CN106140187B - A kind of preparation method of Hydrodemetalation catalyst - Google Patents
A kind of preparation method of Hydrodemetalation catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of Hydrodemetalation catalyst, including following content：（1）Physics expanding agent I is impregnated respectively with alkali metal containing Element Solution I and hydrogenation active component maceration extract I, impregnates physics expanding agent II with alkali metal containing Element Solution II and hydrogenation active component maceration extract II, physics expanding agent I and II after drying, it is spare to spray ammonium salt solution；（2）By step（1）With boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizing agent kneading at plastic, extrusion, molding materials are heat-treated by the physics expanding agent I and II of gained, and modified aluminium oxide supports are made through drying, roasting in treated material；（3）Modified aluminium oxide supports are impregnated with hydrogenation active component maceration extract III, through drying, roasting, catalyst is made.Catalyst activity metal prepared by this method content at macropore is higher, and content is relatively low at aperture, and the Acidity at macropore is obviously improved, and improves the carbon accumulation resisting ability of macropore.
Description
Technical field
The present invention relates to a kind of preparation methods of Hydrodemetalation catalyst, add hydrogen more particularly to a kind of alkali metal containing
The preparation method of catalyst for demetalation.
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.
CN1351115A discloses hydrodemetallization and Hydrobon catalyst and preparation method thereof, and this method is by two kinds of differences
The aluminium oxide of property mixes extruded moulding with the solution etc. of metal containing group vib and group VIII metal, and then dry, roasting obtains
To catalyst of the present invention.A small amount of boron and at least one alkali or alkaline earth metal element are added in catalyst preparation process.
Catalyst of the present invention is suitable for heavy oil hydrodesulfurization and hydrodemetallization process.
The above method prepare residuum hydrogenating and metal-eliminating catalyst active metal component be at the macropore and aperture of carrier
It is uniformly distributed, causes the utilization rate of macropore relatively low, in addition, the surface acid property of carrier is to be improved to improve the anti-of catalyst
Carbon distribution ability.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of Hydrodemetalation catalyst.Party's legal system
Standby catalyst activity metal content at macropore is relatively high, and content is relatively low at aperture, and the Acidity at macropore is bright
It is aobvious to improve, the carbon accumulation resisting ability of macropore is improved, which has high activity and long-term operation stability.
The preparation method of the Hydrodemetalation catalyst of the present invention, including following content：
（1）Physics expanding agent I is impregnated respectively with alkali metal containing Element Solution I and hydrogenation active component maceration extract I, with containing alkali
Metallic element solution II and hydrogenation active component maceration extract II dipping physics expanding agent II, physics expanding agent I and physics expanding agent
II after drying, it is spare to spray ammonium salt solution；
（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, and extrusion, molding materials are placed in closed container and are heat-treated, and treated
Material is made through drying, roasting and contains active component and alkali metals modified alumina support；
（3）Modified aluminium oxide supports are impregnated with hydrogenation active component maceration extract III, through drying, roasting, alkali metal containing is made
Hydrodemetalation catalyst.
In the method for the present invention, step（1）The alkali metal element is one or more of in lithium, sodium, potassium, alkali metal containing
The solution of element is generally the aqueous solution of alkali metal element soluble-salt, and soluble-salt is generally nitrate, chloride, acetic acid
Salt, carbonate etc..
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 oxide weight contains
Amount is the 0.5wt%-0.7wt% of final catalyst weight, and group VIII metal oxide weight content is final catalyst weight
0.03wt%-0.05wt%, the dosage of 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 oxide weight
Content is the 0.3wt%-0.5wt% of final catalyst weight, and group VIII metal oxide weight content is final catalyst weight
The dosage of the 0.01wt%-0.03wt% of amount, maceration extract are physics expanding agent II saturated water adsorptive values.
In the method for the present invention, step（1）In the alkali metal containing Element Solution I, the weight content of alkali metal element is with oxygen
Compound is calculated as the 0.04wt%-0.06wt% of final catalyst weight, and the dosage of solution is physics expanding agent I saturated water adsorptive values.
In the method for the present invention, step（1）In the alkali metal containing Element Solution II, the weight content of alkali metal element is with oxygen
Compound is calculated as the 0.02wt%-0.04wt% of final catalyst weight, and the dosage of solution is physics expanding agent II saturated water adsorptive values.
In the method for the present invention, step（1）The physics expanding agent is that one or more of carbon black powder, charcoal or sawdust are mixed
It closes, preferably carbon black powder, 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.
In the method for the present invention, step（1）The ammonium salt solution is ammonium nitrate, ammonium carbonate, ammonium oxalate, ammonium citrate, carbon
One or more of sour hydrogen ammonium mixes, and the mass concentration of ammonium salt solution is 10%-30%, and the dosage of solution is physics expanding agent I
With the saturated water adsorptive value of physics expanding agent II.
In the method for the present invention, step（1）The dipping carries out as follows：Physics expanding agent I is placed in and sprays rolling
In pot, it is the golden containing alkali of physics expanding agent I saturated water adsorptive values to spray volume into rolling pot in the way of atomization under rotary state
The solution I for belonging to element, makes physics expanding agent I adsorption saturations, drying；Physics expanding agent I after drying, which is replaced in, sprays rolling pot
In, volume is sprayed as physics expanding agent I saturated water adsorptive values gold containing activity into rolling pot in the way of atomization under rotary state
The solution I for belonging to element is then dry；Physics expanding agent II is sprayed using the same manner；Physics expanding agent I after drying and physics
Expanding agent II, which is again placed in, to be sprayed in rolling pot, and into rolling pot, sprinkler body product is physics expanding agent in a manner of atomization under rotary state
I and physics expanding agent II saturated water adsorptive value ammonium salt solutions are spare.
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
6%-8%, the addition of physics expanding agent II is the 3%-5% 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 kind or several in phosphoric acid, phosphate or boric acid
Kind, preferably phosphate, wherein phosphate are selected from one or more of ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate, and chemistry expands
Agent addition in hole 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 sealing container can be autoclave or tube furnace, and the temperature of heat treatment is
120-160 DEG C, processing time is 3-6 hours.
In the method for the present invention, step（2）The drying condition is 1-10 hours dry at 100-130 DEG C；Roasting process
To be roasted 2-4 hours at 500-650 DEG C.
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 VIII with oxide
Race's tenor is calculated as 0.8-3g/100ml with oxide, and volume impregnation, incipient impregnation or spray impregnating may be used
Mode, 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.
Suitable alkali metal, active metallic element and ammonium salt are impregnated on physics expanding agent by the method for the present invention, and with it is quasi-
Modified aluminium oxide supports are made in boehmite kneading, molding, heat treatment, drying, roasting, and final impregnating active component is finally made
Catalyst.When sealing heat treatment, the gas and the water vapour effective modulation chemical property of carrier surface that ammonium salt decomposition generates,
The surface chemical property of carrier, activity is improved after impregnating active metal at the macropore especially formed after the roasting of physics expanding agent
The effect of metal and carrier improves the utilization rate of macropore and the catalytic activity of metal.Physics expanding agent is oxidized when roasting removes
It goes, selects the physics expanding agent with different-grain diameter, form the macropore knot with different pore size accordingly in the final catalyst
Structure.The alkali metal and active metal component loaded in physics expanding agent is loaded on corresponding duct, makes final catalyst
Active component content and alkali metal content at middle macropore significantly increase.In addition, in different-grain diameter physics expanding agent alkali metal and
Active component concentration is distinct, keeps the relatively large place's alkali metal in final catalyst aperture and active component content higher, aperture
Relatively small place's content is relatively low, and duct type is made to be matched well with active component, improves duct and active component
Utilization rate.The presence of alkali metal ion, catalyst neutralisation surface portion acid site, makes surface acid property be improved, effectively
Area carbon is inhibited, catalyst is made to hold the ability enhancing of metal and volume carbon.Active metallic content simultaneously at macropore is higher,
Activity increases, and improves the utilization rate of macropore.The addition of polyethylene glycol makes carbon black powder be uniformly mixed with boehmite when kneading,
Improve the uniformity coefficient of macropore.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）I10 grams of carbon black powder set
It rolls in pot in spray, under rotary state, is sprayed in a manner of being saturated dipping by carbon black powder of the atomizing type into rolling pot oxygen-containing
Change 0.5 gram of molybdenum, the active metal maceration extract of 0.04 gram of nickel oxide, the carbon black powder after dipping is 3 hours dry in 110 DEG C；After drying
Carbon black powder be replaced in spray rolling pot in, under rotary state, by be saturated impregnate in a manner of to rolling pot in spray containing potassium oxide
0.04 gram of wet chemical, the carbon black powder after dipping are 3 hours dry in 110 DEG C.
It is 300 to weigh grain size（Particle by 300 mesh sieve pores but can can't pass 325 mesh sieve pores）II4.3 grams of purpose carbon black powder
It is placed in spray rolling pot, under rotary state, is sprayed and contained in a manner of being saturated dipping by carbon black powder of the atomizing type into rolling pot
0.3 gram of molybdenum oxide, the active metal maceration extract of 0.03 gram of nickel oxide, the carbon black powder after dipping are 3 hours dry in 110 DEG C；It is dry
Carbon black powder afterwards, which is replaced in, to be sprayed in rolling pot, under rotary state, is sprayed into rolling pot containing oxidation in a manner of being saturated and impregnating
The wet chemical that 0.03 gram of potassium, the carbon black powder after dipping are 3 hours dry in 110 DEG C.
By after above-mentioned drying carbon black powder I and carbon black powder II be again placed in spray rolling pot in, under rotary state with saturation
The mode of dipping sprays the sal volatile that stain mass concentration is 20% into rolling pot, and the carbon black powder after dipping is without drying for standby.
Weigh boehmite dry glue powder（Aluminium oxide contents on dry basis 70%）143 grams and above-mentioned steps carbon black powder I and carbon black powder
II, 7.5 grams of sesbania powders, 3 grams of ammonium phosphate are uniformly mixed, and it is 3% that mass concentration, which is added, the polyethylene glycol that average molecular weight is 4000
43 grams of kneadings of aqueous solution, 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
Above-mentioned material is placed in sealing tube furnace and is heat-treated 5 hours in 130 DEG C, is then vented by the cloverleaf pattern item of a diameter of 1.8mm
Water vapour is 4 hours dry in 130 DEG C, and the molding after drying roasts 4 hours at a temperature of 550 DEG C.
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 10.8wt%, and NiO mass percentages are
1.26wt%, potassium oxide mass percentage are 0.07wt%.
Embodiment 2
With embodiment 1, only the grain size of carbon black powder I is 1000 mesh（Particle by 1000 mesh sieve pores but can can't pass 1340
Mesh sieve pore）, weight is 11.4 grams, impregnates and contains 0.7 gram of molybdenum oxide in the activity component impregnation liquid of carbon black powder I, 0.03 gram of nickel oxide,
Alkali metal soln is the sodium nitrate solution containing 0.05 gram of sodium oxide molybdena.The grain size of carbon black powder II is 500 mesh（Particle can pass through 500 mesh
Sieve pore but it can't pass 600 mesh sieve pores）, weight is 7.2 grams, contains molybdenum oxide 0.5 in the activity component impregnation liquid of dipping carbon black powder II
Gram, 0.02 gram of nickel oxide, alkali metal soln is the sodium nitrate solution containing 0.04 gram of sodium oxide molybdena.Ammonium salt solution is that mass concentration is
10% ammonium oxalate solution.The temperature of heat treatment is 140 DEG C, and processing time is 3 hours.The addition of polyglycol solution is 43
Restrain to obtain catalyst C2 of the present invention, catalyst MoO3Mass percentage is 11.2wt%, and NiO mass percentages are
1.25wt%, sodium oxide molybdena mass percentage are 0.09wt%.
Embodiment 3
With embodiment 1, only the grain size of carbon black powder I is 600 mesh（Particle can by 600 mesh sieve pores but can't pass 800 mesh sieve
Hole）, weight is 8.6 grams, and 0.6 gram of molybdenum oxide, 0.05 gram of nickel oxide, alkali gold are contained in the activity component impregnation liquid of dipping carbon black powder I
Belong to the lithium nitrate solution that solution is 0.06 gram of oxide containing lithium.The grain size of carbon black powder II is 400 mesh（Particle can pass through 400 mesh sieve pores
But it can't pass 500 mesh sieve pores）, weight is 5.7 grams, contains 0.4 gram of molybdenum oxide, oxygen in the activity component impregnation liquid of dipping carbon black powder II
Change 0.01 gram of nickel, alkali metal soln is the lithium nitrate solution of 0.02 gram of oxide containing lithium.Ammonium salt solution is the carbon that mass concentration is 30%
Sour hydrogen ammonium salt solution.The temperature of heat treatment is 120 DEG C, and processing time is 6 hours.The addition of polyglycol solution is 100 restraints
Obtain catalyst C3 of the present invention, catalyst MoO3Mass percentage is 10.9wt%, and NiO mass percentages are 1.26wt%,
Lithia mass percentage is 0.08wt%.
Embodiment 4
With embodiment 1, only carbon black powder changes charcoal into, and ammonium salt solution is the ammonium citrate solution that mass concentration is 20%.Heat
The temperature of processing is 160 DEG C, and processing time is 3 hours.The addition of polyglycol solution restrains to obtain catalyst of the present invention for 100
C4, catalyst MoO3Mass percentage is 10.8wt%, and NiO mass percentages are 1.26wt%, potassium oxide quality percentage
Content is 0.07wt%.
Embodiment 5
With embodiment 1, only the grain size of carbon black powder I is 600 mesh（Particle can by 600 mesh sieve pores but can't pass 800 mesh sieve
Hole）, weight is 10.7 grams, contains 0.55 gram of molybdenum oxide, 0.05 gram of nickel oxide, alkali in the activity component impregnation liquid of dipping carbon black powder I
Metallic solution is the lithium nitrate solution of 0.05 gram of oxide containing lithium.The grain size of carbon black powder II is 400 mesh（Particle can be sieved by 400 mesh
Hole but it can't pass 500 mesh sieve pores）, weight is 5.7 grams, contains molybdenum oxide 0.45 in the activity component impregnation liquid of dipping carbon black powder II
Gram, 0.02 gram of nickel oxide, alkali metal soln is the lithium nitrate solution of 0.04 gram of oxide containing lithium.Ammonium salt solution is that mass concentration is
15% ammonium citrate solution.The temperature of heat treatment is 150 DEG C, and processing time is 4 hours.The addition of polyglycol solution is
86 grams, contain MoO with 150 milliliters when dipping38 grams/100 milliliters, NiO0.9 grams/100 milliliters of molybdenum-nickel-ammonia active metal salt is molten
Catalyst C5 of the present invention, catalyst MoO is made in liquid impregnated carrier3Mass percentage is 9wt%, and NiO mass percentages are
0.97wt%, lithia mass percentage are 0.09wt%.
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 10.8wt%, and NiO mass percentages are 1.26wt%, potassium oxide quality
Percentage composition is 0.07wt%.
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 alkali metal is unsupported on carbon black powder, but is added when kneading, and preparing has and implementation
The catalyst C8 of 1 same composition of example.
Comparative example 3
With example 1, only active metal and alkali metal are unsupported on carbon black powder, but are added when kneading, prepare
Catalyst C9 with composition same as Example 1.
Comparative example 4
With example 1, only carrier is not thermally treated, prepares the catalyst C10 with composition same as Example 1.
Comparative example 5
It is 800 mesh to weigh grain size（Particle by 800 mesh sieve pores but can can't pass 1000 mesh sieve pores）14.3 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 dipping by carbon black powder of the atomizing type into rolling pot
0.8 gram of molybdenum oxide, the active metal maceration extract of 0.07 gram of nickel oxide, the carbon black powder after dipping are 3 hours dry in 110 DEG C；It is dry
Carbon black powder afterwards, which is replaced in, to be sprayed in rolling pot, under rotary state, is sprayed into rolling pot containing oxidation in a manner of being saturated and impregnating
The wet chemical that 0.07 gram of potassium, the carbon black powder after dipping are 3 hours dry in 110 DEG C.
Carbon black powder after above-mentioned drying is again placed in spray rolling pot in, under rotary state by be saturated impregnate in a manner of to
The sal volatile that stain mass concentration is 20% is sprayed in rolling pot, the carbon black powder after dipping is without drying for 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 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
Above-mentioned material is placed in sealing tube furnace and is heat-treated 5 hours in 130 DEG C, is then vented water vapour by the cloverleaf pattern item of 1.8mm
4 hours dry in 130 DEG C, the molding after drying roasts 4 hours at a temperature of 550 DEG C.
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 C11, catalyst MoO3Mass percentage is 10.8wt%, and NiO mass percentages are
1.26wt%, potassium oxide mass percentage are 0.07wt%.
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 (15)
1. a kind of preparation method of Hydrodemetalation catalyst, it is characterised in that including following content：（1）With alkali metal containing element
Solution I and hydrogenation active component maceration extract I impregnate physics expanding agent I respectively, with alkali metal containing Element Solution II and hydrogenation activity
Component maceration extract II dipping physics expanding agent II, physics expanding agent I and physics expanding agent II after drying, it is standby to spray ammonium salt solution
With；（2）By step（1）The physics expanding agent I and physics expanding agent II of gained and boehmite dry glue powder, chemical enlargement agent,
At plastic, extrusion, molding materials are placed in closed container and are heat-treated for extrusion aid, peptizing agent kneading, treated material
Through drying, roasting, it is made and contains active component and alkali metals modified alumina support；（3）It is soaked with hydrogenation active component maceration extract III
Hydrodemetalation catalyst is made through drying, roasting in stain modified aluminium oxide supports；The hydrogenation active component be VIB and/
Or group VIII metal, vib metals are molybdenum and/or tungsten, the metal of group VIII is cobalt and/or nickel；Hydrogenation active component is soaked
Stain liquid is one kind in the acid solution containing hydrogenation active component, aqueous solution or ammonia solution；Step（1）The hydrogenation active component
In maceration extract I, vib metals oxide weight content is the 0.5wt%-0.7wt% and/or the of final catalyst weight
Group VIII metal oxide weight content is the 0.03wt%-0.05wt% of final catalyst weight, and the dosage of maceration extract is physics
Expanding agent I saturated water adsorptive values；Step（1）In the hydrogenation active component maceration extract II, vib metals oxide weight content
0.3wt%-0.5wt% and/or group VIII metal oxide weight content for final catalyst weight are final catalyst weight
The dosage of the 0.01wt%-0.03wt% of amount, maceration extract are physics expanding agent II saturated water adsorptive values；Step（1）The alkali metal containing
In Element Solution I, the weight content of alkali metal element is calculated as the 0.04wt%-0.06wt% of final catalyst weight with oxide,
The dosage of solution is physics expanding agent I saturated water adsorptive values；Step（1）In the alkali metal containing Element Solution II, alkali metal element
Weight content the 0.02wt%-0.04wt% of final catalyst weight is calculated as with oxide, the dosage of solution is physics expanding agent
II saturated water adsorptive values；Step（1）The physics expanding agent is the mixing of one or more of carbon black powder, charcoal or sawdust；Step
（1）The grain size of the 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 alkali metal element is selected from lithium, sodium, potassium
Middle one or more, the solution of alkali metal containing element are the aqueous solution of alkali metal element soluble-salt.
3. according to the method for claim 1, it is characterised in that：Step（1）The ammonium salt solution is ammonium nitrate, carbonic acid
One or more of ammonium, ammonium oxalate, ammonium citrate, ammonium hydrogen carbonate mix, and the mass concentration of ammonium salt solution is 10%-30%, molten
The dosage of liquid is the saturated water adsorptive value of physics expanding agent I and physics expanding agent II.
4. according to the method for claim 1, it is characterised in that：Step（1）The dipping carries out as follows：By object
Reason expanding agent I, which is placed in, to be sprayed in rolling pot, and volume is sprayed as physics expanding agent I into rolling pot in the way of atomization under rotary state
The solution I of the alkali metal containing element of saturated water adsorptive value makes physics expanding agent I adsorption saturations, drying；Physics expanding agent after drying
I, which is replaced in, to be sprayed in rolling pot, and spray volume into rolling pot in the way of atomization under rotary state is saturated as physics expanding agent I
The solution I containing active metallic element of water absorption is then dry；Physics expanding agent II is sprayed using the same manner；Object after drying
Reason expanding agent I and physics expanding agent II, which is again placed in, to be sprayed in rolling pot, is sprayed into rolling pot in a manner of atomization under rotary state
Volume is that physics expanding agent I and physics expanding agent II saturated water adsorptive value ammonium salt solutions are spare.
5. 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.
6. 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 6%-8% of boehmite dry glue powder weight.
7. according to the method for claim 1, it is characterised in that：Step（2）Described in physics expanding agent II addition
For the 3%-5% of boehmite dry glue powder weight.
8. 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.
9. according to the method for claim 1, it is characterised in that：Step（2）The chemical enlargement agent is phosphoric acid, phosphate
Or one or more of boric acid, chemical enlargement agent addition are the 3%-5% of boehmite dry glue powder weight.
10. according to the method for claim 1, it is characterised in that：Step（2）The extrusion aid be sesbania powder, starch or
One or more of methylcellulose, extrusion aid addition are the 3%-5% of boehmite dry glue powder weight.
11. 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.
12. according to the method for claim 1, it is characterised in that：Step（2）The closed container is autoclave or tubular type
Stove, heat treatment temperature are 120-160 DEG C, and processing time is 3-6 hours.
13. according to the method for claim 1, it is characterised in that：Step（2）The drying condition is at 100-130 DEG C
It is 1-10 hours dry；Roasting process is to be roasted 2-4 hours at 500-650 DEG C.
14. 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, it is 1-5 hours to use volume impregnation, incipient impregnation or spray impregnation method, dip time.
15. 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.
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| CN109277095B (en) * | 2017-07-20 | 2021-07-30 | 中国石油化工股份有限公司 | Silicon-containing alumina carrier and preparation method and application thereof |
| CN109277108B (en) * | 2017-07-20 | 2021-07-27 | 中国石油化工股份有限公司 | Silicon-containing hydrodemetallization catalyst and preparation method and application thereof |
| CN110935461B (en) * | 2018-09-25 | 2022-07-08 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrodemetallization catalyst |
| CN110935463B (en) * | 2018-09-25 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of hydrodemetallization catalyst |
| CN110935465B (en) * | 2018-09-25 | 2022-06-07 | 中国石油化工股份有限公司 | Preparation method of demetalization catalyst |
| CN110935467B (en) * | 2018-09-25 | 2022-04-08 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN111097458B (en) * | 2018-10-25 | 2022-06-07 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method thereof |
| CN111097432B (en) * | 2018-10-25 | 2022-07-08 | 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 |
| CN111375437B (en) * | 2018-12-29 | 2022-08-12 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst carrier, catalyst and preparation method thereof |
| CN111375419B (en) * | 2018-12-29 | 2022-07-12 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN111375397B (en) * | 2018-12-29 | 2022-08-12 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst carrier, catalyst and preparation method thereof |
| CN109876806A (en) * | 2019-03-13 | 2019-06-14 | 长治市霍家工业有限公司 | A kind of catalyst for hydrogenation and preparation method thereof and purposes |
| CN111821965B (en) * | 2019-04-17 | 2022-07-08 | 中国石油化工股份有限公司 | Carrier and catalyst for hydrogenation protective agent and preparation method thereof |
| CN111821990B (en) * | 2019-04-17 | 2022-07-12 | 中国石油化工股份有限公司 | Residual oil hydrogenation protective agent carrier, catalyst 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 CN201510196358.0A patent/CN106140187B/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 |
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