CN106140187A - 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 the preparation method of a kind of Hydrodemetalation catalyst, including following content: (1) impregnates physics expanding agent I respectively with alkali metal containing Element Solution I and hydrogenation active component impregnation liquid I, physics expanding agent II is impregnated with alkali metal containing Element Solution II and hydrogenation active component impregnation liquid II, physics expanding agent I and II after drying, sprays ammonium salt solution standby；(2) physics expanding agent I with II of step (1) gained is become plastic with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizer kneading, extrusion, molding materials carry out heat treatment, material drying after process, roasting, prepare modified aluminium oxide supports；(3) impregnate modified aluminium oxide supports, drying, roasting with hydrogenation active component impregnation liquid III, prepare catalyst.Catalyst activity metal content at macropore prepared by the method is higher, and at aperture, content is relatively low, 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 the preparation method of a kind of Hydrodemetalation catalyst, more particularly to the preparation method of a kind of alkali metal containing Hydrodemetalation 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.For effectively solving that heavy oil component is excessive at catalyst duct inside diffusional resistance, beavy metal impurity deposition and coking and the problem such as the catalyst activity reduction that causes or inactivation, an urgent demand possesses big pore volume and wide-aperture characteristic at the widely used alumina support of the industries such as petrochemical industry.Large aperture is conducive to macromolecular compound to catalyst granules diffusion inside, and big pore volume is then conducive to improving holding metal or coke ability.
The open a kind of residuum hydrogenating and metal-eliminating catalyst of CN1206037A, the method is simultaneously introduced physics expanding agent and chemical enlargement agent in carrying alumina production procedure, in the way of spray dipping, active component is loaded on carrier again, the pore volume of this catalyst is 0.80-1.20ml/g, and specific surface area is 110-200m2/ g, can several apertures be 15-20nm, and bulk density is 0.50-0.60g/ml.
CN1289640A discloses the preparation method of a kind of carried catalyst for hydrogenation and demetalation.Have employed unsaturation in the method and spray technology, the catalyst after spraying does not does dried, is directly placed in roaster.The method is effectively prevented in follow-up dry run metal salt solution by material lower floor to upper strata or the migration on surface, reduces production cost.
US4,448,896 disclose the catalyst of a kind of hydrodesulfurization and heavy metal, and the preparation method of this catalyst is that active component loads to specific surface area is 100-350m2/ g, pore radius is on the alumina support that pore volume is 0.5-1.5ml/g of 3.75-7500nm, the preparation method of this carrier be activated alumina or activated alumina precursor are mixed with white carbon black, molding, roasting.
CN1351115A open HDM and Hydrobon catalyst and preparation method thereof, two kinds of aluminium oxidies of different nature are mixed extruded moulding with the solution etc. containing group vib metal and group VIII metal by the method, then dry, roasting, obtains catalyst of the present invention.A small amount of boron and at least one alkali metal or alkali earth metal is added in catalyst preparation process.Catalyst of the present invention is applicable to heavy oil hydrodesulfurization and HDM process.
Residuum hydrogenating and metal-eliminating catalyst active metal component prepared by said method is evenly distributed at the macropore and aperture of carrier, and the utilization rate causing macropore is relatively low, it addition, the surface acid property of carrier is to be improved thus improves the carbon accumulation resisting ability of catalyst.
Summary of the invention
For the deficiencies in the prior art, the present invention provides the preparation method of a kind of Hydrodemetalation catalyst.Catalyst activity metal content at macropore prepared by the method is of a relatively high, and at aperture, content is relatively low, and the Acidity at macropore is obviously improved, and improves the carbon accumulation resisting ability of macropore, and this Hydrodemetalation catalyst 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 impregnation liquid I, physics expanding agent II is impregnated with alkali metal containing Element Solution II and hydrogenation active component impregnation liquid II, physics expanding agent I and physics expanding agent II after drying, sprays ammonium salt solution standby；
(2) the physics expanding agent I of step (1) gained is become plastic with physics expanding agent II with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizer kneading, extrusion, molding materials are placed in hermetic container and carry out heat treatment, material drying after process, roasting, prepare containing active component and alkali metals modified alumina support；
(3) impregnate modified aluminium oxide supports, drying, roasting with hydrogenation active component impregnation liquid III, prepare alkali metal containing Hydrodemetalation catalyst.
In the inventive method, alkali metal described in step (1) is selected from lithium, sodium, potassium one or more, the solution of alkali metal containing element is generally the aqueous solution of alkali metal soluble-salt, and soluble-salt is generally nitrate, chloride, acetate, carbonate etc..
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, in step (1) described hydrogenation active component impregnation liquid I, vib metals oxide weight content is the 0.5wt%-0.7wt% of final catalyst weight, group VIII metal oxide weight content is the 0.03wt%-0.05wt% of final catalyst weight, and the consumption of impregnation liquid is physics expanding agent I saturated water adsorptive value.
In the inventive method, in step (1) described hydrogenation active component impregnation liquid II, vib metals oxide weight content is the 0.3wt%-0.5wt% of final catalyst weight, group VIII metal oxide weight content is the 0.01wt%-0.03wt% of final catalyst weight, and the consumption of impregnation liquid is physics expanding agent II saturated water adsorptive value.
In the inventive method, in step (1) described alkali metal containing Element Solution I, the weight content of alkali metal is calculated as the 0.04wt%-0.06wt% of final catalyst weight with oxide, and the consumption of solution is physics expanding agent I saturated water adsorptive value.
In the inventive method, in step (1) described alkali metal containing Element Solution II, the weight content of alkali metal is calculated as the 0.02wt%-0.04wt% of final catalyst weight with oxide, and the consumption of solution is physics expanding agent II saturated water adsorptive value.
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 preferably carbon black powder, 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, ammonium salt solution described in step (1) is one or more mixing in ammonium nitrate, ammonium carbonate, ammonium oxalate, ammonium citrate, ammonium hydrogen carbonate, the mass concentration of ammonium salt solution is 10%-30%, and the consumption of solution is physics expanding agent I and the saturated water adsorptive value of physics expanding agent II.
In the inventive method, the following manner that is impregnated with described in step (1) is carried out: is placed in by physics expanding agent I and sprays in rolling pot, under rotary state, the mode with atomization sprays the volume solution I for the alkali metal containing element of physics expanding agent I saturated water adsorptive value in rolling pot, makes physics expanding agent I absorption saturated, dry；Dried physics expanding agent I is replaced in and sprays in rolling pot, sprays, in rolling pot, the solution I containing active metallic element that volume is physics expanding agent I saturated water adsorptive value in the mode being atomized and be then dried under rotary state；Physics expanding agent II uses the same manner to spray；Dried physics expanding agent I and physics expanding agent II is again placed in spraying in rolling pot, and under rotary state, the mode sprinkler body in rolling pot with atomization amasss as physics expanding agent I and physics expanding agent II saturated water adsorptive value ammonium salt solution standby.
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 3%-5% that addition is boehmite dry glue powder weight of the 6%-8% 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, phosphate or boric acid, 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, the sealing container described in step (2) can be autoclave or tube furnace, and the temperature of heat treatment is 120-160 DEG C, and the process time is 3-6 hour.
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, group VIII 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 alkali metal, active metallic element and ammonium salt are impregnated on physics expanding agent by the inventive method, and with boehmite kneading, molding, heat treatment, be dried, roasting prepare modified aluminium oxide supports, final impregnating active component finally prepares catalyst.When sealing heat treatment, gas that ammonium salt decomposition produces and the water vapour effective modulation chemical property of carrier surface, the surface chemical property of carrier at the macropore especially formed after the roasting of physics expanding agent, improve the effect of active metal and carrier after dipping active metal, improve the utilization rate of macropore and the catalysis activity of metal.Physics expanding agent oxidized removing during roasting, selects the physics expanding agent with different-grain diameter, forms the macroporous structure accordingly with different pore size in the final catalyst.The alkali metal loaded in physics expanding agent and active metal component are loaded on corresponding duct, make in final catalyst active component content and alkali metal content at macropore significantly increase.Additionally, in different-grain diameter physics expanding agent, alkali metal and active component concentration are distinct, make final catalyst aperture relatively large place alkali metal and active component content higher, relatively small place, aperture content is relatively low, make duct type well be mated with active component, improve the utilization rate of duct and active component.The existence of alkali metal ion, catalyst neutralisation surface portion acid site, make surface acid property be improved, effectively inhibit area carbon, the ability making catalyst hold metal and volume carbon strengthens.Active metallic content at macropore is higher simultaneously, and activity increases, and improves the utilization rate of macropore.During kneading, the addition of Polyethylene Glycol makes carbon black powder mix homogeneously with boehmite, improves the uniformity coefficient of macropore.Catalyst of the present invention is applicable to heavy resid HDM field, and this catalyst has higher activity and activity stability.
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
Take industry ammonium heptamolybdate 55g to be placed in ammonia, be stirred, till insoluble matter, add industry basic nickel carbonate 25g, be stirred, till insoluble matter, make containing MoO310 grams/100 milliliters, the molybdenum-nickel-ammonia active metal salt solution of NiO1.2 gram/100 milliliters.The impregnation liquid of the addition preparation variable concentrations of ammonium heptamolybdate and basic nickel carbonate can be regulated as required.
Weigh carbon black powder I10 gram 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 0.5 gram in the way of atomizing type carbon black powder in rolling pot is with saturated dipping, the active metal impregnation liquid of nickel oxide 0.04 gram, the carbon black powder after dipping is dried 3 hours in 110 DEG C；Dried carbon black powder is replaced in and sprays in rolling pot, under rotary state, sprays the wet chemical containing potassium oxide 0.04 gram in the way of saturated dipping in rolling pot, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.
Weigh particle diameter be 300(granule can by 300 mesh sieve holes but can't pass 325 mesh sieve holes) purpose carbon black powder II4.3 gram be placed in spray rolling pot in, under rotary state, spray containing molybdenum oxide 0.3 gram in the way of atomizing type carbon black powder in rolling pot is with saturated dipping, the active metal impregnation liquid of nickel oxide 0.03 gram, the carbon black powder after dipping is dried 3 hours in 110 DEG C；Dried carbon black powder is replaced in and sprays in rolling pot, under rotary state, sprays the wet chemical containing potassium oxide 0.03 gram in the way of saturated dipping in rolling pot, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.
Being again placed in above-mentioned dried carbon black powder I and carbon black powder II spraying in rolling pot, spray, in rolling pot, the sal volatile that stain mass concentration is 20% under rotary state in the way of saturated dipping, 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 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, it is subsequently adding uniform dissolved with 5 grams of nitre aqueous acids continuation kneadings in right amount, screw rod banded extruder is extruded into the cloverleaf pattern bar of a diameter of 1.8mm, above-mentioned material is placed in sealing tube furnace in 130 DEG C of heat treatments 5 hours, then unwatering steam is dried 4 hours in 130 DEG C, dried article shaped is 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 10.8wt%, NiO weight/mass percentage composition be 1.26wt%, potassium oxide weight/mass percentage composition is 0.07wt%.
Embodiment 2
With embodiment 1, simply the particle diameter of carbon black powder I is 1000 mesh (granule can pass through 1000 mesh sieve holes but can't pass 1340 mesh sieve holes), weight is 11.4 grams, containing molybdenum oxide 0.7 gram in the activity component impregnation liquid of dipping carbon black powder I, nickel oxide 0.03 gram, alkali metal soln is the sodium nitrate solution containing sodium oxide 0.05 gram.The particle diameter of carbon black powder II is 500 mesh (granule can pass through 500 mesh sieve holes but can't pass 600 mesh sieve holes), weight is 7.2 grams, containing molybdenum oxide 0.5 gram in the activity component impregnation liquid of dipping carbon black powder II, nickel oxide 0.02 gram, alkali metal soln is the sodium nitrate solution containing sodium oxide 0.04 gram.Ammonium salt solution be mass concentration be the ammonium oxalate solution of 10%.The temperature of heat treatment is 140 DEG C, and the process time is 3 hours.The addition of polyglycol solution is 43 to restrain to obtain catalyst C2 of the present invention, this catalyst MoO3Weight/mass percentage composition be 11.2wt%, NiO weight/mass percentage composition be 1.25wt%, sodium oxide weight/mass percentage composition is 0.09wt%.
Embodiment 3
With embodiment 1, simply the particle diameter of carbon black powder I is 600 mesh (granule can pass through 600 mesh sieve holes but can't pass 800 mesh sieve holes), weight is 8.6 grams, containing molybdenum oxide 0.6 gram in the activity component impregnation liquid of dipping carbon black powder I, nickel oxide 0.05 gram, alkali metal soln is the lithium nitrate solution of oxide containing lithium 0.06 gram.The particle diameter of carbon black powder II is 400 mesh (granule can pass through 400 mesh sieve holes but can't pass 500 mesh sieve holes), weight is 5.7 grams, containing molybdenum oxide 0.4 gram in the activity component impregnation liquid of dipping carbon black powder II, nickel oxide 0.01 gram, alkali metal soln is the lithium nitrate solution of oxide containing lithium 0.02 gram.Ammonium salt solution be mass concentration be the ammonium bicarbonate soln of 30%.The temperature of heat treatment is 120 DEG C, and the process time is 6 hours.The addition of polyglycol solution is 100 to restrain to obtain catalyst C3 of the present invention, this catalyst MoO3Weight/mass percentage composition be 10.9wt%, NiO weight/mass percentage composition be 1.26wt%, lithium oxide weight/mass percentage composition is 0.08wt%.
Embodiment 4
With embodiment 1, simply carbon black powder changes Linesless charcoal into, ammonium salt solution be mass concentration be the ammonium citrate solution of 20%.The temperature of heat treatment is 160 DEG C, and the process time is 3 hours.The addition of polyglycol solution is 100 to restrain to obtain catalyst C4 of the present invention, this catalyst MoO3Weight/mass percentage composition be 10.8wt%, NiO weight/mass percentage composition be 1.26wt%, potassium oxide weight/mass percentage composition is 0.07wt%.
Embodiment 5
With embodiment 1, simply the particle diameter of carbon black powder I is 600 mesh (granule can pass through 600 mesh sieve holes but can't pass 800 mesh sieve holes), weight is 10.7 grams, containing molybdenum oxide 0.55 gram in the activity component impregnation liquid of dipping carbon black powder I, nickel oxide 0.05 gram, alkali metal soln is the lithium nitrate solution of oxide containing lithium 0.05 gram.The particle diameter of carbon black powder II is 400 mesh (granule can pass through 400 mesh sieve holes but can't pass 500 mesh sieve holes), weight is 5.7 grams, containing molybdenum oxide 0.45 gram in the activity component impregnation liquid of dipping carbon black powder II, nickel oxide 0.02 gram, alkali metal soln is the lithium nitrate solution of oxide containing lithium 0.04 gram.Ammonium salt solution be mass concentration be the ammonium citrate solution of 15%.The temperature of heat treatment is 150 DEG C, and the process time is 4 hours.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 9wt%, NiO weight/mass percentage composition be 0.97wt%, lithium oxide weight/mass percentage composition is 0.09wt%.
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 10.8wt%, NiO weight/mass percentage composition be 1.26wt%, potassium oxide weight/mass percentage composition is 0.07wt%.
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 alkali metal 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 alkali metal 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
With example 1, simply carrier is the most thermally treated, and preparation has the catalyst C10 of composition same as in Example 1.
Comparative example 5
Weigh the carbon black powder 14.3 grams 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 in the way of atomizing type carbon black powder in rolling pot is with saturated dipping, the active metal impregnation liquid of nickel oxide 0.07 gram, the carbon black powder after dipping is dried 3 hours in 110 DEG C；Dried carbon black powder is replaced in and sprays in rolling pot, under rotary state, sprays the wet chemical containing potassium oxide 0.07 gram in the way of saturated dipping in rolling pot, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.
Being again placed in above-mentioned dried carbon black powder spraying in rolling pot, spray, in rolling pot, the sal volatile that stain mass concentration is 20% under rotary state in the way of saturated dipping, 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 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, it is subsequently adding uniform dissolved with 5 grams of nitre aqueous acids continuation kneadings in right amount, screw rod banded extruder is extruded into the cloverleaf pattern bar of a diameter of 1.8mm, above-mentioned material is placed in sealing tube furnace in 130 DEG C of heat treatments 5 hours, then unwatering steam is dried 4 hours in 130 DEG C, dried article shaped is 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 C11 of roasting, this catalyst MoO at 550 DEG C3Weight/mass percentage composition be 10.8wt%, NiO weight/mass percentage composition be 1.26wt%, potassium oxide weight/mass percentage composition is 0.07wt%.
The catalyst preparing examples detailed above and comparative example carries out activity rating, relatively above-mentioned each catalyst activity and stability.Raw oil character and evaluation process conditions are shown in Tables 1 and 2, the Activity evaluation of operating 200h is shown in Table 3, increase along with the duration of runs, the activity reduction of catalyst, in order to keep the activity of catalyst to meet production requirement, needing beds temperature raising, the rear catalyst bed temperature rise in 5000 hours that operates is shown in Table 5.
Table 1.
Table 2.
Table 3.
Table 4.
By table 3 data it can be seen that the catalyst that the present invention provides has higher HDM activity compared with reference catalyst.Finding out from the result of table 4, after reacting 5000 hours, the Hydrodemetalation catalyst using the present invention to provide has higher activity stability.
Claims (22)
1. the preparation method of a Hydrodemetalation catalyst, it is characterized in that including following content: (1) impregnates physics expanding agent I respectively with alkali metal containing Element Solution I and hydrogenation active component impregnation liquid I, physics expanding agent II is impregnated with alkali metal containing Element Solution II and hydrogenation active component impregnation liquid II, physics expanding agent I and physics expanding agent II after drying, sprays ammonium salt solution standby；(2) the physics expanding agent I of step (1) gained is become plastic with physics expanding agent II with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizer kneading, extrusion, molding materials are placed in hermetic container and carry out heat treatment, material drying after process, roasting, prepare containing active component and alkali metals modified alumina support；(3) impregnate modified aluminium oxide supports, drying, roasting with hydrogenation active component impregnation liquid III, prepare Hydrodemetalation catalyst.
The most in accordance with the method for claim 1, it is characterised in that: the alkali metal described in step (1) is selected from lithium, sodium, potassium one or more, and the solution of alkali metal containing element is the aqueous solution of alkali metal soluble-salt.
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.
The most in accordance with the method for claim 1, it is characterized in that: in step (1) described hydrogenation active component impregnation liquid I, vib metals oxide weight content is the 0.5wt%-0.7wt% of final catalyst weight, group VIII metal oxide weight content is the 0.03wt%-0.05wt% of final catalyst weight, and the consumption of impregnation liquid is physics expanding agent I saturated water adsorptive value.
The most in accordance with the method for claim 1, it is characterized in that: in step (1) described hydrogenation active component impregnation liquid II, vib metals oxide weight content is the 0.3wt%-0.5wt% of final catalyst weight, group VIII metal oxide weight content is the 0.01wt%-0.03wt% of final catalyst weight, and the consumption of impregnation liquid is physics expanding agent II saturated water adsorptive value.
The most in accordance with the method for claim 1, it is characterized in that: in step (1) described alkali metal containing Element Solution I, the weight content of alkali metal is calculated as the 0.04wt%-0.06wt% of final catalyst weight with oxide, and the consumption of solution is physics expanding agent I saturated water adsorptive value.
The most in accordance with the method for claim 1, it is characterized in that: in step (1) described alkali metal containing Element Solution II, the weight content of alkali metal is calculated as the 0.02wt%-0.04wt% of final catalyst weight with oxide, and the consumption of solution is physics expanding agent II saturated water adsorptive value.
The most in accordance with the method for claim 1, it is characterised in that: step (1) described physics expanding agent is one or more mixing in carbon black powder, Linesless charcoal or wood flour.
The most in accordance with the method for claim 1, it is characterised in that: the particle diameter of step (1) described physics expanding agent I is 600-1000 mesh, and the particle diameter of physics expanding agent II is 300-500 mesh.
The most in accordance with the method for claim 1, it is characterized in that: the ammonium salt solution described in step (1) is one or more mixing in ammonium nitrate, ammonium carbonate, ammonium oxalate, ammonium citrate, ammonium hydrogen carbonate, the mass concentration of ammonium salt solution is 10%-30%, and the consumption of solution is physics expanding agent I and the saturated water adsorptive value of physics expanding agent II.
11. in accordance with the method for claim 1, it is characterized in that: the following manner that is impregnated with described in step (1) is carried out: physics expanding agent I is placed in and sprays in rolling pot, under rotary state, the mode with atomization sprays the volume solution I for the alkali metal containing element of physics expanding agent I saturated water adsorptive value in rolling pot, makes physics expanding agent I absorption saturated, dry；Dried physics expanding agent I is replaced in and sprays in rolling pot, sprays, in rolling pot, the solution I containing active metallic element that volume is physics expanding agent I saturated water adsorptive value in the mode being atomized and be then dried under rotary state；Physics expanding agent II uses the same manner to spray；Dried physics expanding agent I and physics expanding agent II is again placed in spraying in rolling pot, and under rotary state, the mode sprinkler body in rolling pot with atomization amasss as physics expanding agent I and physics expanding agent II saturated water adsorptive value ammonium salt solution standby.
12. 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.
13. in accordance with the method for claim 1, it is characterised in that: the 6%-8% that addition is boehmite dry glue powder weight of the physics expanding agent I described in step (2).
14. in accordance with the method for claim 1, it is characterised in that: the 3%-5% that addition is boehmite dry glue powder weight of the physics expanding agent II described in step (2).
15. 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.
16. 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, phosphate or boric acid, and chemical enlargement agent addition is the 3%-5% of boehmite dry glue powder weight.
17. 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.
18. 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.
19. in accordance with the method for claim 1, it is characterised in that: the sealing container described in step (2) is autoclave or tube furnace, and heat treatment temperature is 120-160 DEG C, and the process time is 3-6 hour.
20. 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.
21. in accordance with the method for claim 1, it is characterized 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, group VIII tenor is calculated as 0.8-3g/100ml with oxide, using volume impregnation, incipient impregnation or spray impregnating mode, dip time is 1-5 hour.
22. 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.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN109277108A (en) * | 2017-07-20 | 2019-01-29 | 中国石油化工股份有限公司 | Siliceous Hydrodemetalation catalyst and its preparation method and application |
| CN109277095A (en) * | 2017-07-20 | 2019-01-29 | 中国石油化工股份有限公司 | Silicon-containing alumina carrier and its preparation method and application |
| 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 |
| CN110935463A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of hydrodemetallization catalyst |
| CN110935467A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN110935461A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrodemetallization catalyst |
| CN110935465A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of demetallization 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 |
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| CN111097432A (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 |
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| CN111375419A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN111375437A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst carrier, catalyst and preparation method thereof |
| CN111821990A (en) * | 2019-04-17 | 2020-10-27 | 中国石油化工股份有限公司 | Residual oil hydrogenation protective agent carrier, catalyst and preparation method thereof |
| CN111821965A (en) * | 2019-04-17 | 2020-10-27 | 中国石油化工股份有限公司 | Carrier and catalyst for hydrogenation protective agent and preparation method thereof |
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| CN109277108A (en) * | 2017-07-20 | 2019-01-29 | 中国石油化工股份有限公司 | Siliceous Hydrodemetalation catalyst and its preparation method and application |
| 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 |
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| 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 |
| CN110935467A (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 |
| CN111097458A (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 |
| CN111097432A (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 |
| 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 |
| 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 |
| CN111375397A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst carrier, catalyst and preparation method thereof |
| CN111375437A (en) * | 2018-12-29 | 2020-07-07 | 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 |
| 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 |
| CN111375419A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Hydrogenation 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 |
| CN111821965A (en) * | 2019-04-17 | 2020-10-27 | 中国石油化工股份有限公司 | Carrier and catalyst for hydrogenation protective agent and preparation method thereof |
| CN111821990A (en) * | 2019-04-17 | 2020-10-27 | 中国石油化工股份有限公司 | Residual oil hydrogenation protective agent carrier, catalyst and preparation method thereof |
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| 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 |
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