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CN110038581A - A method of preparing Hydrobon catalyst - Google Patents

A method of preparing Hydrobon catalyst Download PDF

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Publication number
CN110038581A
CN110038581A CN201810037402.7A CN201810037402A CN110038581A CN 110038581 A CN110038581 A CN 110038581A CN 201810037402 A CN201810037402 A CN 201810037402A CN 110038581 A CN110038581 A CN 110038581A
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aging
catalyst
hydrobon catalyst
weight
follows
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CN201810037402.7A
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CN110038581B (en
Inventor
王海涛
徐学军
王继锋
刘东香
冯小萍
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J23/8885—Tungsten containing also molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of methods for preparing Hydrobon catalyst.The Hydrobon catalyst is first to react the acid solution A containing Ni, Al, sodium tungstate alkaline solution cocurrent, aging is carried out to gained slurries, the acid solution B containing W, Al component is added in the slurries after above-mentioned aging with sodium molybdate alkaline solution cocurrent again, aging is carried out again, and Hydrobon catalyst then is made through post-processing steps such as drying, molding, roastings.The catalyst can be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction, hydrodesulfurization and hydrodenitrogeneration reactivity with higher, especially handle the diesel raw material of high nitrogen high sulfur content.

Description

A method of preparing Hydrobon catalyst
Technical field
The present invention relates to a kind of method for preparing Hydrobon catalyst, especially a kind of body phase Hydrobon catalyst Preparation method.
Background technique
Currently, crude oil heaviness and in poor quality increasingly, the sustainable development of world economy and environmental regulation is increasingly tight in addition Lattice need to produce a large amount of light clean fuels.Exploitation and using super-low sulfur even without sulphur vapour, diesel oil be within the scope of the world today it is clear The trend of clean fuel development.Reaction temperature, hydrogen are such as improved by increasing reaction severity using traditional Hydrobon catalyst The deep desulfuration even ultra-deep desulfurization of diesel oil also may be implemented in partial pressure or reduction reaction velocity etc., but reaction temperature is upper It rises the variation that will lead to product colour and catalyst life shortens, and reducing air speed then means the reduction for the treatment of capacity.For existing For some hydrogenation plants, design pressure has been fixed, and the amplitude for improving hydrogen partial pressure is limited.Therefore, currently by using The catalyst of more high desulfurization activity is one of the important means of deep desulfuration.
Sulfur-containing compound in petroleum distillate containing various structures and different molecular weight, but in the ultra-deep desulfurization stage (sulfur content is lower than 50 μ g/g), the mainly sulfur-containing compound of the substituted base such as removing 4,6- dimethyl Dibenzothiophene class.By Make to produce steric hindrance between sulphur atom and the activated centre of catalyst in the adjacent methyl of sulphur atom, sulphur atom is not easy to connect The activated centre of proximal response, thus lead to reaction rate sharp fall.
Conventional load type hydrogenation catalyst is limited by carrier pore structure, and active metal load capacity is usually no more than 30wt%, the activated centre quantity that loaded catalyst can be provided is limited, although can to activated centre number amount and type distribution Adjustment is optimized, but since the limit bottleneck of activated centre quantity can not be broken through, the space for increasing substantially hydrogenation activity has Limit, is difficult meet the needs of refinery is to V diesel product of producing country.The hydrogenation catalyst of body phase method preparation is most of by active gold Belong to component to constitute, the limitation of tenor can be got rid of, can in any regulating catalyst each active component ratio, improve catalysis The Hydrogenation of agent can be in the item for not improving device reaction severity since bulk phase catalyst has excellent hydrogenation activity Under part, directly production meet National V emission standard without sulfur diesel product, the processing of device can be improved without transformation in original device Amount reduces the production cost of refinery, realizes energy efficiency.
Body phase hydrogenation catalyst is divided into sulphided state body phase hydrogenation catalyst and oxidation state body phase hydrogenation catalyst.Oxidation state body Phase catalyst preparation process is relatively easy, at low cost, industrial application, it mainly uses coprecipitation to prepare, with active gold Belong to based on component, it typically is group VIB metallic elements (Mo, W) and group VIII metal element (Ni), and active metal atom is mutual Staggeredly, reaction compartment is provided for reactant molecule, active metal is exposed to catalyst surface, provides reaction for reactant molecule and lives Property center.Loaded catalyst is formed by mixing compared with low activity one kind activated centre with higher active two class activated centre , and it is two class activated centres that bulk phase catalyst activated centre is substantially all, bulk phase catalyst mainly passes through increase catalyst On activated centre density to greatly improving its catalytic activity.Chianelli etc. proposes spoke edge-seamed edge model to explain The generation in unsupported catalyst activated centre, model is by MoS2/WS2The seamed edge active sites of crystal grain layer side edge are known as spoke edge position, mention For adding hydrogen center, by MoS2/WS2The seamed edge active sites of crystal grain internal layer are known as seamed edge position, provide hydrogenolysis center.Therefore, catalyst Add the distribution of hydrogen and hydrogenolysis activity and active sites closely related.
During the reaction, reactant molecule only reacts in its close catalyst surface, using existing total The catalyst surface active metal dispersion of precipitation method preparation is uneven, while different hydrogenation active metals disorder distributions cause activity There is no good coordinative role between metal, the metal of high-content is easy to happen metallic particles excess accumulation in bulk phase catalyst, Reduce active mutually generation in this way, so that active metal is can't be hydrogenation sites, influence the benefit of the active metal of catalyst With rate, and improve the use cost of catalyst.
CN1951561A discloses the method for preparing hydrogenation catalyst using co-precipitation, and catalyst uses active metal Ni, W Component and precipitating reagent co-precipitation generate NixWyOzIt is molten aluminium salt can be added in above process in composite oxides precursor Liquid, can also to be directly added into aluminium hydroxide after plastic, then with MoO3Mashing mixing, filtering, molding, activation are final catalysis Agent.During this method prepares bulk phase catalyst, molybdenum oxide and NixWyOzComposite oxides are directly beaten mixing, lead to active gold Belong to excess accumulation, reduces the quantity of active phase, reduce the utilization rate of active metal.
CN201410062726.8 discloses a kind of preparation method of non-loading type high-activity hydrogenation catalyst.This method is The acid solution A for containing at least one group VIII metallic compound and at least one vib metals compound is first prepared, and Alkaline solution B containing at least one silicon source or silicon source, two kinds of solution is slowly mixed together into precipitation reactor, in temperature 20 Coprecipitation reaction is carried out between ~ 120 DEG C, pH value 7 ~ 12, obtains slurries, and slurries are subjected to aging, suction filtration, washing, drying, molding And calcination process, obtain catalyst.This method does not use conventional alkaline precipitating agent, but uses and contain a kind of silicon source or silicon source Alkaline solution B do precipitating reagent, although this method changes precipitating reagent, but the active metal without changing bulk phase catalyst disperses Property, active phase amount do not obviously increase, and the utilization rate of metal does not improve.
Ammonium hydrogen carbonate is added in body phase hydrogenation catalyst disclosed in CN102049265A during coprecipitated, Carbon dioxide is added in body phase hydrogenation catalyst disclosed in CN102451703A during coprecipitated, generates carbonate or bicarbonate Salt, the above method is that a certain amount of gas is released in roasting process using it, under the percussion of gas, increases catalysis The Kong Rong of agent, specific surface area.Although this method under the percussion of gas, makes part metals active sites sudden and violent while reaming It is exposed at the surface of catalyst, but catalyst pores easily collapse under gas effect, therefore, the effect to active metal dispersibility is improved It is limited.
CN201510212110.9 discloses a kind of body phase Hydrobon catalyst and preparation method thereof.This method is using just Addition prepares nickel aluminium mixed sediment, prepares tungsten, molybdenum and aluminium mixed sediment using parallel flow precipitation, then after the two is mixed it is old Change after filtering obtained metal mixture and steam treatment and urea is added under appropriate conditions, the material warp after hydro-thermal process Dry, molding, roasting obtain catalyst.Table phase active metallic content is high in the resulting bulk phase catalyst of this method, is easy excessive Accumulation, to influence the active pattern and dispersibility for mutually accumulating pile layer.
Existing coprecipitation method is prepared in bulk phase catalyst technology, and different coprecipitation modes, Gelation Conditions can be living to catalyst Property metal fit system, interaction relationship has very big between the distributions of hydrogenation active metals and different hydrogenation active metals Influence, also result in vulcanization after bulk phase catalyst in MoS2/WS2Pattern occur it is apparent different.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of methods for preparing Hydrobon catalyst.Party's legal system Standby catalyst is a kind of body phase Hydrobon catalyst, and effective active is mutually more, and mutual facilitation is stronger, is had Higher hydrodesulfurization and hydrodenitrogeneration reactivity worth are suitable for applying in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction, special It is not the diesel raw material for handling high nitrogen high sulfur content.
Under distillate ultra-deep hydrodesulfuration reaction environment, nitrogen-containing organic compound present in distillate is de- to hydrogen is added Reaction of Salmon-Saxl generates apparent inhibiting effect, and hydrodesulfurization activity is reduced as the nitrogen content in raw material increases, this is because evaporating Competitive Adsorption, the adsorption energy of nitrogenous compound occur on catalyst activity position for the nitrogenous compound and sulfur-containing compound divided in oil Power is stronger, occupies the active sites on catalyst, and sulfur-containing compound is made to be difficult to approach, it is suppressed that hydrodesulfurization reaction, so When the high heavy diesel of processing nitrogen content produces super-low sulfur product, the hydrodenitrogenationactivity activity that catalyst needs to have excellent, catalysis The hydrodenitrogenationactivity activity of agent improves, and after nitrogen content reduces, the nitrogenous compound that competitive Adsorption occurs with sulfur-containing compound is reduced, and contains Sulphur compound is easier, is also more adsorbed on catalyst activity position, promotes hydrodesulfurization reaction.Therefore, catalysis is improved The hydrodenitrogenationactivity activity of agent has extremely important effect to the ultra-deep hydrodesulfuration activity for improving bulk phase catalyst.
The preparation method of Hydrobon catalyst provided by the invention, comprising:
(1), the acid solution A of the component containing Ni and Al is prepared, the acid solution B of the component containing W and Al is prepared；
(2), acid solution A and sodium tungstate alkaline solution cocurrent are added in reactor tank and carry out plastic reaction, generate tungstenic, nickel, Resulting slurries I are carried out aging by the sediment slurries I of aluminium；
(3), acid solution B and sodium molybdate alkaline solution cocurrent, which are added in the slurries I after aging, carries out plastic reaction, and generation contains Tungsten, molybdenum, nickel, aluminum precipitation object slurries II, continue aging；
(4), step (3) resulting material obtains Hydrobon catalyst through drying, molding, washing, then through drying, roasting.
In the acid solution A of step (1), weight concentration of the Ni in terms of NiO is 5~100g/L, preferably 10~80g/ L, Al are with Al2O3The weight concentration of meter is 2~60g/L, preferably 5~40g/L.In acid solution B, W is with WO3The weight of meter is dense Degree is 2~60g/L, and preferably 10~50g/L, Al is with Al2O3The weight concentration of meter is 2~60g/L, preferably 5~40g/L.
When preparing acid solution A, the nickel source that generally uses can for one of nickel sulfate, nickel nitrate, nickel chloride or Several, silicon source can be one or more of aluminum nitrate, aluminum sulfate, aluminium chloride and aluminium acetate etc..Preparing acid solution B When, for ammonium metatungstate, silicon source can be one of aluminum nitrate, aluminum sulfate, aluminium chloride and aluminium acetate etc. in the tungsten source generally used Or it is several.
Step (2) accounts for hydrofinishing obtained by step (4) as weight of the sodium tungstate alkaline solution introducing W in terms of oxide and urges The 40%~80% of weight of the W in terms of oxide in agent, preferably 51%~75%；Al is introduced by acid solution A with Al2O3Meter Weight account in Hydrobon catalyst obtained by step (4) Al with Al2O3The weight 15%~60% of meter, preferably 25%~49%.Step Suddenly (3) are introduced into weight of the W in terms of oxide as acid solution B and account in Hydrobon catalyst obtained by step (4) W with oxide The 20%~60% of the weight of meter, preferably 25%~49%；It is accounted for as the acid solution B weight for introducing Al and adds hydrogen obtained by step (4) The weight 40%~85% of Al in catalyst for refining, preferably 51%~75%.
The concentration of sodium tungstate alkaline solution described in step (2) is with WO3The weight concentration of meter is 2~70g/L, preferably 4~60g/L.
In step (2), the reaction temperature of plastic is 20~90 DEG C, and preferably 30~70 DEG C, pH value control is 6.0 ~ 10.0, Preferably 7.0 ~ 9.0, gelation time is 0.2 ~ 2.0 hour, preferably 0.3 ~ 1.5 hour.
The concentration of sodium molybdate alkaline solution described in step (3) is with MoO35~80g/L of weight concentration of meter, preferably 10~60g/L.
Step (3) plastic reaction reaction condition are as follows: reaction temperature be 20~90 DEG C, preferably 30~80 DEG C, pH value control 6.0 ~ 11.0, preferably 6.5 ~ 9.0 are made as, gelation time is 0.5 ~ 4.0 hour, preferably 1.0 ~ 3.0 hours.
Aging condition described in step (2) is as follows: aging temperature is 40~90 DEG C, preferably 50~80 DEG C, when aging PH value control is 6.0 ~ 8.0, preferably 6.5 ~ 7.5, and ageing time is 0.1 ~ 1.0 hour, preferably 0.2 ~ 0.8 hour.Aging Carry out under stiring, preferred stirring condition is as follows: speed of agitator is 100~300 revs/min, preferably 150~250 revs/min.
Aging condition described in step (3) is as follows: aging temperature is 40~90 DEG C, preferably 50~80 DEG C, when aging PH value control is 7.5 ~ 11.0, preferably 7.5 ~ 9.5, and ageing time is 1.5 ~ 6.0 hours, preferably 2.0 ~ 5.0 hours.Aging Carry out under stiring, preferred stirring condition is as follows: speed of agitator is 300~500 revs/min, preferably 300~450 revs/min. The pH value of the pH value of step (3) the described aging aging more described than step (2) is at least high by 0.5, preferably at least high by 1.0.
Drying, molding and washing described in step (4) can be carried out using conventional method in that art.Dried strip before molding Part is as follows: it is 1 ~ 48 hour dry at 40 ~ 250 DEG C, preferably 50 ~ 180 DEG C drying 4 ~ 36 hours.In forming process, it can be not required to Shaping assistant is added.Washing is usually used deionized water or containing decomposable salt (such as ammonium acetate, ammonium chloride, ammonium nitrate Deng) solution washing, it is washed till neutrality.
After formation, used drying and roasting can use this field normal condition to step (4), and drying condition is such as Under: 1 ~ 48 hour dry at 40 ~ 250 DEG C, roasting condition is as follows: roasting 1 ~ 24 hour at 350 ~ 650 DEG C, preferably drying condition is such as Under: 4 ~ 36 hours dry at 50 ~ 180 DEG C, roasting condition is as follows: roasting 2 ~ 12 hours at 400 ~ 600 DEG C.
In Hydrobon catalyst of the present invention, adjuvant component preferred Ti and/or Zr.In Hydrobon catalyst system of the present invention During standby, the compound containing adjuvant component, i.e. titanium source and/or zirconium source are preferably added during preparing mixed solution A.Titanium source One of Titanium Nitrate, titanium sulfate, titanium chloride etc. or a variety of can be used, zirconium nitrate, zirconium chloride, zirconium oxychloride etc. can be used in zirconium source One of or it is a variety of.
In the preparation method of Hydrobon catalyst of the present invention, the shape of catalyst can according to need for sheet, it is spherical, Cylindrical bars and irregular strip (clover, bunge bedstraw herb), preferably cylindrical bars and irregular strip (clover, bunge bedstraw herb).Catalyst it is straight Diameter can be the slice of 0.8 ~ 2.0mm and the thick item of > 2.5mm.
The resulting Hydrobon catalyst of step (4) of the present invention is the body phase Hydrobon catalyst of oxidation state, is being used Before conventional method can be used vulcanized.The vulcanization is to convert corresponding sulphur for the oxide of active metal W, Ni and Mo Compound.The vulcanization process can be vulcanized using wet process, can also be used dry pre-sulfiding.The vulcanization process used in the present invention For wet process vulcanization, it can be organic sulfur-containing species, or inorganic sulfur-bearing that vulcanizing agent, which is sulphur-containing substance used in vulcanization, One of substance, such as sulphur, carbon disulfide, dimethyl disulfide etc. are a variety of, sulfurized oil be hydro carbons and/or distillate, Middle hydro carbons is one of hexamethylene, pentamethylene, cycloheptane etc. or a variety of, and distillate is kerosene, normal line diesel oil, normal two wires bavin One of oil etc. are a variety of.The dosage of vulcanizing agent is to be not less than the sulphidity of each active metal in Hydrobon catalyst 80%, it can be according to being actually adjusted, the dosage of vulcanizing agent can be each complete sulphur of active metal in Hydrobon catalyst The theory of change needs the 80% ~ 200% of sulfur content, preferably 100% ~ 150%.Presulfurization condition are as follows: 230 ~ 370 DEG C of temperature, Hydrogen Vapor Pressure 0.3 ~ 6.0h of volume space velocity when 2.0 ~ 10MPa, liquid-1, vulcanization time 3 ~ for 24 hours, preferably are as follows: 250 ~ 350 DEG C of temperature, Hydrogen Vapor Pressure 1.0 ~ 3.0h of volume space velocity when 3.0 ~ 8.0MPa, liquid-1, 5 ~ 16h of vulcanization time.
Vulcanization of the present invention is to convert corresponding sulfide for the oxide of active metal component W, Ni and Mo, Up to sulphided state Hydrobon catalyst；The sulphidity of each active metal is not less than 80% in the catalyst.
The Hydrobon catalyst of the method for the present invention preparation, on the basis of the weight of Hydrobon catalyst, NiO, WO3With MoO3Total content be 40% ~ 95%, preferably 50% ~ 85%, alumina content be 5% ~ 60%, preferably 15% ~ 50%.
In the Hydrobon catalyst of the method for the present invention preparation, the molar ratio of W/Mo is 1:10 ~ 8:1, preferably 1:8 ~ 5: 1, Ni/(Mo+W) molar ratio is 1:12 ~ 12:1, preferably 1:8 ~ 8:1.
The Hydrobon catalyst of the method for the present invention preparation is body phase Hydrobon catalyst, and composition includes hydrogenation activity Metal component WO3, NiO and MoO3And aluminium oxide, after vulcanizing, MoS2/WS2The average tap number of plies be 6.0 ~ 9.0 layers, it is excellent 6.5 ~ 9.0 layers are selected as, MoS2/WS2Lamella average wafer lamella length be 4.0 ~ 6.5nm, preferably 4.5 ~ 6.0nm.
The pore-size distribution of the Hydrobon catalyst of the method for the present invention preparation is as follows: diameter is shared by the hole below 3nm Kong Rong accounts for the 5% ~ 30% of total pore volume, and diameter is that Kong Rong shared by the hole of 3 ~ 10nm accounts for the 50% ~ 80% of total pore volume, and diameter is 10 ~ 15nm Hole shared by Kong Rong account for the 7% ~ 25% of total pore volume, it is 5% ~ 20% that the Kong Rong that diameter is 15nm or more, which accounts for total pore volume,.
The Hydrobon catalyst of the method for the present invention preparation, after vulcanizing, MoS2/WS2It is as follows to accumulate number of plies distribution: accumulation The piece number of plies that the number of plies is 7.0 ~ 9.0 accounts for the total tablet number of plies 55% ~ 85%, preferably 61% ~ 80%；MoS2/WS2Lamella distribution of lengths is as follows: Lamella length is that the piece number of plies of 4.0 ~ 6.0nm accounts for the total tablet number of plies 55.0% ~ 85.0%, preferably 65.0% ~ 80.0%.
The Hydrobon catalyst of the method for the present invention preparation, after vulcanizing, MoS2/WS2It is specific as follows to accumulate number of plies distribution: The piece number of plies of the number of plies less than 4.0 layers accounts for the total tablet number of plies 1% ~ 8%, the piece number of plies that the number of plies is 4.0 to less than 7.0 account for the total tablet number of plies 3% ~ 20%, the piece number of plies that the number of plies is 7.0 ~ 9.0 accounts for the total tablet number of plies 55% ~ 85%, the piece number of plies of the number of plies greater than 9.0 layers account for the total tablet number of plies 5% ~ 20%。
The Hydrobon catalyst of the method for the present invention preparation, after vulcanizing, MoS2/WS2Lamella distribution of lengths is specific as follows: The piece number of plies of the length less than 2.0nm accounts for the total tablet number of plies 1.0% ~ 12.0%, and length is that the piece number of plies of 2.0 to less than 4.0nm accounts for total tablet The number of plies 5.0% ~ 25.0%, length are that the piece number of plies of 4.0 ~ 6.0nm accounts for the total tablet number of plies 55.0% ~ 85.0%, length be greater than 6.0 to The piece number of plies of 8.0nm accounts for the total tablet number of plies 3.0% ~ 15.0%, and the piece number of plies of the length greater than 8.0nm accounts for the total tablet number of plies 0.2% ~ 4.0%.
The property of the Hydrobon catalyst of the method for the present invention preparation is as follows: specific surface area is 180 ~ 500m2/ g, Kong Rongwei 0.20~0.80mL/g。
It can according to need in the Hydrobon catalyst of the method for the present invention preparation containing adjuvant component, adjuvant component is titanium And/or zirconium, weight content of the adjuvant component in Hydrobon catalyst is 20% hereinafter, preferably 15% or less based on the element.
In the Hydrobon catalyst of the method for the present invention preparation, MoS2/WS2The number of plies for accumulating pile is high, and length is small, especially collects In in the number of plies be 6.0 ~ 9.0 layers, lamella length is 4.0 ~ 6.5nm, and the effective active of generation is mutually more, mutual promotion work With stronger, activity is higher, while pore size distribution is suitable for, and high mechanical strength has higher hydrodesulfurization and hydrodenitrogeneration reactivity worth, It is suitable for being applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction, especially handles the diesel raw material of high nitrogen-containing.
The method that the present invention prepares Hydrobon catalyst is first by the mixed solution of Al containing part and Ni and wolframic acid soda Property solution cocurrent carry out coprecipitation reaction, W, Ni, Al mix slurry are subjected to preliminary aging for the first time, generate W, Ni, Al oxygen The predecessor of compound, then the mixed solution of remaining Al, W and sodium molybdate alkaline solution cocurrent are added to the slurries of above-mentioned aging In, it then carries out second of depth aging and prepares tungsten, molybdenum, nickel and aluminium mixed sediment, be finally made catalyst.By to preparation The comprehensively control of step and preparation condition had previously deposited during tungsten, molybdenum, nickel and aluminium mixed sediment particle growth Hydrogenation active metals in metallic oxide precursor object have certain anchoring to act on the hydrogenation active metals in rear deposition, and make Different hydrogenation active metals deposit in an orderly manner in the catalyst, control metal oxide particle increase speed and active metal it Between the probability that contacts with each other, WO3And MoO3The granular size of product is suitable for and its distribution is made to obtain good control, increases sulphur MoS in bulk phase catalyst after change2/WS2The accumulation number of plies, reduce lamella length, optimize the pattern of active phase, generation it is effective Activity is mutually more, and mutual facilitation is stronger, and activity is higher.The catalyst is particularly suitable as the super of light fraction oil In deep hydrodesulfurizationof and denitrification reaction, desulfurization with higher and denitrification activity.
During the present invention prepares Hydrobon catalyst, plastic reaction is carried out using the acid-base property of raw material, avoids list Private NH3·H2O or sodium metaaluminate/sodium hydroxide do precipitating reagent, and tungsten source uses sodium tungstate and ammonium metatungstate, and molybdenum source uses molybdic acid Sodium, plastic utilize the hydrophily of different material in the process, so that reactive metal oxides is had suitable caking property, do not utilize bonding Agent carries out shaping of catalyst, and making finished catalyst not only has good intensity, and active metal dispersibility does not have in catalyst It is destroyed.Meanwhile can not add adhesive or extrusion aid can straight forming, meant that in this way without using such as nitric acid Good pore structure and ratio will not be can be obtained by the corrosion of the acidic materials such as nitric acid in Aci-Jel solvent, reactive metal oxides skeleton The reactive metal oxides of surface area, and sodium tungstate and sodium molybdate price are lower, reduce catalyst preparation cost.
It is with higher in the particularly suitable ultra-deep hydrodesulfuration and denitrification reaction as light fraction oil of the catalyst Hydrodesulfurization and hydrodenitrogenationactivity activity are especially to have higher plus hydrogen in the heavy diesel of working process high nitrogen high sulfur content Denitrogenation and desulphurizing activated.Sulfur content in the heavier diesel fraction is 1000~20000 μ g/g, wherein thiophene and derivatives The content of middle sulphur accounts for 60wt%~85wt% of raw material total sulfur content, and nitrogen content is 200~2000 μ g/g, wherein carbazole and its derivative The content of nitrogen accounts for 60wt%~80wt% of raw material total nitrogen content in object.
Specific embodiment
In the present invention, specific surface area and Kong Rong use low temperature liquid nitrogen determination of adsorption method, and mechanical strength is measured using side pressure method. MoS in the present invention, in bulk phase catalyst2/WS2The accumulation number of plies, lamella length be by transmissioning electric mirror determining, wherein right In W-Ni-Mo catalyst after vulcanizing, that be capable of forming stack layer is active phase MoS2And WS2, the present invention in MoS2/WS2Shape Formula indicates active phase.Hydrobon catalyst of the invention refers to after vulcanizing by unvulcanised state Hydrobon catalyst sulphur Sulphided state Hydrobon catalyst is turned to, that is, refers to sulphided state Hydrobon catalyst.
In the present invention, wt% is mass fraction, and v% is volume fraction.In the present invention, sulphidity uses X Ray Photoelectron energy Spectrometer (XPS) is measured, and the percentage that the content of sulphided state active metal accounts for the active metal total content is activity gold The sulphidity of category.
Embodiment 1
Nickel chloride, aluminium chloride are added to the dissolving tank 1 that deionized water is housed respectively, are configured to acid solution A, in acid solution A Weight concentration of the Ni in terms of NiO is 28g/L, and Al is with Al2O3The weight concentration of meter is 30g/L.Respectively by ammonium metatungstate, aluminium chloride The dissolving tank 2 that deionized water is housed is added, is configured to mixed solution B, W is in solution B with WO3The weight concentration of meter is 30g/L, Al is with Al2O3The weight concentration of meter is 26g/L.Deionized water is added in reactor tank, by weight concentration with WO3The weight of meter is dense Degree is that 27g/L sodium tungstate alkaline solution and acid solution A cocurrent are added in reactor tank, and gelling temperature is maintained at 60 DEG C, cocurrent at 7.8, gelation time control generated nickeliferous, tungsten, aluminum precipitation object slurries I at 50 minutes for pH value control in glue reaction process.Will To sediment slurries I aging under stiring, mixing speed is 220 revs/min, 75 DEG C of aging temperature, the control of aging pH value 7.0, Aging 0.8 hour.After aging, by Mo with MoO3Count the sodium molybdate alkaline solution and acid solution B that weight concentration is 36g/L Cocurrent is added in slurries I, and gelling temperature is maintained at 60 DEG C, and pH value control is 7.8 in cocurrent plastic reaction process, gelation time control System obtained nickel, tungsten, molybdenum, aluminum precipitation object slurries II at 2.0 hours, by the aging under agitation of sediment slurries II, stirring speed Degree is 370 revs/min, and 75 DEG C of aging temperature, pH value control filters the slurries after aging 8.2, ageing time 3.0 hours, filter Cake is 8 hours dry at 120 DEG C, rolls, extruded moulding.It is washed with deionized at room temperature 5 times.Then wet bar is at 80 DEG C dry 10 Hour, 500 DEG C roast 4 hours, obtain catalyst A.Catalyst composition, pore size distribution and main character are shown in Table 1.
Embodiment 2
According to the method for embodiment 1, it is matched by the constituent content of the catalyst B in table 1, nickel chloride, chlorine is added into dissolving tank 1 Change aluminum solutions, zirconyl chloride solution, prepare acid solution A, addition ammonium metatungstate, aluminum nitrate preparation mixing are molten into dissolving tank 2 Liquid B.Deionized water is added in reactor tank, by weight concentration with WO3The weight concentration of meter be 32g/L sodium tungstate alkaline solution and Acid solution A cocurrent is added in reactor tank, and gelling temperature is maintained at 55 DEG C, in cocurrent plastic reaction process pH value control 7.8, Gelation time control generated nickeliferous, tungsten, aluminium, zirconium sediment slurries I at 0.8 hour.It will obtain sediment slurries I under stiring Aging, mixing speed are 190 revs/min, and 72 DEG C of aging temperature, aging pH value is controlled 6.6, aging 0.8 hour.Aging terminates Afterwards, by Mo with MoO3The sodium molybdate alkaline solution and be added in slurries I with acid solution B cocurrent that weight concentration is 40g/L are counted, at Glue temperature is maintained at 48 DEG C, and pH value control is 7.8 in cocurrent plastic reaction process, and gelation time control was at 2.1 hours, reaction knot Nickel, tungsten, molybdenum, aluminium, zirconium sediment slurries II are obtained after beam, by the aging under agitation of sediment slurries II, mixing speed is 390 revs/min, ageing time 4.2 hours, 80 DEG C of aging temperature, aging pH value was controlled 8.0.By the slurries filtering after aging, filter Cake is 8 hours dry at 120 DEG C, and then extruded moulding, is washed with deionized 5 times, and wet bar is 18 hours dry at 80 DEG C, 500 DEG C roasting 5 hours, obtain final catalyst B, composition, pore size distribution and main character are shown in Table 1.
Embodiment 3
According to the method for embodiment 1, it is matched by the constituent content of the catalyst C in table 1, nickel nitrate, chlorine is added into dissolving tank 1 Change aluminium, prepare acid solution A, ammonium metatungstate is added into dissolving tank 2, aluminium chloride prepares acid solution B.Deionized water is added In reactor tank, by weight concentration with WO3The weight concentration of meter is that 40g/L sodium tungstate alkaline solution and acid solution A cocurrent are added In reactor tank, gelling temperature is maintained at 50 DEG C, and pH value control is 7.7 in cocurrent plastic reaction process, and gelation time control is 1.1 Hour, generate nickeliferous, tungsten, aluminum precipitation object slurries I.It will obtain sediment slurries I aging under stiring, mixing speed is 200 turns/ Point, 75 DEG C of aging temperature, aging pH value is controlled 7.2, aging 0.7 hour.After aging, by Mo with MoO3Count weight concentration Be added in slurries I for the sodium molybdate alkaline solution of 48g/L and with acid solution B cocurrent, gelling temperature is maintained at 52 DEG C, cocurrent at 7.8, gelation time control obtained nickel, tungsten, molybdenum, aluminum precipitation at 2.8 hours after reaction for pH value control in glue reaction process Object slurries II, by the aging under agitation of sediment slurries II, mixing speed is 450 revs/min, ageing time 4 hours, aging 74 DEG C of temperature, aging pH value is controlled 8.6.By the slurries filtering after aging, filter cake is 14 hours dry at 80 DEG C, then extrusion at Type is washed with water 5 times, and wet bar is 15 hours dry at 70 DEG C, roasts 4 hours at 550 DEG C, obtains final catalyst C, composition, hole Distribution and main character are shown in Table 1.
Embodiment 4
According to the method for embodiment 1, it is matched by the constituent content of the catalyst D in table 1, nickel chloride, chlorine is added into dissolving tank 1 Change aluminium, prepare acid solution A, ammonium metatungstate is added into dissolving tank 2, aluminium chloride prepares acid solution B.Deionized water is added In reactor tank, by weight concentration with WO3The weight concentration of meter is that 45g/L sodium tungstate alkaline solution and acid solution A cocurrent are added In reactor tank, gelling temperature is maintained at 45 DEG C, and pH value control is 8.0 in cocurrent plastic reaction process, and gelation time control is 50 Minute, generate nickeliferous, tungsten, aluminum precipitation object slurries I.Obtained sediment slurries I is stirred into lower aging, mixing speed is 220 turns/ Point, 78 DEG C of aging temperature, aging pH value is controlled 7.0, aging 0.6 hour.After aging, by Mo with MoO3Count weight concentration Be added in slurries I for the sodium molybdate alkaline solution of 30g/L and with acid solution B cocurrent, gelling temperature is maintained at 65 DEG C, cocurrent at 8.2, gelation time control obtained nickel, tungsten, molybdenum, aluminum precipitation at 2.3 hours after reaction for pH value control in glue reaction process Sediment slurries II are stirred lower aging by object slurries II, and mixing speed is 440 revs/min, and ageing time 4.9 hours, aging temperature 75 DEG C, aging pH value is controlled 8.5.By the slurries filtering after aging, filter cake is 14 hours dry at 110 DEG C, then extruded moulding, It being washed with deionized 5 times, wet bar is 12 hours dry at 90 DEG C, roasts 4 hours at 570 DEG C, obtains final catalyst D, form, Pore size distribution and main character are shown in Table 1.
Comparative example 1
By method disclosed in CN1951561A, preparation and the catalyst of embodiment 1 form identical reference agent E, and detailed process is such as Under:
It is formed by the catalyst of embodiment 1, nickel chloride and ammonium metatungstate preparation is dissolved in deionized water, are configured to mixed solution, Wherein weight concentration of the Ni in terms of NiO is 28g/L, and W is with WO3The weight concentration of meter is 46g/L, and Al is with Al2O3The weight of meter is dense Degree is 38g/L.500mL deionized water is added in reactor tank, is that reaction is added in 10wt% ammonium hydroxide and mixed solution cocurrent by concentration Plastic is carried out in tank, gelling temperature is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control is raw at 3.0 hours At nickeliferous, tungsten sediment slurries.Then aging is carried out, ageing time 3.8 hours, 75 DEG C of aging temperature, pH value controlled when aging After 7.8, filtering, deionized water, aluminium hydroxide and molybdenum trioxide are added in filter cake, is beaten, after mixing, filters, filter Cake is 8 hours dry at 120 DEG C, rolls, extruded moulding.It is washed with deionized at room temperature 5 times.Then wet bar is at 80 DEG C dry 10 Hour, 500 DEG C roast 4 hours, obtain catalyst E.Catalyst composition, pore size distribution and main character are shown in Table 1.
Comparative example 2
It is formed by the catalyst of embodiment 1, aluminium chloride, nickel chloride, ammonium molybdate and ammonium metatungstate is dissolved in deionized water, are configured to Mixed solution, wherein weight concentration of the Ni in terms of NiO is 28g/L, and W is with WO3The weight concentration of meter is 46g/L, and Mo is with MoO3Meter Weight concentration is 27g/L, and Al is with Al2O3The weight concentration of meter is 38g/L.It is 10wt% ammonium hydroxide and mixed solution cocurrent by concentration Be added reactor tank in carry out plastic, gelling temperature is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control is 3.0 Hour, generate tungstenic, nickel, molybdenum, aluminum precipitation object slurries.Then aging is carried out, ageing time 3.8 hours, 75 DEG C of aging temperature, always After 8.0, filtering, filter cake is 8 hours dry at 120 DEG C for pH value control when change, rolls, extruded moulding.Deionized water is used at room temperature Washing 5 times.Then wet bar is 10 hours dry at 80 DEG C, and 500 DEG C roast 4 hours, obtains catalyst F.Catalyst composition, pore size distribution And main character is shown in Table 1.
Comparative example 3
According to method for preparing catalyst disclosed in CN201510212110.9, prepare identical with the catalyst of embodiment 1 composition Reference agent G.Aluminium chloride, nickel chloride solution are added into dissolving tank 1, prepares working solution A, Ni is in terms of NiO in mixed solution A Weight concentration is 28g/L, and Al is with Al2O3The weight concentration of meter is 19g/L.Into dissolving tank 2 be added aluminium chloride, ammonium metatungstate and Ammonium molybdate prepares working solution B, and W is in mixed solution B with WO3The weight concentration of meter is 30g/L, and Mo is with MoO3Counting weight concentration is 36g/L, Al are with Al2O3The weight concentration of meter is 26g/L.It is that solution A, plastic temperature is added in 10wt% ammonium hydroxide under stiring by concentration Degree is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 50 minutes. 500mL deionized water is added in reactor tank, is that 10wt% ammonium hydroxide and solution B cocurrent are added in reactor tank by concentration, gelling temperature Be maintained at 60 DEG C, in cocurrent plastic reaction process pH value control 7.8, gelation time control at 2.0 hours, generate tungstenic, molybdenum, Aluminum precipitation object slurries II.By it is above two containing sediment slurry mix after aging, ageing time 3.8 hours, 75 DEG C of aging temperature, always At the end of change then pH value control is filtered, filter cake carries out hydro-thermal process, hydro-thermal process under the water vapour containing urea 7.8 Condition: the molar ratio of urea and active metal atom total amount is 3:1, and temperature is 230 DEG C, pressure 3.5MPa, and the processing time is 4 Hour, the material after hydro-thermal process is 8 hours dry at 120 DEG C, rolls, extruded moulding.It is washed with deionized at room temperature 5 times. Then wet bar is 10 hours dry at 80 DEG C, and 500 DEG C roast 4 hours, obtains catalyst G.Catalyst composition, pore size distribution and main property Matter is shown in Table 1.
Comparative example 4
By method for preparing catalyst disclosed in CN102049265A, preparation and the catalyst of embodiment 1 form identical reference agent H.Aluminium chloride, nickel chloride, ammonium metatungstate preparating acid sex work solution A are added into dissolving tank, takes 100g ammonium hydrogen carbonate to be made into and rubs The solution that your concentration is 2.0mol/L.500mL water is added into reactor tank, temperature rises to 60 DEG C.It in the case of stirring, will be molten Liquid A, ammonium bicarbonate aqueous solution and concentration be 10wt% ammonium hydroxide cocurrent be added reactor tank in plastic, 60 DEG C of gelling temperature, gelation time 3.0 hours, the pH value of plastic slurry was 7.8.Aging 3.8 hours after cemented into bundles, pH value is 8.0 at the end of aging.So After filter, molybdenum trioxide is added in obtained filter cake, and mashing stirs evenly, and filters, and filter cake is 8 hours dry at 120 DEG C, rolls, and squeezes Item molding.It is washed with deionized at room temperature 5 times.Then wet bar is 10 hours dry at 80 DEG C, and 500 DEG C roast 4 hours, is urged Agent H.Catalyst composition, pore size distribution and main character are shown in Table 1.
Embodiment 5
The present embodiment is WS in sulphided state catalyst2/MoS2The measurement of lamella average length and the average tap pile number of plies.To made The TEM photo of standby bulk phase catalyst is statisticallyd analyze, and statistics area is about 20000nm2, the WS of statistics2/MoS2Lamella Sum is more than 400.According to calculation formula (1) and (2) to bulk phase catalyst WS2/MoS2Lamella average length and average tap pile The number of plies carries out statistics calculating, is as a result listed in table 3.
(1)
(2)
In formula (1), (2),L A For WS2/MoS2Lamella average length,L i For WS2/MoS2Lamella length, nm；n i It is for lengthL i 's WS2/MoS2Piece number of layers,N A For WS2/MoS2The average tap number of plies；N i For WS2/MoS2The number of plies is accumulated,m i It is for the accumulation number of pliesN i WS2/MoS2Piece number of layers.
Using catalyst A, B, C, D of the present invention and comparative example catalyst E, F, G, H, sulphur is carried out on adding hydrogen microreactor Change, the admission space of catalyst is 10mL, vulcanizing agent CS2, sulfurized oil is hexamethylene, CS2Dosage be theory need sulfur content 110%.Presulfurization condition are as follows: 320 DEG C of temperature, Hydrogen Vapor Pressure 6.0MPa, air speed 2.0h-1, time 10h.
Embodiment 6
The present embodiment is catalyst activity evaluation experimental of the present invention, and is compared with comparative example catalyst.It is urged using the present invention Agent A, B, C, D and comparative example catalyst E, F, G, H, on 200mL small hydrogenation device carry out comparative evaluation's test, in order into One step evaluates the ability of catalyst Deitrogenatin, therefore has selected the huge port catalytic diesel oil that nitrogen content is high, difficulty of processing is big former for test Material, raw material main character are shown in Table 4.Catalyst activity evaluates process conditions: hydrogen partial pressure 6.4MPa, and reaction temperature is 360 DEG C, liquid When volume space velocity be 2.0h-1, hydrogen to oil volume ratio 500:1, evaluation result is shown in Table 5.It is examined using gas chromatography-flame photometric detector Sulfur compound and nitride type in device (GC-AED) detection hydrofined oil are surveyed, the results are shown in Table 6 and table 7.
As seen from Table 2, compared with comparative example catalyst, feelings that catalyst of the present invention does not change substantially in active metal amount Under condition, MoS2/WS2The average tap number of plies increase, average platelet length reduces, and hydrogenation sites number increased significantly.From table 3 can be seen that catalyst of the present invention after vulcanizing, MoS2/WS2The accumulation number of plies be concentrated mainly on 6.0 ~ 9.0 layers, lamella length It is concentrated mainly on 4.0 ~ 6.5nm.From table 4, it can be seen that catalyst activity evaluation is high using feedstock oil nitrogen content, this will also increase The difficulty of the ultra-deep hydrodesulfuration of feedstock oil.Find out from the evaluation result of table 5- table 7, catalyst of the present invention has excellent add Hydrogen denitrification activity shows high hydrogenation activity in 1,8-DMCB of removing and Isosorbide-5-Nitrae, 8-TMCB macromolecular nitride, is conducive to Improve the hydrodesulfurization activity of catalyst.Catalyst of the present invention is for working process light fraction oil, in particular for handling nitrogen When the poor-quality diesel-oil by cut fraction that content is high, difficulty of processing is big, there is excellent ultra-deep hydrodesulfuration and nitrogen removal performance, and improve The Cetane number of diesel oil.
The catalyst composition and property of 1 embodiment of table and comparative example preparation
Catalyst number A B C D E F G H
NiO, wt% 19 22 20 16 19 19 19 19
WO3, wt% 35 28 32 33 35 35 35 35
MoO3, wt% 18 18 15 20 18 18 18 18
Al2O3, wt% Surplus Surplus Surplus Surplus Surplus Surplus Surplus Surplus
Other/wt% - ZrO2/3.0 - - - - - -
Specific surface area, m2/g 208 199 197 201 175 179 219 225
Kong Rong, mL/g 0.315 0.306 0.304 0.308 0.271 0.273 0.325 0.334
Mechanical strength, N/mm 21.8 21.9 22.5 22.0 16.7 17.2 15.8 14.7
Pore size distribution, %
< 3nm 12.56 12.95 13.12 12.85 65.16 63.81 11.51 20.18
3nm~10nm 65.12 64.87 64.95 65.09 20.27 21.69 61.52 40.56
10nm~15nm 10.94 10.54 10.62 10.76 8.03 9.12 23.47 30.24
> 15nm 11.38 11.64 11.31 11.30 6.54 5.38 3.50 9.02
MoS in 2 bulk phase catalyst of table2/WS2The average tap number of plies and average platelet length
Catalyst number Average stacking number NA Average length LA, nm
A 8.34 5.02
B 8.26 5.04
C 8.29 4.97
D 8.20 5.03
E 4.88 7.92
F 5.03 8.01
G 5.97 7. 85
H 5.93 7. 62
MoS in 3 bulk phase catalyst of table2/WS2The accumulation number of plies and lamella length distribution
Catalyst number A B C D E F G H
The distribution of the piece number of plies, %
4.0 layers of < 3.98 4.05 4.14 4.22 30.22 32.56 24.98 20.56
4.0 to less than 7.0 layers 11.68 11.56 12.03 12.04 66.22 64.98 71.26 74.26
7.0 ~ 9.0 layers 74.03 73.88 73.11 73.59 3.56 2.46 3.76 5.18
9.0 layers of > 10.31 10.51 10.72 10.15 - - - -
Distribution of lengths, %
< 2.0nm 5.05 6.04 6.21 5.69 1.19 1.23 1.09 1.54
2.0 to less than 4.0nm 14.81 14.36 14.04 14.42 4.58 5.26 4.98 4.74
4.0~6.0nm 73.87 73.34 73.38 73.44 8.27 8.56 8.69 8.19
Greater than 6.0 to 8.0nm 5.38 5.36 5.42 5.46 65.17 64.21 65.59 66.58
> 8.0nm 0.89 0.90 0.95 0.99 20.79 20.74 19.65 18.95
4 feedstock oil main character of table
Project Analyze result
Density (20 DEG C), g/cm3 0.9025
Boiling range range, DEG C 162-375
S, μ g/g 5026
N, μ g/g 1024
5 catalyst activity evaluation result of table
Catalyst number A B C D
It generates oil density (20 DEG C), g/cm3 0.8701 0.8703 0.8702 0.8703
Boiling range range, DEG C 169-371 170-372 168-372 170-372
S, μ g/g 8.1 8.9 8.3 8.7
N, μ g/g 8.6 8.7 8.9 8.8
5 catalyst activity evaluation result of continued
Catalyst number E F G H
It generates oil density (20 DEG C), g/cm3 0.8856 0.8883 0.8804 0.8812
Boiling range range, DEG C 173-374 172-374 176-373 175-373
S, μ g/g 265.6 260.2 217.5 228.6
N, μ g/g 78.2 74.8 60.9 62.1
The content of different sulfide in 6 hydrofined oil of table
Catalyst number A B C D E
Sulfur content in hydrofined oil, μ g/g 8.1 8.9 8.3 8.7 265.6
C1- DBT, μ g/g 0 0 0 0 48.3
4- BMDBT, μ g/g 1.8 2.0 1.9 1.9 69.2
6-BMDBT, μ g/g 2.3 2.4 2.2 2.4 65.6
4,6- BMDBT, μ g/g 4.0 4.5 4.2 4.4 82.5
Continued 6
Catalyst number F G H
Sulfur content in hydrofined oil, μ g/g 260.2 217.5 228.6
C1- DBT, μ g/g 40.7 33.4 37.8
4- BMDBT, μ g/g 61.5 54.9 56.5
6-BMDBT, μ g/g 68.4 56.3 60.3
4,6- BMDBT, μ g/g 89.6 72.9 74.0
The content of different nitride in 7 hydrofined oil of table
Catalyst number A B C D E
Nitrogen content in hydrofined oil, μ g/g 8.6 8.7 8.9 8.8 78.2
1- MCB, μ g/g 1.8 1.7 1.9 1.8 28.3
1,8-BMCB, μ g/g 2.0 1.9 2.0 1.9 34.9
Isosorbide-5-Nitrae, 8- TMCB, μ g/g 4.8 5.1 5.0 5.1 15.0
Continued 7
Catalyst number F G H
Nitrogen content in hydrofined oil, μ g/g 74.8 60.9 62.1
1-MCB, μ g/g 24.2 18.1 17.8
1,8-BMCB, μ g/g 35.3 28.3 29.5
Isosorbide-5-Nitrae, 8-TMCB, μ g/g 15.3 14.5 14.8
Note: the main difficult de- nitrogenous compound of hydrodenitrogeneration is the carbazole (CB) that molecule is larger, has steric hindrance, 1- methyl carbazole (1-MCB), 1,8- Dimethylcarbazole (1,8-BMCB), Isosorbide-5-Nitrae, 8- trimethyl carbazole (Isosorbide-5-Nitrae, 8-TMCB) etc..

Claims (19)

1. a kind of preparation method of Hydrobon catalyst, it is characterised in that: the following steps are included:
(1), the acid solution A of the component containing Ni and Al is prepared, the B containing W and Al component acid solution is prepared；
(2), acid solution A and sodium tungstate alkaline solution cocurrent are added in reactor tank and carry out plastic reaction, generate tungstenic, nickel, Resulting slurries I are carried out aging by the sediment slurries I of aluminium；
(3), acid solution B and sodium molybdate alkaline solution cocurrent, which are added in the slurries I after aging, carries out plastic reaction, and generation contains Tungsten, molybdenum, nickel, aluminum precipitation object slurries II, continue aging；
(4), step (3) resulting material obtains Hydrobon catalyst through drying, molding, washing, then through drying, roasting.
2. according to the method for claim 1, it is characterised in that: in the acid solution A of step (1), weight of the Ni in terms of NiO Amount concentration is 5~100g/L, and preferably 10~80g/L, Al is with Al2O3The weight concentration of meter be 2~60g/L, preferably 5~ 40g/L；In acid solution B, W is with WO3The weight concentration of meter is 2~60g/L, and preferably 10~50g/L, Al is with Al2O3Meter Weight concentration is 2~60g/L, preferably 5~40g/L.
3. according to the method for claim 1, it is characterised in that: step (2) introduces W by sodium tungstate alkaline solution to aoxidize The weight of object meter accounts for 40%~80% of weight of the W in terms of oxide in Hydrobon catalyst obtained by step (4), and preferably 51% ~75%；Al is introduced by acid solution A with Al2O3The weight of meter accounts in Hydrobon catalyst obtained by step (4) Al with Al2O3 The weight 15%~60% of meter, preferably 25%~49%；Step (3) introduces weight of the W in terms of oxide by acid solution B and accounts for step Suddenly obtained by (4) in Hydrobon catalyst weight of the W in terms of oxide 20%~60%, preferably 25%~49%；Pass through acidity The weight that solution B is introduced into Al accounts for the weight 40%~85% of Al in Hydrobon catalyst obtained by step (4), preferably 51%~ 75%。
4. according to the method for claim 1, it is characterised in that: the concentration of sodium tungstate alkaline solution described in step (2) With WO3The weight concentration of meter is 2~70g/L, preferably 4~60g/L.
5. according to the method for claim 1, it is characterised in that: in step (2), the reaction temperature of plastic is 20~90 DEG C, Preferably 30~70 DEG C, pH value control is 6.0 ~ 10.0, preferably 7.0 ~ 9.0, and gelation time is 0.2 ~ 2.0 hour, preferably 0.3 ~ 1.5 hour.
6. according to the method for claim 1, it is characterised in that: aging condition described in step (2) is as follows: aging temperature It is 40~90 DEG C, preferably 50~80 DEG C, pH value control is 6.0 ~ 8.0, preferably 6.5 ~ 7.5 when aging, ageing time 0.1 ~ 1.0 hours, preferably 0.2 ~ 0.8 hour；Aging carries out under stiring, and preferred stirring condition is as follows: speed of agitator 100 ~300 revs/min, preferably 150~250 revs/min.
7. according to the method for claim 1, it is characterised in that: the concentration of sodium molybdate alkaline solution described in step (3) With MoO35~80g/L of weight concentration of meter, preferably 10~60g/L.
8. according to the method for claim 1, it is characterised in that: the reaction condition of step (3) plastic reaction are as follows: reaction temperature It is 20~90 DEG C, preferably 30~80 DEG C, pH value control is 6.0 ~ 11.0, preferably 6.5 ~ 9.0, and gelation time is 0.5 ~ 4.0 Hour, preferably 1.0 ~ 3.0 hours.
9. according to method described in claim 1 or 6, it is characterised in that: aging condition described in step (3) is as follows: aging Temperature is 40~90 DEG C, and preferably 50~80 DEG C, pH value control is 7.5 ~ 11.0, preferably 7.5 ~ 9.5 when aging, ageing time It is 1.5 ~ 6.0 hours, preferably 2.0 ~ 5.0 hours；Aging carries out under stiring, and preferred stirring condition is as follows: speed of agitator It is 300~500 revs/min, preferably 300~450 revs/min.
10. according to the method for claim 9, it is characterised in that: the pH value of step (3) described aging is than described in step (2) The pH value of aging is at least high by 0.5, preferably at least high by 1.0.
11. according to the method for claim 1, it is characterised in that: the drying condition before step (4) molding are as follows: 40 ~ 250 DEG C dry 1 ~ 48 hour, preferably 50 ~ 180 DEG C drying 4 ~ 36 hours；Step (4) after formation, used drying condition Are as follows:, roasting condition 1 ~ 48 hour dry at 40 ~ 250 DEG C are as follows: roast 1 ~ 24 hour, preferably drying condition at 350 ~ 650 DEG C are as follows: 4 ~ 36 hours, preferably roasting condition are dried at 50 ~ 180 DEG C are as follows: are roasted 2 ~ 12 hours at 400 ~ 600 DEG C.
12. according to the method for claim 1, it is characterised in that: in the Hydrobon catalyst, be containing adjuvant component The compound containing adjuvant component, i.e. titanium source and/or zirconium source is added in Ti and/or Zr during preparing mixed solution A.
13. according to the method for claim 1, it is characterised in that: on the basis of the weight of Hydrobon catalyst, NiO, WO3 And MoO3Total content be 40% ~ 95%, preferably 50% ~ 85%, alumina content be 5% ~ 60%, preferably 15% ~ 50%.
14. according to method described in claim 1 or 13, it is characterised in that: in the Hydrobon catalyst, mole of W/Mo Than being 1:12 ~ 12:1, preferably 1:8 ~ 8:1 for 1:10 ~ 8:1, preferably 1:8 ~ 5:1, Ni/(Mo+W) molar ratio.
15. according to the method for claim 1, it is characterised in that Hydrobon catalyst described in step (4) is carried out sulphur Change, sulphided state Hydrobon catalyst is made.
16. according to the method for claim 15, it is characterised in that: the vulcanization is vulcanized using wet process, and vulcanizing agent is to have Machine sulphur-containing substance and/or inorganic sulphur-containing substance, are further selected from one of sulphur, carbon disulfide, dimethyl disulfide or a variety of； Sulfurized oil is hydro carbons and/or distillate, it is preferable that hydro carbons is one of hexamethylene, pentamethylene, cycloheptane or a variety of, fraction Oil is one of kerosene, normal line diesel oil, normal two wires diesel oil or a variety of；Presulfurization condition are as follows: 230 ~ 370 DEG C of temperature, hydrogen 0.3 ~ 6.0h of volume space velocity when 2.0 ~ 10MPa of pressure, liquid-1, vulcanization time 3 ~ for 24 hours, preferably are as follows: 250 ~ 350 DEG C of temperature, hydrogen 1.0 ~ 3.0h of volume space velocity when 3.0 ~ 8.0MPa of pressure, liquid-1, 5 ~ 16h of vulcanization time.
17. according to method described in claim 15 or 16, it is characterised in that: in sulphided state Hydrobon catalyst, each activity The sulphidity of metal is not less than 80%.
18. according to method described in claim 15,16 or 17, it is characterised in that: the Hydrobon catalyst after vulcanizing, MoS2/WS2The average tap number of plies be 6.0 ~ 9.0 layers, preferably 6.5 ~ 9.0 layers, MoS2/WS2Lamella average wafer lamella it is long Degree is 4.0 ~ 6.5nm, preferably 4.5 ~ 6.0nm.
19. according to method described in claim 15,16 or 17, it is characterised in that: the Hydrobon catalyst after vulcanizing, The piece number of plies that the accumulation number of plies is 7.0 ~ 9.0 accounts for the total tablet number of plies 55% ~ 85%, preferably 61% ~ 80%；MoS2/WS2Lamella distribution of lengths As follows: lamella length is that the piece number of plies of 4.0 ~ 6.0nm accounts for the total tablet number of plies 55.0% ~ 85.0%, preferably 65.0% ~ 80.0%.
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