CN1769385A - Middle distillate oil hydrogenation catalyst and its preparation method - Google Patents
Middle distillate oil hydrogenation catalyst and its preparation method Download PDFInfo
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Abstract
The invention discloses the distillate oil hydrotreating catalyst. The catalyst uses the modified Y zeolite, Beta zeolite and aluminum oxide as carrier, and uses the metal at the VIB and VIII as active metal componemt. The Y zeolite is modified by metallic cation exchanging. The catalyst possesses many advantages, as follow: the good open cycle, hydrogenation, isomerization activity, at the mild condition, improving the cetane number, reducing the condensation point, improving the product quality and keeping the higher diesel oil productivity.
Description
Technical field
The present invention relates to a kind of catalyst for hydrogenation of fraction oil and preparation method thereof, especially for hydrotreating catalyst of poor-quality diesel-oil by cut fraction hydrogenation for producing low solidifying point clean diesel and preparation method thereof.
Background technology
Because the development of the catalytic cracking technology of China is very fast, fluid catalytic cracking (FCC) and fluid catalytic cracking of heavy oil (RFCC) device are occupied an leading position in secondary processing, cause catalytic diesel oil (LCO) to account for 1/3rd of diesel oil total amount.But the foreign matter content height in the catalytic diesel oil, stability is poor, the aromaticity content height, especially cetane value is low.Along with catalysis technique develops towards the deep processing direction, it is poorer that the quality of catalytic diesel oil will become.And new environmental regulation has proposed more harsh requirement to diesel quality.Therefore the quality that how further to improve diesel oil is the important topic that people pay close attention to.
The most of crude oil of China all belongs to paraffinic crude, the zero pour height on the other hand.Especially in the winter time, the vast northern area temperature of China is low, not only needs clean diesel, more needs low freezing point diesel oil.For solving this contradiction, most refineries adopt and reduce the operating method that diesel oil do and produce low-coagulation diesel oil, have reduced production of diesel oil, and this mode not only is not inconsistent with the social demand of current raising diesel and gasoline ratio, has reduced economic benefit of enterprises yet.
In fact improving diesel-fuel cetane number and isomery, to reduce condensation point be conflicting, the different hydrocarbons of same carbon number, and for the highest, aromatic hydrocarbon is the cetane value minimum of condensed ring aromatic hydrocarbon particularly with the cetane value of alkane.And the isomery degree of hydro carbons is high more, and number of rings is many more, and its cetane value is low more, along with cycloalkanes and aromatic hydrocarbon with the increase of side chain lengths, its cetane value is high more, but increases with the side chain ramose, cetane value reduces.And isomery degree height, the diesel oil distillate condensation point is low.But the isomery degree is too high, and scission reaction also takes place easily, reduces diesel product yield, the easy carbon distribution inactivation of catalyzer.
The technology of improving diesel quality, reduction condensation point of diesel oil at present is mainly the hydrocracking technology of high-yield diesel oil, the MCI technology that improves diesel cetane-number and hydrodewaxing, isomerization-visbreaking technology.The hydrocracking technology that adopts high-yield diesel oil mainly is to produce the hydrocracking catalyst that high-grade low-freezing diesel oil is developed at heavy distillate, as USP 4,985,134, USP 4,820,402, CN1393522A etc. is though the diesel product quality has raising by a relatively large margin, it is big that condensation point reduces amplitude, but pressure rating height, diesel yield are low.Though and the depression of the freezing point amplitude of employing hydrodewaxing technology is big, diesel yield is low, as U.S. Pat P 5833840, USP 5965474, USP 5286370.The MCI technology that improves diesel cetane-number can satisfy the requirement that improves diesel cetane-number, but it is little that condensation point reduces amplitude, and same isomerization-visbreaking technology is as U.S. Pat P6153548,5932088, the pour point depression requirement can be satisfied, but the requirement that improves diesel cetane-number simultaneously can not be satisfied.
Reduce condensation point of diesel oil simultaneously for reaching the raising diesel cetane-number, and guarantee certain diesel yield, present many employings group and technology, as hydrofining and/or hydrocracking and hydrodewaxing, hydro-upgrading and hydrodewaxing, hydro-upgrading and isomerization-visbreaking or the like just can reach effect preferably.
CN1257107A discloses a kind of method of producing high-grade low-freezing diesel oil by distillate, is hydrofining directly to be connected with hydrodewaxing react.The NiO content of its Hydrobon catalyst is higher, and the anti-coking performance is good; Hydrodewaxing catalyst is group vib and/or the VIII family non-precious metal catalyst that loads on the ZSM-5 zeolite, because the duct feature of ZSM-5 only be cracked into small molecules after normal paraffin enters and just can diffuse out, so diesel yield is low.Although hydrofining and hydrodewaxing combination process can prolong the pour point depression catalyst life, and remove impurity such as sulphur, nitrogen in the distillate, improve its oxidation stability to a certain extent, can not effectively improve diesel cetane-number.
Summary of the invention
The object of the present invention is to provide a kind of catalyst for hydrogenation of fraction oil and preparation method thereof.This catalyzer is used to handle poor-quality diesel-oil by cut fraction, can improve cetane value to greatest extent, reduces condensation point, and keeps higher diesel yield.
Catalyst for hydrogenation of fraction oil of the present invention comprises following component: modified Y zeolite, β zeolite, aluminum oxide and reactive metal.Wherein active metal component is one or more in group vib and the group VIII metal.Each components contents is as follows in this catalyzer: the weight percent with catalyzer is a benchmark, and the content of group vib metal oxide is 10%-30%, preferably 10%-25%; The content of group VIII metal oxide is 1%-10%, is preferably 1%-9%, is preferably 3%-8%; The content of modified Y zeolite is 1%-20%, is preferably 5%-15%; The content of β zeolite is 1%-20%, is preferably 5%-15%; The content of aluminum oxide is 5%-80%, better is 15%-70%, preferably 20%-60%; The content of tackiness agent is 0-30%, preferably 0-20%.
Hydrotreating catalyst of the present invention is to be carrier with modified Y zeolite, β zeolite and aluminum oxide, and wherein two kinds of different zeolites are as the main acidic components of catalyzer, and aluminum oxide is the auxiliary acid component of catalyzer and main carrier component.
The specific surface area of catalyst for hydrogenation of fraction oil of the present invention is 170-240m
2/ g, pore volume are 0.30-0.35ml/g, and wherein the aperture accounts for the 75%-90% of total pore volume in the pore distribution of 4-10nm, and infrared acidity is 0.34-0.38mmol/g.
The character of employed modified Y zeolite is as follows among the present invention: contain group vib and/or group VIII metallic element 2wt%-10wt% in this modified Y zeolite, SiO
2/ Al
2O
3Mol ratio is 9.0-12.9, and lattice constant is 2.440-2.459nm, and specific surface area is 550-650m
2/ g, pore volume are 0.340-0.370ml/g, and infrared acidity is 1.37-1.60mmol/g, wherein the mol ratio 1 of B acid and L acid: 3-1: 5, and Na
2O weight content＜0.2%, better＜0.15%, best＜0.1%.Wherein said group vib and/or group VIII metallic element are one or more among W, Ni, Co, Fe, the Mo.
The used modified Y zeolite of the present invention prepares as follows:
(1) super-hydrophobic Y zeolite is placed water, its mesolite is 1 with the ratio of the weight of water: 2-10 is preferably 1: 3-8, be warming up to 60 ℃-90 ℃, and stirred 0.5-2.0 hour.
(2) get and contain in group vib and/or the group VIII metal soluble salt one or more and be mixed with solution, add in above-mentioned steps (1) solution, with ammoniacal liquor regulator solution pH value, control pH value is 4-10, solution is under 50-90 ℃, stir fully exchange in aging 2-4 hour, after the filtration, made in dry 8-24 hour at 100 ℃-150 ℃.
Wherein said super-hydrophobic Y zeolite be by Y zeolite at 500～600 ℃, obtain after hydrothermal treatment consists 1-10 hour under 0.01～0.30MPa condition.Wherein the character of Y zeolite is as follows: NaO content is lower than 0.2wt%, silica alumina ratio 6-40 (chemical method), lattice constant 2.440-2.460nm.This Y zeolite can be by NH
4The NaY zeolite makes with silicofluoride liquid phase dealuminzation method, as the method for putting down in writing among the CN 1026313C.
Catalyst for hydrogenation of fraction oil preparation process of the present invention comprises:
(1) modified Y zeolite, β zeolite and aluminum oxide are mixed;
(2) in the mixture of step (1), add tackiness agent or directly add peptizing agent solution and mix and pinch into paste, extruded moulding;
(3),,, obtain support of the catalyst at 350～700 ℃ of roasting 1-12 hours 100～150 ℃ of dryings 0.5～24 hour with above-mentioned forming composition;
(4) preparation contains the dipping solution of group vib metal and/or group VIII metal;
(5) support of the catalyst of gained in 100～150 ℃ of dryings 0.5～24 hour, at 350～700 ℃ of roasting 1-12 hours, obtains the catalyzer finished product in the solution of step (4) configuration behind the dipping in the step (3).
Preferably 100～140 ℃ of the drying temperatures of described carrier and catalyzer are preferably 1～8 hour time of drying.
Preferably 400～650 ℃ of the maturing temperatures of described carrier and catalyzer, roasting time is preferably 1～8 hour.
That the group vib metal of the related use of catalyst for hydrogenation of fraction oil of the present invention is the most frequently used is Mo and/or W, and the group VIII metal is the most frequently used is among Fe, Ni and the Co one or more.
Catalyzer of the present invention is because the Y zeolite of employing after the metallic cation modification, the acid of this modified Y zeolite distributes, especially the ratio of B acid and L acid is more reasonable, so that catalyzer of the present invention can reduce the cracking of diesel oil distillate effectively, guarantee diesel yield, promote the saturated open loop of aromatic hydrogenation, also improved the catalyzer anti-carbon deposition ability simultaneously, prolonged the work-ing life of catalyzer.
In addition, catalyzer of the present invention adopts modified Y zeolite and β zeolite simultaneously, by the synergy of two kinds of zeolites, has improved the isomerization reaction selectivity of catalyzer, when improving cetane value to greatest extent, reduces the condensation point of diesel oil significantly.
Catalyzer of the present invention has preferable open loop, hydrogenation and heterogeneous activity, is suitable for handling poor-quality diesel-oil by cut fraction, under than the demulcent reaction conditions, can improve cetane value to greatest extent, reduces condensation point, improves the quality of products, and keeps higher diesel yield.
Embodiment
The employed β zeolite of catalyst for hydrogenation of fraction oil of the present invention can adopt that all are suitable for β zeolite of the present invention in the prior art, and its character is as follows: SiO
2/ Al
2O
3Mol ratio (chemical method) is 20-120, better is 30-90, Na
2O weight content＜0.2%, better＜0.15%, best＜0.1%, infrared acidity is 0.1-0.7mmol/g, better is 0.15-0.50mmol/g.
β zeolite in the catalyzer of the present invention is preferably selected beta zeolite in small crystal grain for use, and its particle diameter is 1～100nm.Such as the beta zeolite in small crystal grain that adopts the method preparation among the Chinese patent CN1324762A.
The aluminum oxide of using always when aluminum oxide used in the present invention can adopt the preparation catalyst carrier for hydrgenating, preferably adopt aluminum oxide through additive modification, auxiliary agent (in element) content is 3wt%-7wt%, and wherein said auxiliary agent is one or more in boron, fluorine and the zirconium.The character of this modified aluminas: specific surface area is 320-370m
2/ g, pore volume are 0.7～1.1ml/g.This modified aluminas can adopt the preparation method among the Chinese patent CN1458232A: adopt preferably Carbonization Preparation aluminum oxide precursor of ordinary method, get its filter cake, making beating is warming up to 50～90 ℃, is preferably 65～75 ℃, the auxiliary agent that adds certain content, and under 50～90 ℃ of temperature, stirred 5～120 minutes, be preferably 30～90 minutes, filter, drying makes modified aluminas.
Catalyzer of the present invention can use the binder ingredients of aperture refractory inorganic oxides as catalyzer when preparing carriers, as in clay, silicon oxide, aluminum oxide, sial, zirconium white and the titanium oxide-magnesium oxide one or more, be preferably little porous aluminum oxide, its character is as follows: specific surface area 220-300m
2/ g, pore volume are 0.45-0.52ml/g.The weight content of this binder ingredients in final catalyzer is 0～60%.Also can not add binder ingredients when support of the catalyst of the present invention prepares, but directly add peptization acid, mix the moulding of pinching bar.
The present invention can adopt extrusion aid during extrusion in the process of Preparation of Catalyst, extrusion aid commonly used can be: one or more in sesbania powder, citric acid, oxalic acid, Mierocrystalline cellulose, starch, the polymeric surface active agent etc.
Involved in the present invention to peptizing agent can be: one or more in Tai-Ace S 150, citric acid, nitric acid, acetic acid, the oxalic acid etc.
Support shapes after the described moulding can be sheet, spherical, cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei), preferably cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei).The diameter of carrier can be 0.8～2.0mm slice and＞the thick bar of 2.5mm.
The characteristics of catalyzer of the present invention are described below by specific embodiment.
The specific surface area of product of the present invention and pore volume are to adopt ASAP2400, and cryogenic nitrogen absorption (77K) calculates according to BET formula.Acid amount and acid matter adopt infrared spectrometer to record, and the sorbent material that uses is pyridine.
Embodiment 1
The preparation of modified Y zeolite Y-A:
(1) Y zeolite is handled under 0.1MPa, 550 ℃ of water vapour obtained super-hydrophobic Y zeolite Y-W in 2 hours; Wherein Y zeolite is Wenzhou catalyst plant production, and its character is as follows: silica alumina ratio (chemical method) 10.01, lattice constant 2.448nm, Na
2O content 0.05wt%, butt 75wt%.
(2) 300 gram super-hydrophobic Y zeolites are placed 1000ml water, stir and be warming up to 60 ℃.
(3) 181g nickelous nitrate and 29g Xiao Suangu are made into 240ml solution, add in the above-mentioned zeolite solution with ammoniacal liquor, control pH value equals 6, adds back solution aging 2 hours, after the filtration, makes in 8 hours 110 ℃ of dryings, is designated as Y-A, and its physico-chemical property sees Table 1.
Embodiment 2
The preparation of modified Y zeolite Y-B:
Step (1) is with embodiment 1;
Step (2) places 1500ml water with 300 gram super-hydrophobic Y zeolites, stir and be warming up to 80 ℃, and adding 97.8g iron nitrate stirs.
Step (3) is made into 200ml solution with 360g nickelous nitrate and 62g Xiao Suangu, and adds in the above-mentioned zeolite solution with ammoniacal liquor, and control pH value equals 5, added back solution aging 2 hours, and after the filtration, made in 8 hours 110 ℃ of dryings, be designated as Y-B, its physico-chemical property sees Table 1.
Embodiment 3
The preparation of modified Y zeolite Y-C:
Step (1) is handled Y zeolite and was obtained super-hydrophobic Y zeolite in 1 hour under 0.1MPa, 600 ℃ of water vapour; Wherein Y zeolite is Wenzhou catalyst plant production, and its character is as follows: silica alumina ratio (chemical method) 10.01, lattice constant 2.448nm, Na
2O content 0.05wt%, butt 75wt%.
Step (2) places 1600ml water with 400 gram super-hydrophobic Y zeolites, stirs and is warming up to 75 ℃.
Step (3) is made into 460ml solution with 416.3g nickelous nitrate and 69.6g Xiao Suangu, adds in the above-mentioned zeolite solution with ammoniacal liquor, and control pH value equals 6, added back solution aging 2 hours, and after the filtration, made in 8 hours 110 ℃ of dryings, be designated as Y-C, its physico-chemical property sees Table 1.
Embodiment 4
The preparation of beta zeolite in small crystal grain β-A (being undertaken) by the embodiment among the CN 1324762A 8.
Pseudo-boehmite (is contained Al
2O
356.5wt%, the Zhou village catalyst plant), sodium hydroxide (chemical pure, Beijing Chemical Plant), tetraethyl ammonium hydroxide (2.633N, emerging good fortune fine chemistry industry institute product is gone in in a big way in Beijing) add in the deionized water, heating for dissolving, stir, make working solution, with silochrom (80-120 order, igloss 3.7%, Haiyang Chemical Plant, Qingdao) mix with above-mentioned working solution, make the silica gel surface wetting by working solution, the mol ratio of each component is SiO
2/ Al
2O
3=100, Na
2O/SiO
2=0.07, TEAOH/SiO
2=0.12, H
2O/SiO
2=6.5; Add additive vacuum pump oil (seven factories of Dalian Petrochemical Industry Company produce for commercial goods, trade name SY-1634-70, molecular weight 800-1000, polyoxyethylene groups shared weight ratio in said polyalkylene ether is 25%) again, additive/SiO
2(heavy %)=0.5 with gained mixture 120 ℃ of crystallizations 24 hours in autoclave, is warming up to 148 ℃ of reactions 48 hours again, isolates solid product after the reaction, washes with water, and 110 ℃ are drying to obtain the β zeolite, with this β zeolite at 60 ℃, the NH of 1.0N
4Exchange is 4 times in the Cl aqueous solution, exchanges 2 hours at every turn, and 110 ℃ of dryings 2 hours after 550 ℃ of roastings 3 hours or the activation, are designated as β-A, and its physico-chemical property sees Table 1.
Embodiment 5
The preparation of non-beta zeolite in small crystal grain β-B (pressing embodiment 1 method preparation among the Chinese patent CN1059701A)
Get 500g industry β zeolite and place the high-temperature roasting stove, be warming up to 600 ℃ with about 100 ℃/speed at one hour rating, constant temperature calcining is 8 hours then, be cooled to room temperature, make and take off amine β zeolite, in 10 liters of enamel pickling tanks, add 100ml analytical pure concentrated hydrochloric acid, add the 2900ml deionized water again and be made into 0.1N HCl solution, be heated to 55 ℃, add 300g take off amine β zeolite (sial molecular ratio 26.94, hexanaphthene adsorptive capacity＞13m%, NaO% content be＜0.15wt%), stirred 2 hours at 55 ℃ of following constant temperature, filtered water is washed till neutrality then.Zeolite filter cake after the acid treatment is 110-220 ℃ of oven dry down, to butt＞80%.Above-mentioned zeolite is put in the airtight stoving oven of high temperature, is warming up to 550 ℃, feed 100% water vapour simultaneously with about 200 ℃/speed at one hour rating, control pressure 200Kpa, constant temperature and pressure roasting 2 hours promptly gets zeolite beta-B.Its physico-chemical property sees Table 1.This zeolite silica alumina ratio is 63.35 (chemical methods), and NaO% content is＜0.15wt% that relative crystallinity is 110, granularity＞100nm.
Embodiment 6
The preparation of modified aluminas L-1
Get the filter cake after the aluminum oxide precursor washing of Carbonization Preparation, surveying its butt is 20wt%, gets this filter cake 6000 grams, adds 24 liter deionized waters, making beating, and add 200 gram BF
3Diethyl ether solution (BF
3Content 46.8wt%), be warming up to 65 ℃, stirred 1 hour, filter, 110 ℃ of dryings 4 hours, sample is L-1, its physico-chemical property sees Table 1.
Embodiment 7
The preparation of modified aluminas L-2.
Get aluminum oxide precursor washing back filter cake 800 grams of Tai-Ace S 150 method preparation, adds 4 liters of deionized waters, be warming up to 85 ℃ after stirring, add ammonium borofluoride 11 grams, continue stirring 30 minutes, 110 ℃ of dryings 4 hours, sample L-2, its physico-chemical property sees Table 1.
Table 1 sample physico-chemical property
| The embodiment numbering | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Sample number into spectrum | Y-A | Y-B | Y-C | β-A | β-B | L-1 | L-2 |
| NiO，wt％ | 4.12 | 6.3 | 8.9 | - | - | - | - |
| CoO，wt％ | 0.57 | 0.89 | 0.73 | - | - | - | - |
| Fe，wt％ | - | 1.19 | - | - | - | - | - |
| Auxiliary agent (in element) content, wt% | - | - | - | - | - | 6.3 | 5.9 |
| Specific surface area, m 2/g | 612 | 574 | 556 | 650 | 632 | 360 | 320 |
| Pore volume, ml/g | 0.362 | 0.353 | 0.347 | - | - | 0.88 | 0.92 |
| Infrared acidity, mmol/g | 1.476 | 1.575 | 1.529 | 0.33 | 0.31 | - | - |
| The mol ratio of B acid and L acid | 1∶3.5 | 1∶4.6 | 1∶4.8 | - | - | - | - |
| SiO 2/Al 2O 3Mol ratio (chemical method) | 9.87 | 9.59 | 11.2 | 80 | 63.35 | - | - |
| Lattice constant, nm | 2.441 | 2.444 | 2.451 | - | - | - | - |
| Na 2O content, wt% | 0.15 | 0.15 | 0.15 | 0.03 | ＜0.15 | - | - |
| Particle diameter, nm | - | - | - | 80-90 | ＞100 | - | - |
Embodiment 8
The preparation of catalyst used for hydrogenation of distilled oil fraction of the present invention.
With 43 gram Y-A, 40 gram β-A, 412 gram L-1,298 grams are by SB powder (pore volume 0.46ml/g, specific surface area 260m
2/ g) preparation tackiness agent (butt 30wt%), put into rolling machine, grind to squeezing paste, extrusion, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours are with ammonium metawolframate, nickel nitrate aqueous solution dipping, 110 ℃ of dryings 4 hours, 500 ℃ of roastings 3 hours make catalyzer C-1.The catalyzer physico-chemical property sees Table 2.
Embodiment 9
The preparation of catalyst used for hydrogenation of distilled oil fraction of the present invention.
With 41.2 gram Y-A, 78.9 gram β-A, 540 gram L-1,400 grams are by SB powder (pore volume 0.46ml/g, specific surface area 260m
2/ g) preparation tackiness agent (butt 30wt%), put into rolling machine, grind to squeezing paste, extrusion, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours are with ammonium metawolframate, nickel nitrate aqueous solution dipping, 110 ℃ of dryings 4 hours, 500 ℃ of roastings 3 hours make catalyzer C-2, and its physico-chemical property sees Table 2.
Embodiment 10
Catalyst used for hydrogenation of distilled oil fraction preparation of the present invention.
With 33 gram Y-B, 29.5 gram β-A, 269 gram L-2,196 grams are by SB powder (pore volume 0.46ml/g, specific surface area 260m
2/ g) preparation tackiness agent (butt 30wt%), put into rolling machine, grind to squeezing paste, extrusion, 110 ℃ of dryings 4 hours, 500 ℃ of roastings 3 hours are with ammonium metawolframate, nickel nitrate aqueous solution dipping, 110 ℃ of dryings 4 hours, 480 ℃ of roastings 3 hours make catalyzer C-3.The catalyzer physico-chemical property sees Table 2.
Embodiment 11
Catalyst used for hydrogenation of distilled oil fraction C-4 preparation of the present invention.
With 55 gram Y-C, 132 gram β-A, 697 gram L-1,680 grams are by SB powder (pore volume 0.46ml/g, specific surface area 260m
2/ g) preparation tackiness agent (butt 30wt%), put into rolling machine, grind to squeezing paste, extrusion, 120 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours are with ammonium metawolframate, nickel nitrate aqueous solution dipping, 110 ℃ of dryings 4 hours, 520 ℃ of roastings 3 hours make catalyzer C-4, and its physico-chemical property sees Table 2.
Embodiment 12
The preparation of catalyst used for hydrogenation of distilled oil fraction C-5 of the present invention.
With 96.15 gram Y-A, 32.9 gram β-B, 357 gram L-1,500 grams are by SB powder (pore volume 0.46ml/g, specific surface area 260m
2/ g) preparation tackiness agent (butt 30wt%), put into rolling machine, grind to squeezing paste, extrusion, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 3 hours are with ammonium metawolframate, nickel nitrate aqueous solution dipping, 110 ℃ of dryings 4 hours, 500 ℃ of roastings 3 hours make catalyzer C-5.The catalyzer physico-chemical property sees Table 2.
Embodiment 13
The preparation of catalyst used for hydrogenation of distilled oil fraction C-6 of the present invention.
Method is similar to Example 8 substantially with composition, keeps Y-A, β-A content constant, and modified aluminas is changed to SB powder (pore volume 0.46ml/g, specific surface area 260m
2/ g), the gained catalyzer is C-6, its physico-chemical property sees Table 2.
Comparative example-1
This example is the preparation of reference catalyst J-1.
Method is similar to Example 8 substantially with composition, only removes β-A component.Finally consisting of of this catalyzer: Y-A 15wt%, modified aluminas 30wt%, WO
322.32wt%, NiO 5.12wt%, CoO 0.14wt%, surplus is little porous aluminum oxide.The catalyzer physico-chemical property sees Table 2.
Comparative example-2
This example is the preparation of reference catalyst J-2.
Method is similar to Example 8 substantially with composition, keeps β-A content constant, the Y-A component is changed to the super-hydrophobic Y zeolite Y-W (production of Wenzhou catalyst plant) that does not carry out cationic exchange among the embodiment 1.Finally consisting of of this catalyzer: β-A 10wt%, super-hydrophobic Y zeolite 8wt%, modified aluminas 35wt%, WO
322.69wt%, NiO 4.71wt%, surplus is little porous aluminum oxide.The catalyzer physico-chemical property sees Table 2.
Table 2 catalyzer physico-chemical property
| Embodiment of the invention catalyzer | The agent of Comparative Examples reference | |||||||
| The catalyzer numbering | C-1 | C-2 | C-3 | C-4 | C-5 | C-6 | J-1 | J-2 |
| NiO，wt％ | 5.10 | 5.88 | 4.98 | 6.04 | 4.66 | 4.96 | 5.12 | 4.71 |
| CoO，wt％ | 0.14 | 0.15 | 0.12 | 0.12 | 0.14 | 0.16 | 0.14 | - |
| WO 3，wt％ | 26.0 | 22.62 | 25.62 | 23.59 | 23.63 | 20.84 | 22.32 | 22.69 |
| Fe，wt％ | - | - | 0.72 | - | - | - | - | - |
| Modified Y zeolite, wt% | 7 | 5 | 8 | 5 | 14 | 7 | 15 | 8 (Y-W) |
| The β zeolite, wt% | 8 | 12 | 9 | 15 | 6 | 8 | - | 10 |
| Aluminum oxide, wt% | 65 | 63 | 63 | 61 | 50 | 65 | 60 | 57 |
| Tackiness agent, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Specific surface area, m 2/g | 189 | 183 | 186 | 200 | 207 | 176 | 164 | 185 |
| Pore volume, ml/g | 0.305 | 0.303 | 0.321 | 0.327 | 0.333 | 0.335 | 0.334 | 0.323 |
| 4-10nm pore volume integration rate, % | 80 | 82 | 78 | 84 | 79 | 82 | 71 | 69 |
| Infrared acidity, mmol/g | 0.372 | 0.361 | 0.366 | 0.345 | 0.342 | 0.375 | 0.451 | 0.408 |
Embodiment 14-19
Present embodiment illustrates the distillate hydrogenation activity of catalyzer provided by the invention.
Adopting wide petrochemical industry is hydrogenation, the heterogeneous activity of stock oil evaluate catalysts C-1～C-6.Stock oil character sees Table 3.Be reflected on the hydrogenation unit of 200ml and carry out.Reaction conditions is: 360 ℃ of temperature of reaction, hydrogen dividing potential drop 6.5MPa, liquid hourly space velocity 1.2 hours
-1, hydrogen to oil volume ratio 700: 1.Product property is listed in table 4.
Comparative example 3-4
The distillate hydrogenation activity of this comparative example explanation reference catalyst.
Adopting wide petrochemical industry is hydrogenation, the heterogeneous activity of stock oil evaluate catalysts J-1 and J-2.Stock oil character sees Table 3.Be reflected on the hydrogenation unit of 200ml and carry out.Reaction conditions is: 360 ℃ of temperature of reaction, hydrogen dividing potential drop 6.5MPa, liquid hourly space velocity 1.2 hours
-1, hydrogen to oil volume ratio 700: 1.Product property is listed in table 4.
Table 3 stock oil character
| Stock oil | Raw material |
| Density, g/cm 3 | 0.9126 |
| Boiling range, ℃ | |
| IBP/10％ | 175/227 |
| 50％/90％ | 279/348 |
| 95％/EP | 359/370 |
| Sulphur, wt% | 0.55 |
| Nitrogen, μ g/g | 711 |
| Condensation point, ℃ | -3 |
| Cetane value | 25 |
| Aromatic hydrocarbons, wt% | 56.8 |
Table 4 diesel oil hydrogenation modification isomerization-visbreaking evaluating catalyst result
| Numbering | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Embodiment 19 | Comparative example 3 | Comparative example 4 |
| Density, g/cm 3 | 0.8688 | 0.8602 | 0.8680 | 0.8600 | 0.8737 | 0.8781 | 0.8777 | 0.8767 |
| Boiling range, ℃ | ||||||||
| IBP/10％ | 181/217 | 176/227 | 178/217 | 174/225 | 162/215 | 166/219 | 172/216 | 180/225 |
| 30％/50％ | 240/262 | 243/264 | 240/262 | 241/266 | 239/261 | 243/264 | 240/262 | 242/263 |
| 70％/90％ | 291/333 | 293/324 | 293/337 | 291/327 | 291/333 | 294/337 | 292/337 | 292/333 |
| 95％/EP | 348/367 | 350/367 | 357/368 | 348/366 | 351/364 | 356/369 | 357/367 | 350/366 |
| Diesel yield, wt% | 99.6 | 99.1 | 98.3 | 97.2 | 97.3 | 98.7 | 95.7 | 93.8 |
| Cetane value | 35.2 | 35.4 | 34.5 | 35.6 | 36.7 | 34.2 | 32.2 | 33.5 |
| Cetane value is carried the width of cloth | 10.2 | 10.4 | 9.5 | 10.6 | 11.7 | 9.2 | 7.2 | 8.5 |
| Condensation point, ℃ | -20 | -26 | -20 | -30 | -22 | -19 | -12 | -20 |
| Nitrogen, μ g.g -1 | 2.0 | 2.0 | 2.3 | 2.0 | 2.5 | 2.1 | 2.6 | 2.8 |
| Sulphur, μ g.g -1 | 22 | 25 | 22 | 27 | 19 | 29 | 35 | 39 |
By table 1 data as can be seen, the y-type zeolite after the modification, little although its infrared total acidity changes, its B acid ratio reduces greatly, and the increasing degree of L acid ratio is enhanced, but also contain the active ingredient of hydrogenating function.Reaction result by table 4 can be found out, compares with comparative example 4, and catalyzer of the present invention guarantees diesel yield to reducing the cracking of diesel oil distillate, and it is very strong to improve diesel cetane-number and isomerization reaction selectivity.
Adopt modified Y zeolite and β zeolite in the catalyzer of the present invention simultaneously, synergy by two kinds of zeolites, make catalyzer have ability of aromatic hydrocarbons open loop preferably and preferable heterogeneous activity simultaneously, and the catalyzer aperture accounts for the 75%-90% of total pore volume in the pore distribution of 4-10nm, the aperture is very concentrated, help the diffusion of stock oil like this, better bring into play catalytic activity.By the result of table 4 as can be seen, catalyzer of the present invention is used to improve the diesel oil distillate quality, has very high diesel oil distillate yield and good pour point depression effect, under identical diesel oil distillate yield, the product condensation point reduces 10-25 ℃, and cetane value improves 8-12 unit, obviously is better than the comparison catalyzer.
In the catalyzer of the present invention, compare with the catalyzer that non-beta zeolite in small crystal grain is prepared, increase in the catalyst reaction active centre that contains beta zeolite in small crystal grain, and the beta zeolite in small crystal grain duct shortens, be beneficial to the diffusion of reactant and resultant, thereby diesel yield is increased, it is bigger that condensation point reduces amplitude.The prepared catalyzer of the catalyzer that adopts the modified aluminas preparation and common aluminum oxide is compared (embodiment 8 and embodiment 13), the yield height of diesel oil, and cetane value has a big increase, and it is big that condensation point reduces amplitude.
In addition, catalyzer running after 1200 hours active and selectivity do not find reduction, illustrate that catalyzer of the present invention has lower lytic activity, higher diesel oil isomerization-visbreaking activity, hydro-upgrading activity and satisfactory stability.
Claims (13)
1, a kind of catalyst for hydrogenation of fraction oil, with zeolite and aluminum oxide is carrier, with in group vib and the group VIII metal one or more is active metal component, it is characterized in that wherein the character of employed modified Y zeolite is as follows: contain group vib and/or group VIII metallic element 2wt%-10wt%, SiO
2/ Al
2O
3Mol ratio is 9.0-12.9, and lattice constant is 2.440-2.459nm, and specific surface area is 550-650m
2/ g, pore volume are 0.340-0.370ml/g, and infrared acidity is 1.37-1.60mmol/g, wherein the mol ratio 1 of B acid and L acid: 3-1: 5, and Na
2O weight content＜0.2%.
2, catalyzer according to claim 1, it is characterized in that each components contents is as follows in this catalyzer: the weight with catalyzer is benchmark, the content of group vib metal oxide is 10%-30%, the content of group VIII metal oxide is 1%-10%, the content of modified Y zeolite is 1%-20%, the content of β zeolite is 1%-20%, and the content of aluminum oxide is 5%-80%, and the content of tackiness agent is 0～30%;
3, catalyzer according to claim 1, the content that it is characterized in that modified Y zeolite in this catalyzer is 5wt%-15wt%; The content of β zeolite is 5wt%-15wt%; The content of aluminum oxide is 15wt%-70wt%; The content of group vib metal oxide is 10wt%-25wt%; The content of group VIII metal oxide is 1wt%-9wt%.
4, catalyzer according to claim 1 is characterized in that described group vib metal is W and/or Mo, and the group VIII metal is one or more among Fe, Ni and the Co.
5, catalyzer according to claim 1, the specific surface area that it is characterized in that this catalyzer is 170-240m
2/ g, pore volume are 0.30-0.35ml/g, and wherein the aperture accounts for the 75%-90% of total pore volume in the pore distribution of 4-10nm, and infrared acidity is 0.34-0.38mmol/g.
6, catalyzer according to claim 1 is characterized in that the character of described β zeolite is as follows: SiO
2/ Al
2O
3Mol ratio is 20-120, Na
2O weight content＜0.2%, infrared acidity are 0.1-0.7mmol/g.
7, catalyzer according to claim 1 is characterized in that the character of described β zeolite is as follows: SiO
2/ Al
2O
3Mol ratio is 30-90, Na
2O weight content＜0.15%, infrared acidity are 0.15-0.50mmol/g.
8, according to claim 5 or 6 described catalyzer, it is characterized in that described β zeolite is a beta zeolite in small crystal grain, its particle diameter is 1～100nm.
9, catalyzer according to claim 1 is characterized in that described aluminum oxide is the aluminum oxide through additive modification, and auxiliary agent is 3wt%-7wt% in element content, and wherein said auxiliary agent is one or more in boron, fluorine and the zirconium; The character of this modified aluminas is as follows: specific surface area is 320-370m
2/ g, pore volume are 0.7～1.1ml/g.
10, the arbitrary described Preparation of catalysts method of claim 1～9 comprises the steps:
(1) modified Y zeolite, β zeolite and aluminum oxide are mixed;
(2) in the mixture of step (1), add tackiness agent or directly add peptizing agent solution and mix and pinch into paste, extruded moulding;
(3),,, obtain support of the catalyst at 350～700 ℃ of roasting 1-12 hours 100～150 ℃ of dryings 0.5～24 hour with above-mentioned forming composition;
(4) after the support of the catalyst of gained is flooded in the step (3),,, obtain the catalyzer finished product at 350～700 ℃ of roasting 1-12 hours in 100～150 ℃ of dryings 0.5～24 hour in containing group vib metal and/or group VIII metallic solution;
11, Preparation of catalysts method according to claim 10 is characterized in that the preparation method of described modified Y zeolite comprises the steps:
(1) super-hydrophobic Y zeolite is placed water, its mesolite is 1 with the ratio of the weight of water: 2-10, be warming up to 60 ℃-90 ℃, and stirred 0.5-2.0 hour.
(2) get and contain in group vib and/or the group VIII metal soluble salt one or more and be mixed with solution, add in above-mentioned steps (1) solution, with ammoniacal liquor regulator solution pH value, control pH value is 4-10, solution is under 50-90 ℃, stir fully exchange in aging 2-4 hour, after the filtration, made in dry 8-24 hour at 100 ℃-150 ℃.
12, Preparation of catalysts method according to claim 11, it is characterized in that described super-hydrophobic Y zeolite is Y zeolite and obtains after the hydrothermal treatment consists under 500～600 ℃, 0.01～0.30MPa condition, wherein the character of Y zeolite is as follows: silica alumina ratio 6-40, lattice constant 2.440-2.460nm, NaO content is lower than 0.2wt%.
13, Preparation of catalysts method according to claim 11 is characterized in that the described super-hydrophobic Y zeolite of step (1) and the ratio of the weight of water are 1: 3-8,
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143366A (en) * | 2011-12-06 | 2013-06-12 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst for unsaturated compound |
| CN103301874A (en) * | 2012-03-12 | 2013-09-18 | 中国科学院化学研究所 | Method for improving selective hydrogenation ring opening of polycyclic aromatic hydrocarbon and catalyst composition thereof |
| US11090638B2 (en) | 2011-12-22 | 2021-08-17 | Advanced Refining Technologies Llc | Silica containing alumina supports, catalysts made therefrom and processes using the same |
-
2004
- 2004-10-29 CN CNB2004100507205A patent/CN100496731C/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143366A (en) * | 2011-12-06 | 2013-06-12 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst for unsaturated compound |
| CN103143366B (en) * | 2011-12-06 | 2015-05-13 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst for unsaturated compound |
| US9422486B2 (en) | 2011-12-06 | 2016-08-23 | Petrochina Company Limited | Selective hydrogenation catalyst for unsaturated compound |
| US9611435B2 (en) | 2011-12-06 | 2017-04-04 | Petrochina Company Limited | Method for selective hydrogenation of unsaturated compound |
| US11090638B2 (en) | 2011-12-22 | 2021-08-17 | Advanced Refining Technologies Llc | Silica containing alumina supports, catalysts made therefrom and processes using the same |
| US11642664B2 (en) | 2011-12-22 | 2023-05-09 | Advanced Refining Technologies Llc | Silica containing alumina supports, catalysts made therefrom and processes using the same |
| CN103301874A (en) * | 2012-03-12 | 2013-09-18 | 中国科学院化学研究所 | Method for improving selective hydrogenation ring opening of polycyclic aromatic hydrocarbon and catalyst composition thereof |
| CN103301874B (en) * | 2012-03-12 | 2015-03-11 | 中国科学院化学研究所 | Method for improving selective hydrogenation ring opening of polycyclic aromatic hydrocarbon and catalyst composition thereof |
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