CN101088613A - Prepn process of REY molecular sieve - Google Patents
Prepn process of REY molecular sieve Download PDFInfo
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- CN101088613A CN101088613A CN 200610087535 CN200610087535A CN101088613A CN 101088613 A CN101088613 A CN 101088613A CN 200610087535 CN200610087535 CN 200610087535 CN 200610087535 A CN200610087535 A CN 200610087535A CN 101088613 A CN101088613 A CN 101088613A
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Abstract
The present invention discloses preparation process of REY molecular sieve, and features that REY molecular sieve is made to contact first with RE ion containing water solution or contact with RE ion containing water solution and Al ion containing solution or colloid, then with precipitant to precipitate partial RE onto the molecular sieve, and finally with ammonium salt aqua after being hydrothermal treated. The precipitant is water solution of soluble carbonate or alkaline water solution.
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve, more particularly, is a kind of preparation method who is used as the REY type molecular sieve of catalyst and cracking of hydrocarbon active component.
Background technology
Catalytic cracking process is important heavy oil lighting technology, and is one of main source of each oil plant 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 compound of green coke such as colloid and asphalitine in the residual oil, more contain than multi-metal (as nickel, vanadium etc.).In cracking reaction, metals such as nickel, vanadium are deposited on the catalyst, cause catalyst activity to reduce, vanadium particularly, the vanadium of high oxidation state animal migration under the high-temperature water thermal environment is strong, and the structure of molecules of active components sieve causes the irreversible inactivation of catalyst in the heavy damage catalyst.Thereby when meeting with pollution of vanadium, must constantly from catalytic cracking unit, unload agent and replenish new agent, make the catalyst consumption increase, operating cost significantly improves.For this reason, molecular sieve catalyst must improve the ability of preventing from heavy metal pollution.In recent years, it is more as the patent report that the vanadium trapping agent improves anti-pollution of vanadium to add rare earth in catalyst, as: US4988653 adopts and uses aluminium oxide and rare earth oxide as the vanadium trapping agent.EP89306806.4 discloses the catalytic cracking catalyst that contains bastnaesite and aluminium oxide, wherein bastnaesite is a kind ofly usually to deposit the Rare-earth Fluoro-carbonate Minerals of getting off with zinc, crude mineral contains the rare earth element (in oxide) of 65-80% usually, has the performance that improves the catalyst preventing from heavy metal.US5324416 adopts the carbonate of bastnaesite or barium to capture component as metal, adopts simultaneously to contain the trapping agent of the magnesium of spinel structure as oxysulfide.US4900428 is with rare-earth precipitation or be impregnated into and play anti-vanadium effect on the catalyst.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 catalyst utilizes rare earth-activated silica, thereby improves its heavy oil cracking activity and preventing from heavy metal pollution ability, reduces olefins in FCC gasoline and sulfur content.Mostly the above patent is to become in the glue process or add one or more components that play anti-vanadium effect after the moulding to improve the anti-vanadium performance of catalyst at catalyst.
Recently, the composition restriction that environmental regulation is formed vehicle fuel is strict day by day, and " the motor petrol harmful substance control criterion " as State Environmental Protection Administration's formulation in 1999 requires olefin(e) centent＜35v% in the gasoline.Surpass 75% blend component in China's gasoline product and derive from catalytic cracking unit, it is increasing to make that catalytic cracking unit faces the pressure that product property adjusts.The key that reduces catalytic cracking gasoline olefine content is to improve the activity of catalytic cracking poising agent, increases the hydrogen migration ability of catalyst, with the alkene in the saturated gasoline, but keep good coke selectivity (He, MY, Catal.Today simultaneously, 73 (1-2), 49-55,2002).This requires catalyst that high hydro-thermal activity stability is arranged.
The REY molecular sieve that makes after the rare earth exchanged is the high activity constituent element of catalytic cracking catalyst.REY molecular sieve middle rare earth ion is moved in the sodalite cage and is formed the multinuclear cationic structural that contains oxo bridge, 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 transformation activity and the selectivity of catalyst.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 molecular sieve hexatomic 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 sintering temperature not only requires height to the material of roasting apparatus, and the rare earth ion that has been in the sodalite cage has the trend (Zeolites, 6 (4), 235,1986) of returning big cage.On the other hand, it has been generally acknowledged that must have in the REY molecular sieve sufficiently high content of rare earth be the necessary condition of molecular sieve with Gao Re and hydrothermal stability (USP3140249, USP3140250, USP3140251, USP3140252, USP3140253).
For further improving the catalytic performance of REY zeolite, relevant patent documentation has proposed a lot of method of modifying.
CN1449306 discloses has molecular sieve catalyst that strengthens lewis acidity and preparation method thereof.Effectively added the organo-metallic compound that promotes dehydrogenation, increases lewis acidity in this catalytic component molecular sieve.This compound is in the non-skeleton part of molecular sieve, preferred aluminium acetylacetonate.These non-framework ingredients do not influence the zeolite structure cell and shrink, but increase active.
US5037531 discloses a kind of catalytic cracking catalyst, and this catalyst contains the framework dealumination Y zeolite component 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 this method comprises mixes exchange and hydrothermal calcine with ammonium ion and rare earth ion earlier 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.The inventive method gained Y zeolite can significantly reduce the olefin(e) centent of FCC gasoline, can keep good coke selectivity simultaneously.
CN1330981A discloses a kind of phosphorous Y zeolite and preparation method thereof.This phosphorous 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.The preparation method be contain the Y zeolite of rare earth and siliceous, phosphorus solution its soak, the oven dry back is at 550-850 ℃ of hydrothermal calcine.This P-contained zeolite is higher through hydrothermal treatment consists post crystallization degree, and better catalytic performance is arranged, and the Cracking catalyst that contains this phosphorous Y zeolite has stronger heavy oil conversion performance and better product distribution.
CN1325940A discloses a kind of phosphorous hydrocarbon cracking catalyzer and preparation.This catalyst is by two kinds of aluminium 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 catalyst 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 spray-drying after the solution containing phosphate processing obtain.This catalyst 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 catalyst is made up of zeolite type active component, amorphous silicon aluminum oxide and kaolin, wherein active component is made up of 0.5-5% (accounting for the percentage by weight of FCC catalyst, 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 Y zeolite of phosphorus and rare earth is to mix exchange by the NaY zeolite after handling through hydrothermal calcine through rare earth and ammonium salt, with the phosphorus compound reaction, carries out the calcination process second time then.Wherein, RE
2O
3The weight ratio of/Y zeolite is 0.02-0.18, and the weight ratio of ammonium salt/Y zeolite is 0.1-1.0, and the weight ratio of P/Y zeolite is 0.003-0.05, and sintering temperature is 250-750 ℃, water vapor condition 5-100%, time 0.2-3.5 hour.Content of rare earth accounts for 2-12% on the gained PREY zeolite, and lattice constant is 24.45-24.46 , and phosphorus content accounts for 0.2-3% (in P).Compare with conventional catalyst, guaranteeing obviously to reduce the olefin(e) centent of gasoline under the prerequisite that other products distribute and octane number is constant substantially.
CN1284403A discloses a kind of improved rare earth exchanged Y zeolite and preparation thereof.The relative crystallinity of this zeolite is at 65-85%, and the percentage that the second hole volume accounts for total pore volume is 20-80%.Its preparation method is 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 zeolite has higher heavy oil conversion performance, and residual oil raw material is mixed in suitable processing.
CN1217231A discloses a kind of phosphorous faujasite hydrocarbon cracking catalyzer and preparation method thereof.This catalyst contains the heavy % of heavy %, clay 0-75 of heavy %, al binder (in aluminium oxide) 10-60 of heavy %, rare earth oxide 0.1-40 of faujasite 10-60 heavy %, phosphorus 0.01-1.5, and described al binder is respectively from boehmite and aluminium colloidal sol.Described phosphorous faujasite be with faujasite and phosphorus-containing 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 vapour.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.
More than improve and adopt conventional rare earth ionic liquid phase exchange in the preparation of REY molecular sieve, rare earth utilization rate utilization rate 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 oxalates 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.The precipitating rare earth precursor that forms comprises rare earth oxalate.Compare with conventional REY, REHY or REUSY, this preparation of molecular sieve is simple, rare earth utilization rate 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.
CN86107531A 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 cations position is H
+, NH
4 +Or Na
+Occupy.The Cracking catalyst of this molecular sieve preparation can effectively reduce hydrogen transfer reaction, significantly weakens the structure cell shrinkage phenomenon in heat and hydrothermal aging process, has the performance of anti-sodium and heavy metal pollution.
Though above patent precipitating rare earth has improved the rare earth utilization rate, the super steady processing of molecular sieve back lattice constant is little, active low.
Summary of the invention
The purpose of this invention is to provide a kind of simple and easy to doly, can shorten the preparation method of the REY molecular sieve of flow process.
The preparation method of REY molecular sieve provided by the invention, be characterised in that the NaY molecular sieve contacted with the aqueous solution that contains rare earth ion or with the aqueous solution that contains rare earth ion with contain the aluminum ions aqueous solution and contact after, with add precipitating reagent and contact and make the part rare-earth precipitation on molecular sieve, carry out hydrothermal treatment consists again, contact with ammonium salt aqueous solution at last, wherein said precipitating reagent is solvable carbonate aqueous solution or alkaline aqueous solution.
Preparation method provided by the invention is that NaY is being introduced precipitating rare earth in the molecular sieve modified process, when this molecular sieve is contacted with barium oxide, has good hydrothermal stability.For example, after 800 ℃ of experience, 100% steam, 17 hours hydrothermal treatment consists, has higher index little alive.The REY molecular sieve of method preparation provided by the invention as the active component of catalytic cracking catalyst, is applicable to the high heavy oil of processing content of vanadium, and the cracking reaction activity is good.
The specific embodiment
The preparation method of REY molecular sieve provided by the invention more particularly comprises the steps:
(1) the NaY molecular sieve of silica alumina ratio 〉=4.5 is contacted with the aqueous solution that contains rare earth ion or with the aqueous solution that contains rare earth ion with contain the aluminum ions aqueous solution and contact, wherein, in rare earth oxide, the preferred 0.12-0.30 of ratio of rare earth ion and molecular sieve solid, more preferably 0.13-0.20, in aluminium oxide, aluminium ion is 0-0.1 with the ratio of molecular sieve solid, preferred 0-0.05, liquid-solid ratio is 4-20, preferred 8-15, reaction temperature is 60-95 ℃, reaction time is 10-120min, in this reacting slurry, add precipitating reagent, when precipitating reagent is solvable carbonate aqueous solution, in carbonate, precipitating reagent is more preferably 0.3-0.7 of 0.1-1.5 with the ratio of rare earth oxide; When precipitating reagent was alkaline aqueous solution, control precipitating reagent addition to molecular sieve pulp pH value was 6.0-10.0, filtration then, wash the filter cake product;
(2) step (1) gained filter cake product is carried out hydrothermal treatment consists, condition is temperature 450-800 ℃, and the time is 0.5-4h, and ambiance is the water vapour atmosphere of water content 10-100 volume %;
(3) with the product and the aqueous solution contact filtration washing that contain ammonium ion and phosphate anion of step (2) through hydrothermal treatment consists, wherein ammonium salt is 0.1-1.0 with the ratio of molecular sieve solid, and the ratio of phosphate anion and molecular sieve solid is that 0-0.07, liquid-solid ratio are that 4-20, reaction temperature are that 60-95 ℃, reaction time are 30-120min
Among the preparation method provided by the invention, in the step (1) said rare-earth ion solution be comprise lanthanum, cerium, praseodymium, neodymium ion one or more at the interior chloride or the aqueous solution of nitrate, wherein preferred rare-earth ion solution is the rare earths salt of rich lanthanum.
The said aqueous solution or the sodium aluminate solution that contains chloride, sulfate or nitrate that aluminium ion solution is aluminium in the step (1), said colloid are aluminium colloidal sol or through the boehmite of acidifying, wherein preferred aluminium colloidal sol.
The said solvable carbonate of step (1) is selected from carbonic hydroammonium, ammonium carbonate, sodium carbonate or sodium acid carbonate.Wherein preferred carbonic hydroammonium.Said alkaline aqueous solution is selected from ammonia spirit, water glass solution or alkaline molecular sieve synthesis mother liquid, wherein preferred ammonia spirit.
Said rare earth ion is preferably 0.13-0.20 with the ratio of molecular sieve solid in the step (1), and aluminium ion is preferred .0-0.05 with the ratio of molecular sieve solid, and solid-to-liquid ratio is preferably 8-15, and reaction temperature is preferably 70-80 ℃.
In the step (1), when precipitating reagent was solvable carbonate aqueous solution, in carbonate, precipitating reagent was 0.1-1.5 with the ratio of rare earth oxide, is preferably 0.3-0.7; When precipitating reagent was alkaline aqueous solution, control precipitating reagent addition to molecular sieve pulp pH value was 7.0-9.0.
Among the preparation method provided by the invention, in the said step (2), the hydrothermal treatment consists optimum condition is temperature 580-700 ℃, and ambiance is the water vapour atmosphere of water content 100 volume %.
Among the preparation method provided by the invention, ammonium salt is preferably 0.3-0.6 with the ratio of molecular sieve solid in the said step (3), and phosphate anion is preferably 0-0.04 with the ratio of molecular sieve solid, and liquid-solid ratio is preferably 8-15.
Said ammonium salt is selected from one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate and the ammonium carbonate in the step (3); Said phosphorus-containing compound is selected from one or more of ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid, aluminum phosphate and sodium phosphate
The preparation method of molecular sieve of the present invention be characterised in that rare earth with add aluminium simultaneously partly precipitated on Y molecular sieve, hydrothermal calcine then.Behind the experience hydrothermal calcine, the rare earth on the molecular sieve exists with two kinds of forms, and the part rare earth enters in the little cage of molecular sieve with ionic condition, and another part rare earth is scattered in the molecular sieve surface mutually with rare earth oxide.This preparation method is simple and easy to do, and rare earth utilization rate height has shortened the preparation flow of molecular sieve, has saved production cost.
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 industry analytical method (RIPP test method) ", volumes such as Yang Cuiding, Science Press, nineteen ninety version) measure.
Embodiment 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 that 231g/l is (with RE
2O
3Meter) mixing RECl
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 %, 706 milliliters down together), in 80 ℃ of exchanges 0.5 hour, add carbonic hydroammonium (chemical pure, Tianjin Nankai chemical plant produces, down together) 100 grams again, constant temperature stirred after 0.5 hour, filter drip washing, with filter cake roasting 2 hours in 650 ℃, 100% steam atmosphere, obtain 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) 1000 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 V-1.Physical data sees Table 1.
Embodiment 2
Get 1000 gram NaY molecular sieves, after 10 liters of deionized water making beating, adding concentration is that 231g/l is (with RE
2O
3Meter) RECl
3620 milliliters of solution, (the Shandong catalyst plant is produced, Al to add aluminium colloidal sol again
2O
3Account for 22%) 240 grams, in 90 ℃ of exchanges 1 hour, add carbonic hydroammonium 75 gram again, constant temperature stirred after 0.3 hour, filtered drip washing, with filter cake roasting 2 hours in 620 ℃, 100% steam atmosphere, obtained 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 and (analyze pure, Beijing Yili Fine Chemicals Co., Ltd. produces, down together) 500 grams, in 70 ℃ of exchanges 1.5 hours, filter drip washing, the filter cake oven dry promptly gets molecular sieve of the present invention, is designated as V-2.Physical data sees Table 1.
Embodiment 3
Get 1000 gram NaY molecular sieves, after 10 liters of deionized water making beating, adding concentration is that 231g/l is (with RE
2O
3Meter) RECl
3580 milliliters of solution in 90 ℃ of exchanges 1 hour, add carbonic hydroammonium 75 gram again, and constant temperature stirred after 1 hour, filtered drip washing, with filter cake roasting 2 hours in 620 ℃, 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, adding ammonium dihydrogen phosphate (ADP) (analyzes purely, Beijing Yili Fine Chemicals Co., Ltd. produces, down with) 40.5 restrains, 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 V-3.Physical data sees Table 1.
Embodiment 4
Get 1000 gram NaY molecular sieves, after 10 liters of deionized water making beating, adding concentration is that 231g/l is (with RE
2O
3Meter) RECl
3706 milliliters of solution, adding aluminum sulfate again (analyzes pure, chemical reagent three factories in Tianjin produce) 240 grams, in 90 ℃ of exchanges 1 hour, add carbonic hydroammonium 75 grams again, constant temperature stirred after 0.25 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 ammonium nitrate and (analyze 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 V-4.Physical data sees Table 1.
Embodiment 5
Get 1000 gram NaY molecular sieves, after 10 liters of deionized water making beating, adding concentration is that 231g/l is (with RE
2O
3Meter) RECl
3730 milliliters of solution, in 70 ℃ of exchanges 1 hour, slowly adding 25% ammonia spirit (analyzes pure, Beijing Chemical Plant's production) transferring molecular sieve pulp pH value is 8.0, constant temperature stirred after 0.25 hour, filter 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 ammonium nitrate solid 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 V-5.Physical data sees Table 1.
Comparative Examples 1
Prepare phosphorous and Y zeolite rare earth by CN1353086A
Get 1000 gram NaY molecular sieves, after 8 liters of deionized water making beating, adding concentration is that 100g/l is (with RE
2O
3Meter) RECl
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(chemical pure, Red Star chemical plant, Beijing produces), 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 REY molecular sieve, be designated as D1.Physical data sees Table 1.
Comparative Examples 2
Two roasting REY molecular sieves are handed in preparation conventional two
Get 1000 gram NaY molecular sieves, after 10 liters of deionized water making beating, adding concentration is that 157g/l is (with RE
2O
3Meter) RECl
31250 milliliters of solution in 85 ℃ of exchanges 1 hour, filter drip washing, with filter cake roasting 2 hours in 600 ℃ of air atmospheres, obtain molecular sieve dry powder then.Get this molecular sieve dry powder 1000 grams (dry basis), after 8 liters of deionized water making beating, adding concentration is that 157g/l is (with RE
2O
3Meter) RECl
3900 milliliters of solution in 85 ℃ of exchanges 0.75 hour, filter drip washing, and the filter cake oven dry promptly gets two and hands over two roasting REY molecular sieves, is designated as D2.Physical data sees Table 1.
Comparative Examples 3
Prepare rare-earth Y molecular sieve by CN1053808A.
Get 1000 gram NaY molecular sieves, after 10 liters of deionized water making beating, adding concentration is that 157g/l is (with RE
2O
3Meter) RECl
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 D3.Physical data sees Table 1.
Comparative Examples 4
Prepare hyperastable Y-type RE molecular sieve by CN1436728A.
Get 1000 gram NaY, add the making beating of 10 liters of deionized waters after, add ammonium chloride 1000 grams, oxalic acid (chemical pure, the Beijing Chemical Plant produces) 230 grams, adding ammoniacal liquor adjusting slurry pH is 3.2,90 ℃ of following stirring reactions 1 hour, adding concentration when reaction finishes was that 157g/l is (with RE
2O
3Meter) RECl
3900 milliliters of solution fully stir 20min, filter, and washing, 700 ℃ of wet cakes self steam was handled 2 hours, must contain hyperastable Y-type RE molecular sieve D4.Physical data sees Table 1.
Table 1
| The molecular sieve numbering | V-1 | V-2 | V-3 | V-4 | V-5 | D1 | D2 | D3 | D4 |
| RE 2O 3, heavy % | 17.5 | 14.3 | 15.3 | 16.9 | 18.2 | 14.6 | 18.5 | 13.3 | 14.5 |
| P 2O 5, heavy % | 0 | 0 | 2.4 | 0 | 0 | 2.1 | 0 | 0 | 0 |
| Na 2O, heavy % | 1.1 | 1.8 | 1.4 | 1.4 | 1.7 | 3.8 | 1.9 | 4.2 | 4.3 |
| Lattice constant () | 24.62 | 24.66 | 24.64 | 24.66 | 24.65 | 24.64 | 24.69 | 24.66 | 24.55 |
Embodiment 6
Present embodiment illustrates the hydrothermal stability of the REY molecular sieve of method preparation provided by the invention.
With each 100 gram (butt) of molecular sieve V-1, V-2, V-3, V-4, D1, D2, D3 and D4, 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 the little index alive of mensuration in the automatic micro-activity instrument for evaluating of catalytic cracking (productions of Beijing information automation company).The mat activity test method adopt RIPP 92-90 method (see " petrochemical industry analytical method (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
| Sieve particle is under 800 ℃, 100% water vapor condition after aging 17 hours | |||||||||
| The molecular sieve numbering | V-1 | V-2 | V-3 | V-4 | V-5 | D1 | D2 | D3 | D4 |
| Lattice constant () | 24.39 | 24.35 | 24.34 | 24.37 | 24.38 | 24.30 | 24.42 | 24.34 | 24.28 |
| MA | 67 | 64 | 65 | 67 | 67 | 59 | 66 | 58 | 50 |
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 harsh conditions hydrothermal treatment consists, the good hydrothermal stability of molecular sieve is described.Hand over two roasting REY molecular sieves to compare with conventional two, the preparation method is easy, and the hydro-thermal activity stability increases simultaneously.
Embodiment 7
Present embodiment illustrates the hydrothermal stability of REY molecular sieve under pollution of vanadium of method preparation provided by the invention.
Containing the vanadium preparation of granules, is that 157g/l is (with RE with concentration
2O
3Meter) RECl
31250 milliliters of solution add 25% ammoniacal liquor, and adjusting slurry pH value is 8.5, add ammonium metavanadate (analyzes pure, the Beijing Chemical Plant produces) 21 and restrain, pulled an oar 1 hour, place 120 ℃ of oven dry of air dry oven 16 hours, gained particle pulverize in mortar is called the vanadium particle.
In embodiment 6, sodium oxide molybdena is lower than the molecular sieve powder of 0.5 heavy % and the vanadium particle is even by weight 95%: 5% mechanical mixture, 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 the little index alive of mensuration in the automatic micro-activity instrument for evaluating of catalytic cracking (productions of Beijing information automation company).Except that molecular sieve and vanadium particle hybrid particles 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
| Molecular sieve and vanadium particle hybrid particles are under 800 ℃, 100% water vapor condition after aging 17 hours | |||||||||
| The molecular sieve numbering | V-1 | V-2 | V-3 | V-4 | V-5 | D1 | D2 | D3 | D4 |
| Lattice constant () | 24.37 | 24.32 | 24.31 | 24.36 | 24.36 | 24.29 | 24.36 | 24.29 | 24.25 |
| MA | 42 | 42 | 40 | 43 | 44 | 26 | 36 | 27 | 20 |
The high oxidation state vanadium is under the high-temperature water heat condition, and animal migration is strong, to molecular sieve structure and active destruction seriously.Data as seen from table 3, molecular sieve in the example of the present invention with contain the vanadium particle and closely contact down, after experience harsh conditions 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 activity can provide strong heavy oil cracking ability to become reconciled.
Claims (17)
1. the preparation method of a REY molecular sieve, be characterised in that this method comprise the NaY molecular sieve contacted with the aqueous solution that contains rare earth ion or with the aqueous solution that contains rare earth ion with contain aluminum ions solution or colloid and contact after, with add precipitating reagent and contact and make the part rare-earth precipitation on molecular sieve, carry out hydrothermal treatment consists again, contact with ammonium salt aqueous solution at last, wherein said precipitating reagent is solvable carbonate aqueous solution or alkaline aqueous solution.
2. according to the preparation method of claim 1, it is characterized in that this method comprises the steps:
(1) the NaY molecular sieve of silica alumina ratio 〉=4.5 is contacted with the aqueous solution that contains rare earth ion or with the aqueous solution that contains rare earth ion with contain aluminum ions solution or colloid and contact, wherein, in rare earth oxide, the ratio 0.12-0.30 of rare earth ion and molecular sieve solid, in aluminium oxide, aluminium ion is 0-0.1 with the ratio of molecular sieve solid weight, liquid-solid ratio is 4-20, reaction temperature is 60-95 ℃, reaction time is 10-120min, in this reacting slurry, add precipitating reagent, when precipitating reagent is solvable carbonate aqueous solution, in carbonate, precipitating reagent is 0.1-1.5 with the ratio of rare earth oxide; When precipitating reagent was alkaline aqueous solution, control precipitating reagent addition to molecular sieve pulp pH value was 6.0-10.0, filtration then, wash the filter cake product;
(2) step (1) gained filter cake product is carried out hydrothermal treatment consists, condition is temperature 450-800 ℃, and the time is 0.5-4h, and ambiance is the water vapour atmosphere of water content 10-100 volume %;
(3) with the product and the aqueous solution contact filtration washing that contain ammonium ion and phosphate anion of step (2) through hydrothermal treatment consists, wherein ammonium salt is 0.1-1.0 with the ratio of molecular sieve solid weight, and the ratio of phosphate anion and molecular sieve solid weight is that 0-0.07, liquid-solid ratio are that 4-20, reaction temperature are that 60-95 ℃, reaction time are 30-120min.
3. according to the preparation method of claim 2, it is characterized in that said rare-earth ion solution in the step (1) be comprise lanthanum, cerium, praseodymium, neodymium ion one or more at the interior chloride or the aqueous solution of nitrate.
4. according to the preparation method of claim 3, it is characterized in that said rare-earth ion solution is the rare earths salt of rich lanthanum.
5. according to the preparation method of claim 2, it is characterized in that the said aqueous solution or the sodium aluminate solution that contains chloride, sulfate or nitrate that aluminium ion solution is aluminium, said colloid is an aluminium colloidal sol or through the boehmite of acidifying
6. according to the preparation method of claim 5, it is characterized in that said colloid is an aluminium colloidal sol.
7. according to the preparation method of claim 2, it is characterized in that the said solvable carbonate of step (1) is selected from carbonic hydroammonium, ammonium carbonate, sodium carbonate or sodium acid carbonate.
8. according to the preparation method of claim 7, wherein said soluble carbon hydrochlorate is a carbonic hydroammonium.
9. according to the preparation method of claim 2, it is characterized in that the said alkaline aqueous solution of step (1) is selected from ammonia spirit, water glass solution or alkaline molecular sieve synthesis mother liquid.
10. according to the preparation method of claim 9, it is characterized in that said alkaline aqueous solution is an ammonia spirit.
11. according to the preparation method of claim 2, it is characterized in that the ratio of said rare earth ion and molecular sieve solid is 0.13-0.20 in the step (1), aluminium ion is 0-0.05 with the ratio of molecular sieve solid, solid-to-liquid ratio is 8-15, and reaction temperature is 70-80 ℃.
12., it is characterized in that in the step (1) that when precipitating reagent was solvable carbonate aqueous solution, in carbonate, precipitating reagent was 0.1-1.5 with the ratio of rare earth oxide according to the preparation method of claim 2.
13. according to the preparation method of claim 12, wherein precipitating reagent is 0.3-0.7 with the ratio of rare earth oxide.
14., it is characterized in that in the step (1) that when precipitating reagent was alkaline aqueous solution, control precipitating reagent addition to molecular sieve pulp pH value was 7.0-9.0 according to the preparation method of claim 2.
15., it is characterized in that in the step (2) that the hydrothermal treatment consists condition is temperature 580-700 ℃ according to the preparation method of claim 2, ambiance is the water vapour atmosphere of water content 100 volume %.
16. according to the preparation method of claim 2, it is characterized in that the middle ammonium salt of step (3) and the ratio of molecular sieve solid weight are 0.3-0.6, phosphate anion is 0-0.04 with the ratio of molecular sieve solid, liquid-solid ratio is 8-15.
17., it is characterized in that said ammonium salt in the step (3) is selected from one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate or the ammonium carbonate according to the preparation method of claim 2; Said phosphorus-containing compound is selected from one or more in ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphoric acid, aluminum phosphate or the sodium phosphate.
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