CN109772469A - A kind of silicon modified zirconia catalyst carrier and its preparation method and application - Google Patents
A kind of silicon modified zirconia catalyst carrier and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to catalyst field, a kind of silicon modified zirconia catalyst carrier and its preparation method and application is disclosed.This method includes the Contact operation for contacting modified silicon oil and nano zirconium dioxide dispersion liquid with alumina support, and the modified silicon oil is selected from one of alkyl modified silicon oil, polyether modified silicon oil, epoxy modified polysiloxane, amino-modified silicone oil, polyester modification silicone oil and hydroxyl modification silicone oil or a variety of.By means of the present invention, the Surface acidity and acid strength property for improving carrier, become the carrier that can prepare high-activity hydrogenation catalyst.
Description
Technical field
The present invention relates to catalyst fields, and in particular, to a kind of silicon modified zirconia catalyst carrier and preparation method thereof and
Using.
Background technique
Content containing nitrogen, sulphur, oxygen and metal impurities in crude oil is continuously increased, and crude oil degree of heaviness is constantly deepened,
True pendulum is had become in face of people, the presence of these impurity not only makes catalyst poisoning in subsequent processes, but also meeting
The pernicious gases such as a large amount of sulfur and nitrogen oxides are given off, the health and the protection of environment of the mankind are injured.Use work
Property catalyst high, that stability is good process conditions can not only be made to mitigate, moreover it is possible to reduce hydrogen consumption, have the function that energy-saving.
The purpose of weighted BMO spaces is the impurity such as nitrogen, sulphur, oxygen in removing feedstock oil, the quality and quantity of intermediate oil
All it increased.It requires to pre-process feedstock oil with hydroforming reaction for example, being hydrocracked, prevent miscellaneous in crude oil
Matter makes catalyst poisoning, catalyst once be poisoned, caused by loss it is inestimable.So hydroprocessing processes are oil refining process
In indispensable and particularly significant one of step.It is known in the art, without the active group of calcined catalyst
Divide dispersibility high, there is only weaker model ylid bloom action power between active metal and carrier, therefore it is anti-to effectively improve catalyst
Answer activity.The development of the catalyst of high activity, high stability is always the bottleneck of this field institute Gonna breakthrough, industrial using high living
Property, high stability catalyst not only can voluminous target product, but also reaction can also be made to carry out under relatively mild conditions, transported
Turn cycle stretch-out, reduces production cost.
There are direct correlation relationship, the removing of raw material well cuts needs for catalyst surface acidity and the activity of catalyst
Catalyst has the function of hydrogenolysis, this kind reaction occurs on the acid site of catalyst, therefore, weakens the strong of active component and carrier
Interaction force has catalyst suitable acid, becomes the key for preparing high-activity hydrogenation catalyst.And the master of catalyst
Property and carrier is wanted to have very close relationship.
CN200410050777.5 discloses a kind of preparation method of macropore alumina supporter.Auxiliary agent containing boric acid is molten
Liquid is added in aluminium oxide precursor and mixed material containing expanding agent, is obtained after kneading, molding, drying, roasting final
Carrier, the auxiliary agents such as silicon, phosphorus, magnesium, zinc, titanium can also be contained in compounding agent solution.But the above method is drawn by the way of kneading
Enter auxiliary agent titanium, titanium is unevenly distributed in alumina carrier surface, affects the physical and chemical performance of carrier.
CN201410029452.2 discloses one kind, and the invention discloses one kind plus fluorine richness boehmite catalyst to carry
Body material and preparation method.Fluorine-containing auxiliary agent is added during plastic, fluoro-containing alumina dry glue powder is obtained after high-temperature roasting.It adopts
The dry glue powder prepared with this method is used to prepare catalyst, though activity is improved, the fluorine generated in operation process is lost, and generates
Hydrogen fluoride, which has device, significantly to be corroded, and is unfavorable for producing.
CN99113284.X 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.
Summary of the invention
The object of the present invention is to provide a kind of silicon modified zirconia catalyst carriers and its preparation method and application, through the invention
Method, improve the Surface acidity and acid strength property of carrier, high-activity hydrogenation catalyst can be prepared by becoming
Carrier.
To achieve the goals above, the present invention provides a kind of preparation method of silicon modified zirconia catalyst carrier, this method
Including the Contact operation for contacting modified silicon oil and nano zirconium dioxide dispersion liquid with alumina support, the modified silicon oil
For one in alkyl modified silicon oil, polyether modified silicon oil, epoxy modified polysiloxane, amino-modified silicone oil and hydroxyl modification silicone oil
Kind is a variety of.
The present invention also provides the silicon modified zirconia catalyst carriers of above-mentioned method preparation.
The present invention also provides above-mentioned silicon modified zirconia catalyst carriers to prepare the application in hydrotreating catalyst.
The present inventor is by further investigation discovery, by dispersing suitable modified silicon oil and nano zirconium dioxide
Liquid is impregnated on alumina support, since modified silicon oil had not only had hydrophilic radical but also has hydrophobic grouping, is impregnated into aluminium oxide
The corresponding position in surface can improve the acid amount and acid strength of oxidation aluminium surface, make aluminium oxide by the coordinative role of Si and Zr
The weak acid on surface and middle strong acid acid measure improvement, improve active component in the dispersion degree of carrier surface, being capable of forming has more
The reaction center of high activity.Furthermore it is possible to which on catalyst plus hydrogen center and acid centre is made to obtain good matching, raising is urged
The service performance of agent.
Through the above technical solutions, the preparation method of silicon modified zirconia catalyst carrier provided by the invention is easy to operate, urges
The activity and long period stability of agent are high.Modified aluminium oxide supports prepared by the present invention increase with middle strong acid content, strong acid
Content is reduced.The increase of the middle strong acid content of catalyst is conducive to macromolecular substances side chain break and transfer in reaction process,
Catalyst hydrogenolysis performance is greatly improved.And strong acid content be less able to reduce colloid catalyst surface coking degree,
Improve the run stability of catalyst.The hydrotreating catalyst prepared using silicon modified zirconia catalyst carrier of the invention,
Desulfurization and denitrification activity are greatly improved.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation method of silicon modified zirconia catalyst carrier, this method includes by modified silicon oil and receiving
The Contact operation that rice zirconium dioxide dispersion liquid is contacted with alumina support, the modified silicon oil are selected from alkyl-modified silicon
One of oil, polyether modified silicon oil, epoxy modified polysiloxane, amino-modified silicone oil, polyester modification silicone oil and hydroxyl modification silicone oil
Or it is a variety of.
According to the present invention, for the alumina support, there is no particular limitation, can be oxygen commonly used in the art
Change alumina supporter.It can be prepared by conventional method in that art as the alumina support, it is preferable that made by the following method
It is standby to obtain.
It is 310-360m by specific surface area2The macropore aluminum hydroxide solid elastomer powder of/g, Kong Rongwei 0.9-1.2mL/g, specific surface
Product is 240-280m2The aperture aluminum hydroxide solid elastomer powder and sesbania powder of/g, Kong Rongwei 0.5-0.6mL/g carry out dry blending process (example
Can such as be carried out in roller) 3-60 minutes, preferably 5-15 minutes, macropore aluminum hydroxide solid elastomer powder and aperture aluminium hydroxide
The weight ratio of dry glue powder is 1:0.1-10, and sesbania powder dosage is the 0.5-5%, preferably 1%-3% of carrier inventory.Then uniformly
Be added citric acid and nitric acid aqueous solution (it is above-mentioned it is dry-mixed after material and the weight ratio of the aqueous solution be 1:1.2-1.5, this is water-soluble
Contain citric acid 1.5-2.5 weight %, nitric acid 4-6 weight % in liquid, the concentration of nitric acid is 65-68 weight %), material is rolled
After (such as can be carried out in roller) and forming, it is dried and above-mentioned alumina support is made in roasting.Wherein, when rolling
Between can be 5-40 minute, preferably 10-30 minutes, temperature be 5-40 DEG C, preferably 10-30 DEG C；Forming can use ability
The forming method of domain routine carries out, such as can carry out extrusion；The condition of the drying may include: that drying temperature is 15-180
DEG C, drying time is 0.2-30 hours, it is preferable that drying temperature is 40-180 DEG C, and drying time is 3-8 hours；The roasting
Condition may include: maturing temperature be 180-600 DEG C, calcining time be 0.2-30 hours, it is preferable that maturing temperature 400-
600 DEG C, calcining time is 3-8 hours.
According to the present invention, the Contact operation can be carried out using any one mode in following manner A-C.
Mode A: being configured to mixed solution for modified silicon oil and nano zirconium dioxide dispersion liquid, by alumina support with mix
Solution contact；
Mode B: it after alumina support is contacted with modified silicon oil solution, then contacts with nano zirconium dioxide dispersion liquid；
Mode C: it after alumina support is contacted with nano zirconium dioxide dispersion liquid, then contacts with modified silicon oil solution.
According to the present invention, as long as above-mentioned contact can guarantee solution being uniformly distributed in alumina support, such as can
Dipping, sprinkling etc. are thought, wherein it is preferred that carrying out by the way of dipping.The mode of the dipping can be incipient impregnation or full
And dipping, preferably incipient impregnation.There is no particular limitation for the condition of the contact, and time of contact can be 1 hour or more,
Preferably 5-40 hours, more preferably 5-30 hours, Contact Temperature can be 5-40 DEG C, preferably 15-30 DEG C.Specifically, on
It states in mode A, the time of contact is more preferably 5-15 hours；In aforesaid way B, alumina support is molten with modified silicon oil
The time of contact of liquid is preferably 2-15 hours, and the time of contact with nano zirconium dioxide dispersion liquid is preferably 2-15 hours；It is above-mentioned
In mode C, the time of contact of alumina support and nano zirconium dioxide dispersion liquid is preferably 2-15 hours, with modified silicon oil solution
Time of contact be preferably 2-15 hours.
According to the present invention, in order to enable Si, Zr to be preferably distributed in oxidation aluminium surface, in aforesaid way B, aluminium oxide
Carrier disperses after contacting with modified silicon oil solution by drying (such as room temperature can be used and dry mode), then with nano zirconium dioxide
Liquid contact；In aforesaid way C, after contacting with nano zirconium dioxide dispersion liquid by drying (such as room is can be used in alumina support
Temperature dries mode), then contacted with modified silicon oil solution.
According to the present invention, in order to simplify operation, enable to be evenly distributed from Si, Zr in oxidation aluminium surface, reach best association
Same-action；It is described to connect in preferred situation simultaneously in order to keep the more suitable and sour distribution of acid strength of modified support more reasonable
Process is touched to carry out using aforesaid way A.
In the present invention, the modified silicon oil be selected from alkyl modified silicon oil, polyether modified silicon oil, epoxy modified polysiloxane,
One of amino-modified silicone oil, hydroxyl modification silicone oil are a variety of.
The alkyl modified silicon oil well known in the art as above-mentioned " alkyl modified silicon oil ", can be commercially available,
Such as the alkyl-silicone oil of Qingdao De Ming Chemical Co., Ltd. production, model DM-A601 can be available commercially from.
The polyether modified silicon oil well known in the art as above-mentioned " polyether modified silicon oil ", can be commercially available,
Such as Laiyang Sheng Bang organosilicon Science and Technology Ltd. polyether modified silicon oil, trade mark SI-X221 can be available commercially from.
The epoxy modified polysiloxane well known in the art as above-mentioned " epoxy modified polysiloxane ", can be commercially available,
Such as Laiyang Sheng Bang organosilicon Science and Technology Ltd. epoxy modified polysiloxane, trade mark SI-203 can be available commercially from.
The amino-modified silicone oil well known in the art as above-mentioned " amino-modified silicone oil ", can be commercially available,
Such as the amido silicon oil of Qingdao De Ming Chemical Co., Ltd. production, trade mark DM-8040 can be available commercially from.
The hydroxyl modification silicone oil well known in the art as above-mentioned " hydroxyl modification silicone oil ", can be commercially available,
Such as it can be available commercially from the hydroxy silicon oil of Jiangsu Quan Li Chemical Co., Ltd. production, the trade mark is VST-203V etc..
In the present invention, consider that the modified silicon oil is preferably selected from polyethers from the service performance for significantly optimizing carrier
One of modified silicon oil, amino-modified silicone oil, hydroxyl modification silicone oil and epoxy modified polysiloxane are a variety of.
In the present invention, there is no particular limitation for the nano zirconium dioxide dispersion liquid, can be conventional using this field
It is prepared by method.Preferably, the nano zirconium dioxide dispersion liquid is by carrying out ammonium citrate and zirconium oxychloride aqueous solution
It contacts and obtains.
Here, the dosage molar ratio of the ammonium citrate and zirconium oxychloride can be 1:0.1-10, preferably 1:0.5-8.
The content of zirconium oxychloride in the zirconium oxychloride aqueous solution can be 0.1-10 weight %, preferably 1-5 weight %.
For ammonium citrate and zirconium oxychloride aqueous solution are carried out the way of contact, there is no particular limitation, as long as can obtain
Nano zirconium dioxide dispersion liquid, such as suitable ammonium citrate can be added to the zirconium oxychloride aqueous solution of high-speed stirred
In, mixing time can be 5-30min, preferably 10-25min.
In the present invention, the content of the nano zirconium dioxide in the nano zirconium dioxide dispersion liquid can be 1-10 weight
Measure %, preferably 3-7 weight %.In addition, the content of the ammonium citrate in the nano zirconium dioxide dispersion liquid can be 0.5-
1.5 weight %, preferably 0.8-1.2 weight %.
In the present invention, relative to 100 parts by weight of alumina support, the dosage of the modified silicon oil is 0.5-12 weight
Measure part, preferably 2-10 parts by weight, more preferably 4-8 parts by weight.
In the present invention, the nano zirconium dioxide point relative to 100 parts by weight of alumina support, in terms of zirconium dioxide
The dosage of dispersion liquid is 0.01-12 parts by weight, preferably 0.05-6 parts by weight, more preferably 1.5-4.5 parts by weight.
By making the dosage of modified silicon oil and nano zirconium dioxide dispersion liquid within the above range, it can further promote Si
With the coordinative role of Zr, improve the surface nature of alumina support, to obtain acid amount and the more suitable aluminium oxide of acid strength
Carrier.
According to the present invention, this method further includes by the oxygen after contacting with organically-modified silicone oil and nano zirconium dioxide dispersion liquid
Change the process that alumina supporter is dried and roasts.There is no particular limitation for the drying and roasting, can be conventional using this field
The condition used carries out.Specifically, it is 15-170 DEG C that the condition of the drying, which may include: drying temperature, and drying time is
0.2-30 hours, it is preferable that drying temperature is 40-170 DEG C, and drying time is 3-8 hours；The condition of the roasting can wrap
Include: maturing temperature is 180-600 DEG C, and calcining time is 0.2-30 hour, it is preferable that maturing temperature is 400-600 DEG C, when roasting
Between be 3-8 hours.To atmosphere, there is no particular limitation in dry and roasting process, can in the atmosphere of this field routine into
Row, such as can carry out in air.
Alumina support of the invention can contain inorganic assistant component, wherein inorganic assistant component can for selected from phosphorus,
One of boron, zirconium, titanium and fluorine are a variety of.For the dosage of inorganic assistant component, there is no particular limitation, can be this field
Conventional amount used, for example, the dosage of inorganic assistant component can be 0.5-5.5 relative to 100 parts by weight of alumina support
Parts by weight, preferably 1.5-3.5 parts by weight.
The present invention also provides the silicon modified zirconia catalyst carriers of above method preparation.It is prepared by the method for the present invention
Silicon modified zirconia catalyst carrier is more suitable and carries as carrier of hydrogenating catalyst, especially heavy oil hydrodesulfurization catalyst
Body, hydrodenitrogenation catalyst carrier.
The present invention also provides above-mentioned silicon modified zirconia catalyst carriers to prepare the application in hydrotreating catalyst.
Embodiment
The present invention will be described in detail by way of examples below.
In following embodiment, using Micromeritics Instrument Corp. U.S.A's ASAP2405 physical adsorption appearance measurement sample specific surface area,
Kong Rong and aperture, liquid N2Make adsorbate, adsorption temp is -196 DEG C, and the specific surface area of sample is calculated using BET method.
NH3- TPD measurement carries out on Micromeritics Instrument Corp. U.S.A's autocatalyst characterization system AutoChem2920, urges
At 400 DEG C with helium purge 1h, rear helium atmosphere is cooled to room temperature agent, absorption ammonia to being saturated, purging to baseline it is steady after,
140 DEG C of progress temperature programmed desorptions are warming up to, heating rate is 10 DEG C of min-1, 150-250 DEG C of acidity, 250-400 DEG C of acidity
400-500 DEG C of acidity passes through NH3- TPD method measures.
In following embodiment, macropore aluminum hydroxide solid elastomer powder is the city that the Yantai Heng Hui Chemical Co., Ltd. trade mark is YH-28
Sell product；Aperture aluminum hydroxide solid elastomer powder is the commercially available product that the Shandong Yun Neng company trade mark is DYD-102；Sesbania powder is Shandong Province Kenli
The commercially available product of sesbania gum factory, county production；Hydroxyl modification silicone oil is that the trade mark of Jiangsu Quan Li Chemical Co., Ltd. production is VST-203V
Commercially available product；Polyether modified silicon oil is the commercially available product that the trade mark of Laiyang Sheng Bang organosilicon Science and Technology Ltd. production is SI-X221；
Amino-modified silicone oil is that the trade mark of Qingdao De Ming Chemical Co., Ltd. production is the commercially available product of DM-8040 company.
In following embodiment, unless otherwise specified, the atmosphere of low temperature drying and high-temperature roasting is air atmosphere.
In following embodiment, nano zirconium dioxide dispersion liquid the preparation method is as follows: suitable ammonium citrate is added to
In the zirconium oxychloride aqueous solution of high-speed stirred, 30min is stirred.
Preparation example 1
This preparation example is used to illustrate the preparation method of alumina support.
Macropore aluminum hydroxide solid elastomer powder 150g, aperture aluminum hydroxide solid elastomer powder 50g are taken, sesbania powder 6g is added, is uniformly mixed
Afterwards, it pours into roller, dry-mixed 5 minutes.Then the aqueous solution 170g for being uniformly added into citric acid and nitric acid (wherein contains citric acid
6g, concentration are the nitric acid 9.23g of 3.2 weight %).Material is rolled 20 minutes, with the clover orifice plate extrusion of diameter 1.7mm.
120 DEG C after drying 4 hours 550 DEG C roast 5 hours.Alumina support after roasting is denoted as Z0.The materialization of alumina support Z0
Matter is as shown in table 1.
Embodiment 1
Preparation of nano zirconium dioxide dispersion liquid, the content of nano zirconium dioxide is 3 weight % in dispersion liquid, ammonium citrate
Content is 0.8 weight %, and volume 30mL obtains solution A, wherein the amount in terms of nano zirconium dioxide is 2.4g；
Amino-modified silicone oil 4.0g is weighed, appropriate amount of deionized water dissolution is added, volume 30mL obtains solution B；Not
In the case where disconnected stirring, solution B is poured slowly into solution A, appropriate amount of deionized water is added, final volume 85mL is configured to
Solution C.
100g alumina support Z0 is weighed, alumina support is uniformly impregnated in solution C, dipping is after 8 hours, through 120
DEG C dry 3 hours, 450 DEG C roasted 3 hours, obtain silicon modified zirconia catalyst carrier Z1.The physico-chemical property of carrier Z1 such as 1 institute of table
Show.
Embodiment 2
Hydroxyl modification silicone oil 8.0g is weighed, (nanometer two in dispersion liquid are added in the nano zirconium dioxide dispersion liquid of preparation
The content of zirconium oxide is 4 weight %, and the content of ammonium citrate is 1.2 weight %, and the amount in terms of nano zirconium dioxide is 3.6g),
Final volume is 85mL, obtains solution D.
100g alumina support Z0 is weighed, alumina support is uniformly impregnated in solution D, dipping is after 10 hours, through 150
DEG C dry 6 hours, 400 DEG C roasted 3 hours, obtain silicon modified zirconia catalyst carrier Z2.The physico-chemical property of carrier Z2 such as 1 institute of table
Show.
Embodiment 3
Polyether modified silicon oil 7.0g is weighed, (nanometer two in dispersion liquid are added in the nano zirconium dioxide dispersion liquid of preparation
The content of zirconium oxide is 4 weight %, and the content of ammonium citrate is 1.2 weight %, and the amount of nano zirconium dioxide meter is 3.6g), most
Final volume is 85mL, obtains solution E.
100g alumina support Z0 is weighed, alumina support is uniformly impregnated in solution E, dipping is after 10 hours, through 130
DEG C dry 2 hours, 450 DEG C roasted 4 hours, obtain silicon modified zirconia catalyst carrier Z3.The physico-chemical property of carrier Z3 such as 1 institute of table
Show.
Embodiment 4
Amino-modified silicone oil 7.0g is weighed, (nanometer two in dispersion liquid are added in the nano zirconium dioxide dispersion liquid of preparation
The content of zirconium oxide is 4 weight %, and the content of ammonium citrate is 1.2 weight %, and the amount of nano zirconium dioxide meter is 3.6g), most
Final volume is 85mL, obtains solution F.
100g alumina support Z0 is weighed, alumina support is uniformly impregnated in solution F, dipping is after 10 hours, through 150
DEG C dry 2 hours, 400 DEG C roasted 4 hours, obtain silicon modified zirconia catalyst carrier Z4.The physico-chemical property of carrier Z4 such as 1 institute of table
Show.
Embodiment 5
Solution A and solution B are prepared according to the method for embodiment 1.
100g alumina support Z0 is weighed, alumina support is uniformly impregnated in solution A, dipping is after 10 hours, room temperature
It dries, then alumina support is uniformly impregnated in solution B, dipping is 3 hours dry through 120 DEG C after 10 hours, 450 DEG C of roastings 3
Hour, obtain silicon modified zirconia catalyst carrier Z5.The physico-chemical property of carrier Z5 is as shown in table 1.
Embodiment 6
Solution A and solution B are prepared according to the method for embodiment 1.
100g alumina support Z0 is weighed, alumina support is uniformly impregnated in solution B, dipping is after 10 hours, room temperature
It dries, then alumina support is uniformly impregnated in solution A, dipping is 3 hours dry through 120 DEG C after 10 hours, 450 DEG C of roastings 3
Hour, obtain silicon modified zirconia catalyst carrier Z6.The physico-chemical property of carrier Z6 is as shown in table 1.
Comparative example 1
Macropore aluminum hydroxide solid elastomer powder 180g, aperture aluminum hydroxide solid elastomer powder 80g are weighed, sesbania powder 6g is added, mixing is equal
It after even, pours into roller, dry-mixed 5 minutes.Amino-modified silicone oil 12.0g is weighed, nano zirconium dioxide dispersion liquid 15.0g (receives
Rice zirconium dioxide content is 0.53g), the aqueous solution that citric acid and nitric acid is then added (wherein contains citric acid 6g, concentration is
The nitric acid 9.23g of 3.2 weight %) 170g, then 20min is rolled, with the clover orifice plate extrusion of diameter 1.7mm.120 DEG C of dryings 4
It is roasted 5 hours for 550 DEG C after hour, obtains carrier D1.The physico-chemical property of carrier D1 is as shown in table 1.
Comparative example 2
Macropore aluminum hydroxide solid elastomer powder 180g, aperture aluminum hydroxide solid elastomer powder 80g are weighed, sesbania powder 6g is added, mixing is equal
It after even, pours into roller, dry-mixed 5 minutes.It is added in the aqueous solution of citric acid and nitric acid (dense wherein containing citric acid 6g
Degree is the nitric acid 9.23g of 3.2 weight %), solution quality 170g, then 20min is rolled, it is squeezed with the clover orifice plate of diameter 1.7mm
Item.130 DEG C after drying 4 hours 550 DEG C roast 6 hours, obtain carrier D2.The physico-chemical property of carrier D2 is as shown in table 1.
Table 1
As shown in Table 1, method provided by the invention keeps alumina support flat by the synergistic effect between auxiliary agent Si and zirconium
Equal aperture increases, the weak acid on surface and middle strong acid content increase, and strong acid content significantly reduces, and can reduce colloid in catalyst table
The coking degree in face improves the long-term operation stability of catalyst.Further, according to the comparison of Z1 and Z5, Z6 it is found that logical
It crosses by the way of being impregnated while in aforesaid way A, the specific surface area of silicon modified zirconia catalyst carrier can be further increased
And Kong Rong, and the weak acid on surface and middle strong acid content increase, and strong acid content is reduced, and is more applicable for preparing at high-activity hydrogenation
Manage catalyst.
Preparation example 2
The above-mentioned silicon modified zirconia catalyst carrier Z1 of 50g is weighed, the solution with 47g containing Mo, Ni, P (wherein contains molybdenum oxide
18g, basic nickel carbonate 6.5g, phosphatase 24 .5g) incipient impregnation is carried out, after sample room temperature is dried after dipping, through 120 DEG C dry 3
Hour, 450 DEG C roast 3 hours, and obtaining catalyst C1, (with oxide weight content meter, which becomes MoO323.5 weights
Measure %, NiO 4.2 weight %, P2O53.5 weight %).
Preparation example 3
Catalyst is prepared with the method for above-mentioned preparation example 2, unlike, replace silicon modified zirconia to urge using alumina support Z0
Agent carrier Z1, catalyst C2 is made, and (in terms of oxide weight, which becomes MoO323.5 weight %, NiO 4.2
Weight %, P2O53.5 weight %).
Test case
Under feedstock oil and process conditions same case, active appraisal experiment, relative activity are carried out to catalyst C1 and C2
Using the hydrodesulfurization activity of catalyst C2 and hydrodenitrogenationactivity activity as reference, calculation formula is as follows:
The hydrodesulfurization of the hydrodesulfurization activity ÷ catalyst C2 of relatively desulphurizing activated=catalyst C1 of catalyst C1 is living
Property × 100%；
The hydrodenitrogeneration of opposite denitrification activity=catalyst C1 hydrodenitrogenationactivity activity ÷ catalyst C2 of catalyst C1 is living
Property × 100%；
Also, the opposite desulfurization of catalyst C2 and opposite denitrification activity are denoted as 100.
Wherein, when nitrogen content is 100-10000ppm, nitrogen analysis is according to SH/T 0704-2001 boat sample introduction chemiluminescence
Method carries out, and when nitrogen content is less than 100ppm, nitrogen analysis is carried out according to 0657 oxidizing fire of SH/T and chemoluminescence method.Sulphur contains
When amount is 1-1000ppm, sulphur content determination is carried out according to SH/T0689-2000 ultraviolet fluorescence method, when sulfur content is greater than 1000ppm,
Sulphur content determination is carried out according to GB/T387-90 tube oven method.
What is measured the results are shown in Table 2.
Table 2
| Catalyst | C1 | C2 |
| Feedstock oil sulfur content (%) | 1.70 | 1.70 |
| Feedstock oil nitrogen content (μ gg-1) | 1580 | 1580 |
| It reacts stagnation pressure (MPa) | 8.0 | 8.0 |
| Reaction temperature (DEG C) | 378 | 378 |
| Hydrogen-oil ratio (V/V) | 1000:1 | 1000:1 |
| Volume space velocity (h-1) | 1.0 | 1.0 |
| Opposite denitrification activity (%) | 130 | 100 |
| Relatively desulphurizing activated (%) | 125 | 100 |
As shown in Table 2, the hydrotreating catalyst of the carrier preparation provided using the method for the present invention, desulfurization and denitrogenation are living
Property be greatly improved, especially denitrification activity raising become apparent.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of silicon modified zirconia catalyst carrier, which is characterized in that this method includes by modified silicon oil and nanometer
The Contact operation that zirconium dioxide dispersion liquid is contacted with alumina support, the modified silicon oil be selected from alkyl modified silicon oil,
One of polyether modified silicon oil, epoxy modified polysiloxane, amino-modified silicone oil, polyester modification silicone oil and hydroxyl modification silicone oil are more
Kind.
2. according to the method described in claim 1, wherein, the Contact operation can be using any one in following manner A-C
Kind mode carries out,
Mode A: modified silicon oil and nano zirconium dioxide dispersion liquid are configured to mixed solution, by alumina support and mixed solution
Contact；
Mode B: it after alumina support is contacted with modified silicon oil solution, then contacts with nano zirconium dioxide dispersion liquid；
Mode C: it after alumina support is contacted with nano zirconium dioxide dispersion liquid, then contacts with modified silicon oil solution.
3. method according to claim 1 or 2, wherein the nano zirconium dioxide dispersion liquid by by ammonium citrate with
Zirconium oxychloride aqueous solution, which is contacted, to be obtained；
Preferably, the dosage molar ratio of the ammonium citrate and zirconium oxychloride is 1:0.1-10, in the zirconium oxychloride aqueous solution
Zirconium oxychloride content be 0.1-10 weight %；
Preferably, the content of the nano zirconium dioxide in the nano zirconium dioxide dispersion liquid is 1-10 weight %.
4. method according to claim 1 or 2, wherein relative to 100 parts by weight of alumina support, the modification
The dosage of silicone oil is 0.5-12 parts by weight, preferably 2-10 weight, more preferably 4-8 weight %.
5. method according to claim 1 or 2, wherein relative to 100 parts by weight of alumina support, with titanium dioxide
The dosage of the nano zirconium dioxide dispersion liquid of zirconium meter is 0.01-12 parts by weight, preferably 0.05-6 parts by weight, more preferably 1.5-
4.5 parts by weight.
6. method according to claim 1 or 2, wherein the modified silicon oil is polyether modified silicon oil.
7. method according to claim 1 or 2, wherein this method further include by with organically-modified silicone oil and nano-silica
The process that alumina support after changing the contact of zirconium dispersion liquid is dried and roasts.
8. the condition of the drying includes: that temperature is 15-170 DEG C according to the method described in claim 7, wherein, the time is
0.2-30 hours, it is preferable that temperature is 40-170 DEG C, and the time is 3-8 hours；
The condition of the roasting includes: that maturing temperature is 180-600 DEG C, and calcining time is 0.2-30 hours, it is preferable that roasting temperature
Degree is 400-600 DEG C, and calcining time is 3-8 hours.
9. the silicon modified zirconia catalyst carrier of the preparation of method described in any one of -8 according to claim 1.
10. silicon modified zirconia catalyst carrier as claimed in claim 9 is preparing the application in hydrotreating catalyst.
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| CN112657522A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
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|---|---|---|---|---|
| CN105709849A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of modified aluminium oxide-based carrier |
| CN105709788A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN106669863A (en) * | 2015-11-10 | 2017-05-17 | 中国石油化工股份有限公司 | Modification method of hydro-upgrading catalyst carrier |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105709849A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of modified aluminium oxide-based carrier |
| CN105709788A (en) * | 2014-12-02 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN106669863A (en) * | 2015-11-10 | 2017-05-17 | 中国石油化工股份有限公司 | Modification method of hydro-upgrading catalyst carrier |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112657522A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN112657522B (en) * | 2019-10-15 | 2023-11-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
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