One kind hydrogenation nickel removal catalyst and preparation method thereofTechnical field
The present invention relates to one kind hydrogenation nickel removal catalyst and preparation method thereof, a kind of heavy-oil hydrogenation nickel removal is related in particular toCatalyst and preparation method thereof.
Background technology
Heavy oil includes the Atmospheric vacuum residual oil in crude oil, heavy crude, oil-sand, synthetic heavy oil product etc..Containing big in the oilThe heavy metal of amount（Such as Ni, V）, sulphur, the impurity such as nitrogen, and pitch and gum level are higher, therefore mink cell focus hydrogenation dress at presentBefore putting, hydrogenation protecting agent and Hydrodemetalation catalyst are all filled with.Such catalyst needs larger aperture and pore volume, meetsDemetalization and the needs of asphalitine conversion.Catalyst can several apertures typically in more than 15nm, general alumina support sintering temperatureAll more than 800 DEG C, the temperature that molybdenum oxide distils in the catalyst is 800 DEG C.If it is calcined at a lower temperature, it may be considered thatKneading mode carries out catalyst preparation, but catalyst pore-size distribution does not reach the needs of demetalization performance.
US4448896, US4102822 etc. expand the aperture of alumina support with the physics such as carbon black, starch expanding agent.ButPore size distribution is not concentrated, and intensity is poor.CN1209355A proposes a kind of macropore alumina supporter and preparation method thereof, higher than room temperatureUnder conditions of, peptization or curing are carried out to boehmite raw material, the material after shaping is with the compound containing ammonium ionReason, the pore volume that a diameter of 10 ~ 20nm of carrier hole is made account for the 70 ~ 85% of total pore volume, and its processing procedure is more complicated.
CN95105207, US4562059 etc. disclose a kind of method that swing method prepares hydrogenation catalyst.This method is being madeIt is relatively complicated, it is necessary to swing repeatedly during standby carrier, industrially it is difficult to realize.
US4443558 prepares catalyst using the method for kneading completely, one-step shaping, it is low to prepare cost.But catalystUsing the method for adding alkali after first acid adding, the addition of strong acid causes catalyst aperture to diminish, and pore volume reduces.US5089453 is using mixedPinching method prepares residual oil hydrocatalyst, and is used as auxiliary agent by the use of phosphorus.Because metal is the aluminum oxide of the addition in the form of metal salt in powderIn powder, easily cause Active components distribution inequality and catalyst strength is poor.
CN99113299 prepares high activity hydrotransforming catalyst for residual oil using complete kneading method, and this method is in preparation processMiddle introducing molecular sieve, improves acidity of catalyst, and the de- carbon residue performance of catalyst is further lifted.This method is prepared notIt is adapted to catalyst for demetalation, catalyst for demetalation needs relatively low acidity, and otherwise catalyst carbon deposition is too high, and inactivation is very fast.
In residual oil or mink cell focus hydroprocessing processes, the metal deposit such as vanadium and nickel in raw material is the master of catalyst inactivationReason is wanted, the demetallization per of usual Hydrodemetalation catalyst maintains 70% or so, but for metallic nickel, compares and be difficult toRemoving, general nickel removal rate will be less than vanadium removal rate.Because vanadium is with VO2+Form is present, and being combined in porphyrin compound will be less thanMetallic nickel, so as to which vanadium metal is easier to remove.Content of vanadium is higher in high-sulfur residual oil at present, existing residuum hydrogenating and metal-eliminating catalysisMetal is removed for agent, and there is no problem, and demetallization per is substantially all more than 80%, but in high nitrogen residual oil, metal nickel contentHigher, demetallization per will be less than 50% substantially.Therefore, for residuum hydrogenating and metal-eliminating catalyst at this stage, mainly considerImprove the nickel removal effect in demetalization performance.
It is main in Hydrodemetalation catalyst R＆D process at this stage to consider to hold metal problem, improve catalyst pores hold or（With）Aperture.In terms of demetallization per raising, mainly from catalyst grade with system consideration or technical process temperature raising.US4448896, US4102822, CN200410037669, CN200410071123, CN1209355A etc. are mainly from carrier systemCatalyst holds metal ability from the aspect of standby, improves catalyst stability.Currently without specifically for raising nickel removal aspect of performanceCatalyst preparation technology explanation.
The content of the invention
For it is nickelic in current part residual oil raw material the characteristics of, the present invention provide a kind of high-activity hydrogenation nickel removal catalyst andIts preparation method.
A kind of preparation method for being hydrogenated with nickel removal catalyst, comprises the following steps：（1）Weigh shaped alumina alumina supporter；（2）Match somebody with somebodyActive metal maceration extract processed, shaped alumina alumina supporter is subjected to active metal dipping, then drying process；（3）It is dried to urgeAgent carries out high temperature-low temperature roasting successively；（4）Catalyst after roasting uses gluconic acid ammonium salt solution immersion treatment, scrubbed,Final catalyst is made after drying.
The inventive method, step（1）Middle shaped alumina alumina supporter can be that commercial goods can also be entered according to prior artRow self-control.The pore structure of shaped alumina alumina supporter meets the needs of catalyst for demetalation performance.The shaped alumina alumina supporter isSpherical, bar shaped, piece shape or granulated, pore diameter range are 10 ~ 30nm, preferably 15 ~ 25nm.
The inventive method, step（2）The active component of middle active metal maceration extract is VIII and group vib metal, whereinGroup VIII metal is Co and Ni, and group vib metal is Mo and W.Group VIII metal counts weight content as 5- using oxide in catalyst15%, group vib metal counts weight content as 1-5% using oxide.Drying temperature is 100 ~ 250 DEG C, and drying time is 1 ~ 6h.
The inventive method, step（2）Also contain appropriate ethylenediamine tetra-acetic acid, ethylenediamine tetrem in activity component impregnation liquidThe mass concentration of aqueous acid is 1%-10%, preferably 3-8%.Nickel removal effect can be significantly improved by adding appropriate ethylenediamine tetra-acetic acidRate.
The inventive method, step（2）Active metal dipping included volume impregnation, incipient impregnation or spray dipping, leachingThe stain time is 1-5 hours.
The inventive method, step（3）Described in high temperature-low temperature roasting process high temperature scope be 600 DEG C ~ 450 DEG C, it is lowWarm scope is less than 450 DEG C.
The inventive method, step（3）In roasting process can also be divided into high temperature section, middle-temperature section, low-temperature zone；High-temperature temperatureFor：600 ~ 500 DEG C, medium temperature temperature is：400 ~ 350 DEG C, cryogenic temperature is：300~150℃；Every section of roasting time is at least 0.5 ~1h.It is preferred that high temperature section roasting is by the way of microwave calcining.Microwave calcining is the same as the ethylenediamine tetra-acetic acid synergy tool addedThere is optimal nickel removal effect.
The inventive method, step（4）Middle to use gluconic acid aqueous ammonium, the mass concentration of gluconic acid aqueous ammonium is5-30%, preferably 10-20%.Immersion used volume to soak, soak time 0.5-5h, and soaking temperature is 40-80 DEG C, is preferably soakedThe bubble time is 1-3h, and soaking temperature is 50-70 DEG C.The mass content for washing the ammonium ion into catalyst is less than 0.5%, is preferably0.05-0.3.The catalyst handled using gluconic acid aqueous ammonium after roasting can reduce catalyst activity component between carrierInteraction, and then improve the activity of catalyst.
A kind of catalyst prepared using above method, group VIII metal counts weight content as 5- using oxide in catalyst15%, group vib metal counts weight content as 1-5% using oxide, and pore diameter range is 15 ~ 20nm, and the active metal sulphides number of plies is 5~10。
The inventive method baking modes unlike traditional preparation methods are different, and the baking modes can reduce carrier pairThe influence of active metal, advantageously form the more active metal phase suitable for nickel removal.Catalyst prepared by the present invention, sulfideThe number of plies is more, has good active structure, is advantageous to activated centre activity raising and the formation of active phase.More sulfideThe number of plies is advantageous to abolish the steric hindrance in aromatic ring such as NI, S in asphalitine and colloid, improves desulfurization and nickel removal performance.
Embodiment
The present invention program and effect are further described with reference to embodiment, but is not limited to following examples.Using saturatingRadio mirror carries out catalyst vulcanization thing analysis.
Embodiment 1
Weigh industrial demetalization bar shaped alumina support（Sinopec catalyst Co. Fushun branch company produces, and aperture is18nm）100g；Mo-Ni-P solution is prepared, oxidation molybdenum concentration is：12.7g/100ml, oxidation nickel concentration are：3.0g/100ml ；1.5h is dried at 180 DEG C after taking 100ml solution dipping 3h；Dry after terminating, carry out roasting 0.5h at 600 DEG C first, then1h is calcined at 350 DEG C again, is finally calcined 0.5h at 250 DEG C, is used mass concentration to cross volume for 10% gluconic acid aqueous ammoniumThe catalyst after above-mentioned roasting is soaked, the bubble time is 3h, and soaking temperature is 50 DEG C.Washing quality of ammonium ion into catalyst containsAmount is less than 0.5%, and catalyst A is made after drying.
Embodiment 2
It is to prepare in Mo-Ni-P solution containing the ethylenediamine tetra-acetic acid that mass concentration is 5% with embodiment 1, catalysis is madeAgent is A1.
Embodiment 3
It is to use microwave calcining with the difference of embodiment 1, it is A2 that catalyst, which is made,.
Embodiment 4
It is to use microwave calcining with the difference of embodiment 2, it is A12 that catalyst, which is made,.
Embodiment 5
Weigh industrial catalyst for demetalation carrier（Catalyst Fushun branch company produces, aperture 15nm）100g;Prepare Mo-Ni-P solution, oxidation molybdenum concentration are：12.7g/100ml, oxidation nickel concentration are：3.0g/100ml ；Take 100ml solution to impregnate, enterRow catalyst impregnates 3h, and 5h is dried at 120 DEG C；Dry after terminating, carry out microwave calcining 2h at 500 DEG C first, then again 4001h is calcined at DEG C, is finally calcined 0.5h at 150 DEG C, uses mass concentration to cross volume immersion for 20% gluconic acid aqueous ammoniumCarrier after above-mentioned roasting, soak time 1h, soaking temperature are 70 DEG C.Washing mass content of ammonium ion into catalyst is smallIn 0.5%, obtained catalyst B is dried.
Embodiment 6
Step is with embodiment 1, except that high temperature section temperature is 550 DEG C, catalyst C is made.
Embodiment 7
Step is with embodiment 1, except that middle-temperature section temperature is 380 DEG C, catalyst D is made.
Comparative example 1
Weigh industrial catalyst for demetalation carrier（Catalyst Fushun branch company produces, aperture 18nm）100g;Prepare Mo-Ni-P solution, oxidation molybdenum concentration are：12.7g/100ml, oxidation nickel concentration are：3.0g/100ml；After taking 100ml solution dipping 3h1.5h is dried at 180 DEG C；After 450 DEG C of roasting 3h, catalyst E is made.
The catalyst prepared by embodiment and comparative example is evaluated on 200ml fixed bed hydrogenation experimental rigs, it is formerMaterial oil nature and 500h result of the tests are shown in Table 1.
Table 1
The Hydrodemetalation catalyst prepared it can be seen from the above results using this method, nickel removal performance are significantly improved.