CN1289821A

CN1289821A - Hydrotransforming catalyst for residual oil and its preparing process

Info

Publication number: CN1289821A
Application number: CN 99113299
Authority: CN
Inventors: 王纲; 方维平; 王永林; 孙素华; 陈金汤
Original assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals; China Petrochemical Corp
Current assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals; China Petrochemical Corp
Priority date: 1999-09-29
Filing date: 1999-09-29
Publication date: 2001-04-04
Anticipated expiration: 2019-09-29
Also published as: CN1091134C

Abstract

A high-activity hydrotransforming cat/alyst for residual oil is prepared from gamma-Al2O3 and low-SilAl molecular sieve as carrier matrix, metal elements in VIII and VIB family (Mo-Ni) as active component and Ti as active assistant through mixing dry aluminium hydroxide with molecular sieve, adding alkaline solution of VIB family's metal, kneading, adding acidic solution of VIII and VIB family's metals, kneading, extruding out, drying and calcining.

Description

A kind of hydrotransforming catalyst for residual oil and preparation method thereof

The present invention relates to a kind of catalyst for hydrotreatment of residual oil and preparation method thereof, particularly hydrotransforming catalyst for residual oil and preparation method thereof.

Impurity in the residual oil such as S, N, carbon residue and heavy metal etc. must remove the requirement that could satisfy the catalytic cracking charging effectively, if the too high meeting of foreign matter content causes the downstream catalytic cracking catalyst to be poisoned, because contain plurality of impurities in the residual oil, must adopt catalyzer classification filling technology, along with each bed of reactant flow process, impurity more and more is difficult to remove, therefore require the back segment catalyzer must have higher activity, the main effect of hydrotransforming catalyst for residual oil promptly is the S that removes to greatest extent through in demetalization and the sweetening agent bed material, N, carbon residue etc., but its mainly to act on be to remove nitrogen and reduce carbon residue.Typical hydrogenation conversion catalyst is carrier matrix usually with the activated alumina, is active ingredient with Mo and/or W and Ni and/or Co.The production high-performance, catalyzer is researchist's a major objective cheaply.

People adopt the approach of simplifying catalyst preparation process to reduce the catalyzer cost usually, adopt mixed fully method of pinching to substitute the method for " pickling process " or " mix and soak combination " as Chinese patent ZL1070418A, one-step moulding prepares catalyzer, simultaneously, Preparation of catalysts adopts the method that only adds sour peptization, because this method is in catalyst preparation process, reactive metal adds with the form of solid salt, therefore, a large amount of acid must be added and just the aluminum oxide peptization can be made, make pore volume, the specific surface loss of aluminum oxide powder serious, cause final activity of such catalysts unsatisfactory.People improve the method that catalyst activity usually adopts auxiliary agents such as interpolation such as Ti, Zr, P, B, F, as U.S. Pat 5,089,453 report, it has introduced auxiliary agent Ti in hydrodenitrification/conversion catalyst, activity of such catalysts is improved, its Preparation of catalysts adopts and adds acid earlier, add alkali neutral method again, but strong acid that elder generation adds and aluminum oxide still act on stronger, make pore volume, the specific surface of aluminum oxide powder lose serious, cause pore volume, the specific surface of final catalyzer to reduce greatly, make final activity of such catalysts still undesirable.

In fact, the acid sites of catalyst for hydrotreatment of residual oil is to denitrogenation and to take off carbon residue influence bigger, and all there is acid insufficient shortcoming in above-mentioned catalyzer, and acid deficiency causes denitrogenation and take off the carbon residue activity lower.

Purpose of the present invention promptly is to remedy above-mentioned the deficiencies in the prior art, provides a kind of residual oil to take off the high hydrotreating catalyst of impurity activity, and another object of the present invention provides this Preparation of catalysts method.

Catalyzer of the present invention contains MoO by weight ₃20～30%, be preferably 24～28%; NiO5～12% is preferably 7～10%; TiO ₂3～8%, be preferably 4～6%, molecular sieve content is 3.0～10.0, is preferably 5.0～8.0, surplus is Al ₂O ₃, the catalyzer pore volume is 0.36～0.60ml/g, is preferably 0.40～0.46ml/g, specific surface is 190～260m ²/ g is preferably 220～260m ²/ g, bulk density is 0.70～0.90g/ml, is preferably 0.75～0.85g/ml, and pore volume and specific surface are measured by the nitrogen low-temperature adsorption, and infrared acidity is by the chemisorbed pyridine assay method.

Above-mentioned molecular sieve SiO ₂/ Al ₂O ₃Be 5～20.

Preparation of catalysts process of the present invention is: aluminum hydroxide solid elastomer powder and above-mentioned molecular sieve are mixed by a certain percentage, add an amount of basic solution that is dissolved with VI B family reactive metal earlier, after fully mixed the pinching, add a certain amount of acidic solution that is dissolved with VIII family and IV B family metal again, mix and pinch into after the plastic, material is made final catalyzer through extrusion, drying and roasting.

Above-mentioned aluminum hydroxide solid elastomer powder is commercially available aluminum hydroxide solid elastomer powder, and this aluminum hydroxide solid elastomer powder can be converted into γ-Al 450-700 ℃ of roasting ₂O ₃When mentioning aluminum hydroxide solid elastomer (below, all be meant this type) mixes the aluminum hydroxide solid elastomer powder of calculated amount and the molecular sieve of calculated amount, adds a certain amount of NH of containing then ₃15～20wt%, MoO ₃The basic solution of 24～30wt%, thorough mixing, treat that material is all wetted after, add a certain amount of Ni8 of containing～12% again, the acidic solution of Ti4～8% mixes and pinches into plastic, extruded moulding on banded extruder, drying, roasting promptly obtains catalyzer.

In above preparation process, if get 336g (butt 75%) aluminum hydroxide solid elastomer powder and 68g (butt is 93.5%) molecular sieve, then the above-mentioned basic solution of Jia Ruing is 300-350g, and acidic solution is 350-400g.Catalyst shape can be cylinder or three (four) leaf grass, and drying temperature is 100～120 ℃, and the time is 3～6 hours.During roasting, the heating-up time is 4～6 hours, and constant temperature 2～4 hours, thermostat temperature are 490 ℃～600 ℃.

In catalyst for hydrotreatment of residual oil, introduce a kind of molecular sieve of low silica-alumina ratio, improved the acidity of catalyzer.In preparation process; because the basic solution that elder generation adds; absorption also is covered in the aluminum hydroxide solid elastomer powder and low silica-alumina ratio internal and external surface of molecular sieve formation one deck alkalescence " protective membrane "; can slow down the strong interaction of acid and aluminium hydroxide when adding the acidic solution peptization more greatly; reduced the loss of raw material pore volume and specific surface, made final catalyzer have higher pore volume and specific surface.

Catalyzer of the present invention can be used for hydrogenating desulfurization, the denitrogenation of residual oil and takes off carbon residue, when especially using with hydrogenating desulfurization/catalyst for demetalation grating, after sulfuration, under the hydrocracking condition, when handling poor residuum, shows higher denitrogenation and takes off the carbon residue activity.

Further describe technical characterictic of the present invention below by comparative example and embodiment, but be not limited to embodiment.

Embodiment 1

Take by weighing aluminum hydroxide solid elastomer powder 336g (production of butt 75% Qilu Petrochemical company) and SiO ₂/ Al ₂O ₃Be 8 molecular sieve 68g, in premixed device, mix, add molybdenum acid ammonia solution 327g then, wherein MoO ₃Concentration is 28%, and it is wetting with mixture to be fully mixed to alkali lye, adds the 366g acidic solution then, contains NiCl in the acid liquid ₂17.9%, TiCl ₃11.8%, fully mix and pinch to plastic, on preceding crowded formula twin screw banded extruder, be extruded into the Herba Galii Bungei bar that diameter is 1.1 * 1.2mm, the gained catalyzer was 100 ℃ of dryings 4 hours; 490 ℃ of roastings 3 hours, catalyst A, its character sees Table 1.

Embodiment 2

Change aluminum hydroxide solid elastomer powder among the embodiment 1 into 252g, molecular sieve (SiO ₂/ Al ₂O ₃Be 12) 135g, other implementation conditions are constant, get catalyst B, and its character sees Table 1, i.e. the cost example.

Embodiment 3

Change aluminium hydroxide among the embodiment 1 into 294g in rubber powder, molecular sieve (SiO ₂/ Al ₂O ₃Be 18) 100g, both cost examples, catalyzer numbering C, its character sees Table 1.

Comparative example 1

This comparison example is to prepare catalyzer by the method that ZL1070418A describes.

Take by weighing the identical aluminium hydroxide (containing butt 75%) of 347g and embodiment 1, three halogenated titanium solution 45g (contain TiCl ₃17%), mixes.Measure 200ml distilled water, add 6g ammonium hydrogencarbonate and 7g boric acid, stirring and dissolving is added to this solution and contains in the Ti-Al mixture, mixes.Add 40g1 again: 1 salpeter solution mixes.Add 100g molybdic oxide and 36g basic nickel carbonate (containing nickel oxide 49%) again, mix and pinch into uniform plastic, extrusion was descended dry 4 hours at 100 ℃ then, 550 ℃ of following roastings 3 hours, got catalyzer D, and its character sees Table 1.

Comparative example 2

This Comparative Examples is by US5, and 089,453 described method prepares catalyzer.

With 177gTiCl ₄Slowly add in the 600g water, stir, add 400gNi (C then until limpid ₂H ₃O ₂) ₂4H ₂O, this solution pH value is 1.5, label is 2A;

Solution 2B is by containing MoO ₃28.9%, NH ₄The solution 753ml of OH26.5% and the dense NH of 100g ₄OH solution mixes.

Take by weighing the identical aluminium hydroxide of 1013g and embodiment 1, add 2A solution earlier, after mixing 20 minutes, mixed pinching do not stop adding 2B solution, remix 20 minutes is extrusion then, at 1150 °F, and under the airflow condition, drying, roasting 2 hours, catalyzer is numbered E, and its character sees Table 1.

Embodiment 4

Under the same process condition, comparative catalyst A, B, C, D, E, desulfurization, the denitrogenation that when handling isolated island vacuum residuum, shows and take off the carbon residue performance.Estimate stock oil character and estimate processing condition and see Table 2 and table 3 respectively, evaluation result sees Table 4.

Table 1 catalyst property

Catalyzer	????A	????B	????C	?D	?E
Catalyzer	????A	????B	????C	?D	?E	Pore volume, ml/g specific surface, m ²/ g can several apertures, and nm piles ratio, g/ml MoO ₃，wt％ NiO，wt％ TiO ₂The wt% molecular sieve content, the wt% meleic acid distributes, mmol～160 ℃～250 ℃～350 ℃～450 ℃	????0.46 ????269 ????6.0 ????0.85 ????20.5 ????8.3 ????4.4 ????3.8 ????0.386 ????0.225 ????0.112 ????0.085	????0.54 ????256 ????5.8 ????0.89 ????24 ????9.4 ????5.8 ????7.9 ????0.459 ????0.288 ????0.162 ????0.105	????0.55 ????249 ????7.0 ????0.75 ????20.2 ????8.0 ????4.5 ????5.6 ????0.341 ????0.199 ????0.093 ????0.072	?0.38 ?1.93 ?6.5 ?0.88 ?25.1 ?4.3 ?0.2 ?0.312 ?0.185 ?0.072 ?0.032	?0.37 ?228 ?7.2 ?0.88 ?22.6 ?9.8 ?6.3 ?0.356 ?0.191 ?0.081 ?0.048

From table 1 meleic acid distribution results as seen, catalyst A of the present invention, B, the total acidity of C is much higher than the comparative catalyst.

Table 2 stock oil character density (20 ℃) g/cm ³1.018S, W% 2.56N, W% 0.76CCR, W% 15.6

Table 3 is estimated processing condition

Catalyst loading one anti-HDM/HDS 120

Ml two anti-HDN/HC 180

Pressure, MPa 14.7

Air speed, h ^-10.33

Temperature, ℃ 400

Hydrogen-oil ratio, (v) 1000

Table 4 activity rating result ^*

Catalyst A B C D E

Desulfurization degree, % 87 86 88 86 87

Denitrification percent, % 63 65 62 60 54

Take off carbon yield, % 65 67 64 55 58

^*Turn round the sampling analysis result after 300 hours as seen from Table 4, and the performance of catalyzer of the present invention is better than the comparative catalyst, denitrogenation particularly of the present invention and take off the carbon residue performance significantly better than the comparative catalyst.

Claims

1, a kind of catalyst for hydrotreatment of residual oil contains MoO by weight ₃20～30%, NiO5～12%, TiO ₂3～8%, molecular sieve content is 3.0～10.0, surplus is γ-Al ₂O ₃, the catalyzer pore volume is 0.36～0.60ml/g, specific surface is 190～280m ²/ g.

2,, it is characterized in that containing by weight MoO according to the catalyzer of claim 1 ₃22～28%, NiO7～10%, TiO ₂4～6%, molecular sieve 5.0～8.0, catalyzer pore volume are that 0.40～0.46ml/g, specific surface are 220～260m ²/ g, bulk density are 0.70～0.90g/ml.

3,, it is characterized in that the SiO of described molecular sieve according to the catalyzer of claim 1 ₂/ Al ₂O ₃Be 5～20.

4,, it is characterized in that described bulk density is 0.75～0.85g/ml according to the catalyzer of claim 2.

5, a kind of preparation method of claim 1 hydrotransforming catalyst for residual oil may further comprise the steps:

(1) aluminum hydroxide solid elastomer powder and molecular sieve are pressed the calculated amount mixed, add the basic solution that is dissolved with VI B family reactive metal, fully mix and pinch;

(2) add a certain amount of acidic solution that is dissolved with VIII family and IV B family metal in the material that in (1), obtains again, mix pinch into plastic it;

(3) the plastic extruded moulding, drying and the roasting that obtain in (2) step, make catalyzer.

6,, it is characterized in that the basic solution described in the step (1) contains NH by weight according to the method for claim 5 ₃15～20%, MoO ₃24～30%.

7, according to the method for claim 5, it is characterized in that described in the step (2) acidic solution contain Ni8～12% by weight, Ti4～8%.

8, according to the method for claim 5, it is characterized in that the drying temperature described in the step (3) is 100～120 ℃, the time is 3～6 hours.

9, according to the method for claim 5, it is characterized in that the roasting condition described in the step (3) is: 490 ℃～600 ℃ constant temperature 2～4 hours.

10, according to the method for claim 5, the heating-up time that it is characterized in that roasting described in the step (3) is 4～6 hours,