CN105363480A - Method for preparing hydrodesulfurization catalyst - Google Patents
Method for preparing hydrodesulfurization catalyst Download PDFInfo
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- CN105363480A CN105363480A CN201510842130.4A CN201510842130A CN105363480A CN 105363480 A CN105363480 A CN 105363480A CN 201510842130 A CN201510842130 A CN 201510842130A CN 105363480 A CN105363480 A CN 105363480A
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Abstract
The present invention proposes a method for preparing a hydrodesulfurization catalyst and aims at solving problems of low activity and undesirable desulfurization effect of the hydrodesulfurization catalyst in the prior art. The method comprises the specific steps of: using a sol-gel method to prepare a TiO2-Al2O3 complex carrier, adding one or more compounds containing nickel, molybdenum, tungsten and cobalt into distilled water to prepare a salt solution, fully immersing the TiO2-Al2O3 complex carrier into the salt solution to obtain a mixture containing an activated metal component, kneading and molding after an auxiliary agent is added into the prepared mixture to obtain a molded substance, drying and calcining the molded substance to obtain a catalyst precursor, and reducing the catalyst precursor by using hydrogen and passivating the catalyst precursor by using nitrogen to prepare a finished catalyst. According to the method for preparing the hydrodesulfurization catalyst, hydrodesulfurization effect of a catalyst activated component can be better achieved, so that the purposes of not excessively consuming a raw material while ultra-deep desulfurization is performed and reducing a manufacturing cost are achieved.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of preparation method of Hydrobon catalyst.
Background technology
Along with the continuous increase of oil extraction amount, in crude oil, sulfur content also constantly increases, and sulfide wherein not only makes grade of oil be deteriorated, and has heavy corrosion effect to refinery equipment.Therefore, desulfuration efficiency has become the major technique brainstorm subject of petroleum chemical industry.Sulfur method comparatively conventional in current petroleum refining process comprises hydrodesulfurization etc., and namely hydrodesulfurization carries out catalytic hydrogenation under certain temperature and pressure, makes S in petroleum distillate with H
2the form removing of S.Affect the many factors of oil hydrodesulfurization efficiency, Hydrobon catalyst performance is one of factor of key.Existing Hydrobon catalyst is primarily of active component, additive and carrier composition, and therefore the raising of Hydrobon catalyst performance is mainly from the better carrier of searching, the higher active component of screening and auxiliary agent and preparation method's expansion efficiently.In order to realize deep desulfuration, Hydrobon catalyst experienced by from traditional molybdenum sulfide base desulphurization catalyst, and to the catalyst such as metal nitride, carbide, metal current phosphide, as the new study hotspot of Hydrobon catalyst, receives much concern.Therefore, the present invention proposes the preparation method of the higher Hydrobon catalyst of a kind of activity to improve the efficiency of oil hydrodesulfurization, thus improves the quality of oil, improves the cleannes of fuel oil.
Summary of the invention
Technical problem to be solved by this invention is the low and technical problem causing desulfurized effect poor of the Hydrobon catalyst overall activity prepared in prior art, provide a kind of preparation method of Hydrobon catalyst, the method can realize catalyst activity component hydrodesulfurization effect and better play, consumption raw material is exceeded, the object cut down finished cost while reaching ultra-deep desulfurization.
To achieve these goals, the technical solution used in the present invention is, a kind of method preparing Hydrobon catalyst, adopts co-impregnation to prepare this catalyst, specifically comprises the following steps:
Step one: adopt sol-gel process to prepare TiO2-Al2O3 complexes carrier, be specially: first adopt aluminum nitrate and polyethylene glycol to join in distilled water and be mixed with saturated solution, dripping ammoniacal liquor is 8.5 ~ 10 to pH, the concentration of ammoniacal liquor is 10wt% ~ 25wt%, still aging 12 hours, after air dry oven drying, to deliver in roaster roasting under the condition of 500-650 DEG C obtain Al2O3 rubber powder; Then in above-mentioned aluminium oxide rubber powder, to add after the mixing of titanium-containing compound, peptizing agent and distilled water obtained TiO2-Al2O3 complexes carrier after still aging, dry and roasting.
Step 2: one or more compounds of nickeliferous, molybdenum, tungsten and cobalt are joined in distilled water and carries out being uniformly mixed preparing salting liquid, then obtained TiO2-Al2O3 complexes carrier thorough impregnation is obtained in this salting liquid the mixture containing activated metal component;
Step 3: the mixture obtained in step 2 carries out kneading, shaping after adding auxiliary agent, obtain article shaped;
Step 4: article shaped step 3 obtained is through 120 DEG C of dryings 3 hours and 500 DEG C of roastings, 3 hours obtained catalyst precursors;
Step 5: the catalyst precursor hydrogen reducing obtained in step 4 is obtained finished catalyst; First rise to 350 DEG C with the speed of 5 DEG C/min, then rise to 600 DEG C of reductase 12s hour with the speed of 1 DEG C/min, be then down to room temperature, and adopt nitrogen inerting process 2 hours.
As a modification of the present invention, the article shaped in step 4 is at 100-150 DEG C of dry 2-5 hour, and sintering temperature is 550-650 DEG C, and roasting time is 2 ~ 4 hours.
As a modification of the present invention, the auxiliary agent added in step 3 comprises phosphorus-containing compound and/or silicon-containing compound.
As a modification of the present invention, described phosphorus-containing compound select in phosphoric acid, diammonium hydrogen phosphate or ammonium phosphate one or more.
As a modification of the present invention, described peptizing agent comprise in glacial acetic acid, ethanol, ethylene glycol, glycerine one or more.
As a modification of the present invention, described titanium-containing compound adopts butyl titanate.
Described reactive compound comprise nickel compound, molybdenum compound, cobalt compound, tungsten compound one or more; Described nickel compound is one or more in nickel oxide, basic nickel carbonate, nickelous carbonate; Described molybdenum compound is molybdenum trioxide; Described cobalt compound is one or more in cobalt oxide, basic cobaltous carbonate, cobalt carbonate; Described tungsten compound is tungstic acid.
Hydrobon catalyst, comprise carrier, active component and auxiliary agent, described carrier is, described active component comprise in nickel oxide, molybdenum trioxide, tungstic acid, cobalt oxide one or more, described auxiliary agent comprises at least one in binding agent, pore creating material, described binding agent comprise in Ludox, CMC one or both, described pore creating material comprise in sesbania powder, concave convex rod one or both.
Relative to prior art, the TiO2-Al2O3 complexes carrier that the present invention adopts sol-gel process to prepare both had had the overall skeleton of Al2O3, keep again the catalytic performance that TiO2 is excellent, prevent and adopt Al2O3 as the reunion of small-particle in its surface particles during single carrier in the past, thus effectively to improve prepared take metal phosphide as the hydrodesulfurization activity of the Hydrobon catalyst of auxiliary agent; This preparation method is simple, be easy to operation, obtained catalyst has good catalytic activity and stability, catalyst granules has large aperture and high porosity, thus making above-mentioned catalyst possess higher suction-operated to the element sulphur in oil, the effect when desulfurization process significantly improves.
Detailed description of the invention
In order to deepen the understanding of the present invention and understanding, below the invention will be further described and introduce.
Adopt co-impregnation to prepare a method for Hydrobon catalyst, specifically comprise the following steps:
Step one: adopt sol-gel process to prepare TiO2-Al2O3 complexes carrier, be specially: first adopt aluminum nitrate and polyethylene glycol to join in distilled water and be mixed with saturated solution, dripping ammoniacal liquor is 9 to pH, the concentration of ammoniacal liquor is 10wt% ~ 25wt%, still aging 12 hours, after air dry oven drying, to deliver in roaster roasting under the condition of 500-650 DEG C obtain Al2O3 rubber powder; Then in above-mentioned aluminium oxide rubber powder, to add after the mixing of butyl titanate, glacial acetic acid, ethanol and distilled water obtained TiO2-Al2O3 complexes carrier after still aging, dry and roasting.
Step 2: one or more compounds of nickeliferous, molybdenum, tungsten and cobalt are joined in distilled water and carries out being uniformly mixed preparing salting liquid, then obtained TiO2-Al2O3 complexes carrier thorough impregnation is obtained in this salting liquid the mixture containing activated metal component.
Step 3: the mixture obtained in step 2 carries out kneading, shaping after adding the auxiliary agent of phosphorus-containing compound, obtain article shaped.
Step 4: article shaped step 3 obtained is at 100-150 DEG C of dry 2-5 hour, and sintering temperature is 550-650 DEG C, roasting time is 2 ~ 4 hours obtained catalyst precursors; Preferably, at 120 DEG C of dryings 3 hours and 500 DEG C of roastings, 3 hours obtained catalyst precursors.
Step 5: the catalyst precursor hydrogen reducing obtained in step 4 is obtained finished catalyst; First rise to 350 DEG C with the speed of 5 DEG C/min, then rise to 600 DEG C of reductase 12s hour with the speed of 1 DEG C/min, be then down to room temperature, and adopt nitrogen inerting process 2 hours.
Preferably, the selection of auxiliary phosphoric acid of above-mentioned phosphorus-containing compound.
In above-mentioned preparation method, adopt co-impregnation supported active metals nickel (Ni), tungsten (W), molybdenum (Mo) and cobalt (Co) compound in TiO2-Al2O3 complexes carrier, relatively be conducive to forming the active phase of W-Ni and the active phase of Co-Mo, adding polyethylene glycol when adopting sol-gel process to prepare TiO2-Al2O3 complexes carrier can make the hydroxide colloid in carrier plastic process adsorb more water or hydroxyl, make it to form porous in drying and roasting process afterwards, improve suction dehydrogenation capacity and the speed of catalyst.The active phase of W-Ni of prepared Hydrobon catalyst finished product and the matched well of the active phase of Co-Mo, the Hydrogenation of catalyst and hydrogenolysis performance are reached coordinate well, and catalyst has more granule, more high surface area and porous, increase substantially the combination property of catalyst.
It should be noted that above-described embodiment, be not used for limiting protection scope of the present invention, equivalents done on the basis of technique scheme or the alternative scope all falling into the claims in the present invention and protect.
Claims (6)
1. prepare a method for Hydrobon catalyst, first prepare carrier, then adopted by carrier co-impregnation to be immersed in completely in activated metal mixed liquor to prepare Hydrobon catalyst, it is characterized in that: the method specifically comprises the following steps:
Step one: adopt sol-gel process to prepare TiO2-Al2O3 complexes carrier, be specially: first adopt aluminum nitrate and polyethylene glycol to join in distilled water and be mixed with saturated solution, dripping ammoniacal liquor is 8.5 ~ 10 to pH, the concentration of ammoniacal liquor is 10wt% ~ 25wt%, still aging 12 hours, after air dry oven drying, to deliver in roaster roasting under the condition of 500 ~ 650 DEG C obtain Al2O3 rubber powder; Then in above-mentioned aluminium oxide rubber powder, to add after titanium-containing compound and peptizing agent mixing obtained TiO2-Al2O3 complexes carrier after still aging, dry and roasting;
Step 2: one or more compounds of nickeliferous, molybdenum, tungsten and cobalt are joined in distilled water and carries out being uniformly mixed preparing salting liquid, then obtained TiO2-Al2O3 complexes carrier thorough impregnation is obtained in this salting liquid the mixture containing activated metal component;
Step 3: the mixture obtained in step 2 carries out kneading, shaping after adding auxiliary agent, obtain article shaped;
Step 4: article shaped drying step 3 obtained, roasting obtain catalyst precursor;
Step 5: the catalyst precursor obtained in step 4 is first obtained finished catalyst with after hydrogen reducing with nitrogen inerting process.
2. prepare the method for Hydrobon catalyst as claimed in claim 1, it is characterized in that, the auxiliary agent added in step 3 comprises phosphorus-containing compound and/or silicon-containing compound.
3. prepare the method for Hydrobon catalyst as claimed in claim 2, it is characterized in that, described phosphorus-containing compound select in phosphoric acid, diammonium hydrogen phosphate or ammonium phosphate one or more.
4. prepare the method for Hydrobon catalyst as claimed in claim 3, it is characterized in that, the article shaped in step 4 was 100 ~ 150 DEG C of dryings 2 ~ 5 hours, and sintering temperature is 550 ~ 650 DEG C, and roasting time is 2 ~ 4 hours.
5. prepare the method for Hydrobon catalyst as claimed in claim 1, it is characterized in that, in step 5, in hydrogen reduction, variations in temperature is first rise to 350 DEG C with the speed of 5 DEG C/min, then rise to 600 DEG C of reductase 12s hour with the speed of 1 DEG C/min, is then down to room temperature.
6. prepare the method for Hydrobon catalyst as claimed in claim 1, it is characterized in that, described titanium-containing compound adopts butyl titanate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106187829A (en) * | 2016-07-29 | 2016-12-07 | 万华化学集团股份有限公司 | A kind of method preparing ethylenediamine base esilate |
| CN108160082A (en) * | 2017-12-27 | 2018-06-15 | 洛阳神佳窑业有限公司 | A kind of preparation method of Hydrobon catalyst |
| CN112569956A (en) * | 2020-12-08 | 2021-03-30 | 润和催化材料(浙江)有限公司 | Claus tail gas hydrodesulfurization catalyst and preparation method and application thereof |
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| CN102247864A (en) * | 2011-05-26 | 2011-11-23 | 中国海洋石油总公司 | Preparation method of catalyst for hydrogenation desulfurization and denitrification of light-weight oil |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106187829A (en) * | 2016-07-29 | 2016-12-07 | 万华化学集团股份有限公司 | A kind of method preparing ethylenediamine base esilate |
| CN106187829B (en) * | 2016-07-29 | 2017-12-15 | 万华化学集团股份有限公司 | A kind of method for preparing ethylenediamine base esilate |
| CN108160082A (en) * | 2017-12-27 | 2018-06-15 | 洛阳神佳窑业有限公司 | A kind of preparation method of Hydrobon catalyst |
| CN112569956A (en) * | 2020-12-08 | 2021-03-30 | 润和催化材料(浙江)有限公司 | Claus tail gas hydrodesulfurization catalyst and preparation method and application thereof |
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Application publication date: 20160302 |