CN101199935A - Titania-alumina mixed oxide hydrodesulfurization catalyst and preparing process thereof - Google Patents
Titania-alumina mixed oxide hydrodesulfurization catalyst and preparing process thereof Download PDFInfo
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Abstract
The utility model relates to a synthesis of a titania-alumina mixed oxide material and a catalyst carrier of a supported deep hydrodesulfurization catalyst by taking the compound as the carrier. 1)take the tetrabutyl titanate and the aluminum chloride or the pseudo-boehmite as the raw material, prepare the mesoporous mixed oxide material of TiO2-Al2O3 with the sol-gel method, and use the material as the carrier of the diesel oil deep hydrodesulfurization catalyst; 2)use the dipping method by modifying the active metal variety and the dipping method to get highly dispersed supported mesoporous hydrodesulfurization catalyst of TiO2-Al2O3 compound material after baking; in the diesel oil hydrogenation deep desulfurization reaction, the desulfurization capability is good, and the desulfurization rate can reach 99 percent; if the reaction can be operated under a relative relaxative condition, the sulfur in the diesel oil can be desorbed from 1300ppm to below 15 ppm, or from the 430ppm to below 1ppm; the sulfur content in the product can meet the standard of Europe IV.
Description
Technical field
The present invention relates to a kind of TiO
2-Al
2O
3The preparation of the synthetic and support type deep hydrodesulfurizationof catalyst take these composite oxides as carrier of composite oxide material.
Background technology
Along with the quickening of vehicle diesel oil trend in the world wide, the demand of diesel oil is increasing, but the waste gas that produces behind the diesel combustion is also serious day by day to the harm of environment.Therefore, the low sulfuration of diesel oil is subjected to the common concern of countries in the world.By the American-European diesel oil environmental regulation of having put into effect, the content of restriction sulphur and polycyclic aromatic hydrocarbon is the key issue of producing clean diesel.Though the sulfur content index reduces significantly than before in China's diesel oil, compare with advanced country and to still have big gap, diesel oil is carried out the research of deep hydrodesulfurizationof, producing " clean diesel " becomes one of important topic of oil refining worker.
With regard to present appointed condition, conventional hydrofinishing is difficult to reach the requirement of ultra-deep desulfurization, in order to reduce sulfur content, and the response parameter that only changes, but that this method requires equipment is high, and running cost also uprises thereupon.
Just at present both at home and abroad to the research of diesel fuel desulfurization, thiophene and thiophene derivant, especially 4-MDBT particularly 4 in the sulfur-containing compound in the diesel oil, the most difficult the removing of 6-dimethyl Dibenzothiophene; It is the biggest obstacle of present diesel deep desulfurization.Its key is the efficient deep hydrodesulfurizationof catalyst of exploitation, and the design of new material research and development can effectively promote the performance quality of catalyst.At present, the raising that the exploitation of the carrier material of Hydrobon catalyst mainly is to maximally utilise the increase of specific area of carrier material and active component decentralization to be increasing the number in activated centre, and utilize the active component surface can increase and the increase of blemish improve the activity in activated centre.Therefore develop new carrier material and just become the key issue that improves hydrogenation catalyst performance with the decentralization that improves specific surface area of catalyst and stability and raising metal active constituent.
But adopt the catalyst of conventional carrier diesel hydrogenation for removal sulphur (for example with Al
2O
3NiMo, CoMo or NiW catalyst for carrier) be difficult to remove the sulfur-containing compound of DBT derivative class, thus be difficult to reach the effect of deep desulfuration.Simultaneously, because TiO
2Specific area is relative with pore volume less, and separately using time tool intensity, poor heat stability are unfavorable for the carrying out of high pressure and macromolecular reaction.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of aluminum titanium composite oxide.Its technology path is such: adopt the sol-gal process self assembly to go out bi-component TiO in building-up process
2-Al
2O
3Composite oxide material is aggregate by abundant hydroxyl and static, hydrogen bond action with two kinds of raw material self assemblies, has adopted the means such as speed control method, guarantees the control of assembling process and the quality of assembly element.Its advantage is that process conditions are relatively simple, is easy to control, need not to use expensive template agent in its building-up process.
The objective of the invention is to implement like this:
(1) at first make it form white gels with the ammonia solvent of 2.5～5M inorganic aluminate aluminium chloride or aluminum nitrate, centrifugal then, with the washing of redistilled water or deionized water and vacuum filtration 3-5 time, nitric acid dissolve with 5M makes it form aluminium colloidal sol afterwards, in ultrasonic water bath, act on 10～20 minutes standby, the temperature of water＜32 ℃, with butyl titanate ethanol, the dissolving of 1: 12 by weight～30: 0.3: 1 ratio of nitric acid and deionized water forms titanium colloidal sol, afterwards under intense stirring condition, titanium colloidal sol is dropwise splashed into aluminium colloidal sol, continue to stir and make it form gel, in the process that drips, need to control drop rate, be 4ml/ minute, above process is at room temperature carried out, temperature＜35 ℃, with the gel that makes in temperature is 100～110 ℃ vacuum drying chamber or condition be the micro-wave oven inner drying 15 minutes of 800W, roasting obtains aluminum titanium composite oxide under 400～900 ℃ of degree afterwards; The amount ratio of butyl titanate and aluminium chloride or aluminum nitrate is by TiO in the complex carrier that makes
2Quality counts 5～50%;
(2) with equal-volume step impregnation method load NiMo, CoMo or CoNiMo on aluminum titanium composite oxide, wherein the Mo loading is with MoO
3Meter, mass fraction for the aluminum titanium composite oxide be carrier catalyst quality 12～20%, Ni or Co loading be in NiO or CoO, mass fraction be with the aluminum titanium composite oxide be carrier catalyst quality 3～5%; Or with equal-volume co-impregnation carrying metal active component Ni and W, W content is with WO
3Meter, mass fraction for the aluminum titanium composite oxide be carrier catalyst quality 20～30%, Ni content is in NiO, mass fraction for the aluminum titanium composite oxide be carrier catalyst quality 3～5%;
(3) or to titania-alumina mixed oxide carry out P and F modification, wherein the content of P and F is 1～6% of titania-alumina mixed oxide quality;
TiO
2-Al
2O
3Composite oxide carrier has overcome pure TiO
2Weak point, its specific area, pore volume and aperture and conventional hydrodesulfurization catalyst support γ-Al
2O
3Similar, and surface acidity and acid strength distribute and all are better than conventional Al
2O
3Carrier can make to have more Mo or the unsaturated active sites of W on the catalyst, has improved the surface nature of catalyst, thereby has formed more S anion vacancies that link to each other with Mo or W, is conducive to the reduction of molybdenum or tungsten species, promotes the carrying out of deep hydrodesulfurizationof reaction.And in composite oxides, introduce an amount of P or F auxiliary agent, and can change the distribution of structural behaviour and carrier surface acid strength and the sour kind of carrier, and then change the hydrodesulfurization activity of composite carried catalyst, promote the carrying out of deep hydrodesulfurizationof reaction.The present invention adopts the sol-gal process self assembly to go out to have Large ratio surface, mesoporous TiO
2-Al
2O
3Composite oxide carrier and active good hydrofinishing deep desulfurization catalyst have satisfied the requirement of deep hydrodesulfurizationof of diesel oil.
The present invention synthesize with TiO
2-Al
2O
3Composite oxides are that the Hydrobon catalyst of carrier has high surface area and mesoporous feature, and specific area is 230～350m
2/ g, pore volume are 0.7～1.1ml/g, aperture 9～14nm, and also catalyst surface is acid and the acid strength distribution but all is better than Al
2O
3Carrier.Take the FCC diesel oil in the different places of production as raw material, to TiO
2-Al
2O
3Composite oxides are that the catalyst of carrier carries out active appraisal experiment, and the effect of discovery catalyst desulfurizing is better than the Al with routine
2O
3Catalyst for carrier.NiW/TiO for example
2-Al
2O
3It is that sulphur in the FCC diesel oil of 1300ppm is removed to below the 15ppm that catalyst can make sulfur content, can make by the sulfur content in the miscella of FCC diesel oil and hydrogenated diesel oil allotment to be removed to below the 0.02ppm from 430ppm sulphur, satisfies Europe IV standard.
The specific embodiment
Embodiment 1
Take by weighing a certain amount of AlCl
3Or Al (NO
3)
3, the ammonia solvent of employing 5M, the amount of used ammoniacal liquor is for just making AlCl
3Or Al (NO
3)
3Form the amount of gel, then centrifugal, wash above-mentioned alumina gel with deionized water, filtering and washing under vacuum state is until the pH value of system is greater than 9.20.Then add in proportion the nitric acid dispergation of 5M, until the pH value of system is about 4.20, the aluminium colloidal sol that obtains acts on 10 minutes in ultrasonic water bath, and (in the whole ultrasonic procedure in the ultrasonic pond temperature of water less than 32 ℃) takes by weighing a certain amount of Ti (OC
4H
9)
4Be dissolved in the ethanol Ti (OC
4H
9)
4With the mol ratio of ethanol be 1: 5, obtain the butyl titanate solution A; Water, nitric acid are dissolved in the ethanol successively, and the mol ratio of water, nitric acid, ethanol is 1: 0.3: 10, obtains solution B; A and B solution were stirred respectively 20 minutes; Under the room temperature, solution A is poured in the acid buret, splashed into gradually then in the solution B of vigorous stirring, continue stirring and obtained colloidal sol C in 10～30 minutes; Colloidal sol C is poured in the acid buret, splash into gradually in the aluminium colloidal sol of vigorous stirring, in the process that drips, regulate the speed that drips, after dripping off, vigorous stirring is until form gel, then with this gel in 110 ℃ of lower vacuum drying 10 hours (vacuum is less than 80mmHg), distinguish roasting 3 hours in that 400 ℃ and 500 ℃ are lower afterwards; The product of gained is TiO
2-Al
2O
3Composite oxide carrier, Ti (OC
4H
9)
4With AlCl
3Or Al (NO
3)
3Consumption by TiO contained in the complex carrier that makes
2Mass fraction calculate the TiO in this complex carrier
2Be 5%～50% by mass fraction.
Adopt the equal-volume step impregnation method at TiO
2-Al
2O
3Load NiMo active component is prepared into NiMo/TiO on the complex carrier
2-Al
2O
3Catalyst, Mo is with MoO in the catalyst
3Meter, mass fraction is 16%.Ni is in NiO, and mass fraction is 3.5%.The used raw material of incipient impregnation is respectively molybdenum acid ammonia and nickel nitrate, and the order of dipping is Ni behind the first Mo.After the incipient impregnation, ultrasonic wave disperseed 20 minutes, descended dry 12 hours at 110 ℃ then, and under 500 ℃, roasting is 4 hours in the air atmosphere afterwards.
Embodiment 2
With embodiment 1 method, the gel that obtains then is in 110 ℃ of following vacuum drying 10 hours (vacuum is less than 80mmHg), roasting 4 hours under 400 ℃, 500 ℃, 550 ℃, 600 ℃, 700 ℃, 800 ℃ and 900 ℃ of different temperatures respectively afterwards obtains the composite oxide carrier of different sintering temperatures.
Embodiment 3
With embodiment 1 method, in the process of carrier and catalyst drying, replace conventional oven drying with microwave drying, adopt " beautiful " micro-wave oven, under the power of 800W, dry 15 minutes.
Embodiment 4
With embodiment 1 method, prepared TiO
2-Al
2O
3Behind the complex carrier, equal-volume floods NiW altogether on complex carrier, preparation NiW/TiO
2-Al
2O
3Catalyst, W is with WO in the catalyst
3Meter, mass fraction is 28%.Ni is in NiO, and mass fraction is 3.5%.The used raw material of incipient impregnation is respectively metatungstic acid ammonia and nickel nitrate.After the impregnating metal active component, ultrasonic wave disperseed 20 minutes, descended dry 12 hours at 110 ℃ then, and under 500 ℃, roasting is 4 hours in the air atmosphere afterwards.
Embodiment 5
With embodiment 1 method, prepared TiO
2-Al
2O
3Behind the complex carrier, at complex carrier first-class volume step impregnation CoMo or CoNiMo, preparation CoMo/TiO
2-Al
2O
3Or CoNiMo/TiO
2-Al
2O
3Catalyst, Mo is with MoO in the catalyst
3Meter, mass fraction is 15.5%.Ni is in NiO, and mass fraction is 3.5%.CoNiMo/TiO
2-Al
2O
3Mo is with MoO in the catalyst
3Meter, mass fraction be 15.5%, Ni and Co in NiO and CoO, (NiO+CoO) mass fraction is 3.5%.The used raw material of incipient impregnation is respectively ammonium molybdate, nickel nitrate and cobalt nitrate.After the impregnating metal active component, ultrasonic wave disperseed 20 minutes, descended dry 12 hours at 110 ℃ then, and under 500 ℃, roasting is 4 hours in the air atmosphere afterwards.
Embodiment 6
With embodiment 1 method, with boehmite substitute for Al Cl
3Prepare according to the method described above TiO
2-Al
2O
3Complex carrier.Boehmite adopts the ethanol dissolving, wherein the amount of used ethanol is 1.1～1.3 times of boehmite quality, fully stirs 30 minutes, obtains slurries, drip slowly afterwards titanium colloidal sol, stir and treat to descend each roasting 3 hours at 400 ℃ and 500 ℃ after it becomes gel.The product of gained is TiO
2-Al
2O
3Complex carrier, employed Ti (OC
4H
9)
4Quality press respectively TiO contained in the carrier
2Mass fraction calculate the TiO in this complex carrier
2Be 5～50% by mass fraction.
With embodiment 1 method and embodiment 4 methods, at this TiO
2-Al
2O
3The NiMo of load equal in quality mark and NiW metal active constituent prepare NiMo/TiO on the complex carrier
2-Al
2O
3And NiW/TiO
2-Al
2O
3Catalyst.
Embodiment 7
With embodiment 1 method, take by weighing diammonium hydrogen phosphate, with incipient impregnation AlCl behind the deionized water dissolving
3, lower dry 4 hours at 110 ℃.Prepare the TiO of P modification with embodiment 1 method afterwards
2-Al
2O
3Composite oxide carrier.Wherein the mass fraction of P in complex carrier is respectively 0.5%, 1%, 2%, 3% and 4%.
Embodiment 8
With embodiment 7 methods, change diammonium hydrogen phosphate into ammonium fluoride, the mass fraction of F in complex carrier still is 0.5%, 1%, 2%, 3%, 4% and 5%.
Claims (3)
1. the preparation method of a titanium aluminium complex carrier Hydrobon catalyst, it is characterized in that: (1) at first makes it form white gels with the ammonia solvent of 2.5～5M inorganic aluminate aluminium chloride or aluminum nitrate, centrifugal then, with the washing of redistilled water or deionized water and vacuum filtration 3-5 time, nitric acid dissolve with 5M makes it form aluminium colloidal sol afterwards, in ultrasonic water bath, act on 10～20 minutes standby, the temperature of water＜32 ℃, with butyl titanate ethanol, nitric acid and deionized water are that dissolving in 1: 12～30: 0.3: 1 forms titanium colloidal sol by weight, afterwards under intense stirring condition, titanium colloidal sol is dropwise splashed into aluminium colloidal sol, continue to stir and make it form gel, in the process that drips, need to control drop rate, be 4ml/ minute, above process is at room temperature carried out, temperature＜35 ℃, with the gel that makes in temperature is 100～110 ℃ vacuum drying chamber or condition be the micro-wave oven inner drying 15 minutes of 800W, obtain aluminum titanium composite oxide 400～900 ℃ of following roastings afterwards; The amount ratio of butyl titanate and aluminium chloride or aluminum nitrate is by TiO in the complex carrier that makes
2Quality counts 5～50%;
(2) with equal-volume step impregnation method load NiMo, CoMo or CoNiMo on aluminum titanium composite oxide, wherein the Mo loading is with MoO
3Meter, mass fraction for the aluminum titanium composite oxide be carrier catalyst quality 12～20%, Ni or Co loading be in NiO or CoO, mass fraction be with the aluminum titanium composite oxide be carrier catalyst quality 3～5%; Or with equal-volume co-impregnation carrying metal active component Ni and W, W content is with WO
3Meter, mass fraction for the aluminum titanium composite oxide be carrier catalyst quality 20～30%, Ni content is in NiO, mass fraction for the aluminum titanium composite oxide be carrier catalyst quality 3～5%;
(3) or to titania-alumina mixed oxide carry out P and F modification, wherein the content of P and F is 1～6% of titania-alumina mixed oxide quality, and P is diammonium hydrogen phosphate with F or becomes ammonium fluoride.
2. according to the described preparation method of claim 1, it is characterized in that: the specific area of aluminum titanium composite oxide is 230～350m
2/ g, pore volume are 0.7～1.1cm
-3/ g, aperture 9～14nm.
3. titanium aluminium complex carrier Hydrobon catalyst is characterized in that: it is that carrier according to preparation method's preparation of claim 1 is an aluminum titanium composite oxide, load NiMo, CoMo, CoNiMo or metal active constituent Ni and W catalyst.
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| CNB2006101652027A CN100548479C (en) | 2006-12-14 | 2006-12-14 | A kind of titania-alumina mixed oxide Hydrobon catalyst and preparation method |
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