selected from vanadium and/or niobium, counted by oxide and on the basis of catalyst, the introduction volume of the metal component of group VIII makes the content of the metal component of group VIII in final catalyst be 0.1-0.7 weight %, the introduction volume of the Group VB metal component makes the content of the Group VB metal component in final catalyst be 1-4 weight %, the step（2）Drying condition include：Temperature is 100-140 DEG C.
9th, the method according to 8, it is characterized in that, the introduction volume of the metal component of group VIII makes the content of the metal component of group VIII in final catalyst be 0.2-0.6 weight %, and the introduction volume of the Group VB metal component makes the content of the Group VB metal component in final catalyst be 1.5-3.5 weight %.
10. the method according to 6,7 or 8 any one, it is characterised in that the method that hydrogenation active metals component is introduced on carrier is infusion process.
11st, the method according to 7 or 8, it is characterised in that the hydrated alumina is selected from boehmite.
12nd, the method according to 7, it is characterised in that counted by oxide and on the basis of the carrier, the introduction volume of the compound of the alkaline including earth metal component makes the content of alkaline earth metal component in final carrier be 0.1-6 weight %.
13rd, the method according to 12, it is characterised in that counted by oxide and on the basis of the carrier, the introduction volume of the compound of the alkaline including earth metal component makes the content of alkaline earth metal component in final carrier be 0.3-4 weight %.
14th, the method according to 13, it is characterised in that counted by oxide and on the basis of the carrier, the introduction volume of the compound of the alkaline including earth metal component makes the content of alkaline earth metal component in final carrier be 0.5-2.5 weight %.
15. application of the hydrogenation activity guard catalyst in hydrocarbon oil hydrogenation processing in claim 1-6 described in any one.
The catalyst provided according to the present invention, wherein, characterized with mercury injection method, the pore volume of the shaping carrier is 0.5-1 mls/g, and specific surface area is 30-150 meters2/ gram, wherein, the pore volume in a diameter of 12-15nm holes accounts for the 10-22% of total pore volume, and the pore volume in a diameter of 100-200nm holes accounts for the 40-70% of total pore volume；It is preferred that the pore volume of the shaping carrier is 0.5-0.8 mls/g, specific surface area is 50-130 meters2/ gram, wherein, the pore volume in a diameter of 12-15nm holes accounts for the 10-20% of total pore volume, and the pore volume in a diameter of 100-200nm holes accounts for the 45-70% of total pore volume.
The hydrogenation protecting catalyst provided according to the present invention; wherein; the preferred metal component of group VIII of hydrogenation active metals component is cobalt and/or nickel; the metal component of Group VB is vanadium and/or niobium; counted by oxide and on the basis of catalyst; the content of the metal component of group VIII is to less than or equal to 0.8 weight % more than 0; it is preferred that 0.1-0.7 weight %; more preferably 0.2-0.6 weight %; the content of the Group VB metal component is to less than or equal to 4 weight % more than 0; it is preferred that 1-4 weight %, more preferably 1.5-3.5 weight %.
On the premise of being enough described hydrogenation active metals component being carried on the carrier, the carrying method is not particularly limited the present invention, it is preferred that method be infusion process, include prepare containing the metal compound dipping solution, afterwards with the solution impregnate described in carrier.Described dipping method is conventional method, for example, it may be excessive immersion stain, hole saturation infusion process.The described one or more contained in soluble compound of the metal component compound selected from V B races in them, for example, can be selected from the one or more in such as vanadic anhydride, ammonium vanadate, ammonium metavanadate, vanadic sulfate, vanadium heteropoly acid, ammonium metavanadate preferably wherein, ammonium vanadate.The described one or more contained in soluble compound of the compound selected from them selected from VIII race's metal component, one or more in such as soluble complexes of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt, preferably cobalt nitrate, basic cobaltous carbonate；One or more in nickel nitrate, nickel acetate, basic nickel carbonate, the soluble complexes of nickel chloride and nickel, preferably nickel nitrate, basic nickel carbonate.
The catalyst provided according to the present invention, containing any performance for not influenceing the present invention to provide catalyst or can also can improve the adjuvant component for the catalyst performance that the present invention is provided.Phosphorus component can such as be contained, counted by element and on the basis of catalyst, the content of the auxiliary agent is no more than 10 weight %, preferably 0.5-5 weight %.
The preparation method of the hydrogenation protecting catalyst provided according to the present invention; the preparation method of wherein described carrier; including a kind of hydrated alumina to be mixed to and introduced in the mixture the compound of alkaline including earth metal component, shaping, drying with a kind of Alpha-alumina and is calcined; sintering temperature is 750-1000 DEG C; preferably 800-950 DEG C, roasting time is 1-10 hours, preferably 2-8 hours; wherein, the hydrated alumina and the mixing ratio of Alpha-alumina counted using butt is 20-75:25-80（Wherein, 20-75 refers to hydrated alumina parts per hundred parts（In terms of butt）With in the mixture of Alpha-alumina, the value of hydrated alumina number changes between 20-75, and 25-80 refers to hydrated alumina parts per hundred parts（In terms of butt）With in the mixture of Alpha-alumina, the value of Alpha-alumina number changes between 25-80）, preferably 30-70:30-70.The pore volume of the hydrated alumina is 0.9-1.4 mls/g, and preferably 0.95-1.3 mls/g, be 100-350 meters than surface2/ gram, preferably 120-300 meters2/ gram, most probable bore dia is 8-30nm, preferably 10-25nm.The method that alkaline including earth metal component composition is introduced into the hydrated alumina and Alpha-alumina mixture is conventional method, for example, it may be directly by the compound of the desired amount of alkaline including earth metal component in foregoing hydrated alumina with being mixed into Alpha-alumina mixed process.
Specific the embodiment of carrier is prepared at one, the method that alkaline including earth metal component composition is introduced into the hydrated alumina and Alpha-alumina mixture is that alkaline including earth metal component composition is configured into the aqueous solution, the aqueous solution is mixed into while the hydrated alumina is mixed with Alpha-alumina or is again mixed into the aqueous solution after the hydrated alumina is mixed with Alpha-alumina, aftershaping, drying and be calcined.The alkaline including earth metal component composition can be the one or more in the water soluble compound of arbitrary alkaline including earth metal component.For example, the one or more in the water-soluble inorganic salt of alkaline including earth metal component.
The Alpha-alumina can be commercially available commodity（Commodity alpha-alumina）Or by hydrated alumina（Alumina hydrate powder）Obtained through high-temperature roasting.It is being enough hydrated alumina roasting phase transformation being converted under conditions of Alpha-alumina, this process can be realized using arbitrary existing method, not limit this present invention.
On the premise of being enough to make final carrier meet application claims, the present invention is not specially required to the hydrated alumina, can be hydrated alumina prepared by any prior art.It is preferred that hydrated alumina be selected from pore volume be 0.9-1.4 mls/g, more preferably 0.95-1.3 mls/g, than surface be 100-350 meters2/ gram, more preferably 120-300 meters2/ gram, most can and bore dia 8-30nm, more preferably 10-25nm hydrated alumina；Further preferred hydrated alumina is the hydrated alumina containing boehmite.Here, the pore volume of the hydrated alumina, specific surface area and most can and aperture, be by the hydrated alumina in 600 DEG C roasting 4 hours after, by BET nitrogen absorption under low temperature characterize obtain.
The mixing of the hydrated alumina and Alpha-alumina uses conventional method, and meets the mixing ratio of the hydrated alumina counted using butt and Alpha-alumina as 20-75:25-80, preferably 30-70:30-70.
The carrier in the present invention, various easily operated shaping carriers, such as spherical, cellular, nest like, tablet or bar shaped are can be made into depending on different requirements（Clover, butterfly, cylinder etc.）.Shaping can be carried out according to a conventional method.In shaping, such as extruded moulding, to ensure that the shaping is smoothed out, can add water, extrusion aid and/or adhesive, with or without expanding agent, then extrusion molding is dried and is calcined afterwards into described mixture.The extrusion aid, the species of peptizing agent and consumption are known to those skilled in the art, such as common extrusion aid can be selected from the one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH, the peptizing agent can be inorganic acid and/or organic acid, and described expanding agent can be the one or more in starch, synthetic cellulose, polymeric alcohol and surfactant.Synthetic cellulose therein is preferably the one or more in hydroxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably the one or more in the one or more in polyethylene glycol, poly- propyl alcohol, polyvinyl alcohol, surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and its derivative, molecular weight is 200-10000 propylene alcohol copolymer and maleic acid copolymer.
In the present invention, the shaping, the method dried and be calcined are conventional method.Wherein, it is 750-1000 DEG C that the condition of roasting, which preferably includes sintering temperature, and roasting time is 1-10 hours, and it is 800-950 DEG C that the condition being further preferably calcined, which includes sintering temperature, and roasting time is 2-8 hours.
The preparation method provided according to the present invention, when also containing in the catalyst selected from components such as phosphorus, the step of also including introducing the components such as phosphorus, the introducing method of the components such as the phosphorus can pass through number of ways, for example, it may be the compound containing the auxiliary agent is directly mixed, is molded and is calcined with the mixture of Alpha-alumina with hydrated alumina；Can be that the compound containing the auxiliary agent and the compound containing hydrogenation active metals component are configured to after mixed solution to contact with the carrier；It can also be individually to prepare the compound containing auxiliary agent after solution and contact and be calcined with the carrier.When auxiliary agent and hydrogenation active metals introduce the carrier respectively, it is preferred that contacted and be calcined with the carrier with containing auxiliary compound solution first, the solution again with the compound containing hydrogenation active metals component is contacted afterwards, for example pass through the method for dipping, the sintering temperature is 250-600 DEG C, preferably 350-500 DEG C, roasting time is 2-8 hours, preferably 3-6 hours.
According to the conventional method in this area, the hydrotreating catalyst is before the use, generally can be in presence of hydrogen, at a temperature of 140-370 DEG C presulfurization is carried out with sulphur, hydrogen sulfide or containing sulfur feedstock, this presulfurization can carry out also In-situ sulphiding in device outside device, and the active metal component that it is loaded is converted into metal sulfide component.
The protective agent when protective agent that the present invention is provided as heavier hydrocarbon feeds suitable for being processed; the heavy raw oil for the high nitrogen high metal content of work high-sulfur inferior that is particularly suitable for use in also includes the protective agent of decompression residuum; the protective agent is loaded on hydrogenation catalyst top; the problem of industrial hydrogenation plant bed fouling, blocking can effectively be solved, pressure drop is excessive and be forced shut-down, extends the service life of downstream hydrogenation catalyst.
Embodiment
The present invention is described further for following example.
Agents useful for same in example, except as expressly described, is chemically pure reagent.
Press mercury method（RIPP149-90）Determine specific surface area, pore volume and pore size distribution of aluminum oxide shaping carrier etc.（Yang Cui is fixed etc., Petrochemical Engineering Analysis method, publishing house of the academy of sciences, 1990, the 421-423 pages）.
BET nitrogen absorption under low temperature methods（RIPP151-90）Determine specific surface area, pore volume and pore size distribution of hydrated alumina etc.（Yang Cui is fixed etc., Petrochemical Engineering Analysis method, publishing house of the academy of sciences, 1990, the 424-426 pages）.
Butt assay method, in 600 DEG C of roasting temperature 4h, afterwards, calculates the mass percent of sample and sample before roasting after roasting, is the butt of the sample to take appropriate amount of sample.
Using XRF methods（RIPP132-90）Determine constituent content in solid sample（Yang Cui is fixed etc., Petrochemical Engineering Analysis method, publishing house of the academy of sciences, 1990, the 371-375 pages）.
Embodiment 1-5 illustrates to prepare carrier of catalyst of the present invention and preparation method thereof.
Embodiment 1
Weigh 200g hydrated aluminas（Chang Ling oil refining catalyst factory is available commercially from, butt is 65 weight %.Pore volume is 1.05 mls/g, and specific surface area is 230 meters2/ gram, most probable bore dia is 20nm）, 70 grams of alpha-aluminas（Formed within 6 hours in roasting at 1400 DEG C by the hydrated alumina used in the present embodiment）, 9 grams of sesbania powders and magnesium carbonate（AlfaAesar (Tianjin) Chemical Co., Ltd.）10 grams of mixing, add 330 milliliters of the aqueous solution containing 7.5 grams of nitric acid afterwards, after being well mixed, kneading and extruded in double screw banded extruder with φ 2.0mm cylindrical orifice plate, afterwards, wet bar is dried 4 hours through 120 DEG C and is calcined 2 hours after 850 DEG C, obtains carrier T-1 of the present invention.Measure carrier T-1 ratio surface, can several apertures, pore volume, pore size distribution, the results are shown in Table 1.
Embodiment 2
Weigh 180g dry glue powders（Chang Ling oil refining catalyst factory is available commercially from, butt is 65 weight %.Pore volume is 1.05 mls/g, and specific surface area is 285 meters2/ gram, most probable bore dia is 20nm）, 120 grams of alpha-aluminas（It is available commercially from Beijing Shun Chuan Environmental Protection Technology Co., Ltd）, 9 grams of sesbania powders and 5 grams of magnesium nitrates（AlfaAesar (Tianjin) Chemical Co., Ltd.）Mixing, adds 330 milliliters of the aqueous solution containing 8.0 grams of acetic acid afterwards, kneading and is extruded after being well mixed in double screw banded extruder with φ 2.0mm cylindrical orifice plate, afterwards, and wet bar dries 4 hours after 850 DEG C of roastings 2 hours through 120 DEG C, obtains carrier T-2 of the present invention.Measure carrier T-2 ratio surface, can several apertures, pore volume, pore size distribution, the results are shown in Table 1.
Embodiment 3
Weigh 150g dry glue powders（Yantai Heng Hui Chemical Co., Ltd.s are available commercially from, butt is 68 weight %.Pore volume is 1.08 mls/g, and specific surface area is 188 meters2/ gram, most probable bore dia is 22nm）, 150 grams of alpha-aluminas（It is available commercially from Beijing Shun Chuan Environmental Protection Technology Co., Ltd）, 9 grams of sesbania powders, 9 grams of methylcellulose and 5.0 grams of calcium carbonate（Chemical Reagent Co., Ltd., Sinopharm Group）Mixing, adds 300 milliliters of the aqueous solution containing 10 grams of nitric acid afterwards, is molded after being well mixed according to roller forming method, obtains particle diameter for 5.5-6.5mm spheric granules.Wet bar is dried 4 hours through 120 DEG C and is calcined 2 hours after 800 DEG C, obtains carrier T-3 of the present invention.Measure carrier T-3 ratio surface, can several apertures, pore volume, pore size distribution, the results are shown in Table 1.
Embodiment 4
Weigh 260g dry glue powders（Chang Ling oil refining catalyst factory is available commercially from, butt is 65 weight %.Pore volume is 1.05 mls/g, and specific surface area is 220 meters2/ gram, most probable bore dia is 20nm）, 140 grams of alpha-aluminas（Be the same as Example 1）, 9 grams of sesbania powders, 9 grams of methylcellulose and 4.8 grams of magnesium hydroxides（Chemical Reagent Co., Ltd., Sinopharm Group）Mixing, add afterwards 5% 300 milliliters of ammonia spirit, kneading and extruded after being well mixed in double screw banded extruder with φ 2.0mm cylindrical orifice plate, wet bar dries 4 hours after 800 DEG C of roastings 2 hours through 120 DEG C, obtains carrier T-4 of the present invention.Measure carrier T-4 ratio surface, can several apertures, pore volume, the results are shown in Table 1.
Embodiment 5
Weigh 260g dry glue powders（Yantai Heng Hui Chemical Co., Ltd.s are available commercially from, butt is 68 weight %.Pore volume is 1.08 mls/g, and specific surface area is 200 meters2/ gram, most probable bore dia is 22nm）, 140 grams of alpha-aluminas（Be the same as Example 1）, 9 grams of sesbania powders, 9 grams of methylcellulose mixing adds 300 milliliters of the aqueous solution containing 10 grams of nitric acid afterwards, and extruded moulding after being well mixed, wet bar is dried 4 hours through 120 DEG C and is calcined 2 hours after 800 DEG C, obtains carrier T-4 of the present invention.Measure carrier T-4 ratio surface, can several apertures, pore volume, the results are shown in Table 1.
Comparative example 1-4 explanations prepare reference catalyst carrier and preparation method thereof.
Comparative example 1
Weigh 300 grams of dry glue powders（Chang Ling oil refining catalyst factory is available commercially from, butt is 65 weight %.Pore volume is 0.8 ml/g, and specific surface area is 320 meters2/ gram, most probable bore dia is 10nm）, 9 grams of sesbania powders, it is well mixed after add 360 milliliters of mixed-formings of solution containing 12 grams of nitric acid, wet bar is dried 4 hours through 120 DEG C and is calcined 2 hours after in 850 DEG C, obtains carrier D-1.Measure carrier D-1 ratio surface, can several apertures, pore volume, the results are shown in Table 1.
Comparative example 2
Weigh 300 grams of dry glue powders（Chang Ling oil refining catalyst factory is available commercially from, butt is 65 weight %.Pore volume is 0.8 ml/g, and specific surface area is 303 meters2/ gram, most probable bore dia is 11nm）, 9 grams of sesbania powders, it is well mixed after add 360 milliliters of mixed-formings of solution containing 12 grams of nitric acid, wet bar is dried 4 hours through 120 DEG C and is calcined 2 hours after in 950 DEG C, obtains carrier D-2.Measure carrier D-2 ratio surface, can several apertures, pore volume, the results are shown in Table 1.
Comparative example 3
Weigh dry glue powder（Chang Ling oil refining catalyst factory is available commercially from, butt is 65 weight %.Pore volume is 0.8 ml/g, and specific surface area is 290 meters2/ gram, most probable bore dia is 11nm）300 grams, add 24 grams of carbon black powder, 12 grams of mixing of sesbania powder, 360 milliliters of the aqueous solution for 85 weight % 2.4 grams of phosphoric acid containing concentration is added afterwards, kneading 15 minutes, Φ 1.5mm butterfly bar is extruded on double screw banded extruder, wet bar is dried 4 hours through 120 DEG C and is calcined 2 hours after 850 DEG C, obtains carrier D-3.Measure carrier D-3 ratio surface, can several apertures, pore volume, the results are shown in Table 1.
Comparative example 4
Weigh 300 grams of dry glue powders（Chang Ling oil refining catalyst factory is available commercially from, butt is 65 weight %.Pore volume is 0.65 ml/g, and specific surface area is 288 meters2/ gram, most probable bore dia is 9nm）, 9 grams of sesbania powders, addition contains magnesium nitrate after being well mixed（AlfaAesar (Tianjin) Chemical Co., Ltd.）6 grams 360 milliliters of mixed-formings of solution, wet bar is dried 4 hours through 120 DEG C and is calcined 2 hours after in 950 DEG C, obtains carrier D-4.Measure carrier D-4 ratio surface, can several apertures, pore volume, the results are shown in Table 1.
Table 1
Embodiment 6-10 is the explanation present invention provide catalyst and preparation method thereof.
Embodiment 6
100 grams of carrier T1 are taken, contain V with 110 milliliters2O528.6 g/l, NiO5 g/l of ammonium metavanadate and nickel nitrate mixed solution impregnates 1 hour, and 120 DEG C dry 4 hours, and 400 DEG C are calcined 3 hours, obtain hydrogenation protecting catalyst C1 of the present invention.Wherein, the content of hydrogenation active metals component is listed in table 2.
Embodiment 7
100 grams of carrier T2 are taken, contain V with 110 milliliters2O528.6 g/l, CoO5 g/l of ammonium metavanadate and cobalt nitrate mixed solution impregnates 1 hour, and 120 DEG C dry 4 hours, and 400 DEG C are calcined 3 hours, obtain hydrogenation protecting catalyst C2 of the present invention.Wherein, the content of hydrogenation active metals component is listed in table 2.
Embodiment 8
100 carrier T3 are taken, contain V with 110 milliliters2O525 g/l, NiO3 g/l of ammonium metavanadate and nickel nitrate mixed solution impregnates 1 hour, and 120 DEG C dry 4 hours, and 400 DEG C are calcined 3 hours, obtain hydrogenation protecting catalyst C3 of the present invention.Wherein, the content of hydrogenation active metals component is listed in table 2.
Embodiment 9
100 grams of carrier T4 are taken, contain V with 110 milliliters2O525 g/l, CoO3 g/l of ammonium metavanadate and cobalt nitrate mixed solution impregnates 1 hour, and 120 DEG C dry 4 hours, and 400 DEG C are calcined 3 hours, obtain hydrogenation protecting catalyst C4 of the present invention.Wherein, the content of hydrogenation active metals component is listed in table 2.
Embodiment 10
100 grams of carrier T5 are taken, contain V with 110 milliliters2O519.0 g/l, NiO2 g/l of ammonium metavanadate and nickel nitrate mixed solution impregnates 1 hour, and 120 DEG C dry 4 hours, and 400 DEG C are calcined 3 hours, obtain hydrogenation protecting catalyst C5 of the present invention.Wherein, the content of hydrogenation active metals component is listed in table 2.
Contrast row 5
100 grams of carrier D1 are taken, contain V with 110 milliliters2O528.6 g/l, NiO5 g/l of ammonium metavanadate and nickel nitrate mixed solution impregnates 1 hour, and 120 DEG C dry 4 hours, and 400 DEG C are calcined 3 hours, obtain hydrogenation protecting catalyst DC1.Wherein, the content of hydrogenation active metals component is listed in table 2.
Comparative example 6
100 grams of carrier D4 are taken, contain V with 110 milliliters2O525 g/l, NiO3 g/l of ammonium metavanadate and nickel nitrate mixed solution impregnates 1 hour, and 120 DEG C dry 4 hours, and 400 DEG C are calcined 3 hours, obtain hydrogenation protecting catalyst DC2.Wherein, the content of hydrogenation active metals component is listed in table 2.
Table 2
Embodiment 11-12 illustrates that the present invention provides the performance of hydrogenation protecting agent.
Embodiment 11
Protective agent TC-1 is evaluated on 200ml medium-sized evaluating apparatus, raw materials used oil is decompression residuum, and wherein Fe contents are that 50 μ g/g, Ca contents are 25 μ g/g.Appreciation condition is 375 DEG C of reaction temperature, hydrogen dividing potential drop 13MPa, volume space velocity 0.6h-1, hydrogen to oil volume ratio 600.Fe, Ca deposition and coke content in sampling analysis protective agent after evaluating 3 months.As a result it is listed in table 3.
Using XRF methods（XRF semi-quantitative analyses（B-U））Determine element of Fe, Ca contents in solid sample.
Using infrared absorption method（RIPP106-90）Determine carbon deposit content in protective agent（Yang Cui is fixed etc., Petrochemical Engineering Analysis method, publishing house of the academy of sciences, page 1990,302）.
Embodiment 12
According to the identical condition evaluating protective agent TC-2 of example 11, Fe, Ca deposition and coke content in sampling analysis protective agent after evaluating 3 months.As a result it is listed in table 3.
Comparative example 7-8 illustrates the performance of reference catalyst.
Comparative example 7
According to the identical condition evaluating DC-1 of example 11.Fe, Ca deposition and coke content in sampling analysis protective agent after evaluating 3 months.As a result it is listed in table 3.
Comparative example 8
According to the identical condition evaluating DC-2 of example 11.Fe, Ca deposition and coke content in sampling analysis protective agent after evaluating 3 months.As a result it is listed in table 3.
Table 3
| Example number | Catalyst is numbered | Fe, Ca deposit total amount, w% | Carbon content, w% |
| Embodiment 11 | TC-1 | 14.25 | 15.02 |
| Embodiment 12 | TC-2 | 14.28 | 14.83 |
| Comparative example 7 | DC-1 | 11.60 | 17.98 |
| Comparative example 8 | DC-2 | 10.12 | 18.69 |
Above evaluation result shows, compared with the hydrogenation protecting agent that prior art is provided, and the protective agent prepared by carrier that the present invention is provided holds metal ability and significantly improves and have certain anti-carbon deposition ability.
Claims (15)
1. a kind of hydrogenation protecting catalyst, the hydrogenation active metals component containing carrier and load on this carrier, wherein; the carrier contains aluminum oxide and alkaline earth metal component; characterized with mercury injection method, the pore volume of the carrier is 0.5-1 mls/g, and specific surface area is 30-150 meters2/ gram, most probable pore size is 80-300nm, the carrier is in bimodal pore distribution in a diameter of 12-15nm and a diameter of 100-200nm, the pore volume in a diameter of 12-15nm holes accounts for the 10-22% of total pore volume, the pore volume in a diameter of 100-200nm holes accounts for the 40-70% of total pore volume, the hydrogenation active metals component is selected from least one metal component of group VIII and at least one Group VB metal component, counted by oxide and on the basis of catalyst, the content of the metal component of group VIII is to less than or equal to 0.8 weight % more than 0, the content of Group VB metal component is to less than or equal to 5 weight % more than 0.
2. catalyst according to claim 1, it is characterised in that the pore volume of the carrier is 0.5-0.8 mls/g, specific surface area is 50-130 meters2/ gram, most probable pore size is 80-280nm, and the pore volume in a diameter of 12-15nm holes accounts for the 10-20% of total pore volume, and the pore volume in a diameter of 100-200nm holes accounts for the 45-70% of total pore volume；The metal component of group VIII is selected from nickel and/or cobalt, and Group VB metal component is selected from vanadium and/or niobium, counted by oxide and on the basis of catalyst, and the content of the metal component of group VIII is 0.1-0.7 weight %, and the content of Group VB metal component is 1-4 weight %.
3. catalyst according to claim 2, it is characterised in that counted by oxide and on the basis of catalyst, the content of VIII race metal component is 0.1-0.6 weight %, and the content of the Vth B races metal component is 1.5-3.5 weight %.
4. catalyst according to claim 1, it is characterised in that one or more of the alkaline earth metal component in beryllium, magnesium, calcium, strontium and barium, on the basis of the carrier and in terms of oxide, the content of alkaline-earth metal is 0.1-6 weight % in the carrier.
5. catalyst according to claim 4, it is characterised in that the alkaline earth metal component is magnesium, on the basis of the carrier and in terms of oxide, the content of alkaline-earth metal is 0.3-4 weight % in the carrier.
6. catalyst according to claim 5, it is characterised in that on the basis of the carrier and in terms of oxide, the content of alkaline-earth metal is 0.5-2.5 weight % in the carrier.
7. a kind of preparation method of hydrogenation protecting catalyst, comprises the following steps：
(1) carrier is prepared, including a kind of hydrated alumina to be mixed to and introduced in the mixture the compound of alkaline including earth metal component, shaping, drying with a kind of Alpha-alumina and is calcined, wherein, the sintering temperature is 750-1000 DEG C, roasting time is 1-10 hours, and the hydrated alumina counted using butt and the mixing ratio of Alpha-alumina is 20-75:25-80, the pore volume of the hydrated alumina is 0.9-1.4 mls/g, is 2/ gram of 100-350 rice, most probable bore dia 8-30nm than surface；
(2) hydrogenation active metals component is introduced on the carrier that step (1) is obtained, the hydrogenation active metals component is selected from least one metal component of group VIII and at least one Group VB metal component, counted by oxide and on the basis of catalyst, the introduction volume of the metal component of group VIII makes the content of the metal component of group VIII in final catalyst be to less than or equal to 0.8 weight % more than 0, the introduction volume of the Group VB metal component makes the content of the Group VB metal component in final catalyst be to less than or equal to 5 weight % more than 0, dry and be calcined afterwards, described drying condition includes：Temperature is 100-250 DEG C, and the time is 1-10 hours, and roasting condition includes：Temperature is 360-500 DEG C, and the time is 1-10 hours.
8. the sintering temperature in method according to claim 7, the step (1) is 800-950 DEG C, roasting time is 2-8 hours, and the hydrated alumina counted using butt and the mixing ratio of Alpha-alumina is 30-70:30-70, the pore volume of the hydrated alumina is 0.95-1.3 mls/g, is 2/ gram of 120-300 rice, most probable bore dia 10-25nm than surface；The metal component of VIIIth race is selected from nickel and/or cobalt, the metal component of Group VB is selected from vanadium and/or niobium, counted by oxide and on the basis of catalyst, the introduction volume of the metal component of group VIII makes the content of the metal component of group VIII in final catalyst be 0.1-0.7 weight %, the introduction volume of the Group VB metal component makes the content of the Group VB metal component in final catalyst be 1-4 weight %, and the drying condition of the step (2) includes：Temperature is 100-140 DEG C.
9. method according to claim 8, it is characterized in that, the introduction volume of the metal component of group VIII makes the content of the metal component of group VIII in final catalyst be 0.2-0.6 weight %, and the introduction volume of the Group VB metal component makes the content of the Group VB metal component in final catalyst be 1.5-3.5 weight %.
10. the method according to any one of claim 7 or 8, it is characterised in that the method that hydrogenation active metals component is introduced on carrier is infusion process.
11. the method according to claim 7 or 8, it is characterised in that the hydrated alumina is selected from boehmite.
12. method according to claim 7, it is characterised in that counted by oxide and on the basis of the carrier, the introduction volume of the compound of the alkaline including earth metal component makes the content of alkaline earth metal component in final carrier be 0.1-6 weight %.
13. method according to claim 12, it is characterised in that counted by oxide and on the basis of the carrier, the introduction volume of the compound of the alkaline including earth metal component makes the content of alkaline earth metal component in final carrier be 0.3-4 weight %.
14. method according to claim 13, it is characterised in that counted by oxide and on the basis of the carrier, the introduction volume of the compound of the alkaline including earth metal component makes the content of alkaline earth metal component in final carrier be 0.5-2.5 weight %.
15. application of the hydrogenation protecting catalyst in hydrocarbon oil hydrogenation processing in claim 1-6 described in any one.
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| US4530911A (en) * | 1984-05-18 | 1985-07-23 | Shell Oil Company | Hydrodenitrification catalyst |
| CN1044569C (en) * | 1994-11-04 | 1999-08-11 | 德清县化工技术开发有限公司 | Titania support and its production and application |
| CN1429890A (en) * | 2001-12-31 | 2003-07-16 | 北京燕山石油化工公司研究院 | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use |
| CN101069853A (en) * | 2006-05-13 | 2007-11-14 | 林方 | Aluminium oxide carrier containing magnesium and phosphor and preparing method |
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2013
- 2013-07-22 CN CN201310308432.4A patent/CN104324723B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4530911A (en) * | 1984-05-18 | 1985-07-23 | Shell Oil Company | Hydrodenitrification catalyst |
| CN1044569C (en) * | 1994-11-04 | 1999-08-11 | 德清县化工技术开发有限公司 | Titania support and its production and application |
| CN1429890A (en) * | 2001-12-31 | 2003-07-16 | 北京燕山石油化工公司研究院 | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use |
| CN101069853A (en) * | 2006-05-13 | 2007-11-14 | 林方 | Aluminium oxide carrier containing magnesium and phosphor and preparing method |
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