CN101088917A - Y-type molecular sieve containing P and RE and its prepn process - Google Patents

Abstract

The present invention discloses one kind of Y-type molecular sieve containing P and RE, and features that the molecular sieve contains RE accounting in RE oxide of 12.0-16.0 wt% and P accounting in P2O5 of 0.5-7.0 wt%, and has 31P MAS NMR spectrum with peak area of resonant signals in chemical shift of -14+/-2 ppm and -23+/-2 ppm accounting for 85 % of the total peak area and 27Al MAS NMR spectrum with peak area of resonant signals in chemical shift of 0+/-2 ppm accounting for over 20 % of the total peak area. The molecular sieve is used as active component of catalytic cracking catalyst, especially suitable for heavy oil with high V content.

Description

Y zeolite of a kind of phosphorous and rare earth and preparation method thereof

Technical field

The invention relates to a kind of active component that is used for cracking hydrocarbon and preparation method thereof, more particularly, is Y zeolite about a kind of phosphorous and rare earth and preparation method thereof.

Background technology

Catalytic cracking process is important heavy oil lighting technology, and is one of main source of each refinery economic benefit.Because resource-constrained, catalytically cracked material has been turned to by traditional decompression fraction oil mixes residual oil or pure resid feed.Not only contain the easily macromolecular cpd of green coke such as colloid and bituminous matter in the residual oil, more contain than multi-metal (as nickel, vanadium etc.).In cracking reaction, metal deposition such as nickel, vanadium cause catalyst activity to reduce on catalyzer, vanadium particularly, the vanadium of high oxidation state transport property under the high-temperature water thermal environment is strong, and the structure of molecules of active components sieve causes the irreversible inactivation of catalyzer in the havoc catalyzer.Thereby when meeting with pollution of vanadium, must constantly from catalytic cracking unit, unload agent and replenish new agent, make the catalyzer consumption increase, process cost significantly improves.For this reason, molecular sieve catalyst must improve the ability of preventing from heavy metal pollution.

In recent years, the interpolation rare earth is more as the patent report that the vanadium trapping agent improves anti-pollution of vanadium in catalyzer.For example, US4988653 is disclosed is to adopt aluminum oxide and rare earth oxide as the vanadium trapping agent; EP89306806.4 discloses the catalytic cracking catalyst that contains hamartite and aluminum oxide, performance with preventing from heavy metal, wherein hamartite is a kind ofly usually to deposit the Rare-earth Fluoro-carbonate Minerals of getting off, the rough rare earth element (in oxide compound) that generally contains 65-80% with zinc; The disclosed catalyzer of US5324416 adopts the carbonate of hamartite or barium to capture component as metal, adopts simultaneously to contain the trapping agent of the magnesium of spinel structure as oxysulfide; The US4900428 disclosed method is with rare-earth precipitation or is impregnated into and plays anti-vanadium effect on the catalyzer; CN86107531A and CN86107598A disclose with RE (OH) ₃Rare earth introducing method for precursor; It is the semi-synthetic Hydrocarban coversion catalysts of the silica sol binder of 0.1-20% that CN1417297A discloses a kind of rare earth salts (in REO) that contains, this catalyzer utilizes rare earth-activated silicon oxide, thereby improve its heavy oil cracking activity and preventing from heavy metal pollution ability, reduce olefins in FCC gasoline and sulphur content.Mostly the above patent documentation is by becoming in the glue process at catalyzer or adding one or more components that play anti-vanadium effect after the moulding and improve the anti-vanadium performance of catalyzer.

In recent years, the composition restriction that environmental regulation is formed vehicle fuel is strict day by day, and " the motor spirit objectionable impurities control criterion " as China national Environmental Protection Administration formulation in 1999 requires content of olefin in gasoline＜35v%.In China, surpass 75% blend component in the gasoline product and derive from catalytic cracking unit, it is increasing to make that catalytic cracking unit faces the pressure that product property adjusts.

In order to reduce catalytic cracking gasoline olefine content, aspect catalyzer, its key factor is to improve the activity of catalytic cracking poiser, increases the hydrogen transference ability of catalyzer, with the alkene in the saturated gasoline, but keep good coke selectivity (He, MY, Catal.Today simultaneously, 73 (1-2), 49-55,2002), therefore require catalyzer that high hydro-thermal activity stability is arranged.

The REY molecular sieve that the NaY molecular sieve makes after rare earth exchanged is one of main active component of cracking catalyst.It has been generally acknowledged that, must have in the REY molecular sieve sufficiently high content of rare earth be the prerequisite of molecular sieve with Gao Re and hydrothermal stability (USP3140249, USP3140250, USP3140251, USP3140252, USP3140253).REY molecular sieve middle-weight rare earths ion migration also forms the multinuclear cationic structural that contains oxo bridge in the sodalite cage, increased the stability of acid site under the high-temperature water thermal environment of molecular sieve, improve the cracking activity and the activity stability of molecular sieve catalyst, thereby improved the heavy oil conversion activity and the selectivity of catalyzer.But when the aqueous solution of NaY molecular sieve and rare-earth salts carried out ion-exchange at normal temperatures and pressures, the hydrated rare-earth ion of about 0.4 nanometer of diameter was difficult to enter the sodalite cage by Y zeolite six-ring window (diameter 0.26 nanometer).Therefore, in REY molecular sieve preparation process, must remove and be centered around rare earth ion hydration layer on every side by roasting, make rare earth ion can enter the sodalite cage, simultaneously the sodium ion in these cages also comes out in the supercage by means of the roasting process migration, is further ion-exchange create conditions (USP3402996).For promoting that rare earth ion migrates in the sodalite cage, adopt the method for high-temperature roasting usually, but too high maturing temperature not only requires to the material of roasting apparatus high, and the rare earth ion that has been in the sodalite cage has the trend (Zeolites that returns big cage, 6 (4), 235,1986).

In order further to improve the catalytic performance of REY zeolite, relevant document has proposed a lot of method of modifying.

Disclose among the CN1449306 and had molecular sieve catalyst that strengthens lewis acidity and preparation method thereof.Effectively added the organometallic compound that promotes dehydrogenation, increases lewis acidity in this catalyst molecule sieve, the preferred aluminium acetylacetonate of this compound is in the non-skeleton part of molecular sieve, does not influence the zeolite structure cell and shrinks, but increase active.

USP5037531 discloses a kind of catalytic cracking catalyst, and this catalyzer contains the framework dealumination y-type zeolite composition that adopts aluminium exchange and rare earth exchanged, has good gasoline selective.

CN1353086A discloses a kind of preparation method of Y zeolite of phosphorous and rare earth, and the gained Y zeolite can significantly reduce the olefin(e) centent of FCC gasoline, can keep good coke selectivity simultaneously.Described method comprises earlier mixes exchange and hydrothermal calcine with ammonium ion and rare earth ion with the NaY molecular sieve, then with 0.2～10 weight % on itself and the phosphorus compound reaction bonded (with P ₂O ₅Meter) phosphorus carries out hydrothermal calcine again.

CN1330981A discloses a kind of P-contained Y-zeolite and preparation method thereof.Said P-contained Y-zeolite contains phosphorus, also contains a kind of silicon components and rare earth component, and described silicon components is to get on the method load of silicon compound solution dipping zeolite, with SiO ₂Meter, the content of described silicon components are the heavy % of 1-15, with P ₂O ₅Meter, the content of described phosphorus component are the heavy % of 0.1-15, and in rare earth oxide, described rare earth components contents is the heavy % of 0.2-15.This molecular sieve is that Y zeolite and the solution siliceous, phosphorus that will contain rare earth soak altogether, and the oven dry back obtains at 550-850 ℃ of hydrothermal calcine.This P-contained Y-zeolite is higher through hydrothermal treatment consists post crystallization degree, and better catalytic performance is arranged, and the cracking catalyst that contains this P-contained Y-zeolite have stronger heavy oil conversion performance and better product distribute.

CN1325940A discloses a kind of phosphorated hydrocarbon cracking catalyzer and preparation.This catalyzer is by two kinds of aluminum oxide of the clay of the Y zeolite of the heavy % of 10-60 or Y zeolite and MFI structure molecular screen and/or beta-molecular sieve, the heavy % of 0-75, the heavy % of 10-60, with P ₂O ₅The phosphorus of the heavy % of the 0.1-7.0 of meter and with RE ₂O ₃The rare earth of the heavy % of the 0-20 of meter is formed.This catalyzer is with the molecular sieve after handling through solution containing phosphate, with or does not mix with the molecular sieve of handling without phosphorus solution, mix with clay and double aluminium binder again, in 500 ℃ of roastings or spraying drying after the solution containing phosphate processing obtain.This catalyzer can be reduced to olefin(e) centent in the product gasoline fraction 20～26 heavy %.

CN1317547A discloses a kind of FCC Catalysts and its preparation method that reduces content of olefin in gasoline.This catalyzer is made up of zeolite type active ingredient, amorphous silicon aluminum oxide and kaolin, wherein active ingredient is made up of 0.5-5% (accounting for the weight percent of FCC catalyzer, down together) ZSM-5,0.5-15% rare earth exchanged Y zeolite, 20-40% phosphorus and the composite modified overstable gamma zeolite of rare earth.The composite modified overstable gamma zeolite of phosphorus and rare earth is to mix exchange by the NaY zeolite through rare earth and ammonium salt, after handling through hydrothermal calcine, with the phosphorus compound reaction, carries out that calcination process for the second time obtains again, wherein, and RE ₂O ₃The weight ratio of/Y zeolite is 0.02-0.18, the weight ratio of ammonium salt/Y zeolite is 0.1-1.0, the weight ratio of P/Y zeolite is 0.003-0.05, maturing temperature is 250-750 ℃, water vapor condition 5-100%, time 0.2-3.5 hour, content of rare earth accounted for 2-12% on the gained zeolite, lattice constant is 24.45-24.46 , and phosphorus content accounts for 0.2-3% (in P).This catalyzer is compared with conventional catalyst, is guaranteeing obviously to reduce the olefin(e) centent of gasoline under the prerequisite that other products distribute and gasoline octane rating is constant substantially.

CN1284403A discloses a kind of rare earth exchanged Y zeolite and preparation method thereof.The relative crystallinity of this zeolite is at 65-85%, and the percentage ratio that the second hole volume accounts for total pore volume is 20-80%.Its preparation method is with Na ₂O content is that the rare earth exchanged Y zeolite of the heavy % of 2.5-8 is dry then with a kind of siliceous solution impregnation, make said rare earth exchanged Y zeolite contain 1-15 heavily the silicon of the dipping of % (with SiO ₂Meter), the rare earth exchanged Y zeolite that then gained is flooded silicon in water vapour atmosphere in 500-850 ℃ of hydrothermal calcine 0.5-30 hour.This rare earth exchanged Y zeolite has higher heavy oil conversion performance, and residual oil raw material is mixed in suitable processing.

CN1217231A discloses a kind of phosphorous faujusite hydrocarbon cracking catalyzer and preparation method thereof.This catalyzer contains the heavy % of heavy %, clay 0-75 of heavy %, al binder (in aluminum oxide) 10-60 of heavy %, rare earth oxide 0.1-40 of faujusite 10-60 heavy %, phosphorus 0.01-1.5, and described al binder is respectively from pseudo-boehmite and aluminium colloidal sol.Described phosphorous faujusite be with faujusite and P contained compound aqueous solution evenly after, left standstill 0-8 hour, drying prepares more than 0.5 hour in 450-600 ℃ of roasting.

CN1053808A discloses a kind of preparation method of rare-earth Y molecular sieve, is NaY molecular sieve and rare earth ion are carried out the primary ions exchange in the aqueous solution after, and roasting is 1～3 hour in 450～600 ℃, 100% water vapor.This method has been simplified preparation flow, has reduced rare earth consumption and production cost, and the molecular sieve of this method preparation can be few by anticommutative rare earth content when further carrying out the ammonium exchange, has higher hydro-thermal structural stability and Geng Gao cracking activity stability.

The said REY molecular sieve of above document obtains with conventional rare earth ionic liquid phase exchange exchange, and the rare earth utilization ratio is low.

CN1436728A discloses a kind of preparation method of hyperastable Y-type RE molecular sieve, be to be raw material with NaY type molecular sieve, contain oxalic acid or oxalate and composition thereof in the chemical dealuminization complexing agent, introduce rare earth ion in the chemical dealuminization reaction later stage simultaneously, form rare-earth precipitation, pass through hydrothermal treatment consists again, can realize the purpose of super stabilizing and introducing rare earth ion and independent phase oxidation rare earth.Compare with conventional REY, REHY or REUSY, this preparation of molecular sieve is simple, rare earth utilization ratio height has simultaneously that aluminium is evenly distributed, characteristics such as secondary pore prosperity, good hydrothermal stability, active height, anti-pollution of vanadium ability are strong, is applicable to the preparation catalyst for heavy oil catalytic cracking.

CN8610753 1A and CN86107598A disclose and have contained molecular sieve of rare earth oxide and preparation method thereof.The rare earth of this molecular sieve is all with RE ₂O ₃Or RE (OH) ₃State exists, and the exchangeable cation position is H ⁺, NH ₄ ⁺Or Na ⁺Occupy.The cracking catalyst of this molecular sieve preparation can effectively reduce hydrogen transfer reactions, significantly weakens the structure cell shrinkage phenomenon in heat and hydrothermal aging process, has the performance of anti-sodium and heavy metal contamination.

Above patent documentation is by the mode of precipitating rare earth, though improved the rare earth utilization ratio, it is little that the molecular sieve super stabilizing is handled the back lattice constant.

Corma A, Fornes V, Kolodziejski, et al.Orthophosphoric acid interactions withultrastable zeolite Y:infrared and NMR studies.J.Catal., 1994,145:27-36. and Vistad  .B., Hansen E.W., Akporiaye D.E., et al Multinuclear NMR Analysis ofSAPO-34 Gels in the Presence and Absence of HF:The Initial Gel.J.Phys.Chem.A 1999,103, bibliographical informations such as 2540-2552 adopt MAS NMR characterized by techniques and inquire into chemical environment and the state of phosphorus in molecular sieve, the gained result shows that the difference of the residing chemical environment of phosphorus is very big for the chemical property and the catalytic performance influence of molecular sieve.

Summary of the invention

The contriver is surprised to find that by a large amount of compound experiments and phenetic analysis, a kind of Y zeolite of phosphorous and rare earth, have under the situation of identical content of rare earth and phosphorus content with said phosphorous and Y zeolite rare earth of prior art (as CN1353086A), its ³¹In the P MAS NMR spectrum, chemical shift be-14 ± 2ppm with-23 ± 2ppm resonance signal and ²⁷In the Al MAS NMR spectrum, the feature of chemical shift 0 ± 2ppm resonance signal but is different from prior art.

Therefore, one of purpose of the present invention provides a kind of Y zeolite that is different from a kind of phosphorous and rare earth of prior art feature, two of purpose provides the preparation method of this molecular sieve, and three of purpose provides the application as active component in catalyst for heavy oil catalytic cracking of this molecular sieve.

The Y zeolite of phosphorous and rare earth provided by the invention is characterized in that in this molecular sieve, accounts for the heavy % of 12.0-16.0 in the rare earth oxide content of rare earth, with P ₂O ₅The meter phosphorus content accounts for the heavy % of 0.5-7.0, this molecular sieve ³¹In the P MAS NMR spectrum, the percentage ratio that chemical shift accounts for total peak area for the peak area of-14 ± 2ppm and-23 ± 2ppm resonance signal is greater than 85%, molecular sieve ²⁷In the Al MAS NMR spectrum, the peak area of chemical shift 0 ± 2ppm resonance signal accounts for the percentage ratio of total peak area greater than 20%.

The present invention also provides the preparation method of the Y zeolite of above-mentioned phosphorous and rare earth, be characterised in that with the NaY molecular sieve with carry out hydrothermal treatment consists again after the aqueous solution of the aqueous solution that contains rare earth ion and phosphorus aluminium properties-correcting agent contacts, contact with ammonium salt aqueous solution at last, wherein said phosphorus aluminium properties-correcting agent is to be 0.2-2.0 with containing aluminum ion solution or colloid and the P contained compound aqueous solution at the phosphorus al mole ratio, slurry pH value is 4-7, and temperature is to contact under the 0-100 ℃ of condition to obtain.

The Y zeolite of phosphorous and rare earth provided by the invention, be in the molecular sieve modified process of NaY, to introduce phosphorus aluminium properties-correcting agent, phosphorus aluminium properties-correcting agent and rare-earth action partly precipitated are on Y molecular sieve, the ammonium exchange obtains after experiencing hydrothermal calcine then, this preparation method is simple and easy to do, the preparation flow of molecular sieve is short, saves production cost.When this molecular sieve contacts with barium oxide, has good hydrothermal stability.For example, after 800 ℃ of experience, 100% water vapour, 17 hours hydrothermal treatment consists, has higher index little alive.

The Y zeolite of phosphorous and rare earth provided by the invention can be used as the active ingredient of catalytic cracking catalyst, is applicable to the high heavy oil catalytic cracking process of processing content of vanadium, and the cracking reaction activity is good.

Description of drawings

Fig. 1～Fig. 4 the invention provides molecular sieve-4 A-1～A-4's ³¹P MAS NMR spectrogram.

Fig. 5 is Comparative Examples 1 molecular sieve DB1's ³¹P MAS NMR spectrogram.

Fig. 6～Fig. 9 the invention provides molecular sieve-4 A-1～A-4's ²⁷Al MAS NMR spectrogram.

Figure 10, Figure 11 are respectively contrast molecular sieve DB1, the DB2 of Comparative Examples 1,2 preparation ²⁷Al MASNMR spectrogram.

Embodiment

The Y zeolite of phosphorous and rare earth provided by the invention, the heavy % of the preferred 1.0-3.0 of said content of rare earth, this molecular sieve ³¹In the P MAS NMR spectrum, chemical shift is preferably greater than 90% for the percentage ratio that the peak area of-14 ± 2ppm and-23 ± 2ppm resonance signal accounts for total peak area, molecular sieve ²⁷In the Al MAS NMR spectrum, the peak area of chemical shift 0 ± 2ppm resonance signal accounts for the percentage ratio of total peak area greater than 20%.

The Y zeolite of phosphorous and rare earth provided by the invention, ³¹In the P MAS NMR spectrum ,-14 ± 2ppm resonance signal characterizes the characteristic peak of unbodied aluminum phosphate, it has been generally acknowledged that the resonance signal at this place is associated with the short chain poly-phosphate; What-23 ± 2ppm resonance signal characterized also is the characteristic peak of amorphous phosphoric acid aluminium, it has been generally acknowledged that the resonance signal and the acid sites direct correlation at this place.

The Y zeolite of phosphorous and rare earth provided by the invention, its ²⁷In the Al MAS NMR spectrum, the resonance signal at chemical shift 0 ± 2ppm place characterizes hexa-coordinate non-framework aluminum species.

The Y zeolite of phosphorous and rare earth provided by the invention, rare earth on the molecular sieve exists with two kinds of forms, the part rare earth enters in the little cage of molecular sieve with ionic condition, another part rare earth is scattered in the molecular sieve surface mutually with rare earth oxide, advantage is when this molecular sieve is contacted with barium oxide, has good hydrothermal stability.

The Y zeolite of phosphorous and rare earth provided by the invention, lattice constant is preferably 24.55-24.70 .

Preparation method provided by the invention more particularly comprises the steps:

(1) the NaY molecular sieve with silica alumina ratio 〉=4.5 contacts with the aqueous solution of the aqueous solution that contains rare earth ion with phosphorus aluminium properties-correcting agent, wherein, is 0.12-0.30 in rare earth oxide, rare earth ion with the ratio of molecular sieve solid weight, is 0.01-0.1 in Vanadium Pentoxide in FLAKES, phosphorus aluminium properties-correcting agent with the ratio of molecular sieve solid weight, liquid-solid ratio is 4-20, and temperature of reaction is 60-95 ℃, and the reaction times is 10-120min, after filtration, get the filter cake product after the drip washing; Said phosphorus aluminium properties-correcting agent is to be 0.2-2.0 with containing aluminum ion solution or colloid and the P contained compound aqueous solution at the phosphorus al mole ratio, and slurry pH value is 4-7, and temperature is that contact obtains under the 0-100 ℃ of condition;

(2) be to handle 0.5-4h under the 10-100 volume % water vapour atmosphere to step (1) gained filter cake product at 450-800 ℃, ambiance;

(3) step (2) products therefrom is contacted with ammonium salt aqueous solution, wherein ammonium salt is 0.1-1.0 with the ratio of molecular sieve solid weight, and liquid-solid ratio is 4-20, and temperature of reaction is 60-95 ℃, filters then, washs.

Among the preparation method provided by the invention, the preferred 0.13-0.20 of ratio of the said rare earth ion of step (1) (in rare earth oxide) and molecular sieve solid weight, the preferred 0.1-0.05 of ratio of phosphorus aluminium properties-correcting agent (in Vanadium Pentoxide in FLAKES) and molecular sieve solid weight, the preferred 8-15 of liquid-solid ratio, the preferred 70-80 of temperature of reaction ℃.

Said rare-earth ion solution is one or more muriate or the aqueous solution of nitrate, the wherein rare earths salt of preferred rich lanthanum that is selected from lanthanum, cerium, praseodymium and neodymium ion in the step (1); One of said aqueous solution that contains muriate, vitriol and nitrate that aluminum ion solution is selected from aluminium or sodium aluminate solution, the said aluminum ion colloid that contains is selected from aluminium colloidal sol or through the acidifying pseudo-boehmite, wherein is preferably aluminium colloidal sol.

The said P contained compound of step (1) is selected from one or more of ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, phosphoric acid, aluminum phosphate and sodium phosphate.

The said phosphorus aluminium of step (1) properties-correcting agent is to contact with the aqueous solution of P contained compound and obtain containing the aluminum ions aqueous solution or colloid, wherein, the preferred 0.3-1.0 of phosphorus al mole ratio, the preferred 5-6 of slurry pH value, the preferred 10-40 of temperature of reaction ℃, preferred 2-6 of reaction times hour.

Among the preparation method provided by the invention, step (2) is that step (1) gained filter cake product is carried out hydrothermal treatment consists, and optimum condition is temperature 550-700 ℃ and handles 1.5-3h down that ambiance is the water vapour atmosphere of 100 volume %.

Among the preparation method provided by the invention, step (3) is that step (2) products obtained therefrom is contacted with the aqueous solution that contains ammonium ion, and wherein ammonium salt is preferred 0.3-0.6 with the ratio of molecular sieve solid weight, the preferred 8-15 of liquid-solid ratio, the preferred 80-90 of temperature of reaction ℃, preferred 40-90min of reaction times.

Said ammonium salt is selected from one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, bicarbonate of ammonia, ammonium oxalate and volatile salt in the step (3).

By the following examples the present invention is further described, but content not thereby limiting the invention.

In following embodiment and Comparative Examples in the materialization data of gained sample, listed P ₂O ₅, RE ₂O ₃And Na ₂O content is by x-ray fluorescence spectrometry; Lattice constant by X-ray diffraction method (XRD) adopt the RIPP145-90 standard method (see " petrochemical complex analytical procedure (RIPP test method) ", volumes such as Yang Cuiding, Science Press, nineteen ninety version) measure.

NMR analyzes the nuclear magnetic resonance analyser with Varian Unityinova 300M, and experimental temperature is a room temperature, ²⁷Al MASNMR spectrogram condition determination frequency 78.2MHz, pulse width 2.0s, relaxation time 0.1s calibrates with aluminum nitrate; ³¹P MAS NMR spectrogram condition determination frequency 121.5MHz, pulse width 4.0s, relaxation time 3s, liquid phosphoric acid calibration with 85%.Because therefore solid sample nucleus magnetic resonance peak overlapping adopts gauss of distribution function that the nuclear-magnetism spectrum is carried out spectrum unscrambling, used software is the Nuts analysis software of Varian company.

Embodiment 1

Under the room temperature, with (NH ₄) ₃PO ₄(chemical pure, Red Star chemical plant, Beijing produces, down together) 55 grams join 800 gram water dissolution, slowly join the gram of 240 in mechanical stirring aluminium colloidal sol (Al ₂O ₃Account for 22%, the Shandong catalyst plant is produced, down with) in, continue to stir 2 hours, obtain the phosphorus al mole ratio and be 0.36 phosphorus aluminium properties-correcting agent 1.

Get 1000 gram NaY molecular sieves (dry basis, the Shandong catalyst plant is produced, down together), after 8 liters of deionized waters making beating, adding concentration is the RECl of 231g/l ₃(the Shandong catalyst plant provides solution, wherein La ₂O ₃Account for 52.5 heavy %, CeO ₂Account for 46.5 heavy %, Pr ₂O ₅Account for 0.6 heavy %, Nd ₂O ₃Account for 0.4 heavy %, down with) 576 milliliters, in 85 ℃ of exchanges 0.5 hour, add above-mentioned phosphorus aluminium properties-correcting agent 1 again, constant temperature stirred after 0.5 hour, filtered drip washing, with filter cake roasting 2 hours in 600 ℃, 100% steam atmosphere, obtained molecular sieve dry powder then.Get this molecular sieve dry powder 1000 grams (dry basis), after 8 liters of deionized water making beating, add ammonium chloride (chemical pure, Tianjin is stepped on peaking chemical reagent work and is produced, down together) 500 grams, in 85 ℃ of exchanges 0.5 hour, filter drip washing, the filter cake oven dry promptly gets molecular sieve of the present invention, is designated as A-1.The physical data of A-1 sample reaches ²⁷AlMAS NMR and ³¹List in the table 1 peak position in the P MAS NMR spectrogram, its ³¹P MAS NMR spectrum is seen shown in Figure 1, ²⁷Al MAS NMR spectrum is seen Fig. 6.

Embodiment 2

Under the room temperature, with (NH ₄) ₃PO ₄82 grams join 800 gram water dissolution, slowly join in the gram of 240 in the mechanical stirring aluminium colloidal sol, continue to stir 16 hours.The phosphorus al mole ratio is 0.53 phosphorus aluminium properties-correcting agent 2.

Get 1000 gram NaY molecular sieves, after 10 liters of deionized water making beating, adding concentration is the RECl of 157g/l ₃1875 milliliters of solution in 90 ℃ of exchanges 1 hour, add above-mentioned phosphorus aluminium properties-correcting agent 2 again, and constant temperature stirred after 0.25 hour, filtered drip washing, with filter cake roasting 2 hours in 580 ℃, 100% steam atmosphere, obtain molecular sieve dry powder then.Get this molecular sieve dry powder 1000 grams (dry basis), after 10 liters of deionized water making beating, add ammonium sulfate solids (analytical pure, Beijing Yili Fine Chemicals Co., Ltd. produces, down together) 800 grams, in 90 ℃ of exchanges 1 hour, filter drip washing, the filter cake oven dry promptly gets molecular sieve of the present invention, is designated as A-2.The physical data of sample reaches ²⁷Al MAS NMR and ³¹List in the table 1 peak position in the P MAS NMR spectrogram, its ³¹P MAS NMR composes as shown in Figure 2, ²⁷Al MAS NMR spectrum as shown in Figure 7.

Embodiment 3

Under the room temperature, with H ₃PO ₄(85%, analytical pure, Beijing Chemical Plant) 21 grams join 400 gram water dissolution, slowly join in the gram of 120 in the mechanical stirring aluminium colloidal sol, continue to stir 1 hour, and adding 25% ammoniacal liquor (analytical pure, the Beijing Chemical Plant produces) adjust pH is 5.6, continues to stir 2 hours.Get phosphorus aluminium properties-correcting agent 3, the phosphorus al mole ratio is 0.35.

Get 1000 gram NaY molecular sieves (dry basis, the Shandong catalyst plant is produced), after 10 liters of deionized water making beating, adding concentration is the RECl of 231g/l ₃576 milliliters of solution in 90 ℃ of exchanges 1 hour, add above-mentioned phosphorus aluminium properties-correcting agent 3 again, and constant temperature stirred after 1 hour, filtered drip washing, with filter cake roasting 2 hours in 600 ℃, 100% steam atmosphere, obtain molecular sieve dry powder then.Get this molecular sieve dry powder 1000 grams (dry basis), after 10 liters of deionized water making beating, add chloride solid 500 grams,, filter drip washing, place the baking oven oven dry promptly to get molecular sieve of the present invention, be designated as A-3 in 75 ℃ of exchanges 1 hour.The physical data of sample reaches ²⁷AlMAS NMR and ³¹List in the table 1 peak position in the P MAS NMR spectrogram, its ³¹P MAS NMR composes as shown in Figure 3, ²⁷Al MAS NMR spectrum as shown in Figure 8.

Embodiment 4

Under the room temperature, with (NH ₄) ₃PO ₄82 grams join 800 gram water dissolution, slowly join in the aqueous solution of dissolving 18 hydrazine aluminum sulfates (analytical pure, Tianjin chemical reagent three factories) 376 grams in the mechanical stirring, continue to stir 3 hours.Get phosphorus aluminium properties-correcting agent 4, the phosphorus al mole ratio is 0.36.

Get 1000 gram NaY molecular sieves, after 10 liters of deionized water making beating, adding concentration is the RECl of 231g/l ₃576 milliliters of solution in 90 ℃ of exchanges 1 hour, are gone into above-mentioned phosphorus aluminium properties-correcting agent 4 again, and constant temperature stirred after 0.25 hour, and filtration drip washing with filter cake roasting 2 hours in 600 ℃, 100% steam atmosphere, obtains molecular sieve dry powder then.Get this molecular sieve dry powder 1000 grams (dry basis), after 10 liters of deionized water making beating, add ammonium nitrate (analytical pure, Beijing Yili Fine Chemicals Co., Ltd. produces, down together) 500 grams, in 75 ℃ of exchanges 1 hour, filter drip washing, the filter cake oven dry promptly gets molecular sieve of the present invention, is designated as A-4.The physical data of sample reaches ²⁷Al MAS NMR and ³¹It is listed in the table 1 in the peak position in the P MAS NMR spectrogram ³¹P MAS NMR composes as shown in Figure 4, ²⁷Al MAS NMR spectrum as shown in Figure 9.

Comparative Examples 1

The explanation of this Comparative Examples prepares the process of the Y zeolite of phosphorous and rare earth according to CN1353086A.

Get 1000 gram NaY molecular sieves, after 10 liters of deionized water making beating, adding concentration is the RECl of 100g/l ₃2000 milliliters of solution in 90 ℃ of exchanges 1 hour, filter drip washing, with filter cake roasting 2 hours in 570 ℃, 100% steam atmosphere, obtain the REY molecular sieve then.With 145 ml deionized water dissolving, 4.4 gram (NH ₄) ₃PO ₄, dipping 100 gram REY molecular sieves (in butt).Put into muffle furnace 600 ℃ of following roastings 1 hour after the sample oven dry that dipping is good, obtain phosphorous and contrast Y zeolite rare earth, be designated as DB1.The physical data of sample reaches ²⁷Al MAS NMR and ³¹List in the table 1 peak position in the P MAS NMR spectrogram, its ³¹P MAS NMR composes as shown in Figure 5, ²⁷Al MAS NMR spectrum as shown in figure 10.

Comparative Examples 2

The explanation of this Comparative Examples prepares the process of rare-earth Y molecular sieve according to CN1053808A.

Get 1000 gram NaY molecular sieves, after 10 liters of deionized water making beating, adding concentration is the RECl of 157g/l ₃1250 milliliters of solution in 85 ℃ of exchanges 1 hour, filter drip washing, with dried filter cake roasting 2 hours in 600 ℃, 100% steam atmosphere, obtain molecular sieve dry powder then.Promptly get the REY molecular sieve among the CN1053808A, be designated as DB2.The physical data of sample reaches ²⁷List in the table 1 peak position in the Al MAS NMR spectrogram, its ²⁷Al MAS NMR spectrum as shown in figure 11.

Table 1

The molecular sieve numbering	A-1	A-2	A-3	A-4	DB1	DB2
							RE 2O 3, heavy %	14.1	15.4	12.9	14.4	14.6	13.3
P 2O 5, heavy %	1.3	2.5	1.1	2.3	2.1	0
							Na 2O, heavy %	1.0	1.1	1.4	1.3	3.8	4.2
Lattice constant ()	24.64	24.65	24.64	24.63	24.64	24.66
							31Position/peak area ratio appears in the PNMR peak	-12.628/ 37.43％	-14.411/ 25.57％	-22.774 100％	-15.664/ 83.63％	-13.46/ 30.83％
-20.721/ 62.56％	-24.95/ 74.43％		-23.74/ 6.85％	-23.199/ 48.06％
					-28.34/ 9.52％	-29.17/ 21.1％
			27Position/peak area ratio appears in Al NMR peak	58.092/ 35.15％				58.726/ 41.80％	59.493/ 25.10％	58.517/ 39.74％	59.657/ 33.85％	59.395/ 36.96％
49.475/ 17.2％	49.794/ 21.19％	53.342/ 24.43％			49.871/ 33.39％	53.366/ 34.68％	52.164 32.79％，
				38.271/ 19.49％				35.53/ 16.35％	32.781/ 13.58％	30.676/ 6.13％	33.662/ 20.12％	30.555/ 19.21％
-1.72/ 28.15％	-0.894 20.65％	1.777/ 36.89％			-0.818/ 20.74％	0.989/ 11.35％	1.24/ 11.04％

Embodiment 5

Present embodiment illustrates that the hydrothermal stability of the contrast molecular sieve of molecular sieve provided by the invention and prior art compares.

With each 100 gram (butt) of molecular sieve-4 A-1, A-2, A-3, A-4, DB1 and DB2 of embodiment 1-4 preparation, carry out ion-exchange repeatedly respectively, make remaining Na on the molecular sieve with ammonium chloride ₂O content is lower than 0.5 heavy %, and the ion-exchange condition is molecular sieve: NH ₄Cl: deionized water=1: 1: 15 (weight ratio), 90 ℃ the exchange 1 hour, the filter cake behind the filtration washing is in 120 ℃ of oven dry.Gained molecular sieve powder compressing tablet, be ground into 20-40 order particle, in on the fixed bed hydrothermal treatment device through 100% steam, 800 ℃ of conditions under after aging 17 hours, go up in the automatic micro-activity instrument for evaluating of catalytic cracking (Beijing information automation company product) and to measure little index alive.

The mat activity test method adopt RIPP 92-90 method (see " petrochemical complex analytical procedure (RIPP test method) ", volumes such as Yang Cuiding, Science Press, nineteen ninety version) measure.Except that the sieve particle of hydrothermal aging after 17 hours loading amount in reactor was 2 grams, other test methods were all identical with RIPP 92-90 method.Little index alive (MA) is listed in table 2.

Table 2

The molecular sieve numbering	A-1	A-2	A-3	A-4	DB1	DB2
							Lattice constant ()	24.34	24.35	24.34	24.36	24.30	24.34
MA	63	64	62	65	59	58

From table 2 data as seen, the molecular sieve in the example of the present invention has kept higher balance structure cell and the activity of Geng Gao after experience severe condition hydrothermal treatment consists, the good hydrothermal stability of molecular sieve is described.

Embodiment 6

Present embodiment illustrates the hydrothermal stability comparative data of molecular sieve under pollution of vanadium of molecular sieve provided by the invention and prior art.

Contain the vanadium granules preparation: with concentration is that 157g/l is (with RE ₂O ₃Meter) RECl ₃1250 milliliters of solution add 25% ammoniacal liquor, and adjusting slurry pH value is 8.5, add ammonium meta-vanadate (analytical pure, the Beijing Chemical Plant produces) 21 grams, pulled an oar 1 hour, place 120 ℃ of oven dry of air dry oven 16 hours, gained particle grinding powder in mortar is called the vanadium particle.

The molecular sieve powder and the vanadium particle that sodium oxide among the embodiment 5 are lower than 0.5 heavy % are even by weight 95%: 5% mechanically mixing, compressing tablet, be ground into 20-40 order particle, in on the fixed bed hydrothermal treatment device through 100% steam, 800 ℃ of conditions under after aging 17 hours, on the automatic micro-activity instrument for evaluating of catalytic cracking, measure little index alive.

Except that molecular sieve and vanadium particle composite grain in reactor the loading amount of hydrothermal aging after 17 hours is that other test methods are all identical with RIPP 92-90 method 2 grams.Little index alive is listed in table 3.

Table 3

The molecular sieve numbering	A-1	A-2	A-3	A-4	DB1	DB2
							Lattice constant ()	24.31	24.32	24.30	24.36	24.29	24.29
MA	34	36	36	40	26	27

The high oxidation state vanadium is under the high-temperature water heat condition, and transport property is strong, to molecular sieve structure and active destruction seriously.Data as seen from table 3, molecular sieve provided by the invention with contain the vanadium particle and closely contact down, after experience severe condition hydrothermal treatment consists, (Comparative Examples) molecular sieve compared to existing technology, kept more suitable balance structure cell, and show higher index little alive, show that the anti-vanadium ability of molecular sieve of the present invention is strong.

In heavy oil catalytic cracking process, the product selectivity that balance structure cell that the Y molecular sieve maintenance is suitable and high reactivity can provide strong heavy oil cracking ability to become reconciled.

Claims (15)

1. the Y zeolite of a phosphorous and rare earth is characterized in that this molecular sieve accounts for the heavy % of 12.0-16.0 in the rare earth oxide content of rare earth, with P ₂O ₅The meter phosphorus content accounts for the heavy % of 0.5-7.0, this molecular sieve ³¹In the PMASNMR spectrum, the percentage ratio that chemical shift accounts for total peak area for the peak area of-14 ± 2ppm and-23 ± 2ppm resonance signal is greater than 85%, molecular sieve ²⁷In the AlMASNMR spectrum, the peak area of chemical shift 0 ± 2ppm resonance signal accounts for the percentage ratio of total peak area greater than 20%.

2. according to the molecular sieve of claim 1, it is characterized in that this molecular sieve is with P ₂O ₅The meter phosphorus content accounts for the heavy % of 1.0-3.0, this molecular sieve ³¹In the PMASNMR spectrum, chemical shift accounts for the percentage ratio of total peak area greater than 90% for the peak area of-14 ± 2ppm and-23 ± 2ppm resonance signal.

3. according to the molecular sieve of claim 1, the lattice constant that it is characterized in that this molecular sieve is 24.55-24.70 .

4. the preparation method of the Y zeolite of the phosphorous and rare earth of one of claim 1-3, be characterised in that with the NaY molecular sieve with carry out hydrothermal treatment consists again after the aqueous solution of the aqueous solution that contains rare earth ion and phosphorus aluminium properties-correcting agent contacts, contact with ammonium salt aqueous solution at last, wherein said phosphorus aluminium properties-correcting agent is to be 0.2-2.0 with containing aluminum ion solution or colloid and the P contained compound aqueous solution at the phosphorus al mole ratio, slurry pH value is 4-7, and temperature is to contact under the 0-100 ℃ of condition to obtain.

5. according to the method for claim 4, it is characterized in that said phosphorus aluminium properties-correcting agent is is 0.3-1.0 with containing aluminum ion solution or colloid and the P contained compound aqueous solution at the phosphorus al mole ratio, slurry pH value is 5-6, temperature is to contact under the 10-40 ℃ of condition to obtain.

6. according to the method for claim 4 or 5, it is characterized in that one of said aqueous solution that contains muriate, vitriol and nitrate that aluminum ion solution is selected from aluminium or sodium aluminate solution, saidly contain that the aluminum ion colloid is selected from aluminium colloidal sol or through the acidifying pseudo-boehmite.

7. according to the method for claim 4 or 5, it is characterized in that the said aluminum ion colloid that contains is an aluminium colloidal sol.

8. according to the method for claim 4 or 5, it is characterized in that said P contained compound is selected from one or more in ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, phosphoric acid, aluminum phosphate and the sodium phosphate.

9. according to the method for claim 4, it is characterized in that this method comprises the steps:

(1) the NaY molecular sieve with silica alumina ratio 〉=4.5 contacts with the aqueous solution of the aqueous solution that contains rare earth ion with phosphorus aluminium properties-correcting agent, wherein, is 0.12-0.30 in rare earth oxide, rare earth ion with the ratio of molecular sieve solid weight, is 0.01-0.1 in Vanadium Pentoxide in FLAKES, phosphorus aluminium properties-correcting agent with the ratio of molecular sieve solid weight, liquid-solid ratio is 4-20, and temperature of reaction is 60-95 ℃, after the reaction times is 10-120min, filter, get the filter cake product after the drip washing;

(2) be to handle 0.5-4h under the 10-100 volume % water vapour atmosphere to step (1) gained filter cake product at 450-800 ℃, ambiance;

(3) step (2) products therefrom is contacted with ammonium salt aqueous solution, wherein ammonium salt is 0.1-1.0 with the ratio of molecular sieve solid weight, and liquid-solid ratio is 4-20, and temperature of reaction is 60-95 ℃, filters then, washs.

10. according to the method for claim 9, the said rare earth ion of step (1) is 0.13-0.20 with the ratio of molecular sieve solid weight, and phosphorus aluminium properties-correcting agent is 0.05-0.1 with the ratio of molecular sieve solid weight, and liquid-solid ratio is 8-15, and temperature of reaction is 70-80 ℃.

11. according to the method for claim 9, it is characterized in that the said aqueous solution that contains rare earth ion in the step (1) be comprise in lanthanum, cerium, praseodymium and the neodymium ion one or more muriate or the aqueous solution of nitrate.

12., it is characterized in that the said aqueous solution that contains rare earth ion is the rare earths salt of rich lanthanum according to the method for claim 9.

13., it is characterized in that step (2) is that step (1) gained filter cake product is handled under 550-700 ℃, 100 volume % water vapour atmospheres according to the method for claim 9.

14., it is characterized in that ammonium salt in the said step (3) is selected from one or more of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, bicarbonate of ammonia, ammonium oxalate and volatile salt according to the method for claim 9.

15. the Y zeolite of the phosphorous and rare earth of claim 1-3 as the active ingredient of catalytic cracking catalyst, is applied to process the high heavy oil of content of vanadium.

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