CN104549390B

CN104549390B - Hydrogenation-denickelefication catalyst and preparation method thereof

Info

Publication number: CN104549390B
Application number: CN201310499275.XA
Authority: CN
Inventors: 隋宝宽; 刘文洁; 王刚; 蒋立敬; 安昇
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2013-10-23
Filing date: 2013-10-23
Publication date: 2017-02-08
Anticipated expiration: 2033-10-23
Also published as: CN104549390A

Abstract

The invention discloses a preparation method of a hydrogenation-denickelefication catalyst. The method comprises the following steps: (1) weighing and taking a molded alumina carrier; (2) preparing an active metallic impregnation liquid, performing active metallic impregnation on the molded alumina carrier, and drying the impregnated molded alumina carrier; (3) calcinating the dried catalyst under high temperature and lower temperature successively so as to obtain the hydrogenation-denickelefication catalyst. Aiming at the characteristic of high nickel in the raw materials of current partial residual oil, the catalyst disclosed by the invention has efficient performance of denickelefication.

Description

A kind of hydrogenation nickel removal catalyst and preparation method thereof

Technical field

The present invention relates to a kind of hydrogenation nickel removal catalyst and preparation method thereof, relate in particular to a kind of heavy-oil hydrogenation nickel removal Catalyst and preparation method thereof.

Background technology

Heavy oil includes Atmospheric vacuum residual oil in crude oil, heavy crude, oil-sand, synthetic heavy oil product etc..Contain big in this oil The heavy metal of amount（As Ni, V）, sulphur, the impurity such as nitrogen, and pitch and gum level higher, therefore mink cell focus hydrogenation dress at present Before putting, all it is filled with hydrogenation protecting agent and Hydrodemetalation catalyst.Such catalyst needs larger aperture and pore volume, meets Demetalization and the needs of asphalitine conversion.Catalyst can several apertures typically in more than 15nm, general alumina support sintering temperature All more than 800 DEG C, the temperature that molybdenum oxide distils in the catalyst is 800 DEG C.If roasting at a lower temperature it may be considered that Kneading 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 expanding agent such as carbon black, starch.But Pore size distribution is not concentrated, and intensity is poor.CN1209355A proposes a kind of macropore alumina supporter and preparation method thereof, higher than room temperature Under conditions of, peptization or curing are carried out to boehmite raw material, the material after shaping is with the compound containing ammonium ion Reason, the pore volume of a diameter of 10 ~ 20nm of prepared carrier hole accounts 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.The method is in system During standby carrier, need to swing repeatedly, relatively complicated, industrially it is difficult to realize.

US4443558 prepares catalyst, one-step shaping using the method for kneading completely, and preparation cost is low.But catalyst Method using adding alkali after first acid adding, the addition of strong acid leads to catalyst aperture to diminish, and pore volume reduces.US5089453 is using mixed Pinching method prepares residual oil hydrocatalyst, and with phosphorus as auxiliary agent.Because metal is the aluminum oxide being added in the form of metal salt in powder In 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 the method is in preparation process Middle introducing molecular sieve, improves acidity of catalyst, and the de- carbon residue performance of catalyst is further lifted.The method is prepared not Suitable 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 in raw material and nickel is the master of catalyst inactivation Want reason, the demetallization per of usual Hydrodemetalation catalyst maintains 70% about, but for metallic nickel, is relatively difficult to Removing, general nickel removal rate will be less than vanadium removal rate.Because vanadium is with VO²⁺Form exists, and combines and can will be less than in porphyrin compound Metallic nickel, thus vanadium metal is easier to remove.In high-sulfur residual oil, content of vanadium is higher at present, existing residuum hydrogenating and metal-eliminating catalysis For agent removing metal there is no problem, demetallization per substantially all more than 80%, but in high nitrogen residual oil, metal nickel content Higher, demetallization per will be less than 50% substantially.Therefore, for residuum hydrogenating and metal-eliminating catalyst at this stage, mainly consider Improve the nickel removal effect in demetalization performance.

Main in Hydrodemetalation catalyst R＆D process at this stage consider to hold metal problem, improve catalyst pores hold or （With）Aperture.In terms of demetallization per raising, mainly consider or technical process temperature raising from catalyst grade part system. US4448896, US4102822, CN200410037669, CN200410071123, CN1209355A etc. are mainly from carrier system From the aspect of standby, catalyst holds metal ability, improves catalyst stability.Currently without be specifically designed for improve nickel removal aspect of performance Catalyst preparation technology explanation.

Content of the invention

For nickelic feature in current part residual oil raw material, the present invention provide a kind of high-activity hydrogenation nickel removal catalyst and Its preparation method.

A kind of preparation method of hydrogenation nickel removal catalyst, comprises the steps：（1）Weigh shaped alumina alumina supporter；（2）Join Active metal maceration extract processed, shaped alumina alumina supporter is carried out active metal dipping, then dried process；（3）Dried urge Agent carries out high temperature-low temperature roasting process successively and hydrogenation nickel removal catalyst is obtained.

The inventive method, step（1）Middle shaped alumina alumina supporter can also can enter according to prior art for commercial goods Row self-control.The pore structure of shaped alumina alumina supporter meets the needs of catalyst for demetalation performance.Described shaped alumina alumina supporter is Spherical, bar shaped, piece shape or granulated, pore diameter range is 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, wherein Group VIII metal is Co and Ni, and group vib metal is Mo and W.In catalyst, group VIII metal counts weight content as 5- with oxide 15%, group vib metal counts weight content as 1-5% with oxide.Baking temperature is 100 ~ 250 DEG C, and drying time is 1 ~ 6h.

The inventive method, step（2）Appropriate ethylenediamine tetra-acetic acid, ethylenediamine tetrem is also contained in activity component impregnation liquid The mass concentration of aqueous acid is 1%-10%, preferably 3-8%.Add appropriate ethylenediamine tetra-acetic acid can significantly improve nickel removal effect Rate.

The inventive method, step（2）Active metal dipping included volume impregnation, incipient impregnation or spray dipping, leaching The stain time is 1-5 hour.

The inventive method, step（3）Described in high temperature-low temperature roasting process high temperature scope be 600 DEG C ~ 450 DEG C, low Warm 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 temperature For：600 ~ 500 DEG C, middle temperature temperature is：400 ~ 350 DEG C, cryogenic temperature is：300~150℃；Every section of roasting time at least 0.5 ~ 1h.Preferably high temperature section roasting is by the way of microwave calcining.What microwave calcining added together ethylenediamine tetra-acetic acid synergy has There is the nickel removal effect of optimum.

A kind of catalyst of employing above method preparation, in catalyst, group VIII metal counts weight content as 5- with oxide 15%, group vib metal counts weight content as 1-5% with oxide, and pore diameter range is 15 ~ 20nm, and the active metal sulphides number of plies is 5 ~10.

The inventive method is different from baking modes unlike traditional preparation methods, and this baking modes can reduce carrier pair The impact of active metal, advantageously forms the more active metal phase being suitable to nickel removal.The catalyst of present invention preparation, sulfide The number of plies is more, has good active structure, is conducive to activated centre activity to improve the formation with active phase.More sulfide It is sterically hindered in aromatic ring that the number of plies is conducive to abolishing NI, S etc. in asphalitine and colloid, improves desulfurization and nickel removal performance.

Specific embodiment

Further describe the present invention program and effect with reference to embodiment, but be not limited to following examples.Using saturating Radio 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 is 18nm）100g；Prepare Mo-Ni-P solution, oxidation molybdenum concentration is：12.7g/100ml, aoxidizing nickel concentration is：3.0g/100ml ； 1.5h is dried at 180 DEG C after taking 100ml solution impregnation 3h；After drying terminates, carry out roasting 0.5h at 600 DEG C first, then Roasting 1h at 350 DEG C again, finally in 250 DEG C of roasting 0.5h, prepared catalyst A.

Embodiment 2

It is to prepare the ethylenediamine tetra-acetic acid being 5% containing mass concentration in Mo-Ni-P solution with embodiment 1, catalysis is obtained Agent is A1.

Embodiment 3

It is to adopt microwave calcining with embodiment 1 difference, prepared catalyst is A2.

Embodiment 4

It is to adopt microwave calcining with embodiment 2 difference, prepared catalyst is A12.

Embodiment 5

Weigh industrial catalyst for demetalation carrier（Catalyst Fushun branch company produces, and aperture is 15nm）100g;Prepare Mo- Ni-P solution, aoxidizing molybdenum concentration is：12.7g/100ml, aoxidizing nickel concentration is：3.0g/100ml ；Take 100ml solution impregnation, enter Row catalyst impregnates 3h, 5h is dried at 120 DEG C；After drying terminates, carry out microwave calcining 2h at 500 DEG C first, then again 400 Roasting 1h at DEG C, finally in 150 DEG C of roasting 0.5h, prepared catalyst B.

Embodiment 6

Step is with embodiment 1, except that high temperature section temperature is 550 DEG C, prepared catalyst C.

Embodiment 7

Step is with embodiment 1, except that middle-temperature section temperature is 380 DEG C, prepared catalyst D.

Comparative example 1

Weigh industrial catalyst for demetalation carrier（Catalyst Fushun branch company produces, and aperture is 18nm）100g;Prepare Mo- Ni-P solution, aoxidizing molybdenum concentration is：12.7g/100ml, aoxidizing nickel concentration is：3.0g/100ml；After taking 100ml solution impregnation 3h 1.5h is dried at 180 DEG C；After 450 DEG C of roasting 3h, prepared catalyst E.

200ml fixed bed hydrogenation experimental rig is evaluated to the catalyst prepared by embodiment and comparative example, former Material oil nature and 500h result of the test are shown in Table 1.

Table 1

By the above results as can be seen that adopting the Hydrodemetalation catalyst of the method preparation, nickel removal performance significantly improves.

Claims

1. a kind of hydrogenation nickel removal catalyst preparation method it is characterised in that：Comprise the steps：（1）Weigh formed alumina Carrier；（2）Prepare active metal maceration extract, shaped alumina alumina supporter is carried out active metal dipping, then dried process；（3） Dried catalyst carries out high temperature-low temperature roasting process successively and hydrogenation nickel removal catalyst, step is obtained（2）Active metal impregnates The active component of liquid is VIII and group vib metal, and wherein group VIII metal is Co and Ni, and group vib metal is Mo and W, step （3）Described in high temperature-low temperature roasting process high temperature scope be 600 DEG C ~ 450 DEG C, high temperature section roasting adopts microwave calcining.

2. method according to claim 1 it is characterised in that：Step（1）Shaped alumina alumina supporter is spherical, bar shaped, piece Shape or granulated, pore diameter range is 10 ~ 30nm.

3. method according to claim 1 it is characterised in that：Step（2）Baking temperature is 100 ~ 250 DEG C, drying time For 1 ~ 6h.

4. method according to claim 1 it is characterised in that：Step（2）Also contain appropriate in activity component impregnation liquid Ethylenediamine tetra-acetic acid, the mass concentration of edta solution is 1%-10%.

5. method according to claim 1 it is characterised in that：Step（2）Active metal dipping included volume impregnation, etc. Volume impregnation or spray dipping, dip time is 1-5 hour.

6. method according to claim 1 it is characterised in that：Step（3）Roasting process is divided into high temperature section, middle-temperature section, Low-temperature zone；High-temperature temperature is：600 ~ 500 DEG C, middle temperature temperature is：400 ~ 350 DEG C, cryogenic temperature is：300~150℃；Every section of roasting The burning time is at least 0.5 ~ 1h.

7. a kind of preparation of employing claim 1 to 6 either method catalyst it is characterised in that：Group VIII metal in catalyst Weight content is counted as 5-15% with oxide, group vib metal counts weight content as 1-5% with oxide, pore diameter range be 15 ~ 20nm, the active metal sulphides number of plies is 5 ~ 10.