Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, its preparation and application thereof
A modified Y-type molecular sieve has a modifying metal content of about 0.5-6.3 wt % calculated on the basis of an oxide of the modifying metal and a sodium content of no more than about 0.5 wt % calculated on the basis of sodium oxide. The modifying metal is magnesium and/or calcium. The modified Y-type molecular sieve has a proportion of non-framework aluminum content to the total aluminum content of no more than about 20%, a total pore volume of about 0.33-0.39 ml/g, a proportion of the pore volume of secondary pores having a pore size of 2-100 nm to the total pore volume of about 10-25%, a lattice constant of about 2.440-2.455 nm, a lattice collapse temperature of not lower than about 1040° C., and a ratio of B acid to L acid in the total acid content of no less than about 2.30.
1. A modified Y-type molecular sieve, having a modifying metal content of 0.5-6.3 wt %, calculated on the basis of an oxide of the modifying metal, and a sodium content of no more than 0.5 wt %, calculated on the basis of sodium oxide, on a dry basis and based on the weight of said modified Y-type molecular sieve, said modifying metal being magnesium, calcium, or a combination thereof; wherein the modified Y-type molecular sieve has a proportion of non-framework aluminum content to the total aluminum content of no more than 20%, a total pore volume of 0.33-0.39 ml/g, a proportion of the pore volume of secondary pores having a pore size of 2-100 nm to the total pore volume of 10-25%, a lattice constant of 2.440-2.455 nm, a lattice collapse temperature of not lower than 1040° C., and a ratio of B acid to L acid in the total acid content of no less than 2.30, as determined by pyridine adsorption infrared spectroscopy at 200° C.
2. The modified Y-type molecular sieve according to claim 1 , wherein the modified Y-type molecular sieve has a proportion of the pore volume of secondary pores having a pore size of 2-100 nm to the total pore volume of 15-21%.
3. The modified Y-type molecular sieve according to claim 2 , wherein the modified Y-type molecular sieve has a proportion of non-framework aluminum content to the total aluminum content of 13-19%, and a framework silica-alumina ratio, calculated as SiO 2 /Al 2 O 3 molar ratio, of 7.3-14.
4. The modified Y-type molecular sieve according to claim 1 , wherein the modified Y-type molecular sieve has a lattice collapse temperature of 1040-1080° C.
5. The modified Y-type molecular sieve according to claim 4 , wherein the modified Y-type molecular sieve has a ratio of B acid to L acid in the total acid content of 2.3-5.0, as determined by pyridine adsorption infrared spectroscopy at 200° C.
6. The modified Y-type molecular sieve according to claim 1 , wherein the modified Y-type molecular sieve has a relative crystalline retention of 33% or more after aging at 800° C. under atmospheric pressure in a 100% steam atmosphere for 17 hours.
7. The modified Y-type molecular sieve according to claim 1 , wherein the modifying metal is magnesium, and the modified Y-type molecular sieve has a magnesium content of 0.5-4.5 wt %, calculated on the basis of magnesium oxide, a sodium content of 0.2-0.5 wt %, calculated on the basis of sodium oxide, a lattice constant of 2.442-2.452 nm, and a framework silica-alumina ratio of 8.4-12.6, calculated as SiO 2 /Al 2 O 3 molar ratio; or
the modifying metal is calcium, and the modified Y-type molecular sieve has a calcium content of 0.7-6.3 wt %, calculated on the basis of calcium oxide, a sodium content of 0.2-0.5 wt %, calculated on the basis of sodium oxide, a lattice constant of 2.442-2.452 nm, and a framework silica-alumina ratio of 8.0-12.6, calculated as SiO 2 /Al 2 O 3 molar ratio.
8. The modified Y-type molecular sieve according to claim 1 , wherein the modified Y-type molecular sieve has an Ols electron binding energy of no greater than 532.55 eV.
9. The modified Y-type molecular sieve according to claim 1 , wherein the modified Y-type molecular sieve has a relative crystallinity of 58-75%.
10. A method for preparing a modified Y-type molecular sieve according to claim 1 , comprising the steps of:
(1) contacting a NaY molecular sieve with a solution of a soluble magnesium salt, a soluble calcium salt, or a combination thereof for ion exchange reaction to obtain a Y-type molecular sieve comprising magnesium, calcium, or a combination thereof with reduced sodium content;
(2) subjecting the Y-type molecular sieve obtained in step (1) to roasting at a temperature of 350-480° C. in an atmosphere of 30-90 vol % of steam for 4.5-7 hours, and optionally drying, to obtain a Y-type molecular sieve with reduced lattice constant; and
(3) contacting the Y-type molecular sieve with reduced lattice constant with gaseous silicon tetrachloride for reaction at a weight ratio of SiCl 4 to the Y-type molecular sieve with reduced lattice constant, on a dry basis, of 0.1:1 to 0.7:1, at a reaction temperature of 200-650° C. for a reaction time of 10 minutes to 5 hours, to obtain the modified Y-type molecular sieve.
11. The method according to claim 10 , wherein the Y-type molecular sieve obtained in step (1) has a lattice constant of 2.465-2.472 nm, and a sodium content of no more than 8.8 wt %, calculated on the basis of sodium oxide.
12. The method according to claim 11 , wherein the Y-type molecular sieve obtained in step (1) has a magnesium content of 0.5-7.0 wt %, calculated on the basis of MgO, a sodium content of 4-8.8 wt %, calculated on the basis of sodium oxide, and a lattice constant of 2.465-2.472 nm; or
the Y-type molecular sieve obtained in step (1) has a calcium content of 0.8-10 wt %, calculated on the basis of CaO, a sodium content of 4-8.8 wt %, calculated on the basis of sodium oxide, and a lattice constant of 2.465-2.472 nm.
13. The method according to claim 10 , wherein in step (1), the NaY molecular sieve, the soluble magnesium salt, the soluble calcium salt, and water are mixed at a weight ratio of the NaY molecular sieve:the total of the soluble magnesium salt and the soluble calcium salt:H 2 O of 1:0.005-0.28:5-15 for ion exchange.
14. The method according to claim 10 , wherein step (1) further comprises mixing the NaY molecular sieve with water, and adding thereto a soluble magnesium salt, a soluble calcium salt, a solution of a soluble calcium salt, or a solution of a soluble magnesium salt under stirring to conduct an ion exchange reaction
at an exchange temperature of 15-95° C. for an exchange time of 30-120 minutes.
15. The method according to claim 14 , wherein the soluble magnesium salt is magnesium chloride, magnesium nitrate, or a combination thereof, and the soluble calcium salt is calcium chloride, calcium nitrate, or a combination thereof.
16. The method according to claim 10 , wherein in step (2), the roasting temperature is 380-470° C., the roasting atmosphere is an atmosphere of 40-80% steam, and the roasting time is 5-6 hours.
17. The method according to claim 10 , wherein step (3) further comprises washing the modified Y-type molecular sieve with water under conditions including: a ratio of molecular sieve:H 2 O of 1:5-20, a pH of 2.5-5.0, and a washing temperature of 30-60° C.
18. The method according to claim 10 , wherein the Y-type molecular sieve with reduced lattice constant obtained in step (2) has a lattice constant of 2.450-2.462 nm and a water content of no more than 1 wt %.
19. A catalytic cracking catalyst, comprising 10-50 wt %, on a dry basis, of a modified Y-type molecular sieve, 10-40 wt % of an alumina binder, calculated on the basis of alumina, and 10-80 wt %, on a dry basis, of a clay, based on the weight of the catalytic cracking catalyst; wherein the modified Y-type molecular sieve is a modified Y-type molecular sieve according to claim 1 .
20. A method for catalytic cracking of hydrocarbon oils, comprising contacting a hydrocarbon oil with a catalytic cracking catalyst comprising the modified Y-type molecular sieve according to claim 1 .