CN1803996A - Diesel oil hydrotreating catalyst and method for preparing the same - Google Patents
Diesel oil hydrotreating catalyst and method for preparing the same Download PDFInfo
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Abstract
The disclosed catalyst special to low-grade diesel fuel hydrotreatment comprises: given the catalyst, 1-70wt% SiO2-Al2O3 with quasi-thin diaspore structure, 1-60wt% Y-form molecular sieve, and 5-80wt% Al2O3; wherein, given the oxide, 1-15wt% VIII metal constituent, and 10-40wt% VIB metal constituent. The product is prepared by mixing, forming, baking and then adding at least one of former metal constituent.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, more specifically to a kind of catalyst for hydrogenation treatment of diesel oil and preparation method thereof.
Background technology
Along with the year by year increase of market to the diesel oil demand, high-yield diesel oil becomes a direction of catalytic cracking process development.The characteristics of catalytic cracking diesel oil are sulphur, nitrogen and aromaticity content height, cetane value is low, storage stability is poor, and the quantity discharged of toxic gas is big during burning.In the presence of hydrotreating catalyst, diesel oil is carried out hydrotreatment can remove wherein sulphur, nitrogen and reduction aromaticity content, the quality of diesel oil is improved.
Hydrotreating catalyst generally contains carrier and at least a group vib and at least a group VIII metal component that load 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 10-30 heavy %, 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, described 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.Described 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 consist of aluminum oxide 40-80 heavy %, amorphous aluminum silicide 0-20 heavy %, the molecular sieve 5-30 of this catalyzer weigh %, and described 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 VIII family metal oxide are the heavy % of 2-15.
US5,030,780 disclose a kind of saturation process of aromatic hydroxy compound, this method has been used a kind of catalyzer, described catalyzer contains the hydrogenation metal that loads on a kind of carrier, described 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, described zeolite comprises the various crystalline silico-alumino zeolites of known nature or synthetic, as faujusite, mordenite, the erionite zeolite, y-type zeolite, X type zeolite, the L zeolite, omega zeolite, the ZSM-4 zeolite, Beta zeolite etc.
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 at the active low shortcoming of existing monox-alumina containning catalyst for hydrogenation treatment of diesel oil, a kind of new preparation high reactivity catalyst for hydrogenation treatment of diesel oil method and the catalyzer that is prepared by this method are provided.
Method provided by the invention comprises a kind of silica-alumina, the precursor of aluminum oxide and/or aluminum oxide and Y zeolite mix, moulding and roasting, introduce at least a group VIII and at least a group vib metal component afterwards in the mixture after roasting, wherein, described 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, the group VIII metal component of 1-15 weight %, the group vib metal component of 10-40 weight %.
Catalyzer provided by the invention contains silica-alumina, aluminum oxide, Y zeolite and is selected from group VIII and the metal component of group vib, the method preparation that this catalyzer is provided by the invention described above.
Compare with the catalyst for hydrogenation treatment of diesel oil that existing method provides, the catalyzer that the inventive method provides not only has higher desulfurization, denitrification activity, can make at least 1.5 units of diesel cetane-number increase rate increase simultaneously.
Embodiment
According to method provided by the invention, described silica-alumina with structure of similar to thin diaspore, preferred N value is 0.1-1, the silicon oxide that contains 5-60 weight % after the roasting, the aluminum oxide of 40-95 weight %, further preferred N value is 0.2-0.8, contains the silicon oxide of 10-45 weight % after the roasting, the aluminum oxide of 55-90 weight %; Described N=P1/P2, P1 are the solid of described 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 described 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 300M type nuclear magnetic resonance spectrometer in the Al NMR spectrogram.
Described silica-alumina can be commercially available commodity or adopt any one prior art for preparing.For example a kind of silica-alumina with structure of similar to thin diaspore, the Siral series silica-alumina of producing for German Condea company.
One preferred, preparation N value for the method for the silica-alumina with structure of similar to thin diaspore of 0.1-1 is, the mixed solution that at first prepares a kind of pseudo-boehmite and water, introduce a kind of solution of silicon-containing compound, aging and drying afterwards, described aging condition is: carry out under pH value 7.5-11, the temperature 75-120 ℃ condition, time 6-24 hour, be preferably: pH value 8-10, temperature 80-98 ℃, time 12-24 hour.Described 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 the solution of at least a aluminum contained compound is mixed, becomes glue with the solution of a kind of alkali or acid and to wear out, described 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 potassium hydroxide; Preferred salt is selected from one or more in bicarbonate of ammonia, volatile salt, sodium bicarbonate, yellow soda ash, saleratus, the salt of wormwood.
Described acid is protonic acid or is the tart oxide compound that in water medium 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 described 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 to contain in the mixed solution and stream adding reaction vessel of solution with pseudo-boehmite and water of silicon-containing compound, the concentration of silicon-containing compound solution and consumption make the silicon oxide that contains 5-60 weight % in the final silica-alumina, 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 that preferred preparation has the silica-alumina of structure of similar to thin diaspore 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, and temperature 30-75 ℃ was worn out 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 product 12-24 hour of descending aging step (3) to obtain;
(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 by 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 2.420-2.455 nanometer, and the silica-alumina mol ratio can reach 100 in the skeleton, is preferably to reach 60; Can be by 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 by the rare earth compound aqueous solution being handled the rare earth Y type zeolite molecular sieve of Y zeolite in conjunction with the preparation of one or many hydrothermal treatment consists.With the catalyzer is benchmark, and the content of described type zeolite molecular sieve is the heavy % of 1-60, is preferably the heavy % of 15-50.
Described 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 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, be preferably gama-alumina and contain one or more that one or more dose the gama-alumina of component among being selected from titanium, magnesium, boron, zirconium, thorium, niobium, rare earth.
The precursor of described 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 titaniferous, magnesium, boron, zirconium, thorium, niobium, rare earth one or more.
Described moulding adopts customary way to carry out, and all can as methods such as compressing tablet, spin, extrusions.When adopting the customary way moulding, for guarantee moulding carry out smoothly in described 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 described extrusion aid and consumption all can be this area routines, and for example common extrusion aid can be selected from one or more in sesbania powder, methylcellulose gum, starch, polyvinyl alcohol, the poly-ethanol.
This area customary way and condition are adopted in described roasting, can be 350-650 ℃ as maturing temperature; Be preferably 400-600 ℃, roasting time is 2-6 hour, is preferably 3-5 hour.
According to method provided by the invention, the method of at least a group VIII of described introducing and at least a group vib metal component, be under the condition on the mixture that is enough to after metal component with at least a group VIII and at least a group vib is deposited on described roasting, with the mixture after the described roasting with contain at least a group VIII and contact with at least a group vib solution of metal compound, as by methods such as ion-exchange, dipping, co-precipitation, preferred pickling process, drying, roasting or not roasting afterwards.The condition of described drying and roasting is the habitual condition of preparation catalyzer, as drying temperature is 80-350 ℃, be preferably 100-300 ℃, 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.Described group VIII metal component is preferably cobalt and/or nickel, and the group vib metal component is preferably molybdenum and/or tungsten.In oxide compound and with the catalyzer is benchmark, describedly contain the content of metal component at least a group VIII and at least a group vib solution of metal compound and the consumption of solution makes the group VIII metal component that contains 1-15 weight % in the final catalyzer, be preferably 2-8 weight %; The group vib metal component of 5-40 weight % is preferably 10-35 weight %.
Described group VIII metallic compound is selected from one or more in the soluble compound of these metals, for example, can be in the nitrate, 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, also comprise and introduce organic step in the mixture after described roasting, described 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 to contact with described mixture behind the independent obtain solution of organism through roasting.When organism and group VIII and group vib metal component are introduced described mixture through roasting respectively, preferred at first contact with mixture after this roasting with containing the solution of metal compound of at least a group VIII and at least a group vib, contact with containing organic solution more afterwards, as method by dipping.Described 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.
Described organism can be contain oxygen and/or nitrogenous organic one or more.As 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 ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), acetate, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, in 2-CDTA, the citric acid one or more, organic compounds containing nitrogen can be quadrol or EDTA.
According to method provided by the invention, can also in catalyzer, introduce the material that any material that the catalytic performance of the bright catalyzer that provides of this friend is not provided maybe can improve the catalytic performance of catalyzer provided by the invention.As introducing in the components such as fluorine, phosphorus, boron one or more, 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 described catalyzer, its introducing method can be that the compound that will contain described auxiliary agent directly mixes with silica-alumina, aluminum oxide and Y zeolite, moulding and roasting; Can be the compound that will contain described auxiliary agent with contain group VIII and the group vib metallic compound be mixed with mixing solutions after contact with described mixture through roasting; Can also be to contact and roasting with described 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 described mixture through roasting respectively, it is preferred that at first auxiliary compound solution contacts with described mixture through roasting and roasting with containing, afterwards again with contain group VIII and contact with the group vib solution of metal compound, for example by methods such as ion-exchange, dipping, co-precipitation, preferred pickling process, described maturing temperature is 350-550 ℃, is preferably 400-500 ℃, roasting time is 2-8 hour, is preferably 3-6 hour.
According to catalyzer provided by the invention, described group VIII metal component is preferably cobalt and/or nickel, and the group vib metal component is preferably molybdenum and/or tungsten.In oxide compound and with the catalyzer is benchmark, and the content of group VIII metal component is 1-10 weight %, is preferably 2-8 weight %, and the content of group vib metal component is 5-40 weight %, is preferably 10-35 weight %.
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 original position vulcanizing in device outside device, is translated into sulfide type.
Catalyzer provided by the invention is applicable to hydrocarbon raw material carried out hydrotreatment, with produce low-sulfur, the hydrocarbon fraction of 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.
To the present invention be described by example below.
Agents useful for same in the example 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 test method), 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, determines 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.
Example 1-5 explanation the present invention adopts has silica-alumina of structure of similar to thin diaspore and preparation method thereof.
Example 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 1500 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, stirring also is 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.Filter cake filters after each washing with deionized water wash 5 times, 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.
Example 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, stirring also is 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.Filter cake filters after each washing with deionized water wash 5 times, 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.
Example 3
Take by weighing 800 gram aluminum nitrates (Beijing chemical reagent factory product), be dissolved into 1.6 liters of aluminum nitrate solution a4 (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 b4 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 c4 with deionized water; Get 120 gram sodium hydroxide, be dissolved into 150 ml soln d4 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 40 ℃, and stream adds solution a3 and b3, it is 7.3 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 40 ℃, 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 9.7, and temperature is 35 ℃, was warming up to 98 ℃ and 18 hours after-filtration of constant temperature.Filter cake filters after each washing with deionized water wash 6 times, 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.
Example 4
Get 1.6 liters of (Al of industrial sulphuric acid aluminum solutions a4
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 b4 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 c4.Get 50 gram sodium hydroxide, be dissolved into 150 ml soln d4 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 60 ℃, and stream adds solution a4 and b4, 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 c4 and d4 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.Filter cake filters after each washing with deionized water wash 5 times, the filter cake after the last washing 120 ℃ dry 15 hours down, obtain silica-alumina M-4.The crystalline phase of M-4, the content of silicon oxide, aluminum oxide and N value are listed in the table 1.
Example 5
Described silica-alumina is the commodity silica-alumina, and its trade mark is Siral40 (a Condea company product).The crystalline phase of this product, the content of silicon oxide, aluminum oxide and N value are listed in the table 1.
Comparative Examples 1
The method preparation contrast amorphous silicon aluminium M-5 that provides according to example 1 among the patent CN1123383C: 4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain alum liquor (a), Al
2O
3The about 4g/100ml of concentration.Strong aqua is added an amount of distilled water diluting into about 10% weak ammonia (b).10 liters of distilled water are joined in the concentrated sodium silicate of modulus 3.0 of 4.8 liters of a kind of technical grades, obtain rare water glass solution (c).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has Tai-Ace S 150 and ammoniacal liquor respectively simultaneously, by preparation 600g amorphous aluminum silicide product set (a) flow so that the neutralization reaction time at one hour, and the flow of adjusting rapidly (b) makes the pH value of system remain on 7-8, and the temperature of the hierarchy of control is about 65 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 15 minutes, by finally containing SiO
2Amount begins to add metering (c) 3.3 liters, adds in 10 minutes, and the weathering process of beginning system keeps the pH value 8.0, temperature 60-65 ℃.Aging after 50 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (d).(d) after under 110 ℃ dry 8 hours, pulverized, sieves, obtain silica-alumina M-5.The crystalline phase of M-5, the content of silicon oxide, aluminum oxide and N value are listed in the table 1.
Table 1
| Example | 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 | 39 | 61 | Pseudo-boehmite | 0.78 |
| 4 | M-4 | 43 | 57 | Pseudo-boehmite | 0.41 |
| 5 | Siral40 | 40 | 60 | Pseudo-boehmite | 0.12 |
| Comparative Examples 1 | M-5 | 30 | 70 | Amorphous | 0.09 |
Example 6-12 explanation the inventive method and the catalyzer for preparing by the inventive method.
Example 6
With 51 gram M1,154 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 80 gram Y zeolite (Chang Ling refinery catalyst plant products, lattice constant 24.53 dusts, 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, 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, afterwards in 120 ℃ of oven dry 4 hours, 480 ℃ of roastings 4 hours obtain catalyzer CH-1.Each components contents sees Table 2 among the catalyzer CH-1.
Example 7
With 51 gram M1,154 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 80 gram Y zeolite (Chang Ling refinery catalyst plant products, lattice constant 24.53 dusts, 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, get 180 grams with containing ammonium metawolframate 79.4 grams after being cooled to room temperature, 72.1 gram nickelous nitrate, the aqueous solution dipping that the aqueous solution of citric acid 20.8 grams is 148 milliliters 2 hours, afterwards in 120 ℃ of oven dry 4 hours, 480 ℃ of roastings 4 hours obtain catalyzer CH-2.The mol ratio of citric acid and metallic nickel is 0.4 catalyzer among the catalyzer CH-2, and other each components contents sees Table 2 among the CH-2.
Example 8
With 52 gram M3,154 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) mix with 52 gram type Y molecular sieves, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 4 hours, 580 ℃ of roastings 4 hours are cooled to and get 180 grams after the room temperature with the aqueous solution dipping that contains 150 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-3.Each components contents sees Table 2 among the catalyzer CH-3.
Comparative Examples 2
This Comparative Examples explanation reference catalyst and preparation thereof
Get 54 gram M-5,154 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 80 gram Y zeolite (Chang Ling refinery catalyst plant products, lattice constant 24.53 dusts, 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, be cooled to and get 180 grams after the room temperature with the aqueous solution dipping that contains 150 milliliters of ammonium metawolframate 79.4 grams, 72.1 nickelous nitrates 2 hours, afterwards in 120 ℃ of oven dry 4 hours, 480 ℃ of roastings 4 hours, obtain catalyzer W.Each components contents sees Table 2 among the catalyzer W.
Example 9
With 77 gram Siral 40 (production of Condea company), 44 gram pseudo-boehmites (the long catalyst plant product of Chang Ling oil refining) and 147 gram USY type molecular sieve (Chang Ling refinery catalyst plant products, lattice constant 24.62 dusts, butt 75 heavy %) mix, be extruded into circumscribed circle diameter and be 1.5 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 4 hours, 500 ℃ of roastings 4 hours, be cooled to and get 100 grams after the room temperature with 80 milliliters of dippings of the aqueous solution that contains ammonium paramolybdate 5.1 grams 2 hours, after 400 ℃ of roasting 4 hours and being cooled to room temperature, get 80 grams with containing ammonium metawolframate 26.6 grams, nickelous nitrate 19.4 grams, the aqueous solution of citric acid 14 grams flooded 2 hours for 68 milliliters once more, in 200 ℃ of oven dry 6 hours, obtain catalyzer CH-4 afterwards.The mol ratio of citric acid and metallic nickel is 1 among the catalyzer CH-4, and other each components contents sees Table 2.
Example 10
With 26 gram M-4,133 gram SB powder (production of Condea company) and 108 gram PY type molecular sieve (Chang Ling refinery catalyst plant product, lattice constant 24.60 dusts, P
2O
5Content: 6 heavy %, butt 73 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, get 100 grams with containing 84 milliliters of dippings of the aqueous solution that ammonium paramolybdate 7.4 restrains after being cooled to room temperature, after 300 ℃ of roastings 3 hours and being cooled to room temperature, get 80 grams and flooded once more 2 hours, afterwards in 120 ℃ of oven dry 4 hours with the aqueous solution that contains ammonium metawolframate 37.8 grams, nickelous nitrate 9.4 grams, 480 ℃ of roastings 4 hours, obtain catalyzer CH-5.Each components contents sees Table 2 among the catalyzer CH-5.
Example 11
With 152 the gram M-2 with, 62 gram pseudo-boehmites (Shandong Aluminum Plant's product), 55 gram USY type molecular sieve (Chang Ling refinery catalyst plant products, lattice constant 24.62 dusts, butt 74 heavy %) mix, be extruded into circumscribed circle diameter and be 1.3 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 4 hours, 450 ℃ of roastings 4 hours, be cooled to and get 100 grams after the room temperature with the aqueous solution dipping that contains ammonium metawolframate 32 grams, nickelous nitrate 26 grams, glycerol 1.8 grams 2 hours, afterwards in 120 ℃ of oven dry 4 hours, 180 ℃ of dryings 4 hours obtain catalyzer CH-6.The mol ratio of glycerol and nickel is 0.3 among the catalyzer CH-6, and other each components contents sees Table 2.
Example 12
Get 128 gram M-2,102 gram pseudo-boehmites (Shanxi Aluminium Plant product) and 40 gram REY type molecular sieve (Chang Ling refinery catalyst plant product, lattice constant 24.48, RE
2O
3Content: 8 heavy %, butt 76 heavy %) mix, be extruded into the trilobal bar of circumscribed circle diameter for millimeter, wet bar was in 120 ℃ of oven dry 4 hours, 580 ℃ of roastings 4 hours are got 100 grams with the 82 milliliters of dippings of solution that contain ammonium metawolframate 59 grams, 18 gram nickelous nitrates, ethylene glycol 9.2 gram water, afterwards in 120 ℃ of oven dry 4 hours after being cooled to room temperature, 230 ℃ of roastings 4 hours obtain catalyzer CH-7.The mol ratio of ethylene glycol and nickel is 2.3 among the catalyzer CH-7, and other each components contents sees Table 2.
Table 2
| Example | Catalyzer | The heavy % of silica-alumina | The heavy % of molecular sieve | The heavy % of aluminum oxide | The heavy % of NiO | MoO 3Heavy % | WO 3Heavy % |
| 6 | CH-1 | M-1，13.6 | 20.4 | 34 | 7.0 | / | 25 |
| 7 | CH-2 | M-1，13.6 | 20.4 | 34 | 7.0 | / | 25 |
| 8 | CH-3 | M-3，13.6 | 20.4 | 34 | 7.0 | / | 25 |
| Comparative Examples 2 | W | M-5，13.6 | 20.4 | 34 | 7.0 | / | 25 |
| 9 | CH-4 | Siral-40， 21.8 | 39.8 | 10.9 | 4.5 | 3.0 | 20 |
| 10 | CH-5 | M-4，6.7 | 26.8 | 33.5 | 2.0 | 5.0 | 26 |
| 11 | CH-6 | M-2，45 | 15.0 | 15.0 | 5 | / | 20 |
| 12 | CH-7 | M-4，32.5 | 9.8 | 22.7 | 3.0 | / | 32 |
Example 13-15
Following example illustrates the performance of catalyzer provided by the invention.
With density is 0.9188 gram per centimeter
3Sulphur content is that 4000ppm, nitrogen content are 501ppm, cetane value is that 28.5 catalytic cracking diesel oil is a raw material, on 30 milliliters of fixed bed devices, estimate the performance of catalyzer CH1 provided by the invention, CH2 and CH3, the catalyzer loading amount is 20 milliliters, and reaction conditions is: 360 ℃ of temperature, pressure 6.4MPa, liquid hourly space velocity 1.3 hours
-1, hydrogen to oil volume ratio 500, the results are shown in Table 3.
Comparative Examples 3
According to example 13 identical condition evaluating reference catalyst W, the results are shown in Table 3.
Table 3
| Example | 13 | 14 | 15 | Comparative Examples 3 |
| Catalyzer | CH1 | CH2 | CH3 | W |
| Product density, gram per centimeter 3 | 0.8832 | 0.8817 | 0.8702 | 0.8861 |
| Desulfurization degree, heavy % | 93.5 | 94.1 | 95.3 | 92.1 |
| Denitrification percent, heavy % | 99.2 | 99.2 | 99.4 | 91.3 |
| The product cetane value | 37.2 | 37.5 | 38.8 | 35.7 |
| The cetane value increased value | 8.7 | 9.0 | 10.3 | 7.2 |
| Density reduction value, gram per centimeter 3 | 0.0356 | 0.0371 | 0.0486 | 0.0327 |
| Diesel yield, V% | ＞95 | ＞95 | ＞95 | ＞95 |
The result that table 3 provides shows, compares with reference catalyst, and catalyzer provided by the invention not only has higher desulfurization, denitrification activity, can make at least 1.5 units of diesel cetane-number increase rate increase simultaneously.
Claims (11)
1, a kind of preparation method of catalyst for hydrogenation treatment of diesel oil, comprise a kind of silica-alumina, the precursor of aluminum oxide and/or aluminum oxide and Y zeolite mix, moulding and roasting, introduce at least a group VIII and at least a group vib metal component afterwards in the mixture after roasting, wherein, described 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, the group VIII metal component of 1-15 weight %, the group vib metal component of 10-40 weight %.
2, method according to claim 1 is characterized in that, described 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 described 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 described silica-alumina
27Chemical shift is the peak area at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
3, method according to claim 2 is characterized in that, described N value with silica-alumina of structure of similar to thin diaspore is 0.2-0.8, contains the silicon oxide of 10-45 weight % after the roasting, the aluminum oxide of 55-90 weight %.
4, method according to claim 1, it is characterized in that, described preparation method with silica-alumina of structure of similar to thin diaspore comprises: the mixed solution for preparing a kind of pseudo-boehmite and water, introduce a kind of solution of silicon-containing compound afterwards, aging and dry, described aging condition is: pH value 7.5-11, temperature 75-120 ℃, time 6-24 hour, described drying conditions is: temperature 80-300 ℃, time 2-24 hour, after the concentration of described silicon-containing compound solution and consumption made final silica-alumina roasting, the content of silicon oxide was 5-60 weight %.
5, method according to claim 4, it is characterized in that, described aging condition is: pH value 8-10, temperature 80-98 ℃, time 12-24 hour, described drying conditions is: temperature 100-150 ℃, time 4-20 hour, after the concentration of described silicon-containing compound solution and consumption made final silica-alumina roasting, the content of silicon oxide was 10-45 weight %.
6, method according to claim 4, it is characterized in that, described pseudo-boehmite and the mixed solution of water are that the solution with at least a aluminum contained compound mixes, becomes glue and aged method to prepare with the solution of a kind of alkali or acid, described aged condition is that pH is 7-8.5, and temperature is that 30-75 ℃, time are 5-120 minute.
7, method according to claim 4 is characterized in that, described silicon-containing compound be any water-soluble silicon-containing compound or in water medium hydrolysis can form the silicon-containing compound of silicon gel or colloidal sol.
8, method according to claim 7 is characterized in that, described silicon-containing compound is selected from one or more in water glass, silicon sol and the silicon ester.
9, method according to claim 1, it is characterized in that, described method also is included in and introduces organic step in the mixture after the described roasting, described organism is selected from and contains in oxygen or the nitrogenous organism one or more, and organic introducing amount makes that the mol ratio of organism and group VIII metal component is 0.1-5 in the final catalyzer.
10, method according to claim 9, it is characterized in that, described oxygenatedchemicals is selected from one or more in organic alcohol, the organic acid, organic compounds containing nitrogen is an organic amine, and described organic introducing amount makes the mol ratio of organism and group VIII metal component in the final catalyzer for being 0.2-2.5.
11, a kind of catalyst for hydrogenation treatment of diesel oil, this catalyzer contain silica-alumina, aluminum oxide, Y zeolite and are selected from group VIII and the metal component of group vib, and this catalyzer is according to any described method preparation among the claim 1-10.
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