CN1027632C

CN1027632C - Process for preparing high-Si zeolite containing rare-earth five-membered ring structure

Info

Publication number: CN1027632C
Application number: CN 90104732
Authority: CN
Inventors: 付维; 舒兴田; 祝惠华; 何鸣元
Original assignee: Sinopec Research Institute of Petroleum Processing
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Priority date: 1990-07-23
Filing date: 1990-07-23
Publication date: 1995-02-15
Anticipated expiration: 2005-07-23
Also published as: CN1058382A

Abstract

The present invention relates to a method for synthesizing high silicon zeolite containing rare earth without using amine, which comprises: a colloidal system with water glass, aluminum phosphate and inorganic acid as raw materials and REY or REHY zeolite as crystal seeds is crystallized at 130 to 200 DEG C for 12 to 60 hours, and then, products are filtered, washed and dried. The zeolite has an X-ray diffraction spectrogram of the ZSM-5 zeolite group and has pore canals narrower than those of ZSM-5 zeolite. The zeolite can be used in the application field of ZSM-5 zeolite, for example the zeolite can be used as auxiliary agents of cracking catalysts to simultaneously increase the gasoline octane number and maintains a high gasoline yield. Besides, the zeolite has favorable activity stability.

Description

Process for preparing high-Si zeolite containing rare-earth five-membered ring structure

The present invention relates to a kind of preparation method of five-membered ring structure high-silicon zeolite of containing rare earth, specifically relate to the preparation method who does not use organic amine of a kind of ZSM-5 of having zeolite family five-membered ring structure high-silicon zeolite x-ray diffraction spectra, that contain rare earth.

Early seventies has unique pore passage structure by the ZSM-5 zeolite (USP3702886) of U.S. Mobil company invention, is widely used in alkylation, isomerization, disproportionation, catalytic cracking, catalytic dewaxing and by in the reaction process such as methanol synthesized gasoline.Early stage synthetic ZSM-5 zeolite is to use organic amine as template, because organic amine price height, and poisonous, so people have also done a large amount of research work to the ZSM-5 zeolite synthesis method of not using organic amine when using its synthetic ZSM-5 zeolite.GerOffen.2,643, use in 929(1977) alcohols such as Virahol to replace the synthetic ZSM-5 zeolite of organic amine.USP4,175, use NH in 114(1979) ₄OH and ethanol substitute organic amine and prepare the ZSM-5 zeolite.EP111 has reported that use water glass, aluminum phosphate and phosphoric acid synthesize the ZSM-5 zeolite in 748(1984).Be the synthetic ZSM-5 zeolite of raw material with water glass, inorganic aluminate and mineral acid among the CN85100463.

People have done widely its absorption of change or catalytic performance in each metal ion species and the compound introducing zeolite thereof and have explored on the other hand, USP4,374, reported that phosphorus and rare earth are deposited on the contraposition product selectivity that can improve its p-Xylol isomerization catalyzed reaction in the ZSM-5 zeolite in 294(1981).RE on the NaY zeolite exchange ³⁺Ion can make its activity and stability all be significantly improved.But for the ZSM-5 zeolite, the framework si-al ratio height, and unique pore passage structure is arranged, very limited with the rare earth ion that the method for ion-exchange is introduced.CN1020269C has reported the synthetic technology of high-Si zeolite containing rare-earth five-membered ring structure in the presence of organic amine, but the existence of organic amine can cause environmental pollution.

On the basis of existing technology, the purpose of this invention is to provide a kind of method of synthesizing the ZSM-5 zeolite family five-membered ring structure high-silicon zeolite that contains rare earth under the situation of organic amine existence of not having.

The preparation method who contains the five-membered ring structure high-silicon zeolite of rare earth provided by the invention is:

To contain REY or the REHY zeolites that (with oxide compound) rare earth 2～23 heavy % and sodium is lower than 5.0 heavy % is crystal seed, crystal seed is dispersed in the system of being made up of water glass, aluminium salt or aluminate and mineral acid, in the crystal seed salic and all the other components salic weight ratio be 0.05～3.0, each respective components consumption is identical in the ordinary method of the synthetic ZSM-5 zeolite of all the other each amounts of components and no amine, above-mentioned reaction system was descended static crystallization 12～60 hours at 130～200 ℃, filter, washing, dry getting final product.

Said aluminium salt can be Tai-Ace S 150, aluminum chloride, aluminum nitrate or aluminum phosphate, preferably aluminum phosphate.Aluminate can be a sodium metaaluminate.

Preparation method provided by the present invention is preferably:

(with oxide compound) rare earth 2～23 heavy % and sodium are lower than 5.0 heavy %REY or the REHY zeolite is a crystal seed to contain, crystal seed is dispersed in the colloidal dispersion of being made up of water glass, aluminum phosphate and mineral acid, crystal seed salic and colloidal dispersion salic weight ratio be 0.05～3.0, above-mentioned reaction system was 130～200 ℃ of static crystallization 12～60 hours, filter, washing, drying gets final product.

Said crystal seed REY and REHY zeolite can make with the conventional preparation method of REY and REHY zeolite, and for example available following method makes:

(1) preparation REY zeolite

NaY zeolite and re chloride are pressed zeolite (butt): RECl ₃: H ₂O is 1: 0.01～1.0: 10～100, preferably 1: 0.1～0.4: 20～50 weight ratio mixes, at 50～150 ℃, carry out 0.2～2.0 hour ion exchange reaction under best 80～120 ℃, filter, filter cake was 400～600 ℃ of following roastings 0.5～4.0 hour, and the zeolite after the roasting can carry out primary ions permutoid reaction, filtration and roasting process as stated above again, gets final product.

(2) preparation REHY zeolite

NaY zeolite and ammoniumsulphate soln are pressed zeolite (butt): (NH ₄) ₂SO ₄: H ₂O is 1: 0.2～4.0: 10～40, best 1: 0.8～2.0: 20～30 weight ratio mixes, at 50～150 ℃, carry out 0.2～2.0 hour ion exchange reaction under best 80～120 ℃, filter, above-mentioned ion exchange reaction and filtration procedure can repeat 1～2 time, filter cake 400～600 ℃ of following roastings 0.5～4.0 hour in the dry air that flows.Zeolite after the roasting and re chloride are pressed zeolite (butt): RECl ₃: H ₂O is 1: 0.05～1.0: 10～100, and best 1: 0.2～0.8: 20～50 weight ratio mixes, at 50～150 ℃, carry out 0.2～2.0 hour ion exchange reaction under best 80～120 ℃, filter, filter cake gets final product 400～600 ℃ of following roastings 0.5～4.0 hour.

(mol ratio) SiO preferably in the said colloidal dispersion of forming by water glass, aluminum phosphate and mineral acid ₂/ Al ₂O ₃Be 30～120, Na ₂O/Al ₂O ₃Be 2～15, H ₂O/SiO ₂Be 20～100, P ₂O ₅/ Al ₂O ₃Be 0.1～20.Aluminum phosphate can be AlPO ₄, Al(H ₂PO ₄) ₃, Al ₂(HPO ₄) ₃, preferably gluey aluminum phosphate.Mineral acid can be phosphoric acid, sulfuric acid or hydrochloric acid.The consumption of mineral acid is so that its reactant is tied to form colloidal state is advisable, and the pH value that preferably makes its system is 10～12 to be advisable.

Above-mentioned gluey aluminum phosphate can be pressed aluminum oxide: H by pseudo-boehmite and phosphate aqueous solution ₃PO ₄: H ₂O is 1: 1～4: 1～20, and best 1: 1.5～2.5: 2～10 weight ratio mixes and gets, and preferably at room temperature places after 24 hours to re-use.

The supersiliceous zeolite that adopts method provided by the invention to prepare can contain rare earth RE ₂O ₃/ Al ₂O ₃(mol ratio) 0.01～0.5, silica alumina ratio SiO ₂/ Al ₂O ₃(mol ratio) is 20～100.

The supersiliceous zeolite of preparing with the inventive method has the x-ray diffraction spectra of ZSM-5 zeolite family, sees Table 1, and the ZSM-5 zeolite is the ZSM-5 zeolite (silica alumina ratio is 38, and degree of crystallinity is 90%) that Nankai University produces in the table.By finding out in the table that supersiliceous zeolite that the present invention prepares has the five-ring crystalline structure of ZSM-5 zeolite family.This zeolite sees Table 2 to the adsorptive capacity of normal hexane and hexanaphthene, this zeolite has the normal hexane adsorptive capacity of working as with the ZSM-5 zeolite facies as seen from the table, but the adsorptive capacity to hexanaphthene is starkly lower than the ZSM-5 zeolite, so the duct of the orifice throat ratio ZSM-5 zeolite of the five-membered ring structure high-silicon zeolite that the inventive method is prepared is narrow.

The supersiliceous zeolite that contains rare earth with method preparation of the present invention is applicable to the applied field of ZSM-5 zeolite, for example be used for catalytic cracking, catalytic dewaxing, xylene isomerization, alkylation and methanol conversion and generate reaction process such as alkene, with its promotor as the catalytic cracking of hydrocarbon process, can when improving gasoline octane rating, still keep higher yield of gasoline, and this zeolite has good activity stability.

Below will the present invention will be further described by embodiment.

Preparation REY and REHY zeolite:

Get NaY zeolite (silica alumina ratio is 5.0, and Qilu Petrochemical company catalyst plant is produced) 100 grams (butt), being dispersed in 2500 gram concentration is the RECl of 1 heavy % ₃(chemical plant, packet header produces, and contains Ce ₂O ₃49 heavy %, La ₂O ₃24 heavy %) in the solution, stir down, carry out 30 minutes ion exchange reactions under 90 ℃, filter, filter cake carries out above-mentioned ion-exchange, filtration and roasting process once more 550 ℃ of following roastings 2 hours, promptly gets the REY zeolite and (contains RE ₂O ₃19.0 heavy %, Na ₂The heavy % of O1.5, Al ₂O ₃18.5 heavy % and SiO ₂61.0 heavy %) be designated as REY1.

Be that 3.2 and 4.2 NaY zeolite is a raw material with silica alumina ratio respectively, make as stated above and contain RE ₂O ₃23.0 heavy, Na ₂O0.8 heavy %, Al ₂O ₃25.8 heavy and SiO ₂50.1 the REY zeolite of heavy % is designated as REY2 and contains RE ₂O ₃19.5 heavy %, Na ₂O0.5 heavy %, Al ₂O ₃22.2 heavy % and SiO ₂57.8 the REY zeolite of heavy % is designated as REY3.

Get 100 gram (butt) NaY(silica alumina ratios 5.0) to be dispersed in 2100 gram concentration be the (NH of 5 heavy % to zeolite ₄) ₂SO ₄In the solution, carry out ion exchange reaction 30 minutes under 90 ℃, filter, repeat ion-exchange and filtration procedure twice, filter cake roasting 2 hours in 550 ℃ of mobile dry air, it is the RECl of 1.6 heavy % that the sample after the roasting is added to 3000 gram concentration ₃In the solution, under agitation carried out ion exchange reaction 30 minutes in 90 ℃, filter, filter cake is 550 ℃ of following roastings 2 hours, promptly gets to contain RE ₂O ₃10.0 heavy %, Na ₂O0.6 heavy %, Al ₂O ₃20.0 heavy %SiO ₂69.4 the REHY zeolite of heavy %.

Example 1

1, get 60 gram (butt) pseudo-boehmites (Shandong Aluminum Plant's production), stirring and being dispersed in 375 gram concentration down is in the phosphate aqueous solution of 30 heavy %, must contain Al ₂O ₃14.0 the aluminum phosphate colloidal solution of heavy %, room temperature is transferred the usefulness of purchasing.

2, get 2.6 grams and contain RE ₂O ₃19.5 the REY3 zeolite of heavy %, (oil-refining chemical factory in Chang Ling produces, and contains Na to add 195 gram water glass ₂The heavy % of O3.7, SiO ₂11.7 heavy %), stir, add 51.7 grams and contain Al ₂O ₃1.5 the aluminum phosphate colloidal solution of heavy % (goes on foot the gains thin up to containing Al with the 1st ₂O ₃1.5 heavy %), with concentration be the H of 23 heavy % ₃PO ₄It is 11 that solution is transferred the pH value of solution, makes it form gel state, and this system consists of:

0.20RE ₂O ₃3.10Na ₂OAl ₂O ₃50.00SiO ₂4.10P ₂O ₅1680H ₂O 180 ℃ of static crystallization 30 hours, cools off this system then, filters, and is washed to filtrate for neutral, and 110～120 ℃ of dryings promptly get and contain RE ₂O ₃1.9 heavy %, silica alumina ratio are the 36.4(mol ratio) and RE ₂O ₃/ Al ₂O ₃Than (mol ratio) 0.136 supersiliceous zeolite A.

Example 2

Getting 2 gram REY1 zeolites is dispersed in 180 gram water glass (Qilu Petrochemical company catalyst plant is produced, and contains Na ₂The heavy % of O3.8, SiO ₂11.0 heavy %) in the solution, add 43.7 grams under stirring and contain Al ₂O ₃1.1 the aluminum phosphate colloid of heavy % (being got by the 1st step of example 1 gained thin up), slowly adding concentration is that 11.0 phosphoric acid solution to the systems that weigh % form till the gel state, and this system consists of:

0.24RE ₂O ₃3.85Na ₂OAl ₂O ₃70.0SiO ₂6.5P ₂O ₅2765H ₂This system of O was in 180 ℃ of following crystallization 26 hours, and cooling is then filtered, and was washed to filtrate for neutral, and 110 ℃ of dryings promptly get and contain rare earth oxide 1.1 heavy %, and silica alumina ratio is 52.1 and RE ₂O ₃/ Al ₂O ₃Than the supersiliceous zeolite B that is 0.109.

Example 3

1, an amount of pseudo-boehmite adds in the phosphate aqueous solution that concentration is 30 heavy %, constantly stirs, and must contain Al ₂O ₃7.1 heavy % and PO ^3- ₄23.1 the gluey aluminum phosphate solution of heavy %.

2, getting 3 gram REHY zeolites is dispersed in the 195 gram water glass (identical with example 1), stir in the aluminum phosphate solution that adds 53.2 grams salic 0.81 heavy % down (the 1st step of thin up gains and get), with concentration be the phosphoric acid solution of 3.4 heavy % to transfer the pH value of system be 10.8, this system consists of:

0.21RE ₂O ₃2.5Na ₂OAl ₂O ₃90.0SiO ₂8.3P ₂O ₅4950H ₂This system of O was 170 ℃ of following crystallization 26 hours, and cooling is then filtered, and washed with water to filtrate neutrality, and 120 ℃ of dryings promptly get and contain rare earth oxide 1.8 heavy %, and silica alumina ratio is 70.4 and RE ₂O ₃/ Al ₂O ₃Than the supersiliceous zeolite C that is 0.241.

Example 4

Get 2.7 grams and contain RE ₂O ₃23.0 the REY2 zeolite of heavy % is dispersed in 180 gram water glass (identical with the example 2) solution, stirs 42.1 grams of adding down and contains Al ₂O ₃0.80 the aluminum phosphate colloidal solution of heavy % (add the 1st step of dilution example 1 gains and get) slowly drips concentration and is 10.9 and weighs the H of % ₃PO ₄Solution forms to above-mentioned mixed solution till the gel, the consisting of of this system:

0.42RE ₂O ₃7.14Na ₂OAl ₂O ₃99.9SiO ₂8.8P ₂O ₅3980H ₂The above-mentioned colloid of O was in 195 ℃ of following crystallization 13 hours, and cooling is then filtered, and was washed with water to filtrate for neutral, and 110～120 ℃ of dryings promptly get and contain RE ₂O ₃2.2 heavy %, silica alumina ratio are 73.4 and RE ₂O ₃/ Al ₂O ₃Supersiliceous zeolite D than 0.350.

Example 5

Get 1 gram and contain RE ₂O ₃23.0 the REY2 zeolite of heavy %, be dispersed in 180 gram water glass (same) solution with example 2, stir the aluminum phosphate solution that adds 42.1 grams salic 1.0 heavy % down (the 1st step of example 1 gains thin up and get), with concentration is that to transfer the pH value of system be 10.5 for the hydrochloric acid soln of 10.5 heavy %, this system is cooled off then, is filtered 170 ℃ of crystallization 26 hours, wash with water to filtrate for neutral, 110 ℃ of dryings promptly get and contain RE ₂O ₃1.0 heavy %, silica alumina ratio are 60.2 and RE ₂O ₃/ Al ₂O ₃Than the supersiliceous zeolite E that is 0.114.

Example 6

Method preparation by example 5 contains RE ₂O ₃0.9 heavy %, silica alumina ratio are 57.9 and RE ₂O ₃/ Al ₂O ₃Than the supersiliceous zeolite F that is 0.999, just be the pH value of the sulphuric acid soln accent system of 32.0 heavy % with concentration.

Example 7

Getting 2 gram REY2 zeolites is scattered in the 200 gram water glass (identical with example 1), aluminum phosphate solution (the 1st step of example 1 gains thin up forms) 75.8 grams that add salic 1.5 heavy %, stir, slowly adding concentration is that 5.1 phosphoric acid solution to the mixed solutions that weigh % are till the colloidal state, and this system consists of:

0.12RE ₂O ₃·2.2Na ₂O·Al ₂O ₃·35SiO ₂·1575H ₂O

This colloidal state mixed solution was 145 ℃ of crystallization 40 hours, and cooling is then filtered, wash with water to filtrate for neutral, 120 ℃ of dryings promptly get and contain RE ₂O ₃1.5 heavy %, silica alumina ratio are 25.0 and RE ₂O ₃/ Al ₂O ₃Than the supersiliceous zeolite G that is 0.75.

Example 8

Get REY(Chang Ling oil-refining chemical factory and produce RE ₂O ₃=18.0%) zeolite 2 grams, be dispersed in the 180 gram water glass (identical) with water glass in the example 2, stirring and to add alum liquor 52.0 grams that concentration is 3.1 heavy % down, is that the pH value of the phosphoric acid solution accent system of 11.3 heavy % is 10.5～11 with concentration, and this system consists of:

0.23RE ₂O ₃3.97Na ₂OAl ₂O ₃70.0SiO ₂5.48P ₂O ₅2870H ₂The above-mentioned system of O was 180 ℃ of crystallization 26 hours, and cooling is then filtered, and was washed till filtrate for neutral, and 120 ℃ of dryings promptly get the supersiliceous zeolite H that contains rare earth 1.7 heavy %.

The degree of crystallinity that records zeolite H with x-ray diffraction method is 40.3%, is mixed with the part amorphous substance in the sample.As seen embodiment is crystal seed with the REY zeolite thus, it is scattered in no amine exists in the material system that synthesizes ZSM-5 zeolite ordinary method, can synthesize the supersiliceous zeolite that contains rare earth.

Example 9

Survey the crystalline structure of the supersiliceous zeolite that the inventive method makes with x-ray diffraction method, and compare, the results are shown in Table 1 with ZSM-5 zeolite (Nankai University's production).

By table 1 as seen, the supersiliceous zeolite made from the inventive method that contains rare earth has the x-ray diffraction spectra of ZSM-5 zeolite family, so it has the five-ring crystalline structure of ZSM-5 zeolite family.

Example 10

Press zeolite: (NH) ₂SO ₄: H ₂O is 1: 1: 20 a weight ratio, respectively supersiliceous zeolite A～G, ZSM-5 zeolite and acid ammonium solution are mixed, carry out ion exchange reaction half an hour under 90 ℃, filter, repeat ion-exchange again and filter once washing, 110 ℃ of dryings, 550 ℃ of roastings 2 hours promptly get Hydrogen supersiliceous zeolite A～G and Hydrogen ZSM-5 zeolite.

Measure above-mentioned Hydrogen supersiliceous zeolite A～G that contains rare earth and Hydrogen ZSM-5 zeolite and REZSM-5 zeolite * to the absorption property of normal hexane and hexanaphthene with weight absorption instrument, the results are shown in Table 3.

As seen from the table, it is basic identical to the absorption of normal hexane to contain the REZSM-5 zeolite that obtains after the Hydrogen supersiliceous zeolite A～G of rare earth and Hydrogen ZSM-5 zeolite and the rare earth exchanged, but h-type zeolite A～G is starkly lower than Hydrogen ZSM-5 zeolite and REZSM-5 zeolite to the adsorptive capacity of hexanaphthene, it is obviously different that this shows that the duct REZSM-5 zeolite cavity size big or small and that Hydrogen ZSM-5 zeolite and rare earth exchanged obtain of the supersiliceous zeolite that contains rare earth that the present invention prepares has, and the duct of the supersiliceous zeolite that the present invention makes is narrower than the duct of the ZSM-5 Zeolites Zeolites of prior art for preparing.

* REZSM-5 prepare zeolite method is: get a certain amount of ZSM-5 zeolite and re chloride by zeolite: RECl ₃: H ₂O is that 1: 0.5: 20 weight ratio mixes, and carries out ion exchange reaction 1 hour under 90 ℃, filters, repeat above-mentioned ion-exchange again and filter once washing, 110～120 ℃ of dryings, 550 ℃ of roastings 2 hours promptly get rare earth and are designated as the REZSM-5 zeolite from the ZSM-5 zeolite that changes.

Example 11

With h-type zeolite A and Hydrogen ZSM-5 through 800 ℃, 100 ℃ of steam agings were handled after 4 hours, survey the acidity change of aging front and back zeolite with ammonia absorption Differential scanning calorimetry, and on the pulse micro-inverse device, carry out the cracking reaction of n-tetradecane, estimate of the variation of aging front and back zeolite to the catalytic activity of acid catalyzed reaction, the results are shown in Table 4 reaction conditionss is: 480 ℃ of temperature of reaction, zeolite loading amount 0.1 gram, sample size 0.3 μ l.

Can see that from table to after the burin-in process, the reservation amount of the total acid content of rare earth containing high silica zeolite and strong acid amount is higher, its activity stability is also better.

Example 12

The zeolite of the present invention's preparation is used as the activity of such catalysts component.

Silica-alumina gel (contains SiO ₂83 heavy %, Al ₂O ₃17 heavy %, make with step-by-step precipitation method) carrier respectively with h-type zeolite A, B, ZSM-5 and REZSM-5 zeolite by zeolite: carrier is that 20: 80 weight ratio is mixed and divided evenly, spraying drying is that the ammoniumsulphate soln (solution temperature is 60 ℃) of 1 heavy % washs Na to the microballoon with concentration ₂The heavy % of O＜0.15,120 ℃ of dryings, promptly respectively catalyst A ', B ', ZSM-5 ' and REZSM-5 '.Above-mentioned catalyzer through 100% steam aging 4 hours, promptly gets aging catalyst A ", B ", ZSM-5 " and REZSM-5 " under 800 ℃.

On fixed fluidized bed catalytic cracking unit, (boiling range is 197～479 ℃ with the triumph decompressed wax oil, the carbon residue amount is 0.06 heavy %) be stock oil, industrial poiser with Y-7 catalyzer (Qilu Petrochemical company catalyst plant is produced) is a base catalyst, above-mentioned catalyzer is a promotor, carry out catalytic cracking reaction, reaction conditions is: the catalyzer loading amount is 150 gram base catalyst and 7.9 gram promotors, the base catalyst loading amount is 157.9 grams during no promotor, 500 ℃ of temperature of reaction, weight space velocity 8.0 hours ^-1, agent-oil ratio 4.0.Reaction result sees Table 5, and wherein research octane number (RON) (RON) is recorded by chromatography, octane value bucket=octane value * gasoline yield.

As seen from Table 5, add promotor and can improve transformation efficiency and gasoline octane rating, but yield of gasoline descends to some extent, when wherein adding the rare earth containing high silica zeolite promotor, though the amplitude that transformation efficiency improves is lower than the amplitude that has increased when having added ZSM-5 ' and REZSM-5 ' promotor slightly, but yield of gasoline can remain on the higher level, thereby its gasoline octane rating barrelage is higher.During the promotor of interpolation after burin-in process, height when transformation efficiency does not still have auxiliary agent does not want high when yield of gasoline and gasoline octane rating all have promotor and added ZSM-5 " and REZSM-5 " promotor when wherein adding the aging agent of rare earth containing high silica zeolite promotor.So the rare earth containing high silica zeolite of the present invention's preparation has good activity stability, the zeolite after certain burin-in process has catalytic activity preferably.

Table 1

The supersiliceous zeolite ZSM-5 zeolite that contains rare earth

Spacing relative intensity spacing relative intensity

（d）（I/I ₀）（d）（I/I ₀）

11.12 S 11.15 S

9.90 M 10.01 M

7.43 VW 7.43 VW

7.07 VW 7.08 VW

6.70 VW 6.69 VW

6.35 VW 6.35 VW

5.99 VW 6.00 VW

5.70 VW 5.71 VW

5.57 VW 5.57 VW

5.36 VW 5.37 VW

5.14 VW 5.14 VW

5.04 VW 5.03 VW

4.993 VW 4.979 VW

4.610 VW 4.613 VW

4.362 VW 4.357 VW

4.258 VW 4.262 VW

4.083 VW 4.080 VW

4.003 VW 4.005 VW

3.852 VS 3.855 VS

Continuous table 1

The supersiliceous zeolite ZSM-5 zeolite that contains rare earth

Spacing relative intensity spacing relative intensity

（d）（I/I ₀）（d）（I/I ₀）

3.814 S 3.814 S

3.751 W 3.753 W

3.715 M 3.717 M

3.646 W 3.646 W

3.479 VW 3.485 VW

3.440 VW 3.440 VW

3.350 VW 3.354 VW

3.307 VW 3.308 VW

3.242 VW 3.255 VW

3.136 VW 3.139 VW

3.047 VW 3.050 VW

2.992 VW 2.988 VW

2.945 VW 2.943 VW

2.870 VW 2.866 VW

2.734 VW 2.736 VW

2.612 VW 2.610 VW

2.421 VW 2.417 VW

2.400 VW 2.399 VW

2.109 VW 2.110 VW

Annotate: VS, S, M, W and VW represent that respectively this peak intensity is 80～100% of a climax intensity.60～80%, 40～60%, 20～40% and 0～20%.

Table 2

Zeolite adsorption amount (milligram/gram) normal hexane adsorptive capacity

Normal hexane cyclohexane cyclohexane adsorptive capacity

The supersiliceous zeolite * 102.5 14.8 6.81 that contains rare earth

ZSM-5＊ 103.5 32.3 3.2

* be hydrogen zeolite.

Annotate: the cyclohexane kinetic diameter is 0.61 nanometer, and the normal hexane kinetic diameter is 0.43 nanometer; Adsorptive capacity is to be recorded by weight absorption instrument.

Table 3

H-type zeolite adsorptive capacity (milligram/gram) normal hexane adsorptive capacity

Normal hexane cyclohexane cyclohexane adsorptive capacity

A 104.2 15.1 6.90

B 103.5 14.2 7.29

C 101.7 14.6 6.96

D 102.9 13.7 7.51

E 100.8 14.8 6.81

F 102.5 15.0 6.83

G 105.1 15.6 6.74

Hydrogen ZSM-5 103.5 32.3 3.2

REZSM-5 102.7 31.8 3.3

Annotate: the kinetic diameter of normal hexane is 0.43nm.The kinetic diameter 0.61nm of cyclohexane.

Table 4

Zeolite h-type zeolite A Hydrogen ZSM5

Acid before aging, millivolt

HO 1935 1848

H2 960 1015

H5 780 920

H10 635 848

Aging back is acid, millivolt

H0 135 71

H2 41 11

H5 35 4

H10 19 3

Cracking conversion rate, %

(before aging) 100 100

Cracking conversion rate, %

(aging back) 51.3 35.0

Annotate: Ho adsorbs NH after representing adsorption equilibrium ₃Amount, zeolite adsorption during H2, H5 and H10 represent desorption respectively 2 minutes, 5 minutes and 10 minutes

NH ₃Amount.

Table 5

Catalyst product material balance, (heavy %) transformation efficiency gasoline gasoline

H ₂～C ₂C ₃～C ₄The heavy % octane value of gasoline, diesel heavy oil coke octane value

The RON bucket

Y-7 1.55 12.62 46.47 20.24 16.37 2.75 63.39 88.5 41.13

Y-7+A′ 2.70 23.30 43.63 17.11 10.18 3.08 72.71 89.9 39.22

Y-7+B′ 2.54 22.60 43.85 17.03 9.75 3.03 72.02 90.0 39.47

Y-7+ZSM-5′3.42 28.02 40.43 16.57 8.36 3.20 75.07 90.5 36.59

Y-7+REZSM-5′ 3.35 27.62 40.75 16.64 8.53 3.11 74.83 90.4 36.84

Y-7A″ 1.72 18.68 47.66 17.89 11.25 2.8 70.86 89.4 42.61

Y-7+B″ 1.68 18.30 47.37 18.01 11.82 2.82 70.17 89.3 42.30

Y-7+ZSM-5″ 1.46 14.38 6.40 19.67 15.37 2.72 64.96 88.7 41.16

Y-7+REZSM-5″ 1.58 15.00 45.89 19.32 15.41 2.80 65.27 88.8 40.75

Claims

1, a kind of preparation method of high-Si zeolite containing rare-earth five-membered ring structure, be to be crystal seed with REY or REHY zeolite, this crystal seed is evenly dispersed in by water glass, react in the system that aluminium salt or aluminate and mineral acid are formed and make, it is characterized in that, this reaction is to carry out under no amine condition, its preparation process comprises and will contain the heavy % (in oxide compound) of rare earth 2-23, REY or REHY zeolite that sodium content is lower than 5.0 heavy % are dispersed in by water glass, in the system that aluminium salt or aluminate and mineral acid are formed, in the crystal seed salic and all the other components salic weight ratio be 0.05～3.0, all the other each amounts of components are identical with each respective components consumption of conventional synthetic ZSM-5 zeolite, above-mentioned reaction system was descended static crystallization 12-60 hour at 130～200 ℃, filtered, washing, dry getting final product.

2, in accordance with the method for claim 1, it is characterized in that said aluminium salt is Tai-Ace S 150, aluminum nitrate, aluminum chloride or aluminum phosphate, said aluminate are sodium metaaluminate.

3, a kind of preparation method of high-Si zeolite containing rare-earth five-membered ring structure, be to be crystal seed with REY or REHY zeolite, this crystal seed is evenly dispersed in by water glass, in the colloidal dispersion that aluminum phosphate and mineral acid are formed, it is characterized in that this reaction is to carry out under no amine condition, its preparation process comprises, and ± 2-23 rare with containing weighs %(in oxide compound), REY or REHY zeolite that sodium content is lower than 5.0 heavy % are evenly dispersed in by water glass, in the colloidal dispersion that aluminum phosphate and mineral acid are formed, in the crystal seed salic and colloidal dispersion salic weight ratio be 0.05-3.0, above-mentioned reaction system was descended static crystallization 12-60 hour at 130-200 ℃, filtered then, washing, dry getting final product.

4, in accordance with the method for claim 3, it is characterized in that (mol ratio) SiO in the said colloidal dispersion ₂/ Al ₂O ₃=30～120, Na ₂O/Al ₂O ₃=2～15, H ₂O/SiO ₂=20～100, P ₂O ₅/ Al ₂O ₃=0.1～20, the consumption of mineral acid is so that reactant is tied to form colloidal state is advisable.

5, in accordance with the method for claim 3, it is characterized in that said aluminum phosphate is gluey aluminum phosphate.

6, in accordance with the method for claim 5, it is characterized in that said gluey aluminum phosphate by pseudo-boehmite and phosphate aqueous solution by aluminum oxide: H ₃PO ₄: H ₂O=1: 1～4: 1～20 weight ratio mixes and gets.

7, in accordance with the method for claim 4, it is characterized in that the consumption of mineral acid so that the pH value of reaction system is 10～12 to be advisable.

8, in accordance with the method for claim 6, it is characterized in that pseudo-boehmite and phosphate aqueous solution are by aluminum oxide: H ₃PO ₄: H ₂O is that 1: 1.5～2.5: 2～10 weight ratio mixes.