CN1506161A - Ultrastable rare earth Y molecular sieve active component and preparation method thereof - Google Patents
Ultrastable rare earth Y molecular sieve active component and preparation method thereof Download PDFInfo
- Publication number
- CN1506161A CN1506161A CNA021556008A CN02155600A CN1506161A CN 1506161 A CN1506161 A CN 1506161A CN A021556008 A CNA021556008 A CN A021556008A CN 02155600 A CN02155600 A CN 02155600A CN 1506161 A CN1506161 A CN 1506161A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- molecular sieve
- active component
- hyperastable
- roasting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 85
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 61
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 60
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 33
- 239000011574 phosphorus Substances 0.000 claims abstract description 33
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010457 zeolite Substances 0.000 claims abstract description 30
- 239000011734 sodium Substances 0.000 claims abstract description 27
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 25
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 15
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 5
- -1 rare earth compound Chemical class 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 16
- 150000003863 ammonium salts Chemical class 0.000 claims description 11
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 8
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000004254 Ammonium phosphate Substances 0.000 claims description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 28
- 150000001336 alkenes Chemical class 0.000 abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000571 coke Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 238000005336 cracking Methods 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000002283 diesel fuel Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 239000003643 water by type Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000005956 Cosmos caudatus Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008979 phosphorus utilization Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The rare earth ultrastable Y molecular sieve active component is composite modified Y zeolite, and contains 8-25 wt% of rare earth oxide, 0.1-3.0 wt% of phosphorus, 0.3-2.5 wt% of sodium oxide, 30-55% of crystallinity and 2.455-2.477 nm of unit cell parameter. The preparation method is that sodium Y zeolite is used as raw material, rare earth sodium Y is obtained through rare earth exchange and first roasting, and then reacts with rare earth and phosphorus-containing substances step by step, and the second roasting is carried out. The rare earth ultrastable Y molecular sieve is used as an active component of a cracking catalyst, has the effect of obviously reducing gasoline olefin, and shows the characteristics of moderate coke yield and high diesel oil yield. Meanwhile, the method has simple process and high utilization rate of the modified elements.
Description
Technical field
The present invention relates to a kind of super steady rare-earth Y molecular sieve active component and preparation method thereof, more specifically, is that a kind of catalytic cracking process that is applicable to can reduce the active component and preparation method thereof of the Cracking catalyst of gasoline olefin.
Background technology
The olefin content in gasoline height is the one of the main reasons that causes the motor vehicle exhaust emission amount high.In the domestic gasoline total amount nearly the olefin(e) centent of 80% cracking gasoline between 40-60%, bigger from national new standard (olefin(e) centent is no more than 35v%) gap.Exploitation has falls the research emphasis that the strong Cracking catalyst of alkene ability becomes present catalytic field.The preparation of active component is the key technology of olefine lowering catalyst exploitation.
Market from the FCC catalyst of the world, famous AKZO catalyst Co. and GRACE company have corresponding catalyst prod, but the relevant as yet patent report for preparing active component, from the RFG catalyst prod test data analysis that obtains, mainly adopted similar REY molecular sieve as main active component, shown certain alkene ability of falling, outstanding problem is the coke yield height, and octane number and diesel yield obviously descend.People such as the graduate Tan-no of Japan COSMO had once issued two similar patents [USP5646082, USP5705142], the technology of its core is to have adopted a kind of super stable molecular sieve, repeatedly exchange and the repeatedly roasting of different warm areas are adopted in the preparation of this molecular sieve, the technical process more complicated, especially the thermal oscillation of molecular sieve is handled and is difficult to realize in industrial production, has limited the application of this molecular sieve active component.
In the domestic disclosed patent, CN 12989923 and CN 1304980A have reported the method for falling the alkene active component with the modified ZSM-5 preparation, the catalyst that contains modified ZSM-5 or other auxiliary agent has the function of certain reduction content of olefin in gasoline, and octane number increases to some extent simultaneously.In the HY that has developed, REY, REHY, USY, REUSY, ZSM-5 equimolecular sieve, REY generally adopts twice rare earth ion exchanged and twice high-temperature roasting to make, and the content of rare earth height (contains RE
2O
3The heavy % of 16-22), hydrogen transfer activity is the highest, has the very strong alkene ability of falling, but coke and diesel oil poor selectivity.The employing that the first generation olefine lowering catalyst of domestic-developed has part REY as main active component.CN 1317547 discloses a kind of method of making the olefine lowering catalyst active component, be composited with 0.5-5%ZSM-5,0.5-15% rare earth exchanged Y zeolite and 20-40% phosphorus and the composite modified overstable gamma zeolite of rare earth, wherein the content of rare earth of the composite modified Y zeolite of phosphorus and rare earth is 2-12%, cell parameter is 2.445-2.465nm, its method of phosphorus content 0.2-3% (in P) is rare earth modified for carrying out earlier, carries out the phosphorus modification again and handles.
In order to improve the coke selectivity of REY, conventional way is to be raw material with sodium Y zeolite, adopts the method for modifying of " three hand over three roastings ", " one hands over " and " two hand over " employing rare earth exchanged, " three hand over " then uses utilization rates such as phosphorus, magnesium lower, can obtain the composite modified Y zeolite of multielement.It is oversize that the shortcoming of this method of modifying mainly contains (1) preparation technology, the cost height; (2) element such as rare earth and phosphorus substep modification, utilization rate is lower.CN1147420A adopts REY, one of REHY or REX are zeolite seed crystal, crystal seed is evenly dispersed in the colloidal state system of being made up of waterglass, aluminium salt, inorganic acid and water, synthesized the molecular sieve that contains rare earth with MFI structure by crystallization, at high temperature handle with phosphorus-aluminium activator then, obtained phosphorous and molecular sieve rare earth, when being used for hydro carbons pyrolytic conversion reaction, shown excellent hydrothermal stability and good low-carbon alkene selectivity of product.CN1217231A discloses the preparation method of P-contained zeolite molecular sieve, with solution containing phosphate dipping modcfied faujasite molecular sieve, drying is in 450～600 ℃ of roastings more than 0.5 hour, the catalyst that contains this molecular sieve has increased diesel yield, but the effect that reduces gasoline olefin is not described.
In sum, the alkene active component of falling of prior art for preparing has certain alkene ability of falling, major defect shows as complicated process of preparation. raw material are expensive, such as the cost of ZSM-5 about 60,000 yuan/ton, adopt ZSM-5 as falling alkene master active component, about the manufacturing cost of catalyst will double, in addition, existing active component outstanding the alkene function is fallen and in, reduced the light oil productive rate, especially diesel yield.In order to adapt to Cracking catalyst processing heavy raw oil, the requirement of producing low-alkene gasoline is developed the excellent more alkene active component of falling of performance and is seemed very urgent.
Summary of the invention
The object of the present invention is to provide a kind of hyperastable Y-type RE molecular sieve active component and preparation method thereof with the effect of reduction gasoline olefin, this active component hydrogen transfer activity height, coke yield is moderate, the diesel yield height, in addition, it is simple that method has preparation technology, the characteristics that the modifying element utilization rate is high.
For achieving the above object, hyperastable Y-type RE molecular sieve active component of the present invention is a modified Y zeolite, contains rare earth oxide 8～25 heavy %, phosphorus 0.1～3.0 heavy %: sodium oxide molybdena 0.3～2.5 heavy %, degree of crystallinity 30～55%, cell parameter 2.455nm～2.472 nanometers.
The preparation method of hyperastable Y-type RE molecular sieve active component of the present invention is to be raw material with sodium Y zeolite (silica alumina ratio is greater than 4.0, and degree of crystallinity is greater than 75%),, obtains " one hands over a roasting " rare earth sodium Y through rare earth exchanged and roasting for the first time; With rare earth, phosphorus containg substances and ammonium salt reaction, carry out the roasting second time again, obtain to be hyperastable Y-type RE molecular sieve active component of the present invention with phosphorus and rare earth modified modified Y zeolite (claiming super steady rare earth exchanged Y zeolite again) product.Wherein the method for rare earth exchanged and roasting for the first time is: RE
2O
3/ Y zeolite (weight) is 0.10～0.25, best 0) .12～0.22, pH=3.0～4.0,75～95 ℃ of exchange temperature, 0.2～1.5 hour time, best 0.3～1.2 hour, filter, washing, filter cake is at 450～650 ℃, roasting is 0.3～3.5 hour under 1～100% steam, best 0.5～2.5 hour; Wherein " one hand over one roasting " rare earth sodium Y with the condition of rare earth, phosphorus containg substances and ammonium salt reaction and the roasting second time is: P/Y zeolite (weight) is 0.005～0.04, and is best 0.007～0.035, RE
2O
3/ Y zeolite (weight) is 0.05～0.15, and is best 0.07～0.13, NH
4'/Y zeolite (weight) is 0.01～0.5, best 0.03～0.4, pH=2.0～5.0, react certain hour down at 65～95 ℃, filter washing, filter cake is at 400～700 ℃, roasting is 0.3～3.5 hour under 1～100% steam, best 0.5～2.5 hour, finally obtains hyperastable Y-type RE molecular sieve active component-modified Y zeolite that the present invention prepares.
The reactive mode of " one hands over a roasting " rare earth sodium Y of the present invention and rare earth, phosphorus containg substances can be that " one hands over a roasting " rare earth sodium Y at first reacted 0.1～1.0 hour with rare earth, best 0.2～0.8 hour, adding phosphorus containg substances and ammonium salt in reaction system continues to react 0.1～1.5 hour, best 0.2～1.0 hour, filter washing then.
The reactive mode of " one hands over a roasting " rare earth sodium Y of the present invention and rare earth, phosphorus containg substances can also be that " one hands over a roasting " rare earth sodium Y at first reacted 0.1～1.5 hour with phosphorus and ammonium salt, best 0.2～1.0 hour, in reaction system, add rare earth compound and continue reaction 0.1～1.5 hour, filtered washing then in best 0.2～0.8 hour.
The course of reaction order is different, does not influence enforcement of the present invention.
Rare earth compound of the present invention is a rare earth chloride, nitric acid rare earth, sulfuric acid rare earth, preferably rare earth chloride and nitric acid rare earth.Phosphorus containg substances of the present invention is meant that one or more are selected from orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, pyrophosphoric acid etc.
Ammonium salt of the present invention is meant that one or more are selected from ammonium chloride, ammonium nitrate, ammonium carbonate, carbonic hydroammonium, ammonium oxalate, ammonium sulfate, ammonium hydrogen sulfate.
Introduced higher content of rare earth by two-step reaction in the hyperastable Y-type RE molecular sieve active component of the present invention's preparation, molecular sieve keeps big unit cell dimension in modification, has improved hydrogen transfer activity; The effect of adjustment of acidity center intensity and density has been played in the introducing of phosphorus, and the lytic activity of molecular sieve and hydrogen transfer reaction activity are rationally mated; Simultaneously owing to a phosphorus part in the super steady rare earth exchanged Y zeolite may be to enter molecular sieve by exchange, another part then may form composite oxides by phosphorus and rare earth reaction and be evenly distributed on the surface of molecular sieve, the existing chemical action of this modification, physical action is arranged again, structure acidity and surface nature to molecular sieve can play promotor action well, have greatly improved reactivity and coke selectivity.In addition, the method for preparing the hyperastable Y-type RE molecular sieve active component of the present invention also has following characteristics:
Phosphorus and rare earth element are introduced in segmentation in molecular sieve " two hand over " modification, compare with conventional modification, have reduced once exchange and bakes to burn the article operation, and modified technique is simplified, and have reduced production cost.
Because phosphorus and rare earth can carry out precipitation reaction by stoichiometry, excessive phosphorus or rare earth trapping agent each other in the switching architecture, thus improved the utilization rate of modifying element rare earth and phosphorus, saved raw material effectively.
The specific embodiment
Further further specify the present invention below, but the present invention is not limited in these examples with embodiment.
(1) used analysis test method in the example.
1. lattice constant (a
0): the x-ray diffraction method.
2. degree of crystallinity (C/C
0): the x-ray diffraction method.
3. silica alumina ratio: x-ray diffraction method.
4.Na
2O content: flame spectrometry.
5.P content: phosphorus molybdenum colorimetric method.
6.RE
2O
3Content: colorimetric method.
(2) raw materials used specification in the example
1. sodium Y molecular sieve: silica alumina ratio 4.9, degree of crystallinity 88%; Catalyst Factory of Lanzhou Petrochemical Company is produced.
2. orthophosphoric acid: industrial goods, phosphorous 25 heavy %; Ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, ammonium phosphate: solid, industrial goods.
3. earth solution: rare earth chloride: industrial goods, rare earth oxide 250 grams per liters; Nitric acid rare earth: industrial goods, rare earth oxide 248 grams per liters.
4.RSADY molecular sieve, sodium oxide molybdena 1.4%, rare earth oxide 3.0%, degree of crystallinity 60%, cell parameter 2.449nm, Catalyst Factory of Lanzhou Petrochemical Company production.
5. ammonium chloride, ammonium nitrate, ammonium sulfate, solid is industrial goods
Embodiment 1
In having the reactor of heating, add 3000 gram (butt) sodium Y molecular sieve and a certain amount of deionized waters, make the slurries that solid content is 150 grams per liters, slowly add 2.14 liters rare earth chloride, regulation system pH=3.2, be warmed up to 90 ℃, exchange 0.5 hour, filter, washing, filter cake makes " one hands over a roasting " rare earth sodium Y 10% steam and 510 ℃ of following roastings 2.0 hours, and note is modified molecular screen I.In having the reactor of heating, add modified molecular screen I 500 gram (butt) and a certain amount of deionized waters, make the slurries that solid content is 145 grams per liters, the rare earth chloride that slowly adds 0.20 liter, regulation system pH=3.5, be warmed up to 90 ℃, exchange 1.2 hours, add ammonium phosphate 36 grams and ammonium sulfate 200 grams then, stir, about 75 ℃, continue 0.5 hour, filter, washing, filter cake was 50% steam and 650 ℃ of following roastings 2 hours, make hyperastable Y-type RE molecular sieve active component of the present invention, note is modified molecular screen A.
Embodiment 2
In having the reactor of heating, add 3000 gram (butt) sodium Y molecular sieve and a certain amount of deionized waters, make the slurries that solid content is 120 grams per liters, slowly add 1.69 liters nitric acid rare earth, regulation system pH=3.8, be warmed up to 78 ℃, exchange 1.0 hours, filter, washing, filter cake makes " one hands over a roasting " rare earth sodium Y 80% steam and 620 ℃ of following roastings 1.0 hours, and note is modified molecular screen II.In having the reactor of heating, add modified molecular screen II 500 gram (butt) and a certain amount of deionized waters, make the slurries that solid content is 125 grams per liters, the nitric acid rare earth that slowly adds 0.28 liter, regulation system pH=3.9, be warmed up to 85 ℃, exchange 1.5 hours, add diammonium hydrogen phosphate 21 grams and ammonium sulfate 100 grams then, stir, about 70 ℃, continue 1.0 hours, filter, washing, filter cake was 20% steam and 500 ℃ of following roastings 1.5 hours, make hyperastable Y-type RE molecular sieve active component of the present invention, note is modified molecular screen B.
Embodiment 3
In having the reactor of heating, add 3000 gram (butt) sodium Y molecular sieve and a certain amount of deionized waters, make the slurries that solid content is 100 grams per liters, slowly add 2.95 liters nitric acid rare earth, regulation system pH=4.0, be warmed up to 82 ℃, exchange 1.5 hours, filter, washing, filter cake makes " one hands over a roasting " rare earth sodium Y 50% steam and 640 ℃ of following roastings 3.0 hours, and note is modified molecular screen III.In having the reactor of heating, add modified molecular screen III500 gram (butt) and a certain amount of deionized water, make the slurries that solid content is 160 grams per liters, the rare earth chloride that slowly adds 0.12 liter, regulation system pH=3.1, be warmed up to 80 ℃, exchange 0.6 hour, add ammonium dihydrogen phosphate (ADP) 45 grams and ammonium nitrate 70 grams then, stir, about 70 ℃, continue 2.0 hours, filter, washing, filter cake was 85% steam and 490 ℃ of following roastings 1.0 hours, make hyperastable Y-type RE molecular sieve active component of the present invention, note is modified molecular screen C.
Embodiment 4
In having the reactor of heating, add modified molecular screen I 500 gram (butt) and a certain amount of deionized waters that make among the embodiment 1, make the slurries that solid content is 146 grams per liters, add ammonium phosphate 36 grams and ammonium chloride 150 grams, stir, regulation system pH=3.9, be warmed up to 86 ℃, exchange 1.2 hours, slowly add 0.22 liter rare earth chloride then, about 77 ℃, kept 0.5 hour, filter, washing, filter cake was 60% steam and 580 ℃ of following roastings 1.5 hours, make hyperastable Y-type RE molecular sieve active component of the present invention, note is modified molecular screen D.
Embodiment 5
In having the reactor of heating, add modified molecular screen II 500 gram (butt) and a certain amount of deionized waters that make among the embodiment 2, make the slurries that solid content is 126 grams per liters, add orthophosphoric acid 36 grams and ammonium sulfate 500 grams, stir, regulation system pH=3.9, be warmed up to 86 ℃, exchange 1.2 hours, slowly add 0.13 liter nitric acid rare earth then, about 77 ℃, kept 0.5 hour, filter, washing, filter cake was 60% steam and 580 ℃ of following roastings 0.5 hour, make hyperastable Y-type RE molecular sieve active component of the present invention, note is modified molecular screen E.
Comparative Examples 1
In having the reactor of heating, add modified molecular screen I 500 gram (butt) and a certain amount of deionized waters that make among the embodiment 1, make the slurries that solid content is 145 grams per liters, slowly add 0.20 liter rare earth chloride, regulation system pH=3.5, be warmed up to 90 ℃, exchange 1.2 hours, filter, washing, filter cake makes common REY sieve sample 50% steam and 600 ℃ of following roastings 2 hours, and note is modified molecular screen F.
Comparative Examples 2
In having the reactor of heating, add modified molecular screen F 500 gram (butt) and a certain amount of deionized waters, make the slurries that solid content is 145 grams per liters, add ammonium phosphate 36 grams then, stir, be warmed up to 85 ℃, exchange 1.0 hours, filter, washing, filter cake makes the PREY sieve sample 50% steam and 570 ℃ of following roastings 1.5 hours, and note is modified molecular screen G.
The physicochemical property of hyperastable Y-type RE molecular sieve active component of the present invention-modified molecular screen A, the B of embodiment 1-5 preparation, C, D, E is listed in table 1.It can be seen from the table, the sodium oxide molybdena of prepared modified molecular screen is little 2.0% according to the present invention, rare earth oxide between 8%～25%, cell parameter 2.455nm～2.472nm.
The character of the hyperastable Y-type RE molecular sieve of table 1 embodiment 1-5 preparation
| Project | Molecular sieve | Na 2O，m％ | ??P，m％ | ?RE 2O 3，m％ | ?C/C 0，m％ | ???a 0，nm | |
| Embodiment | ??1 | ????A | ????1.05 | ????1.35 | ????19.1 | ????40 | ????2.470 |
| ??2 | ????B | ????1.41 | ????0.84 | ????22.3 | ????34 | ????2.468 | |
| ??3 | ????C | ????0.68 | ????2.10 | ????20.1 | ????38 | ????2.471 | |
| ??4 | ????D | ????1.09 | ????1.37 | ????21.9 | ????37 | ????2.460 | |
| ??5 | ????E | ????1.76 | ????1.65 | ????10.5 | ????45 | ????2.456 | |
The technology and the utilization of materials contrast of several embodiments of the invention and the prepared modified molecular screen of Comparative Examples are listed in the table 2.It can be seen from the table, compare with the molecular sieve modified technology of Comparative Examples, the phosphorus utilization of modified technique of the present invention is high 10 percentage points, and the rare earth utilization rate is high about 20 percentage points, and it is simple to have preparation technology, the characteristics that the modifying element utilization rate is high.
The preparation technology of several molecular sieves of table 3 and utilization of materials contrast
| Project | Modified molecular screen | Preparation technology | Ingredient proportion, m% | Product characteristics, m% | Practical efficiency *, % | ||||
| ????P | ????RE 2O 3 | ????P | ????RE 2O 3 | ????P | ?RE 2O 3 | ||||
| Embodiment | ????1 | ????A | Two hand over two roastings | ????1.5 | ????10.0 | ????1.35 | ????19.1 | ????97 | ???83 |
| ????5 | ????E | Two hand over two roastings | ????1.8 | ????6.5 | ????1.65 | ????15.9 | ????99 | ???85 | |
| Comparative Examples | ????1 | ????F | Two hand over two roastings | ????/ | ????10.0 | ????/ | ????18.0 | ????/ | ???66 |
| ????2 | ????G | Three hand over three roastings | ????1.5 | ????10.0 | ????1.20 | ????17.8 | ????87 | ???67 | |
*: practical efficiency refers to content and feed intake percentage quality between of modifying element in product.
Fall alkene effect and combined reaction performance for what investigate hyperastable Y-type RE molecular sieve active component of the present invention, carried out following experiment.
The method for preparing semi-synthetic Cracking catalyst according to routine, modified molecular screen with 35%, 17% aluminium oxide, 38% kaolin and 10% metallic aluminium sol adhesive and proper amount of deionized water mix, through spraying, washing, drying, make catalyst K, wherein modified molecular screen is respectively embodiment gained modified molecular screen A, B, C, D, E and Comparative Examples gained modified molecular screen F, G, and the RSADY molecular sieve, make Cracking catalyst a, b, c, d, e, f, g and h respectively.
On small fixed flowing bed-tion reacting device (catalyst loading amount 180 grams), be reaction raw materials with the Xinjiang miscella, the reactivity worth of catalyst to be estimated, the product of reaction distributes and the gasoline olefin data are listed in the table 4.Analytical table 4 data are found out, compare with comparative catalyst f, g, and catalyst (a, b, c, d, the e) coke yield of hyperastable Y-type RE molecular sieve active component that contains the present invention preparation is low, the diesel yield height, and bavin/vapour is than increasing, and content of olefin in gasoline is low.(h) compares with the catalyst that contains conventional USY molecular sieve, and the content of olefin in gasoline of catalyst a, b, c, d, e obviously reduces.Show that modified molecular screen A, B, C, D, E that the present invention prepares have the characteristics of obvious reduction cracking gasoline olefin(e) centent, improved coke selectivity simultaneously, improved bavin/vapour ratio.
The evaluation result of the various catalyst of table 4
| Project | Application Example gained catalyst | Use Comparative Examples gained catalyst | With RSADY gained catalyst | |||||
| ????a | ????b | ????c | ????d | ????e | ????f | ????g | ????h | |
| Reaction temperature, ℃ | ????500 | ????500 | ????500 | ????500 | ????500 | ????500 | ????500 | ????500 |
| Oil ratio | ????4.0 | ????4.0 | ????4.0 | ????4.0 | ????4.0 | ????4.0 | ????4.0 | ????4.0 |
| Dry gas, m% | ????2.0 | ????1.8 | ????2.1 | ????2.3 | ????2.0 | ????2.3 | ????2.3 | ????2.0 |
| Liquefied gas, m% | ????15.6 | ????15.0 | ????15.8 | ????16.2 | ????15.2 | ????14.8 | ????14.7 | ????14.3 |
| Gasoline, m% | ????48.1 | ????48.2 | ????49.0 | ????49.2 | ????48.9 | ????50.1 | ????49.9 | ????49.0 |
| Diesel oil, m% | ????21.0 | ????20.3 | ????20.5 | ????19.5 | ????20.4 | ????16.8 | ????17.9 | ????21.8 |
| Heavy oil, m% | ????3.9 | ????4.2 | ????3.9 | ????3.8 | ????4.3 | ????4.8 | ????4.6 | ????4.2 |
| Coke, m% | ????8.2 | ????8.5 | ????8.0 | ????8.5 | ????7.9 | ????9.4 | ????8.6 | ????7.2 |
| Conversion ratio, m% | ????73.9 | ????73.5 | ????74.9 | ????76.2 | ????74.0 | ????76.6 | ????75.5 | ????73.0 |
| Light receipts, m% | ????69.1 | ????68.5 | ????69.5 | ????68.7 | ????69.3 | ????66.9 | ????67.8 | ????70.8 |
| Bavin/vapour ratio | ????0.44 | ????0.42 | ????0.42 | ????0.40 | ????0.42 | ????0.34 | ????0.36 | ????0.44 |
| Gasoline olefin, v% | ????13.3 | ????13.8 | ????14.1 | ????11.9 | ????14.0 | ????14.6 | ????15.6 | ????19.6 |
Claims (11)
1. a hyperastable Y-type RE molecular sieve active component is modified Y zeolite, contains rare earth oxide 8～25 heavy %, phosphorus 0.1～3.0 heavy %; Sodium oxide molybdena 0.3～2.5 heavy %, degree of crystallinity 30～55%, lattice constant 2.455～2.472 nanometers.
2. the preparation method of described kind of hyperastable Y-type RE molecular sieve active component of a claim 1 is a raw material with sodium Y zeolite,, obtains " one hands over a roasting " rare earth sodium Y through rare earth exchanged and roasting for the first time; With rare earth, phosphorus containg substances and ammonium salt reaction, carry out the calcination process second time again, obtain to be hyperastable Y-type RE molecular sieve active component of the present invention with phosphorus and rare earth modified modified Y zeolite.
3. according to the preparation method of the described hyperastable Y-type RE molecular sieve active component of claim 2, its characteristics are that the method for rare earth exchanged and roasting for the first time is: the weight ratio of rare earth oxide/Y zeolite is 0.10～0.25, pH=3.0～4.0,75～95 ℃ of exchange temperature, 0.2～1.5 hour time, filter washing, filter cake is at 450～650 ℃, and roasting is 0.3～3.5 hour under 1～100% steam.
4. according to the preparation method of the described hyperastable Y-type RE molecular sieve active component of claim 2, its characteristics are that the method for rare earth exchanged and roasting for the first time is: the weight ratio of rare earth oxide/Y zeolite is 0.12～0.22, pH=3.0～4.0,75～95 ℃ of exchange temperature, 0.3～1.2 hour time, filter washing, filter cake is at 450～650 ℃, and roasting is 0.5～2.5 hour under 1～100% steam.
5. according to the preparation method of the described hyperastable Y-type RE molecular sieve active component of claim 2, its characteristics are that the condition of " one hands over a roasting " rare earth sodium Y and rare earth, phosphorus containg substances and ammonium salt reaction and roasting for the second time is: the weight ratio of P/Y zeolite is 0.005～0.04, the weight ratio of rare earth oxide/Y zeolite is 0.05～0.15, NH
4 +The weight ratio of/Y zeolite is 0.01～0.5, and pH=2.0～5.0 are 65～95 ℃ of reactions down, after filtration, washing, filter cake is at 400～700 ℃, roasting is 0.3～3.5 hour under 1～100% steam, finally obtains the hyperastable Y-type RE molecular sieve active component of the present invention's preparation.
6. according to the preparation method of the described hyperastable Y-type RE molecular sieve active component of claim 2, its characteristics are that the condition of " one hands over a roasting " rare earth sodium Y and rare earth, phosphorus containg substances and ammonium salt reaction and roasting for the second time is: the weight ratio of P/Y zeolite is 0.007～0.035, the weight ratio of rare earth oxide/Y zeolite is 0.07～0.13, NH
4 +The weight ratio 0.03～0.4 of/Y zeolite, pH=2.0～5.0,65～95 ℃ of reactions down, after filtration, and washing, filter cake is at 400～700 ℃, and roasting is 0.5～2.5 hour under 1～100% steam, finally obtains the hyperastable Y-type RE molecular sieve active component of the present invention's preparation.
7. according to the preparation method of claim 2 or 5 or 6 described hyperastable Y-type RE molecular sieve active components, it is characterized in that described rare earth sodium Y and rare earth, phosphorus containg substances reaction method are that rare earth sodium Y at first reacted 0.1～1.0 hour with rare earth, add phosphorus containg substances and ammonium salt and continue reaction 0.1～1.5 hour.
8. according to the preparation method of claim 2 or 5 or 6 described hyperastable Y-type RE molecular sieve active components, it is characterized in that described rare earth sodium Y and rare earth, phosphorus containg substances reaction method are that rare earth sodium Y at first reacted 0.1～1.5 hour with phosphorus and ammonium salt, add rare earth compound and continue reaction 0.1～1.5 hour.
9. according to the preparation method of any described hyperastable Y-type RE molecular sieve active component in the claim 2 to 6, it is characterized in that rare earth can be a rare earth chloride, nitric acid rare earth, sulfuric acid rare earth.
10. according to the preparation method of any described hyperastable Y-type RE molecular sieve active component in the claim 2 to 6, it is characterized in that described phosphorus containg substances is meant that one or more are selected from orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, pyrophosphoric acid.
11., it is characterized in that described ammonium salt is meant that one or more are selected from ammonium chloride, ammonium nitrate, ammonium carbonate, carbonic hydroammonium, ammonium oxalate, ammonium sulfate, ammonium hydrogen sulfate according to the preparation method of any described hyperastable Y-type RE molecular sieve active component in the claim 2 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02155600 CN1215905C (en) | 2002-12-13 | 2002-12-13 | Ultrastable rare earth Y molecular sieve active component and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02155600 CN1215905C (en) | 2002-12-13 | 2002-12-13 | Ultrastable rare earth Y molecular sieve active component and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1506161A true CN1506161A (en) | 2004-06-23 |
| CN1215905C CN1215905C (en) | 2005-08-24 |
Family
ID=34235971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02155600 Expired - Fee Related CN1215905C (en) | 2002-12-13 | 2002-12-13 | Ultrastable rare earth Y molecular sieve active component and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1215905C (en) |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433857B (en) * | 2007-11-15 | 2011-05-11 | 石大卓越科技股份有限公司 | Method for preparing rare-earth ultra-steady Y molecular sieve |
| CN102309976A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Refined triphenyl fraction catalyst and preparation method and application thereof |
| CN102309977A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Deolefination catalyst and preparation method and application thereof |
| CN103073024A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| CN103084207A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen gasoline yield increase catalysis cracking catalyst and preparation method thereof |
| CN103084206A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen diesel oil yield increase catalysis cracking catalyst and preparation method thereof |
| CN103084205A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen liquefied gas yield increase cracking catalyst and preparation method thereof |
| CN103086397A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Modified Y type molecular sieve |
| CN103084199A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen olefin reduction cracking catalyst and preparation method thereof |
| CN103084200A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen catalysis cracking catalyst and preparation method thereof |
| CN103159227A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Magnesium modified ultrastable rare earth Y-type molecular sieve and preparation method thereof |
| CN103159228A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Ultrastable rare earth Y-type molecular sieve and preparation method thereof |
| CN103265052A (en) * | 2013-05-08 | 2013-08-28 | 广西大学 | High temperature hydrothermal stability REHY molecular sieve, preparation method and applications thereof |
| WO2013177728A1 (en) * | 2012-06-01 | 2013-12-05 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
| WO2013177727A1 (en) * | 2012-06-01 | 2013-12-05 | 中国石油天然气股份有限公司 | Phosphorus-containing ultrastable y-type rare earth molecular sieve and preparation method therefor |
| WO2014000422A1 (en) | 2012-06-27 | 2014-01-03 | 中国石油化工股份有限公司 | Rare-earth contained y type molecular sieve and preparation method thereof |
| WO2014040365A1 (en) | 2012-09-14 | 2014-03-20 | 中国石油化工股份有限公司 | Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor |
| CN103657711A (en) * | 2012-09-14 | 2014-03-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN103962168A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Rare earth ultrastable Y-type molecular sieve and preparation method thereof |
| CN103962167A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Low-coking catalytic cracking catalyst and preparation method thereof |
| CN103962176A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Cracking catalyst for improving octane number of catalytically cracked gasoline |
| CN106268919A (en) * | 2015-06-29 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of containing rare earth with the modified Y catalyst of phosphorus |
| US9630171B2 (en) | 2012-06-27 | 2017-04-25 | China Petroleum & Chemical Corporation | Catalyst containing a modified Y-type zeolite and a preparation process thereof |
| US9844772B2 (en) | 2011-12-15 | 2017-12-19 | Petrochina Company Limited | Heavy oil catalytic cracking catalyst and preparation method therefor |
| CN111744535A (en) * | 2019-03-27 | 2020-10-09 | 中国石油化工股份有限公司 | Catalytic material jointly modified by rare earth and phosphorus and preparation method thereof |
| US10888848B2 (en) | 2017-02-22 | 2021-01-12 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst and preparation thereof |
| US11052381B2 (en) | 2017-02-21 | 2021-07-06 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve, preparation thereof and catalyst comprising the same |
| WO2022148471A1 (en) | 2021-01-11 | 2022-07-14 | 中国石油化工股份有限公司 | Catalytic cracking agent containing phosphorus modified molecular sieve, and preparation method therefor, preparation system thereof and use thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823726B (en) * | 2009-03-04 | 2012-03-07 | 中国石油天然气股份有限公司 | Modified Y molecular sieve |
| CN102019195B (en) * | 2009-09-09 | 2013-02-13 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst containing modified Y molecular sieve |
-
2002
- 2002-12-13 CN CN 02155600 patent/CN1215905C/en not_active Expired - Fee Related
Cited By (64)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433857B (en) * | 2007-11-15 | 2011-05-11 | 石大卓越科技股份有限公司 | Method for preparing rare-earth ultra-steady Y molecular sieve |
| CN102309976B (en) * | 2010-07-07 | 2013-07-24 | 中国石油化工股份有限公司 | Refined triphenyl fraction catalyst and preparation method and application thereof |
| CN102309976A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Refined triphenyl fraction catalyst and preparation method and application thereof |
| CN102309977A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Deolefination catalyst and preparation method and application thereof |
| CN102309977B (en) * | 2010-07-07 | 2013-07-24 | 中国石油化工股份有限公司 | Deolefination catalyst and preparation method and application thereof |
| CN103073024A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| WO2013060099A1 (en) * | 2011-10-26 | 2013-05-02 | 中国石油化工股份有限公司 | Modified y zeolite, method for preparing same, and use thereof |
| US9782757B2 (en) | 2011-10-26 | 2017-10-10 | China Petroleum & Chemical Corporation | Modified Y-type zeolite and preparation process and use thereof |
| CN103084206A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen diesel oil yield increase catalysis cracking catalyst and preparation method thereof |
| CN103086397B (en) * | 2011-10-28 | 2015-05-20 | 中国石油化工股份有限公司 | Modified Y type molecular sieve |
| CN103084200A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen catalysis cracking catalyst and preparation method thereof |
| CN103084199B (en) * | 2011-10-28 | 2014-12-03 | 中国石油化工股份有限公司 | Anti-basic nitrogen olefin reduction cracking catalyst and preparation method thereof |
| CN103084200B (en) * | 2011-10-28 | 2014-10-29 | 中国石油化工股份有限公司 | Anti-basic nitrogen catalysis cracking catalyst and preparation method thereof |
| CN103086397A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Modified Y type molecular sieve |
| CN103084205A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen liquefied gas yield increase cracking catalyst and preparation method thereof |
| CN103084205B (en) * | 2011-10-28 | 2014-12-03 | 中国石油化工股份有限公司 | Anti-basic nitrogen liquefied gas yield increase cracking catalyst and preparation method thereof |
| CN103084206B (en) * | 2011-10-28 | 2014-12-03 | 中国石油化工股份有限公司 | Anti-basic nitrogen diesel oil yield increase catalysis cracking catalyst and preparation method thereof |
| CN103084199A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen olefin reduction cracking catalyst and preparation method thereof |
| CN103084207B (en) * | 2011-10-28 | 2014-12-03 | 中国石油化工股份有限公司 | Anti-basic nitrogen gasoline yield increase catalysis cracking catalyst and preparation method thereof |
| CN103084207A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Anti-basic nitrogen gasoline yield increase catalysis cracking catalyst and preparation method thereof |
| CN103159228B (en) * | 2011-12-15 | 2016-07-13 | 中国石油天然气股份有限公司 | Ultrastable rare earth Y-type molecular sieve and preparation method thereof |
| US9789475B2 (en) | 2011-12-15 | 2017-10-17 | Petrochina Company Limited | Ultra-stable rare earth Y-type molecular sieve and preparation method therefor |
| CN103159227B (en) * | 2011-12-15 | 2015-05-13 | 中国石油天然气股份有限公司 | Magnesium modified ultrastable rare earth Y-type molecular sieve and preparation method thereof |
| US9840422B2 (en) | 2011-12-15 | 2017-12-12 | Petrochina Company Limited | Magnesium modified ultra-stable rare earth Y-type molecular sieve and preparation method therefor |
| US9844772B2 (en) | 2011-12-15 | 2017-12-19 | Petrochina Company Limited | Heavy oil catalytic cracking catalyst and preparation method therefor |
| CN103159228A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Ultrastable rare earth Y-type molecular sieve and preparation method thereof |
| CN103159227A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Magnesium modified ultrastable rare earth Y-type molecular sieve and preparation method thereof |
| JP2015523302A (en) * | 2012-06-01 | 2015-08-13 | 中国石油天然気股▲ふん▼有限公司 | Phosphorus-containing ultra-stabilized rare earth Y-type molecular sieve and production method |
| JP2015523907A (en) * | 2012-06-01 | 2015-08-20 | 中国石油天然気股▲ふん▼有限公司 | Heavy oil high-efficiency catalytic conversion cracking catalyst and production method thereof |
| CN103447063B (en) * | 2012-06-01 | 2016-02-10 | 中国石油天然气股份有限公司 | High-efficiency heavy oil conversion catalytic cracking catalyst and preparation method thereof |
| US9968915B2 (en) | 2012-06-01 | 2018-05-15 | Petrochina Company Limited | Phosphorus-containing ultrastable Y-type rare earth molecular sieve and preparation method therefor |
| US9968918B2 (en) | 2012-06-01 | 2018-05-15 | Petrochina Company Limited | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
| WO2013177728A1 (en) * | 2012-06-01 | 2013-12-05 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst for high-efficiency conversion of heavy oil and preparation method thereof |
| WO2013177727A1 (en) * | 2012-06-01 | 2013-12-05 | 中国石油天然气股份有限公司 | Phosphorus-containing ultrastable y-type rare earth molecular sieve and preparation method therefor |
| EP2860157A4 (en) * | 2012-06-01 | 2015-12-23 | Petrochina Co Ltd | Phosphorus-containing ultrastable y-type rare earth molecular sieve and preparation method therefor |
| CN103447063A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | High-efficiency heavy oil conversion catalytic cracking catalyst and preparation method thereof |
| JP2015525726A (en) * | 2012-06-27 | 2015-09-07 | 中国石油化工股▲ふん▼有限公司 | Y-type zeolite containing rare earth and method for producing the same |
| US9630171B2 (en) | 2012-06-27 | 2017-04-25 | China Petroleum & Chemical Corporation | Catalyst containing a modified Y-type zeolite and a preparation process thereof |
| WO2014000422A1 (en) | 2012-06-27 | 2014-01-03 | 中国石油化工股份有限公司 | Rare-earth contained y type molecular sieve and preparation method thereof |
| US10130944B2 (en) | 2012-06-27 | 2018-11-20 | China Petroleum & Chemical Corporation | Rare earth-containing Y zeolite and a preparation process thereof |
| EP2868629A4 (en) * | 2012-06-27 | 2016-04-20 | China Petroleum & Chemical | Rare-earth contained y type molecular sieve and preparation method thereof |
| AU2013284233B2 (en) * | 2012-06-27 | 2017-02-09 | China Petroleum & Chemical Corporation | Rare-earth contained Y type molecular sieve and preparation method thereof |
| JP2015533637A (en) * | 2012-09-14 | 2015-11-26 | 中国石油化工股▲ふん▼有限公司 | Catalytic cracking catalyst having rare earth-containing Y-type zeolite and method for producing the same |
| US9656255B2 (en) | 2012-09-14 | 2017-05-23 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst having a rare earth-containing Y zeolite and a preparation process thereof |
| EP2896456A4 (en) * | 2012-09-14 | 2016-06-29 | China Petroleum & Chemical | Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor |
| KR102109395B1 (en) * | 2012-09-14 | 2020-05-28 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor |
| KR20150054926A (en) * | 2012-09-14 | 2015-05-20 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor |
| CN103657711A (en) * | 2012-09-14 | 2014-03-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| WO2014040365A1 (en) | 2012-09-14 | 2014-03-20 | 中国石油化工股份有限公司 | Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor |
| CN103657711B (en) * | 2012-09-14 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
| CN103962176B (en) * | 2013-01-30 | 2016-05-11 | 中国石油天然气股份有限公司 | Cracking catalyst for improving octane number of catalytically cracked gasoline |
| CN103962167A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Low-coking catalytic cracking catalyst and preparation method thereof |
| CN103962167B (en) * | 2013-01-30 | 2016-07-13 | 中国石油天然气股份有限公司 | Low-coking catalytic cracking catalyst and preparation method thereof |
| CN103962168B (en) * | 2013-01-30 | 2016-07-13 | 中国石油天然气股份有限公司 | Rare earth ultrastable Y-type molecular sieve and preparation method thereof |
| CN103962168A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Rare earth ultrastable Y-type molecular sieve and preparation method thereof |
| CN103962176A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Cracking catalyst for improving octane number of catalytically cracked gasoline |
| CN103265052A (en) * | 2013-05-08 | 2013-08-28 | 广西大学 | High temperature hydrothermal stability REHY molecular sieve, preparation method and applications thereof |
| CN103265052B (en) * | 2013-05-08 | 2016-08-17 | 广西大学 | High-temperature water heat-staple REHY molecular sieve and its preparation method and application |
| CN106268919B (en) * | 2015-06-29 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of Modified Zeolite Y catalyst containing rare earth and phosphorus |
| CN106268919A (en) * | 2015-06-29 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of containing rare earth with the modified Y catalyst of phosphorus |
| US11052381B2 (en) | 2017-02-21 | 2021-07-06 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve, preparation thereof and catalyst comprising the same |
| US10888848B2 (en) | 2017-02-22 | 2021-01-12 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst and preparation thereof |
| CN111744535A (en) * | 2019-03-27 | 2020-10-09 | 中国石油化工股份有限公司 | Catalytic material jointly modified by rare earth and phosphorus and preparation method thereof |
| WO2022148471A1 (en) | 2021-01-11 | 2022-07-14 | 中国石油化工股份有限公司 | Catalytic cracking agent containing phosphorus modified molecular sieve, and preparation method therefor, preparation system thereof and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1215905C (en) | 2005-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1215905C (en) | Ultrastable rare earth Y molecular sieve active component and preparation method thereof | |
| CN1111136C (en) | Process for preparing Y-type molecular sieve | |
| CN1465527A (en) | MFI structure molecular sieve containing phosphorus and transition metal | |
| CN1055063C (en) | Modified zeolite and manufacture thereof | |
| CN1209288C (en) | Modified faujasite | |
| CN100395029C (en) | Production of liquefied gas cracking catalyst with gasoline olefin content decreasement | |
| CN1043520A (en) | A kind of catalyst for cracking of producing low-carbon alkene | |
| CN1031791C (en) | Preparation of high-silicon Y-shaped molecular sieve | |
| CN1064072C (en) | Catalyst containing modified kaoling for cracking hydrocarbons | |
| CN1042201C (en) | Cracking catalyst of rich producing olefines | |
| CN1176752C (en) | Method for improving catalytic activity of zeolite molecular sieve | |
| CN1279130A (en) | Process for preparing superstable gamma-type molecular sieve | |
| CN1291789C (en) | Hydrocarbon cracking catalyst containing modified faujasite | |
| CN1062750A (en) | The cracking catalyst of phosphorous and hyperastable Y-type RE zeolite | |
| CN1031030A (en) | The preparation of low content of rare earth super-stable Y molecular sieves | |
| CN1104955C (en) | Once-exchanging once-calcining phosphoreted Y-zeolite cracking catalyst and preparing method thereof | |
| CN1247744C (en) | Olefin cracking catalyst for increasing diesel oil yield and preparation method thereof | |
| CN1223403C (en) | Heavy metal-resistant matrix-type cracking catalyst and its preparing process | |
| CN1110532C (en) | Method for preparation of active component of cracking catalyst by once exchange and once calcining | |
| CN1180059C (en) | Hydrocarbon cracking catalyst containing phosphorus and its prepn | |
| CN1048428C (en) | Multi-zeolite catalyzer for preparation of low-carbon olefines | |
| CN1151237C (en) | Catalytic cracking assistant for reducing olefine content in gasoline | |
| CN1136298C (en) | Catalyst for producing middle fraction from Fischer-Tropsch synthetic heavy hydrocarbon and its prepn and use | |
| CN1053918C (en) | Double zeolite catalyst for prepn. of low carbon olefine | |
| CN1064499A (en) | Rare earth Y molecular sieve cracking catalyst and its preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050824 Termination date: 20211213 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |