CN108067210B - A kind of zirconium-containing alumina dry glue powder and its preparation method and application - Google Patents
A kind of zirconium-containing alumina dry glue powder and its preparation method and application Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The present invention discloses a kind of zirconium-containing alumina dry glue powder and its preparation method and application, include the following steps: the mixed serum of (1) preparation of nano zirconium oxide and propylene glycol phenylate, the mass content of nano zircite is 5%-30% in mixed serum, the mass content of propylene glycol phenylate is 0.1%-10%, and the partial size of the nano zircite is 10 ~ 100nm；(2) aluminium salt and precipitating reagent are prepared, and it carries out coprecipitation reaction and obtains the solution containing aluminum hydroxide sol, the mixed solution that step (1) preparation is added after aging 10-30min continues aging, and the additional amount of the mixed solution of step (1) preparation is 1%-10% with the mass content of nano zircite in final catalyst；(3) material after aging obtains zirconium-containing alumina after filtration, washing and drying.This method is conducive to zirconium and is enriched in alumina carrier surface and high degree of dispersion, the physico-chemical property for improving aluminum oxide dry glue powder.
Description
Technical field
The present invention relates to a kind of zirconium-containing alumina dry glue powders and its preparation method and application, relate in particular to a kind of be applicable in
In the zirconium-containing alumina dry glue powder and preparation method thereof of carrier of hydrogenating catalyst.
Background technique
As crude oil heaviness in poor quality is increasingly sharpened the increasingly strict requirement with environmental regulation, oil product lighting is wanted
Ask continuous improvement.In order to reach the requirement of environmental regulation, adding hydrogen is the main method for reducing sulfide in fuel oil, nitride
One of.In hydrogenation process, catalyst is played an important role.Currently, most of used catalyst is to be with aluminium oxide
Carrier, using the VIIIth race and/or group VIB metal as active component.Single alumina surface properties are not able to satisfy making for catalyst
With requiring, for example, the interaction force in oxidation aluminium surface between active metal and carrier is stronger, inactive point easy to form
Spar species make metal active constituent be not easy to vulcanize, and activity reduces.The active force between active component and carrier is reduced, is become
Prepare the key technology of high-activity hydrogenation catalyst.
In order to prepare the hydrotreating catalyst of high activity, high stability, many researchers are to alumina catalyst support
Modification is learned, to reach required physico-chemical property.Magnesium, titanium, boron, fluorine, silicon, zinc, zirconium, vanadium, phosphorus auxiliary agent are such as added, mainly
It is the interaction changed between aluminium oxide and active component and the acidity for aoxidizing aluminium surface, improves alumina stable etc..
EP0339640 discloses a kind of alumina preparation method of the coprecipitation preparation containing titanium, can obtain dispersibility
Good titanium-contained aluminum oxide, but coprecipitation body phase retention problems, the main function of titanium dioxide can not fully play.
And Coprecipitation can not meet simultaneously the coprecipitated of many kinds of substance, affect the physical and chemical performance of carrier.
CN 00123133.2 discloses a kind of preparation method containing Zirconia carrier, mainly in carrier forming process
The carrier containing zirconium oxide is made in middle addition zirconia compound.
CN 99112940.7 discloses a kind of preparation method of hydrocarbon hydrogenizing treamtent catalyst, and carrier is mainly with containing
After the mixed solution of titanium chloride and phosphoric acid and alumina dry glue kneading, extruded moulding is obtained after drying, roasting containing titanium, phosphorus
Alumina support.
CN 200410050777.5 discloses a kind of preparation method of macropore alumina supporter.By the auxiliary agent containing boric acid
Solution is added in aluminium oxide precursor and mixed material containing expanding agent, is obtained most after kneading, molding, drying, roasting
Whole carrier can also contain the auxiliary agents such as silicon, phosphorus, magnesium, zinc, titanium in compounding agent solution.The mode that the above method is all made of kneading is drawn
Enter auxiliary agent titanium, titanium is unevenly distributed in alumina carrier surface, affects the physical and chemical performance of carrier.
CN 200610013758.4 discloses a kind of preparation method of load-type zirconium oxide carrier.The carrier is
Zirconium oxide, aluminium oxide, silica, oxidation state, magnesia, active carbon or molecular sieve are configured to containing zirconium oxide or zirconium nitrate
Solution to carrier carry out incipient impregnation or it is excessive impregnate, carried by the catalyst that drying, roasting obtain loaded zirconia
Body.It is not had a greater change on the catalyst activity of this method preparation.
CN 1289636A discloses a kind of side precipitated titanium salt in aluminum hydroxide slurry and prepare the aluminium hydroxide of titaniferous
Method is easy to cause to corrode to equipment, and the meeting in roasting process due to containing chloride ion and sulfate ion in titanium salt solution
The gas for generating pollution environment, limits industrial application.
CN103100397A discloses a kind of preparation method of hydrotreating catalyst.Alumina dry glue in the preparation method
After powder is carried out wetting mixing or mediated with surfactant first, peptization acid is added, through kneading, molding, dry and roasting, system
Obtain alumina support.The catalyst carrier of this method preparation keeps original cellular structure, improves the reactivity worth of catalyst.
CN103785446A discloses a kind of preparation method of hydrocracking catalyst, the catalyst preparation of this method preparation
Step is cumbersome, and the activity of catalyst does not obtain full raising yet.
CN105176142A discloses a kind of Modified by Aluminum Hydroxide method, and it is low that aminopropyl trimethoxysilane is added in this method
Polymers dries modified aluminum hydroxide slurry to obtain aluminium hydroxide micro powder to Modified by Aluminum Hydroxide.Modified hydroxide
There is no variations very outstanding in aluminium micro mist performance.
CN 102309994A discloses a kind of preparation method of alumina support, and this method is prepared using pH swing method, In
The organic stabilizers such as polyvinyl alcohol, polyethylene glycol -100 are added in ageing process and carry out the excellent boehmite of processability.But
It is that stabilizer is added in ageing process, effect reduces the aggregation extent of aluminium oxide particles mainly to improve crystallinity, and
And many difficulties are brought to subsequent processing, stabilizer containing organic matter in the sewage of generation can cause environmental pollution.
Summary of the invention
Aiming at the shortcomings in the prior art, the present invention provides a kind of zirconium-containing alumina dry glue powder and preparation method thereof and answer
With.This method is conducive to zirconium and is enriched in alumina carrier surface and high degree of dispersion, the physico-chemical property for improving aluminum oxide dry glue powder.
The preparation method of zirconium-containing alumina dry glue powder of the present invention, includes the following steps:
(1) mixed serum of preparation of nano zirconium oxide and propylene glycol phenylate, the quality of nano zircite contains in mixed serum
Amount is 5%- 30%, and preferably 10%-20%, the mass content of propylene glycol phenylate is 0.1%-10%, preferably 0.3%-5%, the nano oxygen
The partial size for changing zirconium is 10 ~ 100nm, preferably 10 ~ 60nm；
(2) aluminium salt and precipitating reagent are prepared, and carries out coprecipitation reaction and obtains the solution containing aluminum hydroxide sol, aging
The mixed solution that step (1) preparation is added after 10-30min continues aging, the additional amount of the mixed solution of step (1) preparation
Mass content with nano zircite in final catalyst is 1%-10%, preferably 2%-6% meter；
(3) material after aging obtains zirconium-containing alumina after filtration, washing and drying.
In the method for the present invention, aluminium salt includes but is not limited to one or more of aluminum sulfate, aluminium chloride, aluminum nitrate, precipitating
Agent includes but is not limited to one or more of sodium hydroxide, ammonium hydroxide, potassium aluminate, sodium aluminate.
In the method for the present invention, coprecipitation reaction is co-precipitation, and the temperature of coprecipitation reaction is 58 DEG C -62 DEG C, and pH is
7.5-8.5, preferably 8.0-8.2, coprecipitation reaction time are 10-100min, and preferably 35-65min is obtained containing aluminium hydroxide
Aluminium hydroxide mass concentration is calculated as 1 ~ 30g/100mL with aluminium oxide in the solution of colloidal sol, relatively fits as 5 ~ 10 g/100mL.
In the method for the present invention, aging temperature is 58 DEG C -62 DEG C before mixed serum is added, and aging pH is 8.0-8.5, is added
Continue aging 15min-50min after mixed serum, aging temperature is compared to improving 2 DEG C -6 DEG C before mixed solution is added, always
Change pH and improves 0.2-1.0.
In the method for the present invention, drying temperature be 80 DEG C -150 DEG C, preferably 100 DEG C -130 DEG C, drying time 1-10h,
It is preferred that 4-8h.
A kind of zirconium-containing alumina dry glue powder prepared using the above method, the zirconium-containing alumina dry glue powder zirconium oxide are contained
Amount is 1% ~ 20%, preferably 2% ~ 8%, and specific surface area is 350 ~ 520m2/ g, preferably 380 ~ 450m20.6 ~ 1.5mL/g of/g, Kong Rongwei,
It is preferred that 0.8 ~ 1.2mL/g, average pore diameter is 7nm ~ 12nm, and preferably 8 ~ 10nm, zirconium dispersion degree is 0.3 ~ 0.5, preferably
0.35~0.4。
Above-mentioned zirconium-containing alumina dry glue powder is as catalyst carrier, especially as answering for carrier of hydrogenating catalyst
With.The hydrotreating catalyst using the VIIIth race and group VIB metal as active metal component, group VIII metal be Co and/or
Ni, group VIB metal is W and/or Mo, and on the basis of the weight of catalyst, content of the group VIII metal in terms of oxide is 1
The wt % of wt % ~ 15, preferably the wt % of 4wt % ~ 10, content of the group VIB metal in terms of oxide are the 10 wt % of wt % ~ 30,
It is preferred that the wt of 15wt % ~ 25 %.The hydrotreating catalyst is using conventional catalysts technology of preparing systems such as kneading method or infusion processes
.
The above-mentioned application using zirconium-containing alumina dry glue powder as the hydrotreating catalyst of carrier in hydroprocessing processes, tool
Precursor reactant condition is as follows: pressure 4-12MPa, preferably 8-10 MPa, 350-380 DEG C of temperature, preferably 365-375 DEG C, hydrogen-oil ratio
For 400:1-1200:1, preferably 600:1-1000:1.
The mixing that nano zircite and propylene glycol phenylate is added in the aluminum hydroxide sol ageing step in the method for the present invention is water-soluble
Liquid inhibits aggregation of the nano zircite on aluminum hydroxide sol, improves phase interaction of the zirconium dioxide with aluminum hydroxide sol
Firmly, stable Al-O-Zr key, zirconium oxide and aluminium oxide are formd in zirconium-containing alumina in uniform distribution, are improved containing zirconium
The materializations such as synergistic effect and zirconium-containing alumina dry glue powder specific surface area, Kong Rong, aperture of zirconium oxide and aluminium oxide in aluminium oxide
Matter can prepare the hydrotreating catalyst of excellent using the zirconium-containing alumina dry glue powder, improve the reaction of catalyst
Activity.
Specific embodiment
The function and effect of the present invention is further illustrated below with reference to embodiment, but following embodiment is not constituted to the present invention
The limitation of method.
Nano zircite of the present invention and the specific preparation process of the mixed serum of propylene glycol phenylate are as follows: by suitable propylene glycol
Phenylate is added in the zirconium oxide slurries of high-speed stirred, mixing time 5-30min, optimal selection 10-25 min.
The specific preparation process of aluminum hydroxide sol of the present invention is as follows: suitable deionized water is added at adhesive dispenser,
It goes to neutralize with the alkaline precipitating agents such as sodium hydroxide or ammonium hydroxide or composite alkali aluminum saline solution such as potassium aluminate or sodium aluminate
Acid aluminium salt solution such as aluminum sulfate, aluminium chloride, aluminum nitrate etc. forms aluminum hydroxide slurry.According to alkali such as sodium aluminate or potassium aluminates
Metal aluminum salt solution can also prepare aluminum hydroxide slurry using the sour precipitating reagent such as hydrochloric acid, nitric acid, carbon dioxide.
The measurement of dispersion degree uses XPS in the method for the present invention, and detailed process is as follows: 1. carry out the sample sample presentation after roasting
XPS(X X-ray photoelectron spectroscopy X) analysis；2. the data after pair analysis carry out arrangement calculating；3. dispersion degree (surface atom mole
Concentration proportion)=Zr At.%/Al At.%.It is produced using ThermoFisher company, the U.S., model is Multilab 2000.In
Catalyst fines are compressed in glove box filled with argon gas, are fixed on the indium foil of sample carrier, sample carrier is then transferred to energy
In the preparation chamber of spectrometer, it is then transferred to after pumping process in analysis cabin.Al K0 is photoelectric flat source, in conjunction with energy Eb=1486.6
eV
Embodiment 1
(1) mixed serum of preparation of nano zirconium oxide and propylene glycol phenylate, the quality of nano zircite contains in mixed serum
Amount is 10%, and the mass content of propylene glycol phenylate is 0.8%, and the partial size of the nano zircite is 8nm；
(2) aluminum sulfate solution that the sodium aluminate solution and concentration that compound concentration is 30g/L are 40g/L, under agitation
Cocurrent is added in neutralization reaction device simultaneously, and control pH value is 8.2, and temperature is 58 DEG C, and neutralizing the time is that 55min is contained
The solution of aluminum hydroxide sol, aluminium hydroxide mass concentration is calculated as 5 g/ with aluminium oxide in the solution containing aluminum hydroxide sol
The mixed solution that step (1) preparation is added after 100mL, aging 10min continues aging, the mixed solution of step (1) preparation
Additional amount with the mass content of nano zircite in final catalyst be 2%；Aging temperature is 58 before mixed serum is added in control
DEG C, aging pH is 8.2, continues aging 20min after mixed serum is added, aging temperature is compared to addition mixed solution premise
2.5 DEG C high, aging pH improves 0.5；
(3) material after aging is filtered, washed, is dried to obtain zirconium-containing alumina A, and physico-chemical property is shown in Table 1, drying temperature
It is 110 DEG C, drying time 6h.
Embodiment 2
(1) mixed serum of preparation of nano zirconium oxide and propylene glycol phenylate, the quality of nano zircite contains in mixed serum
Amount is 15%, and the mass content of propylene glycol phenylate is 1%, and the nano oxidized high partial size is 60nm；
(2) aluminum sulfate solution that the sodium aluminate solution and concentration that compound concentration is 30g/L are 40g/L, under agitation
Cocurrent is added in neutralization reaction device simultaneously, and control pH value is 8.0, and temperature is 60 DEG C, and neutralizing the time is that 35min is contained
There is the solution of aluminum hydroxide sol, aluminium hydroxide mass concentration is calculated as 10 with aluminium oxide in the solution containing aluminum hydroxide sol
The mixed solution that step (1) preparation is added after g/100mL, aging 30min continues aging, and the mixing of step (1) preparation is molten
The additional amount of liquid is with the mass content of nano zircite in final catalyst for 3%；Aging temperature is before mixed serum is added in control
60 DEG C, aging pH is 8.0, continues aging 30min after mixed serum is added, aging temperature is compared to addition mixed solution premise
3.5 DEG C high, aging pH improves 0.5 unit；
(3) material after aging be filtered, washed, dried, roast after obtain zirconium-containing alumina B, physico-chemical property is shown in Table 1,
Drying temperature is 120 DEG C, drying time 6h.
Embodiment 3
(1) mixed serum of preparation of nano zirconium oxide and propylene glycol phenylate, the quality of nano zircite contains in mixed serum
Amount is 20%, and the mass content of propylene glycol phenylate is 2%, and the partial size of the nano zirconium dioxide is 60nm；
(2) aluminum sulfate solution that the sodium aluminate solution and concentration that compound concentration is 30g/L are 40g/L, under agitation
Cocurrent is added in neutralization reaction device simultaneously, and control pH value is 8.0, and temperature is 60 DEG C, and neutralizing the time is that 55min is contained
The solution of aluminum hydroxide sol, aluminium hydroxide mass concentration is calculated as 10 g/ with aluminium oxide in the solution containing aluminum hydroxide sol
The mixed solution that step (1) preparation is added after 100mL, aging 30min continues aging, the mixed solution of step (1) preparation
Additional amount with the mass content of nano zircite in final catalyst be 4%；Aging temperature is before mixed serum is added in control
62 DEG C, aging pH is 8.5, continues 25 min of aging after mixed serum is added, before aging temperature is compared to mixed solution is added
4 DEG C are improved, aging pH improves 0.3 unit；
(3) material after aging be filtered, washed, dried, roast after obtain zirconium-containing alumina C, physico-chemical property is shown in Table 1,
Drying temperature is 120 DEG C, drying time 8h.
Embodiment 4
(1) mixed serum of preparation of nano zirconium oxide and propylene glycol phenylate, the quality of nano zircite contains in mixed serum
Amount is 25%, and the mass content of propylene glycol phenylate is 3%, and the partial size of the nano zircite is 60nm；
(2) aluminum sulfate solution that the sodium aluminate solution and concentration that compound concentration is 30g/L are 40g/L, under agitation
Cocurrent is added in neutralization reaction device simultaneously, and control pH value is 8.2, and temperature is 60 DEG C, and neutralizing the time is that 55min is contained
The solution of aluminum hydroxide sol, aluminium hydroxide mass concentration is calculated as 10 g/ with aluminium oxide in the solution containing aluminum hydroxide sol
The mixed solution that step (1) preparation is added after 100mL, aging 30min continues aging, the mixed solution of step (1) preparation
Additional amount with the mass content of nano zircite in final catalyst be 5%；Aging temperature is before mixed serum is added in control
60 DEG C, aging pH is 8.2, continues 40 min of aging after mixed serum is added, before aging temperature is compared to mixed solution is added
5 DEG C are improved, aging pH improves 0.2 unit；
(3) material after aging be filtered, washed, dried, roast after obtain salic D, physico-chemical property is shown in Table 1, do
Dry temperature is 110, drying time 6h.
Embodiment 5
(1) mixed serum of preparation of nano zirconium oxide and propylene glycol phenylate, the quality of nano zircite contains in mixed serum
Amount is 30%, and the mass content of propylene glycol phenylate is 3.0%, and the partial size of the nano zircite is 60nm；
(2) aluminum sulfate solution that the sodium aluminate solution and concentration that compound concentration is 30g/L are 40g/L, under agitation
Cocurrent is added in neutralization reaction device simultaneously, and control pH value is 8.0, and temperature is 62 DEG C, and neutralizing the time is that 55min is contained
There is the solution of aluminum hydroxide sol, aluminium hydroxide mass concentration is calculated as 10 with aluminium oxide in the solution containing aluminum hydroxide sol
The mixed solution that step (1) preparation is added after g/100mL, aging 30min continues aging, and the mixing of step (1) preparation is molten
The additional amount of liquid is with the mass content of nano zircite in final catalyst for 6%；Aging temperature before mixed serum is added in control
It is 60 DEG C, aging pH is 8.0, continues 30 min of aging after mixed serum is added, aging temperature is compared to addition mixed solution
Preceding to improve 2 DEG C, aging pH improves 0.6 unit.
(3) material after aging be filtered, washed, dried, roast after obtain zirconium-containing alumina E, physico-chemical property is shown in Table 1,
Drying temperature is 130 DEG C, drying time 8h.
Comparative example 1
With embodiment 1, the difference is that obtaining zirconium-containing alumina F without propylene glycol phenylate in slurries, physico-chemical property is shown in Table
1。
Comparative example 2
With embodiment 1, the difference is that nano zircite is added in coprecipitation process, zirconium-containing alumina G, object are obtained
Change property and is shown in Table 1.
Table 1
200 grams of dry glue powder of Examples and Comparative Examples are weighed, 100 grams of SB powder of addition, sesbania powder and each 4 grams of citric acid mix
Acid solution is added after even, the concentration of nitric acid is 2wt% in acid solution, remaining is distilled water.It rolls 15 ~ 25 minutes, uses diameter
Extrusion is carried out for the clover orifice plate of 1.7mm, 12 hours dry through 120 DEG C, 550 DEG C roast 3 hours, obtain catalyst carrier.
Using the maceration extract impregnated carrier containing Mo, Ni, catalyst C-1 to C7 is obtained, the mass content of molybdenum oxide is in catalyst
24%, the mass content of nickel oxide is 4%.Activity rating is carried out to above-mentioned catalyst, feedstock oil is catalytic diesel oil, nitrogen content
For 1500 ng/ul, sulfur content 1.7%, evaluation condition: reaction pressure 8.0MPa, 378 DEG C of reaction temperature, air speed 2.0h-1 , hydrogen
Oil ratio 600:1, evaluation result are shown in Table 2.
2 catalyst activity evaluation result of table
| Catalyst number | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | C-7 |
| Opposite denitrification activity, % | 150 | 152 | 147 | 145 | 135 | 125 | 128 |
| It is relatively desulphurizing activated, % | 136 | 148 | 128 | 128 | 121 | 110 | 115 |
By table 2 it is found that being apparently higher than the catalyst of comparative example preparation using catalyst activity prepared by the method for the present invention.
Claims (16)
1. a kind of preparation method of zirconium-containing alumina dry glue powder, characterized by the following steps:
(1) mixed serum of preparation of nano zirconium oxide and propylene glycol phenylate, the mass content of nano zircite is in mixed serum
5%-30%, the mass content of propylene glycol phenylate are 0.1%-10%, and the partial size of the nano zircite is 10 ~ 100nm；
(2) aluminium salt and precipitating reagent are prepared, and carries out coprecipitation reaction and obtains the solution containing aluminum hydroxide sol, aging 10-
The mixed solution that step (1) preparation is added after 30min continues aging, the additional amount of the mixed solution of step (1) preparation with
The mass content of nano zircite is 1%-10% in final catalyst；
(3) material after aging obtains zirconium-containing alumina after filtration, washing and drying.
2. according to the method described in claim 1, it is characterized by: the quality of nano zircite contains in step (1) mixed serum
Amount is 10%-20%, and the mass content of propylene glycol phenylate is 0.3%-5%, and the partial size of the nano zircite is 10 ~ 60nm.
3. according to the method described in claim 1, it is characterized by: the addition for the mixed solution that in step (2) prepared by step (1)
Amount by the mass content of nano zircite in final catalyst for 2%-6% in terms of.
4. according to the method described in claim 1, it is characterized by: aluminium salt is in aluminum sulfate, aluminium chloride, nitric acid in step (2)
One or more of aluminium, precipitating reagent are one or more of sodium hydroxide, ammonium hydroxide, potassium aluminate, sodium aluminate.
5. according to the method described in claim 1, it is characterized by: in step (2) coprecipitation reaction be co-precipitation, it is coprecipitated
The temperature reacted of forming sediment is 58 DEG C -62 DEG C, pH 7.5-8.5, and the coprecipitation reaction time is 10-100min, is obtained containing hydroxide
Aluminium hydroxide mass concentration is calculated as 1-30g/100mL with aluminium oxide in the solution of Aluminum sol.
6. according to the method described in claim 5, it is characterized by: in step (2) coprecipitation reaction pH be 8.0-8.2, it is coprecipitated
The shallow lake reaction time is 35-65min, obtains aluminium hydroxide mass concentration in the solution containing aluminum hydroxide sol and is calculated as with aluminium oxide
5-10g/100mL。
7. according to the method described in claim 1, it is characterized by: it is 58 that aging temperature before mixed serum is added in step (2)
DEG C -62 DEG C, aging pH is 8.0-8.5, is added after mixed serum and continues aging 15min-50min, aging temperature compared to plus
2 DEG C -6 DEG C are improved before entering mixed solution, aging pH improves 0.2-1.0.
8. according to the method described in claim 1, it is characterized by: drying temperature is 80 DEG C -150 DEG C in step (3), when dry
Between be 1-10h.
9. dry according to the method described in claim 8, it is characterized by: drying temperature is 100 DEG C -130 DEG C in step (3)
Time is 4-8h.
10. a kind of zirconium-containing alumina dry glue powder prepared using claim 1 to 9 either method, it is characterised in that: described to contain zirconium
The content of aluminum oxide dry glue powder zirconium oxide is 1% ~ 20%, and specific surface area is 350 ~ 520m20.6 ~ 1.5mL/g of/g, Kong Rongwei, it is average
Bore dia is 7nm ~ 12nm, and zirconium dispersion degree is 0.3 ~ 0.5.
11. zirconium-containing alumina dry glue powder according to claim 10, it is characterised in that: the zirconium-containing alumina dry glue powder oxygen
The content for changing zirconium is 2% ~ 8%, and specific surface area is 380 ~ 450m20.8 ~ 1.2mL/g of/g, Kong Rongwei, average pore diameter are 8 ~ 10nm,
Zirconium dispersion degree is 0.35 ~ 0.4.
12. application of the zirconium-containing alumina dry glue powder of claim 10 or 11 as catalyst carrier.
13. application of the zirconium-containing alumina dry glue powder of claim 10 or 11 as carrier of hydrogenating catalyst.
14. application according to claim 13, it is characterised in that: hydrotreating catalyst is with the VIIIth race and group VIB gold
Belonging to is active metal component, and group VIII metal is Co and/or Ni, and group VIB metal is W and/or Mo, is with the weight of catalyst
Benchmark, content of the group VIII metal in terms of oxide are 1wt% ~ 15wt%, and content of the group VIB metal in terms of oxide is
10wt%~30wt%。
15. zirconium-containing alumina dry glue powder described in claim 10 or 11 is that the hydrotreating catalyst of carrier preparation is adding at hydrogen
Application during reason, it is characterised in that: specific reaction condition is as follows: pressure 4-12MPa, 350-380 DEG C of temperature, hydrogen-oil ratio
For 400:1-1200:1.
16. application according to claim 15, it is characterised in that: specific reaction condition is as follows: pressure 8-10Mpa, temperature
365-375 DEG C, hydrogen-oil ratio 600:1-1000:1.
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| CN114160058B (en) * | 2021-11-10 | 2023-06-20 | 航天特种材料及工艺技术研究所 | Method for preparing nano aluminum sol by one-step controllable hydrolysis of inorganic aluminum salt |
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