CN106140122B - 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 a kind of preparation methods of boracic Hydrodemetalation catalyst, including following content：（1）Physics expanding agent I is impregnated respectively with hydrogenation active component maceration extract I and boron-containing solution I, physics expanding agent II is impregnated respectively with hydrogenation active component maceration extract II and boron-containing solution II, physics expanding agent I and physics expanding agent II after dipping is then spare with urea liquid dipping physics expanding agent I and physics expanding agent II through drying；（2）By step（1）The physics expanding agent I and physics expanding agent II of gained are with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizing agent kneading at plastic, extrusion, molding is placed in sealing device and is heat-treated, and modified aluminium oxide supports are made through drying, roasting in treated material；（3）Modified aluminium oxide supports are impregnated with hydrogenation active component maceration extract III, dipping rear catalyst is dry, roasts, and boracic Hydrodemetalation catalyst is made.Catalyst activity metal prepared by this method content at macropore is relatively high, and content is relatively low at aperture, and the utilization rate of macropore significantly improves, which has high activity and long-term operation stability.
Description
Technical field
The present invention relates to a kind of preparation methods of boracic Hydrodemetalation catalyst.
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.
CN102652919A is disclosed using boron-containing alumina as the Hydrodemetalation catalyst of carrier, preparation and its application.It should
Catalyst has the hydrogenation active metal component of boron-containing alumina carrier and load on this carrier, which is characterized in that described adds
Hydrogen activity metal component is the group of at least one metal component selected from group vib and at least one metal component selected from V B races
It closes, is counted by oxide and 7 on the basis of catalyst, the content of the group vib metal component is 0.2 weight %-15 weight %, V B
The content of race's metal component is 0.2 weight %-12 weight %.
Residuum hydrogenating and metal-eliminating catalyst active metal component prepared by the above method is punished in the macropore and aperture of carrier
Cloth is more uniform, causes the utilization rate of macropore relatively low.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of boracic Hydrodemetalation catalyst.The party
Catalyst activity metal prepared by the method content at macropore is relatively high, and content is relatively low at aperture, and the utilization rate of macropore is aobvious
It writes and improves, which 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 maceration extract I and boron-containing solution I, uses hydrogenation active component
Maceration extract II and boron-containing solution II impregnates physics expanding agent II respectively, the physics expanding agent I after dipping and physics expanding agent II warps
It is dry, it is then spare with urea liquid dipping physics expanding agent I and physics expanding agent II；
（2）By step（1）The physics expanding agent I and physics expanding agent II of gained expand with boehmite dry glue powder, chemistry
Hole agent, extrusion aid, peptizing agent kneading are at plastic, extrusion, and molding is placed in sealing device and is heat-treated, treated material warp
Dry, roasting, is made and contains active component and boron modification alumina support；
（3）Modified aluminium oxide supports are impregnated with hydrogenation active component maceration extract III, dipping rear catalyst is dry, roasts, system
Obtain boracic Hydrodemetalation catalyst.
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 weight content is with oxygen
Compound is calculated as the 0.6wt%-0.8wt% of final catalyst weight, and group VIII weight metal content is calculated as finally urging with oxide
The 0.3wt%-0.5wt% of agent weight.The dosage of hydrogenation active component maceration extract I is physics expanding agent I saturated water adsorptive values
30%-50%.It is impregnated with the following method when dipping：Physics expanding agent I is placed in and is sprayed in rolling pot, to carbon black under the conditions of rolling
Uniformly the active maceration extract of spray dipping, the physics expanding agent that maceration extract continues after spraying into rolling pot spray distillation in powder
Water makes physics expanding agent I adsorption saturations.
In the method for the present invention, step（1）In the hydrogenation active component maceration extract II, vib metals weight content with
Oxide is calculated as the 0.4wt%-0.6wt% of final catalyst weight, and group VIII weight metal content is calculated as finally with oxide
The 0.1wt%-0.3wt% of catalyst weight.The dosage of hydrogenation active component maceration extract II is physics expanding agent I saturated water adsorptive values
30%-50%.It is impregnated with the following method when dipping：Physics expanding agent I is placed in and is sprayed in rolling pot, to carbon black under the conditions of rolling
Uniformly the active maceration extract of spray dipping, the physics expanding agent that maceration extract continues after spraying into rolling pot spray distillation in powder
Water makes physics expanding agent II adsorption saturations.
In the method for the present invention, step（1）The boron-containing solution I can be the aqueous solution of boric acid or borate, solution
Dosage is the 20%-40% of the saturated water adsorptive value of physics expanding agent I, and the content of boron accounts for catalyst weight in terms of oxide in solution
0.4%-0.6%。
In the method for the present invention, step（1）The boron-containing solution II's can be boric acid or the aqueous solution of borate, solution
Dosage be physics expanding agent I saturated water adsorptive value 20%-40%, the content of boron accounts for catalyst weight in terms of oxide in solution
0.1%-0.3%.
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, the grain size of physics expanding agent I is 600-1000 mesh, and the grain size of physics expanding agent II is 300-500 mesh.
In the method for the present invention, step（1）The urea liquid dosage is the full of physics expanding agent I and physics expanding agent II
And water absorption, the weight of urea and physics expanding agent I and the ratio of physics expanding agent II mass sum total are 0.4 in solution:1-0.8:
1。
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
5%-10%, the addition of physics expanding agent II is the 3%-5% of boehmite dry glue powder weight.
In the method for the present invention, step（2）The sealing heat treatment is to be carried out in autoclave or sealing tube furnace
Heat treatment, treatment temperature be 140-180 DEG C, processing time be 1-4 hours.
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 or more of phosphoric acid or phosphate, preferably
Phosphate, wherein phosphate are selected from one or more of ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate, and chemical enlargement agent is added
Amount 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 7-15g/100ml, Section VII race with oxide
Tenor is calculated as 0.8-3g/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 boron-containing solution, active metallic element solution and urea liquid are impregnated into physics expanding agent by the method for the present invention
On, and modified aluminium oxide supports are made with boehmite kneading, molding, drying, roasting, dipping active component, which is finally made, urges
Agent.When closed heat treatment, the presence of urea makes physics expanding agent surrounding oxidic alumina supporter surface hydroxyl structure be improved.Roasting
Boron uniformly loads to corresponding big hole surface first when burning, since the improvement of surface hydroxyl structure makes the more equal of boron load
Even, boron particles uniform particle diameter, the active component inside following physics expanding agent particle loads to boron modification carrying alumina body surface
Face.The presence of boron has adjusted the surface nature of carrier at macropore, improves the interaction of active component and carrier, improves work
The catalytic activity of property metal.The physics expanding agent with different-grain diameter is selected, making to be formed in final catalyst accordingly has not
With the macroporous structure in aperture, be conducive to mass transfer and the diffusion of reactant.It lives at the macropore formed after being roasted due to physics expanding agent
Active metal and carrier function are suitable after property tenor is relatively high and boron modification, make the catalytic activity of active metal at macropore
It greatly improves.It is easy to the diffusion of residual oil molecule at macropore, and there is higher appearance metal and carbon accumulation resisting ability, makes finally to be catalyzed
Agent has higher catalytic activity and activity stability.The addition of polyethylene glycol makes carbon black powder be mixed with boehmite when kneading
Uniformly, the uniformity coefficient of macropore is improved.Catalyst of the present invention is suitable for heavy resid hydrodemetallization field, this catalyst has
Higher activity and activity stability.
Specific implementation mode
The effect further illustrated the present invention with reference to embodiment and effect, but it is not limited to following embodiment.
Embodiment 1
It takes industrial ammonium heptamolybdate 55g to be placed in ammonium hydroxide, is stirred, until no insoluble matter, add industrial basic carbonate
Nickel 25g, is stirred, and until no insoluble matter, is made containing MoO310 grams/100 milliliters, NiO1.2 grams/100 milliliters of molybdenum-nickel-ammonia
Active metal salt solution.The dipping of the addition preparation various concentration of ammonium heptamolybdate and basic nickel carbonate can be adjusted as needed
Liquid.
It is 800 mesh to weigh grain size（Particle by 800 mesh sieve pores but can can't pass 1000 mesh sieve pores）Carbon black powder I11.4 set
It rolls in pot in spray, under rotary state, is sprayed containing 0.6 gram of molybdenum oxide, nickel oxide with carbon black powder of the atomizing type into rolling pot
0.4 gram of active metal maceration extract 3.4ml, then proceeding to spray distilled water makes carbon black powder adsorption saturation, the carbon black powder after dipping
It is 3 hours dry in 110 DEG C.By the carbon black powder after drying be replaced in spray rolling pot in, under rotary state, with atomizing type to
Carbon black powder in rolling pot sprays the boric acid aqueous solution 3.4ml containing 0.5 gram of boron oxide, and the carbon black powder after dipping is in 110 DEG C dry 3 small
When,
It is 300 to weigh grain size（Particle by 300 mesh sieve pores but can can't pass 325 mesh sieve pores）II4.3 grams of purpose carbon black powder
It is uniformly mixed, is placed in spray rolling pot, under rotary state, sprayed containing molybdenum oxide with carbon black powder of the atomizing type into rolling pot
0.5 gram, the active metal maceration extract 1.3ml of 0.1 gram of nickel oxide, then proceeding to spray distilled water makes carbon black powder adsorption saturation, soaks
Carbon black powder after stain is 3 hours dry in 110 DEG C.Carbon black powder after drying is replaced in spray rolling pot, under rotary state,
Spray the boric acid aqueous solution 1ml containing 0.1 gram of boron oxide with carbon black powder of the atomizing type into rolling pot, the carbon black powder after dipping in
110 DEG C of dryings 3 hours.
By after drying carbon black powder I and carbon black powder II be again placed in spray rolling pot in, under rotary state, with atomizing type
Carbon black powder into rolling pot sprays the aqueous solution containing 7.9 grams of urea in a manner of being saturated dipping, and the carbon black powder after dipping is spare.
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
The cloverleaf pattern item of 1.8mm, molding is placed in sealing tube furnace to be heat-treated 4 hours in 140 DEG C of sealings, then in 120 DEG C of bakings
It is 3 hours dry, the molding after drying 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, is then dried 2 hours in 120 DEG C, then 550
5 hours obtained catalyst C1, catalyst MoO are roasted at DEG C3Mass percentage is that 11.1%, NiO mass percentages are
1.7wt%, boron oxide percentage composition are 0.6wt%.
Embodiment 2
With embodiment 1, only carbon black powder I weight is 14.3 grams, and grain size is 600 mesh（Particle can be by 600 mesh sieve pores but logical
But 800 mesh sieve pore）, 0.8 gram of molybdenum oxide, 0.5 gram of nickel oxide are contained in active component I, activity component impregnation liquid dosage is
7.2ml.Contain 0.6 gram of boron oxide in boron-containing solution I, the dosage of boric acid solution is 7.2 ml, and carbon black powder II weight is 5.7 grams, grain
Diameter is 400 mesh（Particle by 400 mesh sieve pores but can can't pass 500 mesh sieve pores）, 0.6 gram of molybdenum oxide, oxygen are contained in active component II
Change 0.2 gram of nickel, activity component impregnation liquid dosage is 1.2ml.Contain 0.2 gram of boron oxide, the dosage of boric acid solution in boron-containing solution II
For 1.7 ml, urea containing being 7.5 grams in solution.The addition of polyglycol solution is 43 grams, and the temperature of heat treatment is 180
DEG C, processing time is 1 hour, and catalyst C2 of the present invention, catalyst MoO is made3Mass percentage is 11.4wt%, NiO matter
Amount percentage composition is 1.27wt%, and boron oxide mass percentage is 0.8wt%.
Embodiment 3
With embodiment 1, only carbon black powder I weight is 7.2 grams, and grain size is 1000 mesh（Particle can by 1000 mesh sieve pores but
It can't pass 1340 mesh sieve pores）, 0.7 gram of molybdenum oxide, 0.3 gram of nickel oxide are contained in active component I, activity component impregnation liquid dosage is
2.9ml.Contain 0.4 gram of boron oxide in boron-containing solution I, the dosage of boric acid solution is 2.9 ml, and carbon black powder II weight is 7.2 grams, grain
Diameter is 500 mesh（Particle by 500 mesh sieve pores but can can't pass 600 mesh sieve pores）, 0.4 gram of molybdenum oxide, oxygen are contained in active component II
Change 0.3 gram of nickel, activity component impregnation liquid dosage is 2.9ml.Contain 0.3 gram of boron oxide, the dosage of boric acid solution in boron-containing solution II
For 2.9 ml, urea containing being 11.5 grams in solution.The addition of polyglycol solution is 100 grams, and the temperature of heat treatment is 160
DEG C, processing time is 2 hours, and catalyst C3 of the present invention, catalyst MoO is made3Mass percentage is 11.1wt%, NiO matter
Amount percentage composition is 1.6wt%, and boron oxide mass percentage is 0.6wt%.
Embodiment 4
With embodiment 1, only carbon black powder changes charcoal into, and the dosage of charcoal I is 8.6 grams, and the dosage of active component solution I is
The dosage of 4.3ml, boric acid solution I are 2.2 ml, and the dosage of charcoal II is 6.4 grams, and the dosage of active component solution II is
The dosage of 2.6ml, boric acid solution II are 2.6 ml, urea containing being 9 grams in solution.The addition of polyglycol solution is 100
Gram, the temperature of heat treatment is 170 DEG C, and processing time is 3 hours, and catalyst C4 of the present invention, catalyst MoO is made3Quality hundred
It is 1.7wt% to divide content to be 11.1%, NiO mass percentages, and boron oxide percentage composition is 0.6wt%.
Embodiment 5
With embodiment 1, only the dosage of carbon black powder I is 10 grams, and the dosage of active component solution I is 3ml, boric acid solution I
Dosage be 4ml, the dosage of carbon black powder II is 5 grams, and the dosage of active component solution II is 2ml, and the dosage of boric acid solution II is
1.5 ml, urea containing being 10.5 grams in solution.The addition of polyglycol solution is 86 grams, and the temperature of heat treatment is 150 DEG C,
Processing time is 3 hours, contains MoO with 150 milliliters when active metal impregnates38 grams/100 milliliters, NiO0.9 grams/100 milliliters
Catalyst C5 of the present invention, catalyst MoO is made in molybdenum-nickel-ammonia active metal salt solution impregnated carrier3Mass percentage is
9.1wt%, NiO mass percentage are 1.4wt%, and boron oxide mass percentage is 0.6wt%.
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 that 11.1%, NiO mass percentages are 1.7wt%, boron oxide percentage composition
For 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 boron is unsupported on carbon black powder, but is added when kneading, and preparing has and 1 phase of embodiment
With the catalyst C8 of composition.
Comparative example 3
With example 1, only active metal and boron are unsupported on carbon black powder, but are added when kneading, and preparation has
The catalyst C9 of 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）Carbon black powder I15.7 set
It rolls in pot in spray, under rotary state, is sprayed containing 1.1 grams of molybdenum oxide, nickel oxide with carbon black powder of the atomizing type into rolling pot
0.5 gram of active metal maceration extract 4.7ml, then proceeding to spray distilled water makes carbon black powder adsorption saturation, the carbon black powder after dipping
It is 3 hours dry in 110 DEG C.By the carbon black powder after drying be replaced in spray rolling pot in, under rotary state, with atomizing type to
Carbon black powder in rolling pot sprays the boric acid aqueous solution 4.4ml containing 0.6 gram of boron oxide, and the carbon black powder after dipping is in 110 DEG C dry 3 small
When,
Carbon black powder I after drying is again placed in spray rolling pot, under rotary state, with atomizing type into rolling pot
Carbon black powder sprays the aqueous solution containing 7.9 grams of urea in a manner of being saturated dipping, and the carbon black powder after dipping is spare.
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
The cloverleaf pattern item of 1.8mm, molding is placed in sealing tube furnace to be heat-treated 4 hours in 140 DEG C of sealings, then in 120 DEG C of bakings
It is 3 hours dry, the molding after drying 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, is then dried 2 hours in 120 DEG C, then 550
5 hours obtained catalyst C10, catalyst MoO are roasted at DEG C3Mass percentage is that 11.1%, NiO mass percentages are
1.7wt%, boron oxide percentage composition are 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 boracic Hydrodemetalation catalyst, it is characterised in that including following content：（1）Use hydrogenation activity
Component maceration extract I and boron-containing solution I impregnates physics expanding agent I respectively, with hydrogenation active component maceration extract II and boron-containing solution II
Physics expanding agent II is impregnated respectively, then the physics expanding agent I and physics expanding agent II after dipping are soaked through drying with urea liquid
Stain physics expanding agent I and physics expanding agent II is spare；（2）By step（1）The physics expanding agent I and physics expanding agent II of gained with
Boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizing agent kneading are at plastic, extrusion, and molding is placed in sealing device
Middle heat treatment, treated material are made through drying, roasting and contain active component and boron modification alumina support；（3）It is lived with hydrogen is added
Property component maceration extract III impregnate modified aluminium oxide supports, boracic Hydrodemetalation catalyst is made in dry, roasting after dipping；Institute
The hydrogenation active component stated is VIB and/or group VIII metal, and vib metals are molybdenum and/or tungsten, and the metal of group VIII is
Cobalt and/or nickel；Hydrogenation active component maceration extract is one in the acid solution containing hydrogenation active component, aqueous solution or ammonia solution
Kind；Step（1）In the hydrogenation active component maceration extract I, vib metals weight content is calculated as final catalyst with oxide
The 0.6wt%-0.8wt% and/or group VIII weight metal content of weight are calculated as final catalyst weight with oxide
0.3wt%-0.5wt%；The dosage of hydrogenation active component maceration extract I is the 30%-50% of physics expanding agent I saturated water adsorptive values；Step
（1）In the hydrogenation active component maceration extract II, vib metals weight content is calculated as final catalyst weight with oxide
0.4wt%-0.6wt% and/or group VIII weight metal content are calculated as the 0.1wt%- of final catalyst weight with oxide
0.3wt%；The dosage of hydrogenation active component maceration extract II living is the 30%-50% of physics expanding agent I saturated water adsorptive values；Step（1）Institute
The boron-containing solution I stated is the aqueous solution of boric acid or borate, and the dosage of solution is the 20%- of the saturated water adsorptive value of physics expanding agent I
40%, the content of boron accounts for the 0.4%-0.6% of catalyst weight in terms of oxide in solution；Step（1）The boron-containing solution II's
For boric acid or the aqueous solution of borate, the dosage of solution is the 20%-40% of the saturated water adsorptive value of physics expanding agent I, boron in solution
Content the 0.1%-0.3% of catalyst weight is accounted in terms of oxide；Step（1）The physics expanding agent be carbon black powder, charcoal or
One or more of sawdust mixes, and 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；Step（1）The urea liquid dosage is the saturated water adsorptive value of physics expanding agent I and physics expanding agent II, in solution
The ratio of weight and physics expanding agent I and physics expanding agent II the mass sum total of urea is 0.4:1-0.8:1.
2. according to the method for claim 1, it is characterised in that：Step（1）The drying condition be nature dry in the shade or in
50-120 DEG C 1-10 hours dry.
3. according to the method for claim 1, it is characterised in that：Step（2）Described in the addition of physics expanding agent I be
The addition of the 5%-10% of boehmite dry glue powder weight, physics expanding agent II are the 3%- of boehmite dry glue powder weight
5%。
4. according to the method for claim 1, it is characterised in that：Step（2）The sealing heat treatment is in reaction under high pressure
The heat treatment carried out in kettle or sealing tube furnace, treatment temperature are 140-180 DEG C, and processing time is 1-4 hours.
5. according to the method for claim 1, it is characterised in that：Step（2）Mass concentration is added in the kneading process
For 1%-5% Aqueous Solutions of Polyethylene Glycol, the wherein average molecular weight of polyethylene glycol is 1000-4000, and Aqueous Solutions of Polyethylene Glycol adds
It is 30-70 grams/100 grams boehmite dry glue powders to enter amount.
6. according to the method for claim 1, it is characterised in that：Step（2）The chemical enlargement agent is phosphoric acid or phosphoric acid
One or more of salt, chemical enlargement agent addition are the 3%-5% of boehmite dry glue powder weight.
7. according to the method for claim 1, it is characterised in that：Step（2）The extrusion aid is sesbania powder, starch or first
One or more of base cellulose, extrusion aid addition are the 3%-5% of boehmite dry glue powder weight.
8. according to the method for claim 1, it is characterised in that：Step（2）The peptizing agent is formic acid, acetic acid, lemon
The mixing of one or more of acid or nitric acid, addition are the 3%-10% of boehmite dry glue powder weight.
9. according to the method for claim 1, it is characterised in that：Step（2）The drying condition is to be done at 100-130 DEG C
It is 1-10 hours dry；Roasting process is to be roasted 2-4 hours at 500-650 DEG C.
10. according to method as claimed in claim 1 or 2, it is characterised in that：Step（3）The hydrogenation active component maceration extract
In III, vib metals content is calculated as 7-15g/100mL and/or group VIII tenor in terms of oxide with oxide
For 0.8-3g/100mL.
11. according to the method for claim 1, it is characterised in that：Step（3）The drying condition is at 80-120 DEG C
It is 6-10 hours dry；The roasting condition is to be roasted 3-6 hours at 400-600 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510196346.8A CN106140122B (en) | 2015-04-23 | 2015-04-23 | A kind of preparation method of boracic Hydrodemetalation catalyst |
Applications Claiming Priority (1)
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| 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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