CN106140208A - A kind of preparation method of hydrogenation catalyst - Google Patents
A kind of preparation method of hydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of hydrogenation catalyst, including: (1) impregnates physics expanding agent I respectively with containing rare earth element solution I, fluorine-containing solution I and hydrogenation active component impregnation liquid I, impregnating physics expanding agent II with containing rare earth element solution II, fluorine-containing solution II and hydrogenation active component impregnation liquid II, physics expanding agent I and II drying after dipping are 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, dry, 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 utilization rate of macropore significantly improves, and acidity and the heat stability of macropore are obviously improved.
Description
Technical field
The present invention relates to the preparation method of a kind of hydrogenation catalyst, more particularly to a kind of fluorine-containing and preparation method of rare earth element 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.
CN1493662A discloses the preparation method of a kind of hydrotreating catalyst.Method for preparing catalyst feature of the present invention is the feed postition of auxiliary agent fluorine, boehmite and/or aluminium oxide are sufficiently mixed a period of time with the ammonium salt of fluoride or the ammonium salt aqueous solution of fluoride, prepare fluoro-aluminum material, use kneading method or infusion process to prepare hydrotreating catalyst further with this fluoro-aluminum material.Catalyst prepared by the inventive method may be used for the hydroprocessing processes of hydro carbons, the unifining process of particularly middle matter fraction oil.
Residuum hydrogenating and metal-eliminating catalyst or hydrotreating catalyst active metal component prepared by said method are evenly distributed at the macropore and aperture of carrier, the utilization rate causing macropore is relatively low, additionally, acidity and the heat stability of the acidity of catalyst and heat stability, especially macropore remain to be further improved.
Summary of the invention
For the deficiencies in the prior art, the present invention provides the preparation method of a kind of hydrogenation catalyst.Catalyst activity metal content at macropore prepared by the method is of a relatively high, at aperture, content is relatively low, the utilization rate of macropore significantly improves, and the acidity of macropore and heat stability are obviously improved, and this Hydrodemetalation catalyst has high activity and long-term operation stability.
The preparation method of the hydrogenation catalyst of the present invention, including following content:
(1) physics expanding agent I is impregnated respectively with containing rare earth element solution I, fluorine-containing solution I and hydrogenation active component impregnation liquid I, impregnating physics expanding agent II with containing rare earth element solution II, fluorine-containing solution II and hydrogenation active component impregnation liquid II, physics expanding agent I and physics expanding agent II drying after dipping are standby；
(2) the physics expanding agent I of step (1) gained and physics expanding agent II is become plastic with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizer kneading, extrusion, dry, roasting, prepare modified aluminium oxide supports；
(3) impregnate modified aluminium oxide supports, drying, roasting with hydrogenation active component impregnation liquid III, prepare fluorine-containing and rare earth element Hydrodemetalation catalyst.
In the inventive method, the fluorine-containing solution described in step (1) can be the aqueous solution of ammonium fluoride or fluohydric acid gas.
In the inventive method, rare earth element described in step (1) is selected from lanthanum, cerium, praseodymium, ytterbium or samarium one or more, solution containing rare earth element is generally water and/or the ethanol solution of rare earth element soluble-salt, soluble-salt is generally nitrate or chloride, such as Lanthanum (III) nitrate, cerous nitrate, praseodymium nitrate, Ytterbium(III) nitrate., samaric nitrate 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%-1wt% of final catalyst weight, and group VIII metal oxide weight content is the 0.05wt%-0.1wt% of final catalyst weight.
In the inventive method, in step (1) described hydrogenation active component impregnation liquid II, vib metals oxide weight content is the 0.1wt%-0.5wt% of final catalyst weight, and group VIII metal oxide weight content is the 0.01wt%-0.05wt% of final catalyst weight.
In the inventive method, step (1) is described containing in rare earth element solution I, accounts for the 0.4wt %-0.7wt % of catalyst weight, the saturated water adsorptive value that consumption is physics expanding agent I containing rare earth element solution I in terms of oxide.
In the inventive method, step (1) is described containing in rare earth element solution II, accounts for 0.1 wt %-0.3 wt % of catalyst weight, the saturated water adsorptive value that consumption is physics expanding agent I containing rare earth element solution I in terms of oxide.
In the inventive method, in the described fluorine-containing solution I of step (1), accounting for the 0.5wt %-0.8wt % of catalyst weight in terms of simple substance fluoride, the consumption of fluorine-containing solution I is the saturated water adsorptive value of physics expanding agent I.
In the inventive method, in the described fluorine-containing solution II of step (1), accounting for the 0.2wt %-0.4 wt % of catalyst weight in terms of simple substance fluoride, the consumption of fluorine-containing solution II is the saturated water adsorptive value of physics expanding agent II.
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 preferably particle diameter of carbon black powder physics expanding agent I is 600-1000 mesh, and the particle diameter of physics expanding agent II is 300-500 mesh.
In the inventive method, the drying condition described in step (1) is that nature dries in the shade or dry 1-10 hour in 50-120 DEG C.
In the inventive method, the boehmite dry glue powder described in step (2) can be the boehmite dry glue powder using any one method to prepare.
In the inventive method, the 5%-10% that addition is boehmite dry glue powder weight of the 3%-5% that addition is boehmite dry glue powder weight of the physics expanding agent I described in step (2), physics expanding agent II.
In the inventive method, being preferably added to mass concentration in kneading process described in step (2) is 1%-5% Aqueous Solutions of Polyethylene Glycol, wherein the mean molecule quantity of Polyethylene Glycol is 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 gram/100 grams boehmite dry glue powders.
In the inventive method, chemical enlargement agent described in step (2) is one or more in phosphoric acid, 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, 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 8-15g/100ml with oxide, group VIII tenor is calculated as 1-3g/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 fluorine-containing and rare earth element solution and amount of activated metallic element 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.Alumina support after molding is the oxidized removing of physics expanding agent in roasting process, owing to selecting the physics expanding agent with different-grain diameter, therefore forms the macroporous structure accordingly with different pore size.The fluorine, rare earth element and the active metal component that are loaded in physics expanding agent are loaded on corresponding duct, make in final catalyst active component content, fluorine and rare earth element content at macropore significantly increase.Additionally, in different-grain diameter physics expanding agent, active component content, fluorine and rare earth element content are distinct, make relatively large place, final catalyst aperture active component content, fluorine and rare earth element 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 Acidity of the effective modulation of existence of fluorine and rare earth element macropore and heat stability, improve the anti-carbon of catalyst and anti-caking power.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.This catalyst 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 I4.3 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 1 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 Lanthanum (III) nitrate ethanol solution containing lanthana 0.4 gram in the way of atomizing type carbon black powder in rolling pot is with saturated spraying, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.Dried carbon black powder is placed in plastic beaker, impregnates the ammonium fluoride aqueous solution of fluorine-containing 0.7 gram in the way of saturated spraying, and the carbon black powder after dipping is without drying for standby.
Weigh carbon black powder II7.2 gram that particle diameter is 400 mesh (granule can pass through 400 mesh sieve holes but can't pass 500 mesh sieve holes) to be placed in spray rolling pot, under rotary state, spray containing molybdenum oxide 0.2 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 0.01 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 Lanthanum (III) nitrate ethanol solution containing lanthana 0.2 gram in the way of atomizing type carbon black powder in rolling pot is with saturated spraying, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.Dried carbon black powder is placed in plastic beaker, impregnates the ammonium fluoride aqueous solution of fluorine-containing 0.2 gram in the way of saturated spraying, 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 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 130 DEG C dry 4 hours in baking oven, and 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 11.2wt%, NiO weight/mass percentage composition be 1.28wt%, fluorine weight/mass percentage composition is 0.9wt%, and lanthana weight/mass percentage composition is 0.6wt%.
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 5.7 grams, containing molybdenum oxide 0.7 gram in carbon black powder I, nickel oxide 0.1 gram, cerium oxide 0.7 gram, cerium is from cerous nitrate aqueous solution, 0.8 gram of fluorine, fluorine is from aqueous hydrogen fluoride solution.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), and weight is 14.3 grams, containing molybdenum oxide 0.5 gram in carbon black powder II, nickel oxide 0.05 gram, cerium oxide 0.3 gram, cerium is from cerous nitrate aqueous solution, 0.3 gram of fluorine, fluorine is from aqueous hydrogen fluoride solution.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 1.31wt%, fluorine weight/mass percentage composition is 1.1 wt%, and cerium oxide weight/mass percentage composition is 1wt%.
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), and weight is 7.2 grams, containing molybdenum oxide 0.5 gram in carbon black powder I, nickel oxide 0.05 gram, praseodymium oxide 0.5 gram, praseodymium is from praseodymium nitrate aqueous solution, 0.6 gram of fluorine.The particle diameter of carbon black powder II is 300 mesh (granule can pass through 300 mesh sieve holes but can't pass 325 mesh sieve holes), and weight is 10 grams, and containing molybdenum oxide 0.1 gram in carbon black powder II, nickel oxide 0.04 gram, praseodymium oxide 0.1 gram, praseodymium is from praseodymium nitrate aqueous solution, 0.3 gram of fluorine.The addition of polyglycol solution is 43 to restrain to obtain catalyst C3 of the present invention, this catalyst MoO3Weight/mass percentage composition be 10.6wt%, NiO weight/mass percentage composition be 1.3wt%, fluorine weight/mass percentage composition is 0.9wt%, and praseodymium oxide weight/mass percentage composition is 0.6wt%.
Embodiment 4
With embodiment 1, simply carbon black powder changes Linesless charcoal into, and containing molybdenum oxide 0.6 gram in Linesless charcoal I, nickel oxide 0.09 gram, ytterbium oxide 0.6 gram, ytterbium is from Ytterbium(III) nitrate. aqueous solution, 0.5 gram of fluorine.Containing molybdenum oxide 0.3 gram in Linesless charcoal II, nickel oxide 0.02 gram, ytterbium oxide 0.2 gram, ytterbium is from Ytterbium(III) nitrate. aqueous solution, 0.3 gram of fluorine.The addition of polyglycol solution is 43 to restrain to obtain catalyst C4 of the present invention, this catalyst MoO3Weight/mass percentage composition be 10.9wt%, NiO weight/mass percentage composition be 1.32wt%, fluorine weight/mass percentage composition is 0.8wt%, and ytterbium oxide weight/mass percentage composition is 0.8wt%.
Embodiment 5
With embodiment 1, simply containing molybdenum oxide 0.8 gram in carbon black powder I, nickel oxide 0.06 gram, Disamarium trioxide 0.55 gram, samarium is from samaric nitrate aqueous solution, 0.65 gram of fluorine.Containing molybdenum oxide 0.4 gram in carbon black powder II, nickel oxide 0.03 gram, Disamarium trioxide 0.25 gram, samarium is from samaric nitrate aqueous solution, 0.25 gram of fluorine.The addition of polyglycol solution is 86 grams, with 150 milliliters containing MoO during dipping38 grams/100 milliliters, the molybdenum-nickel of NiO0.9 gram/100 milliliters-ammonia active metal salt solution dipping carrier prepares catalyst C5 of the present invention, this catalyst MoO3Weight/mass percentage composition be 9.2wt%, NiO weight/mass percentage composition be 1wt%, fluorine weight/mass percentage composition is 0.9wt%, and Disamarium trioxide weight/mass percentage composition is 0.8wt%.
Embodiment 6
With embodiment 1, simply boehmite does not adds polyglycol solution and prepares catalyst C6 of the present invention, this catalyst MoO when mixing with carbon black powder3Weight/mass percentage composition be 11.2wt%, NiO weight/mass percentage composition be 1.28wt%, fluorine weight/mass percentage composition is 0.9wt%, and lanthana weight/mass 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 fluorine is unsupported on carbon black powder with rare earth element, 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, fluorine, rare earth element 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 11.5 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 1.2 grams in the way of atomizing type carbon black powder in rolling pot is with saturated dipping, the active metal impregnation liquid of nickel oxide 0.08 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 Lanthanum (III) nitrate ethanol solution containing lanthana 0.6 gram in the way of atomizing type carbon black powder in rolling pot is with saturated spraying, and the carbon black powder after dipping is dried 3 hours in 110 DEG C.Dried carbon black powder is placed in plastic beaker, impregnates the ammonium fluoride aqueous solution of fluorine-containing 0.9 gram in the way of saturated spraying, 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, 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 130 DEG C dry 4 hours in baking oven, and 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 C10 of roasting, this catalyst MoO at 550 DEG C3Weight/mass percentage composition be 11.2wt%, NiO weight/mass percentage composition be 1.28wt%, fluorine weight/mass percentage composition is 0.9wt%, and lanthana weight/mass 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 (20)
1. the preparation method of a hydrogenation catalyst, it is characterized in that including following content: (1) impregnates physics expanding agent I respectively with containing rare earth element solution I, fluorine-containing solution I and hydrogenation active component impregnation liquid I, impregnating physics expanding agent II with containing rare earth element solution II, fluorine-containing solution II and hydrogenation active component impregnation liquid II, physics expanding agent I and physics expanding agent II drying after dipping are standby；(2) the physics expanding agent I of step (1) gained and physics expanding agent II is become plastic with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizer kneading, extrusion, dry, roasting, prepare modified aluminium oxide supports；(3) impregnate modified aluminium oxide supports, drying, roasting with hydrogenation active component impregnation liquid III, prepare fluorine-containing and rare earth element Hydrodemetalation catalyst.
The most in accordance with the method for claim 1, its feature exists: in the aqueous solution that fluorine-containing solution is ammonium fluoride or fluohydric acid gas described in step (1).
The most in accordance with the method for claim 1, its feature exists: the rare earth element described in step (1) is selected from lanthanum, cerium, praseodymium, ytterbium or samarium one or more, and the solution containing rare earth element is water and/or the ethanol solution of rare earth element soluble-salt.
4. according to the method described in claim 1 or 2, its feature exists: in the described fluorine-containing solution I of step (1), accounts for the 0.5wt %-0.8wt % of catalyst weight in terms of simple substance fluoride, and the consumption of fluorine-containing solution I is the saturated water adsorptive value of physics expanding agent I.
5. according to the method described in claim 1 or 2, its feature exists: in the described fluorine-containing solution II of step (1), accounts for the 0.2wt %-0.4 wt % of catalyst weight in terms of simple substance fluoride, and the consumption of fluorine-containing solution II is the saturated water adsorptive value of physics expanding agent II.
6. according to the method described in claim 1 or 3, its feature exists: step (1) is described containing in rare earth element solution I, accounts for the 0.4wt %-0.7wt % of catalyst weight, the saturated water adsorptive value that consumption is physics expanding agent I containing rare earth element solution I in terms of oxide.
7. according to the method described in claim 1 or 3, its feature exists: step (1) is described containing in rare earth element solution II, accounts for 0.1 wt %-0.3 wt % of catalyst weight, the saturated water adsorptive value that consumption is physics expanding agent I containing rare earth element solution I in terms of oxide.
The most in accordance with the method for claim 1, its feature exists: 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.
9. according to the method described in claim 1 or 8, its feature exists: in step (1) described hydrogenation active component impregnation liquid I, vib metals oxide weight content is the 0.5wt%-1wt% of final catalyst weight, and group VIII metal oxide weight content is the 0.05wt%-0.1wt% of final catalyst weight.
10. according to the method described in claim 1 or 8, its feature exists: in step (1) described hydrogenation active component impregnation liquid II, vib metals oxide weight content is the 0.1wt%-0.5wt% of final catalyst weight, and group VIII metal oxide weight content is the 0.01wt%-0.05wt% of final catalyst weight.
11. in accordance with the method for claim 1, and its feature exists: 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.
12. in accordance with the method for claim 1, and its feature exists: 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. exist according to the method described in claim 1 or 11, its feature: the 5%-10% that addition is boehmite dry glue powder weight of the 3%-5% that addition is boehmite dry glue powder weight of the physics expanding agent I described in step (2), physics expanding agent II.
14. in accordance with the method for claim 1, its feature exists: 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.
15. in accordance with the method for claim 1, and its feature exists: 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.
16. in accordance with the method for claim 1, and its feature exists: 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.
17. in accordance with the method for claim 1, and its feature exists: 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.
18. in accordance with the method for claim 1, and its feature exists: 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.
19. exist according to the method described in claim 1 or 8, its feature: in the hydrogenation active component impregnation liquid III described in step (3), vib metals content is calculated as 8-15g/100ml with oxide, and group VIII tenor is calculated as 1-3g/100ml with oxide.
20. in accordance with the method for claim 1, and its feature exists: 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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|---|---|---|---|---|
| CN114471503A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, catalyst, preparation method and application thereof |
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| CN114471503A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, catalyst, preparation method and application thereof |
| CN114471503B (en) * | 2020-10-26 | 2023-09-01 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, catalyst, preparation method and application thereof |
| CN119175113A (en) * | 2024-11-19 | 2024-12-24 | 临朐恒辉新材料有限公司 | Terephthalic acid hydrogenation catalyst and preparation method and application thereof |
| CN119175113B (en) * | 2024-11-19 | 2025-01-21 | 临朐恒辉新材料有限公司 | A terephthalic acid hydrogenation catalyst and its preparation method and application |
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