CN101367052B - Aluminum-zirconium composite oxides carrier and supported hydrodesulphurization catalyst - Google Patents
Aluminum-zirconium composite oxides carrier and supported hydrodesulphurization catalyst Download PDFInfo
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Abstract
The invention relates to an Al2O3-ZrO2 multiple oxide and a supported hydrodesulfurization catalyst obtained by taking the multiple oxide as a carrier. The specific surface of the multiple oxide is between 200 and 270 m<2>/g, the pore volume of the multiple oxide is between 0.2 and 0.5 cm<3>/g, and the pore diameter of the multiple oxide is between 4 and 9 nanometers. The multiple oxide carrier can be obtained through assembling and synthesizing aluminum source and zirconium source by the hydrothermal precipitation method, coating method and the like; and the multiple oxide has large specificsurface, appropriate pore canal structure, optimal acid property and redox property, and can be taken as an ideal carrier of diesel hydrodesulfurization catalyst. The invention also provides a deep hydrodesulfurization catalyst obtained by taking the multiple oxide as the carrier, and the catalyst shows better hydrodesulfurization activity than the common catalyst when used in hydrodesulfurization treatment of petroleum products.
Description
Technical field
The present invention relates to a kind of new A l
2O
3-ZrO
2Composite oxides and preparation method thereof and be the supported hydrodesulphurizatiocatalyst catalyst that carrier obtains with these composite oxides.The invention belongs to catalyst technical field.
Background technology
Along with the aggregate demand of vehicle fuel grows with each passing day, the discharge capacity of pollutant is increasing in the vehicle exhaust, and the atmosphere polluting problem that causes is very serious; Meanwhile, people are also more and more stronger to the consciousness of environmental protection.Therefore, market is to the quality requirement increasingly stringent of oil product, and countries in the world have been revised strict standard of fuel in succession.Aspect indexs such as sulfur content, arene content, density and Cetane number to diesel product in new specification have proposed harsher requirement, and are particularly strict more to the requirement of sulfur content and arene content.For example in the Europe IV standard diesel oil index request sulfur content less than 10 μ g/g, total arene content less than 11v%.Though the sulfur content index reduces significantly than before in China's diesel oil, compare with advanced country that still there is a big difference, have the important use meaning so diesel oil is carried out the research of deep hydrofinishing with the production that realizes " clean diesel ".
Reach diesel deep desulfurization and take off fragrant effect, usually need the cooperation of effective catalyst and suitable hydrogenation technique condition; The prior art situation shows, adopts conventional hydrogenation plant and operating condition, can't satisfy the requirement of diesel deep desulfurization.For realizing the low-sulfur index of clean diesel, except optimizing the industrial operation condition, catalyst and new catalytic material that exploitation has higher hydrogenation performance and stability are the keys that addresses this problem.
For the load hydrogenation catalyst for refining, the reactivity worth of the interaction partners catalyst of the surface nature of carrier material and pore structure and carrier and active metal component has crucial influence.Conventional diesel hydrogenation for removal sulphur catalyst is to have the Al than bigger serface
2O
3Perhaps molecular sieve is that Ni (Co) Mo (W) loaded catalyst of carrier is main, though have desulfurized effect preferably, but still be difficult to satisfy the demand of deep desulfuration, main cause is the surface acidity of this carrier and the shortcoming in the acid strength distribution.Therefore, at present the design research and development of novel carriers material of bigger serface, large pore volume and surface acid property optimization and the research of load technology that improves the metal active constituent decentralization, improves the number in activated centre mainly are devoted in the carrier material exploitation of Hydrobon catalyst.Thereby how to make full use of metal active constituent surface can change and the increase of surfaces of carrier materials defect sturcture to optimize the interaction of carrier and metal active constituent, form more metal active position, be the key issue of the catalytic activity of raising catalyst.Be generally the carrier of acquisition than bigger serface and macroporous structure, a lot of researchs all propose to use the template agent to come the synthesis catalytic material, although this method can reach specific area that increases carrier material and the effect of improving pore structure, but, adopt the organic granular template also to increase preparation technology's complexity and catalyst cost.
Summary of the invention
The technical problem underlying that institute of the present invention desire solves provides a kind of aluminum-zirconium composite oxides carrier, passes through ZrO
2And Al
2O
3Compound, become the mesoporous material that has than bigger serface, as the composite oxide carrier of high comprehensive performance, can be used for preparing highly active Hydrobon catalyst.
The present invention provides a kind of load hydrogenation catalyst for refining of realizing deep hydrodesulfurizationof of diesel oil on the other hand, by the characteristics of used aluminum-zirconium composite oxides carrier, makes catalyst have higher hydrodesulfurization activity.
The present invention also provides the method for preparing above-mentioned aluminum-zirconium composite oxides carrier and corresponding load hydrogenation catalyst for refining, the synthesis condition of carrier is relatively simple, be easy to control, and prepares described oxide carrier and need not to use expensive template agent.
The present invention at first provides a kind of aluminum-zirconium composite oxides carrier, for utilizing the synthetic Al that obtains of aluminium source and zirconium source assembling
2O
3-ZrO
2Composite oxides, its specific area are 200～270m
2/ g, pore volume are 0.2～0.5cm
3/ g, aperture 4～9nm.
Literature survey shows in numerous catalyst carriers, to have only ZrO
2Be only oxide acid and alkalescence, the ZrO simultaneously of having simultaneously
2Have cubic phase, monocline mutually with three kinds of crystal formations cube mutually, the acid amount of its different phases, acid strength and acid matter are had nothing in common with each other; In addition, ZrO
2Having good oxidisability and reproducibility, is P-type semiconductor, shows to be easy to produce oxygen vacancies, is easy to provide electronics, makes reactive metal be easy to advantages such as reduction; But ZrO
2Shortcomings such as little, the various crystal formation instability of specific area, easy generation transformation are also arranged as carrier separately, and this has just limited its application prospect as carrier.
On the other hand, with traditional Al
2O
3Carrier is compared, and contains the zirconium complex carrier and has better HDS and HDN performance.And contain the zirconium complex carrier mainly is because ZrO to the raising of HDS process performance
2Improved the surface nature of carrier, as, in aluminium oxide and/or silica, introduce the reduction temperature that an amount of zirconia can reduce active component (for example Mo), make active component be easier to sulfuration, zirconium is all right in addition and the active component effect, active component is reached at carrier surface disperse preferably and thinner granularity, to bring into play better catalytic performance.
The inventor just is being based on such present Research, a kind of composite oxides that contain the aluminium zirconium have been researched and proposed, by zirconic introducing, the surface nature and the pore structure feature of alumina support are suitably improved, can demonstrate better deep desulfuration catalytic performance behind the supported active metal.
According to composite oxide carrier of the present invention, be preferably the synthetic product of introducing the small amounts zirconium in the aluminium oxide, that is, and Al
2O
3-ZrO
2The mass ratio of two kinds of oxides is 95-80: 5-20.
Composite oxide carrier of the present invention can be to utilize the synthetic mesoporous material that obtains of the known preparation technology of catalyst technical field, for example, and can be for obtaining composite oxide material by hydrothermal deposition method and the self assembly of the method for coating.
So the present invention also provides two kinds of methods that prepare this composite oxide carrier:
A kind of hydrothermal deposition method that can be described as comprises: adopting aluminium salt and zirconates is primary raw material, makes it realize the original position homogeneous precipitation under thermal and hydric environment and organic precipitant effect and collects sediment, and described organic precipitant is a urea.
Another kind can be described as the coating method, comprise: adopting aluminium oxide and zirconates is primary raw material, the surface that makes zirconates be coated on aluminium oxide uniformly under the precipitating reagent effect forms binary composite oxides precipitation, and collects this sediment, and described precipitating reagent comprises ammoniacal liquor or ammonium carbonate.
Can use any feasible aluminium salt and zirconates as aluminium source and zirconium source in the said method, for example, described zirconates can comprise one or more in zirconium oxychloride, zirconium nitrate or the zirconium sulfate etc.; The used aluminium salt of hydrothermal deposition method can comprise one or more in aluminum nitrate, aluminum sulfate and the aluminium chloride etc.
One of the method according to this invention makes aluminium salt and zirconates realize that under thermal and hydric environment and organic precipitant effect the original position homogeneous precipitation prepares described composite oxide carrier by the hydrothermal deposition method, and it can comprise following process:
Aluminium salt and zirconates are mixed with the mixed solution of aluminium salt and zirconates with deionized water dissolving;
Precipitating reagent is joined in the mixed solution of this aluminium salt and zirconates and stir, under thermal and hydric environment, make its reaction to generating sediment;
With dry, the roasting in gained sediment washing back, obtain described aluminum-zirconium composite oxides carrier.
In this method, the addition of organic precipitant is in the mole of aluminium salt and zirconates, and organic precipitant: the preferred mole of (aluminium salt+zirconates) is than being 2-20: 1-5.
In the concrete operations, a certain amount of precipitating reagent slowly can be added in aluminium salt and the zirconates mixed solution, continue to stir, precipitating reagent be dissolved fully obtain mixture solution.This process can at room temperature be carried out (not being higher than 32 ℃);
Further this mixture solution is moved in the reactor and reacted 2-8 hour down at 100-180 ℃.The sediment of reaction gained adopts the vacuum filtration method to separate, and washs (washing 3-4 time) with a large amount of deionized waters; And then with absolute ethanol washing (2-3 time);
Place baking oven dry sediment after the washing, drying condition can be 100-120 ℃ of following 5-24 hour.Dried product needs roasting at a certain temperature, thereby obtains aluminum-zirconium composite oxides, and roasting condition can adopt 400-900 ℃ of roasting 3-6 hour.
According to another kind of preparation method provided by the invention, by coating method (also claiming the immersion deposition method) zirconates is deposited on aluminium oxide equably under the effect of precipitating reagent surface is made described carrier, specifically can comprise following process:
Alumina powder is stirred with the deionized water making beating, form uniform aluminium oxide slurries;
Zirconates is mixed with zirconium saline solution with deionized water dissolving, under stirring condition, is added in the aluminium oxide slurries, stir, form mixed serum;
Under stirring condition, in this mixed serum, drip precipitating reagent, form mixed sediment;
With the ultrasonic processing of mixed sediment, filtration, washing, drying and roasting, obtain described zirconia-alumina composite oxide carrier.
Because aluminium oxide is a porous mass, zirconium salt solution is impregnated in the aluminium oxide duct, through the precipitating reagent effect, can be deposited on the surfaces externally and internally of aluminium oxide, thereby usually claim that this method is coating method or immersion deposition method.Preferably, the mol ratio of aluminium oxide and deionized water is in the aluminium oxide slurries of preparation: 1-3: 15-45; The concentration of zirconium saline solution is 0.2-1mol/L, and the concentration of precipitating reagent is: 2-10mol/L, and the mol ratio of precipitating reagent and zirconates is 2-8: 0.5-2.The dripping quantity that can control precipitating reagent in the concrete operations is 4-9 until system pH.
Described sedimentary drying condition is 100-120 ℃ of dry 5-24 hour or microwave drying; Roasting condition is 400-900 ℃ of roasting 3-6 hour.
In the said method, a certain amount of precipitating reagent slowly can be added drop-wise in the mixed serum of zirconates and aluminium oxide, the pH value of regulating mixed liquor is between 4-9, then the ultrasonic processing of mixture 10-30 minute, wore out 2-8 hour under the room temperature, then the mixture vacuum filtration is separated, and wash (washing 3-4 time) with a large amount of deionized waters; And then with absolute ethanol washing 2-3 time.Washing postprecipitation thing carries out drying and roasting.
In the synthetic method provided by the invention, one of characteristics of hydrothermal deposition method are to adopt hydrothermal method and by organic precipitant, synthesize two component Al by the self assembly of hydrothermal deposition method in building-up process
2O
3-ZrO
2Composite oxide material, can control speed and the homogeneity that precipitation generates by suitably controlling and adjust precipitating reagent consumption, hydrothermal temperature and hydro-thermal reaction time, moderate to obtain uniform particles, specific surface and aperture, and two component composite oxide carriers with ideal surfaced character; Advantage on the other hand be synthesis condition relatively simple, be easy to control, need not to use expensive template agent.And the characteristics of the method for coating are to utilize precipitating reagent and ultrasonic treatment technology to make zirconates evenly be deposited on the surface of aluminium oxide singlely, synthesize two component Al
2O
3-ZrO
2Composite oxide material, this process can make by concentration, rate of addition and the zirconium al proportion of control precipitating reagent zirconates more homogeneous, controllably coat (deposition) surface at aluminium oxide, thereby the as far as possible surface area that influences aluminium oxide and the pore passage structure of minimum degree can be given full play to the redox property of zirconium again and to the adjusting function of acidity.
Main feature of the present invention is ZrO
2And Al
2O
3Effectively compound, provide a kind of aluminium zirconium complex carrier of high comprehensive performance, to Al
2O
3Specific area and pore passage structure influence under the little situation, can further improve Al
2O
3Character such as acidity, oxidation-reduction quality; And, because zirconia has different phases, and different phases has different acid matter, so can regulate support acidity matter by control zirconia crystallization process, as, with the aluminium oxide compound tense, because aluminium oxide has promoted the zirconic formation of cubic phase and has stablized, and the zirconia of cubic attitude has higher L acid amount, thereby has improved the L acid amount of carrier, has improved the hydrogenation activity of catalyst; Similarly, because the existing L acid of zirconia of monocline phase has B acid position again, acid amount and acid that the existence of this thing phase can be regulated the middle strong acid of complex carrier distribute.
But need to prove that the method for preparing composite oxide carrier of the present invention is not limited to above-mentioned hydrothermal deposition method and coating method, as long as can realize the even composite methods of two kinds of oxides, all can reach the effect of improving alumina carrier surface character.
Thereby, the invention provides aluminium zirconium composite carrier with suitable specific area and surface nature and high hydrogenation activity, the research and development that this carrier material reached the catalyst that obtains on this basis have most important theories Research Significance and application prospect.
So the present invention also provides two kinds of supported hydrodesulphurizatiocatalyst catalysts, for utilizing the bimetallic catalyst of above-mentioned aluminum-zirconium composite oxides carrier carrying transition metal Mo and Ni or W and Ni, in the Ni-Mo catalyst, MoO
3Load capacity be the 10-30% of total catalyst quality, the load capacity of NiO is the 2-6% of total catalyst quality; In the Ni-W catalyst, the load capacity of NiO is the 3-6% of total catalyst quality, WO
3Load capacity be the 23-28% of total catalyst quality.These two kinds of catalyst can be used for the deep hydrofinishing of oil product, realize efficient deep desulfuration.
Load processing as for reactive metal Mo, Ni and W can be finished according to common process fully, for example, can be common dipping or step impregnation.
With FCC diesel oil is raw material, to Al
2O
3-ZrO
2Composite oxides are that the carrier-borne transition metal catalysts of carrier carries out active appraisal experiment, and the deep desulfuration effect of finding this catalyst is better than the Al with routine
2O
3Catalyst for carrier.
The result shows, under the reaction condition that relaxes: 300～350 ℃ of reaction temperatures, reaction pressure 4～6MPa, hydrogen to oil volume ratio 500～800, volume space velocity is 0.8～1.5h during liquid
-1, catalyst of the present invention can reach more than 90% the desulfurization degree of oil product.For example, can be sulfur content that sulphur in the diesel oil of 1210 μ g/g is removed to 9 μ g/g, satisfy the sulfur content requirement of Europe-IV diesel quality standard.This catalyst also is beneficial to the one-stage hydrogenation of the contour sulfur-bearing of diesel oil, high arene content oil product, for example, can be sulfur content to be removed to 30.5 μ g/g, the poisoning and deactivation of noble metal catalyst when more helping avoiding secondary hydrogenation in the high sulfur diesel of 1810 μ g/g.
In a word, the invention provides a kind of mesoporous Al that has than bigger serface
2O
3-ZrO
2Composite oxide carrier has overcome pure ZrO
2Specific area is little, the weak point of poor stability, its specific area, pore volume and aperture and conventional hydrofining catalyst carrier γ-Al
2O
3Similar, and surface acidity and acid strength distribute and all are better than conventional Al
2O
3Carrier helps the carrying out that deep hydrodesulfurizationof reacts.Further become active good hydrofinishing deep desulfurization catalyst after the carried metal component, satisfied the requirement of diesel oil (especially high sulfur diesel) deep hydrodesulfurizationof.
Description of drawings
Fig. 1 is the XRD spectra according to the synthetic composite oxide carrier of embodiment 1 record method.
Fig. 2 is the Ni-Mo/Al that utilizes the composite oxide carrier of embodiment 1 preparation to obtain
2O
3-ZrO
2The UV-Vis DRS spectrogram of catalyst series (deduction carrier background).
Fig. 3 is the Ni-Mo/Al of embodiment 1 preparation
2O
3-ZrO
2The NH of catalyst series
3-TPD characterization result.
The specific embodiment
Below further specify embodiment of the present invention and the beneficial effect that produced by specific embodiment, understand essence of the present invention place better to help the reader, but but can not be interpreted as any qualification the present invention's practical range.
Embodiment 1
Take by weighing an amount of aluminum nitrate and zirconium oxychloride by a certain percentage, add the proper amount of deionized water stirring and dissolving.Take by weighing certain amount of urea, slowly join in the above-mentioned solution, stirring and dissolving obtains settled solution, and wherein, (aluminum nitrate+zirconium oxychloride): deionized water: the mol ratio of urea is 1: 100: 2.25.
The gained settled solution is transferred in the reactor, and compactedness is 65%, and reactor is put into baking oven, about about 140 ℃ of following isothermal reaction 4h, takes out reactor, is cooled to room temperature, obtains sediment.
The gained sediment is carried out vacuum filter, spend deionised water 3-4 time (till detecting less than chlorion) with liquor argenti nitratis ophthalmicus; Use absolute ethanol washing 2-3 time again; Get filter cake, filter cake is transferred in the beaker,, obtain aluminium zirconium complex carrier at 550 ℃ of following roasting 4h then at 120 ℃ of dry 12h.
The raw materials used aluminum nitrate of above process, zirconium oxychloride quality are respectively by the ZrO in the complex carrier that obtains after the roasting
2The percentage calculation of shared composite oxides gross mass, part carrier character is referring to table 1 and Fig. 1.
Table 1.Al
2O
3-ZrO
2Composite oxides surface nature data
From Fig. 1 the XRD spectra of series aluminum zirconium mixed oxide as seen, complex carrier exists with unformed or ultrafine particle form, and pure ZrO
2The characteristic diffraction peak of tangible monocline phase has appearred in carrier.
Synthesized Al
2O
3-ZrO
2Behind the complex carrier, equal-volume step impregnation Ni and Mo metal component on this complex carrier.Used slaine is respectively nickel nitrate (Ni (NO
3)
26H
2O) and ammonium molybdate ((NH
4)
6Mo
7O
244H
2O).At first with a certain amount of ammonium molybdate ((NH
4)
6Mo
7O
244H
2O) be dissolved in a certain amount of deionized water, be made into dipping solution, different ZrO
2The Al of content
2O
3-ZrO
2Complex carrier is inserted respectively in the dipping solution, makes MoO
3Mass fraction be 20%; Ultrasonic processing is 20 minutes in ultrasonic oscillator; Following dry 12 hours at 110 ℃ then; Under 550 ℃, roasting is 4 hours in the air atmosphere afterwards, obtains the catalyst precarsor of load Mo; Again with a certain amount of nickel nitrate (Ni (NO
3)
26H
2O) be dissolved in a certain amount of deionized water, be made into maceration extract, with load the catalyst precarsor of Mo insert respectively in the maceration extract, the mass fraction that makes NiO is 3.5%; Ultrasonic processing is 20 minutes in the ultrasonic oscillator; Following dry 12 hours at 110 ℃ then; Under 550 ℃, roasting is 4 hours in the air atmosphere afterwards, obtains a series of NiMo/Al
2O
3-ZrO
2Catalyst, the corresponding 1～10# that is designated as.The part catalyst property is referring to table 2, Fig. 2 and Fig. 3.
Table 2.NiMo/Al
2O
3-ZrO
2Catalyst series surface nature data
Fig. 2 is the uv atlas of load series type catalyst, can see, wherein 220～255nm place absworption peak belongs to the four-coordination species of Mo, and the absworption peak at 340～390nm place belongs to body phase MoO
3Or the hexa-coordinate species of Mo.As can be seen from the figure NiMo/Al
2O
3Catalyst exists the absworption peak of the four-coordination species that belong to Mo, along with ZrO
2-Al
2O
3ZrO in the complex carrier
2Increase, the absworption peak that 220～255nm place belongs to the four-coordination species of Mo disappears, and has occurred belonging to the MoO of body phase simultaneously at 340～390nm place
3The perhaps absworption peak of the hexa-coordinate species of Mo, thus help the raising of the catalytic activity of catalyst.
The NH of Fig. 3
3-TPD curve shows that the adding of zirconium reduces the strong acid amount of catalyst, and acid strength also slightly reduces; Weak acid acid slightly raises by force, makes it more help deep hydrodesulfurizationof.
Embodiment 2
Method according to embodiment 1 has been synthesized Al
2O
3-ZrO
2Behind the complex carrier, equal-volume floods the Ni-W metal component altogether and prepares NiW/Al on this complex carrier
2O
3-ZrO
2Hydrogenation catalyst.The load capacity of NiO is 3.5% of a total catalyst quality in the catalyst, WO
3Load capacity be 26% of total catalyst quality.The preparation method is: used slaine is respectively nickel nitrate (Ni (NO
3)
26H
2O) and ammonium metatungstate ((NH
4)
6H
2W
12O
40XH
2O).A certain amount of ammonium metatungstate and nickel nitrate is soluble in water, be made into common dipping solution.Adopt co-impregnation to obtain NiW/Al
2O
3-ZrO
2The bimetallic catalyst presoma after the impregnating metal active component, is put into the ultrasonic processing of ultrasonic oscillator 20 minutes with this catalyst precursor, following dry 12 hours at 110 ℃ then, under 500 ℃, roasting is 4 hours in the air atmosphere afterwards, prepares NiW/Al at last
2O
3-ZrO
2Catalyst.
Embodiment 3
A certain amount of alumina powder of weighing stirs with the proper amount of deionized water making beating, forms uniform aluminium oxide slurries; Wherein in mole, alumina powder: deionized water is: 1: 15;
Zirconium oxychloride is mixed with the zirconium saline solution that concentration is 0.5mol/L with deionized water dissolving;
Under stirring condition, zirconium saline solution is added in the aluminium oxide slurries slowly, stirs, form mixed serum;
Slowly dripping concentration under stirring condition in mixed serum is the ammoniacal liquor of 6mol/L, regulates the pH value and is about 8, makes zirconates be deposited on the surface of aluminium oxide uniformly, obtains mixed sediment;
Mixed sediment is placed the ultrasonic processing of ultrasonator 20 minutes, then at room temperature (be no more than 32 ℃) aging 4 hours;
Mixed sediment vacuum filtration after this ultrasonic processing and the burin-in process is separated, and wash (washing 3-4 time) with a large amount of deionized waters; And then with absolute ethanol washing 2-3 time.
Place baking oven dry sediment after the washing, drying condition can for 120 ℃ following 12 hours, then desciccate was obtained aluminum-zirconium composite oxides carrier in 4 hours 550 ℃ of following roastings.The prepared composite oxides of the character of prepared composite oxides and embodiment 1 are similar.
With these composite oxides is that carrier is according to embodiment 1 preparation corresponding N iMo/Al
2O
3-ZrO
2(be designated as a～e), according to embodiment 2 preparation corresponding N iW/Al
2O
3-ZrO
2Catalyst.
Embodiment 4
Method according to embodiment 3 prepares complex carrier, and different is that wherein zirconates adopts zirconium nitrate, prepares Al
2O
3-ZrO
2The BET characterization data of series composite oxide carrier is similar to embodiment 1 result.
This carrier is further made NiMo/Al respectively through step impregnation Ni-Mo and Ni-W metal component according to the method for embodiment 1
2O
3-ZrO
2(being designated as a '～e ') and NiW/Al
2O
3-ZrO
2Catalyst series.
Embodiment 5
Method according to embodiment 1 prepares complex carrier, and different is that wherein hydrothermal reaction condition is 180 ℃, 4 hours, prepares Al
2O
3-ZrO
2The BET characterization data of series composite oxide carrier is similar to embodiment 1 result.
This carrier further floods Ni-Mo according to the method for embodiment 1 and 2 and Ni-W makes NiMo/Al
2O
3-ZrO
2And NiW/Al
2O
3-ZrO
2Catalyst series.
Embodiment 6
Adopting hydrogenated diesel oil and the formulated according to a certain percentage ready-mixed oil of catalytic cracking diesel oil, is that 5MPa, temperature are 350 ℃, volume space velocity is 1.0h during liquid at pressure
-1With hydrogen to oil volume ratio be under 600 the condition, adopt the catalyst among the embodiment 1, carry out the evaluation of deep hydrodesulfurizationof reactivity worth.The main character of raw materials used oil sees Table 3, and hydrodesulfurization (HDS) reaction result is as shown in table 4 below.
The main character of table 3. feedstock oil
Table 4.NiMo/Al
2O
3-ZrO
2The HDS reaction result of catalyst series
Result from table 4 as can be seen, above-mentioned aluminium zirconium composite carried catalyst, all show good desulfurization degree and higher desulphurizing activated, particularly the zirconium mass fraction is 10% and 15% o'clock, sulfur content obviously reduces in the product, especially during zirconium mass fraction 10%, the sulfur content of product is lower than 10ppm, has satisfied the sulfur content index of Europe-IV standard.
Embodiment 7
Adopting the huge port catalytic cracking diesel oil, is that 5MPa, temperature are 350 ℃, volume space velocity is 1.0h during liquid at pressure
-1With hydrogen to oil volume ratio be under 600 the condition, adopt the part catalyst among the embodiment 3 and 4, carry out the evaluation of deep hydrodesulfurizationof reactivity worth.The main character of raw materials used oil sees Table 5, and the hydrodesulfurization reaction result is as shown in table 6 below.
The main character of table 5. feedstock oil
The HDS result of table 6.NiMo catalyst series
Reaction result from table 6 as can be seen, at the huge port catalytic diesel oil, its sulfur content is during up to 1810 μ g/g, utilize the present invention introduce an amount of zirconic above-mentioned be the catalyst of carrier with the aluminum-zirconium composite oxides, with Al
2O
3Compare for the catalyst of carrier, show better desulphurizing activatedly, the desulfurization degree of diesel oil has reached more than 97%.
Claims (5)
1. the preparation method of an aluminum-zirconium composite oxides carrier comprises:
Adopting aluminium salt and zirconates is primary raw material, makes it realize the original position homogeneous precipitation under thermal and hydric environment and organic precipitant effect and collects sediment, and described organic precipitant is a urea, and the specific area of described carrier is 200～270m
2/ g, pore volume are 0.2～0.5cm
3/ g, aperture 4～9nm, Al
2O
3With ZrO
2The mass ratio of two kinds of oxides is 95-80: 5-20; This preparation method comprises following process:
Aluminium salt and zirconates are mixed with the mixed solution of aluminium salt and zirconates with deionized water dissolving, and described zirconates is a zirconium oxychloride;
Precipitating reagent is joined in the mixed solution of this aluminium salt and zirconates and stir, under thermal and hydric environment, make its reaction to generating sediment;
With dry, the roasting in gained sediment washing back, obtain described aluminum-zirconium composite oxides carrier.
2. preparation method according to claim 1, wherein, described aluminium salt comprises one or more in aluminum nitrate, aluminum sulfate and the aluminium chloride.
3. preparation method according to claim 1 and 2, wherein, the addition of organic precipitant is in the mole of aluminium salt and zirconates, and organic precipitant: the mol ratio of (aluminium salt+zirconates) is 2-20: 1-5.
4. preparation method according to claim 1 wherein, makes the mixed solution of aluminium salt and zirconates and organic precipitant obtain sediment in 2-8 hour 100-180 ℃ of reaction, sediment deionized water and absolute ethanol washing.
5. preparation method according to claim 1, wherein, described sedimentary drying condition is 100-120 ℃ of dry 5-24 hour or microwave drying; Roasting condition is 400-900 ℃ of roasting 3-6 hour.
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| CN105013420B (en) * | 2014-04-17 | 2017-05-03 | 中国石油大学(北京) | Microwave reactor and application thereof |
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