CN105621432A - Modified beta molecular sieve and preparation method thereof - Google Patents
Modified beta molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified beta molecular sieve and a preparation method thereof. The molecular sieve has the following properties: bulk phase silica-alumina ratio is 30-80; surface layer silica-alumina ratio is 50-130; the surface layer silica-alumina ratio is higher by 30-70 than the bulk phase silica-alumina ratio; specific surface area is 400-800m<2>/g; pore volume is 0.2-0.60ml/g; infrared acid content is 0.1-0.6mmol/g; and relative crystallinity is 100-150%. The preparation method of the modified beta molecular sieve comprises the following steps: pretreatment is carried out upon beta molecular sieve obtained after ammonium exchange; drying is carried out; a coke reaction is carried out; high-temperature roasting treatment is carried out; and dealumination treatment, drying and charcoal burning treatment are carried out, such that the modified beta molecular sieve is obtained. The surface layer silica-alumina ratio of the molecular sieve is higher 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 beta 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, cracking function is then provided by molecular sieve, and at present, beta-molecular sieve is due to the three-dimensional twelve-ring structure of its uniqueness, it is made to be widely used in hydrocracking process, especially diesel oil hydrogenation modification process. But owing to the character of acidic zeolite carrier makes it that nitride is especially sensitive, nitride is readily adsorbed in molecular sieve surface and causes molecular sieve poisoning, and therefore activity is substantially reduced, it is difficult to long-term stability in the industrial production and runs. Further, along with the increase of acid density on molecular sieve, the anti-nitrogen ability of catalyst is remarkably decreased. For this problem, at present conventional method is by beta-molecular sieve carrying out dealuminzation or dealumination complement silicon processes and reduces the method for acid site quantity on molecular sieve and solve, but the method processing procedure is to carry out dealuminzation inside and outside whole molecular sieve simultaneously, therefore, while improving the silica alumina ratio of molecular sieve, owing to acid centre reduces, its activity is greatly reduced. So, improving catalyst anti-nitrogen ability and keeping also existing between hydrogenation cracking activity insoluble contradiction, conventional molecular sieve modified process difficult takes into account the two problem simultaneously.
CN201110350743.8 discloses preparation and the method for modifying of a kind of beta-molecular sieve, beta-molecular sieve is modified in conjunction with aluminium salt process by the method by hydrothermal treatment consists, but silica alumina ratio layer is uniformly distributed inside and outside the beta-molecular sieve that the method obtains, when dealumination depth height, reactivity is relatively low, and when either shallow dealumination treatment, then the hydrocracking catalyst less stable prepared.
The preparation method that CN00123130.8 discloses a kind of hydrocracking catalyst containing beta-molecular sieve, in this invention, beta-molecular sieve processing procedure is acid treatment Bound moisture heat treatment process, is difficult to meet the requirement of activity and stability simultaneously.
Summary of the invention
For the deficiencies in the prior art, the present invention puies forward a kind of modified beta molecular sieve and preparation method thereof, and modified molecular screen of the present invention has the feature of sial uneven distribution, and wherein (silica alumina ratio described in literary composition is SiO to the silica alumina ratio of modified beta molecular sieve surface layer2/Al2O3Mol ratio) higher than body phase silica alumina ratio.
The modified beta molecular sieve of the present invention has the property that body phase silica alumina ratio is 30 ~ 80, wherein surface layer silica alumina ratio 50 ~ 130, preferably 60 ~ 120, surface layer silica alumina ratio is higher than body phase silica alumina ratio 30 ~ 70, wherein said surface layer refers to the molecular sieve outer surface thickness range to internal 5 ~ 400nm, preferably 10 ~ 200nm, wherein surface layer is primary in beta-molecular sieve before modified; Modified beta molecular sieve sodium oxide weight/mass percentage composition is less than 1.0%, it is preferable that less than 0.5%; Modified beta molecular sieve specific surface area 400 ~ 800m2/ g, it is preferable that 500 ~ 700m2/ g; Pore volume 0.2 ~ 0.60ml/g, it is preferable that 0.3 ~ 0.5ml/g; Meleic acid content 0.1 ~ 0.6mmol/g, it is preferable that 0.2 ~ 0.5mmol/g; Relative crystallinity 100% ~ 150%, it is preferable that 120% ~ 140%.
The preparation method of modified beta molecular sieve of the present invention, including following content:
(1) in ammonium salt aqueous solution, Ammonium Salt Ionic exchange is carried out with sodium form �� zeolite powder;
(2) beta-molecular sieve after ammonium being exchanged carries out first dealumination treatment, dry;
(3) dried beta-molecular sieve is fully contacted with the unsaturated olefin of liquid or gaseous state, then carries out carbon deposit reaction in oxygen-containing atmosphere;
(4) beta-molecular sieve of carbon deposit carries out quick high-temp calcination process;
(5) molecular sieve after step (4) process carries out second time dealumination treatment;
(6) beta-molecular sieve that step (5) obtains through filtering, dried, carry out process of making charcoal, obtain modified beta molecular sieve.
Ammonium Salt Ionic exchange process described in step (1) is as follows: with sodium form �� zeolite for raw material in ammonia spirit at 60 ~ 120 DEG C, it is preferable that exchanging at 60 ~ 90 DEG C, swap time is 1 ~ 3 hour, and exchange times is 1 ~ 4 time, final obtains the �� zeolite Na after exchange2O content is less than 3.0%; Wherein the silica alumina ratio of sodium form �� zeolite is 20 ~ 30, sodium oxide weight/mass percentage composition 3% ~ 5%; 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 or aluminium salt processing procedure: wherein, hydrothermal conditions is: 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, acetic acid, and mineral acid and/or organic acid are calculated as 0.1 ~ 0.7mol/L with H+; Gu the liquid/ratio 3:1 ~ 30:1 of mineral acid and/or organic acid soln and molecular sieve, 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 one or more in aluminum chloride, aluminum sulfate or aluminum nitrate, and aluminium salt concentration is 0.05 ~ 2mol/L, and aluminium salt treatment temperature is 50 ~ 120 DEG C, and the process time is 0.5 ~ 3 hour.
Baking temperature described in step (2) is 90 ~ 300 DEG C, and drying time is 2 ~ 10 hours.
Unsaturated olefin described in step (3) 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 is immersed 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 (3) 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.
Quick high-temp roasting condition described in step (4) is: sintering temperature is 400 ~ 600 DEG C, and roasting time is 2 ~ 50 minutes, it is preferable that 5 ~ 20 minutes. General processing procedure is add the beta-molecular sieve of carbon deposit to be warming up to roasting in the Muffle furnace of sintering temperature in advance.
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 0.3 ~ 2mol/L, it is preferable that 0.6 ~ 1.5mol/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 (3) described in the inventive method, (4) can also replace in the following way: impregnated in organic solvent by the beta-molecular sieve that step (2) obtains, then rapid draing; One or more in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene or ethylbenzene of wherein said organic solvent, impregnation method adopts supersaturation dipping, and dip time is 1 ~ 5 hour; Baking temperature is 50 ~ 300 DEG C, it is preferable that baking temperature is higher than the boiling point of organic solvent, and drying time is 1 ~ 60 minute, it is preferable that 3 ~ 20 minutes.
The present invention adopts transmission electron microscope X ray electronic spectroscopy to carry out microsection component analyzing to come measure and calculation molecular sieve surface layer and body phase silica alumina ratio.
After beta-molecular sieve is carried out dealuminzation pretreatment by the present invention; by the aluminum position within internal carbon distribution or organic solvent protection molecular sieve; follow-up dealumination treatment process carries out on the outer surface; after dealuminzation terminates; high temperature removes the carbon deposit within molecular sieve or organic solvent again, recovers the acid sites position within molecular sieve. The inventive method, by optionally beta-molecular sieve outer surface being carried out dealuminzation, optionally improves the silica alumina ratio of beta-molecular sieve outer surface. Modified beta 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
(1) taking the former powder 200g of sodium form beta-molecular sieve prepared by test chamber, mix according to liquid-solid ratio 4:1 with the ammonium nitrate that concentration is 1.5mol/L, 80 DEG C exchange 2 hours, repeat this process 2 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 2.5%;
(2) beta-molecular sieve 540 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) first by 200 DEG C of dry 3h of step (3) gained molecular sieve, then, take the molecular sieve 2 hours of heptene soaking step (3) gained, then, heat 20 hours at 150 DEG C at air atmosphere;
(5) molecular sieve after step (4) process is directly placed in the Muffle furnace being previously heated to 450 DEG C, roasting 8 minutes;
(6) molecular sieve of step (5) gained mixes according to the hydrochloric acid solution of liquid-solid ratio 5:1 and H+ concentration 0.8mol/L, and at 90 DEG C, constant temperature processes 2h;
(7) beta-molecular sieve after step (6) acid treatment, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, it is thus achieved that embodiment 1 molecular sieve, is numbered ��-1.
Embodiment 2
(1) taking the former powder 200g of sodium form beta-molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 1.2mol/L, 95 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 1.5%;
(2) step (1) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 5:1, then heats to 50 DEG C, adds H+ and be calculated as the citric acid solution 300ml of 0.3mol/L, isothermal reaction 2 hours in the process of stirring.
(3) first by 120 DEG C of dry 3h of step (2) gained molecular sieve, then, take the molecular sieve 4 hours of heptene soaking step (2) gained, then, heat 15 hours at 300 DEG C at air atmosphere;
(4) molecular sieve after step (3) process is directly placed in the Muffle furnace being previously heated to 500 DEG C, roasting 20 minutes;
(5) molecular sieve of step (4) gained is according to liquid-solid ratio 5:1 and H+The hydrochloric acid solution mixing of concentration 1.0mol/L, at 95 DEG C, constant temperature processes 2h;
(6) the beta-molecular sieve molecular sieve after step (5) acid treatment, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, it is thus achieved that embodiment 2 molecular sieve, is numbered ��-2.
Embodiment 3
(1) taking sodium form beta-molecular sieve molecular screen primary powder 200g prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 1.0mol/L, 65 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 2.2%;
(2) beta-molecular sieve of step (1) gained 530 DEG C, hydrothermal treatment consists 3 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 0.4mol/L, isothermal reaction 2 hours in the process of stirring.
(4) first by 150 DEG C of dry 6h of step (3) gained molecular sieve, then, take the molecular sieve 2 hours of hexadiene soaking step (3) gained, then, heat 15 hours at 200 DEG C at air atmosphere;
(5) molecular sieve after step (4) process is directly placed in the Muffle furnace being previously heated to 500 DEG C, roasting 5 minutes;
(6) step (5) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 5:1, then heats to 70 DEG C, adds H+ and be calculated as the acetum 300ml of 0.8mol/L, isothermal reaction 2 hours in the process of stirring. ;
(7) beta-molecular sieve after step (6) citric acid treatment, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, it is thus achieved that embodiment 3 molecular sieve, is numbered ��-3
Embodiment 4
(1) taking the former powder 200g of sodium form beta-molecular sieve prepared by test chamber, mix according to liquid-solid ratio 4:1 with the ammonium nitrate that concentration is 2.0mol/L, 90 DEG C exchange 2 hours, repeat this process 2 times, and in the Y molecular sieve after exchange, Na content is with Na2O is calculated as 1.8%;
(2) beta-molecular sieve 580 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 75 DEG C, adds the aluminum sulfate solution 300ml of 0.7mol/L, isothermal reaction 2 hours in the process of stirring.
(4) first by 200 DEG C of dry 3h of step (3) gained molecular sieve, then, take the molecular sieve 2 hours of hexadiene soaking step (3) gained, then, heat 20 hours air atmosphere 150 DEG C;
(5) molecular sieve after step (4) process is directly placed in the Muffle furnace being previously heated to 480 DEG C, roasting 30 minutes;
(6) molecular sieve of step (5) gained is according to liquid-solid ratio 5:1 and H+The hydrochloric acid solution mixing of concentration 0.9mol/L, at 85 DEG C, constant temperature processes 3h;
(7) beta-molecular sieve after step (6) acid treatment, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, it is thus achieved that embodiment 4 molecular sieve, is numbered ��-4.
Embodiment 5
Molecular sieve modified processing procedure:
(1) taking the former powder 200g of sodium form beta-molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 1.0mol/L, 70 DEG C exchange 3 hours, repeat this process 3 times, and in the beta-molecular sieve after exchange, Na content is with Na2O is calculated as 2.0%.
(2) step (1) gained molecular sieve mixes with distilled water stirring according to liquid-solid ratio 5:1, then heats to 60 DEG C, adds H in the process of stirring+It is calculated as the citric acid solution 300ml of 0.3mol/L, isothermal reaction 2 hours.
(3) 200 DEG C of dry 4h of step (2) gained molecular sieve;
(4) molecular sieve 3 hours of toluene solvant soaking step (3) gained is taken;
(5) dry 15 minutes of 130 DEG C of molecular sieve after step (4) process;
(6) molecular sieve of step (5) gained is according to liquid-solid ratio 5:1 and H+The hydrochloric acid solution mixing of concentration 0.8mol/L, at 80 DEG C, constant temperature processes 2h;
(7) the beta-molecular sieve molecular sieve after step (6) acid treatment, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, it is thus achieved that embodiment 6 molecular sieve, is numbered ��-5.
Embodiment 6
Molecular sieve modified processing procedure:
(1) taking the former powder 200g of sodium form beta-molecular sieve prepared by test chamber, mix according to liquid-solid ratio 3:1 with the ammonium nitrate that concentration is 1.0mol/L, 70 DEG C exchange 3 hours, repeat this process 3 times, and in the beta-molecular sieve after exchange, Na content is with Na2O is calculated as 2.0%.
(2) beta-molecular sieve 560 DEG C that step (1) is obtained, hydrothermal treatment consists 3 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 300ml of 0.6mol/L, isothermal reaction 2 hours in the process of stirring.
(4) 200 DEG C of dry 4h of step (3) gained molecular sieve;
(5) molecular sieve 3 hours of toluene solvant soaking step (4) gained is taken;
(6) dry 30 minutes of 130 DEG C of molecular sieve after step (5) process;
(7) molecular sieve of step (6) gained is according to liquid-solid ratio 5:1 and H+The hydrochloric acid solution mixing of concentration 0.9mol/L, at 80 DEG C, constant temperature processes 3h;
(8) beta-molecular sieve after step (7) acid treatment, 120 DEG C dry 2 hours, after 550 DEG C of roastings 2 hours, it is thus achieved that embodiment 5 molecular sieve, is numbered ��-6.
Comparative example 1
(1) taking the former powder 200g of sodium form beta-molecular sieve prepared by test chamber, mix according to liquid-solid ratio 6:1 with the ammonium nitrate that concentration is 2.0mol/L, 90 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 1.8%;
(2) beta-molecular sieve that step (1) obtains is at 590 DEG C, hydrothermal treatment consists 3 hours under 0.1MPa;
(3) molecular sieve of step (2) gained mixes according to the hydrochloric acid solution of liquid-solid ratio 5:1 and H+ concentration 0.5mol/L, and at 90 DEG C, constant temperature processes 2h;
(4) beta-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 comparative example 1 molecular sieve, is numbered B-1.
Comparative example 2
(1) taking the former powder 200g of sodium form beta-molecular sieve prepared by test chamber, mix according to liquid-solid ratio 6:1 with the ammonium nitrate that concentration is 2.0mol/L, 90 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 1.8%;
(2) beta-molecular sieve that step (1) obtains is at 560 DEG C, hydrothermal treatment consists 2 hours under 0.1MPa;
(3) molecular sieve of step (2) gained mixes according to the citric acid solution of liquid-solid ratio 5:1 and H+ concentration 0.4mol/L, and at 80 DEG C, constant temperature processes 2h;
(4) beta-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 comparative example 2 molecular sieve, is numbered B-2.
The physicochemical property of embodiment 1 ~ 6 and comparative example 1 ~ 2 modified beta 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 478g and nickel nitrate 488g is dissolved in water, in gained dipping solution, active metal is with WO3 and NiO cubage respectively 40g/100ml and 12g/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 and amorphous silicon aluminium according to the ratio of 1:1:2, is respectively labeled as Z-1, Z-2, Z-3, Z-4, Z-5, Z-6, ZB-1, ZB-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.
The physicochemical property of table 1 embodiment and comparative example molecular sieve.
Table 2 raw oil character.
Table 3 appreciation condition.
Table 4 evaluation result.
Table 5 refining stage generates embodiment 2 and comparative example 1 catalyst stability contrast test under innage nitrogen content.
Table 6 refining stage generates embodiment 3 and comparative example 2 catalyst stability contrast test under innage nitrogen content.
Embodiment 1 ~ 2 and comparative example 1 ~ 2 catalyst contrast test on evaluating apparatus show, adopt catalyst prepared by the inventive method compared with comparative example keeping highly active while, and anti-nitrogen ability is apparently higher than comparative example catalyst.
Claims (19)
1. a modified beta molecular sieve, it is characterized in that: modified beta molecular sieve has the property that body phase silica alumina ratio is 30 ~ 80, wherein surface layer silica alumina ratio 50 ~ 130, surface layer silica alumina ratio is higher than body phase silica alumina ratio 30 ~ 70, wherein said surface layer refers to the molecular sieve outer surface thickness range to internal 5 ~ 400nm, preferably 10 ~ 200nm, wherein surface layer is primary in beta-molecular sieve before modified; Modified beta molecular sieve specific surface area 400 ~ 800m2/g, pore volume 0.2 ~ 0.60ml/g; Meleic acid content 0.1 ~ 0.6mmol/g; Relative crystallinity 100% ~ 150%.
2. the beta-molecular sieve described in claim 1, it is characterised in that: modified beta molecular sieve surface layer refers to the molecular sieve outer surface thickness range to internal 10 ~ 200nm.
3. the preparation method of the modified beta molecular sieve described in a claim 1 or 2, it is characterised in that include following content: (1) carries out Ammonium Salt Ionic exchange with sodium form �� zeolite powder in ammonium salt aqueous solution; (2) beta-molecular sieve after ammonium being exchanged carries out first dealumination treatment, dry; (3) dried beta-molecular sieve is fully contacted with the unsaturated olefin of liquid or gaseous state, then carries out carbon deposit reaction in oxygen-containing atmosphere; (4) beta-molecular sieve of carbon deposit carries out quick high-temp calcination process; (5) molecular sieve after step (4) process carries out second time dealumination treatment; (6) beta-molecular sieve that step (5) obtains through filtering, dried, carry out process of making charcoal, obtain modified beta molecular sieve.
4. 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 or aluminium salt processing procedure.
5. in accordance with the method for claim 4, it is characterised in that: hydrothermal conditions is: temperature is 400 ~ 600 DEG C, and pressure is 0.01 ~ 0.5MPa, and the process time is 1.0 ~ 4.0 hours.
6. in accordance with the method for claim 4, it is characterised 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, acetic acid, and mineral acid and/or organic acid are with H+It is calculated as 0.1 ~ 0.7mol/L, Gu the liquid/ratio 3:1 ~ 30:1 of mineral acid and/or organic acid soln and molecular sieve; Acid treatment temperature 30 ~ 80 DEG C, the process time is 0.5 ~ 3 hour.
7. in accordance with the method for claim 4, 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; Aluminium salt treatment temperature is 50 ~ 120 DEG C, and the process time is 0.5 ~ 3 hour.
8. in accordance with the method for claim 3, it is characterised in that: the baking temperature described in step (2) is 90 ~ 300 DEG C, and drying time is 2 ~ 10 hours.
9. in accordance with the method for claim 3, it is characterised in that: the unsaturated olefin described in step (3) 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 is immersed in liquefied olefines.
10. 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 (3) or the one in the mixture of oxygen and noble gas, oxygen volume fraction in the gas phase is 10% ~ 100%; Carbon deposit reaction condition is: reaction temperature 50 ~ 500 DEG C, and the response time is 1 ~ 50 hour.
11. in accordance with the method for claim 3, it is characterised in that: the quick high-temp roasting condition described in step (4) is: sintering temperature is 400 ~ 600 DEG C, and roasting time is 2 ~ 50 minutes.
12. 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.
13. in accordance with the method for claim 12, 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 with H+It is calculated as 0.3 ~ 2mol/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.
14. in accordance with the method for claim 12, 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.
15. 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.
16. in accordance with the method for claim 3, it is characterised in that: described step (3), (4) replace in the following way: impregnated in organic solvent by the beta-molecular sieve that step (2) obtains, then rapid draing.
17. in accordance with the method for claim 16, it is characterised in that: one or more in alkane, petroleum ether, carbon tetrachloride, benzene, toluene, ethylbenzene, dimethylbenzene or ethylbenzene of wherein said organic solvent.
18. in accordance with the method for claim 16, it is characterised in that impregnation method adopts supersaturation dipping, and dip time is 1 ~ 5 hour.
19. in accordance with the method for claim 16, it is characterised in that: baking temperature is 50 ~ 300 DEG C, and drying time is 1 ~ 60 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410603749.5A CN105621432B (en) | 2014-11-03 | 2014-11-03 | A kind of modified beta molecular sieve and preparation method thereof |
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| WO2021219064A1 (en) | 2020-04-30 | 2021-11-04 | 中国石油化工股份有限公司 | Modified beta zeolite, catalytic cracking catalyst as well as preparation method therefor and application thereof |
| CN114715908A (en) * | 2020-12-22 | 2022-07-08 | 中国石油化工股份有限公司 | Beta molecular sieve and preparation method and application thereof |
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| CN107973307A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Beta molecular sieves a kind of phosphorous and containing carried metal and preparation method thereof |
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| WO2021219064A1 (en) | 2020-04-30 | 2021-11-04 | 中国石油化工股份有限公司 | Modified beta zeolite, catalytic cracking catalyst as well as preparation method therefor and application thereof |
| CN114715908A (en) * | 2020-12-22 | 2022-07-08 | 中国石油化工股份有限公司 | Beta molecular sieve and preparation method and application thereof |
| CN114715908B (en) * | 2020-12-22 | 2023-08-22 | 中国石油化工股份有限公司 | Beta molecular sieve and preparation method and application thereof |
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| CN105621432B (en) | 2017-10-03 |
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