CN103962168A - Rare-earth ultrastable Y-type molecular sieve and preparation method thereof - Google Patents
Rare-earth ultrastable Y-type molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-dispersion rare-earth ultrastable Y-type molecular sieve and a preparation method thereof, and in particular to a modified molecular sieve for preparation of a catalytic cracking catalyst and a preparation method thereof. Since the NaY molecular sieve in the invention is pretreated, the physical and chemical properties such as degree of crystallinity, dispersibility and stability of the zeolite NaY can be improved significantly. Compared with the ultrastable molecular sieve with the same rare earth content prepared by a conventional method, the rare-earth ultrastable Y-type molecular sieve prepared by the two exchange and two calcination method disclosed by the invention has the characteristics of low rare earth content, good dispersibility and stability, low coke yield and strong heavy oil conversion ability; and the has the process is simple, low in cost and pollution-free.
Description
Technical field
The present invention relates to a kind of high dispersive rare earth superstable Y-type molecular sieve and preparation method, particularly a kind of modified molecular screen and preparation method for the preparation of catalytic cracking (FCC) catalyst.
Background technology
Rare earth Y type molecular sieve is one of main active component of FCC catalyst, and its predecessor is NaY molecular sieve, and its physicochemical properties significantly affect the catalysis characteristics of active constituent.
The Hydrothermal Synthesis process of predecessor NaY molecular sieve is a very complicated process.In NaY Crystallization of Zeolite system, both comprise NaY molecular sieve crystal granule, comprised again inorganic ion, also comprised a large amount of colloidal sol and gel.After NaY zeolite-water thermal crystallisation finishes, conventionally to remove inorganic ion and the colloid in molecular sieve by the step such as isolated by filtration, washing.If remove not in time these materials from system, the physicochemical properties of predecessor NaY molecular sieve will be subject to remarkable impact.The now method separating, washing NaY molecular sieves of isolated by filtration in conjunction with washing that adopt more.In water-washing process, the large gel particle that sticks to molecular sieve surface cannot be removed from molecular sieve system.In NaY molecular sieve post-modification process, these colloids that remain in molecular sieve surface are further grown up, and finally form large agglomerated particles, and the utilization ratio of molecular sieve is reduced greatly.Therefore, before molecular sieve modified, should as far as possible the colloid that is attached to molecular sieve outer surface be removed from molecular sieve system, avoid sieve particle to reunite and grow up, to realize high molecular sieve utilization rate.
Predecessor NaY molecular sieve does not have catalytic activity substantially, through NH
4 +after ion-exchanged, Y zeolite shows excellent catalytic activity.Under high-temperature water heat condition, HY framework of molecular sieve Al atom is very active, framework of molecular sieve less stable.Generally, NaY molecular sieve, before using, pass through high volence metal ion or the super steady processing of hydro-thermal, to improve the activity stability of molecular sieve.In numerous modified molecular screens, it is found that rare earth Y type molecular sieve has excellent activity stability.Rare earth ion had both been stablized the skeleton of molecular sieve, had changed again the CHARGE DISTRIBUTION of framework of molecular sieve, had strengthened the reactivity worth in molecular sieve activated centre.
Along with the increase of content of rare earth, adsorption capacity and the increased activity of molecular sieve to reactant molecule, catalyst coking rate increases.Molecular sieve large-area coking will make the diffusion of reactant molecule, and the selective of reaction significantly reduces, and therefore, the content of rare earth in molecular sieve should be in OK range.
For improving the hydrothermal stability of molecular sieve, the industrial stability that also adopts the mode of chemical modification, heat modification or two kinds of method combinations to improve molecular sieve.Molecular sieve water heat is super is surely a kind of method of improving Y zeolite hydrothermal stability generally adopting.In the super steady process of hydro-thermal, NH
4, NaY, RE, NaY or NH
4(RE), NaY molecular sieve, framework of molecular sieve dealuminzation, skeleton stability significantly improves.
Chinese patent CN92114044.4 has reported a kind of preparation method of high-Si Y-type molecular sieve, the RE that this molecular sieve contains 0.0 ~ 5.0wt%
2o
3.This invention is taking NaY molecular sieve as raw material, and under the condition existing through ammonium ion and the exchange of rare earth ion mixed once, heat or hydrothermal treatment consists, ammonium ion successively, the step such as fluosilicic acid dealuminzation is prepared high-Si Y-type molecular sieve.This molecular sieve has high-crystallinity retention rate, high hydrothermal stability, and the feature such as skeleton Al nothing but, but the complicated process of preparation of this molecular sieve, cost is higher, and raw material is to human body and the toxic effect of environment.
US Patent No. 4218307 has been reported a kind of low rare earth superstable Y-type molecular sieve.This invention, taking NaY molecular sieve as raw material, first makes Na in molecular sieve through twice thiamines exchange
2o content is down to 3% left and right, then, then and RECl
3solution exchange, high-temperature water heat treatment, sulphur ammonium exchange and repeatedly after mineral acid treatment, prepare this low content of rare earth super stable molecular sieve.This molecular sieve has high catalytic activity, excellent coke selectivity and relatively low content of rare earth, but its preparation technology is loaded down with trivial details, need take out aluminium through repeatedly exchange and inorganic acid, cannot large-scale industrial production.
Chinese patent CN1031030A discloses a kind of preparation method of low rare earth superstable Y-type molecular sieve.This invention, taking NaY molecular sieve as raw material, is prepared low rare earth superstable Y-type molecular sieve, the RE of molecular sieve through steps such as ammonium ion and the exchange of rare earth ion mixed once, heat or hydrothermal treatment consists, inorganic acid dealuminzations successively
2o
3content is 0.5 ~ 6wt%.This low rare-earth ultra-steady molecular sieve has high reactivity and low coke yield.This molecular sieve is through 800 DEG C, and after 100% steam burin-in process, the retention rate of degree of crystallinity is lower.
Chinese patent CN101722021A provides a kind of rare earth Y type molecular sieve (RE
2o
3content is 4.0 ~ 15wt%) preparation method.Strong alkali solution making beating high silica alumina ratio Y zeolite slurries for the method, 0 ~ 120 DEG C of reaction of temperature range 0.1 ~ 24 hour.Although NaY molecular sieve prepared by the method has higher N
2adsorbance, but its crystal structure has suffered heavy damage.In this process, NaY framework of molecular sieve Si atom is partly dissolved, and molecular sieve silica alumina ratio reduces, and stability significantly reduces.Although this molecular sieve has higher reactivity, NaY molecular sieve need to pass through the technical process such as making beating, and degree of crystallinity is low, poor stability, industrial production poor continuity.
Chinese patent CN1127161 discloses a kind of preparation of rare earth-containing rich silicon ultra stabilization Y-type molecular sieve.The method is taking NaY molecular sieve as raw material, at solid RECl
3siCl while existence
4carry out the reaction of gas phase dealumination complement silicon, a step completes super stabilizing and the rare earth ion exchanged of NaY.According to prepared its lattice constant of the molecular sieve a of the method
0be 2.430～2.460 nanometers, content of rare earth is 0.15～10.0wt%, Na
2o content is less than 1.0wt%.The complicated process of preparation of this molecular sieve, cost is higher, and raw material has certain toxic action to human body and environment.
Chinese patent CN1629258 discloses a kind of preparation method of rare earth superstable Y-type molecular sieve, the method by NaY molecular sieve with containing the aqueous solution of 6～94wt% ammonium salt normal pressure be greater than 90 DEG C and contact more than twice or twice with the weight ratio of molecular sieve 0.1～24 according to ammonium salt to being not more than under the condition of boiling temperature of ammonium salt aqueous solution, make Na in molecular sieve
2o content is reduced to below 1.5wt%, and the aqueous solution that is then 2～10wt% with rare-earth salts content contacts with molecular sieve at 70 DEG C～95 DEG C, and making the content of rare earth in molecular sieve is that 0.5～18wt%(is with RE
2o
3meter), then mix with carrier, be dried, in this molecular sieve process, need be through repeatedly ammonium salt exchange, preparation technology is loaded down with trivial details, ammonia and nitrogen pollution is serious, cost is higher.
Chinese patent CN1506309 has introduced a kind of method of preparing high-activity stable zeolite molecular sieve.The feature of the method is the molecular sieve that exchange is processed to ammonium salt, carries out alkali cleaning, and carries out rare earth ion exchanged and hydrothermal calcine processing, high to prepare degree of crystallinity retention rate, the molecular sieve that stability of catalytic activity is good.The method is the exchange product NH4 of NaY molecular sieve, the process of NaY and alkali effect, and NaY molecular sieve crystallinity, dispersiveness and stability do not improve, and its alkali treatment filter cake and earth solution effect meeting generating portion sediment, the dispersed variation of molecular sieve.
From the prior art, in the NaY Crystallization of Zeolite slurries of preparing due to hydro-thermal method, contain a large amount of unreacted amorphous colloids, in follow-up separation process, colloid can not effectively be removed, cause the NaY molecular sieve crystallinity of preparation low, heat endurance and bad dispersibility.Existing molecular sieve exchange process, there is competition exchange in rare earth ion and ammonium ion, and rare earth ion utilization ratio is low, and molecular sieve crystallinity is low, retains rate variance.Rare earth Y type molecular sieve complicated process of preparation, cost is higher, adopts environmental pollution raw material synthetic more, environment and human body are brought to adverse effect, and existing method does not possess the function of improving molecular sieve dispersiveness.This area needs a kind of method that technique is simple, with low cost, pollution-free, can efficiently improve molecular sieve crystallinity, dispersiveness and stability.
Summary of the invention
The object of the present invention is to provide a kind of rare-earth ultra-steady molecular sieve and preparation method thereof.The catalytic cracking catalyst that adopts this modified molecular screen to prepare has the features such as utilization ratio is high, coke yield is low, activity stability is good, and can improve heavy oil conversion performance.
The preparation method of rare-earth ultra-steady molecular sieve of the present invention, it is characterized in that fresh NaY Crystallization of Zeolite slurries rinse molecular sieve filter cake with the alkali lye of 2～8 times of molecular sieve butt quality in the time of isolated by filtration, concentration of lye is 0.001～0.5mol/l, and alkali liquid temperature is 30～90 DEG C; Concentration of lye is 0.01 ~ 0.1mol/l preferably, preferably 40～80 DEG C of alkali liquid temperatures; Molecular sieve filter cake making beating after alkali lye is rinsed, prepares a friendship one through rare earth ion exchanged, filtration, washing, roasting and roasts molecular sieve, then prepare through ammonium ion exchange, filtration and roasting process the rare-earth ultra-steady molecular sieve that two friendships two roast.
The process that the filter process of fresh NaY Crystallization of Zeolite material is Solid-Liquid Separation, can adopt the general method in this area, both can on Buchner funnel, complete, and also can on horizontal belt filter, complete.
(the pH value of the alkali lye that adopts is close with the pH of NaY molecular sieve mother solution for the low-concentration alkali liquor that the present invention adopts, be about 12 ~ 14) method of rinsing molecular sieve filter cake, under this alkali condition, the unreacted silicon that makes to be attached on molecular sieve filter cake efficiently separates fast with molecular sieve filter cake, has improved degree of crystallinity, stability and the dispersiveness of molecular sieve.As molecular sieve filter cake is pulled an oar in strong base solution, not only can not make unreacted silicon effectively separate with molecular sieve system, and can remarkable saboteur sieve crystal structure, produce more non-framework silicon, reduce the silica alumina ratio of molecular sieve, made degree of crystallinity, stability and the dispersed variation of molecular sieve.
Rare Earth Ion exchange of the present invention can adopt RE ion exchange method general in prior art, condition, and roasting condition.Ammonium ion exchange can adopt ammonium ion exchange method general in prior art, condition equally, and roasting condition.
The present invention also provides a kind of rare-earth ultra-steady molecular sieve obtaining through said method, it is characterized in that rare earth oxide content is 0.1 ~ 5wt%, and sodium oxide content is 0.5 ~ 1.5wt%.
The rare-earth ultra-steady molecular sieve that uses preparation method of the present invention to obtain, when best, the lattice constant of molecular sieve is 2.430 ~ 2.460nm, and the relative crystallinity of molecular sieve is 40 ~ 70wt%, and temperature failure temperature is 1000 ~ 1030 DEG C, in molecular sieve
with Lewis acid ratio is between 3 ~ 1, specific surface is 650 ~ 850mm
2/ g.
The said NaY molecular sieve of the present invention refers to that relative crystallinity is 85 ~ 100%, and framework si-al ratio is 4.5 ~ 5.0, and specific surface is 750 ~ 850mm
2/ g, through the synthetic polycrystalline NaY molecular screen material of hydro-thermal method.Preferably degree of crystallinity is greater than 85%, the NaY molecular screen material that silica alumina ratio is greater than 4.5.
In the present invention, rare earth ion exchanged, to the technical process that obtains a friendship one and roast molecular sieve, is preferably:
Step 1: the molecular sieve filter cake making beating after alkali lye is rinsed, under 10 ~ 30 DEG C of conditions, regulate NaY molecular sieve with hydrochloric acid solution, making molecular sieve pulp pH value is 3.0 ~ 5.0, reacts 5 ~ 60min., the pH of molecular sieve pulp preferably 3.5 ~ 4.5.
Step 2: after step 1 reaction finishes, add wherein soluble rare-earth salt once to exchange, the pH of slurries is 3.0 ~ 4.0,85 ~ 120 DEG C of holding temperatures, reaction 60 ~ 120min., when exchange, pH value preferably 3.5 ~ 3.8, preferably 90 ~ 100 DEG C of temperature.
Step 3: after step 2 reaction finishes, the molecular sieve pulp that step 2 is obtained filters, in the time that molecular sieve pulp isolated by filtration is complete, by butt quality 10 ~ 60%, the distilled water that the solubility ammonium salt that concentration is 100 ~ 200g/l and molecular sieve butt quality are 2 ~ 10 times washs respectively molecular sieve filter cake.Isolated by filtration and wash conditions the present invention are not limited especially, can on the general horizontal belt filter in this area and Buchner funnel, complete.
Step 4: with two sections of temperature control revolving burner roasting molecular sieve filter cakes, one section of sintering temperature is 300 ~ 500 DEG C, and two-stage calcination temperature is 500 ~ 700 DEG C.Molecular sieve is respectively 1 ~ 2 hour the time of staying of each period.Roasting steam is 0 ~ 100% steam.
Hydrochloric acid solution described in step 1 of the present invention is that quality percentage composition is 5 ~ 15% watery hydrochloric acid.
Soluble rare-earth salt described in step 2 of the present invention is nitrate, chloride and the solitary stone ore etc. of lanthanum, cerium.
In the present invention, prepare a friendship one and roast after molecular sieve, then prepare through ammonium ion exchange, filtration and roasting process the rare-earth ultra-steady molecular sieve technical process that two friendships two roast, be preferably:
Step 1: the molecular sieve obtaining after the distilled water making beating rare earth ion exchanged by 5 ~ 10 times of butt quality, and add the solubility ammonium salt of molecular sieve butt quality 10 ~ 50% and 1 ~ 5% organic acid to react in molecular sieve pulp, the temperature of molecular sieve pulp is 85～120 DEG C, reaction 60～120min..The pH value of slurries is 3.0 ~ 5.0, preferably 90～100 DEG C of reaction temperatures, and wherein organic acid can be one or more in oxalic acid, citric acid or EDTA.
Step 2: after step 1 reaction finishes, the molecular sieve pulp that step 1 is obtained filters, in the time that molecular sieve pulp isolated by filtration is complete, by butt quality 10 ~ 60%, the distilled water that the solubility ammonium salt that concentration is 100 ~ 200g/l and molecular sieve butt quality are 2 ~ 10 times washs respectively molecular sieve filter cake.Isolated by filtration and wash conditions the present invention are not limited especially, can on the general horizontal belt filter in this area and Buchner funnel, complete.
Step 3: use revolving burner roasting molecular sieve filter cake, sintering temperature is 500 ~ 700 DEG C again, molecular sieve is in 2 ~ 4 hours time of staying of revolving burner, and roasting steam is 0 ~ 100% steam.
Solubility ammonium salt described in the present invention is one or several of ammonium nitrate, ammonium chloride and ammonium sulfate.
The object of two sections of temperature control rotation roastings described in the present invention is to realize rare earth ion migration and separating on the preliminary dealuminzation of framework of molecular sieve space.
Adopt technical scheme disclosed in this invention, because NaY molecular sieve has first carried out pretreatment, can significantly improve the degree of crystallinity of NaY molecular sieve, the physicochemical properties such as dispersiveness and stability; The super stable molecular sieve of the identical content of rare earth of preparing with conventional method is compared, adopt disclosed in this invention two hand over the Y zeolites prepared of two roasting methods have content of rare earth moderate, dispersed and have good stability, the feature such as the low and heavy oil conversion performance of coke yield is strong, and technique is simple, with low cost, pollution-free, is applicable to large-scale industrial production.
Brief description of the drawings
Accompanying drawing is X-ray diffraction spectrum, the SEM photo of embodiments of the invention and comparative example gained molecular sieve.
The X-ray diffraction spectrum of Fig. 1 S-4 molecular sieve.
The SEM photo of Fig. 2 S-4 molecular sieve.Can find out from the SEM electronic photo of molecular sieve, compared with contrast molecular sieve R-7, S-4 sieve particle distributes more even, and pattern is clearer.
The SEM photo of Fig. 3 R-7 molecular sieve.
Analytical method
Table 1 physicochemical properties analytical method
| Analysis project | Analytical method and standard No. |
| Na 2O,wt% | Atomic absorption method |
| SiO 2,wt% | Atomic absorption method |
| Lattice constant (UCS) angstrom | X-ray diffraction analysis |
| Degree of crystallinity, wt% | X-ray diffraction analysis |
| SiO 2/Al 2O 3,mol/mol | X-ray diffraction analysis |
| Temperature failure temperature, DEG C | Differential scanning calorimeter |
| Granularity, μ m | Laser particle size analyzer |
Lattice constant and the relative crystallinity of NaY molecular sieve are measured by x-ray powder diffraction, and framework of molecular sieve silica alumina ratio is calculated by empirical equation, and computing formula is: Si/Al
2=2* (25.8575-a
0)/(a
0-24.191).
The following examples are for the present invention will be further described, but not thereby limiting the invention.
Comparative example and embodiment NaY Crystallization of Zeolite slurries used are according to document Verified Syntheses of ZeoliticMaterials, 1st Edition[J], 1998,22 (46): 604-605 publish method is synthetic, the solid content of NaY molecular sieve pulp is that the framework si-al ratio of 120g/l(molecular sieve is 4.85, and lattice constant is 2.467nm).
Detailed description of the invention
Embodiment 1
Get fresh NaY crystallization slurries 500ml, and maintain 60 DEG C of crystallization slurry temperatures.Isolated by filtration Crystallization of Zeolite slurries on simulation belt filter, in the time that filter cake chaps, with NaOH solution (50 DEG C) the flushing molecular sieve filter cake of 300ml0.02mol/l (pH is 12.3), and dry, note sample is S-1.
Comparative example 1
(crystallization slurry solid content is 120g/l, framework si-al ratio: 4.85), maintain 60 DEG C of NaY Crystallization of Zeolite slurry temperatures to get fresh NaY crystallization slurries 500ml.Isolated by filtration NaY Crystallization of Zeolite slurries on simulation belt filter, in the time that filter cake chaps, with 300ml distilled water (50 DEG C) flushing NaY molecular sieve filter cake, and dry, note washing sample is R-1.
Comparative example 2
Get fresh NaY crystallization slurries 500ml, maintain 60 DEG C of crystallization slurry temperatures.Isolated by filtration crystallization slurries on simulation belt filter, in the time that filter cake chaps, with 300ml0.8mol/l(pH be 13.9) NaOH solution (50 DEG C) rinse molecular sieve filter cake, and be dried, note sample is R-2.
Comparative example 3
Get fresh NaY crystallization slurries 500ml, maintain 60 DEG C of crystallization slurry temperatures.Isolated by filtration crystallization slurries on simulation belt filter, in the time that filter cake chaps, with 300ml1 × 10
-4mol/l(pH is 10) NaOH solution (50 DEG C) rinse molecular sieve filter cake, and dry, note sample is R-3.
Comparative example 4
Get fresh NaY crystallization slurries 500ml, and maintain 60 DEG C of crystallization slurry temperatures.Isolated by filtration crystallization slurries on simulation belt filter, in the time that filter cake chaps, with 300ml distilled water flushing and to collect filter cake stand-by.According to the method for Chinese patent CN101722022A, 1g NaOH is dissolved in 999g distilled water, after stirring, be warming up to 99 DEG C, the good molecular sieve of above-mentioned filtration (butt is about 50g) is added to this alkali lye, and under stirring condition, 99 DEG C are reacted 5 hours, reaction at the end, filter and collect filter cake, and dry, and note sample is R-4.
The impact of table 2 developing technique of the present invention on NaY molecular sieve physicochemical properties
| Sample | Na 2O/wt% | SiO 2/wt% | C/C 0/wt% | Avalanche temperature/DEG C | D(0,5)/μm |
| S-1 | 12.75 | 57.45 | 94 | 980 | 2.241 |
| R-1 | 13.12 | 58.68 | 79 | 939 | 2.967 |
| R-2 | 14.24 | 55.98 | 75 | 903 | 3.674 |
| R-3 | 12.99 | 58.44 | 84 | 942 | 2.853 |
| R-4 | 13.25 | 57.33 | 82 | 944 | 2.525 |
Table 2 is pretreating process impacts on NaY molecular sieve physicochemical properties.As can be seen from Table 2, without pretreatment, pretreatment alkali concn is too high or too low, technique is all not obvious to the improvement of NaY molecular sieve physicochemical properties, S-1 molecular sieve has high degree of crystallinity, high temperature failure temperature and less particle diameter.
Embodiment 2
Taking S-1 molecular sieve as raw material, the RE of a roasting, H (Na) Y molecular sieve are handed in preparation one.Molecular sieve one hands over the technique of a roasting to be: under room temperature condition, with 250g distilled water making beating 50g S-1 molecular sieve (in butt), after S-1 is uniformly dispersed, add 2.1ml watery hydrochloric acid (13-15wt%), the pH of NaY molecular sieve pulp is 4.0, under room temperature condition, reacts 30min..After question response finishes, molecular sieve pulp is rapidly heated to 95 DEG C, and adds 6.7ml lanthanum nitrate hexahydrate (La
2o
3, 298.2g/l), 95 DEG C of reaction 60min..At the end, isolated by filtration molecular sieve on simulation belt filter, in the time that molecular sieve filter cake chaps, adds the ammonium chloride solution (90 DEG C) of 54ml140g/l and the distilled water (90 DEG C) of 250ml washing molecular sieve filter cake successively in reaction.Collect filter cake and on two sections of temperature control revolving burners roasting molecular sieve filter cake, one section of sintering temperature is 450 DEG C, two-stage calcination temperature is 600 DEG C.Molecular sieve is respectively 60min. the time of staying of each period, and calcination atmosphere is 100% steam.The sample of roasting gained is that a friendship one roasts molecular sieve, and note sample is S-2.
Comparative example 5
Taking R-1 molecular sieve as raw material, adopt the preparation technology of S-2 molecular sieve to prepare the RE that a friendship one roasts, H (Na) Y molecular sieve, remembers that prepared sample is R-5.
Comparative example 6
Taking R-2 molecular sieve as raw material, adopt the preparation technology of S-2 molecular sieve to prepare the RE that a friendship one roasts, H (Na) Y molecular sieve, remembers that prepared sample is R-6.
Comparative example 7
Taking R-3 molecular sieve as raw material, adopt the preparation technology of S-2 molecular sieve to prepare the RE that a friendship one roasts, H (Na) Y molecular sieve, remembers that prepared sample is R-7.
Table 3 one is handed over a roasting RE, the impact of H (Na) Y molecular sieve physicochemical properties
| Sample | Na 2O wt% | RE 2O 3wt% | C/C 0/wt% | a 0/nm |
| S-2 | 3.68 | 3.87 | 71 | 2.464 |
| R-5 | 4.23 | 3.92 | 62 | 2.467 |
| R-6 | 4.57 | 4.11 | 51 | 2.470 |
| R-7 | 3.85 | 3.90 | 65 | 2.466 |
Table 3 is physicochemical properties analysis results that a friendship one roasts molecular sieve, can find out, S-2 molecular sieve disclosed in this invention has Na
2o content is low, degree of crystallinity high.The predecessor NaY molecular sieve of R-5 molecular sieve is owing to not carrying out pretreatment, the Na of molecular sieve
2o content and degree of crystallinity are all lower than S-2 molecular sieve, and the degree of crystallinity that the too high or too low friendship one of pretreatment alkali concn roasts molecular sieve is low.
Embodiment 3, taking S-1 molecular sieve as raw material, adopts the exchange process of S-2 sample, and on simulation belt filter, isolated by filtration obtains RE, NH
4(Na) Y filter cake.Roasting molecular sieve filter cake on revolving burner, sintering temperature is 600 DEG C, and the time of staying of sample is respectively 120min., and calcination atmosphere is 100% steam.Roasting gained sample is that a friendship one roasts molecular sieve, and note sample is S-3.
Table 4 one is handed over the impact of roasting condition on molecular sieve physicochemical properties
| Sample | Na 2O wt% | RE 2O 3wt% | C/C 0/wt% | a 0/nm |
| S-2 | 3.68 | 3.87 | 71 | 24.64 |
| S-3 | 4.23 | 3.77 | 66 | 24.62 |
Table 4 is that a friendship one roasts molecular sieve physicochemical properties, as can be seen from Table 4, adopts the roasting of two sections of temperature control revolving burners can improve the degree of crystallinity of molecular sieve, reduces the Na in molecular sieve
2o content.
Embodiment 4
Taking S-2 molecular sieve as raw material, the RE of two roastings, H (Na) Y molecular sieve are handed in preparation two.Molecular sieve two hands over the technique of two roastings to be: under 10 ~ 30 DEG C of conditions, with 250g distilled water making beating 50g S-2 molecular sieve (in butt), after it is uniformly dispersed, add successively 10g ammonium sulfate (analyzing pure) and 1.5g citric acid (analyzing pure), be rapidly heated to 95 DEG C of reaction 60min..At the end, isolated by filtration molecular sieve pulp on simulation belt filter, in the time that molecular sieve filter cake chaps, adds the ammonium sulfate (90 DEG C) of 54ml140g/L and the distilled water (90 DEG C) of 250ml washing molecular sieve filter cake successively in reaction.Collect filter cake and on temperature control revolving burner roasting molecular sieve filter cake, sintering temperature is that 600 DEG C, roasting time are that 120min., calcination atmosphere are 100% steam.The sample of roasting gained is that two friendships two roast molecular sieve, and note sample is S-4.
Comparative example 8
Taking R-5 molecular sieve as raw material, adopt the two friendship two roasting techniques identical with S-4 molecular sieve to prepare RE, H (Na) Y molecular sieve, note sample is R-8.
Comparative example 9
Taking R-6 molecular sieve as raw material, adopt the two friendship two roasting techniques identical with S-4 molecular sieve to prepare RE, H (Na) Y molecular sieve, note sample is R-9.
Comparative example 10
Taking R-7 molecular sieve as raw material, adopt the two friendship two roasting techniques identical with S-4 molecular sieve to prepare RE, H (Na) Y molecular sieve, note sample is R-10.
Table 5 two is handed over two roasting RE, H (Na) Y molecular sieve physicochemical properties
| Sample | Na 2Owt% | RE 2O 3wt% | C/C 0/wt% | a 0/nm | Avalanche temperature | D(0,5)/um |
| S-4 | 0.65 | 3.98 | 52 | 24.49 | 1019 | 2.79 |
| R-8 | 0.93 | 4.11 | 47 | 24.54 | 1005 | 3.45 |
| R-9 | 1.46 | 4.24 | 39 | 24.56 | 998 | 5.21 |
| R-10 | 0.90 | 4.03 | 55 | 24.52 | 1005 | 3.32 |
Table 4 is physicochemical properties that two friendships two roast molecular sieve.Can find out, S-4 molecular sieve has high degree of crystallinity, low lattice constant and little molecular sieve particle diameter, and pretreatment can improve the physicochemical properties of molecular sieve.
Table 5 is physicochemical properties analysis results that two friendships two roast molecular sieve, can find out, S-4 molecular sieve disclosed in this invention has Na
2the features such as O content is low, and Heat stability is good and lattice constant are low, the predecessor NaY molecular sieve of R-8 molecular sieve is owing to not carrying out pretreatment, the Na of molecular sieve
2o content and heat endurance are all lower than S-4 molecular sieve.Can find out, R-9 and R-10 molecular sieve are because pretreatment alkali concn is too high or too lowly cause two friendships two to roast that molecular sieve crystallinity is low, sodium oxide content is high, molecular sieve particle diameter is large simultaneously.
Fig. 1 is the X-ray diffraction spectrum of S-4 molecular sieve, and the characteristic diffraction peak of molecular sieve is identical with NaY molecular sieve characteristic peak.Fig. 2 and Fig. 3 are respectively the SEM photos of S-4 molecular sieve and R-7 molecular sieve, can find out from the SEM photo of two kinds of molecular sieves, and the dispersiveness of S-4 molecular sieve disclosed in this invention is better.
Embodiment 5, taking S-3 molecular sieve as raw material, adopts the preparation technology of S-4 sieve sample to prepare the RE that two friendships two roast, H (Na) Y molecular sieve, and note sample is S-5.
Embodiment 6, taking S-2 molecular sieve as raw material, adopts the preparation technology of S-4 sieve sample to prepare the RE that two friendships two roast, H (Na) Y molecular sieve.After molecular sieve making beating, do not add citric acid in system, note sample is S-6.
Table 6 two is handed over two roasting molecular sieve physicochemical properties
| Sample | Na 2Owt% | RE 2O 3wt% | C/C 0/wt% | a 0/nm | Avalanche temperature | D(0,5)/um |
| S-4 | 0.65 | 3.98 | 55 | 24.49 | 1019 | 2.79 |
| S-5 | 1.33 | 3.85 | 44 | 24.48 | 1011 | 3.16 |
| S-6 | 1.21 | 3.99 | 57 | 24.55 | 1013 | 2.99 |
Table 6 is physicochemical properties that two friendships two roast molecular sieve, and as can be seen from the table, in a roasting process, the long-time roasting molecular sieve of high temperature reduces molecular sieve crystallinity, and sodium oxide content is high; In secondary exchange process, citric acid has certain destruction to molecular sieve crystallinity, but the reduction of molecular sieve sodium oxide content is had to remarkable effect.
Embodiment 7
Respectively taking S-4 and R-7 sieve sample as raw material, preparation FCC catalyst, and the Catalytic Cracking Performance of catalyst is evaluated with ACE device, catalyst had carried out the processing of high-temperature vapor deactivation before performance evaluation, and (high-temperature vapor deactivation treatment conditions are 800 DEG C, 100% steam, 17 hours).The preparation technology of catalyst is: with 400g water making beating 650g(butt) kaolin, add alumina binder 100g(butt), after fully mixing, add 250g molecular sieve (butt) to system.After slurries are uniformly dispersed, carry out catalyst granulating and forming with spraying drying mode, at 450 DEG C of degree roasting agent 30min., and wash, note is S-7 and R-10 containing the FCC catalyst of S-4 and R-7 molecular sieve respectively.Table 7 and table 8 are respectively catalyst physical and chemical performance analysis and reactivity worth analysis.Table 7 is physical and chemical performance analysis of model catalyst, and as can be seen from the table, the model catalyst S-7 that contains S-4 molecular sieve disclosed by the invention has that sodium oxide content is low, pore volume is large and the feature such as wear resistance is good.Table 8 is reaction results of model catalyst, and reaction raw materials is Lanzhou Petrochemical vacuum gas oil (VGO).From the reaction result of model catalyst, the feature such as it is strong that the S-4 catalyst that contains the open molecular sieve of the present invention has heavy oil conversion performance, and dry gas and coke yield are low.
Table 6 catalyst physical and chemical performance analysis
| Sample | S-7 | R-10 |
| Na 2O(wt%) | 0.10 | 0.12 |
| Pore volume (ml/g) | 0.27 | 0.25 |
| Abrasion index (wt%) | 0.7 | 1.3 |
Table 7 catalyst reaction performance evaluation
Claims (13)
1. the preparation method of a rare earth superstable Y-type molecular sieve, it is characterized in that fresh NaY Crystallization of Zeolite slurries rinse molecular sieve filter cake with the alkali lye of 2～8 times of molecular sieve butt quality in the time of isolated by filtration, concentration of lye is 0.001～0.5mol/L, and alkali liquid temperature is 30～90 DEG C; Molecular sieve filter cake making beating after alkali lye is rinsed, prepares a friendship one through rare earth ion exchanged, filtration, washing, roasting and roasts molecular sieve, then prepare through ammonium ion exchange, filtration and roasting process the rare-earth ultra-steady molecular sieve that two friendships two roast.
2. preparation method according to claim 1, is characterized in that concentration of lye is 0.01 ~ 0.1mol/L.
3. preparation method according to claim 1, is characterized in that, alkali liquid temperature is 40～80 DEG C.
4. preparation method according to claim 1, is characterized in that rare earth ion exchanged to the technical process that obtains a friendship one and roast molecular sieve is:
Step 1: the molecular sieve filter cake making beating after alkali lye is rinsed, under 25 DEG C of conditions, with hydrochloric acid solution adjusting NaY molecular sieve, making molecular sieve pulp pH value is 3.0 ~ 5.0, reaction 5 ~ 60min;
Step 2: after step 1 reaction finishes, add wherein soluble rare-earth salt once to exchange, the pH of slurries is 3.0 ~ 4.0,85 ~ 120 DEG C of holding temperatures, reaction 60 ~ 120min;
Step 3: after step 2 reaction finishes, the molecular sieve pulp that step 2 is obtained filters, in the time that molecular sieve pulp isolated by filtration is complete, by butt quality 10 ~ 60%, the distilled water that the solubility ammonium salt that concentration is 100 ~ 200g/L and molecular sieve butt quality are 2 ~ 10 times washs respectively molecular sieve filter cake;
Step 4: with two sections of temperature control revolving burner roasting molecular sieve filter cakes, one section of sintering temperature is 300 ~ 500 DEG C, and two-stage calcination temperature is 500 ~ 700 DEG C, and molecular sieve is respectively 1 ~ 2 hour the time of staying of each period, and roasting steam is 0 ~ 100% steam.
5. preparation method according to claim 4, is characterized in that hydrochloric acid solution is the watery hydrochloric acid of 5 ~ 15 quality %.
6. preparation method according to claim 4, is characterized in that soluble rare-earth salt is nitrate or the chloride of lanthanum, cerium.
7. preparation method according to claim 4, is characterized in that soluble rare-earth salt is solitary stone ore.
8. preparation method according to claim 4, is characterized in that in step 1, and the pH of molecular sieve pulp is 3.5 ~ 4.5.
9. preparation method according to claim 1, is characterized in that preparing a friendship one and roasts after molecular sieve, then prepares through ammonium ion exchange, filtration and roasting process the rare-earth ultra-steady molecular sieve technical process that two friendships two roast and be:
Step 1: the molecular sieve obtaining after the distilled water making beating rare earth ion exchanged by 5 ~ 10 times of butt quality, and add the solubility ammonium salt of molecular sieve butt quality 10 ~ 50% and 1 ~ 5% organic acid to react in molecular sieve pulp, the reaction temperature of molecular sieve pulp is 85～120 DEG C, reaction 60～120min; The pH value of slurries is 3.0 ~ 5.0, and wherein organic complex is one or more in oxalic acid, citric acid or EDTA.
Step 2: after step 1 reaction finishes, the molecular sieve pulp that step 1 is obtained filters, in the time that molecular sieve pulp isolated by filtration is complete, by butt quality 10 ~ 60%, the distilled water that the solubility ammonium salt that concentration is 100 ~ 200g/L and molecular sieve butt quality are 2 ~ 10 times washs respectively molecular sieve filter cake;
Step 3: use revolving burner roasting molecular sieve filter cake, sintering temperature is 500 ~ 700 DEG C again, molecular sieve is in 2 ~ 4 hours time of staying of revolving burner, and roasting steam is 10 ~ 100% steam.
10. according to the preparation method described in claim 4 or 9, it is characterized in that solubility ammonium salt is one or several of ammonium nitrate, ammonium chloride and ammonium sulfate.
11. preparation methods according to claim 9, the reaction temperature that it is characterized in that molecular sieve pulp in step 1 is 90 ~ 100 DEG C.
12. preparation methods according to claim 1, is characterized in that rare earth ion exchanged to the technical process that obtains a friendship one and roast molecular sieve is:
Step 1: after the molecular sieve filter cake making beating after alkali lye is rinsed, under 25 DEG C of conditions, with hydrochloric acid solution adjusting NaY molecular sieve, making molecular sieve pulp pH value is 3.0 ~ 5.0, reaction 5 ~ 60min;
Step 2: after step 1 reaction finishes, add wherein soluble rare-earth salt once to exchange, the pH of slurries is 3.0 ~ 4.0,85～120 DEG C of holding temperatures, reaction 60～120min;
Step 3: after step 2 reaction finishes, the molecular sieve pulp that step 2 is obtained filters, in the time that molecular sieve pulp isolated by filtration is complete, by butt quality 10 ~ 60%, the distilled water that the solubility ammonium salt that concentration is 100 ~ 200g/L and molecular sieve butt quality are 2 ~ 10 times washs respectively molecular sieve filter cake;
Step 4: with two sections of temperature control revolving burner roasting molecular sieve filter cakes, one section of sintering temperature is 300 ~ 500 DEG C, and two-stage calcination temperature is 500 ~ 700 DEG C, and molecular sieve is respectively 1 ~ 2 hour the time of staying of each period, and roasting steam is 0 ~ 100% steam;
Prepare a friendship one and roast after molecular sieve, then prepare through ammonium ion exchange, filtration and roasting process the rare-earth ultra-steady molecular sieve technical process that two friendships two roast and be:
Step 1: the molecular sieve obtaining after the distilled water making beating rare earth ion exchanged by 5 ~ 10 times of butt quality, and add the solubility ammonium salt of molecular sieve butt quality 10 ~ 50% and 1 ~ 5% organic acid to react in molecular sieve pulp, the reaction temperature of molecular sieve pulp is 85 ~ 120 DEG C, reaction 60 ~ 120min; The pH value of slurries is 3.0 ~ 5.0, and wherein organic complex is one or more in oxalic acid, citric acid or EDTA.
Step 2: after step 1 reaction finishes, the molecular sieve pulp that step 1 is obtained filters, in the time that molecular sieve pulp isolated by filtration is complete, by butt quality 10 ~ 60%, the distilled water that the solubility ammonium salt that concentration is 100 ~ 200g/L and molecular sieve butt quality are 2 ~ 10 times washs respectively molecular sieve filter cake;
Step 3: use revolving burner roasting molecular sieve filter cake, sintering temperature is 500 ~ 700 DEG C again, molecular sieve is in 2 ~ 4 hours time of staying of revolving burner, and roasting steam is 10 ~ 100% steam.
13. 1 kinds of rare earth superstable Y-type molecular sieves that the arbitrary described preparation method of claim 1 to 9 obtains, is characterized in that in rare earth superstable Y-type molecular sieve, rare earth oxide content is 0.1 ~ 5wt%, and sodium oxide content is 0.5 ~ 1.5wt%.
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| CN108128785A (en) * | 2018-03-02 | 2018-06-08 | 浙江大学 | Using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves |
| CN114433182A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Molecular sieve containing rare earth elements and preparation method thereof |
| CN116037196A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Super-stable modified Y-type molecular sieve containing phosphorus and preparation method thereof |
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| CN101722022A (en) * | 2008-10-10 | 2010-06-09 | 中国石油天然气集团公司 | Alkali treatment modifying method of Y-shaped molecular sieve |
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| CN1506161A (en) * | 2002-12-13 | 2004-06-23 | 中国石油天然气股份有限公司 | Ultrastable Y-type RE molecular sieve active component and its prepn process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107089668A (en) * | 2017-05-26 | 2017-08-25 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of Y-shaped molecular sieve containing rare earth |
| CN108128785A (en) * | 2018-03-02 | 2018-06-08 | 浙江大学 | Using nickel amine complex as the method for template one-step synthesis ITE zeolite molecular sieves |
| CN108128785B (en) * | 2018-03-02 | 2020-02-14 | 浙江大学 | Method for synthesizing ITE zeolite molecular sieve by using nickel-amine complex as template agent in one step |
| CN114433182A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Molecular sieve containing rare earth elements and preparation method thereof |
| CN114433182B (en) * | 2020-11-02 | 2023-11-24 | 中国石油化工股份有限公司 | Molecular sieve containing rare earth element and preparation method thereof |
| CN116037196A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Super-stable modified Y-type molecular sieve containing phosphorus and preparation method thereof |
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