CN1727447A - Hydrogenant cracking catalyst of containing zeolite, and preparation method - Google Patents
Hydrogenant cracking catalyst of containing zeolite, and preparation method Download PDFInfo
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Abstract
A hydrocracking catalyst containing zeolite contains matrix (5-85 Wt%), P-contained zeolite (5-85), the metal component in family VIII (1-10) and the metal component in family VIB. Its advantages are high hydrocracking activity and selectivity.
Description
Technical field
The present invention relates to a kind of hydrocracking catalyst and preparation method thereof, more specifically to a kind of hydrocracking catalyst that contains zeolite and preparation method thereof.
Background technology
In recent years, demand to the high-quality intermediate oil in the world wide increases day by day, and that hydrocracking technology has the middle runnings selectivity is good, sulphur in the middle runnings product, nitrogen content are low, advantages such as aromaticity content is few, this impels the hydrocracking technology with voluminous intermediate oil to be developed rapidly, and hydrocracking catalyst is one of wherein important and The key factor.
Hydrocracking catalyst is a kind of dual-function catalyst, and it has lytic activity and hydrogenation activity simultaneously, promptly contains acidic components and hydrogenation activity component simultaneously; The hydrogenation activity component generally is selected from metal, metal oxide and/or the metallic sulfide of group vib and VIII family in the periodic table of elements.The character of acidic components has very important influence to the activity and the selectivity of hydrocracking catalyst production middle runnings.Its acidity is mainly provided by heat-resistant inorganic oxide that constitutes carrier and/or various molecular sieve.
U.S.Patent.No.5,308,742 disclose a kind of mild hydrocracking method, this method catalyst system therefor contains carrier and the group VIII and group vib metal component and the phosphorus that load on this carrier, in oxide compound and with the catalyzer is benchmark, the content of group VIII metal component is 1.0-6.0 weight %, the content of group vib metal component is 12.0-25.0 weight %, the content of phosphorus is 0.1-5.0 weight %, and described carrier contains aluminum oxide or siliceous aluminum oxide and Hydrogen, acidifying sealumination modified Y zeolite.This method is suitable for hydrodemetallation (HDM), hydrogenating desulfurization and the hydrogenated hydrocarbons conversion reaction as hydrocarbon ils such as residual oil.
U.S.Patent.No.6,174,429 disclose a kind of hydrocracking catalyst, at least a acidifying that this catalyzer contains 1-99 weight % contains the aluminium [amorphous, 0.1-80 at least a lattice constant of weight % is 2.438 nanometers, total mol ratio of silicon oxide and aluminum oxide is less than 8, the mol ratio of skeleton silicon oxide and aluminum oxide is less than 20 y-type zeolites greater than total mol ratio, 0.1-30 at least a group VIII metal component of weight %, at least a VI family metal component of 1-40 weight %, 0.1-20 at least a VIIA family element of the phosphorus of weight % and 0-20 weight %.This catalyzer has active and stable preferably when handling high-nitrogen stock.
U.S.Patent.No.6,387,246 disclose a kind of catalyzer, this catalyzer contains: the y-type zeolite of (1) at least a matrix and at least a low-crystallinity is (with respect to the sodium Y zeolite, the degree of crystallinity of this zeolite is less than 60%), (2) at least a hydrogenation-dehydrogenation metal component that is selected from VII and group vib, (3) at least a phosphorus that is selected from, the adjuvant component of boron and silicon, described zeolite has following feature: total silicon/al mole ratio is greater than 15, and wherein framework silicon/al mole ratio is more than or equal to total silicon/aluminum ratio; Pore volume is at least 0.20 milliliter/gram, and bore dia wherein is at least 5 nanoporouss and accounts for total pore volume 8-50%, specific surface 210-800 rice
2/ gram.Described adjuvant component major sedimentary is on described matrix.This catalyzer has hydrogenating desulfurization preferably, denitrification activity simultaneously except that having preferably the hydrocarbon hydrogenation cracking activity.
Have the phosphorus in the phosphoric hydrogenation cracking catalyst now, or be carried on the carrier simultaneously, or at first mix, introduce with the method for zeolite mixing moulding more afterwards with matrix with the method and the reactive metal of dipping, little to the influence of zeolite character.And by habitual as high-temperature water thermal treatment or hydrothermal treatment consists in conjunction with the aluminium-eliminating and silicon-replenishing modification, the degree of crystallinity of y-type zeolite is reduced, the acid amount reduces.But these class methods are little to the intensity effect of y-type zeolite acid.Isomerization reaction selectivity by the hydrocracking catalyst of this class zeolite preparation is lower, and when this class catalyzer was used for the hydrocracking of hydrocarbon ils, it was to the poor selectivity of middle distillate.
Summary of the invention
The purpose of this invention is to provide a kind of new hydrocracking catalyst of zeolite and preparation method thereof that contains.
Catalyzer provided by the invention is made up of the carrier loaded group VIII and the group vib metal component that contain matrix and zeolite, wherein said zeolite is a P-contained zeolite, in oxide compound and with described zeolite is benchmark, and the content of phosphorus is 0.1-15 weight %, described P-contained zeolite
31In the P MAS NMR spectrogram, chemical shift is that the area at 0 ± 1.0ppm peak accounts for the percentage ratio of total peak area less than 1%, with the catalyst weight is benchmark, each components contents is in this catalyzer: matrix 5-85%, zeolite 5-85%, in oxide compound, group VIII metal component 1-10%, group vib metal component 5-40%.
The invention provides the Preparation of catalysts method comprise with matrix mix with zeolite, roasting, and introduce group VIII and group vib metal component in this mixture after roasting, described zeolite is a P-contained zeolite, in oxide compound and with described zeolite is benchmark, the content of phosphorus is 0.1-15 weight %, described P-contained zeolite
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the area at 0 ± 1.0ppm peak accounts for total peak area is not more than 1%.
Provided by the inventionization catalyzer has higher active and to the selectivity of middle distillate when being used for the hydrocarbon oil hydrogenation catalytic cracking reaction.
For example, catalyzer C-4 provided by the invention is a raw material with Saudi Arabia's vacuum gas oil, is 360 ℃ in temperature of reaction, and stagnation pressure is 8.0 MPas, liquid hourly space velocity (LHSV) 0.75 hour
-1, to estimate under hydrogen-oil ratio (volume) 800 conditions, the transformation efficiency (weight) greater than 350 ℃ of components in the stock oil is 59.8%, the selectivity of intermediate oil is 75.3%.And the composition of reference catalyst B-3 is identical with catalyzer C-4, be that contained phosphorus adopts phosphoric acid and matrix and zeolite blended method to introduce in the carrier, with same materials oil, when same reaction conditions is estimated, its transformation efficiency is 52.3%, and the selectivity of intermediate oil is 71.2%.
Embodiment
According to catalyzer provided by the invention, wherein preferred P-contained zeolite
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the area at 0 ± 1.0ppm peak accounts for total peak area is 0.001-0.99%, more preferably 0.001-0.6%.In oxide compound and with described zeolite is benchmark, and the content of described phosphorus is preferably 0.1-10 weight %.
Described P-contained zeolite can be to have in the zeolite of various aluminosilicate zeolite structures one or more, it can be zeolite with macroporous structure, as has a faujusite, the Beta zeolite, the zeolite of omega zeolite structure, it can be zeolite with central hole structure, as has a mordenite, the ZSM-5 zeolite, the ZSM-11 zeolite, the ZSM-22 zeolite, the ZSM-23 zeolite, the ZSM-35 zeolite, the ZSM-48 zeolite, the isostructural zeolite of ZSM-57 zeolite, can be zeolite also, as have the zeolite structured zeolite of Erionite with small structure, the zeolite that ZSM-34 is zeolite structured.Preferably have the faujusite structure zeolite, have the zeolite structured zeolite of Beta, have in the zeolite of mordenite structure one or more.Described zeolite with faujusite structure is preferably y-type zeolite, further preferred wherein be in HY zeolite, rare-earth type Y zeolite REY, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, rare-earth type overstable gamma zeolite REUSY, the dealuminium Y type beta stone one or more.
Cation-bit in the P-contained zeolite in the catalyzer provided by the invention can be occupied by in sodium ion, ammonium ion, the hydrogen ion one or more; Also can be with P-contained zeolite provided by the invention before or after introducing phosphorus, by the ion-exchange of routine, sodium ion wherein, ammonium ion, hydrogen ion can all or part ofly be replaced by other ion.In oxide compound, preferably wherein sodium content is less than 1 weight %, and more preferably sodium content is less than the P-contained zeolite of 0.5 weight %.
Described matrix is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.For example, in the optional self-alumina of described heat-resistingization thing, silicon oxide, titanium oxide, magnesium oxide, aluminum oxide-magnesium oxide, silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, the clay one or more are preferably aluminum oxide and/or silica-alumina.
Described group VIII metal is preferably nickel and/or cobalt, the group vib metal is preferably molybdenum and/or tungsten.Weight with catalyzer is benchmark, the preferred content of described each component is: matrix 5-70 weight %, and zeolite 5-65 weight % is in oxide compound, the content of described VIII family metal component is preferably 2-8 weight %, and the content of group vib metal component is preferably 10-35 weight %.
According to containing not phosphorated zeolite in the catalyzer provided by the invention, described not phosphorated zeolite can be to have in the zeolite of existing aluminosilicate zeolite structure one or more, it can be zeolite with macroporous structure, as has a faujusite, the Beta zeolite, the zeolite of omega zeolite structure, it can be zeolite with central hole structure, as has a mordenite, the ZSM-5 zeolite, the ZSM-11 zeolite, the ZSM-22 zeolite, the ZSM-23 zeolite, the ZSM-35 zeolite, the ZSM-48 zeolite, the isostructural zeolite of ZSM-57 zeolite, can be zeolite also, as have the Erionite zeolite with small structure, the zeolite that ZSM-34 is zeolite structured.Preferably have the zeolite structured zeolite of Beta, have the zeolite of mordenite structure or have in the zeolite structured zeolite of ZSM-5 one or more.In the total amount of catalyzer, the content of described not P-contained zeolite is 0-30 weight %, is preferably 0-15 weight %.
According to method provided by the invention, the preparation method of wherein said P-contained zeolite is included in and introduces phosphorus in the zeolite, use this zeolite of acidiferous solution washing afterwards, described acid is selected from one or more in water miscible organic acid, the mineral acid, describedly contain that acid content is the 0.0001-10.0 mol in the aqueous acid, the temperature of described washing is a room temperature-95 ℃, and the described consumption that contains aqueous acid and washing times make zeolite
31In the P MAS-NMR spectrogram, chemical shift is that the peak area at 0 ± 1.0ppm peak accounts for the percentage ratio of total peak area less than 1%.
Can adopt any one known method in aluminosilicate zeolite, to introduce phosphorus.For example, the preparation method of the applicant's disclosed a kind of P-contained zeolite in CN1088407C, this method comprises directly mixes P contained compound with the weight ratio of raw material zeolite 0.1-40, and in confined conditions in 50-550 ℃ of heating at least 0.1 hour, the product that obtains with deionized water wash reclaims P-contained zeolite to there not being acid ion.
The method of the described zeolite of the acidiferous solution washing of described usefulness, comprise described zeolite and described acidiferous aqueous solution pulp, filtration, the content of described acidiferous aqueous acid medium is preferably the 0.001-8.0 mol, described wash temperature is preferably 30-90 ℃, described acid is selected from one or more organic acids or mineral acid, more preferably one or more in phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartrate, formic acid, the acetate.The consumption of described acid-containing solution and washing times should finally make described zeolite
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the peak area at 0 ± 1.0ppm peak accounts for total peak area is preferably 0.001-0.99%, more preferably 0.001-0.6%.
According to preparation method provided by the invention, also contain ammonium salt in the described acid-containing solution, described ammonium salt can be that any one or a few is selected from organic and/or inorganic water soluble salt of ammonia, as in ammonium sulfate, ammonium chloride and the ammonium nitrate one or more.The content of described ammonium salt in solution is the 0-5 mol, is preferably the 0-2.5 mol.
For described zeolite, before introducing phosphorus and can comprise one or more modification procedure afterwards.Described method of modifying can be any one known method, for example, and the method for the applicant's phosphorous ultrastable Y of disclosed preparation in CN 1279130A.This method comprises: will contain 0.5-5 weight % (with P
2O
5Meter) phosphorus, and Na
2O content is 0.5-6 weight %, and lattice constant is the P-NH of 2.460-2.475 nanometer
4The NAY zeolite in stoving oven under 100% steam atmosphere 450-700 ℃ hydrothermal calcine 0.5-4 hour; Product after the roasting is carried out the reaction of liquid phase aluminium-eliminating and silicon-replenishing; Filter washing then.Prepare the phosphorous Y zeolite that structure cell is contracted to the 2.454-2.457 nanometer thus.
The invention provides the Preparation of catalysts method, comprise according to ordinary method under the condition that is enough to nickel and/or cobalt and molybdenum and/or tungsten metal component be deposited on the mixture, described matrix after the described roasting is contacted with the solution that contains at least a nickel and/or cobalt and molybdenum and/or tungsten metallization compound with the mixture of zeolite, for example by methods such as ion-exchange, dipping, co-precipitation, preferred pickling process.
Said nickel and/or cobalt metallic compound are selected from one or more in the soluble compound of these metals, can be in the nitrate, acetate, soluble carbon hydrochlorate, muriate, soluble complexes of these metals one or more as them.
Said molybdenum and/or tungsten metallization compound are selected from one or more in the soluble compound of these metals, can be in molybdate, paramolybdate, tungstate, metatungstate, the ethyl metatungstate one or more as them.
When the not phosphorated zeolite that contains in the catalyzer except that P-contained zeolite of the present invention, before method provided by the invention also is included in described matrix and contains the phosphate mixture roasting, introduce the step of described not phosphorated zeolite.The introducing of described not phosphorated zeolite can be adopted usual method, for example, phosphorated zeolite not can be mixed forward and backward or introduces simultaneously and mix in described matrix with P-contained zeolite.
Described not phosphorated zeolite can be commercially available commodity, also can be by any one existing method preparation.In oxide compound, preferably wherein sodium content is less than 1 weight %, and more preferably sodium content is less than the zeolite of 0.5 weight %.
According to catalyzer provided by the invention, look the forming composition that various objectives or requirement can be made into various easy handlings, for example microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.
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 hydrocracking, has hydrocarbon fraction than lower boiling and lower molecular weight with production.Described hydrocarbon raw material can be various heavy mineral oils or synthetic oil or their mixed fraction oil, as straight run gas oil (straight run gas oil), vacuum gas oil (vacuum gas oil), metal removal oil (demetallized oils), long residuum (atmosphericresidue), diasphaltene vacuum residuum (deasphalted vacuum residue), coker distillate (coker distillates), catalytic cracking distilled oil (cat craker distillates), shale oil (shale oil), asphalt sand oil (tar sand oil), liquefied coal coil (coal liquid) etc.The hydrocracking that catalyzer provided by the invention is specially adapted to heavy and inferior distillate oil is 149-371 ℃ to produce boiling range, and especially boiling range is the hydrocracking process of 180-370 ℃ of intermediate oil.
When catalyzer provided by the invention is used for distillate hydrocracking, can under the hydrocracking process condition of routine, use, as temperature of reaction 200-650 ℃, preferred 300-510 ℃, reaction pressure 3-24 MPa, preferred 4-15 MPa, liquid hourly space velocity 0.1-10 hour
-1Preferred 0.2-5 hour
-1, hydrogen to oil volume ratio 100-5000, preferred 200-1000.
The following examples will the present invention is described further.
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 zeolite nuclear magnetic spectrogram is measured on Varion INOVA300 type nuclear magnetic resonance analyser, and phosphoric acid is standard specimen.
Comparative Examples 1
P-contained zeolite that reference catalyst is used and preparation method thereof is described.
According to phosphorous overstable gamma zeolite 300 grams of CNl279130A embodiment 1 preparation, count PY-1, its phosphorus content and
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the peak area at 0 ± 1.0ppm peak accounts for total peak area is listed in table 1.
Example 1
Illustrate and the invention provides used P-contained zeolite of catalyzer and preparation method thereof.
Get PY-1 zeolite 100 grams, add 1000 ml deionized water, stirring to pulp is warming up to 95 ℃, adds 1000 milliliters of aqueous nitric acid, and the concentration of nitric acid is 0.005 mol in this solution, reacts 4 hours, filters, and repeats said process 5 times, gets zeolite PYS-1.Its phosphorus content and
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the peak area at 0 ± 1.0ppm peak accounts for total peak area is listed in table 1.
Example 2
Illustrate and the invention provides used P-contained zeolite of catalyzer and preparation method thereof.
Get PY-1 zeolite 100 grams, add 1000 ml deionized water, stirring to pulp is warming up to 95 ℃, adds the mixed aqueous solution of 1000 milliliters of nitric acid and ammonium nitrate, the concentration of nitric acid is 0.005 mol in this solution, the concentration of ammonium nitrate is 1 mol, reacts 4 hours, filters, repeat said process 5 times, get zeolite PYS-2.Its phosphorus content and
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the peak area at 0 ± 1.0ppm peak accounts for total peak area is listed in table 1.
Comparative Examples 2
P-contained zeolite that reference catalyst is used and preparation method thereof is described.
According to CN1088407C embodiment 7 preparation P-contained zeolites 300 grams, count PY-2.Its phosphorus content and
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the peak area at 0 ± 1.0ppm peak accounts for total peak area is listed in table 1.
Example 3
Illustrate and the invention provides used P-contained zeolite of catalyzer and preparation method thereof.
Get PY-2 zeolite 100 grams, roasting is 6 hours in 550 ℃, 100% steam atmosphere, after reducing to room temperature, its hydrochloric acid and aqueous ammonium chloride solution with 1000 milliliters is mixed (tartaric acid concentration of this solution is that 0.2 mol, ammonium chloride concentration are 4.5 mol), be warming up to 95 ℃ of reactions 5 hours, filter, repeat said process 5 times after, with 100ml deionized water wash 2 times, zeolite PYS-3.Its phosphorus content and
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the peak area at 0 ± 1.0ppm peak accounts for total peak area is listed in table 1.
Comparative Examples 3
P-contained zeolite that reference catalyst is used and preparation method thereof is described.
According to CN1088407C embodiment 11 preparation P-contained zeolites 300 grams, count PY-3, its phosphorus content and
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the peak area at 0 ± 1.0ppm peak accounts for total peak area is listed in table 1.
Example 4
Illustrate and the invention provides used P-contained zeolite of catalyzer and preparation method thereof.
Get PY-3 zeolite 100 grams, the mixed aqueous solution that adds 1000 milliliters of acetate and ammonium sulfate, the concentration of acid is 5.0 mol in this solution, and the concentration of ammonium sulfate is 1.0 mol, stirring to pulp, be warming up to 40 ℃, reacted 4 hours, and filtered, repeat said process 5 times, with deionized water wash 2 times, zeolite PYS-4.Its phosphorus content and
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the peak area at 0 ± 1.0ppm peak accounts for total peak area is listed in table 1.
Comparative Examples 4
Phosphorous mordenite that reference catalyst is used and preparation method thereof is described.
According to CN1088407C embodiment 14 preparation P-contained zeolites 300 grams, count PM-4, its phosphorus content and
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the peak area at 0 ± 1.0ppm peak accounts for total peak area is listed in table 1.
Example 5
Illustrate and the invention provides used phosphorous mordenite of catalyzer and preparation method thereof.
Get PM-4 zeolite 100 grams, the mixed aqueous solution that adds 1000 milliliters of nitric acid and ammonium nitrate, the concentration of acid is 0.001 mol in this solution, and the concentration of ammonium nitrate is 1.0 mol, stirring to pulp, be warming up to 40 ℃, reacted 4 hours, and filtered, repeat said process 2 times, with deionized water wash 2 times, zeolite PMS-4.Its phosphorus content and
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the peak area at 0 ± 1.0ppm peak accounts for total peak area is listed in table 1.
Example 6
Illustrate and the invention provides used P-contained zeolite of catalyzer and preparation method thereof.
Get commodity β zeolite (Chang Ling refinery catalyst plant product, silica alumina ratio 28) 300 grams (butt), add 3000 gram (NH
4)
2HPO
4, thorough mixing adds an encloses container, in 300 ℃ of reaction 2hr, with 20 times of deionized water wash, drying, get 100 grams afterwards, add the mixed aqueous solution of 1000 milliliters of citric acids and ammonium acetate, the concentration of acid is 1.0 mol in this solution, the concentration of ammonium acetate is 1.0 mol, and stirring to pulp is warming up to 40 ℃, reacted 4 hours, and filtered, repeat said process 2 times, with deionized water wash 2 times, zeolite PBS-5.Its phosphorus content and
31In the P MAS NMR spectrogram, chemical shift is that the percentage ratio that the peak area at 0 ± 1.0ppm peak accounts for total peak area is listed in table 1.
Table 1
| Example | Numbering | P 2O 5Weight % | Chemical shift ppm | Chemical shift is the peak area and total peak area ratio, % at 0 ± 1.0ppm peak |
| Comparative Examples 1 | PY-1 | 0.8 | 0.05 | 8.34 |
| 1 | PYS-1 | 0.8 | 0.059 | 0.5 |
| 2 | PYS-2 | 0.8 | 0.059 | 0.08 |
| Comparative Examples 2 | PY-2 | 8.0 | 0.05 | 42.0 |
| 3 | PYS-3 | 7.6 | -0.21 | 0.003 |
| Comparative Examples 3 | PY-3 | 2.0 | -0.06 | 45.2 |
| 4 | PYS-4 | 2.0 | -0.038 | 0.004 |
| Comparative Examples 4 | PM-4 | 1.1 | -0.07 | 10.9 |
| 5 | PMS-4 | 1.0 | -0.01 | 0.4 |
| 6 | PBS-5 | 1.7 | 0.03 | 0.3 |
Example 7
Catalysts and its preparation method provided by the invention is described.
With 30 gram (butts, down together) (Shandong Aluminum Plant produces for PYS-1 P-contained zeolite and 70 gram pseudo-boehmites, trade(brand)name SD powder) mixes, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 600 ℃ of roasting temperatures 3 hours, be cooled to after the room temperature with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry product, tungsten oxide content is 82 weight %) 34.65 grams, nickelous nitrate (the new Photochemical agents in Beijing factory product, nickel oxide content is 27.85 weight %) the 24.84 70ml aqueous solution dippings that restrain, 120 ℃ of oven dry were 480 ℃ of roastings 4 hours, obtain catalyzer C-1, its composition sees Table 2.
Example 8
Catalysts and its preparation method provided by the invention is described.
With 30 gram (butts, down together) (Shandong Aluminum Plant produces for PYS-2 P-contained zeolite and 70 gram pseudo-boehmites, trade(brand)name SD powder) mixes, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 600 ℃ of roasting temperatures 3 hours, be cooled to after the room temperature with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry product, tungsten oxide content is 82 weight %) 34.65 grams, nickelous nitrate (the new Photochemical agents in Beijing factory product, nickel oxide content is 27.85 weight %) the 24.84 70ml aqueous solution dippings that restrain, 120 ℃ of oven dry were 480 ℃ of roastings 4 hours, obtain catalyzer C-2, its composition sees Table 2.
Comparative Examples 5
Reference catalyst and preparation method thereof is described.
With 30 gram (butts, down together) (Shandong Aluminum Plant produces for PY-1 P-contained zeolite and 70 gram pseudo-boehmites, trade(brand)name SD powder) mixes, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 600 ℃ of roasting temperatures 3 hours, be cooled to after the room temperature with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry product, tungsten oxide content is 82 weight %) 34.65 grams, nickelous nitrate (the new Photochemical agents in Beijing factory product, nickel oxide content is 27.85 weight %) the 24.84 70ml aqueous solution dippings that restrain, 120 ℃ of oven dry were 480 ℃ of roastings 4 hours, obtain catalyst B-1, its composition sees Table 2.
Example 9
Catalysts and its preparation method provided by the invention is described.
With 16.8 gram (butts, down together) (Shandong Aluminum Plant produces for PBS-5 P-contained zeolite and 70 gram pseudo-boehmites, trade(brand)name SD powder) and 6.5 gram molybdic oxides (Beijing dicyclo chemical reagent factory) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 500 ℃ of roasting temperatures 3 hours, be cooled to after the room temperature with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry product, tungsten oxide content is 82 weight %) 32.23 grams, nickelous nitrate (the new Photochemical agents in Beijing factory product, nickel oxide content is 27.85 weight %) 13.02 grams, Xiao Suangu (Beijing Chemical Plant's product, cobalt oxide content is 25.53%) the 22.3 60ml aqueous solution dippings that restrain, 120 ℃ of oven dry, 450 ℃ of roastings 4 hours, obtain catalyzer C-3, its composition sees Table 2.
Comparative Examples 6
Reference catalyst and preparation method thereof is described.
With 16.8 gram (butts, down together) (Shandong Aluminum Plant produces for PB-5 P-contained zeolite and 70 gram pseudo-boehmites, trade(brand)name SD powder) and 6.5 gram molybdic oxides (Beijing dicyclo chemical reagent factory) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 500 ℃ of roasting temperatures 3 hours, be cooled to after the room temperature with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry product, tungsten oxide content is 82 weight %) 32.23 grams, nickelous nitrate (the new Photochemical agents in Beijing factory product, nickel oxide content is 27.85 weight %) 13.02 grams, Xiao Suangu (Beijing Chemical Plant's product, cobalt oxide content is 25.53%) the 22.3 60ml aqueous solution dippings that restrain, 120 ℃ of oven dry, 450 ℃ of roastings 4 hours, obtain catalyst B-2, its composition sees Table 2.
Example 10
Catalysts and its preparation method provided by the invention is described.
With 25 gram (butts, down together) (Shandong Aluminum Plant produces for PYS-3 P-contained zeolite and 12.5 gram pseudo-boehmites, trade(brand)name SD powder), the silica-alumina powder (trade names Siral40) that 113 gram Sasol produce, 12.5 Beta zeolite (the Chang Ling refinery catalyst plant product that gram Chang Ling catalyst plant is produced, silica alumina ratio 28) mixes, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 550 ℃ of roasting temperatures 4 hours, be cooled to after the room temperature with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry product, tungsten oxide content is 82 weight %) 97.6 grams, nickelous nitrate (the new Photochemical agents in Beijing factory product, nickel oxide content is 27.85 weight %) the 23.34 105ml aqueous solution dippings that restrain, 120 ℃ of oven dry, 450 ℃ of roastings 4 hours, obtain catalyzer C-4, its composition sees Table 2.
Comparative Examples 7
Reference catalyst and preparation method thereof is described.
According to CN1088407C embodiment 7 preparation zeolites 300 grams, different is not introduce phosphorus in the molecular sieve preparation process, and molecular sieve is counted NPY-2.
Restrain (butt, down together) NPY-2 zeolite and contain 3.08 gram NH 21.92
4H
2PO
4The 30ml aqueous solution of (Beijing sharp fine chemistry of benefit company limited), 12.5 (Shandong Aluminum Plant produces the gram pseudo-boehmite, trade(brand)name SD powder), the silica-alumina powder (trade names Siral40) that 113 gram Sasol produce, 12.5 Beta zeolite (the Chang Ling refinery catalyst plant product that gram Chang Ling catalyst plant is produced, silica alumina ratio 28) mixes, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 550 ℃ of roasting temperatures 4 hours, be cooled to after the room temperature with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry product, tungsten oxide content is 82 weight %) 97.6 grams, nickelous nitrate (the new Photochemical agents in Beijing factory product, nickel oxide content is 27.85 weight %) the 23.34 105ml aqueous solution dippings that restrain, 120 ℃ of oven dry, 450 ℃ of roastings 4 hours, obtain catalyst B-3, its composition sees Table 2.
Example 11
Catalysts and its preparation method provided by the invention is described.
With 100 gram (butts, the silica-alumina powder (trade names Siral40) of PBS-5 P-contained zeolite and 66.7 gram Sasol productions down together), the ZSM-5 zeolite (production of Chang Ling refinery catalyst plant) that 100 gram Chang Ling catalyst plants are produced mixes, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 550 ℃ of roasting temperatures 3 hours, be cooled to after the room temperature with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry product, tungsten oxide content is 82 weight %) 61.85 grams, nickelous nitrate (the new Photochemical agents in Beijing factory product, nickel oxide content is 27.85 weight %) the 55.06 175ml aqueous solution dippings that restrain, 120 ℃ of oven dry, 450 ℃ of roastings 3 hours, obtain catalyzer C-5, its composition sees Table 2.
Example 12
Catalysts and its preparation method provided by the invention is described.
With 20 gram (butts, down together) (Shandong Aluminum Plant produces for PYS-2 P-contained zeolite and 130 gram pseudo-boehmites, trade(brand)name SD powder), the silica-alumina powder (trade names Siral40) that 130 gram Sasol produce mixes, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, 120 ℃ of oven dry, 610 ℃ of roasting temperatures 2 hours, be cooled to after the room temperature with containing ammonium metawolframate (Sichuan Zigong Hard Alloy Foundry product, tungsten oxide content is 82 weight %) 115.18 grams, nickelous nitrate (the new Photochemical agents in Beijing factory product, nickel oxide content is 27.85 weight %) the 87.61 190ml aqueous solution dippings that restrain, 120 ℃ of oven dry, 430 ℃ of roastings 4 hours, obtain catalyzer C-6, its composition sees Table 2.
Table 2
| Example | Catalyzer | Matrix, weight % | Zeolite, weight % | NiO weight % | CoO weight % | WO 3Weight % | MoO 3Weight % | ||
| Al 2O 3 | SiO 2- Al 2O 3 | P-contained zeolite | P-contained zeolite not | ||||||
| 7 | C-1 | 51.6 | 0 | 22.1 | 0 | 5.1 | 21.2 | ||
| 8 | C-2 | 51.6 | 0 | 22.1 | 0 | 5.1 | 21.2 | ||
| Comparative Examples 5 | B-1 | 51.6 | 0 | 22.1 | 0 | 5.1 | 21.2 | ||
| 9 | C-3 | 54.1 | 0 | 13.0 | 0 | 2.8 | 4.4 | 20.7 | 5 |
| Comparative Examples 6 | B-2 | 54.1 | 0 | 13.0 | 0 | 2.8 | 4.4 | 20.7 | 5 |
| 10 | C-4 | 5 | 45 | 10 | 5 | 2.6 | 32.4 | ||
| Comparative Examples 7 | B-3 | 5 | 45 | 0 | 15 | 2.6 | 32.4 | ||
| 11 | C-5 | 0 | 20 | 30 | 30 | 4.6 | 15.4 | ||
| 12 | C-6 | 32.5 | 32.5 | 5 | 6.1 | 23.9 | |||
Example 13-15
The performance that the invention provides catalyzer is described.
With the n-decane is raw material, the hydrogenation cracking activity of evaluate catalysts C-1, C-2, C-3 on the small fixed hydroeracking unit, the catalyzer loading amount is 0.2 milliliter, the granules of catalyst diameter is the 0.3-0.45 millimeter, 380 ℃ of temperature of reaction, reaction pressure 2.14 MPas, hydrogen-oil ratio (mol ratio) is 25, liquid hourly space velocity is 30 hours
-1, represent activity of such catalysts with the n-decane per-cent that transforms in the product composition, evaluation result sees Table 3.
Comparative Examples 8-9
The performance of reference catalyst is described.
The evaluation method of catalyst B-1, B-2 is with example 7, and the results are shown in Table 3 for gained.
Table 3
| Example | Catalyzer | Transformation efficiency, % |
| 13 | C-1 | 44.4 |
| 14 | C-2 | 55.4 |
| Comparative Examples 8 | B-1 | 34.4 |
| 15 | C-3 | 40.3 |
| Comparative Examples 9 | B-2 | 36.2 |
The presentation of results of table 3 is compared with reference catalyst, and the catalyzer of the present invention's preparation has better hydrogenation cracking activity.
Example 16-17
The hydrogenation cracking activity and the selectivity that the invention provides catalyzer are described.
Raw materials used oil is Saudi Arabia's vacuum gas oil, and its physico-chemical property sees Table 4.
In this example, the evaluation method of catalyzer is: the particle that catalyzer C-4, C-5 is broken into diameter 2-3 millimeter respectively, in 30 milliliters of fixed-bed reactor, pack into 30 milliliters of catalyzer, under nitrogen atmosphere, use earlier before the reaction and contain the kerosene of 2 heavy % dithiocarbonic anhydride 300 ℃ of following prevulcanizeds 25 hours, switch the reaction raw materials reaction then, temperature of reaction is 360 ℃, and stagnation pressure is 8.0 MPas, liquid hourly space velocity (LHSV) 0.75 hour
-1, hydrogen-oil ratio (volume) 800, the results are shown in Table 5.
With the transformation efficiency of the weight percentage definition catalyzer that transforms greater than 350 ℃ of components in the stock oil,, the results are shown in Table 5 to generate in the oil weight percentage definition selectivity of 170 ℃～350 ℃ cuts and the ratio that generates oily total amount.
Comparative Examples 10
Adopt the identical method evaluate catalysts B-3 of example 16, evaluation result sees Table 5.
Table 4
| Stock oil | |
| Density (20 ℃), g/cm 3 | 0.8932 |
| S, weight % | 2.12 |
| N，mg/l | 683 |
| Simulation distil (ASTM D-2887) | |
| IBP | 305 |
| 83.7 | 350 |
Table 5
| Example | Catalyzer | Transformation efficiency % | Selectivity % |
| 16 | C-4 | 59.8 | 75.3 |
| Comparative Examples 10 | B-3 | 51.2 | 72.3 |
| 17 | C-5 | 63.2 | 73.8 |
The composition of catalyzer C-4 is identical with reference catalyst B-3, be that contained phosphorus adopts phosphoric acid and matrix and zeolite blended method to introduce in the carrier, with same materials oil, when same reaction conditions is estimated, bright transformation efficiency provided by the invention is higher by 8.6% than reference catalyst, and the selectivity of intermediate oil is high by 3.0%.
Claims (21)
1, a kind of hydrocracking catalyst that contains zeolite, form by the carrier loaded group VIII and the group vib metal component that contain matrix and zeolite, it is characterized in that, wherein said zeolite is a P-contained zeolite, in oxide compound and with described zeolite is benchmark, the content of phosphorus is 0.1-15 weight %, described P-contained zeolite
31In the P MAS NMR spectrogram, chemical shift is that the area at 0 ± 1.0ppm peak accounts for the percentage ratio of total peak area less than 1%, with the catalyst weight is benchmark, each components contents is in this catalyzer: matrix 5-85%, zeolite 5-85%, in oxide compound, group VIII metal component 1-10%, group vib metal component 5-40%.
2, catalyzer according to claim 1 is characterized in that, described P-contained zeolite
31In the P MASNMR spectrogram, chemical shift is that the percentage ratio that the area at 0 ± 1.0ppm peak accounts for total peak area is 0.001-0.99%.
3, catalyzer according to claim 2 is characterized in that, described P-contained zeolite
31In the P MASNMR spectrogram, chemical shift is that the percentage ratio that the area at 0 ± 1.0ppm peak accounts for total peak area is 0.001-0.6%.
4, catalyzer according to claim 1 is characterized in that, is benchmark in oxide compound and with described P-contained zeolite, and the content of described phosphorus is 0.1-10 weight %.
5, catalyzer according to claim 1 is characterized in that, described P-contained zeolite is selected from zeolite with faujusite structure, have the zeolite structured zeolite of Beta or have in the zeolite of mordenite structure one or more.
6, catalyzer according to claim 5 is characterized in that, described faujusite is a y-type zeolite.
7, catalyzer according to claim 6, it is characterized in that described y-type zeolite is selected from one or more in HY zeolite, rare-earth type Y zeolite REY, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, rare-earth type overstable gamma zeolite REUSY, the dealuminium Y type beta stone.
8, catalyzer according to claim 1, it is characterized in that described heat-resistingization thing is selected from one or more in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, aluminum oxide-magnesium oxide, silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, the clay.
9, catalyzer according to claim 8 is characterized in that, described heat-resistingization thing is aluminum oxide and/or silica-alumina.
10, catalyzer according to claim 1 is characterized in that, is benchmark with the catalyst weight, described each components contents is: matrix 5-70 weight %, and zeolite 5-65 weight % is in oxide compound, group VIII metal component 2-8 weight %, group vib metal component 10-35 weight %.
According to claim 1 or 10 described catalyzer, it is characterized in that 11, described group VIII metal is selected from nickel and/or cobalt, the group vib metal is selected from molybdenum and/or tungsten.
12, catalyzer according to claim 1 is characterized in that, also contains not phosphorated zeolite in the catalyzer, is benchmark with the catalyzer, and its content is 0-50 weight %.
13, catalyzer according to claim 12 is characterized in that, described not phosphorated zeolite is selected from one or more in the zeolite with existing aluminosilicate zeolite structure, is benchmark with the catalyzer, and its content is 0-35 weight %.
14, catalyzer according to claim 13 is characterized in that, described not phosphorated zeolite is selected to have the zeolite structured zeolite of Beta, have the zeolite of mordenite structure or have in the zeolite structured zeolite of ZSM-5 one or more.
15, the described Preparation of catalysts method of claim 1, comprise with matrix mix with zeolite, roasting, and introduce group VIII and group vib metal component in this mixture after roasting, it is characterized in that, described zeolite is a P-contained zeolite, in oxide compound and with described zeolite is benchmark, and the content of phosphorus is 0.1-15 weight %, described P-contained zeolite
31In the P MAS NMR spectrogram, chemical shift is that the area at 0 ± 1.0ppm peak accounts for the percentage ratio of total peak area less than 1%.
16, method according to claim 15, it is characterized in that, the preparation method of described P-contained zeolite is included in and introduces phosphorus in the zeolite, use this zeolite of acidiferous solution washing afterwards, described acid is selected from one or more in water miscible organic acid, the mineral acid, the described content that contains in the aqueous acid acid is the 0.0001-10.0 mol, and the temperature of described washing is a room temperature-95 ℃, and the described consumption that contains aqueous acid and washing times make described P-contained zeolite
31In the P MAS-NMR spectrogram, chemical shift is that the peak area at 0 ± 1.0ppm peak accounts for the percentage ratio of total peak area less than 1%.
17, method according to claim 16, it is characterized in that, described acid is selected from one or more in phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, citric acid, tartrate, formic acid, the acetate etc., and the content of described acidiferous aqueous acid medium is the 0.001-8.0 mol.
18, method according to claim 16 is characterized in that, the temperature of described washing is 30-90 ℃.
19, method according to claim 16 is characterized in that, also contains ammonium salt in the described acid-containing solution, and its concentration is the 0-5 mol.
20, method according to claim 19 is characterized in that, described ammonium salt is selected from one or more in ammonium sulfate, ammonium chloride and the ammonium nitrate, and its concentration is the 0-2.5 mol.
21, method according to claim 15 is characterized in that, described method comprises that is also introduced the not step of P-contained zeolite, and described not P-contained zeolite can be to mix forward and backward with P-contained zeolite or blended method introducing simultaneously in described matrix.
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