CN105582951B - A kind of preparation method of alkaline including earth metal Hydrodemetalation catalyst - Google Patents
A kind of preparation method of alkaline including earth metal Hydrodemetalation catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of alkaline including earth metal Hydrodemetalation catalyst, including following content：（1）Carbon black powder is impregnated with amount of activated component maceration extract, is then dried, then carbon black powder is impregnated with the solution of alkaline including earth metal element, then drying for standby；（2）By step（1）Carbon black powder after the dipping of gained and boehmite dry glue powder, chemical enlargement agent, extrusion aid and peptizing agent kneading are into plastic, extrusion, drying, it first roasts, then roasts in air atmosphere in a nitrogen atmosphere, be made containing active component and alkali-earth metal modified alumina support；（3）Then residual activity component is loaded on modified aluminium oxide supports, through drying, roasting, alkaline including earth metal 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 thermal stability of macropore significantly improves, and is had broad application prospects in weight, residuum hydrogenating and metal-eliminating reaction.
Description
Technical field
The present invention relates to a kind of preparation methods of alkaline including earth metal 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 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 has macropore appearance and the characteristic of large aperture.Large aperture is conducive to macromolecular chemical combination
For object to catalyst granules diffusion inside, 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 add in physics expanding agent and chemical enlargement agent, then load to active component on carrier in a manner of spraying and impregnate, 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 employed 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 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
Active component loads to specific surface area as 100-350m2/ 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 with carbon black are mixed, 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, the utilization rate for leading to macropore is relatively low, in addition, the thermal stability of carrier needs to be further improved.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of preparation side of alkaline including earth metal Hydrodemetalation catalyst
Method.Catalyst activity metal prepared by this method content at macropore is relatively high, and content is relatively low at aperture, and macropore
Thermal stability significantly improves, which has high activity and long-term operation stability.
The preparation method of the alkaline including earth metal Hydrodemetalation catalyst of the present invention, including following content：
（1）Carbon black powder is impregnated with amount of activated component maceration extract, is then dried, then is soaked with the solution of alkaline including earth metal element
Stain carbon black powder, then drying for 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 is first roasted, is then roasted in air atmosphere into plastic, extrusion, drying in a nitrogen atmosphere, is made containing work
Property component and alkali-earth metal modified alumina support；
（3）Then residual activity component is loaded on modified aluminium oxide supports, through drying, roasting, alkaline including earth metal is made
Hydrodemetalation catalyst.
In the method for the present invention, the activity component impregnation liquid is vib metals compound and/or group VIII metal
Compound solution, can be the acid solution containing active component, aqueous solution or ammonia solution, preferably ammonia solution, more than 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 one or more of ethyl ammonium tungstate, group VIII metallic compound be selected from nickel nitrate, cobalt nitrate, nickel chloride, cobalt chloride,
One or more of nickel acetate, cobalt acetate or metatungstic acid nickel；A concentration of 0.1- of vib metals compound in maceration extract
100g/100ml, a concentration of 0.01-10g/100ml of group VIII metallic compound；
In the method for the present invention, step（1）The weight of active component is impregnated, final catalyst weight is calculated as with oxide
The 0.1wt%-0.8wt% of 0.01wt%-1wt%, preferably vib metals weight content for final catalyst weight, group VIII
Weight metal content is the 0.01wt%-0.05wt% of final catalyst weight.
In the method for the present invention, step（1）The dosage of the active metal maceration extract is carbon black powder saturated water adsorptive value
10%-50%, dipping process are as follows：Carbon black powder is placed in and is sprayed in rolling pot, the uniformly spray leaching into carbon black powder under the conditions of rolling
Stain activity maceration extract, the carbon black powder that maceration extract continues after spraying into rolling pot spray distilled water, make carbon black powder adsorption saturation.
In the method for the present invention, step（1）The alkali earth metal is a kind of or several in beryllium, magnesium, calcium, strontium or barium
Kind, the solution of alkaline including earth metal element is generally the water and/or ethanol solution of alkali earth metal soluble-salt, soluble-salt one
As for nitrate or chloride, as beryllium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, beryllium chloride, magnesium chloride, calcium chloride,
Strontium chloride, barium chloride etc., the 10%-20% of the dosage of solution for the saturated water adsorptive value of carbon black powder, the alkaline earth after dipping in carbon powder
The content of metallic element accounts for the 0.05%-0.1% of catalyst weight in terms of oxide.
In the method for the present invention, step（1）The drying condition dries in the shade or 1-10 hours dry in 50-120 DEG C for nature.
In the method for the present invention, step（2）The addition of carbon black powder after middle dipping is boehmite dry glue powder weight
5%-10%。
In the method for the present invention, step（2）Mass concentration is preferably added in the kneading process as 1%-5% polyethylene glycol water
The average molecular weight 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 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；Nitrogen atmosphere
Lower roasting process is to be roasted 2-4 hours at 500-650 DEG C, and roasting process is small in 400-500 DEG C of roasting 2-4 under air atmosphere
When.
In the method for the present invention, step（3）The load of the surplus active component uses infusion process, and volume may be used
Dipping, incipient impregnation or spray impregnating mode, dip time are 1-5 hours, and the specific concentration of maceration extract can be according to most
Depending on tenor on whole catalyst.
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 roasts 3-6 hours at 400-600 DEG C.
The method of the present invention has the following advantages that compared with prior art：
When carbon black powder step impregnation active metallic element and alkali earth metal, active metal is carried in carbon black powder particles
Portion, alkali earth metal are carried on carbon black powder extra-granular.Molybdenum, nickel isoreactivity metal front in roasting process in a nitrogen atmosphere
Body decomposes, and forms corresponding molybdenum-nickel-oxygen activity metal oxide, active component is avoided to occur with alumina support strong mutual
Effect forms nickel aluminate（NiAl2O4）Structure improves the catalytic activity of active metal component.It roasts in air atmosphere
The oxidized removing of carbon powder in the process forms macropore, and the active metal component and alkali earth metal loaded in carbon powder is born
It is downloaded on corresponding macropore, makes the active component content in final catalyst at macropore and the increase of alkali earth metal content.Alkali
Earth metal element is covered in oxidation aluminium surface, protects part of hydroxyl and prevents aluminum ions migration, substantially increases macropore
Thermal stability, prevent caving in for macropore, catalyst holds the ability enhancing of metal and volume carbon.Active metal at macropore simultaneously
Content is higher, and activity increases, and improves the utilization rate of macropore.The addition of polyethylene glycol makes carbon black powder and boehmite during kneading
It is uniformly mixed, improves the uniformity coefficient of macropore.
Catalyst prepared by the method for the present invention has broad application prospects in weight, residuum hydrogenating and metal-eliminating reaction.
Specific embodiment
The effect further illustrated the present invention with reference to embodiment and effect, but it is not limited to following embodiment.
Embodiment 1
Industrial ammonium heptamolybdate 55g is taken to be placed in ammonium hydroxide, is stirred, until no insoluble matter, adds 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.
Weigh carbon black powder（Water absorption 1ml/g）7.2 grams be placed in spray rolling pot in, under rotary state, with atomizing type to
Carbon black powder in rolling pot is sprayed containing 0.3 gram of molybdenum oxide, and the active metal maceration extract 3ml of 0.03 gram of nickel oxide then proceedes to spray
Distilled water makes carbon black powder adsorption saturation, and the carbon black powder after dipping is 3 hours dry in 110 DEG C.Dried carbon black powder is put again
It is rolled in pot in spray, under rotary state, the nitric acid containing 0.08 gram of calcium oxide is sprayed with carbon black powder of the atomizing type into rolling pot
Calcium aqueous solution 1ml, carbon black powder after dipping in 110 DEG C dry 3 hours it 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% to add in mass concentration, and average molecular weight is 4,000 43 grams of Aqueous Solutions of Polyethylene Glycol
Kneading, then adds in that continue kneading dissolved with the aqueous solution of 5 grams of nitric acid in right amount uniform, is extruded on screw rod banded extruder a diameter of
The cloverleaf pattern item of 1.8mm is dried 3 hours in 120 DEG C, and dried molding is small in 600 DEG C of roastings 4 in a nitrogen atmosphere
When, then roasted 4 hours at a temperature of 450 DEG C in air atmosphere.
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 10.2wt%, and NiO mass percentages are
1.22wt%, calcium oxide mass percentage are 0.07wt%.
Embodiment 2
With embodiment 1, only the dosage of carbon black powder is 12 grams, with 4ml containing 0.1 gram of molybdenum oxide, oxidation when impregnating carbon black powder
The active metal maceration extract of 0.01 gram of nickel, with barium nitrate solution of the 1.5ml containing 0.13 gram of barium monoxide.The addition of polyglycol solution
It measures and restrains to obtain catalyst C2 of the present invention, catalyst MoO for 433Mass percentage is 10wt%, and NiO mass percentages are
1.2wt%, barium monoxide mass percentage are 0.1wt%.
Embodiment 3
With embodiment 1, only the dosage of carbon black powder is 9 grams, with 4.5ml containing 0.5 gram of molybdenum oxide, oxidation when impregnating carbon black powder
The active metal maceration extract of 0.02 gram of nickel, with beryllium nitrate solution of the 1ml containing 0.06 gram of beryllium oxide.The addition of polyglycol solution
Restrain to obtain catalyst C3 of the present invention, catalyst MoO for 1003Mass percentage is 10.5wt%, and NiO mass percentages are
1.22wt%, beryllium oxide mass percentage are 0.05wt%.
Embodiment 4
With embodiment 1, only the dosage of carbon black powder is 14.3 grams, with 3ml containing 0.7 gram of molybdenum oxide, oxygen when impregnating carbon black powder
Change the active metal maceration extract of 0.05 gram of nickel, with magnesium nitrate solutions of the 2ml containing 0.09 gram of magnesia.The addition of polyglycol solution
It measures and restrains to obtain catalyst C4 of the present invention, catalyst MoO for 1003Mass percentage is 10.5wt%, NiO mass percentages
For 1.22wt%, magnesia mass percentage is 0.08wt%.
Embodiment 5
With embodiment 1, only the dosage of carbon black powder is 13 grams, with 4ml containing 0.8 gram of molybdenum oxide, oxidation when impregnating carbon black powder
The active metal maceration extract of 0.04 gram of nickel, with strontium nitrate solutions of the 1.5ml containing 0.1 gram of strontium oxide strontia.The addition of polyglycol solution
It is 86 grams to measure, and contains MoO with 150 milliliters during dipping38 grams/100 milliliters, NiO0.9 grams/100 milliliters of molybdenum-nickel-ammonia active metal
Catalyst C5 of the present invention, catalyst MoO is made in salt solution impregnated carrier3Mass percentage is 8.7wt%, NiO mass percentages
Content is 0.93wt%, and strontium oxide strontia mass percentage is 0.09wt%.
Embodiment 6
With embodiment 1, polyglycol solution is not added in when only boehmite is mixed with carbon black powder the present invention is made and urged
Agent C6, catalyst MoO3Mass percentage is 10.2wt%, and NiO mass percentages are 1.21wt%, calcium oxide quality
Percentage composition is 0.07wt%.
Comparative example 1
With example 1, only active metal is unsupported on carbon black powder, but is added in when kneading, prepare have with
The comparative catalyst C7 of 1 same composition of embodiment.
Comparative example 2
With example 1, only alkaline-earth metal is unsupported on carbon black powder, but is added in when kneading, and preparing has and reality
Apply the catalyst C8 of 1 same composition of example.
Comparative example 3
With example 1, only active metal and alkaline-earth metal are unsupported on carbon black powder, but are added in when kneading, make
The standby catalyst C9 with composition same as Example 1.
Embodiment 7
The present embodiment investigates the thermal stability for the catalyst that embodiment 1,2 is prepared with comparative example 2, and concrete operations are as follows：It will
Embodiment 1,2 and 2 gained catalyst of comparative example are placed in Muffle furnace, are roasted 12 hours in 1000 DEG C, cooled to room temperature, point
The pore structure and specific surface of above-mentioned catalyst and high-temperature roasting procatalyst are not measured, and the results are shown in Table 1.
1 catalyst thermal stability of table.
The thermal stability for introducing alkali earth metal rear catalyst as can be seen from Table 1 significantly improves, at 1000 DEG C
Roasting still has higher specific surface area and Kong Rong after 12 hours.
Activity rating is carried out to catalyst C1 ~ C9 prepared by above-described embodiment and comparative example, more above-mentioned each catalyst is lived
Property and stability.Raw material oil nature and evaluation process conditions are shown in Table 2 and table 3, and the Activity evaluation for operating 200h is shown in Table 4, with
The increase of the duration of runs, the activity of catalyst reduces, in order to which the activity of catalyst is kept to be needed to meet production requirement to urging
Agent bed temperature raising, 5000 hours rear catalyst bed Wen Sheng of operating are shown in Table 5.
2 raw material oil nature of table.
Table 3 evaluates process conditions.
4 Activity evaluation of table.
Table 5 operates 5000 hours rear catalyst bed Wen Sheng.
Catalyst provided by the invention adds hydrogen to take off compared with reference catalyst with higher it can be seen from 4 data of table
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 (16)
1. a kind of preparation method of alkaline including earth metal Hydrodemetalation catalyst, it is characterised in that including following content：（1）With portion
Divide activity component impregnation liquid dipping carbon black powder, then dry, then carbon black powder, Ran Hougan are impregnated with the solution of alkaline including earth metal element
It is dry spare；（2）By step（1）Carbon black powder after the dipping of gained and boehmite dry glue powder, chemical enlargement agent, extrusion aid and
Peptizing agent kneading is first roasted, is then roasted in air atmosphere into plastic, extrusion, drying in a nitrogen atmosphere, is made containing work
Property component and alkali-earth metal modified alumina support；（3）Then residual activity component is loaded on modified aluminium oxide supports, through dry
Dry, roasting, is made alkaline including earth metal Hydrodemetalation catalyst.
2. according to the method for claim 1, it is characterised in that：The activity component impregnation liquid is vib metals
Close object and/or group VIII metal compound solution；Wherein vib metals compound is selected from ammonium molybdate, ammonium tungstate, metatungstic acid
One or more of ammonium or ethyl ammonium tungstate, group VIII metallic compound are selected from nickel nitrate, cobalt nitrate, nickel chloride, chlorination
One or more of cobalt, nickel acetate, cobalt acetate or metatungstic acid nickel；Vib metals compound is a concentration of in maceration extract
0.1-100g/100mL, a concentration of 0.01-10g/100mL of group VIII metallic compound.
3. according to the method for claim 1, it is characterised in that：Step（1）The weight of active component is impregnated, in terms of oxide
0.01wt%-1wt% for final catalyst weight.
4. according to the method described in claim 1 or 3, it is characterised in that：Step（1）It impregnates in active component, vib metals
Weight content is the 0.1wt%-0.8wt% of final catalyst weight, and group VIII weight metal content is final catalyst weight
0.01wt%-0.05wt%.
5. according to the method for claim 1, it is characterised in that：Step（1）The dosage of the active metal maceration extract is
The 10%-50% of carbon black powder saturated water adsorptive value, dipping process are as follows：Carbon black powder is placed in spray rolling pot in, under the conditions of rolling to
Uniformly the active maceration extract of spray dipping, the carbon black powder that maceration extract continues after spraying into rolling pot spray distillation in carbon black powder
Water makes carbon black powder adsorption saturation.
6. according to the method for claim 1, it is characterised in that：Step（1）The alkali earth metal be selected from beryllium, magnesium,
One or more of in calcium, strontium or barium, the content of the alkali earth metal after dipping in carbon black powder accounts for catalyst weight in terms of oxide
The 0.05%-0.1% of amount.
7. according to the method for claim 1, it is characterised in that：Step（1）The drying condition for nature dry in the shade or in
50-120 DEG C 1-10 hours dry.
8. according to the method for claim 1, it is characterised in that：Step（2）The addition of carbon black powder after middle dipping is intends
The 5%-10% of boehmite dry glue powder weight.
9. 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
Enter amount for 30-70 grams/100 grams boehmite dry glue powders.
10. according to the method for claim 1, it is characterised in that：Step（2）The chemical enlargement agent is phosphoric acid, phosphoric acid
One or more of salt or boric acid, chemical enlargement agent addition are the 3%-5% of boehmite dry glue powder weight.
11. according to the method for claim 1, it is characterised in that：Step（2）The extrusion aid be sesbania powder, starch or
One or more of methylcellulose, extrusion aid addition are the 3%-5% of boehmite dry glue powder weight.
12. 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.
13. according to the method for claim 1, it is characterised in that：Step（2）The drying condition is at 100-130 DEG C
It is 1-10 hours dry.
14. according to the method for claim 1, it is characterised in that：Step（2）Under the nitrogen atmosphere roasting process be
500-650 DEG C roasts 2-4 hours, and roasting process is to be roasted 2-4 hours at 400-500 DEG C under air atmosphere.
15. according to the method for claim 1, it is characterised in that：Step（3）The load of the residual activity component uses
Infusion process, dip time are 1-5 hours.
16. 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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| 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 |
| CN111097458B (en) * | 2018-10-25 | 2022-06-07 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method thereof |
| CN112717963B (en) * | 2019-10-28 | 2022-03-04 | 中国石油化工股份有限公司 | Hydrogenation pretreatment catalyst, and preparation method and application thereof |
| CN113042108B (en) * | 2019-12-26 | 2022-06-07 | 中国石油化工股份有限公司 | Catalyst carrier for residual oil hydrotreatment and preparation method of catalyst |
| CN113046124B (en) * | 2019-12-26 | 2022-07-12 | 中国石油化工股份有限公司 | Residual oil hydrodemetalization method |
| CN115518644B (en) * | 2021-06-25 | 2024-01-09 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
| CN116060057A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Residual oil hydrodemetallization catalyst and preparation method thereof |
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