CN102909026B - Take titanium dioxide-aluminum oxide as Hydrogenation active protective agent and the Synthesis and applications thereof of carrier - Google Patents
Take titanium dioxide-aluminum oxide as Hydrogenation active protective agent and the Synthesis and applications thereof of carrier Download PDFInfo
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Abstract
Take titanium dioxide-aluminum oxide as Hydrogenation active protective agent and the Synthesis and applications thereof of carrier; containing titanium dioxide-aluminum oxide shaping carrier and hydrogenation active metals component; wherein; described titanium dioxide-aluminum oxide shaping carrier is made up of the aluminium oxide of 70-99 % by weight and the titanium oxide of 1-30 % by weight; the crushing strength of described shaping carrier is 20-300N/ grain; pore volume is 0.3-0.9 ml/g, and specific area is greater than 30 to being less than or equal to 150 meters
2/ gram.Compared with the Hydrogenation active protective agent provided with prior art; protective agent provided by the invention is a kind of under the prerequisite keeping higher filling voidage and intensity owing to have employed; there is the carrier of higher pore volume and specific area, there is more high activity and stability in hydroprocessing processes.
Description
Technical field
The invention relates to a kind of Hydrogenation active protective agent and preparation method thereof, particularly about a kind of heavy-oil hydrogenation process protective agent and preparation method.
Background technology
Along with the constantly in short supply of crude resources and the continuous increase to high-quality oil product demand, the process throughput of petroleum chemical enterprise's counterweight low grade oils increases year by year.Compared with distillate, containing a large amount of metal impurities such as iron, calcium, sodium, potassium in heavy oil, the heavy oil of a lot of secondary operations, also containing pressed powders such as the catalyst remained in the process of upstream in oil plant, therefore must carry out filtration interception to above impurity and remove before hydrotreatment.For this reason, usually all want the protective agent of grating some on heavy oil hydrogenating treatment catalyst top, to remove metal impurities in feedstock oil and solid particulate matter, major catalyst in guard reactor, avoids rapid catalyst deactivation and pressure drop rise.Usual protective agent requires to have high bed voidage and high strength, and protective agent disclosed in prior art is all based on the element such as silicon, aluminium for this reason, is obtained after shaping by high-temperature roasting, can ensure that protective agent has good intensity while high voidage like this.
ZL99110211 discloses a kind of hydrogenation protecting agent; based on aluminium oxide and silica; oxide simultaneously containing part Fe, Ni, Co, Mo or W; wherein aluminium oxide and silica content are greater than 90%; raw material is based on high ridge powder, alumina powder, feldspar powder and pore creating material; in 1200 ~ 1600 DEG C of roastings after shaping, and loading section active metal, this protective agent has the feature of high strength and raft ratio.
ZL97121095 discloses a kind of heavy oil hydrogenation demetal guard catalyst; to it is characterized in that with the sinter containing inert alumina and alkali metal mineral, for carrier, carrier supporting active component, alkali metal mineral; in alkali metal oxide, content is the 1-3% of vehicle weight.In 1050 ~ 1200 DEG C of roastings after carrier is shaping, and supported active metals.This protective agent has high strength, the feature of low pore volume and low specific surface.
As mentioned above; the hydrogenation protecting agent that prior art provides adopts perforated sectional outward appearance to keep higher bed voidage, as porous ball, porous circular cylinder, honeycomb disk or ring etc. of having loose bowels, because voidage is higher; protective agent crushing strength is difficult to keep, must high temperature in addition roasting.This type of protective agent anti-wear performance and crushing strength good, but deficiency to be pore volume low, specific area is little, limits the performance of their demetalization impurity to a certain extent.
Summary of the invention
The object of the invention is, keeping better wear-resisting with under the prerequisite of crushing strength performance, to provide the better Hydrogenation active protective agent of a kind of new catalytic perfomance and Synthesis and applications thereof.
The present invention relates to following content:
1, a kind of take titanium dioxide-aluminum oxide as the Hydrogenation active protective agent of carrier; containing titanium dioxide-aluminum oxide shaping carrier and hydrogenation active metals component; wherein; described titanium dioxide-aluminum oxide shaping carrier is made up of the aluminium oxide of 70-99 % by weight and the titanium oxide of 1-30 % by weight; the crushing strength of described shaping carrier is 20-300N/ grain; pore volume is 0.3-0.9 ml/g, and specific area is greater than 30 to being less than or equal to 150 meters
2/ gram.
2, the protective agent according to 1; it is characterized in that; described titanium dioxide-aluminum oxide shaping carrier is made up of the aluminium oxide of 75-96 % by weight and the titanium oxide of 4-25 % by weight; the crushing strength of described article shaped is 50-200N/ grain; pore volume is 0.4-0.8 ml/g, and specific area is greater than 50 to being less than or equal to 140 meters
2/ gram.
3, the protective agent according to 2; it is characterized in that; described titanium dioxide-aluminum oxide shaping carrier is made up of the aluminium oxide of 85-96 % by weight and the titanium oxide of 4-15 % by weight; the crushing strength of described article shaped is 70-200N/ grain; pore volume is 0.4-0.8 ml/g, and specific area is greater than 80 to being less than or equal to 120 meters
2/ gram.
4, the protective agent according to 1,2 or 3 any one, is characterized in that, the filling voidage of described titanium dioxide-aluminum oxide shaping carrier is 26-60%.
5, the protective agent according to 1,2 or 3 any one, is characterized in that, the filling voidage of described titanium dioxide-aluminum oxide shaping carrier is 25-50%.
6, the protective agent according to 1; it is characterized in that; described hydrogenation active metals component is selected from least one group VIII metal component and at least one vib metal component; be benchmark with oxide basis and with catalyst; the content of group VIII metal component is for being greater than 0 to being less than or equal to 5 % by weight, and the content of group vib metal component is for being greater than 0 to being less than or equal to 10 % by weight.
7, the protective agent according to 6; it is characterized in that; described group VIII metal component is selected from cobalt and/or nickel; vib metal component is selected from molybdenum and/or tungsten; be benchmark with oxide basis and with catalyst; the content of group VIII metal component is 0.1-3 % by weight, and the content of group vib metal component is 0.5-8 % by weight.
8, the protective agent according to 7, is characterized in that, is benchmark with oxide basis and with catalyst, and the content of group VIII metal component is 0.5-2.5 % by weight, and the content of group vib metal component is 3.5-8 % by weight.
9, the preparation method of Hydrogenation active protective agent described in aforementioned 1, comprise and prepare carrier and the component of load hydrogenation active metals on this carrier, wherein, described carrier is prepared by following step:
(1) hydrated alumina to be mixed with titanium-containing compound and shaping;
(2) the dry also roasting of article shaped step (1) obtained, described baking temperature is 60-300 DEG C, and drying time is 1-10 hour, and sintering temperature is 600-1000 DEG C, and roasting time is 1 ~ 10 hour;
Wherein, the hydrated alumina described in step (1) and the consumption of titanium-containing compound make consisting of of final molding thing: the aluminium oxide of 70-99 % by weight and the titanium oxide of 1-30 % by weight.
10, the method according to 9, is characterized in that, the hydrated alumina described in step (1) and the consumption of titanium-containing compound make consisting of of final molding carrier: the aluminium oxide of 75-96 % by weight and the titanium oxide of 4-25 % by weight; Described baking temperature is 100-250 DEG C, and drying time is 2-8 hour, and sintering temperature is 700-1000 DEG C, and roasting time is 2-5 hour
11, the method according to 9, is characterized in that, described sintering temperature is 850-1000 DEG C.
12, the method according to 9, is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
13, according to 12 method, it is characterized in that, described hydrated alumina is boehmite.
14, the method according to 9, is characterized in that, described titanium-containing compound is selected from titanium oxide, titanate, molecular sieve containing titanium, titaniferous hydrated alumina.
15, the method according to 14, is characterized in that, described titanium-containing compound is selected from titanium oxide, titanate.
16, the method according to 9, is characterized in that, the described shaping pattern of shaping carrier that makes is the spheroid of honeycomb post, Raschig ring or multi-pore channel.
17, the method according to 9, it is characterized in that, described hydrogenation active metals component is selected from least one group VIII metal component and at least one vib metal component, the described method in supported on carriers hydrogenation active metals component is infusion process, be benchmark with oxide basis and with catalyst, described dipping makes the content of the group VIII metal component in final catalyst for being greater than 0 to being less than or equal to 5 % by weight, and the content of group vib metal component is for being greater than 0 to being less than or equal to 10 % by weight.
18, the method according to 17, it is characterized in that, described group VIII metal component is selected from cobalt and/or nickel, vib metal component is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyst, be benchmark with oxide basis and with catalyst, described dipping makes the content of the group VIII metal component in final catalyst be 0.1-3 % by weight, and the content of group vib metal component is 0.5-8 % by weight.
19, the method according to 18, it is characterized in that, be benchmark with oxide basis and with catalyst, be benchmark with oxide basis and with catalyst, described dipping makes the content of the group VIII metal component in final catalyst be 0.5-2.5 % by weight, and the content of group vib metal component is 3.5-8 % by weight.
20, a heavy oil hydrogenation treatment method, under being included in heavy-oil hydrogenation processing reaction condition, by heavy oil feedstock oil and catalyst exposure, wherein, described catalyst comprises at least one catalyst that claim provides any one of claim 1-8.
According to Hydrogenation active protective agent provided by the invention, wherein, described filling voidage is the physical parameter of the described article shaped measured by the following method.Its assay method comprises: article shaped to be measured is placed in container (inside diameter of vessel is greater than 20 times of article shaped average grain diameter to be measured) to 1 liter according to the density of industrial landfill, then slowly pure water is injected, continue the volume adding water to 1 liter afterwards catalyst water suction is saturated, then taken out by catalyst filtration, the volume (liter) of remaining liquid is the bed voidage of catalyst divided by 100%.
The described method preparing shaping carrier can be arbitrary prior art, and to this, the present invention is not particularly limited.Such as, described forming method can be by template extrusion molding, spin or by compressing tablet and be the forming method of several existing forming method combination.For extruded moulding, for ensureing shapingly to carry out smoothly, water, extrusion aid and/or adhesive can be added, then extrusion molding in material (mixture as hydrated alumina and titanium oxide), carrying out drying afterwards and roasting.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, and described peptizing agent can be inorganic acid and/or organic acid.Synthetic cellulose is wherein preferably one or more in CMC, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, and polymeric alcohol is preferably one or more in polyethylene glycol, poly-propyl alcohol, polyvinyl alcohol.
The method of described drying and roasting is field of catalyst preparation customary way.
Described hydrated alumina is selected from mixtures in hibbsite, monohydrate alumina and amorphous hydroted alumina or several, is preferably boehmite.They can be that commercially available commodity also can be prepared by any one method in prior art.
Described titanium-containing compound is selected from one in titanium oxide, titanate, molecular sieve containing titanium, titaniferous hydrated alumina and several, preferential oxidation titanium, titanate.
Be enough under the prerequisite loading on carrier by described hydrogenation active metals component, the method for the present invention to described load hydrogenation active metals component is not particularly limited.Preferred dipping method wherein, the method of described dipping is for preparing hydrogenation class catalyst customary way, can be such as containing being selected from VIII and being selected from the solution impregnating carrier of metal component compound of group vib with excessive, can be with containing being selected from VIII and being selected from the solution hole saturation impregnated carrier of metal component compound of group vib, carry out drying, roasting or not roasting afterwards.The method of described drying and roasting is conventional method, and preferred drying condition comprises: baking temperature is 60 ~ 150 DEG C, and drying time is 1 ~ 10 hour, and preferably baking temperature is 80 ~ 120 DEG C further, and drying time is 2 ~ 8 hours; Preferred roasting condition comprises: sintering temperature is 350-550 DEG C, and roasting time is 1-6 hour, and preferably sintering temperature is 400 ~ 500 DEG C further, and roasting time is 2 ~ 4 hours.
One or more in the described soluble compound be selected from containing the metal component compound being selected from group vib 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 group VIII 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.
Compared with the Hydrogenation active protective agent provided with prior art; protective agent provided by the invention is a kind of under the prerequisite keeping higher filling voidage and intensity owing to have employed; there is the carrier of higher pore volume and specific area, there is more high activity and stability in hydroprocessing processes.This hydrogenation protecting agent is applicable to carry out hydrotreatment to heavier hydrocarbon feeds, to remove wherein metal and solid particulate matter.Described heavier hydrocarbon feeds comprises crude oil, normal pressure or decompression residuum and normal pressure or vacuum distillate.
Detailed description of the invention
The present invention will be further illustrated below by embodiment.
Example 1-4 illustrates and is suitable for preparing carrier that the invention provides catalyst and preparation method thereof.
Example 1
By aluminium hydrate powder 1000 grams, the mixing of 100 grams of titanium dioxides, in a mold compressing for high 10mm, diameter 40mm, wall thickness 2mm, include the honeycomb cylinder in 100 triangle ducts, in 120 DEG C of dryings after 4 hours, in 880 DEG C of roastings 4 hours, obtain carrier Z1.Carrier Z1 physico-chemical property is in table 1.
Example 2
Aluminium hydrate powder 200 grams and aluminum titanate powder 80 grams is mixed, is pressed into the seven apertures in the human head ball that external diameter 16mm includes diameter 3mm duct in a mold, in 80 DEG C of dryings 3 hours, in 950 DEG C of constant temperature 2 hours, obtain carrier Z2.Carrier Z2 physico-chemical property is in table 1.
Example 3
One diaspore powder 200 grams is mixed containing titanium dioxide with 18 grams, double screw banded extruder is extruded into the ring of having loose bowels of external diameter 5.0mm wall thickness 1.5mm, in 120 DEG C of dryings after 2 hours, in 900 DEG C of constant temperature 3 hours, obtain carrier Z3.Carrier Z3 physico-chemical property is in table 1.
Example 4
Aluminium hydrate powder 1000 grams mixed with 40 grams of titanium dioxides, is pressed into high 10mm, diameter 8.0mm, wall thickness 1mm in a mold, include the honeycomb cylinder in 15 irregular ducts, in 100 DEG C of dryings after 4 hours, in 980 DEG C of roastings 2 hours, obtain carrier Z4.Carrier Z4 physico-chemical property is in table 1.
Example 5
40 grams of titanium dioxides are mixed with 500 grams of aluminium hydroxides, plunger type bar extruder is extruded into external diameter 4.5mm wall thickness 1.8mm hollow gear post, in 90 DEG C of dryings 4 hours, in 960 DEG C of roastings 2 hours, obtains carrier Z5.Carrier Z5 physico-chemical property is in table 1.
Comparative example 1-2 illustrates preparation reference catalyst carrier and preparation method thereof.
Comparative example 1
The support porcelain ring DZ1 (aluminium oxide 62 % by weight, other are silicon, calcium, magnesium, potassium etc.) that a kind of commercially available Jiangsu produces.DZ1 physico-chemical property is in table 1.
Comparative example 2
Mixed with 300 grams of aluminium hydrate powders by one diaspore powder 100 grams, double screw banded extruder is extruded into the ring of having loose bowels of external diameter 5.0mm wall thickness 1.5mm, in 120 DEG C of dryings after 2 hours, in 900 DEG C of constant temperature 3 hours, be supported agent DZ2.Proppant DZ2 physico-chemical property is in table 1.
Table 1
Wherein, the measuring method of crushing strength is carried out according to RIPP25-90 catalyst compressive resistance determination method.Vehicle group becomes calculated value, and pore volume, specific area adopt BET to measure.
Example 5-8 illustrates protective agent provided by the invention and preparation method thereof.
Example 5
Get carrier Z2200 gram prepared by example 1, with 500 milliliters containing WO
370 grams per liters, ammonium metatungstate and the nickel nitrate mixed solution of NiO15 grams per liter flood 1 hour, dry 4 hours after filtration in 100 DEG C, and 450 DEG C of roastings 4 hours, obtain protective agent C1.The composition of protective agent C1 is listed in table 2.
Example 6
Get carrier Z2200 gram prepared by example 2, with 500 milliliters containing MoO
350 grams per liters, ammonium molybdate and the nickel nitrate mixed solution of NiO8 grams per liter flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 480 DEG C of roastings 4 hours, obtain protective agent C2.The composition of protective agent C2 is listed in table 2.
Example 7
Get carrier Z3200 gram prepared by example 3, with 500 milliliters containing MoO
380 grams per liters, the ammonium molybdate of NiO20 grams per liter and nickel nitrate solution flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 500 DEG C of roastings 4 hours, obtain protective agent C3.The composition of protective agent C3 is listed in table 2.
Example 8
Get carrier Z5200 gram prepared by example 4, with 500 milliliters containing MoO
340 grams per liters, the molybdic acid acid ammonium of CoO12 grams per liter and cobalt nitrate mixed solution flood 1 hour, dry 4 hours after filtration in 90 DEG C, and 480 DEG C of roastings 4 hours, obtain protective agent C5.The composition of protective agent C5 is listed in table 2.
Comparative example 3
Get carrier DZ1200 gram prepared by comparative example 1, with 500 milliliters containing MoO
370 grams per liters, ammonium molybdate and the nickel nitrate mixed solution of NiO10 grams per liter flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 480 DEG C of roastings 4 hours, obtain protective agent DC1.The composition of protective agent DC1 is listed in table 2.
Comparative example 4
Get carrier DZ2200 gram prepared by comparative example 2, with 500 milliliters containing MoO
350 grams per liters, ammonium molybdate and the nickel nitrate mixed solution of NiO8 grams per liter flood 1 hour, dry 2 hours after filtration in 120 DEG C, and 480 DEG C of roastings 4 hours, obtain protective agent DC2.The composition of protective agent DC2 is listed in table 2.
Table 2
Wherein, active metal component content adopts X-fluorescence part mensuration.
Example 9-12
Example 9-12 illustrates the performance evaluation of hydrogenation protecting catalyst provided by the invention.
Take iron content as 20ppm, calcium content is 125ppm decompression residuum is raw material, evaluate catalysts in 500 milliliters of autoclave reactors.
Getting catalyst C1, C2, C3, C4 slightly after fragmentation, is 1/20 according to catalystoil ratio, reaction temperature 360 DEG C, hydrogen dividing potential drop 10 MPa, mixing speed 180r/min.React sample analysis after 8 hours, adopt plasma emission spectrum (AES/ICP) method to measure the content generating iron, calcium in oil, and calculate demetallization per, the computational methods of total demetallization per are:
The results are shown in table 3.
Comparative example 5-6
According to the HDM performance of method evaluation catalyst CD1, CD2 of example 9, the results are shown in Table 3.
Table 3
| Example number | Protective agent is numbered | Demetallization per/% |
| 9 | C1 | 80 |
| 10 | C2 | 78 |
| 11 | C3 | 85 |
| 12 | C4 | 82 |
| Comparative example 5 | DC1 | 54 |
| Comparative example 6 | DC2 | 75 |
The result of table 3 can illustrate, the demetalization performance of hydrogenation protecting agent provided by the invention significantly improves compared with reference protective agent.
Claims (16)
1. one kind take titanium dioxide-aluminum oxide as the Hydrogenation active protective agent of carrier; containing titanium dioxide-aluminum oxide shaping carrier and hydrogenation active metals component; wherein; the filling voidage of described titanium dioxide-aluminum oxide shaping carrier is 26-60%; described titanium dioxide-aluminum oxide shaping carrier is made up of the aluminium oxide of 85-96 % by weight and the titanium oxide of 4-15 % by weight; the crushing strength of described shaping carrier is 70-200N/ grain, and pore volume is 0.4-0.8 ml/g, and specific area is greater than 80 to being less than or equal to 120 meters
2/ gram, described hydrogenation active metals component is selected from least one group VIII metal component and at least one vib metal component, described group VIII metal component is selected from cobalt and/or nickel, vib metal component is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyst, the content of group VIII metal component is for being greater than 0 to being less than or equal to 5 % by weight, and the content of group vib metal component is for being greater than 0 to being less than or equal to 10 % by weight.
2. protective agent according to claim 1, is characterized in that, the filling voidage of described titanium dioxide-aluminum oxide shaping carrier is 26-50%.
3. protective agent according to claim 1, is characterized in that, is benchmark with oxide basis and with catalyst, and the content of group VIII metal component is 0.1-3 % by weight, and the content of group vib metal component is 0.5-8 % by weight.
4. protective agent according to claim 3, is characterized in that, is benchmark with oxide basis and with catalyst, and the content of group VIII metal component is 0.5-2.5 % by weight, and the content of group vib metal component is 3.5-8 % by weight.
5. the preparation method of Hydrogenation active protective agent described in aforementioned claim 1, comprise and prepare carrier and the component of load hydrogenation active metals on this carrier, wherein, described carrier is prepared by following step:
(1) hydrated alumina to be mixed with titanium-containing compound and shaping;
(2) the dry also roasting of article shaped step (1) obtained, described baking temperature is 60-300 DEG C, and drying time is 1-10 hour, and sintering temperature is 600-1000 DEG C, and roasting time is 1 ~ 10 hour;
Wherein, the hydrated alumina described in step (1) and the consumption of titanium-containing compound make consisting of of final molding thing: the aluminium oxide of 85-96 % by weight and the titanium oxide of 4-15 % by weight.
6. method according to claim 5, is characterized in that, described baking temperature is 100-250 DEG C, and drying time is 2-8 hour, and sintering temperature is 700-1000 DEG C, and roasting time is 2-5 hour.
7. method according to claim 6, is characterized in that, described sintering temperature is 850-1000 DEG C.
8. method according to claim 5, is characterized in that, described hydrated alumina is selected from one or more in boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
9. method according to claim 8, is characterized in that, described hydrated alumina is boehmite.
10. method according to claim 5, is characterized in that, described titanium-containing compound is selected from titanium oxide, titanate, molecular sieve containing titanium, titaniferous hydrated alumina.
11. methods according to claim 10, is characterized in that, described titanium-containing compound is selected from titanium oxide, titanate.
12. methods according to claim 5, is characterized in that, the described shaping pattern of shaping carrier that makes is the spheroid of honeycomb post, Raschig ring or multi-pore channel.
13. methods according to claim 5, it is characterized in that, described hydrogenation active metals component is selected from least one group VIII metal component and at least one vib metal component, the described method in supported on carriers hydrogenation active metals component is infusion process, be benchmark with oxide basis and with catalyst, described dipping makes the content of the group VIII metal component in final catalyst for being greater than 0 to being less than or equal to 5 % by weight, and the content of group vib metal component is for being greater than 0 to being less than or equal to 10 % by weight.
14. methods according to claim 13, it is characterized in that, described group VIII metal component is selected from cobalt and/or nickel, vib metal component is selected from molybdenum and/or tungsten, be benchmark with oxide basis and with catalyst, be benchmark with oxide basis and with catalyst, described dipping makes the content of the group VIII metal component in final catalyst be 0.1-3 % by weight, and the content of group vib metal component is 0.5-8 % by weight.
15. methods according to claim 14, it is characterized in that, be benchmark with oxide basis and with catalyst, be benchmark with oxide basis and with catalyst, described dipping makes the content of the group VIII metal component in final catalyst be 0.5-2.5 % by weight, and the content of group vib metal component is 3.5-8 % by weight.
16. 1 kinds of heavy oil hydrogenation treatment methods, under being included in heavy-oil hydrogenation processing reaction condition, by heavy oil feedstock oil and catalyst exposure, wherein, described catalyst comprises at least one catalyst that claim provides any one of claim 1-4.
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| CN104162439B (en) * | 2013-05-20 | 2017-02-08 | 中国石油化工股份有限公司 | Hydrogenation activity protective catalyst, preparation and applications thereof |
| CN104293382B (en) * | 2013-07-18 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of catalytic cracking material pretreatment method |
| CN103406157B (en) * | 2013-08-16 | 2014-11-26 | 萍乡市安发冶化环保填料有限公司 | Hydrogenation protective agent having higher impurity capability |
| CN103497167B (en) * | 2013-10-14 | 2016-01-20 | 浙江嘉澳环保科技股份有限公司 | The preparation method of the ester modified softening agent of a kind of longer chain fatty acid |
| CN105749923B (en) * | 2014-12-17 | 2018-05-18 | 中国石油化工股份有限公司 | A kind of heavy oil hydrogenating treatment catalyst and its application |
| CN104841491B (en) * | 2015-04-27 | 2017-03-01 | 萍乡市安发冶化环保填料有限公司 | A kind of silk screen hydrogenation protecting agent of pottery |
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