CN106140122A - A kind of preparation method of boracic Hydrodemetalation catalyst - Google Patents
A kind of preparation method of boracic Hydrodemetalation catalyst Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of boracic Hydrodemetalation catalyst, including following content: (1) impregnates physics expanding agent I respectively with hydrogenation active component impregnation liquid I and boron-containing solution I, physics expanding agent II is impregnated respectively with hydrogenation active component impregnation liquid II and boron-containing solution II, physics expanding agent I after dipping and physics expanding agent II drying, then standby with urea liquid dipping physics expanding agent I and physics expanding agent II；(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, article shaped is placed in heat treatment in sealing device, material drying after process, roasting, prepare modified aluminium oxide supports；(3) impregnating modified aluminium oxide supports with hydrogenation active component impregnation liquid III, dipping rear catalyst is dried, roasting, prepares boracic 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 utilization rate of macropore significantly improves, and this Hydrodemetalation catalyst has high activity and long-term operation stability.
Description
Technical field
The present invention relates to the preparation method of a kind of boracic 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.
CN102652919A discloses the Hydrodemetalation catalyst with boron-containing alumina as carrier, prepares and apply.This catalyst has boron-containing alumina carrier and load hydrogenation active metals component on this carrier, it is characterized in that, described hydrogenation active metals component is the combination of at least one metal component selected from group vib and at least one metal component selected from V B race, count and 7 on the basis of catalyst by oxide, the content of described group vib metal component is 0.2 weight %-15 weight %, and the content of V B race metal component is 0.2 weight %-12 weight %.
Residuum hydrogenating and metal-eliminating catalyst active metal component prepared by said method is distribution uniform at the macropore and aperture of carrier, and the utilization rate causing macropore is relatively low.
Summary of the invention
For the deficiencies in the prior art, the present invention provides the preparation method of a kind of boracic 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 utilization rate of macropore significantly improves, and this Hydrodemetalation catalyst has high activity and long-term operation stability.
The preparation method of the boracic Hydrodemetalation catalyst of the present invention, including following content:
(1) physics expanding agent I is impregnated respectively with hydrogenation active component impregnation liquid I and boron-containing solution I, physics expanding agent II is impregnated respectively with hydrogenation active component impregnation liquid II and boron-containing solution II, physics expanding agent I after dipping and physics expanding agent II drying, then standby with urea liquid dipping physics expanding agent I and physics expanding agent II；
(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, article shaped is placed in heat treatment in sealing device, material drying after process, roasting, prepare containing active component and boron modification alumina support；
(3) impregnating modified aluminium oxide supports with hydrogenation active component impregnation liquid III, dipping rear catalyst is dried, roasting, prepares boracic Hydrodemetalation catalyst.
In the inventive method, described hydrogenation active component is VIB and/or group VIII metal, and vib metals is molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；Hydrogenation active component impregnation liquid can be the one in acid solution, aqueous solution or ammonia solution containing hydrogenation active component.
In the inventive method, in step (1) described hydrogenation active component impregnation liquid I, vib metals weight content is calculated as the 0.6wt%-0.8wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.3wt%-0.5wt% of final catalyst weight with oxide.The consumption of hydrogenation active component impregnation liquid I is the 30%-50% of physics expanding agent I saturated water adsorptive value.Dipping with the following method is adopted: be placed in by physics expanding agent I and spray in rolling pot during dipping, under the conditions of rolling, in carbon black powder, uniformly spray impregnates activity impregnation liquid, the physics expanding agent that impregnation liquid continues after spraying end in rolling pot sprays distilled water, makes physics expanding agent I absorption saturated.
In the inventive method, in step (1) described hydrogenation active component impregnation liquid II, vib metals weight content is calculated as the 0.4wt%-0.6wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.1wt%-0.3wt% of final catalyst weight with oxide.The consumption of hydrogenation active component impregnation liquid II is the 30%-50% of physics expanding agent I saturated water adsorptive value.Dipping with the following method is adopted: be placed in by physics expanding agent I and spray in rolling pot during dipping, under the conditions of rolling, in carbon black powder, uniformly spray impregnates activity impregnation liquid, the physics expanding agent that impregnation liquid continues after spraying end in rolling pot sprays distilled water, makes physics expanding agent II absorption saturated.
In the inventive method, the boron-containing solution I described in step (1) can be boric acid or boratory aqueous solution, and the consumption of solution is the 20%-40% of the saturated water adsorptive value of physics expanding agent I, and in solution, the content of boron accounts for the 0.4%-0.6% of catalyst weight in terms of oxide.
In the inventive method, the boron-containing solution II's described in step (1) can be boric acid or boratory aqueous solution, and the consumption of solution is the 20%-40% of the saturated water adsorptive value of physics expanding agent I, and in solution, the content of boron accounts for the 0.1%-0.3% of catalyst weight in terms of oxide.
In the inventive method, step (1) described physics expanding agent is one or more mixing in carbon black powder, Linesless charcoal or wood flour, and the particle diameter of physics expanding agent I is 600-1000 mesh, and the particle diameter of physics expanding agent II is 300-500 mesh.
In the inventive method, the urea liquid consumption described in step (1) is physics expanding agent I and the saturated water adsorptive value of physics expanding agent II, and in solution, the weight of carbamide and the ratio of physics expanding agent I and physics expanding agent II mass sum total are 0.4:1-0.8:1.
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 5%-10% 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, the heat treatment that seals described in step (2) is at autoclave or to seal the heat treatment carried out in tube furnace, and treatment temperature is 140-180 DEG C, and the process time is 1-4 hour.
In the inventive method, being preferably added to mass concentration in kneading process described in step (2) is 1%-5% Aqueous Solutions of Polyethylene Glycol, wherein the mean molecule quantity of Polyethylene Glycol is 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 gram/100 grams boehmite dry glue powders.
In the inventive method, chemical enlargement agent described in step (2) is one or more in phosphoric acid or phosphate, preferably phosphate, wherein one or more in ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate of phosphate, chemical enlargement agent addition is the 3%-5% of boehmite dry glue powder weight.
In the inventive method, the extrusion aid described in step (2) is one or more in sesbania powder, starch or methylcellulose, preferably sesbania powder, and extrusion aid addition is the 3%-5% of boehmite dry glue powder weight.
In the inventive method, the peptizer described in step (2) is one or more mixing in formic acid, acetic acid, citric acid or nitric acid, and addition is the 3%-10% of boehmite dry glue powder weight, depending on last molding effect.
In the inventive method, step (2) described drying condition is to be dried 1-10 hour at 100-130 DEG C；Roasting process is 500-650 DEG C of roasting 2-4 hour.
In the inventive method, the hydrogenation active component impregnation liquid III described in step (3) is to calculate preparation according to final catalyst composition.In hydrogenation active component impregnation liquid III, vib metals content is calculated as 7-15g/100ml with oxide, VII race tenor is calculated as 0.8-3g/100ml with oxide, can be to use volume impregnation, incipient impregnation or spray impregnating mode, and dip time is 1-5 hour.
In the inventive method, the drying condition described in step (3) is to be dried 6-10 hour at 80-120 DEG C；Described roasting condition is roasting 3-6 hour at 400-600 DEG C.
Appropriate boron-containing solution, active metallic element solution and urea liquid are impregnated on physics expanding agent by the inventive method, and with boehmite kneading, molding, be dried, roasting prepares modified aluminium oxide supports, dipping active component finally prepares catalyst.During airtight heat treatment, the existence of carbamide makes physics expanding agent surrounding oxidic alumina supporter surface hydroxyl structure be improved.During roasting, boron loads to corresponding big hole surface the most uniformly, due to the improvement of surface hydroxyl structure make that boron load more uniformly, boron particles uniform particle diameter, the active component within following physics expanding agent granule loads to boron modification alumina carrier surface.The existence of boron have adjusted the surface nature of carrier at macropore, improves the interaction of active component and carrier, improves the catalysis activity of active metal.Select the physics expanding agent with different-grain diameter, make final catalyst is formed mass transfer and the diffusion of the macroporous structure accordingly with different pore size, beneficially reactant.Due at the macropore that formed after physics expanding agent roasting, active metallic content is of a relatively high and after boron modification active metal suitable with carrier function, make the catalysis activity of active metal at macropore be greatly improved.It is prone to the diffusion of residual oil molecule at macropore, and there is higher appearance metal and carbon accumulation resisting ability, make final catalyst have higher catalysis activity and activity stability.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 the carbon black powder I11.4 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 0.6 gram with atomizing type carbon black powder in rolling pot, the active metal impregnation liquid 3.4ml of nickel oxide 0.4 gram, then proceeding to spray distilled water makes carbon black powder absorption saturated, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.Being replaced in by dried carbon black powder in spray rolling pot, under rotary state, spray the boric acid aqueous solution 3.4ml containing boron oxide 0.5 gram with atomizing type carbon black powder in rolling pot, 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) II4.3 gram of mix homogeneously of purpose carbon black powder, it is placed in spray rolling pot, under rotary state, spray containing molybdenum oxide 0.5 gram with atomizing type carbon black powder in rolling pot, the active metal impregnation liquid 1.3ml of nickel oxide 0.1 gram, then proceeding to spray distilled water makes carbon black powder absorption saturated, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.Being replaced in by dried carbon black powder in spray rolling pot, under rotary state, spray the boric acid aqueous solution 1ml containing boron oxide 0.1 gram with atomizing type carbon black powder in rolling pot, the carbon black powder after dipping is dried 3 hours in 110 DEG C.
Being again placed in by dried carbon black powder I and carbon black powder II in spray rolling pot, under rotary state, spray the aqueous solution containing 7.9 grams of carbamide in the way of atomizing type carbon black powder in rolling pot is with saturated dipping, the carbon black powder after dipping is 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, article shaped is placed in sealing tube furnace and seals heat treatment 4 hours in 140 DEG C, then dry 3 hours in 120 DEG C, by dried article shaped roasting 4 hours at a temperature of 550 DEG C.
Above-mentioned material is placed in beaker, with 150 milliliters containing MoO310 grams/100 milliliters, the molybdenum-nickel of NiO1.2 gram/100 milliliters-ammonia active metal salt solution dipping carrier 5 hours, filter off redundant solution, then dry 2 hours in 120 DEG C, then 5 hours prepared catalyst C1 of roasting, this catalyst MoO at 550 DEG C3Weight/mass percentage composition is 11.1%, and NiO weight/mass percentage composition is 1.7wt%, and boron oxide percentage composition is 0.6wt%.
Embodiment 2
With embodiment 1, simply carbon black powder I weight is 14.3 grams, and particle diameter is 600 mesh (granule can pass through 600 mesh sieve holes but can't pass 800 mesh sieve holes), and containing molybdenum oxide 0.8 gram in active component I, nickel oxide 0.5 gram, activity component impregnation liquid consumption is 7.2ml.Containing boron oxide 0.6 gram in boron-containing solution I, the consumption of boric acid solution is 7.2 ml, carbon black powder II weight is 5.7 grams, particle diameter is 400 mesh (granule can pass through 400 mesh sieve holes but can't pass 500 mesh sieve holes), containing molybdenum oxide 0.6 gram in active component II, nickel oxide 0.2 gram, activity component impregnation liquid consumption is 1.2ml.Containing boron oxide 0.2 gram in boron-containing solution II, the consumption of boric acid solution is 1.7 ml, and in solution, containing of carbamide is 7.5 grams.The addition of polyglycol solution is 43 grams, and the temperature of heat treatment is 180 DEG C, and the process time is 1 hour, prepares catalyst C2 of the present invention, this catalyst MoO3Weight/mass percentage composition be 11.4wt%, NiO weight/mass percentage composition be 1.27wt%, boron oxide weight/mass percentage composition is 0.8wt%.
Embodiment 3
With embodiment 1, simply carbon black powder I weight is 7.2 grams, and particle diameter is 1000 mesh (granule can pass through 1000 mesh sieve holes but can't pass 1340 mesh sieve holes), and containing molybdenum oxide 0.7 gram in active component I, nickel oxide 0.3 gram, activity component impregnation liquid consumption is 2.9ml.Containing boron oxide 0.4 gram in boron-containing solution I, the consumption of boric acid solution is 2.9 ml, carbon black powder II weight is 7.2 grams, particle diameter is 500 mesh (granule can pass through 500 mesh sieve holes but can't pass 600 mesh sieve holes), containing molybdenum oxide 0.4 gram in active component II, nickel oxide 0.3 gram, activity component impregnation liquid consumption is 2.9ml.Containing boron oxide 0.3 gram in boron-containing solution II, the consumption of boric acid solution is 2.9 ml, and in solution, containing of carbamide is 11.5 grams.The addition of polyglycol solution is 100 grams, and the temperature of heat treatment is 160 DEG C, and the process time is 2 hours, prepares catalyst C3 of the present invention, this catalyst MoO3Weight/mass percentage composition be 11.1wt%, NiO weight/mass percentage composition be 1.6wt%, boron oxide weight/mass percentage composition is 0.6wt%.
Embodiment 4
With embodiment 1, simply carbon black powder changes Linesless charcoal into, the consumption of Linesless charcoal I is 8.6 grams, the consumption of active component solution I is 4.3ml, the consumption of boric acid solution I is 2.2 ml, and the consumption of Linesless charcoal II is 6.4 grams, and the consumption of active component solution II is 2.6ml, the consumption of boric acid solution II is 2.6 ml, and in solution, containing of carbamide is 9 grams.The addition of polyglycol solution is 100 grams, and the temperature of heat treatment is 170 DEG C, and the process time is 3 hours, prepares catalyst C4 of the present invention, this catalyst MoO3Weight/mass percentage composition is 11.1%, and NiO weight/mass percentage composition is 1.7wt%, and boron oxide percentage composition is 0.6wt%.
Embodiment 5
With embodiment 1, simply the consumption of carbon black powder I is 10 grams, and the consumption of active component solution I is 3ml, the consumption of boric acid solution I is 4ml, and the consumption of carbon black powder II is 5 grams, and the consumption of active component solution II is 2ml, the consumption of boric acid solution II is 1.5 ml, and in solution, containing of carbamide is 10.5 grams.The addition of polyglycol solution is 86 grams, and the temperature of heat treatment is 150 DEG C, and the process time is 3 hours, with 150 milliliters containing MoO during active metal dipping38 grams/100 milliliters, the molybdenum-nickel of NiO0.9 gram/100 milliliters-ammonia active metal salt solution dipping carrier prepares catalyst C5 of the present invention, this catalyst MoO3Weight/mass percentage composition be 9.1wt%, NiO weight/mass percentage composition be 1.4wt%, boron oxide weight/mass percentage composition is 0.6wt%.
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 is 11.1%, and NiO weight/mass percentage composition is 1.7wt%, and boron oxide percentage composition is 0.6wt%.
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 boron 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 boron are unsupported on carbon black powder, but add the when of kneading, and preparation has the catalyst C9 of composition same as in Example 1.
Comparative example 4
Weigh the carbon black powder I15.7 that particle diameter is 800 mesh (granule can pass through 800 mesh sieve holes but can't pass 1000 mesh sieve holes) to be placed in spray rolling pot, under rotary state, spray containing molybdenum oxide 1.1 grams with atomizing type carbon black powder in rolling pot, the active metal impregnation liquid 4.7ml of nickel oxide 0.5 gram, then proceeding to spray distilled water makes carbon black powder absorption saturated, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.Being replaced in by dried carbon black powder in spray rolling pot, under rotary state, spray the boric acid aqueous solution 4.4ml containing boron oxide 0.6 gram with atomizing type carbon black powder in rolling pot, the carbon black powder after dipping is dried 3 hours in 110 DEG C,
Being again placed in by dried carbon black powder I in spray rolling pot, under rotary state, spray the aqueous solution containing 7.9 grams of carbamide in the way of atomizing type carbon black powder in rolling pot is with saturated dipping, the carbon black powder after dipping is 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, article shaped is placed in sealing tube furnace and seals heat treatment 4 hours in 140 DEG C, then dry 3 hours in 120 DEG C, by dried article shaped roasting 4 hours at a temperature of 550 DEG C.
Above-mentioned material is placed in beaker, with 150 milliliters containing MoO310 grams/100 milliliters, the molybdenum-nickel of NiO1.2 gram/100 milliliters-ammonia active metal salt solution dipping carrier 5 hours, filter off redundant solution, then dry 2 hours in 120 DEG C, then 5 hours prepared catalyst C10 of roasting, this catalyst MoO at 550 DEG C3Weight/mass percentage composition is 11.1%, and NiO weight/mass percentage composition is 1.7wt%, and boron oxide percentage composition is 0.6wt%.
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 (18)
1. the preparation method of a boracic Hydrodemetalation catalyst, it is characterized in that including following content: (1) impregnates physics expanding agent I respectively with hydrogenation active component impregnation liquid I and boron-containing solution I, physics expanding agent II is impregnated respectively with hydrogenation active component impregnation liquid II and boron-containing solution II, physics expanding agent I after dipping and physics expanding agent II drying, then standby with urea liquid dipping physics expanding agent I and physics expanding agent II；(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, article shaped is placed in heat treatment in sealing device, material drying after process, roasting, prepare containing active component and boron modification alumina support；(3) modified aluminium oxide supports is impregnated with hydrogenation active component impregnation liquid III, dry, roasting after dipping, prepare boracic Hydrodemetalation catalyst.
The most in accordance with the method for claim 1, it is characterised in that: described hydrogenation active component is VIB and/or group VIII metal, and vib metals is molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；Hydrogenation active component impregnation liquid is the one in the acid solution containing hydrogenation active component, aqueous solution or ammonia solution.
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 weight content is calculated as the 0.6wt%-0.8wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.3wt%-0.5wt% of final catalyst weight with oxide；The consumption of hydrogenation active component impregnation liquid I is the 30%-50% of 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 weight content is calculated as the 0.4wt%-0.6wt% of final catalyst weight with oxide, and group VIII weight metal content is calculated as the 0.1wt%-0.3wt% of final catalyst weight with oxide；The 30%-50% that consumption is physics expanding agent I saturated water adsorptive value of hydrogenation active component impregnation liquid II alive.
The most in accordance with the method for claim 1, it is characterized in that: the boron-containing solution I described in step (1) is boric acid or boratory aqueous solution, the consumption of solution is the 20%-40% of the saturated water adsorptive value of physics expanding agent I, and in solution, the content of boron accounts for the 0.4%-0.6% of catalyst weight in terms of oxide.
The most in accordance with the method for claim 1, it is characterized in that: the boron-containing solution II described in step (1) for boric acid or boratory aqueous solution, the consumption of solution is the 20%-40% of the saturated water adsorptive value of physics expanding agent I, and in solution, the content of boron accounts for the 0.1%-0.3% of catalyst weight in terms of oxide.
The most in accordance with the method for claim 1, it is characterised in that: step (1) described physics expanding agent is one or more mixing in carbon black powder, Linesless charcoal or wood flour, and the particle diameter of physics expanding agent I is 600-1000 mesh, and the particle diameter of physics expanding agent II is 300-500 mesh.
The most in accordance with the method for claim 1, it is characterized in that: the urea liquid consumption described in step (1) is physics expanding agent I and the saturated water adsorptive value of physics expanding agent II, in solution, the weight of carbamide and the ratio of physics expanding agent I and physics expanding agent II mass sum total are 0.4:1-0.8:1.
The most 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.
The most 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 5%-10% that addition is boehmite dry glue powder weight of the physics expanding agent I described in step (2), physics expanding agent II.
11. in accordance with the method for claim 1, it is characterised in that: the heat treatment that seals described in step (2) is at autoclave or to seal the heat treatment carried out in tube furnace, and treatment temperature is 140-180 DEG C, and the process time is 1-4 hour.
12. 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.
13. in accordance with the method for claim 1, it is characterised in that: the chemical enlargement agent described in step (2) is one or more in phosphoric acid or phosphate, and chemical enlargement agent addition is the 3%-5% of boehmite dry glue powder weight.
14. 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.
15. 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.
16. 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.
17. according to the method described in claim 1 or 2, it is characterised in that: in the hydrogenation active component impregnation liquid III described in step (3), vib metals content is calculated as 7-15g/100ml with oxide, and VII race tenor is calculated as 0.8-3g/100ml with oxide.
18. 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112547069A (en) * | 2019-09-10 | 2021-03-26 | 中国石油化工股份有限公司 | Nickel-copper catalyst, preparation method thereof and method for preparing methyl isobutyl alcohol |
| CN112717947A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Boron-containing catalyst and preparation method and application thereof |
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| CN111822011A (en) * | 2019-04-17 | 2020-10-27 | 中国石油化工股份有限公司 | Carrier and catalyst for hydrodesulfurization and preparation method thereof |
| CN112547069A (en) * | 2019-09-10 | 2021-03-26 | 中国石油化工股份有限公司 | Nickel-copper catalyst, preparation method thereof and method for preparing methyl isobutyl alcohol |
| CN112547069B (en) * | 2019-09-10 | 2023-05-30 | 中国石油化工股份有限公司 | Nickel-copper catalyst and preparation method thereof as well as method for preparing methyl isobutyl alcohol |
| CN112717947A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Boron-containing catalyst and preparation method and application thereof |
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| CN106140122B (en) | 2018-08-14 |
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