CN105618115A - Modified Y molecular sieve and preparation method thereof - Google Patents
Modified Y molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified Y molecular sieve and a preparation method thereof. The molecular sieve has the following properties: bulk phase silica-alumina ratio is 10-70; surface layer silica-alumina ratio is 7-30; the surface layer silica-alumina ratio is lower by 5-40 than the bulk phase silica-alumina ratio, wherein the surface layer means the part within the range of 5-400nm from the outer surface to the inside of the molecular sieve; modified Y molecular sieve lattice constant is 2.425-2.455nm; specific surface area is 600-900m<2>/g; pore volume is 0.20-0.70ml/g; and infrared acid content is 0.3-1.5mmol/g. The preparation method of the modified Y molecular sieve comprises the following steps: a preliminary dealumination treatment is carried out upon Y molecular sieve obtained after ammonium exchange; fast drying is carried out; a coke reaction is carried out; high-temperature roasting treatment is carried out; and secondary dealumination treatment, drying and charcoal burning treatment are carried out, such that the modified Y molecular sieve is obtained. The surface layer silica-alumina ratio of the molecular sieve is lower than the bulk phase silica-alumina ratio. The molecular sieve has a good application prospect in a hydro-cracking reaction process.
Description
Technical field
The present invention relates to a kind of modified Y molecular sieve and preparation method thereof.
Background technology
The features such as hydrocracking technology has that adaptability to raw material is strong, production operation and big, the good product quality of products scheme motility, various heavy inferior chargings can be converted into the high-quality jet fuel of market in urgent need, diesel oil, lube basestocks and chemical industry Petroleum and tail oil preparing ethylene by steam cracking raw material, become one of modern oil refining and the most important heavy oil deep processing technique of petro chemical industry, at home and abroad obtain increasingly extensive application. the core of hydrocracking process is hydrocracking catalyst. hydrocracking catalyst is typical bifunctional catalyst, has hydrogenation and cracking dual-use function. wherein hydrogenating function generally has the sulphided state form of W, Mo, Ni isoreactivity metal to provide, and cracking function is then provided by molecular sieve. at China's hydrocracking technology owing to its raw material adapts to strong, the feature that product adjustability is big, therefore, usually adapted to the changes in demand in market as a kind of regulating measure by oil refining enterprise, when between Ru Dang city field alignment, distillate is in great demand, can fecund some midbarrels, market to heavy naphtha in great demand time then can fecund heavy naphtha, therefore, air speed on hydrocracking unit, in the relatively-stationary situation of the operating conditions such as pressure, the temperature raising sensitivity of hydrocracking catalyst is particularly important for device flexible operating, in addition, for setter, owing to hydrogen supply is relatively fixed, therefore, device temperature raising process should reduce the fluctuation of hydrogen gas consumption as much as possible thus being more beneficial for device even running while flexible operating, these are all that the research and development of hydrocracking catalyst are had higher requirement.
At present, hydrocracking process is the most widely used is modified Y molecular sieve, inside and outside conventional processing method molecular sieve, Distribution of silicon and aluminium is uniform, acid centre is uniformly distributed, and when reducing Y molecular sieve silica alumina ratio, improves Y molecular sieve acid site density, temperature raising sensitivity is improved, but meanwhile, second pyrolysis is also significantly increased, hydrogen consumption is substantially improved. And when Y molecular sieve carries out advanced treating, when acid density is too low, catalyst temperature raising sensitivity is poor again.
CN200710158784.0 discloses a kind of hydrocracking catalyst containing Y molecular sieve and preparation method thereof, in this invention, Y type molecular sieve is to obtain after processing hydrothermal treatment consists with the mixed aqueous solution of aluminium salt and acid, the catalyst temperature raising sensitivity prepared is higher, but simultaneously, temperature raising process second pyrolysis substantially increases, hydrogen consumption is notable to rise, and is unfavorable for industrial hydrocracking unit temperature raising process apparatus even running.
CN200810012212.6 discloses a kind of carrier of hydrocracking catalyst and preparation method thereof, and hydrocracking catalyst temperature raising sensitivity prepared by this invention is poor.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of modified molecular screen and preparation method thereof, and (silica alumina ratio described in literary composition is SiO to the silica alumina ratio of modified molecular screen surface layer of the present invention2/Al2O3Mol ratio) lower than body phase silica alumina ratio, to have broad application prospects in the different hydrocracking reaction processes such as high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil hydro-conversion.
The modified Y molecular sieve of the present invention, have the property that body phase silica alumina ratio is 10 ~ 70, wherein surface layer silica alumina ratio 7 ~ 30, it is preferable that 9 ~ 20, surface layer silica alumina ratio is lower than body phase silica alumina ratio 5 ~ 40, wherein said surface layer refers to the molecular sieve outer surface thickness range to internal 5 ~ 400nm, preferably 10 ~ 200nm, more preferably 50 ~ 190nm, surface layer is primary in Y molecular sieve crystal grain before modified, intact with molecular sieve internal cohesion, do not block molecular sieve internal gutter; Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm; Sodium oxide weight/mass percentage composition is less than 1.0%, it is preferable that less than 0.5%; Modified Y molecular sieve specific surface area 600 ~ 900m2/ g, it is preferable that 650 ~ 850m2/ g; Pore volume 0.20 ~ 0.70ml/g, it is preferable that 0.3 ~ 0.6ml/g; Meleic acid content 0.3 ~ 1.5mmol/g, it is preferable that 0.4 ~ 1.2mmol/g; Relative crystallinity 60% ~ 130%, it is preferable that 70% ~ 120%.
The preparation method of modified Y molecular sieve of the present invention, including following content:
(1) Ammonium Salt Ionic exchange reaction is carried out with NaY zeolite for former powder;
(2) Y molecular sieve after ammonium being exchanged carries out first dealumination treatment;
(3) the Y molecular sieve rapid draing that step (2) obtains processes;
(4) Y molecular sieve after rapid draing is fully contacted with the unsaturated olefin of liquid or gaseous state, then carries out carbon deposit reaction in oxygen-containing atmosphere;
(5) molecular sieve after step (4) process carries out second time dealumination treatment;
(6) the Y molecular sieve drying that step (5) obtains, process of making charcoal, obtain modified Y molecular sieve.
Ammonium Salt Ionic exchange process described in step (1) is as follows: with NaY zeolite for raw material in ammonium salt aqueous solution, at 60 ~ 120 DEG C, it is preferable that at 60 ~ 90 DEG C, exchanges 1 ~ 3 hour, and exchange times is 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O content is less than 3.0%; Wherein the silica alumina ratio of NaY zeolite raw material is 3 ~ 6, sodium oxide weight/mass percentage composition 6% ~ 7%; Ammonium salt is one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution concentration 0.3 ~ 6.0mol/L, it is preferable that 1.0 ~ 3.0mol/L.
The described first dealumination treatment process of step (2) can be one or more in hydrothermal treatment consists, acid treatment, aluminium salt process and ammonium fluosilicate processing procedure; Wherein, when hydrothermal treatment process is at self steam or passes into steam, hydrothermal conditions is: treatment temperature is 400 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and the process time is 1.0 ~ 4.0 hours; Mineral acid used by acid treatment process and/or organic acid can be one or more in sulphuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid, mineral acid and/or organic acid are calculated as the liquid-solid mass ratio of 0.1 ~ 0.7mol/L, mineral acid and/or organic acid and molecular sieve for 3:1 ~ 30:1 with H+; Acid treatment temperature 30 ~ 80 DEG C, the process time is 0.5 ~ 3 hour; Aluminium salt used by aluminium salt processing procedure can be aluminum chloride, aluminum sulfate, aluminum nitrate etc. Aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and the process time is 0.5 ~ 3 hour; Ammonium fluosilicate processing procedure is as follows: Y molecular sieve adds water and is made into the water sample mixing of liquid-solid mass ratio 3:1 ~ 6:1, being subsequently adding concentration is 0.3 ~ 1.2mol/L ammonium fluosilicate aqueous solution, processing 0.5 ~ 2 hour in 50 ~ 80 DEG C, wherein ammonium fluosilicate solution addition needs pure fluosilicic acid ammonium 4 ~ 10g to count according to every 100g molecular sieve.
Rapid draing temperature described in step (3) 100 ~ 300 DEG C, drying time is 1 ~ 60 minute, it is preferable that 3 ~ 30 minutes.
Unsaturated olefin described in step (4) is C2~C10Positive structure or isomeric olefine, alkadienes; Wherein said alkene and molecular sieve are fully contacted and refer to that unsaturated olefin diffuses into inside molecular sieve; Gaseous state unsaturated olefin and molecular sieve contact conditions be: pressure 0.1 ~ 1.0MPa, 0.1 ~ 2 hour time of contact; Liquid unsaturated olefin and molecular sieve contact conditions be: pressure 0.1 ~ 1.0MPa, 0.5 ~ 4 hour time of contact, molecular sieve answers thorough impregnation in liquefied olefines. Described alkene and molecular sieve are fully contacted and generally carry out at normal temperatures, and described unsaturated hydrocarbons state phase is under room temperature phase.
The mixture that oxygen-containing atmosphere is air, oxygen and nitrogen described in step (4) or the one in the mixture of oxygen and noble gas, oxygen volume fraction in the gas phase is 10% ~ 100%, it is preferred to air; Carbon deposit reaction condition is: reaction temperature 50 ~ 500 DEG C, it is preferable that 100 ~ 400 DEG C, and the response time is 1 ~ 50 hour, it is preferable that 2 ~ 40 hours.
Second time dealumination treatment process described in step (5) can be acid dealumination process or ammonium fluosilicate dealumination complement silicon process.
Wherein, acid dealumination process is the Y molecular sieve obtained with mineral acid and/or organic acid treating step (4); Mineral acid or organic acid are one or more in sulphuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid, and mineral acid and/or organic acid concentration are with H+It is calculated as 0.4 ~ 2.0mol/L; Gu the liquid/mass ratio of acid dealumination treatment process is 3:1 ~ 30:1; Treatment temperature 60 ~ 120 DEG C, the process time is 0.5 ~ 3 hour.
Ammonium fluosilicate dealumination complement silicon process is add water the Y molecular sieve that step (4) obtains to be made into the water sample mixing of liquid-solid mass ratio 3:1 ~ 6:1, being subsequently adding concentration is 0.8 ~ 2.0mol/L ammonium fluosilicate aqueous solution, processing 1 ~ 4 hour in 70 ~ 120 DEG C, wherein ammonium fluosilicate solution addition needs to deposit ammonium fluosilicate 9 ~ 30g meter according to every 100g molecular sieve.
Treatment conditions of making charcoal described in step (6) are: roasting 2 ~ 4 hours at 400 ~ 600 DEG C, the carbon deposit of residual on elimination molecular sieve.
Step (2), (3), (4) and (5) described in the inventive method can also replace in the following way: the Y molecular sieve after being exchanged by step (1) ammonium carries out dealumination treatment, dry; Impregnate in organic solvent, then rapid draing, carry out alkali desiliconization process after drying.
Wherein, described dealumination treatment can adopt the one or more combination in hydrothermal treatment consists, acid treatment, aluminium salt process or ammonium fluosilicate process; When hydrothermal treatment process is at self steam or passes into steam, hydrothermal conditions is: treatment temperature is 400 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and the process time is 1.0 ~ 6.0 hours; In acid treatment process, mineral acid and/or organic acid are calculated as the liquid-solid mass ratio of 0.4 ~ 2.0mol/L, mineral acid and/or organic acid and molecular sieve for 3:1 ~ 30:1 with H+; Acid treatment temperature 60 ~ 120 DEG C, the process time is 0.5 ~ 3 hour; Aluminium salt used by aluminium salt processing procedure can be aluminum chloride, aluminum sulfate, aluminum nitrate etc. Aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and the process time is 0.5 ~ 3 hour; Ammonium fluosilicate processing procedure is as follows: Y molecular sieve adds water and is made into the water sample mixing of liquid-solid mass ratio 3:1 ~ 6:1, being subsequently adding concentration is 0.6 ~ 2.0mol/L ammonium fluosilicate aqueous solution, processing 1 ~ 4 hour in 70 ~ 120 DEG C, wherein ammonium fluosilicate solution addition needs pure fluosilicic acid ammonium 9 ~ 30g to count according to every 100g molecular sieve.
Described dried process: 90 ~ 300 DEG C dry 2 ~ 10 hours; One or more in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene or ethylbenzene of described organic solvent, impregnation method adopts supersaturation dipping, and dip time is 1 ~ 5 hour; Rapid draing temperature is 50 ~ 300 DEG C, it is preferable that baking temperature is higher than the boiling point of organic solvent, and fast drying time is 1 ~ 60 minute, it is preferable that 3 ~ 20 minutes.
The aqueous solution that alkali liquor is sodium hydroxide or potassium hydroxide that described alkali desiliconization processing procedure uses, wherein the concentration of alkali liquor is 0.1wt% ~ 2wt%. Base extraction temperature 50 ~ 100 DEG C, the process time is 0.5 ~ 4 hour, and the liquid-solid mass ratio of alkali liquor/molecular sieve is 5:1 ~ 10:1.
Y molecular sieve is processed by the inventive method by unsaturated olefin or organic solvent, then adopts the mode of internal dealuminzation or outside desiliconization again, while keeping internal high silica alumina ratio, optionally reduces the silica alumina ratio of Y molecular sieve outer surface. Modified Y molecular sieve of the present invention may be used for preparing hydrocracking catalyst, has broad application prospects in the different hydrocracking reaction processes such as high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil hydro-conversion.
Detailed description of the invention
The present invention is further described by the examples below, but is not so limited the present invention.
Embodiment 1
Molecular sieve modified processing procedure:
(1) taking the former powder 200g of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 0.5mol/L, 70 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.5%;
(2) Y molecular sieve 560 DEG C that step (1) is obtained, hydrothermal treatment consists 2 hours under 0.1MPa;
(3) step (2) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 5:1, then heats to 80 DEG C, adds the aluminum sulfate solution 400ml of 0.5mol/L, isothermal reaction 2 hours in the process of stirring.
(4) molecular sieve taking step (3) gained dries 8 minutes in 140 DEG C;
(5) molecular sieve taking step (4) gained is positioned in the hermetic container of full butadiene atmosphere, controls pressure 0.3MPa and is fully contacted 20 minutes, then, heats 15 hours at 200 DEG C at air atmosphere;
(6) molecular sieve of step (5) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 100ml that concentration is 0.6mol/L, and 80 DEG C process 2 hours;
(7) Y molecular sieve after step (6) ammonium fluosilicate processes, 120 DEG C dry 2 hours, after 550 DEG C of roastings 4 hours, obtains modified Y molecular sieve, is numbered Y-1.
Embodiment 2
Molecular sieve modified processing procedure:
(1) taking the former powder of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 0.8mol/L, 70 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.0%.
(2) Y molecular sieve 600 DEG C that step (1) is obtained, hydrothermal treatment consists 3 hours under 0.1MPa;
(3) molecular sieve of step (2) gained is according to liquid-solid ratio 7:1 and H+Concentration is the hydrochloric acid mixed solution mixing of 1.0mol/L, and 95 DEG C process 2 hours;
(4) 250 DEG C of dry 2h of step (3) gained molecular sieve;
(5) molecular sieve 3 hours of toluene solvant soaking step (4) gained is taken;
(6) dry 25 minutes of 130 DEG C of molecular sieve after step (5) process;
(7) molecular sieve of step (6) gained mixes according to the sodium hydroxide solution of liquid-solid ratio 6:1 and 1.2%, and 80 DEG C process 3 hours;
(8) Y molecular sieve after step (7) alkali processes, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, obtains modified Y molecular sieve, is numbered Y-2.
Embodiment 3
Molecular sieve modified processing procedure:
(1) taking the former powder of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 0.8mol/L, 70 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.0%.
(2) Y molecular sieve 520 DEG C that step (1) is obtained, hydrothermal treatment consists 3 hours under 0.1MPa;
(3) (concentration is with H according to the citric acid solution of liquid-solid ratio 8:1 and 0.5mol/L for step (2) sieve+Meter) mixing, then heat to 50 DEG C, isothermal reaction 2 hours;
(4) dry 40 minutes of 130 DEG C of molecular sieve after step (3) process;
(5) taking the molecular sieve 4 hours of heptene soaking step (4) gained, then, 180 DEG C are heated 30 hours in air atmosphere;
(6) molecular sieve of step (5) gained is according to liquid-solid ratio 7:1 and H+Concentration is the hydrochloric acid mixed solution mixing of 1.0mol/L, and 95 DEG C process 2 hours;
(7) Y molecular sieve after step (6) acid treatment, 120 DEG C dry 2 hours, after 550 DEG C of roastings 4 hours, obtains modified Y molecular sieve, is numbered Y-3.
Embodiment 4
Molecular sieve modified processing procedure:
(1) taking the former powder 200g of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 0.6mol/L, 80 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.0%;
(2) molecular sieve of step (1) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 100ml that concentration is 0.8mol/L, and 80 DEG C process 1.5 hours;
(3) Y molecular sieve 550 DEG C that step (2) is obtained, hydrothermal treatment consists 1.0 hours under 0.1MPa;
(4) step (3) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 5:1, then heats to 80 DEG C, adds the aluminum sulfate solution 400ml of 0.5mol/L, isothermal reaction 2 hours in the process of stirring.
(5) molecular sieve after step (4) process is in 150 DEG C of dry 8h;
(6) molecular sieve 2 hours of normal octane solvent soaking step (5) gained is taken;
(7) molecular sieve after step (6) process dries 12 minutes in 140 DEG C;
(8) Y molecular sieve of step (7) gained mixes according to the sodium hydroxide solution of liquid-solid ratio 5:1 and 0.6%, and 95 DEG C process 2 hours;
(9) Y molecular sieve after step (8) alkali processes, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, obtains modified Y molecular sieve, is numbered Y-4.
Embodiment 5
Molecular sieve modified processing procedure:
(1) taking the former powder 200g of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 0.5mol/L, 70 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.5%;
(2) molecular sieve of step (1) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 100ml that concentration is 0.5mol/L, and 60 DEG C process 1.0 hours;
(3) Y molecular sieve 550 DEG C that step (2) is obtained, hydrothermal treatment consists 1.5 hours under 0.1MPa;
(4) step (3) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 7:1, then heats to 80 DEG C, adds the aluminum sulfate solution 400ml of 0.5mol/L, isothermal reaction 2 hours in the process of stirring.
(5) molecular sieve taking step (4) gained dries 5 minutes in 140 DEG C;
(6) molecular sieve taking step (5) gained is positioned in the hermetic container of full butadiene atmosphere, controls pressure 0.3MPa and is fully contacted 20 minutes, then, heats 15 hours at 200 DEG C at air atmosphere;
(7) molecular sieve of step (6) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 200ml that concentration is 0.9mol/L, and 75 DEG C process 2 hours;
(8) Y molecular sieve after step (7) ammonium fluosilicate processes, 120 DEG C dry 2 hours, after 550 DEG C of roastings 4 hours, obtains modified Y molecular sieve, is numbered Y-5.
Embodiment 6
(1) taking the former powder of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 0.8mol/L, 70 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.0%.
(2) molecular sieve of step (1) gained mixes with distilled water according to liquid-solid ratio 6:1, then, adds the ammonium fluosilicate solution 120ml that concentration is 0.7mol/L, and 70 DEG C process 1.0 hours;
(3) Y molecular sieve 520 DEG C that step (2) is obtained, hydrothermal treatment consists 2 hours under 0.1MPa;
(4) step (3) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 6:1, then heats to 90 DEG C, adds the aluminum sulfate solution 600ml of 0.8mol/L, isothermal reaction 2 hours in the process of stirring.
(5) dry 30 minutes of 130 DEG C of molecular sieve after step (4) process;
(6) taking the molecular sieve 4 hours of heptene soaking step (5) gained, then, 250 DEG C are heated 12 hours in air atmosphere;
(7) molecular sieve of step (6) gained mixes with distilled water according to liquid-solid ratio 5:1, then, adds the ammonium fluosilicate solution 300ml that concentration is 1.5mol/L, and 95 DEG C process 2 hours;
(8) Y molecular sieve after step (7) ammonium fluosilicate processes, 120 DEG C dry 2 hours, after 550 DEG C of roastings 4 hours, obtains modified Y molecular sieve, is numbered Y-6.
Comparative example 1
(1) taking the former powder 200g of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 0.7mol/L, 75 DEG C exchange 3 hours, repeat this process 3 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.3%;
(2) Y molecular sieve 570 DEG C that step (1) is obtained, hydrothermal treatment consists 2 hours under 0.1MPa;
(3) step (2) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 5:1, then heats to 85 DEG C, adds the aluminum sulfate solution 400ml of 0.6mol/L, isothermal reaction 2 hours in the process of stirring.
(4) step (3) aluminum sulfate process after Y molecular sieve, 120 DEG C are dry 2 hours, after 550 DEG C of roastings 2 hours, it is thus achieved that modified Y molecular sieve, are numbered BY-1.
Comparative example 2
(1) taking the former powder 200g of NaY molecular sieve prepared by test chamber, mix according to liquid-solid ratio 6:1 with the ammonium nitrate that concentration is 2.0mol/L, 95 DEG C exchange 3 hours, repeat this process 2 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.0%;
(2) Y molecular sieve that step (1) obtains is at 580 DEG C, hydrothermal treatment consists 3 hours under 0.1Mpa;
(3) molecular sieve of step (2) gained is according to liquid-solid ratio 5:1 and H+The hydrochloric acid solution mixing of concentration 1.2mol/L, at 90 DEG C, constant temperature processes 2h;
(4) Y molecular sieve after step (3) acid treatment, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, it is thus achieved that modified Y molecular sieve, is numbered BY-2.
The physicochemical property of embodiment 1 ~ 6 and comparative example 1 ~ 2 modified Y molecular sieve is listed in the table below 1.
Embodiment 7
(1) configuration W-Ni dipping solution: taking configuration 1000ml dipping solution after ammonium metatungstate 430g and nickel nitrate 440g is dissolved in water, in gained dipping solution, active metal is with WO3With NiO cubage respectively 36g/100ml and 11g/100ml, solution numbers RY;
(2) molecular sieve that respectively prepared by Example 1 ~ 6 molecular sieve and comparative example 1 ~ 2 method, is mixed with carrier with aluminium oxide according to the ratio of 50:50, is respectively labeled as ZY-1, ZY-2, ZY-3, ZY-4, ZY-5, ZY-6, ZBY-1, ZBY-2;
(3) impregnation liquid RY impregnates carrier in (2) respectively, obtains catalyst and is designated as Cat-1, Cat-2, Cat-3, Cat-4, Cat-5, Cat-6, BCat-1 and BCat-2 respectively.
In order to investigate embodiment and comparative example prepares the reactivity worth of catalyst, catalyst has been carried out evaluation test on midget plant, evaluating apparatus adopts single hop series connection once to pass through flow process, one anti-filling industrial wide variety of pretreating catalyst by hydrocracking FF-36(Sinopec Fushun Petrochemical Research Institute), two instead load the hydrocracking catalyst prepared according to embodiment 1 ~ 6 and comparative example 1 ~ 2 respectively, and feedstock property, appreciation condition and evaluation result are listed in table 2 ~ table 6.
Result analyzed by table 1 embodiment and comparative example molecular sieve.
Table 2 raw oil character.
Table 3 appreciation condition.
Table 4 evaluation result.
Table 5 embodiment 1 investigates test with comparative example 1 catalyst differential responses temperature.
Table 6 embodiment 2 investigates test with comparative example 2 catalyst differential responses temperature.
By adopting embodiment 1 and comparative example 1 catalyst contrast test on evaluating apparatus to show, catalyst prepared by the inventive method is adopted to have better operating flexibility, in temperature raising process, product slates amplitude of variation is bigger, can switch and carry out fecund Petroleum and produce the operation of Petroleum both of which less, simultaneously, owing to the present invention adopts specific process modified Y molecular sieve, while improving the outside acid centre of molecular sieve, remain the high silica alumina ratio within molecular sieve, acid centre is less, the secondary cracking that temperature raising process causes significantly reduces, therefore, relative to comparative example 1 catalyst, embodiment 1 catalyst hydrogen consumption increasing degree in temperature raising process is less, it is more beneficial for the quiet run of device. the contrast test of embodiment 2 and comparative example 2 catalyst then shows, embodiment 2 catalyst has better temperature raising sensitivity, about 15 percentage points are improved more than 350 DEG C of fraction conversion ratios when reaction temperature is increased to the process of 380 DEG C from 372 DEG C, and comparative example 2 only improves about 7 percentage points, comparing comparative example 2 catalyst, embodiment 2 catalyst shows bigger working place. therefore, all in all catalyst of the present invention shows good temperature raising sensitivity, device operating flexibility and relatively low chemical hydrogen consumption.
Claims (30)
1. a modified Y molecular sieve, it is characterized in that having the property that body phase silica alumina ratio is 10 ~ 70, surface layer silica alumina ratio 7 ~ 30, surface layer silica alumina ratio is lower than body phase silica alumina ratio 5 ~ 40, wherein said surface layer refers to the molecular sieve outer surface thickness range to internal 5 ~ 400nm, and surface layer is primary in Y molecular sieve crystal grain before modified; Modified Y molecular sieve lattice constant is 2.425 ~ 2.455nm; Modified Y molecular sieve specific surface area 600 ~ 900m2/ g, pore volume 0.20 ~ 0.70ml/g; Meleic acid content 0.3 ~ 1.5mmol/g; Relative crystallinity 60% ~ 130%.
2. the molecular sieve described in claim 1, it is characterised in that: described surface layer refers to the molecular sieve outer surface thickness range to internal 10 ~ 200nm.
3. the preparation method of the modified Y molecular sieve described in a claim 1 or 2, it is characterised in that include following content: (1) carries out Ammonium Salt Ionic exchange reaction with NaY zeolite for former powder; (2) Y molecular sieve after ammonium being exchanged carries out first dealumination treatment; (3) the Y molecular sieve rapid draing that step (2) obtains processes; (4) Y molecular sieve after rapid draing is fully contacted with the unsaturated olefin of liquid or gaseous state, then carries out carbon deposit reaction in oxygen-containing atmosphere; (5) molecular sieve after step (4) process carries out second time dealumination treatment; (6) the Y molecular sieve drying that step (5) obtains, process of making charcoal, obtain modified Y molecular sieve.
4. in accordance with the method for claim 3, it is characterised in that: Ammonium Salt Ionic exchange process described in step (1) is as follows: with NaY zeolite for raw material in ammonium salt aqueous solution, at 60 ~ 120 DEG C, exchange 1 ~ 3 hour, exchange times is 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O content is less than 3.0%; Wherein the silica alumina ratio of NaY zeolite raw material is 3 ~ 6, sodium oxide weight/mass percentage composition 6% ~ 7%; Ammonium salt is one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, ammonium salt aqueous solution concentration 0.3 ~ 6.0mol/L.
5. in accordance with the method for claim 3, it is characterised in that: the described first dealumination treatment process of step (2) is one or more in hydrothermal treatment consists, acid treatment, aluminium salt process and ammonium fluosilicate processing procedure.
6. in accordance with the method for claim 5, it is characterized in that: when hydrothermal treatment process is at self steam or passes into steam, hydrothermal conditions is: treatment temperature is 400 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and the process time is 1.0 ~ 4.0 hours.
7. in accordance with the method for claim 5, it is characterized in that: mineral acid used by acid treatment process and/or organic acid are one or more in sulphuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid, mineral acid and/or organic acid are calculated as the liquid-solid mass ratio of 0.1 ~ 0.7mol/L, mineral acid and/or organic acid and molecular sieve for 3:1 ~ 30:1 with H+; Acid treatment temperature 30 ~ 80 DEG C, the process time is 0.5 ~ 3 hour.
8. in accordance with the method for claim 5, it is characterised in that: the aluminium salt used by aluminium salt processing procedure is one or more in aluminum chloride, aluminum sulfate or aluminum nitrate, and aluminium salt concentration is 0.05 ~ 2mol/L; Treatment temperature is 50 ~ 120 DEG C, and the process time is 0.5 ~ 3 hour.
9. in accordance with the method for claim 5, it is characterized in that: ammonium fluosilicate processing procedure is as follows: Y molecular sieve adds water and is made into the water sample mixing of liquid-solid mass ratio 3:1 ~ 6:1, being subsequently adding concentration is 0.3 ~ 1.2mol/L ammonium fluosilicate aqueous solution, processing 0.5 ~ 2 hour in 50 ~ 80 DEG C, wherein ammonium fluosilicate solution addition needs pure fluosilicic acid ammonium 4 ~ 10g to count according to every 100g molecular sieve.
10. in accordance with the method for claim 3, it is characterised in that: the rapid draing temperature described in step (3) 100 ~ 300 DEG C, drying time is 1 ~ 60 minute.
11. in accordance with the method for claim 3, it is characterised in that: the unsaturated olefin described in step (4) is C2~C10Positive structure or isomeric olefine, alkadienes; Gaseous state unsaturated olefin and molecular sieve contact conditions be: pressure 0.1 ~ 1.0MPa, 0.1 ~ 2 hour time of contact; Liquid unsaturated olefin and molecular sieve contact conditions be: pressure 0.1 ~ 1.0MPa, 0.5 ~ 4 hour time of contact, molecular sieve thorough impregnation is in liquefied olefines.
12. in accordance with the method for claim 3, it is characterised in that: the mixture that oxygen-containing atmosphere is air, oxygen and nitrogen described in step (4) or the one in the mixture of oxygen and noble gas, oxygen volume fraction in the gas phase is 10% ~ 100%.
13. in accordance with the method for claim 3, it is characterised in that: carbon deposit reaction condition is: reaction temperature 50 ~ 500 DEG C, and the response time is 1 ~ 50 hour.
14. in accordance with the method for claim 3, it is characterised in that: second time dealumination treatment process described in step (5) is acid dealumination process or ammonium fluosilicate dealumination complement silicon process.
15. in accordance with the method for claim 14, it is characterised in that: acid dealumination process is the Y molecular sieve obtained with mineral acid and/or organic acid treating step (4); Mineral acid or organic acid are one or more in sulphuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid or acetic acid, and mineral acid and/or organic acid concentration are calculated as 0.4 ~ 2.0mol/L with H+; Gu the liquid/mass ratio of acid dealumination treatment process is 3:1 ~ 30:1; Treatment temperature 60 ~ 120 DEG C, the process time is 0.5 ~ 3 hour.
16. in accordance with the method for claim 14, it is characterized in that: ammonium fluosilicate dealumination complement silicon process is add water the Y molecular sieve that step (4) obtains to be made into the water sample mixing of liquid-solid mass ratio 3:1 ~ 6:1, being subsequently adding concentration is 0.8 ~ 2.0mol/L ammonium fluosilicate aqueous solution, processing 1 ~ 4 hour in 70 ~ 120 DEG C, wherein ammonium fluosilicate solution addition needs to deposit ammonium fluosilicate 9 ~ 30g meter according to every 100g molecular sieve.
17. in accordance with the method for claim 3, it is characterised in that: the treatment conditions of making charcoal described in step (6) are: roasting 2 ~ 4 hours at 400 ~ 600 DEG C.
18. in accordance with the method for claim 3, it is characterised in that: described step (2), (3), (4) and (5) replaces in the following way: the Y molecular sieve after being exchanged by step (1) ammonium carries out dealumination treatment, dry; Impregnate in organic solvent, then rapid draing, carry out alkali desiliconization process after drying.
19. in accordance with the method for claim 18, it is characterised in that: described dealumination treatment adopts the one or more combination in hydrothermal treatment consists, acid treatment, aluminium salt process or ammonium fluosilicate process.
20. in accordance with the method for claim 19, it is characterized in that: when hydrothermal treatment process is at self steam or passes into steam, hydrothermal conditions is: treatment temperature is 400 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and the process time is 1.0 ~ 6.0 hours.
21. in accordance with the method for claim 19, it is characterised in that: in acid treatment process, mineral acid and/or organic acid are calculated as the liquid-solid mass ratio of 0.4 ~ 2.0mol/L, mineral acid and/or organic acid and molecular sieve for 3:1 ~ 30:1 with H+; Acid treatment temperature 60 ~ 120 DEG C, the process time is 0.5 ~ 3 hour.
22. in accordance with the method for claim 19, it is characterized in that: the aluminium salt used by aluminium salt processing procedure is one or more in aluminum chloride, aluminum sulfate or aluminum nitrate, aluminium salt concentration is 0.05 ~ 2mol/L, and treatment temperature is 50 ~ 120 DEG C, and the process time is 0.5 ~ 3 hour.
23. in accordance with the method for claim 19, it is characterized in that: ammonium fluosilicate processing procedure is as follows: Y molecular sieve adds water and is made into the water sample mixing of liquid-solid mass ratio 3:1 ~ 6:1, being subsequently adding concentration is 0.6 ~ 2.0mol/L ammonium fluosilicate aqueous solution, processing 1 ~ 4 hour in 70 ~ 120 DEG C, wherein ammonium fluosilicate solution addition needs pure fluosilicic acid ammonium 9 ~ 30g to count according to every 100g molecular sieve.
24. in accordance with the method for claim 18, it is characterised in that: described dried process: 90 ~ 300 DEG C dry 2 ~ 10 hours.
25. in accordance with the method for claim 18, it is characterised in that: one or more in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene or ethylbenzene of described organic solvent.
26. in accordance with the method for claim 18, it is characterised in that: impregnation method adopts supersaturation dipping, and dip time is 1 ~ 5 hour.
27. in accordance with the method for claim 18, it is characterised in that: rapid draing temperature is 50 ~ 300 DEG C, and fast drying time is 1 ~ 60 minute.
28. the method described in claim 18 or 27, it is characterised in that: rapid draing temperature is higher than organic solvent boiling point, and fast drying time is 3 ~ 20 minutes.
29. in accordance with the method for claim 18, it is characterised in that: the aqueous solution that alkali liquor is sodium hydroxide or potassium hydroxide that described alkali desiliconization processing procedure uses, wherein the concentration of alkali liquor is 0.1wt% ~ 2wt%; Base extraction temperature 50 ~ 100 DEG C, the process time is 0.5 ~ 4 hour, and the liquid-solid mass ratio of alkali liquor/molecular sieve is 5:1 ~ 10:1.
30. the application that the modified Y molecular sieve described in a claim 1 or 2 is in the hydrocracking reaction process of high-yield diesel oil, more producing chemical industry raw material and catalytic diesel oil hydro-conversion.
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