CN103801316B - The preparation method of Hydrobon catalyst - Google Patents
The preparation method of Hydrobon catalyst Download PDFInfo
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- CN103801316B CN103801316B CN201210442651.7A CN201210442651A CN103801316B CN 103801316 B CN103801316 B CN 103801316B CN 201210442651 A CN201210442651 A CN 201210442651A CN 103801316 B CN103801316 B CN 103801316B
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Abstract
The invention discloses a kind of preparation method of Hydrobon catalyst. The preparation method of this catalyst is as follows: prepare W, Ni, Al, Mg composite oxides precursor by coprecipitation, and in precipitation process, introduce large molecule polyethylene glycol, through moulding, washing, be dried and roasting, obtain catalyst intermediate, with the specific dipping of the maceration extract containing Co, Mo, drying and roasting, obtain Hydrobon catalyst. Prepared catalyst has more granule, high surface area more, make active metal under homodisperse prerequisite, form the mixed type activated centre of Hydrogenation and hydrogenolysis Performance Match excellence, to realize the better collaborative performance of catalyst activity component hydrogenation and hydrogenolysis desulfidation, when reaching ultra-deep desulfurization, exceed consumption hydrogen, the object cutting down finished cost.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst preparation method, particularly diesel oil ultra-deep hydrodesulfuration catalyst systemPreparation Method.
Background technology
The heaviness of crude oil, the high sulfuration trend of the crude oil that in poor quality causes, in further expansion, it is reported, at present in the worldSweet crude only accounts for 17wt%, and the sour crude of sulfur-bearing > 2wt% is up to 58wt%.
SOx, NOx, CH and the soots etc. that sulphur, nitrogen and aromatic hydrocarbons etc. in diesel oil give off in combustion process can cause formingAcid rain, photochemical fog, carcinogenic substance etc., cause severe contamination to environment, residents ' health caused to serious harm, based on these various countriesGovernment more and more pays close attention to atmosphere is clean, more and more stricter to the requirement of derv fuel specification. Following clean diesel specification forwardThe future development without sulfuration, low aromatic hydrocarbons, low-density, high cetane number.
Diesel oil hydrofining raw material is straight bavin, burnt bavin mostly, urge one or both or two or more mixing in bavin etc.Oil. In recent years refinery processes the high-sulphur crude in the areas such as the Middle East in a large number, the sulfur content in perfectly straight diesel oil is increased substantially, catalysisThe rising that refining residual oil, wax oil ratio are mixed in cracking makes the large molecular sulfur compound of some higher boilings, the nitride in catalytic diesel oil and encircles moreThe gatherings such as aromatic hydrocarbons, the reactivity worth of actual diesel oil hydrofining raw material further reduces, and difficulty of processing increases greatly.
Main three class sulfide in diesel oil distillate are alkylthrophene, alkylbenzene bithiophene and methyldibenzothiophene. ItsThe complexity of desulfurization is thiophene < benzothiophene < dibenzothiophenes, the 4-MDBT of β substd and 4,6-DMDBT hydrogenationDesulphurization reaction activity is minimum. Much research shows, 4-MDBT and 4, the 6-DMDBT hydrodesulfurization in different catalysts is mainly logicalCrossing hydrogenation path realizes. Hydrogenolysis desulfurization and the hydrogenation of DBT on the different activities such as Co-Mo, Ni-W metal component catalyst is de-The ratio of sulphur has bigger difference.
While producing the diesel oil of sulfur-bearing 350 μ g/g, the sulfide that all reactivities are high and the dibenzothiophenes of unsubstitutedCan be removed. But produce sulfur-bearing 50 μ g/g or 10 μ g/g and following clean diesel, reactivity is poor, molecule is large, getDai Ji must remove at the dibenzothiophenes class sulfide of 4 or 4,6.
Large molecule basic nitrogen compound, polycyclic aromatic hydrocarbon etc. in feedstock oil are with 4, and 6-DMDBT class sulfide structure has similarProperty, reaction mechanism has similitude, is all that the first hydrogenation of aromatic ring is saturated, then carries out next step reaction. The compound meeting of these typesInteract with catalyst surface in a similar fashion, competitive Adsorption, blocks its hydrogenation reaction mutually. Especially in feedstock oilLarge molecule basic nitrogen compound, more much easier in the absorption of catalyst surface than sulfur-containing compound and aromatic hydrocarbons, its existence suppresses to addHydrogen desulphurization reaction, particularly impact be difficult to remove 4, the hydrodesulfurization of 6-DMDBT.
The Hydrogenation of catalyst excellence, can provide more hydrogenation sites, faster in ultra-deep desulfurization process,More nitride, the polycyclic aromatic hydrocarbons etc. of transforming, reduce it to 4-MDBT and 4, the impact of 6-DMDBT class sulfide hydrodesulfurization,Can easierly realize the production object of low-sulfur, low aromatic hydrocarbons, low-density, high cetane number clean diesel.
It is generally acknowledged, the substd that the S atom of 4-MDBT and 4,6-DMDBT is contiguous, to S atom at catalyst tableThe end of face connects absorption and has obstruction, causes its reactivity low, and desulfurization major part is by the absorption that lies low of aromatic ring, and hydrogenation path is comeRealize. And if catalyst can provide activated centre, more seamed edge position, just can increase 4-MDBT and 4,6-DMDBT end evenThe ratio of absorption, rises its ratio of passing through hydrogenolysis desulfurization, improves its reactivity, exceeds again consumption in processHydrogen.
CN101172261A discloses the standby W-Mo-Ni hydrogenation catalyst of a kind of body phase legal system, and this catalyst adopts activeThe saline mixed solution of metal Ni, W component and auxiliary agent and sodium aluminate solution co-precipitation generate NixWyOz composite oxidesPrecursor, then with MoO3Making beating mixing, filtration, moulding, activation are final catalyst, and supporting of active metal is unrestricted,More active metal total amounts can be provided. Though the W-Mo-Ni series hydrocatalyst of high metal has good Hydrogenation, Ke YidaTo the object of ultra-deep desulfurization, but in diesel hydrogenation for removal sulphur process, the sulfide that reactivity is high and the hexichol of unsubstitutedPart in bithiophene class sulfide also can realize desulfurization by hydrogenation path, and too much consumption hydrogen increases processing cost,Too high total metal content has also increased the cost of investment of catalyst simultaneously.
In the coprecipitation process of current disclosed most of bulk phase catalyst at the beginning of activity forms mutually to particle sizeAll do not do any restriction, if just formed large crystal grain in this step, in each step so afterwards, be difficult to makeFinal catalyst obtains high specific area, even if metal has obtained being uniformly distributed, also has part and is wrapped in bulky grainMetal can not play one's part to the full, and becomes invalid component, reduces the utilization rate of metal.
CN101089132A discloses the Hydrobon catalyst of tetra-kinds of active metal components of a kind of W-Mo-Ni-Co, though adoptBy the W-Mo-Ni-Co-P active component of special ratios, make hydrogenolysis desulfurization performance and the good hydrogenation of W-Ni type that Co-Mo type is goodDesulfurization performance has obtained comprehensive utilization, but supporting of its active component is all to realize by saturated total immersion technology, active metalLoading is restricted, and more active metal total amount cannot be provided; Active component W-Mo-Ni-Co-P is at primary drying simultaneouslyThe condition that in roasting process, the active phase front of uncontrollable hydrogenation activity phase and hydrogenolysis body forms, thus make hydrogenation and the hydrogen of catalystSeparate desulphurizing activated can not well synergy. Though add the surface nature of phosphorus energy modulation carrier in maceration extract, improve carrierAnd the interaction between active metal, but in dipping process, the effect of phosphorus and carrier surface group can weaken active componentAbsorption on carrier, easily reunites active component, reduces the decentralization of active component in catalyst, thereby reduces catalysisAgent activity.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of Hydrobon catalyst. The method canWith under the homodisperse prerequisite of active metal, form the mixed type activated centre of Hydrogenation and hydrogenolysis Performance Match excellence,Have more granule, tuftlet group more simultaneously, larger surface area is provided, more seamed edge position, to realize catalyst activity componentHydrogenation and hydrogenolysis desulfidation be collaborative performance better, exceeds consumption hydrogen when reaching ultra-deep desulfurization, reduces processingThe object of cost.
The preparation method of Hydrobon catalyst of the present invention, comprising: (1) by coprecipitation prepare W, Ni, Al, Mg are compoundOxide precursor, (2), by W, Ni, Al, the moulding of Mg composite oxides precursor, washing, is dried and roasting, obtains in catalystMesosome, (3) preparation is containing the maceration extract of Co, Mo, in the catalyst that the maceration extract impregnation steps (2) that (4) obtain by step (3) obtainsMesosome, drying and roasting, obtain Hydrobon catalyst; Wherein step (1) process is as follows: by the salt of tungstenic, nickel, aluminium, magnesiumSolution carries out with alkaline precipitating agent and flows plastic and react, and controlling the pH value of reaction system is 8.0 ~ 10.5, and preferably 8.0 ~ 9.5,Then aging, filter, dry, obtain W, Ni, Al, Mg composite oxides precursor, wherein before plastic and/or in plastic processAdding molecular weight is that 200 ~ 10000(is preferably 1000 ~ 10000) polyethylene glycol, make W, Ni, Al, Mg composite oxides predecessorIn thing, the weight content of polyethylene glycol is 1% ~ 10%, is preferably 1% ~ 5%; Step (3) process is as follows: by molybdenum source, cobalt source, organic carboxylicAcid, ammonia and water are mixed with in the maceration extract containing Co, Mo, and wherein the mol ratio of organic carboxyl acid used and Co is 0.5 ~ 1.2, maceration extractThe concentration of middle ammonia is 10wt% ~ 25wt%.
In the inventive method, the temperature of step (1) plastic reaction is 30 ~ 80 DEG C, plastic reaction time 0.5 ~ 2.0h. AlkalescencePrecipitating reagent can be inorganic or organic alkaline water soluble compound, as NaOH, sodium carbonate, sodium acid carbonate, ammoniacal liquor, ureaDeng in one or more, be preferably ammoniacal liquor, the concentration of ammoniacal liquor can be any feasible ratio. Filtration temperature after aging is bestTemperature below polyethylene glycol freezing point is filtered, and the polyethylene glycol adding is retained in filter cake, to increase the bonding of materialPerformance, greasy property and plasticity, make it easier moulding, extrude.
In the inventive method, step (3) organic carboxyl acid can be carboxylic acid (citric acid, tartaric acid), amino acid (ammonia three secondAcid, ethylenediamine tetra-acetic acid) in one or more, optimization citric acid. In every 100 milliliters of maceration extracts, contain MoO317 ~ 33g, containsCoO3~7g。
The present invention contains two or more hydroxyls containing also adding as required one or more in the maceration extract of Co, MoThe polyalcohol of base, such as one or more in sweet mellow wine, ethylene glycol, glycerine, the mol ratio of polyalcohol and Co is 0.1 ~0.5。
In a step in step (1) or a few step, add required catalyst promoter and/or add component. Auxiliary agent generally comprisesP, F, Ti, Si, B, Zr etc. one or more. Add component and be generally refractory porous mass and precursor thereof, as clay, amorphousSial, titanium oxide, zirconia, molecular sieve etc. Add the method for auxiliary agent and interpolation component to adopt this area conventional method. Above-mentioned helpingAgent and/or the weight content of interpolation component in catalyst are, below 50%, to be preferably below 40%. A step in step (1) orIn several steps, preferably add auxiliary agent P and/or Si, make in Hydrobon catalyst, P is with P2O5The weight content of meter is 0.1% ~ 8.0%,Si is with SiO2The weight content of meter is 0.7% ~ 8.0%.
The preparation method of Hydrobon catalyst of the present invention, step (2) can adopt conventional forming method, such as being squeezed intoType method etc. In forming process, can add appropriate shaping assistant, such as adhesive, extrusion aid etc. Described washing can be adoptedWith water purification washing and/or ethanolic solution washing, wash temperature is generally 50 DEG C ~ 70 DEG C, preferably can make most of polyethylene glycol moltenSolution, in cleaning solution, is also removed polyethylene glycol in washing away impurity. Described drying condition is as follows: dry at 50 ~ 120 DEG C2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 DEG C of roasting 3 ~ 6h.
The preparation method of Hydrobon catalyst of the present invention, step (4) dipping used can adopt saturated infusion process. DippingAfter, drying condition is as follows: at 60 ~ 150 DEG C of dry 2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 DEG C of roasting 3 ~ 6h.
In the preparation method of Hydrobon catalyst of the present invention, the consumption of each raw material is determined as required, W, Ni, Al, MgIn composite oxides, the mol ratio of W and Ni is 0.29 ~ 2.58, is preferably 0.44 ~ 1.84, Al2O3Account for W, Ni, Al, Mg composite oxygenCompound weight is 2.0% ~ 60.0%, be preferably 20.0% ~ 60.0%, MgO account for 0.7% of W, Ni, Al, Mg composite oxides weight ~8.0%, be preferably 1.0% ~ 7.0%; In gained catalyst, the mol ratio of Mo and Co is 0.26 ~ 6.51, is preferably 0.83 ~ 4.69, WWith the mol ratio of Mo be 0.45 ~ 4.97, be preferably 0.7 ~ 3.1.
The character of Hydrobon catalyst of the present invention is as follows: pore volume is 0.15 ~ 0.65ml/g, and specific area is 130 ~380m2/g。
In bulk phase catalyst, the fit system of active metal is very large to the performance impact of catalyst. The inventive method is logicalAfter first adopting coprecipitation to prepare W, Ni, Al, Mg composite oxides precursor, then catalyst intermediate is made in moulding, thenUtilize specific dipping method supported active metal Co and Mo, be conducive to like this form the active phase of W-Ni and the active phase of Co-Mo. AdoptPrepare in W, Ni, Al, Mg composite oxides precursor process and add large molecule polyethylene glycol by coprecipitation, make W, Ni, Al, MgAgglomeration at the beginning of composite oxides precursor particle forms is controlled, form there is more granule, tuftlet group, more moreSeamed edge position, more W, the Ni composite oxides of high surface area, the hydrophily of polyethylene glycol also can be impelled the hydrogen in plastic process in additionOxide colloid adsorbs more water or hydroxyl, makes it to form porous or unsaturated in drying and roasting process afterwards(CUB) anion and cation vacancy, improve suction dehydrogenation capacity and the speed of catalyst, introduces auxiliary agent Mg simultaneously, is conducive toForm with Ni, W metal synergy the compound that hydrogen storage capability is higher, further improve suction dehydrogenation capacity and the speed of catalystDegree, the Hydrogenation of raising catalyst. Preparation is containing organic acid Co, Mo ammoniacal liquor maceration extract, and wherein maceration extract is not only stable, andActive metal wherein and organic acid form chelate, are conducive to Co, Mo and better coordinate and weaken active metal Co, Mo and urgeInteraction between agent intermediate, is more dispersed in catalyst intermediate, promotes the formation of the active phase of Co-Mo, outstandingIt forms more, that granularity is less, active higher II type Co-Mo activity phase, has improved the hydrogenolysis performance of catalyst. MadeThe matched well of the active phase of standby catalyst W-Ni and the active phase of Co-Mo, reaches the Hydrogenation of catalyst and hydrogenolysis performanceCoordinate well, and catalyst has more granule, more seamed edges position, more high surface area and porous, increase substantiallyThe combination property of catalyst.
Detailed description of the invention
The invention provides the preparation method of catalyst, a kind of concrete preparation process is as follows:
(1) prepare W, Ni, Al, Mg composite oxides precursor by coprecipitation
Salting liquid according to the preparation of catalytic component content proportioning containing W, Ni, Al, Mg can be nickelous sulfate, nitre containing nickel saltOne or more in acid nickel, nickel chloride, basic nickel carbonate, nickel oxalate etc., tungsten salt can be in ammonium metatungstate, sodium tungstate etc.One or more, containing aluminium salt can be one or more in aluminium chloride, aluminum nitrate, aluminum sulfate etc., containing magnesium salts can be chlorineChange one or more in the solubility magnesium salts such as magnesium, magnesium nitrate, auxiliary agent Si, P, Ti, B, Zr etc. can need to be by joining according to catalystThan introducing in mixed liquor, preferably Si and/or P, silicon source can be one or more in waterglass, Ludox etc., phosphorus source canTo be one or more in phosphoric acid, phosphorous acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) etc.
In retort, add appropriate water purification, add appropriate large molecule polyethylene glycol to be under agitation heated to plastic temperature,Molecular weight polyethylene glycol is 200 ~ 10000, is preferably 1000 ~ 10000.
By adding in retort and carry out plastic containing salting liquid and alkaline precipitating agent the stream of W, Ni, Al, Mg, then aging,Cooling, filter, dry, obtain W, Ni composite oxides precursor. Wherein, plastic temperature is 30 ~ 80 DEG C, controls retort entoplasmThe pH of liquid is 8.0 ~ 10.5, preferably 8.0 ~ 9.5, and the reaction time is controlled at 0.5 ~ 2.0h; Alkaline precipitating agent can be inorganic orOrganically alkaline water soluble compound, as NaOH, sodium carbonate, sodium acid carbonate, ammoniacal liquor, urea etc., is preferably ammoniacal liquor, ammoniacal liquorConcentration can be any feasible ratio. Wherein slurries aging after, be cooled to the temperature below large molecule polyethylene glycol freezing pointSpend filter, the cooling any mode that can make the cooling of plastic slurries that adopts.
(2) preparation of catalyst intermediate
Add shaping assistant to carry out moulding W, Ni composite oxides precursor, washing, dry and roasting, obtains catalystIntermediate, wherein washing is that the ethanolic solution of formation wet bar 3wt% ~ 5wt% is embathed, the temperature of embathing will make large the dividing of addingSub-polyethylene glycol is dissolved in cleaning solution, to remove polyethylene glycol and impurity. Wherein drying condition be 50 ~ 120 DEG C dry 2 ~8h, roasting condition is at 450 ~ 600 DEG C of roasting 3 ~ 6h. The shape of catalyst can be made sheet, spherical, cylindrical bars as requiredAnd irregular bar (as clover, bunge bedstraw herb), preferably cylindrical bars and irregular bar.
(3) preparation is containing the maceration extract of Co, Mo
Before maceration extract preparation, will first measure the catalyst intermediate water absorption rate of (2) preparing, the concentration of maceration extract and consumption are wantedDetermine according to the water absorption rate of catalyst composition requirement and catalyst intermediate.
Take a certain amount of organic carboxyl acid, also can add polyalcohol, water dissolves, and adds He Mu source, a certain amount of cobalt sourceAnd ammoniacal liquor. In maceration extract, the concentration of ammonia is 10wt% ~ 25wt%. Wherein every 100 milliliters contain MoO317 ~ 33g, containing CoO3 ~ 7g, hasThe mol ratio of machine carboxylic acid and Co is 0.5 ~ 1.2, and the mol ratio of polyalcohol and Co is 0.1 ~ 0.5. The cobalt source choosing providing in maceration extractOne or more in basic cobaltous carbonate, cobalt carbonate, cobalt nitrate etc., the molybdenum source providing is selected from ammonium molybdate, molybdic acid, molybdenum oxide etc.In one or more.
(4) preparation of Hydrobon catalyst
The catalyst intermediate that the maceration extract impregnation steps (2) obtaining by step (3) obtains, drying and roasting, obtainHydrobon catalyst; Wherein dipping adopts saturated infusion process. Drying condition is as follows: at 60 ~ 150 DEG C of dry 2 ~ 8h; Roasting barPart is as follows: at 450 ~ 600 DEG C of roasting 3 ~ 6h.
Further illustrate the solution of the present invention and effect below by specific embodiment. Wt% is mass fraction.
Embodiment 1
In a container A, add 500ml water purification, by 47g ammonium metatungstate, 34g nickel chloride, 9.5g magnesium chloride, 2.5g phosphorusAcid dihydride ammonium, adds wherein and stirs.
In a container B, add 300ml water purification, 47g aluminium chloride is added to wherein stirring and dissolving.
In a container C, compound concentration is with SiO2Rare water glass solution 100ml of (weight) meter 2.2wt%.
After during liquor alumini chloridi in container B is added to container A under stirring, then by the rare waterglass in container CSolution splashes in container A under stirring, and overall solution volume is adjusted to 1000ml with water purification, obtain containing metal W, Ni andAl2O3、MgO、P2O5、SiO2The salting liquid of precursor.
In retort, add 500ml water purification, the polyethylene glycol that 2g molecular weight is 6000 stirs and is warming up to 50 DEG C.
By the ammonia spirit of the salting liquid preparing above and 15wt% and flow plastic, controlling plastic temperature is 50 DEG C, slurries pHBe 8.2 ± 0.2, complete plastic in 1h, then by aging slurries 3 hours, aging end is filtered after slurries are cooled to room temperature,The filter cake obtaining is dry under 70 DEG C of conditions in baking oven, through rolling extruded moulding, with Φ 2.0 clover orifice plate extrusions, moulding barIn the water-bath of 60 DEG C of left and right, embathe with the ethanolic solution of 4wt%, wet bar in baking oven under 110 DEG C of conditions dry 8 hours, thenObtain the catalyst precarsor bar containing active metal W, Ni at 500 DEG C of calcination activation 3h.
By 24g citric acid, 19g basic cobaltous carbonate and 78g ammonium molybdate, being mixed with 300ml ammonia concn is soaking of 18wt%Stain liquid, airtight preservation is stand-by.
Get containing the catalyst precarsor bar of W, Ni and be placed in converter, use the maceration extract 75ml preparing to spray above, sprayedCheng Hou, takes out material in baking oven and is dried 8 hours under 110 DEG C of conditions, and in high temperature furnace, under 500 DEG C of conditions, calcination activation 3 is littleTime, obtain catalyst A of the present invention.
Embodiment 2
The whole preparation process of catalyst is with embodiment 1, wherein in catalyst precarsor bar preparation process, in retort water purificationAdd the polyethylene glycol that 2g molecular weight is 4000, salting liquid preparation, adds ammonium metatungstate 40g, nickel chloride 28g, and aluminium chloride 85g,Magnesium chloride 7.3g, does not add ammonium dihydrogen phosphate (ADP) and rare water glass solution, and maceration extract preparation adds basic cobaltous carbonate 19g, ammonium molybdate77g, citric acid 22g, obtains catalyst B of the present invention.
Embodiment 3
The whole preparation process of catalyst is with embodiment 1, and wherein catalyst precarsor bar preparation process is added in retort water purificationAdd 1g molecular weight and be 6000 polyethylene glycol, salting liquid preparation, adds ammonium metatungstate 36g, nickel chloride 26g, aluminium chloride 97g, chlorineChange magnesium 7.3g, ammonium dihydrogen phosphate (ADP) 2.5g, does not add rare water glass solution, and maceration extract preparation adds basic cobaltous carbonate 19g, ammonium molybdate77g, sweet mellow wine 15g, citric acid 22g, obtains catalyst C of the present invention.
Embodiment 4
The whole preparation process of catalyst is with embodiment 1, wherein in catalyst precarsor bar preparation process in retort water purificationAdd the polyethylene glycol that 3g molecular weight is 6000, salting liquid preparation adds ammonium metatungstate 32g, nickel chloride 23g, and aluminium chloride 105g,Magnesium chloride 7.2g, containing SiO2Rare water glass solution 100ml of (weight) 2.2%, does not add ammonium dihydrogen phosphate (ADP). Maceration extract preparation adds alkaliFormula cobalt carbonate 19g, ammonium molybdate 75g, citric acid 24g, obtains catalyst D of the present invention.
Embodiment 5
The whole preparation process of catalyst is with embodiment 1, wherein in catalyst precarsor bar preparation process in retort water purificationAdd the polyethylene glycol that 2g molecular weight is 6000, salting liquid preparation adds ammonium metatungstate 41g, nickel chloride 25g, aluminium chloride 76g, chlorineChange magnesium 8.5g, add ammonium dihydrogen phosphate (ADP) 2.5g, containing SiO2Rare water glass solution 100ml of (weight) 2.2%. Maceration extract preparation addsBasic cobaltous carbonate 22g, ammonium molybdate 76g, citric acid amount 26, obtains catalyst E of the present invention.
Embodiment 6
The whole preparation process of catalyst is with embodiment 1, wherein in catalyst precarsor bar preparation process in retort water purificationAdd the polyethylene glycol that 2g molecular weight is 6000, salting liquid preparation adds ammonium metatungstate 46g, nickel chloride 27g, and aluminium chloride 64g,Magnesium chloride 7.3g, adds ammonium dihydrogen phosphate (ADP) 2.5g, containing SiO2Rare water glass solution 100ml of (weight) 2.2%. Maceration extract preparation addsEnter basic cobaltous carbonate 25g, ammonium molybdate 77g, citric acid 30g, obtains catalyst F of the present invention.
Comparative example 1
In a container A, add 500ml water purification, 34g nickel chloride, 2.5g ammonium dihydrogen phosphate (ADP) stirring and dissolving, then add 46gAmmonium metatungstate stirring and dissolving, under agitation splashes into containing SiO2Rare water glass solution 32ml of (weight) 7%, is mixed with acid work moltenLiquid 1.
In a container B, add 300ml water purification, then add aluminium chloride 72g stirring and dissolving to be mixed with acid work moltenLiquid 2.
In a plastic cans, add 200ml water purification, temperature rises to 50 DEG C, stir in the situation that by solution 2 and 18wt%Ammoniacal liquor stream add plastic in retort, and plastic temperature 50 C completes plastic in 0.5h, and plastic slurry pH is controlled at9.0 ± 0.2. Then solution 1 is added in plastic cans, then add 18% ammoniacal liquor, regulate slurry pH value 8.5, after cemented into bundlesAging 1 hour, then filter, filter cake joins the container for stirring that 600ml water purification is housed, then adds the making beating of 16.5g molybdenum oxideEvenly, filter, filter cake 80 DEG C dry 5 hours, then extruded moulding, with water purification washing 3 times, wet bar is dry 5 little at 120 DEG CTime, 500 DEG C of calcination activations 4 hours, make catalyst G.
The character of catalyst of the present invention and comparative example catalyst is as table 1.
Table 1 the present invention and comparative example catalyst property
| Catalyst numbering | A | B | C | D | E | F | G |
| Catalyst composition | |||||||
| WO3,wt% | 38.3 | 31.8 | 29.0 | 25.2 | 33.0 | 37.0 | 36.9 |
| MoO3,wt% | 15.4 | 15.0 | 15.0 | 14.9 | 15.0 | 15.0 | 15.1 |
| NiO,wt% | 18.6 | 15.3 | 14.0 | 12.1 | 13.7 | 14.1 | 18.1 |
| CoO,wt% | 3.1 | 3.0 | 3.0 | 3.1 | 3.5 | 4.0 | 0 |
| MgO, wt% | 3.9 | 3.0 | 3.O | 3.0 | 3.5 | 3.0 | 0 |
| SiO2,wt% | 2.0 | 0 | 0 | 2.1 | 2.1 | 2.0 | 2.0 |
| P2O5,wt% | 1.5 | 0 | 1.5 | 0 | 1.5 | 1.5 | 1.5 |
| Al2O3,wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Catalyst property | |||||||
| Specific area, m2/g | 232 | 237 | 231 | 253 | 256 | 249 | 185 |
| Pore volume, mL/g | 0.278 | 0.268 | 0.292 | 0.279 | 0.301 | 0.288 | 0.212 |
| Intensity, N/mm | 22.3 | 22.5 | 21.8 | 23.4 | 22.3 | 23.1 | 18.2 |
Embodiment 7
Be 6.4MPa to catalyst E of the present invention, F and comparative example catalyst G in hydrogen dividing potential drop, reaction temperature is 360 DEG C, volumeAir speed is 2.0h-1, hydrogen to oil volume ratio is under 500 conditions, on 200ml small hydrogenation device, taking Maoming mixed diesel as raw materialCarry out hydrodesulfurization reaction performance evaluation. Feedstock oil main character is as table 2, and evaluating catalyst result is as table 3.
Table 2 feedstock oil main character
| Project | Analysis result |
| Density (20 DEG C), g/cm3 | 0.8615 |
| Boiling range scope, DEG C | 178-370 |
| S，μg/g | 12213 |
| N，μg/g | 295 |
| Cetane number | 45.8 |
Table 3 catalyst hydrogenation desulfurization performance evaluation result
| Catalyst | E | F | G |
| Generate oil density (20 DEG C), g/cm3 | 0.8328 | 0.8322 | 0.8340 |
| Boiling range scope, DEG C | 165-369 | 164-368 | 163-368 |
| S，μg/g | 21 | 12 | 28 |
| N，μg/g | 1.3 | 1.0 | 2.1 |
| Cetane number | 52.3 | 53.0 | 52.3 |
The data of table 3 show, catalyst of the present invention has excellent hydrodesulfurization and hydrodenitrogeneration ability, in suitable reductionAfter tenor, still there is higher desulfurization, denitrification activity than reference agent, can realize low-sulfur, low aromatic hydrocarbons, low-density, Gao ShiliuThe production object of alkane value clean diesel.
Embodiment 8
To contain DBT, 4-MDBT, 4, the toluene solution that tri-kinds of model compound concentration of 6-DMDBT are 2wt% is former respectivelyMaterial, is 2.0MPa at hydrogen pressure, and hydrogen-oil ratio is 200:1, air speed 3h-1, under 320 DEG C of conditions of reaction temperature, on micro-reaction equipmentCatalyst of the present invention and comparative example catalyst are carried out to hydrogenation and the evaluation of hydrogenolysis desulfurization performance.
Reaction is carried out on micro-reaction equipment, and product quantitative analysis is passed through Varian3800 type capillary with qualificationGas chromatograph and FinniganSSQ710X type level Four bar mass spectrograph are used in conjunction to realize.
If with r representative model compound hydrogenation and hydrogenolysis speed ratio, r DBT during taking DBT as model compoundThe ratio value representation of cyclohexyl benzene and biphenyl content in product; R cyclohexyl benzene class and biphenyl during taking 4-MDBT as model compoundThe ratio of class content represents; R 1-methyl-3-(3-methylcyclohexyl benzene while being model compound with 4,6-DMDBT) with 3,The ratio of 3-dimethyl diphenyl content represents, the results are shown in Table 4.
Table 4 the present invention and comparative example catalyst hydrogenation and hydrogenolysis represent product ratio
| Catalyst numbering | E | F | G |
| r(DBT ) | 0.28 | 0.29 | 0.98 |
| r (4-MDBT) | 1.48 | 1.45 | 2.7 |
| r(4,6-DMDBT) | 4.60 | 4.62 | 5.0 |
The data of table 4 show, the hydrogenolysis performance of catalyst of the present invention is better than comparative example catalyst, especially to reactivityHigher DBT class sulfide, can increase substantially its hydrogenolysis desulfurization performance.
DBT class sulfide is as one of main component of diesel oil hydrofining raw material, most of by hydrogenolysis path implementDesulfurization can reduce hydrogen consumption by a relatively large margin, reduces and 4 simultaneously, and the competitive Adsorption of 6-DMDBT class sulfide to hydrogenation sites, fromAnd be 4,6-DMDBT class sulfide provides more hydrogenation reaction activated centre, increases its conversion ratio.
The aggregation of data of table 1, table 3 and table 4 shows, the high metals content catalysts of the present invention is suitably reducing total metal contentIn situation, still there is higher activity, can, in diesel oil hydrogenation ultra-deep desulfurization, not consume hydrogen excessively, reduce processingCost.
Claims (18)
1. a preparation method for Hydrobon catalyst, comprising: (1) prepares W, Ni, Al, Mg combined oxidation by coprecipitationThing precursor, (2), by W, Ni, Al, the moulding of Mg composite oxides precursor, washing, is dried and roasting, obtains in the middle of catalystBody, (3) preparation is containing the maceration extract of Co, Mo, in the middle of the catalyst that the maceration extract impregnation steps (2) that (4) obtain by step (3) obtainsBody, drying and roasting, obtain Hydrobon catalyst; Wherein step (1) process is as follows: by molten the salt of tungstenic, nickel, aluminium, magnesiumLiquid carries out with alkaline precipitating agent and flows plastic and react, and the pH value of controlling reaction system is 8.0 ~ 10.5, then aging, filters, dryDry, obtain W, Ni, Al, Mg composite oxides precursor, wherein before plastic and/or in plastic process, add molecular weight be 200 ~10000 polyethylene glycol, making the weight content of polyethylene glycol in W, Ni, Al, Mg composite oxides precursor is 1% ~ 10%; Step(3) process is as follows: molybdenum source, cobalt source, organic carboxyl acid, ammonia and water are mixed with to the maceration extract containing Co, Mo, wherein organic carboxyl acid usedWith the mol ratio of Co be 0.5 ~ 1.2, in maceration extract, the concentration of ammonia is 10wt% ~ 25wt%.
2. it is characterized in that in accordance with the method for claim 1: the molecular weight of polyethylene glycol is 1000 ~ 10000.
3. according to the method described in claim 1 or 2, it is characterized in that: poly-second in W, Ni, Al, Mg composite oxides precursorThe weight content of glycol is 1% ~ 5%.
4. the pH value that in accordance with the method for claim 1, it is characterized in that step (1) plastic reaction system is 8.0 ~ 9.5.
5. in accordance with the method for claim 1, it is characterized in that step (1) alkaline precipitating agent is NaOH, sodium carbonate, carbonIn acid hydrogen sodium, ammoniacal liquor, urea one or more.
6. in accordance with the method for claim 1, it is characterized in that step (1) alkaline precipitating agent is ammoniacal liquor.
7. in accordance with the method for claim 1, it is characterized in that the filtration temperature of step (1) after aging solidifies at polyethylene glycolThe following temperature of point is filtered.
8. in accordance with the method for claim 1, it is characterized in that washing described in step (2) adopt water purification washing and/orEthanolic solution washing, wash temperature is 50 DEG C ~ 70 DEG C, and polyethylene glycol is dissolved in cleaning solution.
9. in accordance with the method for claim 1, it is characterized in that containing in the maceration extract of Co, Mo in step (3) every 100 millilitersIn maceration extract, contain Mo with MoO3Meter 17 ~ 33g, contains Co in CoO 3 ~ 7g.
10. in accordance with the method for claim 1, it is characterized in that in step (3), organic carboxyl acid used is citric acid, winestoneOne or more in acid, nitrilotriacetic acid, ethylenediamine tetra-acetic acid.
11. in accordance with the method for claim 1, it is characterized in that step (3) is containing adding polyalcohol in the maceration extract of Co, Mo,Polyalcohol is one or more in sweet mellow wine, ethylene glycol, glycerine, and the mol ratio of polyalcohol and Co is 0.1 ~ 0.5.
12. in accordance with the method for claim 1, it is characterized in that the described drying condition of step (2) is as follows: at 50 ~ 120 DEG CDry 2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 DEG C of roasting 3 ~ 6h.
13. in accordance with the method for claim 1, it is characterized in that step (4) dipping used adopts saturated infusion process.
14. in accordance with the method for claim 1, it is characterized in that the drying condition of step (4) is as follows: dry at 60 ~ 150 DEG C2 ~ 8h; Roasting condition is as follows: at 450 ~ 600 DEG C of roasting 3 ~ 6h.
15. in accordance with the method for claim 1, it is characterized in that described W, Ni, Al, Mg composite oxides, W and Ni moleThan being 0.29 ~ 2.58, Al2O3Account for W, Ni, Al, Mg composite oxides weight is that 2.0% ~ 60.0%, MgO accounts for W, Ni, Al, Mg are compound0.7% ~ 8.0% of oxide weight; In gained catalyst, the mol ratio of Mo and Co is that the mol ratio of 0.26 ~ 6.51, W and Mo is0.45~4.97。
16. in accordance with the method for claim 1, it is characterized in that described W, Ni, Al, Mg composite oxides, W and Ni moleThan being 0.44 ~ 1.84, Al2O3Account for W, Ni, Al, Mg composite oxides weight is that 20.0% ~ 60.0%, MgO accounts for W, Ni, Al, Mg are compound1.0% ~ 7.0% of oxide weight; In gained catalyst, the mol ratio of Mo and Co is that the mol ratio of 0.83 ~ 4.69, W and Mo is0.7~3.1。
17. in accordance with the method for claim 1, it is characterized in that adding required catalyst promoter and/or adding in step (1)Add component, auxiliary agent comprises one or more in P, F, Ti, Si, B, Zr, interpolation component be clay, amorphous aluminum silicide, titanium oxide,One or more in zirconia, molecular sieve.
18. in accordance with the method for claim 1, it is characterized in that adding auxiliary agent Si and/or P in step (1), makes hydrodesulfurizationIn catalyst, P is with P2O5The weight content of meter is that 0.1% ~ 8.0%, Si is with SiO2The weight content of meter is 0.7% ~ 8.0%.
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| CN108786869B (en) * | 2017-08-15 | 2021-03-09 | 中国石油天然气股份有限公司 | Diesel oil deep hydrogenation catalyst, preparation method and application thereof |
| CN109894118B (en) * | 2017-12-07 | 2021-09-28 | 中国科学院大连化学物理研究所 | Nickel-based hydrogenation catalyst and application thereof |
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