CN106140183B - A kind of preparation method of the Hydrodemetalation catalyst containing zirconium - Google Patents
A kind of preparation method of the Hydrodemetalation catalyst containing zirconium Download PDFInfo
- Publication number
- CN106140183B CN106140183B CN201510196360.8A CN201510196360A CN106140183B CN 106140183 B CN106140183 B CN 106140183B CN 201510196360 A CN201510196360 A CN 201510196360A CN 106140183 B CN106140183 B CN 106140183B
- Authority
- CN
- China
- Prior art keywords
- expanding agent
- physics expanding
- agent
- weight
- oxide
- 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.)
- Active
Links
Abstract
The invention discloses a kind of preparation methods of Hydrodemetalation catalyst containing zirconium, including following content:(1)Physics expanding agent I is impregnated respectively with hydrogenation active component maceration extract I and I containing zirconium solution, impregnates physics expanding agent II respectively with hydrogenation active component maceration extract II and II containing zirconium solution, and the physics expanding agent I and physics expanding agent II after dipping are through drying for standby;(2)By step(1)The physics expanding agent I and physics expanding agent II of gained are with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizing agent kneading at plastic, extrusion, drying, material after drying first roasts in a nitrogen atmosphere, then roasts in air atmosphere and modified aluminium oxide supports are made;(3)With hydrogenation active component maceration extract III impregnation steps(2)Modified aluminium oxide supports, through drying, roasting, be made Hydrodemetalation catalyst containing zirconium.Catalyst activity metal prepared by this method content at macropore is relatively high, and content is relatively low at aperture, and the utilization rate of macropore significantly improves, which has high activity and long-term operation stability.
Description
Technical field
The present invention relates to a kind of preparation methods of Hydrodemetalation catalyst containing zirconium.
Background technology
With the raising that raw material deep processing requires in world wide, main energy sources structure is gradually to macromolecular and high-carbon direction
Development, it is even more so for China of the universal heaviness of crude oil.Resistance is spread effectively to solve heavy oil component in catalyst duct
Power is excessive, catalyst activity reduction or the problems such as inactivation caused by beavy metal impurity deposition and coking, and an urgent demand is in oil
The widely used alumina support of the industries such as chemical industry has the characteristic of macropore appearance and large aperture.Large aperture is conducive to macromolecular chemical combination
For object to spreading inside catalyst granules, big pore volume, which is then conducive to improve, holds metal or coke ability.
CN1206037A discloses a kind of residuum hydrogenating and metal-eliminating catalyst, and this method is same in carrying alumina production procedure
When physics expanding agent and chemical enlargement agent is added, then active component is loaded on carrier in a manner of spraying and impregnating, the catalysis
The Kong Rongwei 0.80-1.20ml/g of agent, specific surface area 110-200m2/ g, can several apertures be 15-20nm, bulk density is
0.50-0.60g/ml。
CN1289640A discloses a kind of preparation method of carried catalyst for hydrogenation and demetalation.It is used not in this method
Saturation sprays technology, and the catalyst after spraying is not dried, and is directly placed into roaster.After this method effectively prevents
Migration of the metal salt solution from material lower layer to upper layer or surface in continuous drying process, reduces production cost.
US4,448,896 disclose a kind of catalyst of hydrodesulfurization and heavy metal, the preparation method of the catalyst be by
It is 100-350m that active component, which loads to specific surface area,2/ g, pore radius are the Kong Rongwei 0.5-1.5ml/g's of 3.75-7500nm
On alumina support, the preparation method of the carrier be activated alumina or activated alumina precursor are mixed with carbon black, are molded,
Roasting.
CN102989493A discloses a kind of preparation method of heavy-oil hydrogenation processing composite catalyst, and this method is to contain carrier
The silica of weight 2.5%-12%, titanium oxide, zirconium oxide, chromium oxide, boron oxide, lithia, phosphorous oxide, one kind in F or more
Kind aluminium oxide be carrier, supported active metals cobalt, molybdenum, the sulfide of nickel or tungsten, phosphide and sulphur phosphide composite catalyzing
Agent;Active metal accounts for the 5%-50% of catalyst weight.
Residuum hydrogenating and metal-eliminating catalyst active metal component prepared by the above method is punished in the macropore and aperture of carrier
Cloth is more uniform, causes the utilization rate of macropore relatively low.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of the Hydrodemetalation catalyst containing zirconium.The party
Catalyst activity metal prepared by the method content at macropore is relatively high, and content is relatively low at aperture, and the utilization rate of macropore is aobvious
It writes and improves, which has high activity and long-term operation stability.
The preparation method of the Hydrodemetalation catalyst containing zirconium of the present invention, including following content:
(1)Physics expanding agent I is impregnated respectively with hydrogenation active component maceration extract I and I containing zirconium solution, uses hydrogenation active component
Maceration extract II and II containing zirconium solution impregnate physics expanding agent II respectively, the physics expanding agent I after dipping and physics expanding agent II warps
Drying for standby;
(2)By step(1)The physics expanding agent I and physics expanding agent II of gained expand with boehmite dry glue powder, chemistry
Hole agent, extrusion aid, peptizing agent kneading are at plastic, extrusion, drying, it is dry after material first roast in a nitrogen atmosphere, then
It roasts in air atmosphere and modified aluminium oxide supports is made;
(3)With hydrogenation active component maceration extract III impregnation steps(2)Modified aluminium oxide supports, through drying, roasting, system
Zirconium Hydrodemetalation catalyst must be contained.
In the method for the present invention, the hydrogenation active component is VIB and/or group VIII metal, and vib metals are molybdenum
And/or tungsten, the metal of group VIII is cobalt and/or nickel;Hydrogenation active component maceration extract can be to contain hydrogenation active component
One kind in acid solution, aqueous solution or ammonia solution.
In the method for the present invention, step(1)In the hydrogenation active component maceration extract I, vib metals weight content is with oxygen
Compound is calculated as the 0.4wt%-0.6wt% of final catalyst weight, and group VIII weight metal content is calculated as finally urging with oxide
The 0.1wt%-0.3wt% of agent weight.The dosage of active metal maceration extract is physics expanding agent I saturated water adsorptive values.
In the method for the present invention, step(1)In the hydrogenation active component maceration extract II, vib metals weight content with
Oxide is calculated as the 0.1wt%-0.3wt% of final catalyst weight, and group VIII weight metal content is calculated as finally with oxide
The 0.03wt%-0.5wt% of catalyst weight.The dosage of active metal maceration extract is physics expanding agent II saturated water adsorptive values.
In the method for the present invention, step(1)The I containing zirconium solution is the aqueous solution of soluble zirconates, and soluble zirconates can
Think that one or more of zirconium nitrate, zirconium chloride, zirconium sulfate mix, the saturation that the dosage of solution is physics expanding agent I absorbs water
It measures, the content of zirconium accounts for the 0.4%-0.6% of catalyst weight in terms of oxide in physics expanding agent I after dipping.
In the method for the present invention, step(1)The II containing zirconium solution is the aqueous solution of soluble zirconates, and soluble zirconates can
Think that one or more of zirconium nitrate, zirconium chloride, zirconium sulfate mix, the saturation that the dosage of solution is physics expanding agent II absorbs water
It measures, the content of zirconium accounts for the 0.1%-0.3% of catalyst weight in terms of oxide in physics expanding agent II after dipping.
In the method for the present invention, step(1)The physics expanding agent is carbon black powder, charcoal, sawdust, one kind in starch or several
The grain size of kind mixing, physics expanding agent I is 600-1000 mesh, and the grain size of physics expanding agent II is 300-500 mesh.
In the method for the present invention, step(1)The drying condition is that nature dries in the shade or 1-10 hours dry in 50-120 DEG C.
In the method for the present invention, step(2)The boehmite dry glue powder can be prepared using any one method
Boehmite dry glue powder.
In the method for the present invention, step(2)Described in physics expanding agent I addition be boehmite dry glue powder weight
3%-5%, the addition of physics expanding agent II is the 4%-8% of boehmite dry glue powder weight.
In the method for the present invention, step(2)It is 1%-5% polyethylene glycol water that mass concentration is preferably added in the kneading process
Solution, the wherein average molecular weight of polyethylene glycol are 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 grams/100
Gram boehmite dry glue powder.
In the method for the present invention, step(2)The chemical enlargement agent is one or more of phosphoric acid or phosphate, preferably
Phosphate, wherein phosphate are selected from one or more of ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate, and chemical enlargement agent is added
Amount is the 3%-5% of boehmite dry glue powder weight.
In the method for the present invention, step(2)The extrusion aid is one kind or several in sesbania powder, starch or methylcellulose
Kind, preferably sesbania powder, extrusion aid addition are the 3%-5% of boehmite dry glue powder weight.
In the method for the present invention, step(2)The peptizing agent is one kind or several in formic acid, acetic acid, citric acid or nitric acid
Kind mixing, addition is the 3%-10% of boehmite dry glue powder weight, depending on last molding effect.
In the method for the present invention, step(2)The drying condition is 1-10 hours dry at 100-130 DEG C;Nitrogen atmosphere
Lower roasting process is to be roasted 2-4 hours at 500-650 DEG C, and roasting process is that roasting 2-4 is small at 450-550 DEG C under air atmosphere
When.
In the method for the present invention, step(3)The hydrogenation active component maceration extract III is to form to count according to final catalyst
It calculates and prepares.In hydrogenation active component maceration extract III, vib metals content is calculated as 7-15g/100ml, Section VII race with oxide
Tenor is calculated as 0.8-3g/100ml with oxide, and volume impregnation, incipient impregnation or spray impregnating side may be used
Formula, dip time are 1-5 hours.
In the method for the present invention, step(3)The drying condition is 6-10 hours dry at 80-120 DEG C;The roasting
Condition is to be roasted 3-6 hours at 400-600 DEG C.
The method of the present invention is impregnated into suitable containing zirconium solution and active metallic element on physics expanding agent, and with quasi- thin water
Alumina support is made in aluminium stone kneading, molding, drying, roasting, and catalyst is finally made in dipping active component.In a nitrogen atmosphere
When roasting, the active metal being carried in physics expanding agent is first responsible for zirconium surface, forms molybdenum-nickel/zirconium oxide active
Object improves the catalytic activity of active component.The oxidized removing of physics expanding agent is formed greatly in roasting process in air atmosphere
Hole, molybdenum-nickel/zirconium oxide in physics expanding agent are loaded on corresponding macropore, make the activity at macropore in final catalyst
Constituent content increases.The physics expanding agent with different-grain diameter is selected, make to be formed in final catalyst has different holes accordingly
The macroporous structure of diameter is conducive to mass transfer and the diffusion of reactant.The presence of zirconium has adjusted the surface nature of carrier at macropore, improves
The interaction of active component and carrier, improves the catalytic activity of active metal.Active metallic content at macropore simultaneously
Higher, activity increases, and improves the utilization rate of macropore.The addition of polyethylene glycol makes carbon black powder be mixed with boehmite when kneading
Uniformly, the uniformity coefficient of macropore is improved.Catalyst of the present invention is suitable for heavy resid hydrodemetallization field, this catalyst has
Higher activity and activity stability.
Specific implementation mode
The effect further illustrated the present invention with reference to embodiment and effect, but it is not limited to following embodiment.
Embodiment 1
It takes industrial ammonium heptamolybdate 55g to be placed in ammonium hydroxide, is stirred, until no insoluble matter, add industrial basic carbonate
Nickel 25g, is stirred, and until no insoluble matter, is made containing MoO310 grams/100 milliliters, NiO1.2 grams/100 milliliters of molybdenum-nickel-ammonia
Active metal salt solution.The dipping of the addition preparation various concentration of ammonium heptamolybdate and basic nickel carbonate can be adjusted as needed
Liquid.
It is 800 mesh to weigh grain size(Particle by 800 mesh sieve pores but can can't pass 1000 mesh sieve pores)I4.3 grams of carbon black powder
It is placed in spray rolling pot, under rotary state, is sprayed and contained in a manner of being saturated and spraying by carbon black powder of the atomizing type into rolling pot
0.5 gram of molybdenum oxide, the active metal maceration extract of 0.2 gram of nickel oxide, the carbon black powder after dipping are 3 hours dry in 110 DEG C.It will dry
Carbon black powder afterwards is replaced in spray rolling pot, under rotary state, with carbon black powder of the atomizing type into rolling pot to be saturated spray
The mode of leaching sprays the nitric acid aqueous zirconium containing 0.4 gram of zirconium oxide, the carbon black powder after dipping in 110 DEG C dry 3 hours it is spare.
It is 300 to weigh grain size(Particle by 300 mesh sieve pores but can can't pass 325 mesh sieve pores)II11.4 grams of purpose carbon black powder
It is uniformly mixed, is placed in spray rolling pot, under rotary state, with carbon black powder of the atomizing type into rolling pot to be saturated the side sprayed
Formula is sprayed containing 0.1 gram of molybdenum oxide, the active metal maceration extract of 0.03 gram of nickel oxide, and the carbon black powder after dipping is in 110 DEG C dry 3 small
When.Carbon black powder after drying is replaced in spray rolling pot, under rotary state, with carbon black powder of the atomizing type into rolling pot
The nitric acid aqueous zirconium containing 0.3 gram of zirconium oxide is sprayed in such a way that saturation sprays, the carbon black powder after dipping is in 110 DEG C dry 3 small
When it is spare.
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 fields
Cyanines powder, 3 grams of ammonium phosphate are uniformly mixed, and it is 3% that mass concentration, which is added, 43 grams of the Aqueous Solutions of Polyethylene Glycol that average molecular weight is 4000
Kneading, the aqueous solution continuation kneading being then added in right amount dissolved with 5 grams of nitric acid is uniform, is extruded on screw rod banded extruder a diameter of
The cloverleaf pattern item of 1.8mm is dried 3 hours in 120 DEG C, and the molding after drying is small in 600 DEG C of roastings 3 in a nitrogen atmosphere
When, then roasted 4 hours in 500 DEG C in air atmosphere.
Above-mentioned material is placed in beaker, contains MoO with 150 milliliters310 grams/100 milliliters, NiO1.2 grams/100 milliliters
Molybdenum-nickel-ammonia active metal salt solution impregnated carrier 5 hours filters off redundant solution, and 120 DEG C dry 2 hours, then roasted at 550 DEG C
Burn 5 hours obtained catalyst C1, catalyst MoO3Mass percentage is 10.6wt%, and NiO mass percentages are
1.4wt%, zirconium oxide percentage composition are 0.7wt%.
Embodiment 2
With embodiment 1, only carbon black powder I weight is 7.2 grams, and grain size is 600 mesh(Particle can be by 600 mesh sieve pores but logical
But 800 mesh sieve pore), contain 0.6 gram of molybdenum oxide in active component I, 0.3 gram of nickel oxide, containing 0.5 gram of zirconium oxide in I containing zirconium solution,
Carbon black powder II weight is 5.7 grams, and grain size is 400 mesh(Particle by 400 mesh sieve pores but can can't pass 500 mesh sieve pores), activearm
Contain 0.2 gram of molybdenum oxide in point II, 0.04 gram of nickel oxide, containing 0.2 gram of zirconium oxide, the addition of polyglycol solution in II containing zirconium solution
Amount restrains to obtain catalyst C2 of the present invention, catalyst MoO for 433Mass percentage is 10.8wt%, NiO mass percentages
For 1.44wt%, zirconium oxide mass percentage is 0. 7wt%.
Embodiment 3
With embodiment 1, only carbon black powder I weight is 5.7 grams, and grain size is 1000 mesh(Particle can by 1000 mesh sieve pores but
It can't pass 1340 mesh sieve pores), contain 0.4 gram of molybdenum oxide in active component I, 0.1 gram of nickel oxide, containing zirconium oxide 0.6 in I containing zirconium solution
Gram, carbon black powder II weight is 8.6 grams, and grain size is 500 mesh(Particle by 500 mesh sieve pores but can can't pass 600 mesh sieve pores), activity
Contain 0.3 gram of molybdenum oxide in component II, 0.05 gram of nickel oxide contains 0.1 gram of zirconium oxide in II containing zirconium solution, and polyglycol solution adds
Enter amount and restrains to obtain catalyst C3 of the present invention, catalyst MoO for 1003Mass percentage is 10.7wt%, and NiO mass percentages contain
Amount is 1.35wt%, and zirconium oxide mass percentage is 0.7wt%.
Embodiment 4
With embodiment 1, only carbon black powder changes charcoal into, and the addition of polyglycol solution is 100 to restrain of the invention to urge
Agent C4, catalyst MoO3Mass percentage is 10.6wt%, and NiO mass percentages are 1.4wt%, and zirconium oxide percentage contains
Amount is 0.7wt%.
Embodiment 5
With embodiment 1, contain MoO with 150 milliliters when dipping38 grams/100 milliliters, NiO0.9 grams/100 milliliters of molybdenum-nickel-ammonia
Catalyst C5 of the present invention, catalyst MoO is made in active metal salt solution impregnated carrier3Mass percentage is 8.6wt%, NiO
Mass percentage is 1.1wt%, and zirconium oxide mass percentage is 0.7wt%.
Embodiment 6
The obtained present invention of polyglycol solution is not added with embodiment 1, when only boehmite is mixed with carbon black powder to urge
Agent C6, catalyst MoO3Mass percentage is 10.6wt%, and NiO mass percentages are 1.4wt%, and zirconium oxide percentage contains
Amount is 0.7wt%.
Comparative example 1
With example 1, only active metal is unsupported on carbon black powder, but is added when kneading, prepare have with
The comparative catalyst C7 of 1 same composition of embodiment.
Comparative example 2
With example 1, only zirconium is unsupported on carbon black powder, but is added when kneading, and preparing has and 1 phase of embodiment
With the catalyst C8 of composition.
Comparative example 3
With example 1, only active metal and zirconium are unsupported on carbon black powder, but are added when kneading, and preparation has
The catalyst C9 of composition same as Example 1.
Comparative example 4
It is 800 mesh to weigh grain size(Particle by 800 mesh sieve pores but can can't pass 1000 mesh sieve pores)15.7 grams of carbon black powder
It is placed in spray rolling pot, under rotary state, is sprayed and contained in a manner of being saturated and spraying by carbon black powder of the atomizing type into rolling pot
0.6 gram of molybdenum oxide, the active metal maceration extract of 0.23 gram of nickel oxide, the carbon black powder after dipping are 3 hours dry in 110 DEG C.It will do
Carbon black powder after dry is replaced in spray rolling pot, under rotary state, with carbon black powder of the atomizing type into rolling pot to be saturated
The mode sprayed sprays the nitric acid aqueous zirconium containing 0.7 gram of zirconium oxide, the carbon black powder after dipping in 110 DEG C dry 3 hours it is spare.
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 fields
Cyanines powder, 3 grams of ammonium phosphate are uniformly mixed, and it is 3% that mass concentration, which is added, 43 grams of the Aqueous Solutions of Polyethylene Glycol that average molecular weight is 4000
Kneading, the aqueous solution continuation kneading being then added in right amount dissolved with 5 grams of nitric acid is uniform, is extruded on screw rod banded extruder a diameter of
The cloverleaf pattern item of 1.8mm is dried 3 hours in 120 DEG C, and the molding after drying is small in 600 DEG C of roastings 3 in a nitrogen atmosphere
When, then roasted 4 hours in 500 DEG C in air atmosphere.
Above-mentioned material is placed in beaker, contains MoO with 150 milliliters310 grams/100 milliliters, NiO1.2 grams/100 milliliters
Molybdenum-nickel-ammonia active metal salt solution impregnated carrier 5 hours filters off redundant solution, and 120 DEG C dry 2 hours, then roasted at 550 DEG C
Burn 5 hours obtained catalyst C10, catalyst MoO3Mass percentage is 10.6wt%, and NiO mass percentages are
1.4wt%, zirconium oxide percentage composition are 0.7wt%.
The catalyst prepared to examples detailed above and comparative example carries out activity rating, more above-mentioned each catalyst activity and stabilization
Property.Raw material oil nature and evaluation process conditions are shown in Tables 1 and 2, and the Activity evaluation for operating 200h is shown in Table 3, when with operating
Between increase, catalyst activity reduce, in order to keep catalyst activity to meet production requirement, need to catalyst bed
Temperature raising, 5000 hours rear catalyst bed Wen Sheng of operating are shown in Table 4.
Table 1.
Table 2
Table 3.
Table 4.
Catalyst provided by the invention compared with reference catalyst there is higher plus hydrogen to take off it can be seen from 3 data of table
Metal active.Find out after reacting 5000 hours, have using Hydrodemetalation catalyst provided by the invention from the result of table 4
Higher activity stability.
Claims (12)
1. a kind of preparation method of Hydrodemetalation catalyst containing zirconium, it is characterised in that including following content:(1)Use hydrogenation activity
Component maceration extract I and I containing zirconium solution impregnate physics expanding agent I respectively, with hydrogenation active component maceration extract II and II containing zirconium solution
Physics expanding agent II is impregnated respectively, and the physics expanding agent I and physics expanding agent II after dipping are through drying for standby;(2)By step(1)
The physics expanding agent I and physics expanding agent II of gained and boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizing agent are mixed
Plastic, extrusion, drying are pinched into, the material after drying first roasts in a nitrogen atmosphere, and then roasting is made in air atmosphere
Modified aluminium oxide supports;(3)With hydrogenation active component maceration extract III impregnation steps(2)Modified aluminium oxide supports, through drying,
Hydrodemetalation catalyst containing zirconium is made in roasting;The hydrogenation active component is VIB and/or group VIII metal, group VIB
Metal is molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel;Hydrogenation active component maceration extract is to contain hydrogenation activity group
One kind in the acid solution, aqueous solution or the ammonia solution that divide;Step(1)In the hydrogenation active component maceration extract I, group VIB gold
Belong to 0.4wt%-0.6wt% and/or group VIII weight metal content that weight content is calculated as final catalyst weight with oxide
The 0.1wt%-0.3wt% of final catalyst weight is calculated as with oxide;The dosage of active metal maceration extract is full for physics expanding agent I
And water absorption;Step(1)In the hydrogenation active component maceration extract II, vib metals weight content is calculated as most with oxide
The 0.1wt%-0.3wt% and/or group VIII weight metal content of whole catalyst weight are calculated as final catalyst weight with oxide
The 0.03wt%-0.5wt% of amount;The dosage of active metal maceration extract is physics expanding agent II saturated water adsorptive values;Step(1)Described
I containing zirconium solution is the aqueous solution of soluble zirconates, and the dosage of solution is the saturated water adsorptive value of physics expanding agent I, physics after dipping
The content of zirconium accounts for the 0.4%-0.6% of catalyst weight in terms of oxide in expanding agent I;Step(1)The II containing zirconium solution is
The aqueous solution of soluble zirconates, the dosage of solution are the saturated water adsorptive value of physics expanding agent II, after dipping in physics expanding agent II
The content of zirconium accounts for the 0.1%-0.3% of catalyst weight in terms of oxide;Step(1)The physics expanding agent is carbon black powder, charcoal
Or the mixing of one or more of sawdust, the grain size of physics expanding agent I is 600-1000 mesh, and the grain size of physics expanding agent II is
300-500 mesh.
2. according to the method for claim 1, it is characterised in that:Step(1)The drying condition be nature dry in the shade or in
50-120 DEG C 1-10 hours dry.
3. according to the method for claim 1, it is characterised in that:Step(2)Described in the addition of physics expanding agent I be
The addition of the 3%-5% of boehmite dry glue powder weight, physics expanding agent II are the 4%- of boehmite dry glue powder weight
8%。
4. according to the method for claim 1, it is characterised in that:Step(2)Mass concentration is added in the kneading process
For 1%-5% Aqueous Solutions of Polyethylene Glycol, the wherein average molecular weight of polyethylene glycol is 1000-4000, and Aqueous Solutions of Polyethylene Glycol adds
It is 30-70 grams/100 grams boehmite dry glue powders to enter amount.
5. according to the method for claim 1, it is characterised in that:Step(2)The chemical enlargement agent is phosphoric acid or phosphoric acid
One or more of salt, chemical enlargement agent addition are the 3%-5% of boehmite dry glue powder weight.
6. according to the method for claim 1, it is characterised in that:Step(2)The extrusion aid is sesbania powder, starch or first
One or more of base cellulose, extrusion aid addition are the 3%-5% of boehmite dry glue powder weight.
7. according to the method for claim 1, it is characterised in that:Step(2)The peptizing agent is formic acid, acetic acid, lemon
The mixing of one or more of acid or nitric acid, addition are the 3%-10% of boehmite dry glue powder weight.
8. according to the method for claim 1, it is characterised in that:Step(2)The drying condition is to be done at 100-130 DEG C
It is 1-10 hours dry.
9. according to the method for claim 1, it is characterised in that:Step(2)Under the nitrogen atmosphere roasting process be
500-650 DEG C roasts 2-4 hours.
10. according to the method for claim 1, it is characterised in that:Step(2)Under the air atmosphere roasting process be
450-550 DEG C roasts 2-4 hours.
11. according to the method for claim 1, it is characterised in that:Step(3)The hydrogenation active component maceration extract III
In, vib metals content is calculated as 7-15g/100mL with oxide and/or group VIII tenor is calculated as with oxide
0.8-3g/100mL。
12. according to the method for claim 1, it is characterised in that:Step(3)The drying condition is at 80-120 DEG C
It is 6-10 hours dry;The roasting condition is to be roasted 3-6 hours at 400-600 DEG C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510196360.8A CN106140183B (en) | 2015-04-23 | 2015-04-23 | A kind of preparation method of the Hydrodemetalation catalyst containing zirconium |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510196360.8A CN106140183B (en) | 2015-04-23 | 2015-04-23 | A kind of preparation method of the Hydrodemetalation catalyst containing zirconium |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106140183A CN106140183A (en) | 2016-11-23 |
CN106140183B true CN106140183B (en) | 2018-10-12 |
Family
ID=57347855
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510196360.8A Active CN106140183B (en) | 2015-04-23 | 2015-04-23 | A kind of preparation method of the Hydrodemetalation catalyst containing zirconium |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106140183B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109718797B (en) * | 2017-10-27 | 2021-08-06 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
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 |
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 CN201510196360.8A patent/CN106140183B/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 |
Also Published As
Publication number | Publication date |
---|---|
CN106140183A (en) | 2016-11-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106140187B (en) | A kind of preparation method of Hydrodemetalation catalyst | |
CN105582951B (en) | A kind of preparation method of alkaline including earth metal Hydrodemetalation catalyst | |
CN106140182B (en) | A kind of preparation method of heavy oil hydrogenating treatment catalyst | |
CN106140181B (en) | A kind of preparation method of siliceous Hydrodemetalation catalyst | |
CN105521793B (en) | A kind of preparation method of Hydrodemetalation catalyst | |
CN102441398B (en) | Method for preparing hydro-demetalization catalyst | |
CN101376110B (en) | Preparation of hydrogenation catalyst | |
CN103785401B (en) | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst | |
CN105709711A (en) | Preparation method for alumina carrier | |
CN102861615B (en) | Preparation method of macroporous alumina carrier | |
CN103785396A (en) | Preparation method of hydrodemetalization catalyst for heavy oil | |
CN106140122B (en) | A kind of preparation method of boracic Hydrodemetalation catalyst | |
CN106140183B (en) | A kind of preparation method of the Hydrodemetalation catalyst containing zirconium | |
CN102861588B (en) | Residual oil hydrogenation demetalization catalyst and preparation method thereof | |
CN103785399B (en) | A kind of preparation method of Hydrodemetalation catalyst | |
CN105709765B (en) | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst | |
CN105582952B (en) | A kind of preparation method of the Hydrodemetalation catalyst containing rare earth | |
CN106140208B (en) | A kind of preparation method of hydrogenation catalyst | |
CN105582947B (en) | A kind of preparation method of carbon containing residuum hydrogenating and metal-eliminating catalyst | |
CN105618072A (en) | Method for preparing hydrodemetalization catalyst | |
CN105983415B (en) | The preparation method of hydrotreating catalyst | |
CN104549332B (en) | A kind of catalyst for demetalation and preparation method thereof | |
CN107303491A (en) | The preparation method of Hydrodemetalation catalyst | |
CN105521794B (en) | A kind of preparation method of high activity residuum hydrogenating and metal-eliminating catalyst | |
CN105582945B (en) | A kind of preparation method of hydrotreating catalyst |
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 |