CN1069553C - Method for preparation of rare earth Y type molecular sieve - Google Patents
Method for preparation of rare earth Y type molecular sieve Download PDFInfo
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- CN1069553C CN1069553C CN97122145A CN97122145A CN1069553C CN 1069553 C CN1069553 C CN 1069553C CN 97122145 A CN97122145 A CN 97122145A CN 97122145 A CN97122145 A CN 97122145A CN 1069553 C CN1069553 C CN 1069553C
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Abstract
The present invention provides a method for preparing rare earth Y type molecular sieves. The method comprises the following steps: carrying out the rare earth ion exchange of NaY molecular sieves by using a conventional method; putting filtered cakes after filtration into a calcining furnace to calcine for 1 to 4 hours at 450 to 650 DEG C in a 100% steam atmosphere; circularly returning 10 to 40% of calcined products into the next batch of rare earth exchange slurry to continue the previous operation; using the rest of the calcined products as REY molecular sieve products to prepare catalysts; continuously carrying out the operation in such as manner. The present invention uses a 'once exchange and once calcination' technology to prepare products with properties identical to that of REY molecular sieves made up by using a conventional 'twice exchange and twice calcination' technology, and the prepared products have better hydrothermal stability.
Description
The present invention relates to a kind of preparation method of crystalline aluminosilicate faujasite, particularly relate to a kind of preparation method who can be used for the rare earth Y type molecular sieve of catalyst and cracking of hydrocarbon.
Na in the NaY molecular sieve
+By rare earth ion (RE
3+) the REY type molecular sieve that makes after the exchange is the high activity constituent element of catalytic cracking catalyst, though use super-stable Y molecular sieves at present more and more to be used to mix the RFCC of refining residual oil, but catalytic cracking for prevailing wax oil, highly active rare earth Y type molecular sieve is still indispensable, and it still occupies sizable market share in the used molecular sieve of catalytic cracking catalyst.
According to the literature, why to have preferably heat and hydrothermal stability be to contain (P.C.Lyer etc., ACSSyeposiua Series, 368,48,1981) due to the multi-kernel rare-earth cation of oxo bridge owing to move to sodalite cage and formation to the REY molecular sieve.But when NaY molecular sieve and rare-earth ion solution carry out ion-exchange at normal temperatures and pressures, the hydrated rare-earth ion of about 0.79 nanometer of diameter is difficult to hexatomic ring duct by diameter 0.24 nanometer of Y zeolite and is penetrated in the sodalite cage and removes (H.S.Sherry, Adv.chem.Ser., 101,350,1970).Therefore, in the preparation process of REY molecular sieve, be necessary to remove the hydration layer that is centered around around the rare earth ion by roasting, so that the rare earth ion after the dehydration to the sodalite cage so that move in the hexagonal prism, and the sodium ion that is in these cages also moves to supercage by means of roasting.In a word, the result of roasting is the intracrystalline exchange of having quickened between solid ionic, for molecular sieve in the aqueous solution with other cations NH for example
4 +Or RE
3+Exchange and the Na that reduces molecular sieve
+Content has been created condition (USP3,402,996).Therefore, how to promote the migration of rare earth ion, improve the occupation rate that goes up rare earth ion at the cation position that can be lockable (in the little cage), will be directly connected to the performance of REY molecular sieve and influence its activity stability.On the other hand, people think for a long time all the time has sufficiently high content of rare earth for making the catalyst that contains the REY molecular sieve can have higher heat and hydrothermal stability, must making in the molecular sieve, (USP3,140,249, USP3,140,250, USP3,140,251, USP3,140,252, USP3,140,253).Based on above reason, the preparation flow major part of the REY molecular sieve of industrial existing employing all is: RE
3+Exchange-air roasting-RE
3+Exchange-air roasting, i.e. " two hand over two roasting " technology, this technological process is not only loaded down with trivial details, energy consumption is big, and the production cost height that brings greatly owing to the rare earth consumption is inevitable.
The applicant has proposed a kind of preparation method of rare earth Y type molecular sieve in CN1053808A, the principal character of this method is to introduce water vapour in roasting process, i.e. roasting under the circulating water steam atmosphere, the REY molecular sieve that adopts this method of roasting to make compares the content of rare earth height of the REY molecular sieve that makes with conventional air roasting, sodium content is low, and can impel more RE
3+Move to the cation position (in the little cage) that is lockable thus improve the hydrothermal stability and the activity stability of REY molecular sieve, this method is " one hands over a roasting " technology with traditional " two hand over two roastings " work simplification also simultaneously, thereby greatly reduce cost and energy consumption, but this method is owing to lacked a step exchange and an one-step baking, and prepared its content of rare earth of REY molecular sieve and Na content still do not reach the level of " two hand over two roastings " method gained REY molecular sieve.
The objective of the invention is to provide on the basis of existing technology a kind of method of the REY of preparation molecular sieve, make that adopting " once handing over a roasting " technology can obtain having with " two hand over two roastings " rare earth and Na contents level that technology gained REY molecular sieve is suitable has the REY molecular sieve of higher hydro-thermal activity stability simultaneously.
Fig. 1 is the process flow diagram according to preparation rare earth Y type molecular sieve of the present invention.
According to Fig. 1, the method for preparing rare earth Y type molecular sieve provided by the present invention comprises: the NaY molecular sieve is carried out rare earth ion exchanged one time according to conventional method, and the filter cake after it filters enters and carries out hydrothermal calcine in the roaster; With 10～40% of the product after the roasting, described operation above preferred 15～30% circulations are returned and continued in the next group rare earth exchanged slurries, all the other, carry out for the preparation of catalyst so continuously as product.
Said rare earth ion exchanged is carried out according to general condition of the prior art in the inventive method, and the condition that generally adopts in the prior art is: with NaY molecular sieve and mixed chlorinated rare earth solution according to NaY (dry basis): RECl
3: H
2O=1: (0.1～0.4): the weight ratio making beating of (10～30) mixes, and the pH value of slurries is generally 2.3～6.5, and the exchange temperature is generally 60～95 ℃, is generally swap time 0.5～2 hour.The pH value of slurries is generally controlled by the acidity of mixed rare earth solution.
The condition of said hydrothermal calcine is the conventional condition that adopts in the prior art in the method provided by the present invention, it can be the condition of the hydrothermal calcine described in the CN1053808A, the general condition that adopts is: temperature is 450～650 ℃, time is 1～4 hour, and the water vapour weight space velocity is 0.5～4.0 o'clock
-1, but generally need only the requirement that under 100% water vapour atmosphere, can satisfy hydrothermal calcine for the water yield.
In the method provided by the present invention after the said roasting 10～40%, preferred 15～30% cycle stock can carry out rare earth ion exchanged with the NaY slurries, but preferably after NaY is through the pre-exchange of the rare earth ion of certain hour, add cycle stock again, the consumption of cycle stock is a benchmark with the butt weight that feeds intake of NaY this moment, promptly when each rare earth ion exchanged of NaY, all add 10～40% through the cycle stock of above hydrothermal calcine once, can make full use of the exchange capacity of residue rare earth ion in the NaY rare earth exchanged balance rear slurry like this, to improving the Na of molecular sieve rare earth exchanged amount and reduction molecular sieve
2O content is beneficial.
Can also comprise in the method provided by the present invention product after the gained roasting is washed with further reduction Na with rare ammonium salt solution
2O content; Also can after making catalyst, wash again without washing.
The method for preparing rare earth Y type molecular sieve provided by the present invention is characterised in that to be returned the circulation of the product behind the part hydrothermal calcine in the slurries of next group rare earth exchanged, can make full use of the exchange potentiality of rare earth ion more than needed in the rare earth exchanged slurries so on the one hand, improve the content of rare earth of molecular sieve, and make the Na of molecular sieve
2O content further reduces, on the other hand because some molecular sieve has passed through above hydrothermal calcine twice, can promote the migration of molecular sieve middle rare earth ion, improve the occupation rate of rare earth ion on the cation position that can be lockable (in the little cage), impel the Na ion in the molecular sieve in supercage, to move and be easy to be exchanged simultaneously, both improved the hydro-thermal structural stability and the hydro-thermal activity stability of molecular sieve, and to reducing the Na of molecular sieve
2O content is beneficial; Therefore can prepare and tradition " two the hand over two roastings " rare earth Y type molecular sieve that technology gained molecular sieve performance is suitable with " once handing over a roasting " of the present invention technology, so just, make traditional " two hand over two roastings " technological process obtain simplifying, reduce equipment investment, reduced energy consumption and cost; And compare with method described in the CN1053808A, the content of rare earth of the inventive method gained molecular sieve improves, Na
2O content reduces, more near " two hand over two roastings " technology products obtained therefrom.
The following examples will the present invention is described further.In each embodiment and Comparative Examples, the lattice constant a of molecular sieve
0, crystallization reservation degree, Na
2O content and rare earth oxide (RE
2O
3) micro-activity of content and catalyst is respectively according to " petrochemical industry analytical method (RIPP test method) " (volume such as Yang Cuiding, Science Press, nineteen ninety publishes) in RIPP145-90,146-90,127-90,131-90 and 92-90 standard method measure, said butt weight is meant that sample removes the weight (seeing the 32-90 standard method in the above-mentioned reference book) of gained residue behind the volatilizable thing through roasting in 850 ℃/1 hour.
Comparative Examples 1
The effect of this Comparative Examples explanation tradition " two hand over two roastings " technology gained rare earth Y type molecular sieve.
This Comparative Examples molecular sieve is numbered DB-1, it is industrial products of taking from Chang Ling catalyst subsidiary factory of oil-refining chemical factory rare earth Y type molecular sieve workshop, its preparation flow is: rare earth ion exchanged-air atmosphere roasting-rare earth ion exchanged-air atmosphere roasting, roaster bed of material temperature is 520 ℃, the rare earth exchanged condition is 90 ℃ of exchanges 1 hour, and used rare earth content is RECl when exchanging for the first time
3/ molecular sieve=0.22 (weight ratio), used rare earth content is RECl when exchanging for the second time
3/ molecular sieve=0.12 (weight ratio).
The performance of DB-1 sample is listed in the table 1.
With the DB-1 sample according to molecular sieve (dry basis): (NH
4)
2SO
4: H
2O=1: 0.2: 40 weight ratio was 60 ℃ of following pulping and washing twice, each 15 minutes; And then according to molecular sieve (dry basis): H
2O=1: 40 weight ratio was 60 ℃ of following pulping and washing 15 minutes, and the gained sample is designated as DB-1 ' behind the filtration drying, and its performance is listed in the table 1.
Comparative Examples 2
The explanation of this Comparative Examples prepares the effect of REY molecular sieve according to method described in the CN1053808A.
(Chang Ling oil-refining chemical factory catalyst plant is produced, SiO with the NaY molecular sieve
2/ Al
2O
3Mol ratio is 4.9, a
0=2.467 nanometers, Na
2O content is 11.0 heavy %) and the mixed type rare earth chloride (wherein the main component weight percent in the mishmetal consists of: CeO
256.0, La
2O
325.6, Nd
2O
312.7, Pr
2O
3＜4, down with) solution and water is according to NaY (dry basis): RECl
3: H
2O=1: 0.30: 15 weight ratio making beating mixes, the PH of gained slurries is 3.5, it is warming up to 90 ℃ also stirs exchange 1 hour, filter then, with the filter cake after filtering with 10 times of decationized Y sieve water wash to molecular sieve butt weight, the gained filter cake packed into to begin in the tubular type roaster to heat up, and when waiting to be warming up to 200 ℃, beginning to feed weight space velocity is 1.0 o'clock
-1Water vapour, continue to be warming up to 550 ℃, this temperature and at 1.0 o'clock
-1Down roasting 2 hours of water vapour air speed (100% water vapour atmosphere), cooling then, the gained sample is designated as DB-2, its performance is listed in the table 1.Can be used as cycle stock of the present invention among this DB-2 sample embodiment afterwards uses.
According to the washing of the same procedure in the Comparative Examples 1, the sample after the washing is designated as DB-2 ' with the DB-2 sample, and its performance is listed in the table 1.
Comparative Examples 3
According to the method preparation identical with Comparative Examples 2, the raw material proportioning when different is rare earth ion exchanged changes NaY (dry basis): RECl into
3: H
2O=1: 0.2: 15, the gained sample was designated as DB-3, and its performance is listed in the table 1.
According to the washing of the same procedure in the Comparative Examples 1, washing back gained sample is designated as DB-3 ' with the DB-3 sample, and its performance is listed in the table 1.
Comparative Examples 4
According to the method preparation identical with Comparative Examples 2, the raw material proportioning when different is rare earth ion exchanged changes NaY (dry basis): RECl into
3: H
2O=1: 0.25: 15, the gained sample was designated as DB-4, and its performance is listed in the table 1.
With the DB-4 sample according to Comparative Examples 1 in same procedure washing, washing back gained sample is designated as DB-4 ', its performance is listed in the table 1.
Embodiment 1
Present embodiment illustrates that method provided by the invention prepares the effect of REY molecular sieve.
With NaY molecular sieve (with Comparative Examples 1, down with) and re chloride and water according to NaY (dry basis): RECl
3: H
2O=1: 0.30: 15 weight ratio making beating mixes, the PH of gained slurries is 3.5, it is warming up to 90 ℃ also stirs exchange 30 minutes, to wherein adding Comparative Examples 2 gained DB-2 samples and continuing to stir exchange 30 minutes down at 90 ℃, the addition of DB-2 sample (dry basis) is 25% (being that internal circulating load is 25%) of said NaY butt weight, after the filtration, with filter cake with 10 times of decationized Y sieve water wash to filter cake butt weight, then the gained filter cake is packed into and begin in the tubular type roaster to heat up, when waiting to be warming up to 200 ℃, beginning to feed weight space velocity is 1.0 o'clock
-1Water vapour, continue to be warming up to 550 ℃, this temperature and at 1.0 o'clock
-1Down roasting 2 hours of water vapour air speed (100% water vapour atmosphere), cooling then, the gained sample is designated as S-1, its performance is listed in the table 1.
According to the washing of the same procedure in the Comparative Examples 1, the sample after the washing is designated as S-1 ' with the S-1 sample, and its performance is listed in the table 1.
Embodiment 2～9
These embodiment illustrate in the method for the present invention the effect of gained REY molecular sieve under the condition of the different internal circulating loads when of feeding intake.
Prepare the REY molecular sieve according to the same procedure among the embodiment 1, the NaY that different is according to the listed condition of table 1 when changing rare earth exchanged: RE
2Cl
3Ratio and the internal circulating load and the roasting condition of DB-2 sample.The gained molecular sieve is numbered S-2 to S-9 respectively.Washing later on according to the same procedure in the Comparative Examples 1 they, the corresponding molecular sieve of gained is numbered S-2 ' to S-9 '.Its performance is listed in the table 1.
Embodiment 10
Present embodiment illustrates that method provided by the invention still obtains satisfied effect under the situation that commercial scale is amplified.
According to flow process shown in Figure 1, adopt two ion-exchange jars and a rotary roaster, on commercial plant, test, the volume of swap tank is 20 cubic metres, the roaster internal diameter is 550 millimeters, length is 24 meters, and rotating speed is 1.5 rev/mins, and raw material on average is about 2 hours at residing time in furnace (roasting time).The condition of rare earth ion exchanged is with embodiment 1, but the PH of every still is controlled in 3～5 scopes (every still is not necessarily identical) during exchange, filter cake after ion-exchange is filtered is sent in the roaster with 250 kilograms charging rate per hour at the uniform velocity continuously, material layer temperature is 520 ℃ in the stove, be 500 ℃ along the reverse feeding temperature of charging in whole roasting process, flow is 200 kilograms/hour a superheated vapour; 25% circulation of the molecular sieve in roaster exit is returned in the rare earth ion exchanged jar, promptly the molecular sieve that will be equivalent to 25% roaster exit of used NaY butt weight in the swap tank according to the method for embodiment 1 returns and joins in the swap tank, carry out so continuously, treat stable, begin discharging after 48 hours from roaster, restrained from roaster outlet sampling 100 every 4 hours, take a sample and each sample of gained is mixed after five times, promptly get the sample of this example example, be numbered S-10, its performance is listed in the table 1.
According to the washing of the same procedure in the Comparative Examples 1, the sample after the washing is designated as S-10 ' with the S-10 sample, and its performance is listed in the table 1.
Embodiment 11
Present embodiment explanation the inventive method gained rare-earth Y molecular sieve has better hydrothermal stability.
S-1 ' sample and DB-2 ' sample are measured their lattice constant a respectively behind the hydrothermal aging through 760 ℃/4 hours, 800 ℃/4 hours and 820 ℃/4 hours
0With crystallization reservation degree C.R, the results are shown in Table 2 for it.
Table 1
| Sample number into spectrum | Preparation condition | Na 2O content (heavy %) | RE 2O 3Content (heavy %) | a 0(A) | *C.R. (％) | ||||
| NaY∶RECl 3∶H 2O | Internal circulating load (%) | Sintering temperature (℃) | Roasting time (hour) | ||||||
| Comparative Examples 1 | DB-1 | The exchange of two steps | 0 | 520 | 2 | 3.6 | 15.4 | 24.70 | |
| DB-1’ | 0.60 | 70.0 | |||||||
| Comparative Examples 2 | DB-2 | 1∶0.30∶15 | 0 | 550 | 2 | 3.9 | 14.0 | 24.72 | |
| DB-2’ | 0.9 | 56.0 | |||||||
| Comparative Examples 3 | DB-3 | 1∶0.20∶15 | 0 | 550 | 2 | 3.8 | 12.0 | 24.70 | |
| DB-3’ | 0.88 | 57.1 | |||||||
| Comparative Examples 4 | DB-4 | 1∶0.25∶15 | 0 | 550 | 2 | 3.8 | 13.6 | 24.72 | |
| DB-4’ | 0.86 | 57.8 | |||||||
| Embodiment 1 | S-1 | 1∶0.30∶15 | 25 | 550 | 2 | 3.5 | 15.4 | 24.69 | |
| S-1’ | 0.51 | 62.9 | |||||||
| Embodiment 2 | S-2 | 1∶0.20∶15 | 15 | 600 | 1.5 | 3.7 | 13.0 | 24.71 | |
| S-2’ | 0.86 | 57.8 | |||||||
| Embodiment 3 | S-3 | 1∶0.20∶15 | 25 | 550 | 2 | 3.5 | 13.8 | 24.72 | |
| S-3’ | 0.81 | 60.8 | |||||||
| Embodiment 4 | S-4 | 1∶0.20∶15 | 30 | 550 | 2 | 3.5 | 14.6 | 24.72 | |
| S-4’ | 0.77 | 60.1 | |||||||
| Embodiment 5 | S-5 | 1∶0.25∶15 | 15 | 500 | 3 | 3.6 | 14.0 | 24.70 | |
| S-5’ | 0.81 | 58.0 | |||||||
| Embodiment 6 | S-6 | 1∶0.25∶15 | 25 | 550 | 2 | 3.5 | 14.4 | 24.69 | |
| S-6’ | 0.71 | 62.7 | |||||||
| Embodiment 7 | S-7 | 1∶0.25∶15 | 30 | 550 | 2 | 3.5 | 15.0 | 24.73 | |
| S-7’ | 0.77 | 59.9 | |||||||
| Embodiment 8 | S-8 | 1∶0.30∶15 | 15 | 550 | 2 | 3.6 | 15.0 | 24.71 | |
| S-8’ | 0.82 | 58.0 | |||||||
| Embodiment 9 | S-9 | 1∶0.30∶15 | 30 | 550 | 2 | 3.5 | 15.8 | 24.71 | |
| S-9’ | 0.76 | 60.9 | |||||||
| Embodiment 10 | S-10 | 1∶0.30∶15 | 25 | 520 | 2 | 3.5 | 15.8 | 24.73 | |
| S-10’ | 0.55 | 70.0 | |||||||
*C.R. be sample through 800 ℃/4 hours, the crystallization reservation degree before and after the 100% water vapour atmosphere burin-in process.
Table 2
| Sample number into spectrum | After wearing out in 760 ℃/4 hours | After wearing out in 800 ℃/4 hours | After wearing out in 820 ℃/4 hours | |||
| a 0(nanometer) | C.R(％) | a 0(nanometer) | C.R(％) | a 0(nanometer) | C.R(％) | |
| S-1’ | 2.445 | 73.0 | 2.443 | 62.9 | 2.437 | 50.8 |
| DB-2’ | 2.442 | 61.7 | 2.441 | 56.0 | 2.435 | 31.9 |
By table 1 and table 2 data as can be seen, the REY molecular sieve of preparing with method provided by the invention under the condition of identical rare earth consumption than the method gained sample content of rare earth height of CN1053808A, Na
2O content is low, good hydrothermal stability, and reached the level of conventional " two hand over two roastings " method products obtained therefrom (DB-1 and DB-1 ').
Embodiment 12
The REY molecular sieve that the present embodiment explanation is prepared by the inventive method has the higher catalytic cracking activity stability of preparing than conventional method of REY molecular sieve.
Be carrier with kaolin (kaolin company in Suzhou produces, and product type is that machine selects No. 2), (Qilu Petrochemical company Zhou village catalyst plant is produced, Al with aluminium colloidal sol
2O
3Content is 25%) be bonding agent, be active component with embodiment 10, Comparative Examples 1 and Comparative Examples 2 gained sieve sample S-10, DB-1 and DB-2 respectively, according to molecular sieve: bonding agent: spray-drying was made three kinds of catalyst after the slurries that solid content is 35 heavy % were made in the butt weight ratio making beating of kaolin=18: 20: 62; Then with these three kinds of catalyst respectively according to catalyst: ammonium sulfate: the weight ratio of water=1: 0.1: 20 is twice of 60 ℃ of following pulping and washing, each 15 minutes, use again 40 times to the water of catalyst butt weight twice of 60 ℃ of following pulping and washing, each 15 minutes, oven dry then, three kinds of catalyst of gained are designated as CS-10 respectively, CDB-1 and CDB-2.
With above-mentioned three kinds of catalyst respectively through behind 820 ℃/4 hours or 800 ℃/17 hours, the 100% water vapour atmosphere hydrothermal aging, carry out the micro-activity evaluation, the results are shown in Table 3 for it, the activity level of the inventive method gained rare-earth Y molecular sieve and contrast molecular sieve quite (820 ℃/4 hours aging results) as can be seen, but have the comparison hydro-thermal activity stability more much higher (800 ℃/17 hours aging results) than molecular sieve.
Table 3
| CS-10 | CDB-1 | CDB-2 | |
| Index little alive behind 800 ℃/4 hours, 100% steam aging | 73.5 | 72.0 | 72.0 |
| Index little alive behind 800 ℃/17 hours, 100% steam aging | 74.0 | 62.0 | 69.0 |
Claims (4)
1. method for preparing rare earth Y type molecular sieve, it is characterized in that this method comprises: the NaY molecular sieve is carried out rare earth ion exchanged one time, and the filter cake after it filters entered in the roaster under 450～650 ℃, the condition of 100% water vapour atmosphere roasting 1～4 hour; Described operation above the continuation in the next group rare earth exchanged slurries is returned in 10～40% circulations of the product after the roasting, and all the other are used to prepare catalyst as the REY zeolite product, carry out so continuously.
2. according to the process of claim 1 wherein that the condition of said rare earth ion exchanged is: with NaY molecular sieve and mixed chlorinated rare earth solution according to NaY (dry basis): RECl
3: H
2O=1: (0.15～0.4): the weight ratio making beating of (10～30) mixes, and exchanges 0.5～2 hour down at 60～95 ℃.
3. according to the method for claim 1, it is characterized in that 15～30% circulations of the product after the roasting are returned in the slurries of next group rare earth exchanged.
4. according to the method for claim 1 or 3, the product of roasting that it is characterized in that said circulation is to join to continue exchange in these exchange slurries after NaY is through pre-exchange again.
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| CN1088247A (en) * | 1992-12-17 | 1994-06-22 | 中国石油化工总公司石油化工科学研究院 | A kind of preparation method of high-Si Y-type molecular sieve |
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| WO2014000422A1 (en) | 2012-06-27 | 2014-01-03 | 中国石油化工股份有限公司 | Rare-earth contained y type molecular sieve and preparation method thereof |
| US10130944B2 (en) | 2012-06-27 | 2018-11-20 | China Petroleum & Chemical Corporation | Rare earth-containing Y zeolite and a preparation process thereof |
| WO2014040365A1 (en) | 2012-09-14 | 2014-03-20 | 中国石油化工股份有限公司 | Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor |
| US11111152B2 (en) | 2015-08-05 | 2021-09-07 | Petrochina Company Limited | Preparation method for modified molecular sieve and modified molecular sieve-containing catalytic cracking catalyst |
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| CN1220188A (en) | 1999-06-23 |
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