CN1252221C - Hydroprocessing catalyst for petroleum hydrocarbon and preparing method thereof - Google Patents

Hydroprocessing catalyst for petroleum hydrocarbon and preparing method thereof Download PDF

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CN1252221C
CN1252221C CN 02133113 CN02133113A CN1252221C CN 1252221 C CN1252221 C CN 1252221C CN 02133113 CN02133113 CN 02133113 CN 02133113 A CN02133113 A CN 02133113A CN 1252221 C CN1252221 C CN 1252221C
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preparation
molybdenum
catalyst
tungsten
catalyzer
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CN1488720A (en
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何金海
罗锡辉
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The present invention discloses a petroleum hydrocarbon hydrotreatment (hydrodenitrogenation, hydrodesulphurization, hydrodemetalization, hydrosaturation, etc.) catalyst and a preparation method thereof. Pseudo-thin diaspore containing aluminum oxide and a group VIB metal, such as molybdenum or tungsten, are used as raw materials thoroughly mixed, kneaded and extruded to present the shape of a clover strip to obtain an aluminum oxide carrier containing molybdenum or tungsten through the steps, such as drying, high temperature calcining, etc. Then, the carrier is impregnated with a water solution of a compound containing a group VIII metal, such as nickel and/or cobalt to obtain the hydrotreatment catalyst through drying and high temperature calcining.

Description

Hydroprocessing catalyst for petroleum hydrocarbon and preparation method thereof
1, technical field
The present invention relates to a kind of hydroprocessing catalyst for petroleum hydrocarbon and preparation method thereof.
2, background technology
Petroleum fractions especially contains sulphur, nitrogen, oxygen and metal impurity such as (as Ni-V-Fes) in the heavier petroleum fraction.The existence of these impurity not only influences its stability, in use also because of giving off obnoxious flavour (as SO X, NO XDeng) and contaminate environment.In petroleum fractions processing (for example catalytic reforming, hydrocracking, hydroisomerizing etc.) process, also may cause poisoning of catalyst.The main purpose of hydrotreatment is the hazardous compound that removes in the petroleum hydrocarbon, for example organosulfur compound, organic nitrogen compound and organometallic compound etc.
The hydrotreating catalyst of excellent property requires to possess following condition: (1), at first reactive metal such as molybdenum (tungsten), nickel (cobalt) etc. have higher chemical dispersion amount (cda) on catalyst surface; (2), reactive metal has high dispersity and good dispersion state on catalyst surface, " interaction between metal-carrier " intensity is wanted suitably.Simultaneously, from considering that economically the Preparation of catalysts process should be tried one's best simply.
Earlier, hydrocarbon hydrogenizing treamtent catalyst adopts the kneading method preparation.Be about to support material, containing metal compound and add with binding agent and be in the same place,, make catalyzer through steps such as mixing, kneading, moulding, drying and roastings.The advantage that adopts kneading method to prepare catalyzer is that process is simple, and the metals capacity of catalyzer is bigger, and early stage hydrogenation catalyst once was extensive use of this preparation method.Found afterwards, and adopt the activity of such catalysts of kneading method preparation active high, thereby the impregnated gradually method of kneading method was especially replaced by co-impregnation not as catalyst prepared.About relatively low this problem of catalyst activity of kneading method preparation, more general is interpreted as: reactive metal causes activity lower in that to mix the dispersity of pinching catalyst surface lower.Nearest studies show that: adopt the kneading method to prepare catalyzer, reactive metal remains high dispersing in its surface, but dispersion state is bad.Mainly be some interval on catalyst surface, molybdenum (or tungsten) is more concentrated, and other intervals, nickel (or cobalt) is more concentrated.Because at MoNiP/Al 2O 3In the catalyzer, Mo/ NiAtomic ratio should have an optimum value, corresponding to the highest hydrogenation activity of this catalyzer.Will certainly influence activity of such catalysts if depart from optimum value.
At present, mainly be to adopt co-impregnation preparation (U.S. Pat P6,306,289 about hydrocarbon hydrogenizing treamtent catalyst; 4,513,097).Preparation process is carried out in two steps: at first prepare carrier γ-Al 2O 3With this carrier of solution impregnation that contains two or more active ingredient, catalyzer is made in drying, roasting at last then.The advantage that adopts co-impregnation to prepare hydrotreating catalyst is: can be evenly dispersed on the carrier surface to compare fixed ratio height between each active ingredient, thereby active ingredient not only has higher dispersity on catalyst surface, and good dispersion state is arranged.But, adopt this legal system to be equipped with hydrotreating catalyst, each active ingredient loading is subjected to certain restriction.As the higher (MoO for example of active component content 3+ NiO＞28w% or higher) time, not only the specific surface area of catalyzer and pore volume obviously diminish, and on catalyst surface, the dispersion state of active ingredient also can variation.These all can have influence on the performance of catalyst activity.
3, summary of the invention
The objective of the invention is: a kind of preparation method of hydrotreatment catalyst is provided, can be so that reactive metal has better dispersion state at catalyst surface, guarantee that catalyzer under the situation that supports relatively large reactive metal, still has bigger pore volume and specific surface area.
The present invention adopts " pickling process " preparation Mo (W) Ni (Co)/Al 2O 3Hydrotreating catalyst.Different with general " co-impregnation " is, at first active ingredient molybdenum and/or the tungsten with main (also being maximum) of hydrotreating catalyst is incorporated in the aluminum oxide, makes the aluminum oxide that contains molybdenum and/or tungsten.Then, the solution impregnation with containing promoter metal nickel and/or cobalt promptly makes catalyzer.Preparation earlier contains the alumina supporter of molybdenum or tungsten.Because interact between metal-carrier, molybdenum or tungsten itself meeting " automatically " spreads out on alumina surface.So,, can guarantee that equally molybdenum or tungsten have higher dispersity even under the situation of high molybdenum or high W content.Simultaneously, also have higher specific surface area and bigger pore volume.
Hydroprocessing catalyst for petroleum hydrocarbon preparation process of the present invention is as follows:
(1). the compound that will intend thin water aluminum oxide and molybdenum and/or tungsten mixes together, adds binding liquid, through thorough mixing, mediate, be extruded into stripe shape, again through super-dry and roasting, makes the aluminum oxide that contains molybdenum and/or tungsten;
(2). preparation nickel and/or cobalt liquor;
(3). with nickel and/or the saturated dipping of cobalt liquor in the step (2) or spray the alumina supporter that contains molybdenum and/or tungsten, Mo (W) Ni (Co)/Al is made in drying and roasting 2O 3Hydrotreating catalyst.
Wherein the compound of said molybdenum and/or tungsten is preferably molybdenum oxide or ammonium molybdate, ammonium metawolframate in the step (1); Said binding liquid is the aqueous solution of nitric acid or nitric acid+acetic acid preferably.
The solution of preparation nickel and/or cobalt is that nickelous nitrate or basic nickel carbonate and/or Xiao Suangu or cobaltous dihydroxycarbonate is soluble in water in the step (2).
Prepared hydrocarbon hydrogenizing treamtent catalyst has following character according to the present invention:
(1). this catalyzer consist of MoO 325w%～40w% or WO 330w%～45w%, NiO and/or CoO 4.0w%～13w%, all the other are Al 2O 3
(2). the specific surface area of this catalyzer is 200～300m 2/ g; Pore volume is 0.30～0.40ml/g.
(3). active ingredient Mo (W)-Ni (Co) has higher dispersity and preferable dispersion state on this catalyst surface, and allows bigger dispersion amount, thereby the hydrotreatment activity is higher.
Catalyzer of the present invention is suitable for the hydrofining (hydrogenating desulfurization, hydrodenitrification, hydrogenation are saturated, hydrodemetallation (HDM) etc.) of heavy (as VGO, paraffin, Vaseline etc.) and low-density oil cut.The processing condition that catalyzer is suitable for are: temperature of reaction is 230 ℃～420 ℃; Reaction pressure 5.0MPa～15.0MPa; LHSV0.5h -1～3.0h -1Hydrogen/oil ratio is 500～2000 (V/V).
Advantage of the present invention is:
(1), adopt the present invention to prepare hydrocarbon hydrogenizing treamtent catalyst, simple to operate, easy row.
(2) Ni of the present invention and/or Co solution are prepared very easy, quick.Simultaneously, strength of solution can be higher.
(3) catalyzer of the present invention even under the situation of high molybdenum or high W content, can guarantee that equally molybdenum or tungsten have higher dispersity.Simultaneously, also have higher specific surface area and bigger pore volume.The anti-nitrogen performance of its hydrogenation reaction activity and catalyzer all is better than the catalyzer that makes with usual way.
4, embodiment
In order to further specify all main points of the present invention, enumerate following examples and comparative example.
Embodiment 1
(1), contains the preparation of molybdenum aluminum oxide
(a). adhesive preparation: the 55g aperture is intended thin water aluminum oxide and 110ml3%HNO 3Solution mixes, and furnishing is as a form of gel, places 6 hours;
(b). contain the preparation of molybdenum aluminum oxide: the 370g macropore is intended thin water aluminum oxide, 130g MoO 3, 430ml3%HNO 3Solution is mixed together, and adds (a) prepared binding agent, mixes, is kneaded into plastic shape, is extruded into trifolium strip (φ=1.4mm).After wet bar dried in air and spends the night, drying was 3 hours under 120 ℃.
The sample that drying is crossed places High Temperature Furnaces Heating Apparatus, is warming up to 330 ℃ with 3 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 460 ℃ with 3 ℃ of/minute speed again, constant temperature 3 hours.
(2), the preparation of solution containing nickel
With 97.5g Ni (NO 3) 2.6H 2O is dissolved in the 500ml water.Stir.
(3), Preparation of Catalyst
The molybdenum aluminum oxide that contains that 100g step (1) is prepared places the 250ml beaker, adds the above-mentioned Ni solution that contains of 100ml.Stir for several times at interval, moist catalysis dries in air and spends the night, then, moist catalysis 120 ℃ dry 3 hours down.The sample that drying is crossed places High Temperature Furnaces Heating Apparatus, is warming up to 230 ℃ with 3 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 390 ℃ with 3 ℃ of/minute speed again, constant temperature 2 hours.
Embodiment 2
(1), contains the preparation of molybdenum aluminum oxide
(a). adhesive preparation: identical with embodiment 1 (1-a);
(b). contain the preparation of molybdenum aluminum oxide: identical with embodiment 1 (1-b).But macropore is intended thin water aluminum oxide and MoO 3Add-on is respectively 360g and 140g.
(2), the preparation of solution containing nickel
With 116g Ni (NO 3) 26H 2O is dissolved in the 500ml water.Stir.
(3), Preparation of Catalyst
Identical with embodiment 1 (3).
Embodiment 3
(1), contains the preparation of molybdenum aluminum oxide
(a). adhesive preparation: identical with embodiment 1 (1-a);
(b). contain the preparation of molybdenum aluminum oxide: identical with embodiment 1 (1-b);
(2), the preparation of solution containing nickel
Identical with embodiment 2 (2);
(3), Preparation of Catalyst
With 116g Ni (NO 3) 26H 2O is dissolved in the 500ml water, adds 33ml H again 3PO 4(85%), stirs.
Comparative example 1
(1) preparing carriers
Take by weighing and intend thin water aluminum oxide 200g, add 182ml HNO 3(concentration is 3%) and an amount of water.Through thorough mixing, be kneaded into plastic shape after, be extruded into trifolium strip (φ=1.4mm).After wet bar dried in air and spends the night, drying was 3 hours under 110 ℃.
The sample that drying is crossed places High Temperature Furnaces Heating Apparatus, is warming up to 220 ℃ with 5 ℃ of/minute speed, constant temperature calcining 0.5 hour.Be warming up to 478 ℃ with 4 ℃ of/minute speed again, constant temperature 2.5 hours.Be warming up to 640 ℃ with 5 ℃ of/minute speed at last, constant temperature calcining 3 hours.
(2) preparation of Mo-Ni-P solution
With 18.5ml phosphoric acid H 3PO 4(85%) is dissolved in the 560ml water.Under agitation solution is joined 97g molybdenum oxide MoO 3In, be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 65 ℃, under agitation slowly add the 48g basic nickel carbonate, be warming up to again little boil and be heated to throw out dissolve substantially.Filtrate is concentrated into 200ml.
(3) Preparation of Catalyst
Take by weighing the γ-Al of step (1) preparation 2O 3Carrier 100g adds the Mo-Ni-P solution of 150ml according to step (2) preparation, at room temperature flood 4 hours after, leach redundant solution.After moist catalysis dries in air and spends the night, dried 3 hours down at 110 ℃.
The dry catalyst sample of crossing is warming up to 190 ℃ with 3 ℃ of/minute speed, constant temperature calcining 0.5 hour.
Be warming up to 368 ℃ with 3 ℃ of/minute speed again, constant temperature calcining 0.5 hour.Be warming up to 470 ℃ with 3 ℃ of/minute speed at last, constant temperature calcining 3 hours.
More than the physico-chemical property of each routine prepared carrier and catalyzer see Table 1.
The physico-chemical property of each routine carrier of table 1 and catalyzer
Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
Specific surface, m 2/g 260 239 240 152
Pore volume, ml/g 0.370 0.352 0.355 0.280
Chemical constitution, w% MoO 3 NiO P Al 2O 3 24.7 4.90---surplus 28.2 6.00---surplus 28.1 6.02 3.00 surpluses 24.9 4.86 2.60 surpluses
Raw materials used oil properties of evaluation of catalyst activity and reaction process condition see Table 2 and table 3.
Table 2 stock oil character
Stock oil Triumph VGO
Proportion d 4 20g/ml 0.902
Sulphur, w% 0.50
Nitrogen, w% 0.15
Zero pour, ℃ 36
Carbon residue, w% 0.05
Boiling range, ℃
IBP/10％ 291/352
30％/50％ 377/393
70％/90％ 410/440
95％/EBP 449/468
Table 3 hydrodenitrification reaction process condition
Reaction pressure, MPa 6.36
LHSV，h -1 1.20
Hydrogen/oil ratio, v/v 1000∶1
Estimate catalyst system therefor with the grand celebration aviation kerosene cut that contains dithiocarbonic anhydride 1.5% (V), vulcanized 6 hours down at 230 ℃, 260 ℃, 300 ℃ and 370 ℃ respectively.Sulfuration finishes, and swap-in stock oil is stablized under reaction conditions and begun to carry out the hydrodenitrification reaction test after 8 hours.When estimating each routine catalyzer, by the conditioned reaction temperature, making total denitrification percent is 95w%, i.e. it is 0.0075w% that control generates the nitrogen content in the oil.If catalyzer just can reach this denitrification percent than low reaction temperatures the time, show that this catalyzer has higher hydrodenitrification reactive behavior.Vice versa.
Each routine catalyst hydrogenation denitrification activity of table 4 relatively
Catalyzer Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
Temperature of reaction, ℃ 381 375 373 382
Evaluation result shows: adopt the prepared hydrotreating catalyst of the present invention to reach at metal (molybdenum, nickel) content close (embodiment 1) and do not contain under the situation of P, the hydrodenitrification reactive behavior is still basic identical with the catalyzer that adopts dipping method (comparative example 1) preparation.If improve activity of such catalysts metal (Mo, Ni) content, prepared catalyzer will have higher hydrodenitrification reactive behavior (embodiment 2).
This shows, adopt the present invention to prepare hydrotreating catalyst, not only simple to operate, and also catalytic activity can be higher.

Claims (9)

1, a kind of preparation method of hydroprocessing catalyst for petroleum hydrocarbon is characterized in that in the catalyst preparation process at first the active ingredient molybdenum and/or the tungsten of hydrotreating catalyst are incorporated in the aluminum oxide, makes the aluminum oxide that contains molybdenum and/or tungsten; Then, the solution impregnation with containing promoter metal nickel and/or cobalt promptly makes catalyzer.
2,, it is characterized in that catalyst preparation step is as follows according to the described preparation method of claim 1:
(1). the compound that will intend thin water aluminum oxide and molybdenum and/or tungsten mixes together, adds binding liquid, through mixing, mediate, be extruded into stripe shape, again through super-dry and roasting, makes the aluminum oxide that contains molybdenum and/or tungsten;
(2). preparation nickel and/or cobalt liquor;
(3). with nickel and/or the saturated dipping of cobalt liquor in the step (2) or spray the alumina supporter that contains molybdenum and/or tungsten, Mo and/or W and Ni and/or Co/Al are made in drying and roasting 2O 3Hydrotreating catalyst.
3, according to the described preparation method of claim 2, the compound that it is characterized in that said molybdenum in the step (1) and/or tungsten is molybdenum oxide and/or ammonium molybdate, ammonium metawolframate.
4,, it is characterized in that said binding liquid is the mixed aqueous solution of nitric acid or nitric acid and acetic acid in the step (1) according to the described preparation method of claim 2.
5,, it is characterized in that in the step (2) that preparation nickel and/or cobalt liquor are for soluble in water with nickelous nitrate or basic nickel carbonate and/or Xiao Suangu or cobaltous dihydroxycarbonate according to the described preparation method of claim 2.
6, the hydroprocessing catalyst for petroleum hydrocarbon of a kind of claim 1 or the preparation of 2 described methods is characterized in that the MoO that consists of of this catalyzer 325w%～40w% or WO 330w%～45w%, NiO and/or CoO 4.0w%～13w%, all the other are Al 2O 3
7, according to the described catalyzer of claim 6, the specific surface area that it is characterized in that catalyzer is 200～300m 2/ g; Pore volume is 0.30～0.40ml/g.
8, the application of the described catalyzer of a kind of claim 6 in the petroleum fractions unifining process.
9, according to the described application of claim 8, it is characterized in that the processing condition of said unifining process are: temperature of reaction is 230 ℃～420 ℃; Reaction pressure 5.0MPa～15.0MPa; LHSV 0.5h -1～3.0h -1Hydrogen/oil volume ratio is 500～2000.
CN 02133113 2002-10-10 2002-10-10 Hydroprocessing catalyst for petroleum hydrocarbon and preparing method thereof Expired - Lifetime CN1252221C (en)

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Publication number Priority date Publication date Assignee Title
CN100432194C (en) * 2005-10-19 2008-11-12 中国石油化工股份有限公司 Refining catalyst for paraffin-hydrogenating and its preparing process and uses
CN101485953B (en) * 2008-05-27 2011-12-14 北京三聚环保新材料股份有限公司 Method for preparing desulfurizing agent
CN110227481B (en) * 2019-06-25 2022-06-10 中化泉州石化有限公司 Heavy oil hydrotreating catalyst and preparation method thereof

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