CN105582952B - A kind of preparation method of the Hydrodemetalation catalyst containing rare earth - Google Patents
A kind of preparation method of the Hydrodemetalation catalyst containing rare earth Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of Hydrodemetalation catalyst containing rare earth, including following content：（1）Carbon black powder is impregnated respectively with amount of activated component maceration extract and the solution containing thulium, then drying for standby；（2）By step（1）Carbon black powder after the dipping of gained, into plastic, extrusion, drying, roasting, is made with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizing agent kneading and contains active component and rare earth modified alumina support；（3）Then residual activity component is loaded on modified aluminium oxide supports, through drying, roasting, Hydrodemetalation catalyst is made.Catalyst activity metal prepared by this method content at macropore is of a relatively high, and content is relatively low at aperture, and the heat endurance of macropore significantly improves, and the Hydrodemetalation catalyst has high activity and long-term operation stability.
Description
Technical field
The present invention relates to a kind of preparation method of Hydrodemetalation catalyst containing rare earth.
Background technology
With the raising of raw material deep processing requirement 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 in catalyst duct effectively to solve heavy oil component
Power is excessive, beavy metal impurity deposition and coking caused by catalyst activity reduction or inactivation the problems such as, an urgent demand is in oil
The widely used alumina support of the industries such as chemical industry possesses the characteristic of big pore volume and large aperture.Large aperture is advantageous to macromolecular chemical combination
For thing to catalyst granules diffusion inside, big pore volume, which is then advantageous 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 add physics expanding agent and chemical enlargement agent, then active component is loaded on carrier in a manner of spraying and impregnating, the catalysis
The pore volume of agent is 0.80-1.20ml/g, 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.Employed not in this method
Saturation sprays technology, and the catalyst after spraying does not do drying process, is directly placed into roaster.After this method is effectively prevented
Migration of the metal salt solution from material lower floor to upper strata or surface in continuous drying process, reduces production cost.
US4,448,896 disclose the catalyst of a kind 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, the pore volume that pore radius is 3.75-7500nm are 0.5-1.5ml/g's
On alumina support, the preparation method of the carrier be activated alumina or activated alumina precursor are mixed with carbon black, are molded,
Roasting.
The above method prepare residuum hydrogenating and metal-eliminating catalyst active metal component be at the macropore and aperture of carrier
It is uniformly distributed, causes the utilization rate of macropore relatively low, in addition, the heat endurance of carrier needs further to be improved.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of preparation method of the Hydrodemetalation catalyst containing rare earth.Should
Catalyst activity metal prepared by the method content at macropore is of a relatively high, and content is relatively low at aperture, and the heat of macropore is steady
Qualitative to significantly improve, the Hydrodemetalation catalyst has high activity and long-term operation stability.
The preparation method of the Hydrodemetalation catalyst containing rare earth of the present invention, including following content：
（1）Carbon black powder is impregnated respectively with amount of activated component maceration extract and the solution containing thulium, is then dried
It is standby；
（2）By step（1）Carbon black powder after the dipping of gained and boehmite dry glue powder, chemical enlargement agent, extrusion aid,
Peptizing agent kneading extrusion, drying, roasting, is made into plastic and contains active component and rare earth modified alumina support；
（3）Then residual activity component is loaded on modified aluminium oxide supports, through drying, roasting, HDM is made
Catalyst.
In the inventive method, described activity component impregnation liquid is vib metals compound and/or group VIII metal
Compound solution, can be the acid solution containing active component, the aqueous solution or ammonia solution, preferably ammonia solution, above maceration extract
Manner of formulation is known to those skilled in the art；Wherein vib metals compound is selected from ammonium molybdate, ammonium tungstate, ammonium metatungstate
Or the one or more in ethyl ammonium tungstate, group VIII metallic compound be selected from nickel nitrate, cobalt nitrate, nickel chloride, cobalt chloride,
One or more in nickel acetate, cobalt acetate or metatungstic acid nickel；The concentration of vib metals compound is 0.1- in maceration extract
100g/100ml, the concentration of group VIII metallic compound is 0.01-10g/100ml；Step（1）Impregnation method using etc. body
Product dipping.
In the inventive method, step（1）The weight of described amount of activated component maceration extract dipping active component, with oxidation
Thing is calculated as the 0.01wt%-1wt% of final catalyst weight, and preferably vib metals weight content is final catalyst weight
0.1wt%-0.8wt%, group VIII weight metal content are the 0.01wt%-0.05wt% of final catalyst weight.
In the inventive method, step（1）Described thulium is selected from lanthanum, cerium, praseodymium, ytterbium or samarium one or more,
Solution containing thulium is generally the water and/or ethanol solution of rare earth element soluble-salt, and soluble-salt is generally nitre
Hydrochlorate or chloride, such as lanthanum nitrate, cerous nitrate, praseodymium nitrate, ytterbium nitrate, samaric nitrate, the dosage of solution are the saturation of carbon black powder
Water absorption, the content of carbon black powder rare earth elements accounts for the 0.01% ~ 0.05% of catalyst weight in terms of oxide after dipping.
In the inventive method, step（1）Described drying condition is that nature dried in the shade or in 50-120 DEG C of dry 1-10 hour.
In the inventive method, step（2）Described boehmite dry glue powder can be prepared using any one method
Boehmite dry glue powder.
In the inventive method, step（2）The addition of carbon black powder after middle dipping is boehmite dry glue powder weight
5%-10%。
In the inventive method, step（2）It is 1%-5% polyethylene glycol water that mass concentration is preferably added in described kneading process
The mean molecule quantity of solution, wherein polyethylene glycol is 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 grams/100
Gram boehmite dry glue powder.
In the inventive method, step（2）Described chemical enlargement agent is one kind or several in phosphoric acid, phosphate or boric acid
Kind, the one or more of preferably phosphate, wherein phosphate in ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate, chemistry expands
Agent addition in hole is the 3%-5% of boehmite dry glue powder weight.
In the inventive method, step（2）Described 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 inventive method, step（2）Described 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 inventive method, step（2）The drying condition is that 1-10 hours are dried at 100-130 DEG C；Roasting process
To be calcined 2-4 hours at 500-650 DEG C.
In the inventive method, step（3）The load of described surplus active component uses infusion process, can use volume
Dipping, incipient impregnation or spray impregnating mode, dip time is 1-5 hours, and the specific concentration of maceration extract can be according to most
Depending on tenor on whole catalyst.
In the inventive method, step（3）Described drying condition is that 6-10 hours are dried at 80-120 DEG C；The roasting
Condition is that 3-6 hours are calcined at 400-600 DEG C.
Appropriate thulium and active metallic element are impregnated on carbon black powder by the inventive method, and with intending thin water
Modified aluminium oxide supports are made in aluminium stone kneading, shaping, drying, roasting, and catalyst is finally made in dipping active component.It had been calcined
The oxidized removing of carbon powder forms macropore in journey, and the active metal component and thulium loaded in carbon powder is supported
Onto corresponding macropore, significantly increase the active component content in final catalyst at macropore and thulium content.
Thulium is covered in oxidation aluminium surface, protects part of hydroxyl and prevents aluminum ions migration, substantially increases big
The heat endurance in hole, prevents caving in for macropore, and catalyst holds the ability enhancing of metal and volume carbon.Activity gold at macropore simultaneously
It is higher to belong to content, activity increases, and improves the utilization rate of macropore.The addition of polyethylene glycol makes carbon black powder with intending thin water aluminium during kneading
Stone is well mixed, and improves the uniformity coefficient of macropore.
Embodiment
The effect of the present invention and effect are further illustrated with reference to embodiment, but is not limited to following examples.
Embodiment 1
Take industrial ammonium heptamolybdate 55g to be placed in ammoniacal liquor, be stirred, untill no insoluble matter, add industrial basic carbonate
Nickel 25g, is stirred, and untill 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 concentrations of ammonium heptamolybdate and basic nickel carbonate can be adjusted as needed
Liquid.
Weigh 7.2 grams of carbon black powder to be placed in spray rolling pot, under rotary state, with carbon black powder of the atomizing type into rolling pot
Sprayed in a manner of saturation sprays containing 0.3 gram of molybdenum oxide, the active metal maceration extract of 0.03 gram of nickel oxide, the carbon black powder after dipping
Dried 3 hours in 110 DEG C.By dried carbon black powder be replaced in spray rolling pot in, under rotary state, with atomizing type to
Carbon black powder in rolling pot sprays the lanthanum nitrate ethanol solution containing 0.02 gram of lanthana in a manner of saturation sprays, the carbon black after dipping
Powder in 110 DEG C dry 3 hours it is standby.
Weigh boehmite dry glue powder（Aluminum 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 well mixed, and it is 3% to add mass concentration, and mean molecule quantity is 4,000 43 grams of Aqueous Solutions of Polyethylene Glycol
Kneading, then adds in right amount that to continue kneading uniform dissolved with the aqueous solution of 5 grams of nitric acid, is extruded on screw rod banded extruder a diameter of
1.8mm cloverleaf pattern bar, dried 3 hours in 120 DEG C, dried article shaped is calcined 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, redundant solution is filtered off, 120 DEG C dry 2 hours, then roasted at 550 DEG C
Burn 5 hours obtained catalyst C1, catalyst MoO3Weight/mass percentage composition is 10.2wt%, and NiO weight/mass percentage compositions are
1.22wt%, lanthana weight/mass percentage composition are 0.02wt%.
Embodiment 2
With embodiment 1, simply the dosage of carbon black powder is 12 grams, contains 0.1 gram of molybdenum oxide in carbon black powder, 0.01 gram of nickel oxide,
0.03 gram of cerium oxide, the addition of polyglycol solution restrain to obtain catalyst C2 of the present invention, catalyst MoO for 433Quality hundred
It is 10wt% to divide content, and NiO weight/mass percentage compositions are 1.2wt%, and cerium oxide weight/mass percentage composition is 0.03wt%.
Embodiment 3
With embodiment 1, simply the dosage of carbon black powder is 9 grams, and 0.5 gram of molybdenum oxide, 0.02 gram of nickel oxide, oxygen are contained in carbon black powder
Change 0.01 gram of praseodymium, the addition of polyglycol solution restrains to obtain catalyst C3 of the present invention, catalyst MoO for 1003Quality percentage
Content is 10.5wt%, and NiO weight/mass percentage compositions are 1.22wt%, and praseodymium oxide weight/mass percentage composition is 0.01wt%.
Embodiment 4
With embodiment 1, simply the dosage of carbon black powder is 14.3 grams, and 0.7 gram of molybdenum oxide, nickel oxide 0.05 are contained in carbon black powder
Gram, 0.05 gram of ytterbium oxide, the addition of polyglycol solution restrains to obtain catalyst C3 of the present invention, catalyst MoO for 1003Matter
Amount percentage composition is 10.5wt%, and NiO weight/mass percentage compositions are 1.22wt%, and ytterbium oxide weight/mass percentage composition is 0.05wt%.
Embodiment 5
With embodiment 1, simply the dosage of carbon black powder is 13 grams, contains 0.8 gram of molybdenum oxide in carbon black powder, 0.04 gram of nickel oxide,
0.04 gram of samarium oxide, the addition of polyglycol solution are 86 grams, contain MoO with 150 milliliters during dipping38 grams/100 milliliters,
Catalyst C5 of the present invention, the catalyst is made in NiO0.9 grams/100 milliliters of molybdenum-nickel-ammonia active metal salt solution impregnated carrier
MoO3Weight/mass percentage composition is 8.7wt%, and NiO weight/mass percentage compositions are 0.93wt%, and samarium oxide weight/mass percentage composition is
0.04wt%。
Embodiment 6
With embodiment 1, the polyglycol solution obtained present invention is not added when simply boehmite mixes with carbon black powder and is urged
Agent C6, catalyst MoO3Weight/mass percentage composition is 10.2wt%, and NiO weight/mass percentage compositions are 1.21wt%, lanthana quality
Percentage composition is 0.02wt%.
Comparative example 1
With example 1, simply active metal is unsupported on carbon black powder, but is added when kneading, prepare have with
The comparative catalyst C7 of the same composition of embodiment 1.
Comparative example 2
With example 1, simply rare earth metal is unsupported on carbon black powder, but is added when kneading, and preparing has and reality
Apply the catalyst C8 of the same composition of example 1.
Comparative example 3
With example 1, simply active metal and rare earth metal are unsupported on carbon black powder, but are added when kneading, make
The standby catalyst C9 with composition same as Example 1.
Embodiment 7
The present embodiment investigates the heat endurance for the catalyst that embodiment 1,2 is prepared with comparative example 2, and concrete operations are as follows：
Embodiment 1,2 and the gained catalyst of comparative example 2 are placed in Muffle furnace, are calcined 12 hours in 1000 DEG C, it is naturally cold
But to room temperature, the pore structure of above-mentioned catalyst and high-temperature roasting procatalyst is measured respectively and than surface, as a result as shown in table 1.
The catalyst heat endurance of table 1 is investigated.
The heat endurance for introducing rare earth element rear catalyst as can be seen from Table 1 significantly improves, in 1000 DEG C of roastings
Still there is higher specific surface area and pore volume after 12 hours.
Carry out activity rating to catalyst prepared by examples detailed above and comparative example, more above-mentioned each catalyst activity and stably
Property.Raw material oil nature and evaluation process conditions be shown in Table 2 and table 3, the Activity evaluation for operating 200h is shown in Table 4, with operating when
Between increase, catalyst activity reduction, in order to keep catalyst activity to meet production requirement, it is necessary to beds
Temperature raising, operating rear catalyst bed temperature rise in 5000 hours are shown in Table 5.
Table 2.
Table 3.
Table 4.
| Project | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| It is de-（Nickel+vanadium）Rate, % | 80 | 78 | 84 | 88 | 73 | 74 | 53 | 70 | 41 |
Table 5.
Catalyst provided by the invention compared with reference catalyst there is higher hydrogenation to take off it can be seen from the data of table 4
Metal active.Find out after reacting 5000 hours, have using Hydrodemetalation catalyst provided by the invention from the result of table 5
Higher activity stability.
Claims (14)
1. the preparation method of a kind of Hydrodemetalation catalyst containing rare earth, it is characterised in that including following content：（1）It is living with part
Property component maceration extract and the solution containing thulium impregnate carbon black powder respectively, then drying for standby；（2）By step（1）Institute
Carbon black powder after the dipping obtained, into plastic, squeezes with boehmite dry glue powder, chemical enlargement agent, extrusion aid and peptizing agent kneading
Bar, drying, roasting, it is made and contains active component and rare earth modified alumina support；（3）Then loaded on modified aluminium oxide supports
Residual activity component, through drying, roasting, Hydrodemetalation catalyst is made.
2. in accordance with the method for claim 1, it is characterised in that：Described activity component impregnation liquid is vib metals
Compound and/or group VIII metal compound solution, selected from the acid solution containing active component, the aqueous solution or ammonia solution；Wherein
One or more of the group vib metallic compound in ammonium molybdate, ammonium tungstate, ammonium metatungstate or ethyl ammonium tungstate, group VIII
The one kind or several of metallic compound in nickel nitrate, cobalt nitrate, nickel chloride, cobalt chloride, nickel acetate, cobalt acetate or metatungstic acid nickel
Kind；The concentration of vib metals compound is 0.1-100g/100mL in maceration extract, the concentration of group VIII metallic compound
For 0.01-10g/100mL.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described amount of activated component maceration extract dipping
The weight of active component, the 0.01wt%-1wt% of final catalyst weight is calculated as with oxide.
4. according to the method described in claim 1 or 2, it is characterised in that：Step（1）Described amount of activated component maceration extract leaching
The weight of stain active component, in terms of oxide, vib metals weight content is the 0.1wt%- of final catalyst weight
0.8wt%, group VIII weight metal content are the 0.01wt%-0.05wt% of final catalyst weight.
5. in accordance with the method for claim 1, it is characterised in that：Step（1）Described thulium be selected from lanthanum, cerium,
Praseodymium, ytterbium or samarium are one or more of, and the solution containing thulium is the water and/or ethanol solution of rare earth element soluble-salt,
The dosage of solution be carbon black powder saturated water adsorptive value, rare earth element content in terms of oxide, account for catalyst weight 0.01% ~
0.05%。
6. in accordance with the method for claim 1, it is characterised in that：Step（1）Described drying condition be nature dry in the shade or in
50-120 DEG C of dry 1-10 hour.
7. in accordance with the method for claim 1, it is characterised in that：Step（2）The addition of carbon black powder after middle dipping is plan
The 5%-10% of boehmite dry glue powder weight.
8. in accordance with the method for claim 1, it is characterised in that：Step（2）Mass concentration is added in described kneading process
For 1%-5% Aqueous Solutions of Polyethylene Glycol, the wherein mean molecule quantity 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.
9. in accordance with the method for claim 1, it is characterised in that：Step（2）Described chemical enlargement agent is phosphoric acid, phosphate
Or the one or more in boric acid, wherein one or more of the phosphate in ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate,
Chemical enlargement agent addition is the 3%-5% of boehmite dry glue powder weight.
10. in accordance with the method for claim 1, it is characterised in that：Step（2）Described extrusion aid be sesbania powder, starch or
One or more in methylcellulose, extrusion aid addition are the 3%-5% of boehmite dry glue powder weight.
11. in accordance with the method for claim 1, it is characterised in that：Step（2）Described peptizing agent is formic acid, acetic acid, lemon
One or more in acid or nitric acid, addition are the 3%-10% of boehmite dry glue powder weight.
12. in accordance with the method for claim 1, it is characterised in that：Step（2）The drying condition is at 100-130 DEG C
Dry 1-10 hours；Roasting process is to be calcined 2-4 hours at 500-650 DEG C.
13. in accordance with the method for claim 1, it is characterised in that：Step（3）The load of described residual activity component uses
Infusion process, selected from the one kind crossed in volume impregnation, incipient impregnation or spray impregnation method, dip time is 1-5 hours.
14. in accordance with the method for claim 1, it is characterised in that：Step（3）Described drying condition is at 80-120 DEG C
Dry 6-10 hours；The roasting condition is that 3-6 hours are calcined at 400-600 DEG C.
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| CN107774278B (en) * | 2016-08-31 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of preparation method of flue gas reduction and desulfurization catalyst |
| CN110090636B (en) * | 2018-01-30 | 2021-11-12 | 中国石油化工股份有限公司 | Cerium-containing aluminum hydroxide dry glue powder and preparation method thereof, and alumina carrier and application thereof |
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