CN106140208B - A kind of preparation method of hydrogenation catalyst - Google Patents
A kind of preparation method of hydrogenation catalyst Download PDFInfo
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- CN106140208B CN106140208B CN201510196354.2A CN201510196354A CN106140208B CN 106140208 B CN106140208 B CN 106140208B CN 201510196354 A CN201510196354 A CN 201510196354A CN 106140208 B CN106140208 B CN 106140208B
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Abstract
The invention discloses a kind of preparation methods of hydrogenation catalyst, including：（1）Physics expanding agent I is impregnated respectively with I containing rare earth element solution, fluorine-containing solution I and hydrogenation active component maceration extract I, physics expanding agent II is impregnated with II containing rare earth element solution, fluorine-containing solution II and hydrogenation active component maceration extract II, physics the expanding agent I and II after dipping are through drying for standby；（2）By step（1）For the physics expanding agent I and II of gained with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizing agent kneading at plastic, modified aluminium oxide supports are made in extrusion, drying, roasting；（3）Modified aluminium oxide supports are impregnated with hydrogenation active component maceration extract III, through drying, roasting, catalyst is made.Catalyst activity metal prepared by this method content at macropore is higher, and content is relatively low at aperture, and the utilization rate of macropore significantly improves, and the acidity and thermal stability of macropore are obviously improved.
Description
Technical field
The present invention relates to a kind of preparation methods of hydrogenation catalyst, adding hydrogen more particularly to the fluorine-containing and rare earth element of one kind
The preparation method of catalyst for demetalation.
Background technology
With the raising that raw material deep processing requires in world wide, main energy sources structure is gradually to macromolecular and high-carbon direction
Development, it is even more so for China of the universal heaviness of crude oil.Resistance is spread effectively to solve heavy oil component in catalyst duct
Power is excessive, catalyst activity reduction or the problems such as inactivation caused by beavy metal impurity deposition and coking, and an urgent demand is in oil
The widely used alumina support of the industries such as chemical industry has the characteristic of macropore appearance and large aperture.Large aperture is conducive to macromolecular chemical combination
For object to spreading inside catalyst granules, big pore volume, which is then conducive to improve, holds metal or coke ability.
CN1206037A discloses a kind of residuum hydrogenating and metal-eliminating catalyst, and this method is same in carrying alumina production procedure
When physics expanding agent and chemical enlargement agent is added, then active component is loaded on carrier in a manner of spraying and impregnating, the catalysis
The Kong Rongwei 0.80-1.20ml/g of agent, specific surface area 110-200m2/ g, can several apertures be 15-20nm, bulk density is
0.50-0.60g/ml。
CN1289640A discloses a kind of preparation method of carried catalyst for hydrogenation and demetalation.It is used not in this method
Saturation sprays technology, and the catalyst after spraying is not dried, and is directly placed into roaster.After this method effectively prevents
Migration of the metal salt solution from material lower layer to upper layer or surface in continuous drying process, reduces production cost.
US4,448,896 disclose a kind of catalyst of hydrodesulfurization and heavy metal, the preparation method of the catalyst be by
It is 100-350m that active component, which loads to specific surface area,2/ g, pore radius are the Kong Rongwei 0.5-1.5ml/g's of 3.75-7500nm
On alumina support, the preparation method of the carrier be activated alumina or activated alumina precursor are mixed with carbon black, are molded,
Roasting.
CN1493662A discloses a kind of preparation method of hydrotreating catalyst.Method for preparing catalyst feature of the present invention exists
In the feed postition of auxiliary agent fluorine, by the ammonium salt aqueous solution of the ammonium salt or fluoride of boehmite and/or aluminium oxide and fluoride
It is sufficiently mixed a period of time, fluoro- aluminium material is made, kneading method is further used with the fluoro- aluminium material or infusion process prepares plus hydrogen
Handle catalyst.Catalyst prepared by the method for the present invention can be used for the hydroprocessing processes of hydro carbons, especially middle matter fraction oil
Unifining process.
Residuum hydrogenating and metal-eliminating catalyst or hydrotreating catalyst active metal component prepared by the above method is in carrier
Macropore and aperture at be evenly distributed, cause the utilization rate of macropore relatively low, in addition, the acidity and thermal stability of catalyst, especially
It is macropore acidity and thermal stability remain to be further improved.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of hydrogenation catalyst.Prepared by this method urges
Agent active metal content at macropore is relatively high, and content is relatively low at aperture, and the utilization rate of macropore significantly improves, and big
The acidity and thermal stability in hole are obviously improved, which 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 is impregnated respectively with I containing rare earth element solution, fluorine-containing solution I and hydrogenation active component maceration extract I
I impregnates physics expanding agent II, after dipping with II containing rare earth element solution, fluorine-containing solution II and hydrogenation active component maceration extract II
Physics expanding agent I and physics expanding agent II through drying for standby；
（2）By step（1）The physics expanding agent I and physics expanding agent II of gained expand with boehmite dry glue powder, chemistry
At plastic, modified aluminium oxide supports are made in extrusion, drying, roasting for hole agent, extrusion aid, peptizing agent kneading；
（3）Modified aluminium oxide supports are impregnated with hydrogenation active component maceration extract III, through drying, roasting, are made fluorine-containing and dilute
Earth elements Hydrodemetalation catalyst.
In the method for the present invention, step（1）The fluorine-containing solution can be the aqueous solution of ammonium fluoride or hydrogen fluoride.
In the method for the present invention, step（1）The rare earth element is one or more of in lanthanum, cerium, praseodymium, ytterbium or samarium, contains
The solution of rare earth element is generally the water and/or ethanol solution of rare earth element soluble-salt, soluble-salt be generally nitrate or
Chloride, such as lanthanum nitrate, cerous nitrate, praseodymium nitrate, ytterbium nitrate, samaric nitrate.
In the method for the present invention, the hydrogenation active component is VIB and/or group VIII metal, and vib metals are molybdenum
And/or tungsten, the metal of group VIII is cobalt and/or nickel；Hydrogenation active component maceration extract can be to contain hydrogenation active component
One kind in acid solution, aqueous solution or ammonia solution.
In the method for the present invention, step（1）In the hydrogenation active component maceration extract I, vib metals oxide weight contains
Amount is the 0.5wt%-1wt% of final catalyst weight, and group VIII metal oxide weight content is final catalyst weight
0.05wt%-0.1wt%。
In the method for the present invention, step（1）In the hydrogenation active component maceration extract II, vib metals oxide weight
Content is the 0.1wt%-0.5wt% of final catalyst weight, and group VIII metal oxide weight content is final catalyst weight
The 0.01wt%-0.05wt% of amount.
In the method for the present invention, step（1）In the I containing rare earth element solution, catalyst weight is accounted in terms of oxide
The dosage of 0.4wt %-0.7wt %, the I containing rare earth element solution are the saturated water adsorptive value of physics expanding agent I.
In the method for the present invention, step（1）In the II containing rare earth element solution, catalyst weight is accounted in terms of oxide
The dosage of 0.1 wt %-0.3 wt %, the I containing rare earth element solution is the saturated water adsorptive value of physics expanding agent I.
In the method for the present invention, step（1）In the fluorine-containing solution I, the 0.5wt %- of catalyst weight are accounted in terms of simple substance fluoride
0.8wt %, the dosage of fluorine-containing solution I are the saturated water adsorptive value of physics expanding agent I.
In the method for the present invention, step（1）In the fluorine-containing solution II, the 0.2wt %- of catalyst weight are accounted in terms of simple substance fluoride
0.4 wt %, the dosage of fluorine-containing solution II are the saturated water adsorptive value of physics expanding agent II.
In the method for the present invention, step（1）The physics expanding agent is that one or more of carbon black powder, charcoal or sawdust are mixed
It closes, preferably the grain size of carbon black powder physics expanding agent I is 600-1000 mesh, and the grain size of physics expanding agent II is 300-500 mesh.
In the method for the present invention, step（1）The drying condition is that nature dries in the shade or 1-10 hours dry in 50-120 DEG C.
In the method for the present invention, step（2）The boehmite dry glue powder can be prepared using any one method
Boehmite dry glue powder.
In the method for the present invention, step（2）Described in physics expanding agent I addition be boehmite dry glue powder weight
3%-5%, the addition of physics expanding agent II is the 5%-10% of boehmite dry glue powder weight.
In the method for the present invention, step（2）It is 1%-5% polyethylene glycol water that mass concentration is preferably added in the kneading process
Solution, the wherein average molecular weight of polyethylene glycol are 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 grams/100
Gram boehmite dry glue powder.
In the method for the present invention, step（2）The chemical enlargement agent is one kind or several in phosphoric acid, phosphate or boric acid
Kind, preferably phosphate, wherein phosphate are selected from one or more of ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate, and chemistry expands
Agent addition in hole is the 3%-5% of boehmite dry glue powder weight.
In the method for the present invention, step（2）The extrusion aid is one kind or several in sesbania powder, starch or methylcellulose
Kind, preferably sesbania powder, extrusion aid addition are the 3%-5% of boehmite dry glue powder weight.
In the method for the present invention, step（2）The peptizing agent is one kind or several in formic acid, acetic acid, citric acid or nitric acid
Kind mixing, addition is the 3%-10% of boehmite dry glue powder weight, depending on last molding effect.
In the method for the present invention, step（2）The drying condition is 1-10 hours dry at 100-130 DEG C；Roasting process
To be roasted 2-4 hours at 500-650 DEG C.
In the method for the present invention, step（3）The hydrogenation active component maceration extract III is to form to count according to final catalyst
It calculates and prepares.In hydrogenation active component maceration extract III, vib metals content is calculated as 8-15g/100ml, Section VIII with oxide
Race's tenor is calculated as 1-3g/100ml with oxide, and volume impregnation, incipient impregnation or spray impregnating side may be used
Formula, dip time are 1-5 hours..
In the method for the present invention, step（3）The drying condition is 6-10 hours dry at 80-120 DEG C；The roasting
Condition is to be roasted 3-6 hours at 400-600 DEG C.
Suitable fluorine-containing and rare earth element solution and amount of activated metallic element are impregnated into physics and expanded by the method for the present invention
In the agent of hole, and modified aluminium oxide supports are made with boehmite kneading, molding, drying, roasting, dipping active component is finally made
Obtain catalyst.Alumina support after molding oxidized removing of physics expanding agent in roasting process, since selection has difference
The physics expanding agent of grain size, therefore form the macroporous structure with different pore size accordingly.The fluorine that is loaded in physics expanding agent,
Rare earth element and active metal component are loaded on corresponding duct, and the active component in final catalyst at macropore is made to contain
Amount, fluorine and rare earth element content significantly increase.In addition, active component content, fluorine and rare earth member in different-grain diameter physics expanding agent
Cellulose content is distinct, keeps the relatively large place's active component content in final catalyst aperture, fluorine and rare earth element content higher, hole
The relatively small place's content of diameter is relatively low, and duct type is made to be matched well with active component, improves duct and active component
Utilization rate.Fluorine and rare earth element there are the Acidity and thermal stability of effective modulation macropore, improve catalyst
Anti-carbon and anti-caking power.Active metallic content simultaneously at macropore is higher, and activity increases, and improves the utilization rate of macropore.
The addition of polyethylene glycol makes carbon black powder be uniformly mixed with boehmite when kneading, improves the uniformity coefficient of macropore.The catalysis
Agent is suitable for heavy resid hydrodemetallization field, which has higher activity and activity stability.
Specific implementation mode
The effect further illustrated the present invention with reference to embodiment and effect, but it is not limited to following embodiment.
Embodiment 1
It takes industrial ammonium heptamolybdate 55g to be placed in ammonium hydroxide, is stirred, until no insoluble matter, add industrial basic carbonate
Nickel 25g, is stirred, and until no insoluble matter, is made containing MoO310 grams/100 milliliters, NiO1.2 grams/100 milliliters of molybdenum-nickel-ammonia
Active metal salt solution.The dipping of the addition preparation various concentration of ammonium heptamolybdate and basic nickel carbonate can be adjusted as needed
Liquid.
It is 800 mesh to weigh grain size（Particle by 800 mesh sieve pores but can can't pass 1000 mesh sieve pores）I4.3 grams of carbon black powder
It is placed in spray rolling pot, under rotary state, is sprayed and contained in a manner of being saturated dipping by carbon black powder of the atomizing type into rolling pot
1 gram of molybdenum oxide, the active metal maceration extract of 0.07 gram of nickel oxide, the carbon black powder after dipping are 3 hours dry in 110 DEG C；After drying
Carbon black powder be replaced in spray rolling pot in, under rotary state, with atomizing type to rolling pot in carbon black powder sprayed with being saturated
Mode spray the lanthanum nitrate ethanol solution containing 0.4 gram of lanthana, the carbon black powder after dipping is 3 hours dry in 110 DEG C.After drying
Carbon black powder be placed in plastic beaker, by saturation spray in a manner of impregnate fluorine-containing 0.7 gram of ammonium fluoride aqueous solution, the carbon after dipping
Black powder is without drying for standby.
It is 400 mesh to weigh grain size（Particle by 400 mesh sieve pores but can can't pass 500 mesh sieve pores）II7.2 grams of carbon black powder
It is placed in spray rolling pot, under rotary state, is sprayed and contained in a manner of being saturated dipping by carbon black powder of the atomizing type into rolling pot
0.2 gram of molybdenum oxide, the active metal maceration extract of 0.01 gram of nickel oxide, the carbon black powder after dipping are 3 hours dry in 110 DEG C；It is dry
Carbon black powder afterwards, which is replaced in, to be sprayed in rolling pot, under rotary state, with carbon black powder of the atomizing type into rolling pot to be saturated spray
The mode of leaching sprays the lanthanum nitrate ethanol solution containing 0.2 gram of lanthana, and the carbon black powder after dipping is 3 hours dry in 110 DEG C.It is dry
Carbon black powder afterwards is placed in plastic beaker, fluorine-containing 0.2 gram of ammonium fluoride aqueous solution is impregnated in such a way that saturation sprays, after dipping
Carbon black powder is without drying for standby.
Weigh boehmite dry glue powder（Aluminium oxide contents on dry basis 70%）143 grams and above-mentioned steps carbon black powder I and carbon black powder
II, 7.5 grams of sesbania powders, 3 grams of ammonium phosphate are uniformly mixed, and it is 3% that mass concentration, which is added, the polyethylene glycol that average molecular weight is 4000
43 grams of kneadings of aqueous solution, the aqueous solution continuation kneading being then added in right amount dissolved with 5 grams of nitric acid is uniform, is extruded on screw rod banded extruder
Above-mentioned material is placed in baking oven 130 DEG C of dryings 4 hours by the cloverleaf pattern item of a diameter of 1.8mm, it is dry after molding in
It is roasted 4 hours at a temperature of 550 DEG C.
Above-mentioned material is placed in beaker, contains MoO with 150 milliliters310 grams/100 milliliters, NiO1.2 grams/100 milliliters
Molybdenum-nickel-ammonia active metal salt solution impregnated carrier 5 hours filters off redundant solution, and 120 DEG C dry 2 hours, then roasted at 550 DEG C
Burn 5 hours obtained catalyst C1, catalyst MoO3Mass percentage is 11.2wt%, and NiO mass percentages are
1.28wt%, fluorine mass percentage are 0.9wt%, and lanthana mass percentage is 0.6wt%.
Embodiment 2
With embodiment 1, only the grain size of carbon black powder I is 1000 mesh（Particle by 1000 mesh sieve pores but can can't pass 1340
Mesh sieve pore）, weight is 5.7 grams, 0.7 gram of molybdenum oxide is contained in carbon black powder I, 0.1 gram of nickel oxide, 0.7 gram of cerium oxide, cerium is from nitric acid
Cerium aqueous solution, 0.8 gram of fluorine, fluorine come from aqueous hydrogen fluoride solution.The grain size of carbon black powder II is 500 mesh（Particle can pass through 500 mesh sieve pores
But it can't pass 600 mesh sieve pores）, weight is 14.3 grams, contains 0.5 gram of molybdenum oxide, 0.05 gram of nickel oxide, cerium oxide in carbon black powder II
0.3 gram, cerium comes from cerous nitrate aqueous solution, 0.3 gram of fluorine, and fluorine comes from aqueous hydrogen fluoride solution.The addition of polyglycol solution is 43
Restrain to obtain catalyst C2 of the present invention, catalyst MoO3Mass percentage is 11.2wt%, and NiO mass percentages are
1.31wt%, fluorine mass percentage are 1.1 wt%, and cerium oxide mass percentage is 1wt%.
Embodiment 3
With embodiment 1, only the grain size of carbon black powder I is 600 mesh（Particle can by 600 mesh sieve pores but can't pass 800 mesh sieve
Hole）, weight is 7.2 grams, 0.5 gram of molybdenum oxide is contained in carbon black powder I, 0.05 gram of nickel oxide, 0.5 gram of praseodymium oxide, praseodymium is from praseodymium nitrate
Aqueous solution, 0.6 gram of fluorine.The grain size of carbon black powder II is 300 mesh（Particle by 300 mesh sieve pores but can can't pass 325 mesh sieve pores）, weight
Amount is 10 grams, contains 0.1 gram of molybdenum oxide in carbon black powder II, 0.04 gram of nickel oxide, 0.1 gram of praseodymium oxide, and praseodymium comes from praseodymium nitrate aqueous solution,
0.3 gram of fluorine.The addition of polyglycol solution restrains to obtain catalyst C3 of the present invention, catalyst MoO for 433Mass percentage
For 10.6wt%, NiO mass percentages are 1.3wt%, and fluorine mass percentage is 0.9wt%, and praseodymium oxide mass percentage is
0.6wt%。
Embodiment 4
With embodiment 1, only carbon black powder changes charcoal into, contains 0.6 gram of molybdenum oxide, 0.09 gram of nickel oxide, ytterbium oxide in charcoal I
0.6 gram, ytterbium comes from ytterbium nitrate aqueous solution, 0.5 gram of fluorine.Contain 0.3 gram of molybdenum oxide, 0.02 gram of nickel oxide, ytterbium oxide 0.2 in charcoal II
Gram, ytterbium comes from ytterbium nitrate aqueous solution, 0.3 gram of fluorine.The addition of polyglycol solution restrains to obtain catalyst C4 of the present invention for 43, should
Catalyst MoO3Mass percentage is 10.9wt%, and NiO mass percentages are 1.32wt%, and fluorine mass percentage is
0.8wt%, ytterbium oxide mass percentage are 0.8wt%.
Embodiment 5
With embodiment 1,0.8 gram of molybdenum oxide is only contained in carbon black powder I, 0.06 gram of nickel oxide, 0.55 gram of samarium oxide, samarium comes from
Samaric nitrate aqueous solution, 0.65 gram of fluorine.Contain 0.4 gram of molybdenum oxide, 0.03 gram of nickel oxide, 0.25 gram of samarium oxide, samarium in carbon black powder II
From samaric nitrate aqueous solution, 0.25 gram of fluorine.The addition of polyglycol solution is 86 grams, with 150 milliliters containing MoO when dipping38 grams/
100 milliliters, catalyst C5 of the present invention is made in NiO0.9 grams/100 milliliters of molybdenum-nickel-ammonia active metal salt solution impregnated carrier, should
Catalyst MoO3Mass percentage is 9.2wt%, and NiO mass percentages are 1wt%, and fluorine mass percentage is 0.9wt%,
Samarium oxide mass percentage is 0.8wt%.
Embodiment 6
The obtained present invention of polyglycol solution is not added with embodiment 1, when only boehmite is mixed with carbon black powder to urge
Agent C6, catalyst MoO3Mass percentage is 11.2wt%, and NiO mass percentages are 1.28wt%, fluorine quality percentage
Content is 0.9wt%, and lanthana mass percentage is 0.6wt%.
Comparative example 1
With example 1, only active metal is unsupported on carbon black powder, but is added when kneading, prepare have with
The comparative catalyst C7 of 1 same composition of embodiment.
Comparative example 2
With example 1, only fluorine and rare earth element are unsupported on carbon black powder, but are added when kneading, and preparation has
The catalyst C8 of composition same as Example 1.
Comparative example 3
With example 1, only active metal, fluorine, rare earth element are unsupported on carbon black powder, but are added when kneading,
Prepare the catalyst C9 with composition same as Example 1.
Comparative example 4
It is 800 mesh to weigh grain size（Particle by 800 mesh sieve pores but can can't pass 1000 mesh sieve pores）11.5 grams of carbon black powder
It is placed in spray rolling pot, under rotary state, is sprayed and contained in a manner of being saturated dipping by carbon black powder of the atomizing type into rolling pot
1.2 grams of molybdenum oxide, the active metal maceration extract of 0.08 gram of nickel oxide, the carbon black powder after dipping are 3 hours dry in 110 DEG C；It is dry
Carbon black powder afterwards, which is replaced in, to be sprayed in rolling pot, under rotary state, with carbon black powder of the atomizing type into rolling pot to be saturated spray
The mode of leaching sprays the lanthanum nitrate ethanol solution containing 0.6 gram of lanthana, and the carbon black powder after dipping is 3 hours dry in 110 DEG C.It is dry
Carbon black powder afterwards is placed in plastic beaker, fluorine-containing 0.9 gram of ammonium fluoride aqueous solution is impregnated in such a way that saturation sprays, after dipping
Carbon black powder is without drying for standby.
Weigh boehmite dry glue powder（Aluminium oxide contents on dry basis 70%）143 grams and above-mentioned steps carbon black powder, 7.5 grams of fields
Cyanines powder, 3 grams of ammonium phosphate are uniformly mixed, and it is 3% that mass concentration, which is added, 43 grams of the Aqueous Solutions of Polyethylene Glycol that average molecular weight is 4000
Kneading, the aqueous solution continuation kneading being then added in right amount dissolved with 5 grams of nitric acid is uniform, is extruded on screw rod banded extruder a diameter of
Above-mentioned material is placed in baking oven 130 DEG C of dryings 4 hours by the cloverleaf pattern item of 1.8mm, it is dry after molding in 550 DEG C
Roasting temperature 4 hours.
Above-mentioned material is placed in beaker, contains MoO with 150 milliliters310 grams/100 milliliters, NiO1.2 grams/100 milliliters
Molybdenum-nickel-ammonia active metal salt solution impregnated carrier 5 hours filters off redundant solution, and 120 DEG C dry 2 hours, then roasted at 550 DEG C
Burn 5 hours obtained catalyst C10, catalyst MoO3Mass percentage is 11.2wt%, and NiO mass percentages are
1.28wt%, fluorine mass percentage are 0.9wt%, and lanthana mass percentage is 0.6wt%.
The catalyst prepared to examples detailed above and comparative example carries out activity rating, more above-mentioned each catalyst activity and stabilization
Property.Raw material oil nature and evaluation process conditions are shown in Tables 1 and 2, and the Activity evaluation for operating 200h is shown in Table 3, when with operating
Between increase, catalyst activity reduce, in order to keep catalyst activity to meet production requirement, need to catalyst bed
Temperature raising, 5000 hours rear catalyst bed Wen Sheng of operating are shown in Table 4.
Table 1.
Table 2.
Table 3.
Table 4.
Catalyst provided by the invention compared with reference catalyst there is higher plus hydrogen to take off it can be seen from 3 data of table
Metal active.Find out after reacting 5000 hours, have using Hydrodemetalation catalyst provided by the invention from the result of table 4
Higher activity stability.
Claims (11)
1. a kind of preparation method of hydrogenation catalyst, it is characterised in that including following content：（1）With I containing rare earth element solution, contain
Fluorine solution I and hydrogenation active component maceration extract I impregnate physics expanding agent I respectively, with II containing rare earth element solution, fluorine-containing solution II
Physics expanding agent II is impregnated with hydrogenation active component maceration extract II, the physics expanding agent I and physics expanding agent II after dipping are through dry
It is dry spare；（2）By step（1）The physics expanding agent I and physics expanding agent II of gained and boehmite dry glue powder, chemical enlargement
At plastic, modified aluminium oxide supports are made in extrusion, drying, roasting for agent, extrusion aid, peptizing agent kneading；（3）Use hydrogenation activity
Component maceration extract III impregnates modified aluminium oxide supports, and through drying, roasting, fluorine-containing and rare earth element hydrodemetallisation catalyst is made
Agent；Step（1）The rare earth element is one or more of in lanthanum, cerium, praseodymium, ytterbium or samarium, and the solution containing rare earth element is dilute
The water and/or ethanol solution of earth elements soluble-salt；Step（1）In the fluorine-containing solution I, catalyst weight is accounted in terms of simple substance fluoride
0.5wt%-0.8wt%, the dosage of fluorine-containing solution I is the saturated water adsorptive value of physics expanding agent I；Step（1）The fluorine-containing solution
In II, the 0.2wt%-0.4wt% of catalyst weight is accounted in terms of simple substance fluoride, the dosage of fluorine-containing solution II is the full of physics expanding agent II
And water absorption；Step（1）In the I containing rare earth element solution, the 0.4wt %-0.7wt% of catalyst weight are accounted in terms of oxide,
The dosage of the I containing rare earth element solution is the saturated water adsorptive value of physics expanding agent I；Step（1）In the II containing rare earth element solution,
The dosage that the 0.1wt %-0.3wt%, the II containing rare earth element solution of catalyst weight are accounted in terms of oxide is physics expanding agent II's
Saturated water adsorptive value；The hydrogenation active component is VIB and/or group VIII metal, and vib metals are molybdenum and/or tungsten, the
The metal of VIII group is cobalt and/or nickel；Hydrogenation active component maceration extract be the acid solution containing hydrogenation active component, aqueous solution or
One kind in ammonia solution；Step（1）In the hydrogenation active component maceration extract I, vib metals oxide weight content is most
The 0.5wt%-1wt% and/or group VIII metal oxide weight content of whole catalyst weight are final catalyst weight
0.05wt%-0.1wt%；Step（1）In the hydrogenation active component maceration extract II, vib metals oxide weight content is
The 0.1wt%-0.5wt% and/or group VIII metal oxide weight content of final catalyst weight are final catalyst weight
0.01wt%-0.05wt%；Step（1）The physics expanding agent is the mixing of one or more of carbon black powder, charcoal or sawdust,
The grain size of physics expanding agent I is 600-1000 mesh, and the grain size of physics expanding agent II is 300-500 mesh.
2. according to the method for claim 1, feature exists：In step（1）The fluorine-containing solution is ammonium fluoride or fluorine
Change the aqueous solution of hydrogen.
3. according to the method for claim 1, feature exists：Step（1）The drying condition is that nature dries in the shade or in 50-
120 DEG C 1-10 hours dry.
4. according to the method for claim 1, feature exists：Step（2）Described in the addition of physics expanding agent I be quasi-
The addition of the 3%-5% of boehmite dry glue powder weight, physics expanding agent II are the 5%-10% of boehmite dry glue powder weight.
5. according to the method for claim 1, feature exists：Step（2）Mass concentration is added in the kneading process is
1%-5% Aqueous Solutions of Polyethylene Glycol, the wherein average molecular weight of polyethylene glycol are 1000-4000, the addition of Aqueous Solutions of Polyethylene Glycol
Amount is 30-70 grams/100 grams boehmite dry glue powders.
6. according to the method for claim 1, feature exists：Step（2）The chemical enlargement agent be phosphoric acid, phosphate or
One or more of boric acid, chemical enlargement agent addition are the 3%-5% of boehmite dry glue powder weight.
7. according to the method for claim 1, feature exists：Step（2）The extrusion aid is sesbania powder, starch or methyl
One or more of cellulose, extrusion aid addition are the 3%-5% of boehmite dry glue powder weight.
8. according to the method for claim 1, feature exists：Step（2）The peptizing agent is formic acid, acetic acid, citric acid
Or the mixing of one or more of nitric acid, addition are the 3%-10% of boehmite dry glue powder weight.
9. according to the method for claim 1, feature exists：Step（2）The drying condition is dry at 100-130 DEG C
1-10 hours；Roasting process is to be roasted 2-4 hours at 500-650 DEG C.
10. according to the method for claim 1, feature exists：Step（3）In the hydrogenation active component maceration extract III,
Vib metals content is calculated as 8-15g/100mL with oxide and/or group VIII tenor is calculated as 1-3g/ with oxide
100mL。
11. according to the method for claim 1, feature exists：Step（3）The drying condition is to be done at 80-120 DEG C
It is 6-10 hours dry；The roasting condition is to be roasted 3-6 hours at 400-600 DEG C.
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