CN1020269C - Penta-ring structure high silicon zeolite containing rave earth and synthesis - Google Patents
Penta-ring structure high silicon zeolite containing rave earth and synthesis Download PDFInfo
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- CN1020269C CN1020269C CN 89108836 CN89108836A CN1020269C CN 1020269 C CN1020269 C CN 1020269C CN 89108836 CN89108836 CN 89108836 CN 89108836 A CN89108836 A CN 89108836A CN 1020269 C CN1020269 C CN 1020269C
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Abstract
The present invention relates to rare earth containing high silicon zeolite with five membered ring structure, which has an X-ray diffraction spectrogram of the ZSM-5 zeolite group and has narrower pore diameters than ZSM-5 zeolite. The anhydrous chemical expression formula is XRE2O3. YNa2O. Al2O3. ZSiO2, wherein X=0.01-0.30, Y=0.4-0.6, and Z=20-100. The zeolite is synthesized by using REY or REHY zeolite as crystal seeds. The zeolite can be used as a catalytic cracking catalyst promoter to increase the gasoline octane number and can also be used in the processes of catalytic dewaxing, xylene isomerization, etc. for enhancing selectivity.
Description
The invention relates to a kind of synthetic method that contains the five-membered ring structure high-silicon zeolite of rare earth, exactly, about a kind of ZSM-5 of having zeolite family x-ray diffraction spectra, contain the synthetic method of the five-membered ring structure high-silicon zeolite of rare earth.
The sixties Mo ZSM-5 zeolite (USP3,702,886) developed of U.S. Mobil Oil Corporation be a kind of have five-membered ring structure, the aperture is the supersiliceous zeolite of 0.54 * 0.56 nanometer, its framework si-al ratio is more than 12.Because this zeolite has unique pore structure, thereby it is applied in the processes such as isomerization, disproportionation, catalytic cracking, catalytic dewaxing as catalytic material.Because of its in industrial critical role, promoted the fundamental research widely that people carry out its ion exchangeable the subject of knowledge and the object of knowledge.
As everyone knows, the absorption property of zeolite and catalytic performance can carry out modulation by ion exchange technique.For example NaA zeolite and Ca
++The CaA zeolite that obtains after the exchange for just, the isomery hydro carbons has good separating power, thereby is applied to the dewaxing process (USP3,201,490) in the petroleum refining industry; And for example NaY zeolite and RE
3+Its active and stability of the REY zeolite that obtains after the exchange all is better than the former significantly, thereby becomes over nearly more than 20 years most widely used active component (USP3,402,996) in the catalytic cracking catalyst.
Obviously, various ion is introduced the ZSM-5 zeolite and also must be brought influence to the absorption property and the catalytic performance of ZSM-5 zeolite.For example, can infer: after ZSM-5 zeolite intracrystalline is introduced rare earth, its duct will narrow down, and its acidity and cracking activity all will increase.Yet the fact is: though the ZSM-5 zeolite can be gone up the positively charged ion of monovalence and some divalence by conventional ion exchange technique exchange, but it is quite difficult wanting to be similar to the such Tricationic of rare earth in the intracrystalline introducing, its major cause is that this class ion is difficult to and low-density framework aluminum atom negative electricity center coordination mutually (P.Cho and F.G.Dwyer, ACS Symp.Ser., 218,59～78,1983).How in ZSM-5 zeolite synthesis process, to introduce intracrystalline as for the trivalent ion that rare earth is such, be not reported so far.
Purpose of the present invention just provides a kind of synthetic method that contains the five-membered ring structure high-silicon zeolite of rare earth.
The five-membered ring structure high-silicon zeolite that contains rare earth that the present invention makes has the x-ray diffraction spectra of ZSM-5 zeolite family, sees Table 1 column data; Because of it has than ZSM-5 is the big absorption ratio to normal hexane/hexanaphthene, is little aperture so this supersiliceous zeolite has than ZSM-5; Its anhydrous state chemical constitution formula is as follows: XRE
2O
3YNa
2OAl
2O
3ZSiO
2, wherein X=0.01～0.30, Y=0.4～0.6, Z=20～100.
Table 1
Supersiliceous zeolite ZSM-5 of the present invention
Spacing (d) relative intensity (I/Io) spacing (d) relative intensity (I/Io)
11.20 M 11.16 S
9.99 VS 10.03 M
9.71 VW 9.70 VW
7.46 VW 7.43 VW
7.12 VW 7.09 VW
6.73 VW 6.70 VW
6.38 VW 6.36 VW
6.01 VW 5.99 VW
5.72 VW 5.71 VW
5.37 VW 5.37 VW
5.15 VW 5.15 VW
4.987 W 4.991 VW
4.625 VW 4.616 VW
4.374 VW 4.365 VW
4.271 VW 4.265 VW
4.096 VW 4.086 VW
4.017 VW 4.005 VW
3.863 VS 3.856 VS
3.823 VS 3.819 S
3.760 M 3.755 W
3.721 W 3.719 M
Continuous table 1
Supersiliceous zeolite ZSM-5 of the present invention
3.654 W 3.650 W
3.602 VW 3.596 VW
3.491 VW 3.487 VW
3.448 VW 3.443 VW
3.358 VW 3.351 VW
3.321 W 3.311 VW
3.254 VW 3.260 VW
3.181 VW 3.182 VW
3.142 VW 3.140 VW
3.056 VW 3.053 VW
2.999 VW 2.988 VW
2.977 VW 2.970 VW
2.947 VW 2.943 VW
2.870 VW 2.866 VW
2.786 VW 2.786 VW
2.736 VW 2.736 VW
2.688 VW 2.686 VW
2.661 VW 2.662 VW
2.613 VW 2.610 VW
2.595 VW 2.574 VW
2.518 VW 2.516 VW
2.492 VW 2.489 VW
2.420 VW 2.417 VW
2.401 VW 2.399 VW
2.328 VW 2.323 VW
2.111 VW 2.110 VW
VS：80～100%;S：60～80%;M：40～60%;W：20～40%;VW：＜20%。
The preparation method of the five-membered ring structure high-silicon zeolite that contains rare earth provided by the present invention is as follows:
1, in the NaY zeolite be initiator make contain rare earth 2～23%, sodium≤5.0%(all with oxide weight) REY or REHY zeolite;
2, be crystal seed with above-mentioned REY or REHY zeolite, with its be evenly dispersed in be used for conventional synthetic ZSM-5 zeolite contain any organic amine, Na
2O, Al
2O
3, SiO
2, H
2In the colloidal state system of O, the consumption of crystal seed is with each self-contained Al in crystal seed and the colloidal state system
2O
3Weight ratio be 0.05～7.0 to be advisable;
3, the colloidal state system that will contain crystal seed is at 130～200 ℃, leaves standstill crystallization 16～60 hours under best 150～180 ℃, and best 18～28 hours, after filtration, wash, be drying to obtain the five-membered ring structure high-silicon zeolite that contains rare earth provided by the present invention.
Wherein said REY prepare zeolite method as crystal seed is as follows: with NaY zeolite and re chloride according to zeolite (base burns): RECl
3: H
2O is 1: 0.01～1.0: 10～100, is preferably 1: 0.01～0.4: 20～50 weight ratio is at 50～150 ℃, and best 60～120 ℃ of exchanges 0.2～2.0 hour are down filtered, and filter cake was 400～600 ℃ of roastings 0.5～4.0 hour.Zeolite after the roasting can carry out the exchange second time, roasting as stated above.
Wherein said REHY prepare zeolite method as crystal seed is as follows: with NaY zeolite and ammonium sulfate solution according to zeolite (base burns): (NH
4)
2SO
4: H
2O is 1: 0.2～4.0: 10～40, is preferably 1: 0.8～2.0: 20～30 weight ratio is at 50～150 ℃, best 80～120 ℃ of exchanges 0.2～2.0 hour down.This exchange step can repeat 1～2 time.Filter filter cake 400～600 ℃ of roastings 0.5～4.0 hour in the dry air that flows.Zeolite after the roasting and re chloride are according to zeolite (base burns): RECl
3: H
2O is 1: 0.05～1.0: 10～100, and best 1: 0.2～0.8: 20～50 weight ratio is at 50～150 ℃, and best 80～120 ℃ exchange 0.2～2.0 hour down, filter.
The five-membered ring structure high-silicon zeolite that contains rare earth that makes with the present invention is through the NH of routine
+ 4Ion-exchange flush away Na
+After be aided with SiO
2, Al
2O
3Or SiO
2Al
2O
3Can be used as assisted catalyst for catalyzing cracking to improve product gasoline octane rating bucket in carrier, for example, with triumph decompressed wax oil (197～479 ℃ of boiling ranges) is that stock oil is when carrying out catalytic cracking, adding zeolite provided by the present invention is promotor, when the zeolite consumption is catalyzer general reserve 1 weight %, the more conventional cracking catalyst of product gasoline octane rating bucket and be that the cracking catalyst of auxiliary agent improves 4～12% and 6～14% respectively with ZSM-5, coking yield are that the cracking catalyst of promotor reduces by 10～20% than ZSM-5 then.This zeolite also can be used for processes such as catalytic dewaxing, xylene isomerization to improve selectivity.
Following example will give further instruction to the preparation method who contains the five-membered ring structure high-silicon zeolite of rare earth provided by the present invention.
Example 1
The preparation of crystal seed REY and REHY.
Getting silica alumina ratio and be 5.0(X optical diffraction method measures) NaY zeolite 100 grams (base burns), be dispersed in 2500 grams, 1 heavy %RECl
3(chemical plant, packet header Industrial products wherein contain Ce
2O
349%, La
2O
324%) in the solution, 90 ℃ of ion-exchange under agitation 30 minutes is filtered, and filter cake was 550 ℃ of following roastings 2 hours.Repeat above-mentioned exchange one roasting once, obtain consisting of RE
2O
319.0%, Na
2O1.5%, Al
2O
318.5%, SiO
261.0% REY zeolite (Na wherein
2O is recorded by atomic absorption spectrum, and all the other compositions are recorded by the X-ray fluorometric method).
Be that 3.2 and 4.2 NaY zeolite is a starting raw material with silica alumina ratio respectively, make as stated above to form and be respectively RE
2O
322.5%, Na
2O0.8%, Al
2O
325.8%, SiO
250.1% and RE
2O
319.5%, Na
2O0.5%, Al
2O
322.2%, SiO
257.8% REY zeolite.
Get silica alumina ratio and be 5.0 NaY zeolite 100 grams, be dispersed in 2100 grams, 5 heavy %(NH
4)
2SO
4In (Beijing Chemical Plant's product, chemical pure) solution, ion-exchange is 30 minutes under boiling temperature, mends into distilled water constant to keep liquor capacity during exchange at any time.The roasting 2 hours in 550 ℃ of mobile dry air of dope filtration after the exchange, filter cake.Sample after the roasting joins 5000 grams, 1 heavy %RECl
3In the solution, 90 ℃ of ion-exchange under agitation 30 minutes obtains consisting of RE after the filtration
2O
316.0%, Na
2O0.8%, Al
2O
321.0%, SiO
262.2% REHY zeolite.
Example 2～11
Prepare the five-membered ring structure high-silicon zeolite that contains rare earth by method provided by the invention.
Getting a certain amount of (by burning base) is that ethamine (Shanghai insecticide factory Industrial products, the content 40 heavy %) solution of 0.371 grams per milliliter is dispersed in 283 grams and contains Na as the REY of crystal seed or REHY zeolite and 15 ml concns
2O3.1%, SiO
29.9% water glass (Nanjing inorganic chemical industry factory Industrial products, SiO
2Content 28.0%, modulus 3.2) in the solution, under agitation adds the AlCl of different aluminum contents
3(Beijing Chemical Plant's product, chemical pure) solution 41.4 grams, PH to 10.5～11.0 of adjusting system with 10 heavy % hydrochloric acid make it to form gel, can calculate the colloidal that generates by charging capacity and consist of: 26C
2H
5NH
212Na
2OnRE
2O
3Al
2O
3100SiO
2MH
2O, m=3740 in the example 9,10,11, m=3470 in all the other examples.
Colloid is put into the crystallizing kettle crystallization, cool off, filter, be washed to neutrality then, 110～120 ℃ of oven dry promptly get the said five-membered ring structure high-silicon zeolite that contains rare earth among the present invention.
Each parameter value sees Table 2 in the example.
Above-mentioned each sample all has the listed x-ray diffraction spectra of table 1, and their weight compositional analysis and absorption property analytical resultss are separately listed in table 3 and the table 4 respectively.Na
2O content is recorded by atomic absorption spectrum, RE
2O
3, Al
2O
3, SiO
2Content is recorded by the X-ray fluorometric method.Absorption property is measured with weight absorption instrument, and the sample before the absorption is in advance through 850 ℃ of roastings 2 hours, and adsorptive pressure is 39 mmhg, and adsorption temp is 18～20 ℃, and adsorption time is 2 hours.
Table 3
The example compositional analysis, heavy % sial rubs
You compare * RE2O3 Na2O Al2O3 SiO2
2 1.5 0.6 2.0 95.9 81.52
3 2.0 0.6 2.2 95.4 73.71
4 0.7 0.8 2.4 96.1 68.07
5 0.5 0.9 2.6 96.0 62.76
6 1.5 0.6 2.0 95.9 81.52
7 1.5 0.6 2.0 95.9 81.52
8 1.5 0.6 2.0 95.9 81.52
9 1.1 0.7 2.2 96.0 74.19
10 0.9 0.8 2.3 96.0 70.96
11 1.2 0.7 2.3 95.8 70.81
ZSM-5 0 1.4 2.2 96.4 74.49
REZSM-5 0.45 0.5 2.2 96.85 74.83
* calculate by compositional analysis.
Table 4
The example adsorptive capacity, milligram/gram normal hexane adsorptive capacity
Normal hexane * cyclohexane * * cyclohexane adsorptive capacity
2 102.5 13.3 7.70
3 104.5 10.8 9.68
4 103.6 14.4 7.19
5 101.5 12.8 7.92
9 103.5 12.8 8.09
10 101.5 14.5 7.00
11 101.5 12.8 7.93
ZSM-5 112.0 52.2 1.98
REZSM-5 111.8 55.1 2.03
* the normal hexane kinetic diameter is 0.43 nanometer;
* hexanaphthene kinetic diameter is 0.61 nanometer.
Example 12
Prepare the five-membered ring structure high-silicon zeolite that contains rare earth by method provided by the invention.
Getting ethylamine solution that 2.0 grams (by burning base) are 0.371 grams per milliliter as REY zeolite (initial NaY silica alumina ratio is 5.0) and 5 ml concns of crystal seed is dispersed in 200 and restrains and contain Na
2O3.3%, SiO
2In 10.0% the water glass solution, under agitation add Al
2O
3Content is 1.3% AlCl
3Solution 43.6 grams, PH to 10.5～11.0 of adjusting system with 10 heavy % hydrochloric acid make the formation gel, can calculate the colloidal that generates by charging capacity and consist of: 4.5C
2H
5NH
24.2Na
2O0.12RE
2O
3Al
2O
338.4SiO
21500H
2O.Colloid is added in the crystallizing kettle, and neutrality, 110～120 ℃ of oven dry are cooled off, filter, are washed to 180 ℃ of crystallization 16 hours then.
This sample has the listed x-ray diffraction spectra of table 1, and its weight compositional analysis and the silica alumina ratio that calculates are thus listed in the table 5.
Table 5
RE2O3, Na2O, Al2O3, SiO2, sial
The heavy % mol ratio of the heavy % of the heavy % of heavy %
1.5 0.7 4.5 93.3 35.25
Comparative example
For comparing, prepare ZSM-5 zeolite and REZSM-5 zeolite by the method for prior art with the said five-membered ring structure high-silicon zeolite that contains rare earth among the present invention.
The ethylamine solution of getting 2.0 gram (burn base) ZSM-5 zeolite (dying of Shanghai seven factory's industrial goods, silica alumina ratio 60) crystal seeds and 15 ml concns and be 0.371 grams per milliliter is dispersed in 283 and restrains and contain Na
2O3.1%, SiO
2In 9.9% the water glass solution, stir down slowly adding and contain Al
2O
31.16% AlCl
3Solution 41.4 grams; PH to 10.5～11.0 of adjusting system with 10 heavy % hydrochloric acid make it to form gel, can calculate the colloidal that generates by charging capacity and consist of: 26C
2H
5NH
212Na
2OAl
2O
3100SiO
23470H
2O.Colloid is added in the crystallizing kettle about 20 hours of 160～170 ℃ of following crystallization, cool off, filter, be washed to neutrality, 110～120 ℃ then and be drying to obtain the ZSM-5 zeolite.
Get a certain amount of above-mentioned ZSM-5 zeolite that synthesizes through 550 ℃ of roastings after 2 hours, according to zeolite: RECl
3: the weight ratio of deionized water=1: 0.5: 20,90 ℃ of ion-exchanges twice under agitation, each 30 minutes, filter, 110～120 ℃ are drying to obtain the REZSM-5 zeolite.
The X-ray diffraction data of above-mentioned ZSM-5 and REZSM-5 zeolite, weight compositional analysis and absorption property analytical results are listed in table 1, table 3 and the table 4 respectively.
Example 13
When the five-membered ring structure high-silicon zeolite that contains rare earth provided by the invention is used as assisted catalyst for catalyzing cracking, have the advantages that to improve product gasoline octane rating bucket, reduce coking yield.
Respectively with silica gel (water glass and sulfuric acid reaction make), aluminium glue (intending thin water aluminium powder and hydrochloric acid reaction makes), (step-by-step precipitation method makes alumino silica gel, wherein contains SiO
283 heavy %, Al
2O
317 heavy %) be promotor carrier precursor, according to zeolite (burn base): the weight ratio of carrier=20: 80 adds the ZSM-5 that makes in the zeolite that makes in the example 2,3,4,11,12 and the comparative example and REZSM-5 zeolite water respectively and grinds the back and add in the carrier precursor glue, spraying drying behind the homogeneous is used NH then
+ 4Exchange and be washed to the Na in the microballoon
2O＜0.15%, 120 ℃ is drying to obtain the catalytic cracking promotor.
On fixed fluidized bed catalytic cracking unit with triumph decompressed wax oil (197～479 ℃ of boiling ranges, carbon residue amount 0.06 heavy %) be stock oil, poiser with Y-7 cracking catalyst (Zhou village, Shandong catalyst plant Industrial products) is a base catalyst, the bodying agent loading amount is 150 grams, the device of promotor accounts for 1.0 heavy % of bodying agent in zeolite weight, under the reaction conditions of 500 ℃ of temperature of reaction, weight space velocity 8.0, agent-oil ratio (calculating) 4.0, the performance of above-mentioned each promotor is evaluated, be the results are shown in table 6 by bodying agent.Wherein research octane number (RON) system is recorded by chromatography; Octane value bucket=research octane number (RON) X gasoline yield; * the auxiliary agent carrier is SiO
2, * * auxiliary agent carrier is Al
2O
3, all the other auxiliary agent carriers are SiO
2Al
2O
3
Can find out by table 6 data: use the five-membered ring structure high-silicon zeolite that contains rare earth provided by the invention as assisted catalyst for catalyzing cracking, can make the transformation efficiency of conventional cracking catalyst improve 12～19%; Octane value bucket raising 6～14%, coking yield than the ZSM-5 promotor reduce by 10～20%.
Claims (7)
1, a kind of preparation method with high-Si zeolite containing rare-earth five-membered ring structure of ZSM-5 zeolite family x-ray diffraction spectra, it is characterized in that this zeolite prepares by following method: in the REY or the REHY zeolite that contain rare earth 2～23%, sodium≤5.0% (all with oxide weight) is crystal seed, with crystal seed be evenly dispersed in be used for conventional synthetic ZSM-5 zeolite contain any organic amine, Na
2O, Al
2O
3, SiO
2, H
2In the colloidal state system of O, the consumption of crystal seed is with each self-contained Al in crystal seed and the colloidal state system
2O
3Weight ratio be 0.05～7.0 to be advisable, under 130～200 ℃, leave standstill 16～60 hours after-filtration of crystallization, washing, drying.
2,, it is characterized in that said REY zeolite seed crystal prepares by following method according to the described preparation method of claim 1: with NaY zeolite and re chloride according to zeolite (base burns): RECl
3: H
2O is: 1: 0.01～1.0: 10～100 weight ratio exchanges 0.2～2.0 hour down at 50～150 ℃, filters, and filter cake was 400～600 ℃ of roastings 0.5～4.0 hour, and the zeolite after the roasting can repeat above-mentioned steps and carry out the exchange second time, roasting.
3,, it is characterized in that said REHY zeolite seed crystal prepares by following method according to the described preparation method of claim 1: with NaY zeolite and ammonium sulfate solution according to zeolite (base burns): (NH
4)
2SO
4: H
2O is 1: 0.2～0.4: 10～40 weight ratio 50～150 ℃ of exchanges 0.2～2.0 hour down, this exchange step can repeat 1～2 time, filter, filter cake 400～600 ℃ of roastings 0.5～4.0 hour in the dry air that flows, the zeolite after the roasting and re chloride are according to zeolite (it is basic to burn): RECl
3: H
2O is 1: 0.05～1.0: 10～100 weight ratio 50～150 ℃ of exchanges 0.2～2.0 hour down, filters.
4,, it is characterized in that the said crystallization that leaves standstill carried out 18～28 hours under 150～180 ℃ according to the described preparation method of claim 1.
5,, it is characterized in that said NaY zeolite and re chloride are according to zeolite (base burns): RECl according to the described preparation method of claim 2
3: H
2O is that 1: 0.1～0.4: 20～50 weight ratio exchanges under 60～120 ℃.
6,, it is characterized in that said NaY zeolite and ammonium sulfate solution are according to zeolite (burn base): (NH according to the described preparation method of claim 3
4)
2SO
4: H
2O is that 1: 0.8～2.0: 20～30 weight ratio exchanges under 80～120 ℃.
7,, it is characterized in that said zeolite and re chloride are according to zeolite (base burns): RECl according to the described preparation method of claim 3
3: H
2O is that 1: 0.2～0.8: 20～50 weight ratio exchanges under 80～120 ℃.
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|---|---|---|---|
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|---|---|---|---|
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| CN1020269C true CN1020269C (en) | 1993-04-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101052136B1 (en) * | 2002-08-28 | 2011-07-26 | 알베마를 네덜란드 비.브이. | Process for preparing doped pentasil zeolite using doped reactant |
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|---|---|---|---|---|
| CN1041399C (en) * | 1994-12-30 | 1998-12-30 | 中国石油化工总公司 | Rare-earth-ZSM5/ZSM11 cocrystallization zeolite |
| CN1048655C (en) * | 1996-06-24 | 2000-01-26 | 中国石油化工总公司 | Alkyl catalyst and application thereof |
| CN1078821C (en) * | 1997-08-27 | 2002-02-06 | 中国石油化工集团公司 | Beta zeolite containing rare-earth and preparation method therefor |
| BR0313908B1 (en) * | 2002-08-28 | 2013-07-09 | process for preparing doped pentasil zeolites using doped faujasite seeds | |
| BR0313822B1 (en) * | 2002-08-28 | 2012-09-18 | process for the preparation of doped pentasil-type zeolite using doped seeds. | |
| CN1257769C (en) | 2003-10-31 | 2006-05-31 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphor and metal component and its use |
| JP5053098B2 (en) | 2004-12-28 | 2012-10-17 | 中國石油化工股▲フン▼有限公司 | Catalyst and method for cracking hydrocarbons |
| CN100357399C (en) | 2005-03-31 | 2007-12-26 | 中国石油化工股份有限公司 | Process for preparing cracking catalyst |
| CN101134913B (en) | 2006-08-31 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrocarbons catalytic conversion method |
| CN101134172B (en) | 2006-08-31 | 2010-10-27 | 中国石油化工股份有限公司 | Hydrocarbons conversion catalyzer |
| CN103204519B (en) * | 2013-04-15 | 2015-06-03 | 珠海市吉昌稀土有限公司 | Synthetic method of rare-earth silicon-aluminum molecular sieve |
-
1989
- 1989-11-30 CN CN 89108836 patent/CN1020269C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101052136B1 (en) * | 2002-08-28 | 2011-07-26 | 알베마를 네덜란드 비.브이. | Process for preparing doped pentasil zeolite using doped reactant |
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| Publication number | Publication date |
|---|---|
| CN1052290A (en) | 1991-06-19 |
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