CN1215905C - Ultrastable Y-type RE molecular sieve active component and its prepn process - Google Patents
Ultrastable Y-type RE molecular sieve active component and its prepn process Download PDFInfo
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Abstract
The present invention relates to a rare earth ultrlstable Y molecular sieve whose active component is composite modified Y zeolite, which comprises 8 to 25 wt% of oxidized rare earth, 0.1 to 3.0 wt% of phosphorus and 0.3 to 2.5 wt% of sodium oxide. Crystallinity is from 30 to 55%, and unit cell parameter is from 2.455 to 2.477 nanometers. In the preparing method of the rare earth ultrlstable Y molecular sieve, sodium Y zeolite is used as raw material; 'one exchange and one calcination' rare earth sodium Y is obtained by a rare earth exchange and a primary calcination; then the rare earth sodium Y reacts with rare earth and a phosphorus-containing substance; finally a secondary calcination is carried out. When used as the active component of cracking catalysts, the rare earth ultrlstable Y molecular sieve has an obvious effect of lowering gasoline alkene and displays the characteristics of moderate coke yield and high diesel oil yield. Simultaneously, the method has the advantages of simple technology and high utilizing rate of 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, CN12989923 and CN1304980A 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.CN1317547 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, and 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, and is 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 ℃, and 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 rare earth chloride or nitric acid rare earth or sulfuric acid rare earth, preferably rare earth chloride or 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), the material of diammonium hydrogen phosphate, aluminum phosphate, sodium dihydrogen phosphate, sodium hydrogen phosphate, pyrophosphoric acid.
Ammonium salt of the present invention is meant that one or more are selected from the material of 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 III 500 gram (butt) and a certain amount of deionized waters, 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 the described hyperastable Y-type RE molecular sieve active component of 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 is rare earth chloride or nitric acid rare earth or 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), the material of 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 the material of 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.
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| Publication number | Priority date | Publication date | Assignee | Title |
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2002
- 2002-12-13 CN CN 02155600 patent/CN1215905C/en not_active Expired - Fee Related
Cited By (4)
| 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 | Modified Y molecular sieve-containing catalytic cracking catalyst |
| US9789475B2 (en) | 2011-12-15 | 2017-10-17 | Petrochina Company Limited | Ultra-stable rare earth Y-type molecular sieve and preparation method therefor |
| 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 |
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