CN101463271B - Hydrogenation modifying catalyst for poor quality diesel oil and its preparing process - Google Patents
Hydrogenation modifying catalyst for poor quality diesel oil and its preparing process Download PDFInfo
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Abstract
The invention discloses a hydro-upgrading catalyst for inferior diesel and a preparation method thereof. The preparation method comprises the steps of: mixing, forming and roasting silicon oxide-alumina, alumina and/or a precursor of the alumina and Y-shaped molecular sieve, then introducing an effective dose of metallic components selected from at least one Group VII and at least one Group VI into the roasted forming composition; the preparation method is characterized in that the silicon oxide-alumina is selected from at least two the silicon oxide-alumina having different N values, the difference between the N values of the silicon oxide-alumina is 0.02-0.2. Compared with the prior art, the catalyst provided by the invention method has better upgrading performance for the inferior diesel.
Description
Technical field
The present invention relates to a kind of catalyst for hydro-upgrading and preparation method thereof, more specifically to a kind of Catalysts and its preparation method that is used for hydro-upgrading of inferior diesel.
Background technology
Along with the year by year increase of market to the diesel oil demand, the upgrading paid more and more attention of poor ignition quality fuel.Gelatin liquefaction diesel oil and the upgrading problem that in China's diesel pool, accounts for the catalytic diesel oil of very big proportion have also caused people's attention, and its common feature is a nitrogen and aromaticity content is high, cetane value is low, density is big, storage stability is poor.In the presence of catalyst for hydro-upgrading, these poor ignition quality fuels are carried out hydro-upgrading can remove wherein nitrogen and reduction aromaticity content, improve diesel cetane-number, the quality of diesel oil is improved.
Catalyst for hydro-upgrading generally contains carrier and loads at least a group vib and at least a group VIII metal component on this carrier; Also contain adjuvant components such as fluorine, phosphorus in some catalyzer; Support of the catalyst is aluminum oxide and/or silicon oxide, and some catalyzer also contains zeolite.
CN1054150C discloses a kind of catalyst for hydrocracking diesel oil, and carrier that this catalyzer is made up of aluminum oxide, amorphous aluminum silicide and molecular sieve and the hydrogenation active metals that loads on this carrier are formed WO in the catalyzer
3Content be that the content of the heavy % of 10-30, NiO is that the content of the heavy % of 2-15, molecular sieve is that the content of the heavy % of 5-45, aluminum oxide is that the content of the heavy % of 30-70, amorphous aluminum silicide is the heavy % of 5-25; Said molecular sieve is a Y zeolite; Its infrared total acid content is 0.5-1 mmole/gram, and lattice constant is the 2.436-2.444 nanometer.Said aluminum oxide is pore volume 0.8-1.1 milliliter/gram; Surface-area 230-400 rice
2The little porous aluminum oxide of/gram.
CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, and the aluminum oxide 40-80 that consists of of this catalyzer weighs %, the heavy % of amorphous aluminum silicide 0-20, the heavy % of molecular sieve 5-30, and said molecular sieve is pore volume 0.40-0.52 milliliter/gram, specific surface 750-900 rice
2/ gram, lattice constant 2.420-2.500, the Y zeolite of silica alumina ratio 7-15, the heavy % of group vib metal content 10-30, the content of V111 family metal oxide are the heavy % of 2-15.
US5; 030; 780 disclose a kind of saturation process of aromatic hydroxy compound, and this method has been used a kind of catalyzer, and said catalyzer contains the hydrogenation metal that loads on a kind of carrier; Said support of the catalyst contains a kind of zeolite and a kind of porous heat-resistant inorganic oxide; Particularly contain the heat-resistant inorganic oxide that is dispersed in the silicon-aluminium in the alumina host, said zeolite comprises the various crystalline silico-alumino zeolites of known nature or synthetic, like faujusite, mordenite, erionite zeolite, y-type zeolite, X type zeolite, L zeolite, omega zeolite, ZSM-4 zeolite, Beta zeolite etc.
CN1803996A discloses a kind of catalyst for hydrogenation treatment of diesel oil and preparation method thereof; This Preparation of catalysts method; Comprise precursor and Y zeolite mixing, moulding and roasting with a kind of silica-alumina, aluminum oxide and/or aluminum oxide; Introduce at least a group VIII and at least a group vib metal component afterwards in the mixture after roasting, wherein, said silica-alumina has structure of similar to thin diaspore; With the catalyzer is benchmark; The consumption of each component makes the silica-alumina that contains 1-70 weight % in the final catalyzer, the Y zeolite of 1-60 weight %, the aluminum oxide of 5-80 weight %, in oxide compound, and the group vib metal component of the group VIII metal component of 1-15 weight %, 10-40 weight %.In preferred embodiment, said N value with silica-alumina of structure of similar to thin diaspore is 0.1-1, contains the silicon oxide of 5-60 weight % after the roasting, the aluminum oxide of 40-95 weight %; Described N=P1/P2, P1 are the solid of said silica-alumina
27Chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the Al NMR spectrogram, and P2 is the solid of said silica-alumina
27Chemical shift is the peak area at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
Compare with the catalyzer of the compound preparation of molecular sieve with single aluminum oxide, the monox-alumina containning catalyst for hydrogenation treatment of diesel oil performance that prior art provides improves, but activity is still lower.
Summary of the invention
The objective of the invention is to the existing low shortcoming of monox-alumina containning diesel oil hydrogenation modification catalyst activity, a kind of new preparation high reactivity catalyst for hydro-upgrading of inferior diesel method and the catalyzer that is prepared by this method are provided.
The present invention provides a kind of preparation method of catalyst for hydro-upgrading of inferior diesel; Comprise precursor and Y zeolite mixing, moulding and roasting with silica-alumina, aluminum oxide and/or aluminum oxide; That in said forming composition, introduces significant quantity afterwards is selected from least a group VIII and at least a VI family metal component; It is characterized in that; Said silica-alumina is selected from the silica-alumina that at least two kinds of N values vary in size, and the difference of the N value of said silica-alumina is 0.02～0.2.
Catalyzer provided by the invention contains the hydrogenation active metals component of silica-alumina, aluminum oxide, Y zeolite and significant quantity, and this catalyzer is by aforementioned method preparation provided by the invention.
Compare with the diesel oil hydrogenation modification catalyzer that existing method provides; The catalyzer that provides by method provided by the invention; Because employing is selected from least two kinds of different silica-aluminas with structure of similar to thin diaspore of N value and prepares; This catalyzer not only has higher desulfurization, denitrification activity, can make at least 0.7 unit of diesel cetane-number increase rate increase simultaneously.
Embodiment
According to method provided by the invention, the difference of said N value is preferably 0.04～0.15.Described N=P1/P2, P1 are the solid of said silica-alumina
27Chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the Al NMR spectrogram, and P2 is the solid of said silica-alumina
27Chemical shift is the peak area at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
27The chemical shift at each peak and each peak area are that reference is measured with saturated aluminum sulfate aqueous solution on Varian UnityInova 300 M type nuclear magnetic resonance spectrometers in the Al NMR spectrogram.
The consumption ratio of the silica-alumina that said N value varies in size is preferably 1: 0.1-10 more is preferably 1: 0.2-8.
According to method provided by the invention, be 0.02～0.2 in the difference that satisfies the N value, under preferred 0.04～0.15 the condition, said silica-alumina can be to can be used as the silica-alumina that support of the catalyst is used arbitrarily.The preferred silica-alumina that wherein has structure of similar to thin diaspore.With said silica-alumina is benchmark, and said silica-alumina contains the silicon oxide of 5-60 weight % after roasting, and the aluminum oxide of 40-95 weight % further preferably contains the silicon oxide of 10-45 weight %, the aluminum oxide of 55-90 weight %.
Described silica-alumina can be commercially available commodity or adopt any one existing method preparation.For example, a kind of commodity silica-alumina with structure of similar to thin diaspore is the Siral series silica-alumina that German Condea company produces.
In preferred embodiment, said silica-alumina with structure of similar to thin diaspore can adopt the method preparation that comprises the steps: prepare the mixed solution of a kind of pseudo-boehmite and water, introduce a kind of solution of silicon-containing compound, aging and drying afterwards.Described aging condition is: pH value 7-11, temperature 75-120 ℃, time 6-24 hour are preferably: pH value 7-8.5, temperature 80-98 ℃, time 12-24 hour.With said silica-alumina is benchmark; The consumption of each component preferably makes said silica-alumina after roasting, contain the silicon oxide of 5-60 weight %; The aluminum oxide of 40-95 weight % contains the silicon oxide of 10-45 weight %, the aluminum oxide of 55-90 weight % after the further preferred roasting.Said drying is conventional drying, and drying temperature can be that 80-300 ℃, time of drying can be 2-24 hour, and preferred drying temperature is that 100-150 ℃, time of drying are 4-20 hour.
The preparation method of the mixed solution of described pseudo-boehmite and water can be that directly the pseudo-boehmite that any one is commercially available mixes with water and obtains, and also can be that the method that adopts routine to prepare pseudo-boehmite prepares.For example, can be that the solution of at least a aluminum contained compound is mixed, becomes glue with the solution of a kind of alkali or acid and wears out, said aged condition: pH is 7-8.5, temperature is that 30-75 ℃, time are 5-120 minute.
Described aluminum contained compound is selected from one or more in Tai-Ace S 150, sodium metaaluminate, aluminum nitrate, aluminum chloride, aluminum alkoxide, the aluminum alkyls, is preferably in Tai-Ace S 150, sodium metaaluminate, aluminum nitrate, the aluminum chloride one or more.
Described alkali be oxyhydroxide or in water medium hydrolysis make the aqueous solution be the salt of alkalescence, preferred oxyhydroxide is selected from one or more in ammoniacal liquor, sodium hydroxide, the Pottasium Hydroxide; Preferred salt is selected from one or more in bicarbonate of ammonia, volatile salt, sodium hydrogencarbonate, yellow soda ash, saleratus, the salt of wormwood.
Described acid is protonic acid or in water medium, is the tart oxide compound that preferred protonic acid is selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid; Preferred oxide compound is a carbonic acid gas.
The introducing of the solution of said silicon-containing compound is that the solution with silicon-containing compound mixes with the mixed solution of water with prepared pseudo-boehmite; For example; Can be under agitation the solution of silicon-containing compound to be joined in the mixed solution of pseudo-boehmite and water; Also can be that mixed solution and the stream of the solution that contains silicon-containing compound with pseudo-boehmite and water is added in the reaction vessel; The concentration of silicon-containing compound solution and consumption make the silicon oxide that contains 5-60 weight % in final silicon oxide one aluminum oxide, are preferably 10-45 weight %.
Described silicon-containing compound can be any water-soluble silicon-containing compound and the silicon-containing compound that can hydrolysis in water medium forms silicon gel, colloidal sol.For example, one or more in the compounds such as water glass, the water-sol and silicon ester.
According to method provided by the invention, the embodiment of a said silica-alumina of preferred preparation may further comprise the steps:
(1) a kind of solution that contains aluminium salt and a kind of alkaline solution or acid solution and stream are joined be carried out to the glue reaction in the reaction vessel, reaction conditions: the pH value is 6.5-8.5, and temperature is 30-75 ℃;
(2) product that step (1) is generated is at pH 7-8.5, temperature 30-75 ℃ aging 5-120 minute down;
(3) under agitation, a kind of solution of silicon-containing compound is joined in the product that step (2) obtains;
(4) at pH 8-10,80-98 ℃ of following product 12-24 hour of obtaining of aging step (3);
(5) product that wash, filtration step (4) obtains;
(6) product that obtains of drying step (5) obtains described silica-alumina.
According to method provided by the invention, wherein said y-type zeolite molecular sieve can be commercially available commodity, also can adopt any one existing method preparation.For example, it can be that a kind of lattice constant is in the 2.452-2.475 nanometer range and the y-type zeolite molecular sieve of silica in the 3.5-7 scope; Can be through with after y-type zeolite molecular sieve and the ammonium ion exchange; Carry out the ultrastable Y molecular sieve that the one or many hydrothermal treatment consists is produced; This y-type zeolite molecular sieve lattice constant is the 2.420-2.462 nanometer, and the silica-alumina mol ratio can reach 100 in the skeleton, is preferably to reach 60; Can be through after the inorganic ammonium solution exchange with y-type zeolite molecular sieve and one or more phosphides, carry out the phosphorous ultrastable Y molecular sieve that the one or many hydrothermal treatment consists is produced; Can be through the rare earth compound aqueous solution is handled the rare earth Y type zeolite molecular sieve that Y zeolite combines the preparation of one or many hydrothermal treatment consists.
Said aluminum oxide is selected among γ, η, θ, δ and the χ one or more transition aluminas; Also can be to contain one or more to be selected among silicon, titanium, magnesium, boron, zirconium, thorium, niobium, the rare earth among one or more γ, η, θ, δ and χ that dose component one or more transition aluminas, one or more dose the gama-alumina of component among being selected from silicon, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth with containing one or more to be preferably gama-alumina.
The precursor of said aluminum oxide; Can be to be selected among hibbsite, monohydrate alumina and the amorphous hydroted alumina one or more, also can be among hibbsite, monohydrate alumina and the amorphous hydroted alumina of siliceous, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth one or more.
Said moulding adopts customary way to carry out, and all can like methods such as compressing tablet, spin, extrusions.When adopting the customary way moulding, for guarantee moulding carry out smoothly in said mixture, introduce auxiliary agent and allow, for example when extrusion, can in mixture, introduce an amount of extrusion aid and water, extrusion moulding afterwards.The kind of said extrusion aid and consumption all can be that this area is conventional, and for example common extrusion aid can be selected from sesbania powder, methylcellulose gum, starch, Z 150PH, gather in the ethanol one or more.
This area customary way and condition are adopted in described roasting, can be 350-650 ℃ like maturing temperature; Be preferably 400-600 ℃, roasting time is 2-6 hour, is preferably 3-5 hour.
The method that is selected from least a group VIII and at least a VI family metal component of said introducing significant quantity is a conventional process.For example; Under the condition in the moulding after being enough to that at least a group VIII of being selected from of significant quantity and at least a VI family metal component be deposited on said roasting; With the forming composition after the described roasting with contain at least a group VIII of being selected from of significant quantity and contact with at least a VI family solution of metal compound; As passing through methods such as dipping, co-precipitation, preferred pickling process, drying, roasting or not roasting afterwards.The condition of said drying and roasting is the habitual condition of preparation catalyzer; Like drying temperature is 80-350 ℃, is preferably 100-300 ℃, and be 1-24 hour time of drying; Be preferably 2-12 hour; Maturing temperature is 350-550 ℃ and is preferably 400-500 ℃ that roasting time is 1-10 hour, is preferably 2-8 hour.
Said group VIII metallic compound is selected from one or more in the soluble compound of these metals, for example, can be in the nitrate salt, acetate, carbonate, muriate, soluble complexes of these metals one or more.
Said group vib metallic compound is selected from one or more in the soluble compound of these metals, for example, can be in molybdate, paramolybdate, tungstate, metatungstate, the ethyl metatungstate one or more.
According to method provided by the invention, be benchmark with the catalyzer, the consumption of said each component makes the silica-alumina that contains 1-80 weight % in the final catalyzer; Be preferably 5-75 weight %, the Y zeolite of 1-20 weight %, be preferably the heavy % of 1-15, the aluminum oxide of 5-80 weight %; Be preferably 8-70 weight %, in oxide compound, the group VIII metal component of 1-15 weight %; Be preferably 2-8 weight %, the group vib metal component of 10-40 weight % is preferably 10-35 weight %.
According to method provided by the invention, can also in catalyzer, introduce the material that any material that does not influence the catalytic performance of catalyzer provided by the invention maybe can improve the catalytic performance of catalyzer provided by the invention.As can introduce in the components such as fluorine, phosphorus, boron one or more, and be benchmark in element and with the catalyzer, the introducing amount of above-mentioned auxiliary agent is 0-10 weight %, is preferably 0.5-5 weight %.
When also containing one or more the adjuvant component that is selected from fluorine, phosphorus and the boron in the said catalyzer, its introducing method can be directly with silicon oxide one aluminum oxide, aluminum oxide with Y zeolite mixes, moulding and roasting with the compound that contains said auxiliary agent; Can be with the compound that contains said auxiliary agent with contain group VIII and the group vib metallic compound be mixed with mixing solutions after contact with said mixture through roasting; Can also be with contacting and roasting with said mixture behind the independent obtain solution of the compound that contains auxiliary agent through roasting.When auxiliary agent and group VIII and group vib metal are introduced said mixture through roasting respectively, preferably at first contact also roasting with said mixture through roasting with containing auxiliary compound solution, afterwards again with contain group VIII and contact with the group vib solution of metal compound; For example through methods such as IX, dipping, co-precipitation; Preferred pickling process, said maturing temperature is 350-550 ℃, is preferably 400-500 ℃; Roasting time is 2-8 hour, is preferably 3-6 hour.
Show that like the disclosed content of CN1803996A it is favourable to improving catalyst performance in the Preparation of catalysts process, to introduce organism.Therefore; According to method provided by the invention; Also be included in the forming composition after the said roasting and introduce organism; Said organic introducing method, can be with organism with contain at least a group VIII and contact with described mixture after the group vib metallic compound is mixed with mixing solutions through roasting with at least a being selected from; Can also be with contacting with said mixture behind the independent obtain solution of organism through roasting.When organism and group VIII and group vib metal component are introduced said mixture through roasting respectively; Preferred at first contact with the mixture after the solution of metal compound that contains at least a group VIII and at least a group vib and this roasting; Contact with containing organic solution more afterwards, like method through dipping.Said organic introducing amount makes that the mol ratio of organism and group VIII metal component is 0.1-5 in the final catalyzer, is preferably 0.2-2.5.
Said organism can be contain oxygen and/or nitrogenous organic one or more.Like oxygen-containing organic compound can be in organic alcohol, the organic acid one or more, and organic compounds containing nitrogen can be one or more in the organic amine.Preferred oxygenatedchemicals can be terepthaloyl moietie, USP Kosher, polyoxyethylene glycol (molecular weight is 200-1500), acetate, toxilic acid, oxalic acid, nitrilotriacetic acid, 1; In 2-CDTA, the Hydrocerol A one or more, organic compounds containing nitrogen can be quadrol or EDTA.
According to the ordinary method in this area; Catalyzer provided by the invention is before using; Usually can be in the presence of hydrogen; Under 140-370 ℃ temperature, carry out prevulcanized with sulphur, hydrogen sulfide or sulfur-bearing raw material, this prevulcanized can be carried out also can in device, original position vulcanizing outside device, is translated into sulfide type.
Catalyzer provided by the invention is applicable to hydrocarbon raw material is carried out hydrotreatment, to produce the hydrocarbon fraction of low-sulfur, low nitrogen and low fragrant content.Being specially adapted to improve diesel cetane-number is the hydro-upgrading process of the diesel oil hydrogenation modification of purpose, especially poor ignition quality fuel.
Following instance will further specify the present invention.
Agents useful for same in the instance except that specifying, is chemically pure reagent.
The hydrogenation activity component concentration adopts x-ray fluorescence spectrometry [Yang Cuiding etc., petrochemical complex analytical procedure (RIPP TP), Science Press, 1990, P380].
The X-ray diffracting spectrum of silica-alumina is measured on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44KV, 40mA, sweep velocity is 2 °/minute, confirms the crystalline phase of sample according to the X-ray diffracting spectrum.Before the mensuration, sample is at first in 600 ℃ of roastings 2 hours.
Instance 1-5 explanation the present invention adopts has silica-alumina of structure of similar to thin diaspore and preparation method thereof.
Instance 1
Take by weighing 515 gram aluminum chlorides (Beijing chemical reagent factory product), be dissolved into 1.6 liters of aluminum trichloride solution a1 (Al with deionized water
2O
3Concentration is 65 grams per liters); 500 milliliters of strong aquas (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1 500 ml soln b1 with deionized water; The modulus of getting technical grade is 3.26, SiO
2Content is 220 milliliters of the water glass solutions (Chang Ling refinery product) of 280 grams per liters, is diluted to 1000 ml soln c1 with deionized water; Get 75 gram sodium hydroxide, be dissolved into 150 ml soln d1 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stir and be heated to 40 ℃, and stream adds solution a1 and b1; It is 7 that the adjusting flow makes the pH value of reaction system, and reaction product is gone into digestion tank and worn out, aging condition: pH is 7; Temperature is 45 ℃; Digestion time is 30 minutes, behind aging the end, under agitation adds solution c1 and d1 successively.This moment, the pH of reaction system was 8.9, and temperature is 50 ℃, was warming up to 85 ℃ and 23 hours after-filtration of constant temperature.Cakes with deionized water washing 5 times is filtered after each washing, the filter cake after the last washing 110 ℃ dry 20 hours down, obtain silica-alumina M-1.The crystalline phase of M-1, the content of silicon oxide, aluminum oxide and N value are listed in the table 1.
Instance 2
Take by weighing 800 gram aluminum nitrates (Beijing chemical reagent factory product), be dissolved into 1.6 liters of aluminum nitrate solution a2 (Al with deionized water
2O
3Concentration is 65 grams per liters); 500 milliliters of strong aquas (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b2 with deionized water; The modulus of getting technical grade is 3.26, SiO
2Content is 60 milliliters of the water glass solutions (Chang Ling refinery product) of 280 grams per liters, is diluted to 240 ml soln c2 with deionized water; Get 75 gram sodium hydroxide, be dissolved into 150 ml soln d2 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stir and be heated to 50 ℃, and stream adds solution a2 and b2; It is 8 that the adjusting flow makes the pH value of reaction system, and reaction product is gone into digestion tank and worn out, and aging condition is that pH is 7.6; Temperature is 60 ℃; Digestion time is 30 minutes, behind aging the end, under agitation adds solution c2 and d2 successively.This moment, the pH of reaction system was 8.5, and temperature is 65 ℃, was warming up to 90 ℃ and 13 hours after-filtration of constant temperature.Cakes with deionized water washing 5 times is filtered after each washing, the filter cake after the last washing 150 ℃ dry 6 hours down, obtain silica-alumina M-2.The crystalline phase of M-2, the content of silicon oxide, aluminum oxide and N value are listed in the table 1.
Instance 3
Get 1.6 liters of (Al of industrial sulphuric acid aluminum solutions a3
2O
3Concentration is about 98 grams per liters, free acid content 1.5 grams per liters).500 milliliters of strong aquas (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b3 with deionized water.Get the modulus 3.26 of technical grade, SiO
2Content is 220 milliliters of the water glass solutions of 280 grams per liters, is diluted to 1000 milliliters with deionized water, obtains solution c3.Get 50 gram sodium hydroxide, be dissolved into 150 ml soln d3 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stir and be heated to 60 ℃, and stream adds solution a3 and b3; It is 7.5 that the adjusting flow makes the pH value of reaction system, and reaction product is gone into digestion tank and worn out, and aging condition is that pH is 7; Temperature is 70 ℃; Digestion time is 15 minutes, behind aging the end, under agitation adds solution c3 and d3 successively.This moment, the pH of reaction system was 8.5, and temperature is 70 ℃, was warming up to 98 ℃ and 16 hours after-filtration of constant temperature.Cakes with deionized water washing 5 times is filtered after each washing, the filter cake after the last washing 120 ℃ dry 15 hours down, obtain silica-alumina M-3.The crystalline phase of M-3, the content of silicon oxide, aluminum oxide and N value are listed in the table 1.
Instance 4
Said silica-alumina is the commodity silica-alumina, and its trade mark is Siral40 (a Condea Company products).The crystalline phase of this product, the content of silicon oxide, aluminum oxide and N value are listed in the table 1.
Table 1
| Instance | SiO 2-Al 2O 3 | SiO 2, weight % | Al 2O 3, weight % | Crystalline phase | The N value |
| 1 | M-1 | 41 | 59 | Pseudo-boehmite | 0.27 |
| 2 | M-2 | 15 | 85 | Pseudo-boehmite | 0.21 |
| 3 | M-3 | 43 | 57 | Pseudo-boehmite | 0.41 |
| 4 | Siral40 | 40 | 60 | Pseudo-boehmite | 0.12 |
Comparative Examples 1
With 167 gram M1,77 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 26.7 gram Y zeolite (Chang Ling refinery catalyst plant product, lattice constant 24.60 dusts; Butt 75 heavy %) mix; Be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar is in 120 ℃ of oven dry 4 hours, 450 ℃ of roastings 4 hours; Be cooled to and get 180 grams after the room temperature with the aqueous solution dipping that contains 148 milliliters of ammonium metawolframate 79.4 grams, 72.1 gram nickelous nitrates 2 hours; In 120 ℃ of oven dry 4 hours, 480 ℃ of roastings 4 hours obtained catalyzer DCH-1 afterwards.Each components contents is seen table 2 among the catalyzer CH-1.
Comparative Examples 2
With 167 gram M2,77 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 26.7 gram Y zeolite (Chang Ling refinery catalyst plant product, lattice constant 24.60 dusts; Butt 75 heavy %) mix; Be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar is in 120 ℃ of oven dry 4 hours, 450 ℃ of roastings 4 hours; Be cooled to and get 180 grams after the room temperature with the aqueous solution dipping that contains 148 milliliters of ammonium metawolframate 79.4 grams, 72.1 gram nickelous nitrates 2 hours; In 120 ℃ of oven dry 4 hours, 480 ℃ of roastings 4 hours obtained catalyzer DCH-2 afterwards.Each components contents is seen table 2 among the catalyzer CH-2.
Comparative Examples 3
With 167 gram M3,77 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 26.7 gram Y zeolite (Chang Ling refinery catalyst plant product, lattice constant 24.60 dusts; Butt 75 heavy %) mix; Be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar is in 120 ℃ of oven dry 4 hours, 450 ℃ of roastings 4 hours; Be cooled to and get 180 grams after the room temperature with the aqueous solution dipping that contains 148 milliliters of ammonium metawolframate 79.4 grams, 72.1 gram nickelous nitrates 2 hours; In 120 ℃ of oven dry 4 hours, 480 ℃ of roastings 4 hours obtained catalyzer DCH-3 afterwards.Each components contents is seen table 2 among the catalyzer CH-3.
Instance 5-9 explanation the inventive method and the catalyzer for preparing by this method.
Instance 5
With 129 gram M1,38 gram M2,77 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 26.7 gram Y zeolite (Chang Ling refinery catalyst plant products; Lattice constant 24.60 dusts, heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar; Wet bar was in 120 ℃ of oven dry 4 hours; 450 ℃ of roastings 4 hours are cooled to and get 180 grams after the room temperature with the aqueous solution dipping that contains 148 milliliters of ammonium metawolframate 79.4 grams, 72.1 gram nickelous nitrates 2 hours, afterwards in 120 ℃ of oven dry 4 hours; 480 ℃ of roastings 4 hours obtain catalyzer CH-1.Each components contents is seen table 2 among the catalyzer CH-1.
Instance 6
With 32.5 gram M1,134.5 gram M3,77 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 26.7 gram Y zeolite (Chang Ling refinery catalyst plant products; Lattice constant 24.60 dusts, heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar; Wet bar was in 120 ℃ of oven dry 4 hours; 450 ℃ of roastings 4 hours are cooled to and get 180 grams after the room temperature with the aqueous solution dipping that contains 148 milliliters of ammonium metawolframate 79.4 grams, 72.1 gram nickelous nitrates 2 hours, afterwards in 120 ℃ of oven dry 4 hours; 480 ℃ of roastings 4 hours obtain catalyzer CH-2.Each components contents is seen table 2 among the catalyzer CH-2.
Instance 7
With 126.2 gram M1,27.6 gram M2,55.4 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 26.7 gram Y zeolite (Chang Ling refinery catalyst plant products; Lattice constant 24.48 dusts, heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar; Wet bar was in 120 ℃ of oven dry 4 hours; 470 ℃ of roastings 3 hours are got 180 grams with the 150 milliliters of dippings of the aqueous solution that contain ammonium metawolframate 106.2 grams, 32.4 gram nickelous nitrates after being cooled to room temperature, afterwards in 120 ℃ of oven dry 3 hours; 470 ℃ of roastings 4 hours obtain catalyzer CH-3.Each components contents is seen table 2 among the catalyzer CH-3.
Instance 8
With 23.9 gram M1,150.4 gram M3,98 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 32.0 gram PY type molecular sieve (Chang Ling refinery catalyst plant product, lattice constant 24.53 dusts, P
2O
5Content: 3.5 heavy %, butt 75 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar; Wet bar was in 120 ℃ of oven dry 4 hours; 450 ℃ of roastings 4 hours are cooled to and get 180 grams after the room temperature with the aqueous solution dipping that contains ammonium metawolframate 57.6 grams, nickelous nitrate 46.8 grams 2 hours, afterwards in 120 ℃ of oven dry 3 hours; 480 ℃ of roastings 3 hours obtain catalyzer CH-4.Each components contents is seen table 2 among the catalyzer CH-4.
Instance 9
With 140.5 gram M2,17.5 gram Siral40,61.5 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 17.0 gram PY type molecular sieve (Chang Ling refinery catalyst plant products; Lattice constant 24.55 dusts; The heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 4 hours; 450 ℃ of roastings 4 hours; Be cooled to and get 180 grams after the room temperature with 138 milliliters of dippings of the aqueous solution that contain 51.1 gram molybdenum acid ammonias and 35.3 gram nickelous nitrates 1 hour, 120 ℃ of dryings are 4 hours afterwards, and 450 ℃ of activation obtained catalyzer CH-5 in 3 hours.Each components contents is seen table 2 among the catalyzer CH-5.
Table 2
| Instance | Catalyzer | The heavy % of silica-alumina | The heavy % of molecular sieve | The heavy % of aluminum oxide | The heavy % of NiO | MoO 3Heavy % | WO 3Heavy % |
| Comparative Examples 1 | ?DCH-1 | M-1，44.2 | 6.8 | 17.0 | 7.0 | / | 25 |
| Comparative Examples 2 | ?DCH-2 | M-2，44.2 | 6.8 | 17.0 | 7.0 | / | 25 |
| Comparative Examples 3 | ?DCH-3 | M-3，44.2 | 6.8 | 17.0 | 7.0 | / | 25 |
| 5 | ?CH-1 | M-1，34.2 M-2，10.0 | 6.8 | 17.0 | 7.0 | / | 25 |
| 6 | ?CH-2 | M-1，8.6 M-3，35.6 | 6.8 | 17.0 | 7.0 | / | 25 |
| 7 | ?CH-3 | M-1，32.0 M-2，7.0 | 14.3 | 11.7 | 3.0 | / | 32 |
| 8 | ?CH-4 | M-1，7.0 M-3，44.0 | 9.0 | 15.0 | 5.0 | / | 20 |
| 9 | ?CH-5 | M-2，43.0 Siral40，5.5 | 5.0 | 25.0 | 3.5 | 18 | / |
Instance 10-11
Following instance is explained the performance of catalyzer provided by the invention.
With density is 0.9206 gram per centimeter
3Sulphur content is that 4500ppm, nitrogen content are 710ppm; Cetane value is that 27.2 catalytic cracking diesel oil is a raw material, on 30 milliliters of fixed bed devices, estimates the performance of catalyzer CH1 provided by the invention, CH2, and reaction conditions is: 360 ℃ of temperature, pressure 6.4MPa, liquid hourly space velocity 1.3 hours
-1, hydrogen to oil volume ratio 600, the result lists in the table 3.
Comparative Examples 4-6
With and reaction conditions difference evaluate catalysts DCH-1 oily with embodiment 10 same materials, DCH-2, DCH-3, the result lists in the table 3.
Table 3
| Instance | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 | 10 | 11 |
| Catalyzer | DCH-1 | DCH-2 | DCH-3 | CH-1 | CH-2 |
| Product density, gram per centimeter 3 | 0.8904 | 0.8919 | 0.8869 | 0.8881 | 0.8854 |
| Desulfurization degree, heavy % | 92.7 | 92.4 | 93.6 | 94.2 | 94.5 |
| Denitrification percent, heavy % | 98.2 | 97.3 | 98.4 | 98.4 | 98.7 |
| The cetane value increased value | 7.0 | 6.7 | 7.9 | 7.7 | 8.6 |
| Density reduction value, gram per centimeter 3 | 0.0302 | 0.0287 | 0.0337 | 0.0325 | 0.0352 |
| Diesel yield, V% | 97.5 | 98.1 | 97.0 | 98.3 | 98.0 |
The result that table 3 provides shows; Be that the diesel oil hydrogenation modification catalyzer that the acidic components method provides is compared with single silica-alumina; Employing combined oxidation silicon-aluminum oxide that the inventive method provides is that acidic components prepare catalyzer and not only have higher desulfurization, denitrification activity and diesel yield, can make the diesel cetane-number increase rate increase by 0.7～1.5 unit simultaneously.
Claims (10)
1. the preparation method of a catalyst for hydro-upgrading of inferior diesel; Comprise precursor and Y zeolite mixing, moulding and roasting with silica-alumina, aluminum oxide and/or aluminum oxide; That in said forming composition, introduces significant quantity afterwards is selected from least a group VIII and at least a VI family metal component; It is characterized in that said silica-alumina is selected from the silica-alumina that at least two kinds of N values vary in size, the difference of the N value of said silica-alumina is 0.02-0.2; Described N=P1/P2, P1 are the solid of said silica-alumina
27Chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the Al NMR spectrogram, and P2 is the solid of said silica-alumina
27Chemical shift is the peak area at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
2. according to the said method of claim 1, it is characterized in that the difference of said N value is 0.04-0.15.
3. according to the said method of claim 1, it is characterized in that the consumption ratio of the silica-alumina that said N value varies in size is 1: 0.1-10.
4. according to the said method of claim 3, it is characterized in that the consumption ratio of the silica-alumina that said N value varies in size is 1: 0.2-8.
5. according to the said method of claim 1, it is characterized in that described silica-alumina has structure of similar to thin diaspore.
6. according to claim 1,2,3,4 or 5 said methods, it is characterized in that described silica-alumina contains the silicon oxide of 5-60 weight % after roasting, the aluminum oxide of 40-95 weight %.
7. according to the said method of claim 6, it is characterized in that described silica-alumina contains the silicon oxide of 10-45 weight % after roasting, the aluminum oxide of 55-90 weight %.
8. according to the said method of claim 1, it is characterized in that, is benchmark with the catalyzer; The consumption of each component makes the silica-alumina that contains 1-80 weight % in the final catalyzer; The Y zeolite of 1-20 weight %, the aluminum oxide of 5-80 weight % is in oxide compound; The group VIII metal component of 1-15 weight %, the group vib metal component of 10-40 weight %.
9. according to the said method of claim 8, it is characterized in that, is benchmark with the catalyzer; The consumption of said each component makes the silica-alumina that contains 5-75 weight % in the final catalyzer; The Y zeolite of 1-15 weight %, the aluminum oxide of 8-70 weight % is in oxide compound; The group VIII metal component of 2-8 weight %, the group vib metal component of 10-35 weight %.
10. catalyst for hydro-upgrading of inferior diesel contains the hydrogenation active metals component of silica-alumina, aluminum oxide, Y zeolite and significant quantity, it is characterized in that said catalyzer is by any method preparation of claim 1-9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5030780A (en) * | 1990-07-26 | 1991-07-09 | Union Oil Company Of California | Aromatic saturation process with a silica-alumina and zeolite catalyst |
| CN1803996A (en) * | 2005-01-14 | 2006-07-19 | 中国石油化工股份有限公司 | Diesel oil hydrotreating catalyst and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030780A (en) * | 1990-07-26 | 1991-07-09 | Union Oil Company Of California | Aromatic saturation process with a silica-alumina and zeolite catalyst |
| CN1803996A (en) * | 2005-01-14 | 2006-07-19 | 中国石油化工股份有限公司 | Diesel oil hydrotreating catalyst and method for preparing the same |
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