CN106140182A - A kind of preparation method of heavy oil hydrogenating treatment catalyst - Google Patents
A kind of preparation method of heavy oil hydrogenating treatment catalyst Download PDFInfo
- Publication number
- CN106140182A CN106140182A CN201510196347.2A CN201510196347A CN106140182A CN 106140182 A CN106140182 A CN 106140182A CN 201510196347 A CN201510196347 A CN 201510196347A CN 106140182 A CN106140182 A CN 106140182A
- Authority
- CN
- China
- Prior art keywords
- active component
- expanding agent
- physics expanding
- hydrogenation active
- weight
- 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
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the preparation method of a kind of heavy oil hydrogenating treatment catalyst, including following content: (1) impregnates physics expanding agent I respectively with hydrogenation active component impregnation liquid I and titaniferous solution I, impregnating physics expanding agent II respectively with hydrogenation active component impregnation liquid II and titaniferous solution II, physics expanding agent I and physics expanding agent II drying after dipping are standby；(2) the physics expanding agent I of step (1) gained, physics expanding agent II are become plastic with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizer kneading, extrusion, dry, roasting, prepare modified aluminium oxide supports；(3) modified aluminium oxide supports obtained by hydrogenation active component impregnation liquid III impregnation steps (2), drying, roasting, prepare heavy oil hydrogenating treatment catalyst.Catalyst activity metal content at macropore prepared by the method is of a relatively high, at aperture, content is relatively low, and be multicomponent reactive component at macropore, the utilization rate of macropore significantly improves, and this heavy oil hydrogenating treatment catalyst has preferable hydrodesulfurization and hydrodenitrogenationactivity activity.
Description
Technical field
The present invention relates to the preparation method of a kind of heavy oil hydrogenating treatment catalyst.
Background technology
The raising required along with raw material deep processing in world wide, main energy sources structure gradually develops to macromole and high-carbon direction, and China of heaviness universal for crude oil is all the more so.Impurity in heavy oil particularly residual oil such as S, N, carbon residue and heavy metal etc. must effectively remove the requirement that could meet catalytic cracking feeds, if the too high meeting of impurity content causes downstream catalytic Cracking catalyst to be poisoned.Hydrocarbon hydrogenizing treamtent catalyst is many with aluminium oxide as carrier, with Mo and/or W and Ni and/or Co as active component at present.
Open a kind of heavy oil hydrogenating treatment catalyst of CN1289822A and preparation method thereof, this catalyst is with aluminium oxide as carrier matrix, and with vib metals and group VIII metallic element, particularly Mo-Ni for active component, interpolation Ti is coagent.The preparation method of catalyst uses full kneading method, will be the aluminum hydroxide solid elastomer powder that can be converted into aluminium oxide through roasting, it is initially charged a kind of alkaline solution containing vib metals, fully kneading, to aluminium hydrate powder completely by alkalies moistening, adding a kind of group VIII and the acid solution of vib metals element, kneading becomes plastic to material, extruded moulding, dry, roasting, obtain catalyst.
The open a kind of heavy oil hydrogenating treatment catalyst of CN1110304A, with the aluminium oxide of siliceous and phosphorus as carrier, the carrier being particularly mixed with little porous aluminum oxide by a kind of siliceous and phosphorus macroporous aluminium oxide, support molybdenum, nickel, P elements.Owing to the silicon in carrier and phosphorus substep plastic method add, making silicon and phosphorus major part be dispersed in alumina surface, can play one's part to the full, catalyst has suitable surface nature simultaneously, has good nitrogen removal performance.
Open a kind of catalyst for hydrotreating heavy fraction of oil of CN1854260A and preparation method thereof.Catalyst carrier of the present invention is made up of the siliceous and macroporous aluminium oxide of boron and little porous aluminum oxide, and supports at least one vib metals and group VIII metallic element.Silicon and boron in carrier join in macroporous aluminium oxide by substep plastic method, and silicon and boron major part are dispersed in alumina surface, can play synergism more fully.Catalyst has suitable Acidity simultaneously, thus surface goes out higher hydrodenitrogenationactivity activity and activity stability.
Catalyst for hydrotreatment of residual oil active metal component prepared by said method is distribution uniform at the macropore and aperture of carrier, and the utilization rate causing macropore is relatively low.
Summary of the invention
For the deficiencies in the prior art, the present invention provides the preparation method of a kind of heavy oil hydrogenating treatment catalyst.Catalyst activity metal content at macropore prepared by the method is of a relatively high, at aperture, content is relatively low, and be multicomponent reactive component at macropore, the utilization rate of macropore significantly improves, and this heavy oil hydrogenating treatment catalyst has preferable hydrodesulfurization and hydrodenitrogenationactivity activity.
The preparation method of the heavy oil hydrogenating treatment catalyst of the present invention, including following content:
(1) impregnating physics expanding agent I respectively with hydrogenation active component impregnation liquid I and titaniferous solution I, impregnate physics expanding agent II respectively with hydrogenation active component impregnation liquid II and titaniferous solution II, physics expanding agent I and physics expanding agent II drying after dipping are standby；
(2) the physics expanding agent I of step (1) gained, physics expanding agent II are become plastic with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizer kneading, extrusion, dry, roasting, prepare modified aluminium oxide supports；
(3) modified aluminium oxide supports obtained by hydrogenation active component impregnation liquid III impregnation steps (2), drying, roasting, prepare heavy oil hydrogenating treatment catalyst.
In the inventive method, described hydrogenation active component is VIB and/or group VIII metal, and vib metals is molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；Hydrogenation active component impregnation liquid can be the one in acid solution, aqueous solution or ammonia solution containing hydrogenation active component.
In the inventive method, hydrogenation active component I described in step (1) is at least to contain a kind of active component different from step (3) hydrogenation active component III composition, if step (3) hydrogenation active component III is molybdenum/nickel, active component I described in step (1) can be one or more mixing in molybdenum/cobalt, tungsten/cobalt, tungsten/nickel, molybdenum/cobalt/nickel, tungsten/cobalt/nickel, tungsten/molybdenum/cobalt/nickel.
In the inventive method, hydrogenation active component II described in step (1) is at least to contain a kind of active component different from step (3) hydrogenation active component III composition, if step (3) hydrogenation active component III is molybdenum/nickel, hydrogenation active component II described in step (1) can be one or more mixing in molybdenum/cobalt, tungsten/cobalt, tungsten/nickel, molybdenum/cobalt/nickel, tungsten/cobalt/nickel, tungsten/molybdenum/cobalt/nickel.
In the inventive method, in hydrogenation active component impregnation liquid I described in step (1), vib metals weight content is calculated as the 0.8wt%-1.0wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.5wt%-0.7wt% of final catalyst weight with oxide.Hydrogenation active component impregnation liquid I consumption is the saturated water adsorptive value of physics expanding agent I.
In the inventive method, in hydrogenation active component impregnation liquid II described in step (1), vib metals weight content is calculated as the 0.3wt%-0.5wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.2wt%-0.4wt% of final catalyst weight with oxide.Hydrogenation active component impregnation liquid II consumption is the saturated water adsorptive value of physics expanding agent II.
In the inventive method, titaniferous solution described in step (1) can be ethanol solution or the titanium tetrachloride solution of butyl titanate, isopropyl titanate or tetraethyl titanate etc., the consumption of titaniferous solution I is the saturated water adsorptive value of physics expanding agent I, and after dipping, in physics expanding agent I, Ti content accounts for the 0.6%-0.8% of catalyst weight in terms of oxide；The consumption of titaniferous solution II is the saturated water adsorptive value of physics expanding agent II, and after dipping, in physics expanding agent II, the content of titanium accounts for the 0.1%-0.3% of catalyst weight in terms of oxide.
In the inventive method, step (1) described physics expanding agent is one or more mixing in carbon black powder, Linesless charcoal or wood flour, and the particle diameter of physics expanding agent I is 600-1000 mesh, and the particle diameter of physics expanding agent II is 300-500 mesh.
In the inventive method, the drying condition described in step (1) is that nature dries in the shade or dry 1-10 hour in 50-120 DEG C.
In the inventive method, the boehmite dry glue powder described in step (2) can be the boehmite dry glue powder using any one method to prepare.
In the inventive method, the 4%-8% that addition is boehmite dry glue powder weight of the 3%-5% that addition is boehmite dry glue powder weight of the physics expanding agent I described in step (2), physics expanding agent II.
In the inventive method, being preferably added to mass concentration in kneading process described in step (2) is 1%-5% Aqueous Solutions of Polyethylene Glycol, wherein the mean molecule quantity of Polyethylene Glycol is 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 gram/100 grams boehmite dry glue powders.
In the inventive method, chemical enlargement agent described in step (2) is one or more in phosphoric acid or phosphate, preferably phosphate, wherein one or more in ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate of phosphate, chemical enlargement agent addition is the 3%-5% of boehmite dry glue powder weight.
In the inventive method, the extrusion aid described in step (2) is one or more in sesbania powder, starch or methylcellulose, preferably sesbania powder, and extrusion aid addition is the 3%-5% of boehmite dry glue powder weight.
In the inventive method, the peptizer described in step (2) is one or more mixing in formic acid, acetic acid, citric acid or nitric acid, and addition is the 3%-10% of boehmite dry glue powder weight, depending on last molding effect.
In the inventive method, step (2) described drying condition is to be dried 1-10 hour at 100-130 DEG C；Roasting process is 500-650 DEG C of roasting 2-4 hour.
In the inventive method, the hydrogenation active component impregnation liquid III described in step (3) is to calculate preparation according to final catalyst composition.In hydrogenation active component impregnation liquid III, vib metals content is calculated as 7-15g/100ml with oxide, VII race tenor is calculated as 0.8-3g/100ml with oxide, can be to use volume impregnation, incipient impregnation or spray impregnating mode, and dip time is 1-5 hour.
In the inventive method, the drying condition described in step (3) is to be dried 6-10 hour at 80-120 DEG C；Described roasting condition is roasting 3-6 hour at 400-600 DEG C.
Appropriate titaniferous solution and active metallic element are impregnated on physics expanding agent by the inventive method, and with boehmite kneading, molding, be dried, roasting prepares alumina support, dipping active component finally prepares catalyst.The active component of physics expanding agent pre-preg is a kind of from the active component that the later stage impregnates different, forms multicomponent reactive component at the macropore so formed after physics expanding agent roasting, improves the catalysis activity of active component.Select the physics expanding agent with different-grain diameter, make final catalyst is formed mass transfer and the diffusion of the macroporous structure accordingly with different pore size, beneficially reactant.It addition, active metal component loads at corresponding macropore, make in final catalyst the active component content at macropore significantly increase, improve the utilization rate of macropore.The existence of titanium have adjusted the surface nature of carrier at macropore, improves the interaction of active component and carrier, improves the catalysis activity of active metal.During kneading, the addition of Polyethylene Glycol makes physics expanding agent mix homogeneously with boehmite, improves the uniformity coefficient of macropore.
Detailed description of the invention
Further illustrate effect and the effect of the present invention below in conjunction with embodiment, but be not limited to following example.
Embodiment 1
Weigh the carbon black powder I4.3 that particle diameter is 800 mesh (granule can pass through 800 mesh sieve holes but can't pass 1000 mesh sieve holes) to be placed in spray rolling pot, under rotary state, spray containing molybdenum oxide 0.8 gram with atomizing type carbon black powder in rolling pot, the active metal impregnation liquid of cobalt oxide 0.6 gram makes carbon black powder absorption saturated, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.Dried carbon black powder is replaced in spray rolling pot, under rotary state, spraying the ethanol solution of the butyl titanate containing titanium oxide 0.6 gram with atomizing type carbon black powder in rolling pot makes carbon black powder absorption saturated, the carbon black powder after dipping in 110 DEG C be dried 3 hours standby.
Weigh particle diameter be 300(granule can by 300 mesh sieve holes but can't pass 325 mesh sieve holes) purpose carbon black powder II11.4 gram be placed in spray rolling pot in, under rotary state, spray containing molybdenum oxide 0.4 gram with atomizing type carbon black powder in rolling pot, the active metal impregnation liquid of cobalt oxide 0.2 gram makes carbon black powder absorption saturated, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.Dried carbon black powder is replaced in spray rolling pot, under rotary state, spraying the ethanol solution of the butyl titanate containing titanium oxide 0.2 gram with atomizing type carbon black powder in rolling pot makes carbon black powder absorption saturated, the carbon black powder after dipping in 110 DEG C be dried 3 hours standby.
Weigh boehmite dry glue powder (aluminium oxide contents on dry basis 70%) 143 grams and above-mentioned steps carbon black powder, 7.5 grams of sesbania powder, 3 grams of ammonium phosphate mix homogeneously, adding mass concentration is 3%, mean molecule quantity is 43 grams of kneadings of Aqueous Solutions of Polyethylene Glycol of 4000, is subsequently adding and continues kneading uniformly dissolved with 5 grams of nitre aqueous acids in right amount, is extruded into the cloverleaf pattern bar of a diameter of 1.8mm on screw rod banded extruder, dry 3 hours in 120 DEG C, by dried article shaped roasting 4 hours at a temperature of 550 DEG C.
Above-mentioned material is placed in beaker, with 150 milliliters containing MoO310 grams/100 milliliters, the molybdenum-nickel of NiO1.2 gram/100 milliliters-ammonia active metal salt solution dipping carrier 5 hours, filter off redundant solution, dry 2 hours for 120 DEG C, then 5 hours prepared catalyst C1 of roasting, this catalyst MoO at 550 DEG C3Weight/mass percentage composition be 11.2wt%, NiO weight/mass percentage composition be 1.1wt%, CoO weight/mass percentage composition is 0.8wt%, and titanium oxide percentage composition is 0.8wt%.
Embodiment 2
With embodiment 1, simply carbon black powder I weight is 7.2 grams, particle diameter is 600 mesh (granule can pass through 600 mesh sieve holes but can't pass 800 mesh sieve holes), containing tungsten oxide 0.9 gram in hydrogenation active component impregnation liquid I, nickel oxide 0.5 gram, containing titanium oxide 0.7 gram in titaniferous solution I, titanium solution is tetraethyl titanate ethanol solution, carbon black powder II weight is 5.7 grams, particle diameter is 400 mesh (granule can pass through 400 mesh sieve holes but can't pass 500 mesh sieve holes), containing tungsten oxide 0.3 gram in hydrogenation active component impregnation liquid II, nickel oxide 0.4 gram, containing titanium oxide 0.1 gram in titaniferous solution II, titanium solution is tetraethyl titanate ethanol solution, the addition of polyglycol solution is 43 to restrain to obtain catalyst C2 of the present invention, this catalyst MoO3Weight/mass percentage composition is 10wt%, WO3Weight/mass percentage composition be 1.2wt%, NiO weight/mass percentage composition be 1.2wt%, titanium oxide weight/mass percentage composition is 0. 8wt%.
Embodiment 3
With embodiment 1, simply carbon black powder I weight is 5.7 grams, particle diameter is 1000 mesh (granule can pass through 1000 mesh sieve holes but can't pass 1340 mesh sieve holes), containing tungsten oxide 1.0 grams in hydrogenation active component impregnation liquid I, cobalt oxide 0.7 gram, containing titanium oxide 0.8 gram in titaniferous solution I, carbon black powder II weight is 8.6 grams, particle diameter is 500 mesh (granule can pass through 500 mesh sieve holes but can't pass 600 mesh sieve holes), containing tungsten oxide 0.5 gram in hydrogenation active component impregnation liquid II, cobalt oxide 0.3 gram, containing titanium oxide 0.3 gram in titaniferous solution II, the addition of polyglycol solution is 100 to restrain to obtain catalyst C3 of the present invention, this catalyst MoO3Weight/mass percentage composition is 10wt%, WO3Weight/mass percentage composition be 1.5wt%, NiO weight/mass percentage composition be 1.2wt%, CoO weight/mass percentage composition be 1.0wt%, titanium oxide weight/mass percentage composition is 1.1wt%.
Embodiment 4
With embodiment 1, simply carbon black powder changes Linesless charcoal into, Linesless charcoal I weight is 5 grams, containing tungsten oxide 0.85 gram in hydrogenation active component impregnation liquid I, and nickel oxide 0.55 gram, Linesless charcoal II weight is 7.2 grams, containing molybdenum oxide 0.45 gram in hydrogenation active component impregnation liquid II, cobalt oxide 0.3 gram, during dipping Linesless charcoal, activity component impregnation liquid is containing molybdenum oxide 0.3 gram, tungsten oxide 0.4 gram, nickel oxide 0.05 gram.The addition of polyglycol solution is 100 to restrain to obtain catalyst C4 of the present invention, this catalyst MoO3Weight/mass percentage composition is 10.5wt%, WO3Weight/mass percentage composition be 0.85wt%, NiO weight/mass percentage composition be 1.7wt%, CoO weight/mass percentage composition be 0.3wt%, titanium oxide weight/mass percentage composition is 0.8wt%.
Embodiment 5
With embodiment 1, simply carbon black powder I weight is 6.4 grams, and carbon black powder II weight is 10 grams, and the addition of polyglycol solution is 86 grams, with 150 milliliters containing MoO during dipping38 grams/100 milliliters, the molybdenum-nickel of NiO0.9 gram/100 milliliters-ammonia active metal salt solution dipping carrier prepares catalyst C5 of the present invention, this catalyst MoO3Weight/mass percentage composition be 9.2wt%, NiO weight/mass percentage composition be 0.9wt%, CoO weight/mass percentage composition be 0.8wt%, titanium oxide weight/mass percentage composition is 0.8wt%.
Embodiment 6
With embodiment 1, simply boehmite does not adds polyglycol solution and prepares catalyst C6 of the present invention, this catalyst MoO when mixing with carbon black powder3Weight/mass percentage composition be 11.2wt%, NiO weight/mass percentage composition be 1.1wt%, CoO weight/mass percentage composition is 0.8wt%, and titanium oxide percentage composition is 0.8wt%.
Comparative example 1
With example 1, simply active metal is unsupported on carbon black powder, but adds kneading when, and preparation has the comparative catalyst C7 of composition same as in Example 1.
Comparative example 2
With example 1, simply titanium is unsupported on carbon black powder, but adds the when of kneading, and preparation has the catalyst C8 of composition same as in Example 1.
Comparative example 3
With example 1, simply active metal and titanium are unsupported on carbon black powder, but add the when of kneading, and preparation has the catalyst C9 of composition same as in Example 1.
Comparative example 4
Weigh the carbon black powder I15.6 that particle diameter is 800 mesh (granule can pass through 800 mesh sieve holes but can't pass 1000 mesh sieve holes) to be placed in spray rolling pot, under rotary state, spray containing molybdenum oxide 1.2 grams with atomizing type carbon black powder in rolling pot, the active metal impregnation liquid of cobalt oxide 0.8 gram makes carbon black powder absorption saturated, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.Dried carbon black powder is replaced in spray rolling pot, under rotary state, spraying the ethanol solution of the butyl titanate containing titanium oxide 0.8 gram with atomizing type carbon black powder in rolling pot makes carbon black powder absorption saturated, the carbon black powder after dipping in 110 DEG C be dried 3 hours standby.
Weigh boehmite dry glue powder (aluminium oxide contents on dry basis 70%) 143 grams and above-mentioned steps carbon black powder, 7.5 grams of sesbania powder, 3 grams of ammonium phosphate mix homogeneously, adding mass concentration is 3%, mean molecule quantity is 43 grams of kneadings of Aqueous Solutions of Polyethylene Glycol of 4000, is subsequently adding and continues kneading uniformly dissolved with 5 grams of nitre aqueous acids in right amount, is extruded into the cloverleaf pattern bar of a diameter of 1.8mm on screw rod banded extruder, dry 3 hours in 120 DEG C, by dried article shaped roasting 4 hours at a temperature of 550 DEG C.
Above-mentioned material is placed in beaker, with 150 milliliters containing MoO310 grams/100 milliliters, the molybdenum-nickel of NiO1.2 gram/100 milliliters-ammonia active metal salt solution dipping carrier 5 hours, filter off redundant solution, dry 2 hours for 120 DEG C, then 5 hours prepared catalyst C10 of roasting, this catalyst MoO at 550 DEG C3Weight/mass percentage composition be 11.2wt%, NiO weight/mass percentage composition be 1.1wt%, CoO weight/mass percentage composition is 0.8wt%, and titanium oxide percentage composition is 0.8wt%.
The catalyst preparing examples detailed above and comparative example carries out activity rating, relatively above-mentioned each catalyst activity.Raw oil character is shown in Table 1.When evaluating catalyst, pass through beds after hydrogen and raw oil mixing, first pass through Hydrodemetalation catalyst, then through above each example catalyst.The process conditions used during evaluation are the most identical, are respectively as follows: reaction pressure, 14.6MPa, reaction temperature 400 DEG C, total liquid hourly space velocity (LHSV), 0.6 h-1, hydrogen to oil volume ratio, 1000.Reactor volume is: Ф 25mm × 2000mm.Loaded catalyst is respectively as follows: catalyst for demetalation 80cm3, above each example catalyst, 120 cm3.The Activity evaluation of operating 200h is shown in Table 2.
Table 1.
Table 2.
By table 2 data it can be seen that the catalyst that the present invention provides has higher hydrodesulfurization and hydrodenitrogenationactivity activity compared with reference catalyst.
Claims (19)
1. the preparation method of a heavy oil hydrogenating treatment catalyst, it is characterized in that including following content: (1) impregnates physics expanding agent I respectively with hydrogenation active component impregnation liquid I and titaniferous solution I, impregnating physics expanding agent II respectively with hydrogenation active component impregnation liquid II and titaniferous solution II, physics expanding agent I and physics expanding agent II drying after dipping are standby；(2) the physics expanding agent I of step (1) gained, physics expanding agent II are become plastic with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizer kneading, extrusion, dry, roasting, prepare modified aluminium oxide supports；(3) modified aluminium oxide supports obtained by hydrogenation active component impregnation liquid III impregnation steps (2), drying, roasting, prepare heavy oil hydrogenating treatment catalyst.
The most in accordance with the method for claim 1, it is characterised in that: described hydrogenation active component is VIB and/or group VIII metal, and vib metals is molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；Hydrogenation active component impregnation liquid is the one in the acid solution containing hydrogenation active component, aqueous solution or ammonia solution.
3. according to the method described in claim 1 or 2, it is characterised in that: hydrogenation active component I described in step (1) is at least to contain a kind of active component different from step (3) hydrogenation active component III composition.
4. according to the method described in claim 1 or 2, it is characterised in that: hydrogenation active component II described in step (1) is at least to contain a kind of active component different from step (3) hydrogenation active component III composition.
5. according to the method described in claim 1 or 2, it is characterized in that: in the hydrogenation active component impregnation liquid I described in step (1), vib metals weight content is calculated as the 0.8wt%-1.0wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.5wt%-0.7wt% of final catalyst weight with oxide；Hydrogenation active component impregnation liquid I consumption is the saturated water adsorptive value of physics expanding agent I.
6. according to the method described in claim 1 or 2, it is characterized in that: in the hydrogenation active component impregnation liquid II described in step (1), vib metals weight content is calculated as the 0.3wt%-0.5wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.2wt%-0.4wt% of final catalyst weight with oxide；Hydrogenation active component impregnation liquid II consumption is the saturated water adsorptive value of physics expanding agent II.
The most in accordance with the method for claim 1, it is characterised in that: the ethanol solution that titaniferous solution is butyl titanate, isopropyl titanate or tetraethyl titanate described in step (1) or the one in titanium tetrachloride solution.
8. according to the method described in claim 1 or 7, it is characterised in that: the saturated water adsorptive value that consumption is physics expanding agent I of the titaniferous solution I described in step (1), after dipping, in physics expanding agent I, Ti content accounts for the 0.6%-0.8% of catalyst weight in terms of oxide.
9. according to the method described in claim 1 or 7, it is characterized in that: the saturated water adsorptive value that consumption is physics expanding agent II of the titaniferous solution II described in step (1), after dipping, in physics expanding agent II, the content of titanium accounts for the 0.1%-0.3% of catalyst weight in terms of oxide.
The most in accordance with the method for claim 1, it is characterized in that: step (1) described physics expanding agent is one or more mixing in carbon black powder, Linesless charcoal or wood flour, the particle diameter of physics expanding agent I is 600-1000 mesh, and the particle diameter of physics expanding agent II is 300-500 mesh.
11. in accordance with the method for claim 1, it is characterised in that: the drying condition described in step (1) is that nature dries in the shade or dry 1-10 hour in 50-120 DEG C.
12. in accordance with the method for claim 1, it is characterised in that: the 4%-8% that addition is boehmite dry glue powder weight of the 3%-5% that addition is boehmite dry glue powder weight of the physics expanding agent I described in step (2), physics expanding agent II.
13. in accordance with the method for claim 1, it is characterized in that: adding mass concentration in the kneading process described in step (2) is 1%-5% Aqueous Solutions of Polyethylene Glycol, wherein the mean molecule quantity of Polyethylene Glycol is 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 gram/100 grams boehmite dry glue powders.
14. in accordance with the method for claim 1, it is characterised in that: the chemical enlargement agent described in step (2) is one or more in phosphoric acid or phosphate, and chemical enlargement agent addition is the 3%-5% of boehmite dry glue powder weight.
15. in accordance with the method for claim 1, it is characterised in that: the extrusion aid described in step (2) is one or more in sesbania powder, starch or methylcellulose, and extrusion aid addition is the 3%-5% of boehmite dry glue powder weight.
16. in accordance with the method for claim 1, it is characterised in that: the peptizer described in step (2) is one or more mixing in formic acid, acetic acid, citric acid or nitric acid, and addition is the 3%-10% of boehmite dry glue powder weight.
17. in accordance with the method for claim 1, it is characterised in that: step (2) described drying condition is to be dried 1-10 hour at 100-130 DEG C；Roasting process is 500-650 DEG C of roasting 2-4 hour.
18. according to the method described in claim 1 or 2, it is characterised in that: in the hydrogenation active component impregnation liquid III described in step (3), vib metals content is calculated as 7-15g/100ml with oxide, and VII race tenor is calculated as 0.8-3g/100ml with oxide.
19. in accordance with the method for claim 1, it is characterised in that: the drying condition described in step (3) is to be dried 6-10 hour at 80-120 DEG C；Described roasting condition is roasting 3-6 hour at 400-600 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510196347.2A CN106140182B (en) | 2015-04-23 | 2015-04-23 | A kind of preparation method of heavy oil hydrogenating treatment catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510196347.2A CN106140182B (en) | 2015-04-23 | 2015-04-23 | A kind of preparation method of heavy oil hydrogenating treatment catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106140182A true CN106140182A (en) | 2016-11-23 |
| CN106140182B CN106140182B (en) | 2018-07-03 |
Family
ID=57346494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510196347.2A Active CN106140182B (en) | 2015-04-23 | 2015-04-23 | A kind of preparation method of heavy oil hydrogenating treatment catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106140182B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110935462A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN111097469A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method thereof |
| CN111375401A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method thereof |
| CN111821988A (en) * | 2019-04-17 | 2020-10-27 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN112717949A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method and application thereof |
| CN112934209A (en) * | 2021-02-05 | 2021-06-11 | 山东公泉化工股份有限公司 | High-desulfurization-activity hydrotreating catalyst carrier and preparation method of catalyst |
| CN114433053A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN114433109A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrogenation pretreatment catalyst, and preparation method and application thereof |
| CN116328782A (en) * | 2021-12-24 | 2023-06-27 | 中国石油天然气股份有限公司 | Hydrodemetallization catalyst for titanium-containing residual oil and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
| CN1206037A (en) * | 1997-07-22 | 1999-01-27 | 中国石油化工总公司 | Residuum hydrogenating and metal-eliminating catalyst |
| CN1289640A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing carried catalyst for hydrogenation and demetalation |
| CN102441368A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydro-demetalization catalyst for heavy oil |
| CN102728373A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN102728374A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of hydrotreatment catalyst |
-
2015
- 2015-04-23 CN CN201510196347.2A patent/CN106140182B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
| CN1206037A (en) * | 1997-07-22 | 1999-01-27 | 中国石油化工总公司 | Residuum hydrogenating and metal-eliminating catalyst |
| CN1289640A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing carried catalyst for hydrogenation and demetalation |
| CN102441368A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydro-demetalization catalyst for heavy oil |
| CN102728373A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN102728374A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of hydrotreatment catalyst |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110935462B (en) * | 2018-09-25 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN110935462A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN111097469A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method thereof |
| CN111097469B (en) * | 2018-10-25 | 2022-10-11 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method thereof |
| CN111375401A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method thereof |
| CN111821988A (en) * | 2019-04-17 | 2020-10-27 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN111821988B (en) * | 2019-04-17 | 2022-07-12 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN112717949B (en) * | 2019-10-28 | 2022-07-12 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method and application thereof |
| CN112717949A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method and application thereof |
| CN114433053A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN114433109A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrogenation pretreatment catalyst, and preparation method and application thereof |
| CN114433109B (en) * | 2020-10-19 | 2023-05-30 | 中国石油化工股份有限公司 | Hydrogenation pretreatment catalyst and preparation method and application thereof |
| CN114433053B (en) * | 2020-10-19 | 2023-10-10 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method and application thereof |
| CN112934209A (en) * | 2021-02-05 | 2021-06-11 | 山东公泉化工股份有限公司 | High-desulfurization-activity hydrotreating catalyst carrier and preparation method of catalyst |
| CN116328782A (en) * | 2021-12-24 | 2023-06-27 | 中国石油天然气股份有限公司 | Hydrodemetallization catalyst for titanium-containing residual oil and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106140182B (en) | 2018-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106140182A (en) | A kind of preparation method of heavy oil hydrogenating treatment catalyst | |
| CN106140187B (en) | A kind of preparation method of Hydrodemetalation catalyst | |
| CN102441398B (en) | Method for preparing hydro-demetalization catalyst | |
| WO2018161952A1 (en) | Method for preparing hydrotreating catalyst by impregnation method | |
| CN101376110B (en) | Preparation of hydrogenation catalyst | |
| CN106140181B (en) | A kind of preparation method of siliceous Hydrodemetalation catalyst | |
| CN102463150B (en) | Preparation method of hydroprocessing catalyst | |
| CN105582951B (en) | A kind of preparation method of alkaline including earth metal Hydrodemetalation catalyst | |
| CN101590433A (en) | Modified aluminium oxide supports and the hydrogenation catalyst and the preparation method that make by this carrier | |
| CN102451722B (en) | Preparation method of eggshell-type hydrogenation catalyst | |
| CN105521793B (en) | A kind of preparation method of Hydrodemetalation catalyst | |
| CN103785396B (en) | A kind of preparation method of catalyst for heavy oil hydrogenation demetal | |
| CN103785401A (en) | Preparation method of hydrodemetalization catalyst for residuum | |
| CN108452845B (en) | Wax oil hydrogenation catalyst and preparation method thereof | |
| CN109304183A (en) | Handle the hydrotreating catalyst and the preparation method and application thereof of inferior oil material | |
| CN106140122B (en) | A kind of preparation method of boracic Hydrodemetalation catalyst | |
| CN102861588A (en) | Residual oil hydrogenation demetalization catalyst and preparation method thereof | |
| CN102994141A (en) | Inferior aviation kerosene hydrotreating method | |
| CN106140183B (en) | A kind of preparation method of the Hydrodemetalation catalyst containing zirconium | |
| CN111250103B (en) | Supported hydrogenation catalyst and preparation method thereof | |
| CN103506149A (en) | Preparation method of hydrocracking catalyst controlling active metal distribution | |
| CN112705246A (en) | Desulfurization and dearomatization catalyst and preparation method thereof | |
| CN106140208B (en) | A kind of preparation method of hydrogenation catalyst | |
| CN105582952B (en) | A kind of preparation method of the Hydrodemetalation catalyst containing rare earth | |
| CN107961771B (en) | Alumina carrier and preparation method thereof, and hydrofining catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |