CN1049406C - Phosphorus and RE containing molecular sieve with MFI structure - Google Patents
Phosphorus and RE containing molecular sieve with MFI structure Download PDFInfo
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- CN1049406C CN1049406C CN95116458A CN95116458A CN1049406C CN 1049406 C CN1049406 C CN 1049406C CN 95116458 A CN95116458 A CN 95116458A CN 95116458 A CN95116458 A CN 95116458A CN 1049406 C CN1049406 C CN 1049406C
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Abstract
The present invention relates to a molecular sieve containing phosphorus and rare earth and having an MFI structure, which has an anhydraus chemical expression (measured by the oxide molar ratio)of aRF2O3/bNa2 O/Al2O3/cP2O5/dSiO2, wherein a=0.01 to 0.25, b=0.005 to 0.02, c=0.2 to 1.0, d=35 to 120. An X-ray diffraction spectrogram is shown as the chart 1. The rare earth in the components is contained in molecular sieve crystals, and the phosphorus in the components and aluminum in a framework of the molecular sieve are chemically combined. The adsorption weight ratio of the present invention to n-hexane and cyclohexane is 4 to 5. When the present invention is used for high temperature conversion reaction of hydrocarbons, the molecular sieve has the advantages of excellent hydrothermal active stability and favorable low-carbon olefinic hydrocarbon product selectivity.
Description
The invention relates to a kind of molecular sieve of the MFI of having structure.More particularly, the invention relates to a kind of molecular sieve of phosphorous and rare earth element with MFI structure.
Zeolite with MFI structure (structure type symbol of recommending by International Union for Pure and AppliedChemistry in 1978), as ZSM-5, the shape selectivity energy that since coming out, has just brought with its unique pore passage structure and being widely used in the various catalytic conversion reactions of hydro carbons.When continually developing its new purposes, people have carried out various improvement to its synthetic method, as adopting more cheap organic formwork agent, substituting organic amine, replace organic raw material (no amine is synthetic) or the like with inorganic raw material with other organism such as alcohol.On the other hand, people also do a lot of work so that it can adapt to some specific technological process to the improvement of its performance.
USP4 after mixing with NH4-ZSM-5 with ammonium hydrogen phosphate or primary ammonium phosphate in 399,059 and drying, makes the ZSM-5 zeolite of phosphorus modification through 500 ℃ of roastings.When being used for xylene isomerization reaction, this zeolite can significantly improve its contraposition product selectivity.
USP4,578, in 371 solid phosphoric acid aluminium is joined in the reaction mixture of being made up of water, silica source, alkali metal hydroxide and aluminum compound, add 95～230 ℃ of crystallizations under the condition of organic compound in nothing, directly synthesized phosphorated ZSM-5 zeolite.
USP4,605, disclose in 637 and a kind ofly handled the high silica ZSM-5 class zeolite of silica alumina ratio 70 or more to reach the hydrothermal method that improves its acidic catalyst activity purpose with aluminum phosphate, promptly zeolite is contacted in the presence of aqueous liquid medium with the aluminum phosphate of volume of activation, make the aluminium atomic migration in the zeolite to improve its cracking activity.
USP5 relates to a kind of ZSM-5 zeolite with the phosphorus modification in 171,921.This ZSM-5 zeolite has 20～60 surface silicon aluminum ratio, with phosphorus compound dipping after 500～700 ℃ of steam-treated can make with this zeolite is that the catalyzer of active ingredient is used for C
3～C
20Hydrocarbon changes into C
2～C
5During the reaction of alkene, have than being the higher activity of not phosphorus-containing catalyst of active ingredient greater than 60 HZSM-5 with the surface silicon aluminum ratio.
Though it is the activity of such catalysts of active ingredient that the ZSM-5 zeolite of above-mentioned phosphorus modification can improve with this zeolite, but in some reaction process, particularly relate to high temperature and water vapour atmosphere at those, in processes such as catalytic cracking or cracking, the regeneration of catalyzer hydro-thermal, dealuminzation can take place and cause activity to descend gradually in the ZSM-5 zeolite.
USP4,302,622 relate to a kind of can be simultaneously phosphorous and the zeolite of rare earth, this zeolite has at least 12 silica alumina ratio, 1～12 restricted index, can make rare earth and phosphorus be deposited on zeolite surface after handling successively with compounds containing rare earth and P contained compound.The catalyzer that with this zeolite is active ingredient has shown 1 of good dialkyl benzene, the selectivity of 4-isomer in the conversion process of organic compound.
In addition, USP5 has adopted silicofluoride in 080,878, and particularly ammonium silicofluoride is handled NH
4-ZSM-5 zeolite makes its surface enrichment silicon, to reduce the activity of outer surface of zeolite.
The applicant's USP5 discloses a kind of supersiliceous zeolite with five-membered ring structure that contains rare earth in 232,675, and the anhydrous chemical constitution expression formula (in oxide mol ratio) of this zeolite is XRE
2O
3YNa
2OAl
2O
3ZSiO
2, wherein X=0.01～0.30, Y=0.4～1.0, Z=20～60, it is 2～4 times of HZSM-5 to the ratio of the adsorptive capacity of normal hexane and hexanaphthene, thereby it has the duct narrower than ZSM-5 zeolite.This zeolite is to be crystal seed in the zeolite that is selected from one of REY, REHY or REX that contains rare earth 2～27%, sodium≤0.7% (all with oxide weight), with crystal seed be evenly dispersed in form by water glass, aluminium salt, mineral acid and water, SiO
2/ Al
2O
3=30～120, Na
2O/Al
2O
3=2～15, H
2O/SiO
2In the colloidal state system of=20～100 (being mol ratio), under 130～200 ℃, best 160～190 ℃, left standstill crystallization 12～60 hours, be prepared in best 16～30 hours.With ZSM-5 zeolite facies ratio, this zeolite has better catalytic activity and hydrothermal stability.
The objective of the invention is under the high-temperature water vapor condition, to have the molecular sieve of excellent hydro-thermal activity stability providing a kind of on the basis of above-mentioned prior art.
Another object of the present invention provides a kind of preparation method of above-mentioned molecular sieve.
The present invention is to provide a kind of molecular sieve that contains phosphorus and rare earth and have the MFI structure, its anhydrous chemical constitution expression formula (with the molar ratio computing of oxide compound) is: aRE
2O
3BNa
2OAl
2O
3CP
2O
5DSiO
2, wherein a=0.01～0.25, b=0.005～0.02, c=0.2～1.0, d=35～120; Its x-ray diffraction spectra is as shown in table 1; Rare earth during it is formed is included in the molecular sieve intracrystalline; Phosphorus during it is formed combines with the aluminum chemistry in the framework of molecular sieve; Its absorption weight ratio to normal hexane and hexanaphthene is 4～5.This molecular sieve is prepared into by the following step: with the faujusite that contains rare earth is crystal seed, makes the reactant system of being made up of water glass, aluminium salt, mineral acid and water carry out crystallization; The ion-exchange of gained crystallization product is become the ammonium type; With silicofluoric acid it is carried out dealuminzation; Under water vapor and pyritous atmosphere, it is carried out activation treatment with phosphorus-aluminium activator.
According to the molecular sieve that contains phosphorus and rare earth and have the MFI structure provided by the invention, it has following feature:
1. its anhydrous chemical constitution expression formula (with the molar ratio computing of oxide compound) is:
ARE
2O
3BNa
2OAl
2O
3CP
2O
5DSiO
2Wherein:
a＝0.01～0.25；
b＝0.005～0.02；
c＝0.2～1.0；
d＝35～120。
2. its X-ray diffractogram is as shown in table 1.The represented relative intensity of each symbol is worth as follows in the table: VS:80～100%; S:60～80%; M:40～60%, W:20～40%, VW:＜20%.
Table 1
D value (* 10
-1Nanometer) I/I
0
11.2±0.2 VS
10.1±0.2 M
9.8±0.2 VW
3.85±0.04 VS
3.81±0.04 S
3.75±0.04 W
3.72±0.04 M
3.65±0.04 M
3.60±0.04 W
3. the rare earth during it is formed is included in the molecular sieve intracrystalline, the employed faujasite seeds that contains rare earth when this rare earth synthesizes from molecular sieve.
4. the phosphorus during it is formed combines with the aluminum chemistry in the framework of molecular sieve, and this molecular sieve exists
27Not only have in the AlNMR spectrum corresponding to Al (4 Si) coordination (being that the Al atom forms tetrahedral structures by oxygen and four Si atoms), chemical shift is the spectrum peak of 55ppm, and have corresponding to Al (4P) coordination (being that the Al atom is by oxygen and four P atoms formation tetrahedral structures), chemical shift is the spectrum peak of 39ppm; This molecular sieve exists
31Then have corresponding to P (4Al) coordination in the PNMR spectrum and (promptly exist PO
4Tetrahedron and adjacent AlO
4Tetrahedral interaction), chemical shift is-the spectrum peak of 29ppm, as shown in Figure 1.
And the phosphorus during this molecular sieve is formed is evenly distributed in the molecular sieve crystalline phase, and the analytical results of transmission electron microscope-energy dispersion spectrum (TEM-EDS) shows that phosphorus content and the molecule sieve nest phosphorus content in mutually in any single crystal grain is close
5. its absorption weight ratio to normal hexane and hexanaphthene is 4～5.At 40 ℃ of adsorption temps, adsorption time 3 hours, absorption relative pressure P/P
0Under=0.20～0.25 the condition, this molecular sieve is 98～105 a milligrams/gram to the adsorptive capacity of normal hexane, is 20～25 milligrams/gram to the adsorptive capacity of hexanaphthene.This absorption weight ratio of 4～5 is higher than corresponding this ratio 2～2.5 of ZSM-5 zeolite significantly.
According to method provided by the invention, this phosphorous and rare earth and the molecular sieve with MFI structure are prepared into through the following steps:
1. according to USP5,232, method described in 675 is carried out crystallization: in the zeolite that is selected from one of REY, REHY or REX that contains rare earth 2～27%, sodium≤0.7%, (all with oxide weight) is crystal seed, with crystal seed be evenly dispersed in form by water glass, aluminium salt, mineral acid and water, SiO
2/ Al
2O
3=30～20, Na
2O/Al
2O
3=2～15, H
2O/SiO
2In the colloidal state system of=20～100 (being mol ratio), under 130～200 ℃, best 160～190 ℃, left standstill crystallization 12～60 hours, best 16～30 hours.
The preparation method of used REY zeolite seed crystal is as follows: with NaY zeolite and RECl
3Solution is according to zeolite (base burns): RECl
3: H
2O is 1: 0.01～1.0: 10～100, being preferably 1: 0.1～0.5: 20～50 weight ratio is at 50～150 ℃, best 60～120 ℃ of down exchanges 0.2～2.0 hour are filtered, filter cake roasting 0.5～4.0 hour in 400～600 ℃ of mobile dry air or 100% water vapor.Zeolite after the roasting can repeat above-mentioned exchange, roasting.
The preparation method of used REHY zeolite seed crystal is as follows: with NaY zeolite and (NH
4)
2SO
4The aqueous solution is according to zeolite (burn base): (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 ℃, and best 80～120 ℃ of exchanges 0.2～2.0 hour are down filtered.This exchange, filtration step can repeat 1～2 time.Filter cake 400～600 ℃ of roastings 0.5～4.0 hour in the dry air that flows.Zeolite after the roasting and RECl
3Solution is according to zeolite (base burns): RECl
3: H
2O be 1: 0.05～1.0: 10～100 best 1: 0.2～0.8: 20～50 weight ratios at 50～150 ℃, best 80～120 ℃ of down exchanges 0.2～2.0 hour are filtered.Filter cake can be in the dry air that flows 400～600 ℃ of roastings 0.5～4.0 hour, also can not roasting.
The preparation method of used REX zeolite seed crystal is as follows: with NaX zeolite and RECl
3Solution is according to zeolite (base burns): RECl
3: H
2O is 1: 0.01～1.0: 10～100, best 1: 0.1～0.6: 20～60 weight ratio is at 50～150 ℃, best 60～120 ℃ of down exchanges 0.2～2.0 hour are filtered, filter cake roasting 0.5～4.0 hour in 400～550 ℃ of mobile dry air or 100% water vapor.Zeolite after the roasting can repeat above-mentioned exchange, roasting.
The consumption of the above-mentioned faujasite seeds that contains rare earth is with contained RE in the crystal seed
2O
3With contained Al in the colloidal state system
2O
3Mol ratio be 0.01～0.40 to be advisable.
Used aluminium salt is selected from the aluminium salt of Tai-Ace S 150, aluminum chloride or phosphoric acid: AlPO
4, Al
2(HPO
4)
3, Al (H
2PO
4)
3
Used mineral acid is selected from phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid.It is 10～12 that the consumption of mineral acid should make the pH of reaction system.
Having following weight by the resulting crystallization product of this crystallization forms: RE
2O
30.1 Na～2.5%,
2O 2.0～3.5%, Al
2O
35.2 SiO～6.0%,
289.5～91.5%.
2. ion-exchange transfers the ammonium type to: according to crystallization product: (NH
4)
2SO
4: H
2O is 1: 0.2～1.0: 5～20, is preferably 1: 0.3～0.7: 10～15 weight ratio is at 50～90 ℃, best 60～80 ℃ of exchanges 0.5～2.0 hour down, best 1.0～1.5 hours.
Transfer Na in the crystallization product of ammonium type to
2The content of O will be reduced to below the 0.1 heavy %.
3. dealuminzation: will transfer the crystallization product of ammonium type and fluorine silicic acid aqueous solution to according to crystallization product: H
2SiF
6: H
2O is 1: 0.05～0.30: 3～20, is preferably 1: 0.10～0.20: 5～10 weight ratio is at 40～90 ℃, best 60～80 ℃ of reactions 1～5 hour down, best 2～4 hours.
The framework silicon-aluminum mol ratio will reach 40～120 in the crystallization product behind the dealuminzation.
4. activation: the crystallization product behind the dealuminzation and phosphorus-aluminium activator are mixed according to 1: 0.05～0.80 weight ratio, 90～130 ℃ of dryings 0.3～6 hour, 350～700 ℃, best 450～600 ℃ water vapour atmosphere reacted 0.5～3 hour down.
Wherein said phosphorus-aluminium activator is according to Al by the aluminium source that is selected from pseudo-boehmite or aluminium hydroxide and phosphoric acid
2O
3: H
3PO
4=1.0: 0.1～40 weight ratio is formed.
Provided by the invention phosphorous and rare earth that is prepared into aforesaid method and the molecular sieve with MFI structure have the hydrothermal stability that is better than conventional H ZSM-5 zeolite.For example through 800 ℃, 100% steam-treated after 2 hours, it is bimodal that conventional H ZSM-5 zeolite is at 2 θ that the diffraction of 24.30～24.40 ° of (CuK α target) positions has been become by original simple spike, and its crystal formation also changes oblique system into by original isometric system; And the diffractogram, the crystal formation that the invention provides molecular sieve all remain unchanged.Fig. 2 is the HZSM-5 zeolite and the invention provides molecular sieve in 800 ℃, 2 hours forward and backward X-ray diffraction results of processing of 100% water vapor that wherein a and b are respectively the forward and backward spectral lines of HZSM-5 zeolite water thermal treatment; C and d the invention provides molecular sieve water heat to handle forward and backward spectral line.
Molecular sieve provided by the invention can be used as multiple hydrocarbon conversion reactions activity of such catalysts component, is specially adapted to the reaction process that those relate to the high-temperature water vapor condition.For example, be that the catalyzer that contains this molecular sieve has demonstrated the characteristics that activity stability is good, the purpose selectivity of product is high in the reactions such as the petroleum hydrocarbon catalytic pyrolysis of purpose or catalytic cracking with low-carbon olefines high-output or low-carbon (LC) isomeric olefine etc.
Fig. 1 the invention provides molecular sieve
31P NMR spectrogram.
Fig. 2 is the ZSM-5 zeolite and the invention provides the forward and backward X-ray diffractogram (part) of molecular sieve water heat processing.
Following example will give further instruction to the present invention, but not thereby limiting the invention.
Be like this preparation in order to the REY zeolite of doing crystal seed in the example: NaY zeolite 150 grams (base burns) of getting silica alumina ratio (mol ratio) and be 5.0 (x-ray diffraction method mensuration) are dispersed in 3150 grams 1.5 and weigh %RECl
3(wherein contain Ce
2O
349 heavy %, La
2O
324 heavy %) in the solution, stir following 90 ℃ of ion-exchanges 30 minutes, the roasting 2 hours in 550 ℃ of dry air of the filter cake after the filtration repeats above-mentioned exchange-roasting and once promptly gets RE
2O
3Content is the REY of 18.2 heavy %.
In the example in the chemical constitution of molecular sieve sodium, aluminium and silicon record with chemical method, rare earth and phosphorus record with the X-ray fluorometric method.
Example 1
150 gram REY crystal seeds are dispersed in 11.3 kilograms contain 3.5 heavy %Na
2O and 11.1 heavy %SiO
2Water glass in, stir and to add 1300 grams down and contain 2.5 heavy %Al
2O
3Alum liquor, with the sulfuric acid of 20 heavy % system pH is transferred to 11.5 and makes it to form gel.This gel filters 180 ℃ of following crystallization 16 hours, and washing obtains crystallization product.
Get the above-mentioned crystallization product that makes 1000 grams, add ammonium sulfate solution 6250 grams of 8 heavy %, stir following 60 ℃ of ion-exchanges 1 hour, filter, washing repeats above-mentioned exchange process and once obtains ammonium type crystallization product.
Get 100 gram ammonium type crystallization products, add fluorine silicic acid aqueous solution 1600 grams of 0.5 heavy %, stirred following 50 ℃ of dealumination reactions 5 hours.
Add in the crystallization product behind above-mentioned dealuminzation forms by pseudo-boehmite and phosphoric acid, contain 4.4 weight %Al
2O
3Phosphorus-aluminium activator 8.4 grams and 40 gram water, it is mixed, 120 ± 10 ℃ of dryings 4 hours, the reaction 1.5 hours down of 600 ℃ of water vapour atmospheres, products therefrom is a molecular sieve provided by the invention.
The anhydrous chemical constitution of this molecular sieve is: 0.11RE
2O
30.02Na
2OAl
2O
30.26P
2O
537.6SiO
2Its X-ray diffraction data is as shown in table 2; This molecular sieve is respectively 100.1 milligrams/gram and 23.9 milligrams/gram to the adsorptive capacity of normal hexane and hexanaphthene; The middle mutually P of this molecule sieve nest
2O
5P in three single crystal grains that content is 1.55 heavy %, take out at random
2O
5Content is respectively 1.40 heavy %, 1.43 heavy % and 1.47 heavy % (survey of TEM-EDS method).Table 2d value (* 10
-1Nanometer) I/I
0, * 100
11.19 85
10.04 51
9.78 16
9.02 4
7.45 2
6.71 8
6.37 14
6.00 18
5.71 15
5.37 4
5.14 3
5.04 7
4.981 8
4.618 7
4.365 9
4.264 15
4.090 2
4.009 7
3.856 100
3.814 73
3.751 36
3.718 50
3.649 28
3.595 4
3.486 6
3.442 12
3.354 9
3.310 11
3.246 4
3.185 3
3.139 3
3.051 12
Example 2
Get ammonium type crystallization product 100 grams that make in the example 1, add 1.25 heavy % fluorine silicic acid aqueous solution 1000 grams, stirred following 70 ℃ of dealumination reactions 3 hours.
Add in the crystallization product behind above-mentioned dealuminzation forms by aluminium hydrate powder and phosphoric acid, contain 1.45 weight %Al
2O
3Phosphorus-aluminium activator 16.8 grams and 70 gram water, it is mixed, 120 ± 10 ℃ of dryings 5 hours, the reaction 2 hours down of 550 ℃ of water vapour atmospheres, products therefrom is a molecular sieve provided by the invention.
The anhydrous chemical constitution of this molecular sieve is: 0.08RE
2O
30.01Na
2OAl
2O
30.57P
2O
550.9SiO
2Its X-ray diffraction data and table 2 are similar; Its adsorptive capacity to normal hexane and hexanaphthene is respectively 99.7 milligrams/gram and 23.7 milligrams/gram; The middle mutually P of this molecule sieve nest
2O
5Content is 2.50 heavy %, P in three single crystal grains of Qu Chuing at random
2O
5Content is respectively 2.17 heavy %, 2.21 heavy % and 2.29 heavy %.
Example 3
Get ammonium type crystallization product 185 grams that make in the example 1, add 3.2 heavy % fluorine silicic acid aqueous solution 925 grams, stirred following 60 ℃ of dealumination reactions 4 hours.
Add in the crystallization product behind above-mentioned dealuminzation forms by pseudo-boehmite and phosphoric acid, contain 5.0 weight %Al
2O
3Phosphorus-aluminium activator 37.3 grams and 90 gram water, it is mixed, 120 ± 10 ℃ of dryings 6 hours, the reaction 2 hours down of 500 ℃ of water vapour atmospheres, products therefrom is a molecular sieve provided by the invention.
The anhydrous chemical constitution of this molecular sieve is: 0.05RE
2O
30.01Na
2OAl
2O
30.79P
2O
552.0SiO
2Its X-ray diffraction data and table 2 are similar; Its adsorptive capacity to normal hexane and hexanaphthene is respectively 99.6 milligrams/gram and 23.2 milligrams/gram; The middle mutually P of this molecule sieve nest
2O
5Content is 3.37 heavy %, P in three single crystal grains of Qu Chuing at random
2O
5Content be respectively 3.00 heavy %, 3.03 heavy % and 3.10 heavy %.
Example 4
Get ammonium type crystallization product 100 grams that make in the example 1, add 1.25 heavy % fluorine silicic acid aqueous solution 1000 grams, stirred following 70 ℃ of dealumination reactions 3 hours.
Add in the crystallization product behind above-mentioned dealuminzation forms by pseudo-boehmite and phosphoric acid, contain 3.0 weight %Al
2O
3Phosphorus-aluminium activator 25.1 grams and 80 gram water, it is mixed, 120 ± 10 ℃ of dryings 5 hours, the reaction 2.5 hours down of 450 ℃ of water vapour atmospheres, products therefrom is a molecular sieve provided by the invention.
The anhydrous chemical constitution of this molecular sieve is: 0.10RE
2O
30.01Na
2OAl
2O
30.95P
2O
541.8SiO
2Its X-ray diffraction data and table 2 are similar; Its adsorptive capacity to normal hexane and hexanaphthene is respectively 98.9 milligrams/gram and 20.9 milligrams/gram; The middle mutually P of this molecule sieve nest
2O
5Content is 4.86 heavy %, P in three single crystal grains of Qu Chuing at random
2O
5Content be respectively 4.37 heavy %, 4.41 heavy % and 4.50 heavy %.
Example 5
Get ammonium type crystallization product 205 grams that make in the example 1, add 2.5 heavy % fluorine silicic acid aqueous solution 1640 grams, stirred following 70 ℃ of dealumination reactions 3 hours.
Add in the crystallization product behind above-mentioned dealuminzation forms by pseudo-boehmite and phosphoric acid, contain 4.4 weight %Al
2O
3Phosphorus-aluminium activator 30.5 grams and 80 gram water, it is mixed, 100 ± 10 ℃ of dryings 20 minutes, reaction is 2 hours in 500 ℃ of self water vapour atmospheres, products therefrom is a molecular sieve provided by the invention.
The anhydrous chemical constitution of this molecular sieve is: 0.06RE
2O
30.07Na
2OAl
2O
30.80P
2O
566.9SiO
2Its X-ray diffraction data and table 2 are similar; Its adsorptive capacity to normal hexane and hexanaphthene is respectively 101.1 milligrams/gram and 21.1 milligrams/gram; The middle mutually P of this molecule sieve nest
2O
5Content is 2.70 heavy %, P in three single crystal grains of Qu Chuing at random
2O
5Content be respectively 2.43 heavy %, 2.50 heavy % and 2.52 heavy %.
Example 6
Get ammonium type crystallization product 115 grams that make in the example 1, add 4.6 heavy % fluorine silicic acid aqueous solution 700 grams, stirred following 80 ℃ of dealumination reactions 2.5 hours.
Add in the crystallization product behind above-mentioned dealuminzation forms by aluminium hydrate powder and phosphoric acid, contain 1.0 weight %Al
2O
3Phosphorus-aluminium activator 34.8 grams and 50 gram water, it is mixed, 120 ± 10 ℃ of dryings 4 hours, the reaction 3 hours down of 400 ℃ of water vapour atmospheres, products therefrom is a molecular sieve provided by the invention.
The anhydrous chemical constitution of this molecular sieve is: 0.23RE
2O
30.014Na
2OAl
2O
30.97P
2O
5117.0SiO
2Its X-ray diffraction data and table 2 are similar; Its adsorptive capacity to normal hexane and hexanaphthene is respectively 100.9 milligrams/gram and 22.1 milligrams/gram; The middle mutually P of this molecule sieve nest
2O
5Content is 1.90 heavy %, P in three single crystal grains of Qu Chuing at random
2O
5Content be respectively 1.71 heavy %, 1.76 heavy % and 1.80 heavy %.
Comparative example 1
Get 5 gram ZSM-5 zeolites and be dispersed in 1 liter Na as crystal seed
2O content is 40.5 grams per liters, SiO
2Content is in the water glass of 126.0 grams per liters, and then to add 71.6 gram concentration be the ethylamine solution of 33 heavy %, stirs to add 43.7 after 10 minutes and restrain Al
2O
3Content is the alum liquor of 7.0 heavy %, transfers the pH of system to make it to form gel with dilute sulphuric acid, the consisting of of this gel: 7.9Na
2OAl
2O
370.0SiO
217.5C
2H
5NH
22915H
2O in 44 hours after-filtration of 135 ℃ of following crystallizations, washing, carries out ammonium exchange according to the method described in the example 1 with the gained crystallization product with ammonium sulfate solution then, obtains silica alumina ratio and be 45.8 ammonium type ZSM-5 zeolite.
This NH
4-ZSM-5 zeolite records its adsorptive capacity to normal hexane and hexanaphthene through 500 ℃ of roastings and is respectively 104.6 milligrams/gram and 45.2 milligrams/gram after 2 hours.
Comparative example 2
Making silica alumina ratio with reference to the method for comparative example 1 is 76 ammonium type ZSM-5 zeolite, 96 grams, adds phosphoric acid and the 100 gram water of 15 grams, 22 heavy %, evenly mixed, 120 ± 10 ℃ of dryings 2 hours, and 500 ℃ of roastings 2 hours promptly get the P-ZSM-5 zeolite.
With 840 grams, 1.5 heavy %RECl
3Solution is to above-mentioned P-ZSM-5 zeolite ion-exchange 3 hours, and the filter cake after the filtration was in 100 ± 10 ℃ of dryings 30 minutes, and roasting is 3 hours in 500 ℃ of dry air, and obtaining chemical constitution formula is 0.09RE
2O
30.008Na
2O0.94P
2O
5Al
2O
376.0SiO
2The RE-P-ZSM5 zeolite.
This zeolite is respectively 103.7 milligrams/gram and 44.8 milligrams/gram to the adsorptive capacity of normal hexane and hexanaphthene.
Example 7
The characteristics of the suitable voluminous isomeric olefine that this example is shown when molecular sieve provided by the invention is described as the active ingredient of hydrocarbon conversion catalyst.
(step-by-step precipitation method makes, wherein SiO with alumino silica gel
283 heavy %, Al
2O
317 heavy %), Y zeolite mixes with the molecular sieve of example 3, comparative example 1, comparative example 2 weight ratio by 80: 10: 10 respectively, the ammoniumsulphate soln with 1 heavy % behind the spray shaping is washed till Na in 60 ℃ with microballoon
2The heavy % in O＜0.15,120 ℃ of oven dry.
It is that raw material is estimated that above-mentioned three catalyst samples are gone up with wax oil A (performance sees Table 3) at small-sized riser fluid catalytic cracking (ARCO device) after 10 hours through 760 ℃, 100% steam aging respectively.Reaction conditions is: 520 ℃, when agent-oil ratio 8, air speed 10
-1Reaction result is listed in table 4.
By table 4 data as can be seen: molecular sieve of the present invention is that the catalyzer of the active ingredient catalyzer transformation efficiency that is active ingredient than conventional ZSM5 zeolite is high 4～6 percentage points, the overall yield of low 4～5 percentage points of heavy oil productive rate, high about 3 percentage points of gasoline yield, iso-butylene and isopentene is high 0.60～0.66 percentage point, in other words, molecular sieve provided by the invention is applicable to the catalytic cracking process of voluminous isomery low-carbon alkene.
Table 3
| Wax oil A | Wax oil B | |
| Boiling range, ℃ UOP K value density (20 ℃), grams per milliliter viscosity (80 ℃), millimeter 2/ second carbon residue, heavy % sulphur content, heavy % nitrogen content, heavy % Ni content, ppm V content, ppm | 249～508 11.56 0.9249 52.9 0.20 0.23 0.18 0.3 ＜0.1 | 262～＞544 12.1 0.8849 14.02 0.55 0.16 0.26 0.5 ＜0.1 |
Table 4
| Used molecular sieve in the catalyzer | Example 3 | Comparative example 1 | Comparative example 2 |
| Material balance, heavy % H 2～C 2 C 3～C 4 C 5 +Gasoline, diesel heavy oil coke transformation efficiency, heavy % | 2.85 21.19 36.04 19.38 15.27 5.28 65.35 | 2.67 19.24 32.79 19.78 20.60 4.92 59.62 | 2.70 20.27 33.49 19.51 19.00 5.03 61.49 |
| Gas yield, heavy % C 2 ＝ C 3 ＝Total C 4 ＝Total C 5 ＝Different C 4 ＝Different C 5 ＝Different C 4 ＝+ different C 5 ＝ | 1.11 9.49 8.34 6.86 3.79 4.49 8.28 | 1.07 8.43 8.46 6.32 3.41 4.21 7.62 | 1.09 8.74 8.40 6.52 3.45 4.23 7.68 |
Example 8
Good heavy oil conversion performance and low-carbon alkene product selectivity that this example is shown when molecular sieve provided by the invention is described as the active ingredient of hydrocarbon conversion catalyst.
170 kilograms of kaolin are dispersed in 380 kg of water, its pH are transferred to 1.0, add 174 kilograms of pseudo-boehmites, mix back 70 ℃ and promptly got carrier pulp in aging 1 hour with the hydrochloric acid of 30 heavy %.Carrier (by butt) is mixed with the molecular sieve of example 2 and comparative example 1 weight ratio according to 82: 18 respectively, with the ammoniumsulphate soln of 1 heavy % microballoon is washed Na behind the spray shaping
2The heavy % in O＜0.15,120 ℃ of oven dry.
Above-mentioned two catalyst samples are that raw material is estimated with wax oil B (performance sees Table 3) through 760 ℃, 100% steam aging on the small fixed flowing bed catalytic cracking unit after 10 hours respectively.Reaction conditions is: 520 ℃, when agent-oil ratio 5, air speed 1.0
-1, catalyzer loading amount 180 gram.Reaction result is listed in table 5.
By table 5 data as can be seen: molecular sieve of the present invention is that the catalyzer of the active ingredient catalyzer transformation efficiency that is active ingredient than conventional ZSM-5 zeolite is high 7 percentage points, low 6 percentage points of heavy oil productive rate, productivity of propylene are high 4 percentage points, in other words, molecular sieve provided by the invention is applicable to that to produce propylene be the catalytic pyrolysis process of main purpose.
Table 5
| The used molecular sieve of catalyzer | Example 2 | Comparative example 1 |
| Material balance, heavy % reacted gas is H wherein 2 CH 4 C 2H 6 C 2H 4 C 3H 8 C 3H 6Different C 4H 10Positive C 4H 10Positive C 4H 8-1 different C 4H 8-1 along C 4H 8-2 anti-C 4H 8-2 gasoline (C 5 +～220 ℃) diesel oil (221～330 ℃) heavy oil (＞330 ℃) coke transformation efficiency, heavy % | 52.83 0.66 2.50 1.36 6.05 4.41 20.99 3.14 1.09 1.87 5.10 3.27 2.39 28.19 6.73 5.90 6.36 88.37 | 43.81 0.65 2.71 1.51 4.36 2.36 16.70 2.04 0.96 1.96 5.18 3.12 2.26 30.64 7.34 11.99 6.22 80.62 |
Claims (10)
1. a molecular sieve that contains phosphorus and rare earth and have the MFI structure is characterized in that its anhydrous chemical constitution expression formula in oxide mol ratio is: aRE
2O
3BNa
2OAl
2O
3CP
2O
5DSiO
2, wherein a=0.01-0.25, b=0.005-0.02, c=0.2-1.0, d=35-120; Its x-ray diffraction spectra is as shown in the table; Rare earth during it is formed is included in the molecular sieve intracrystalline; Phosphorus during it is formed combines with the aluminum chemistry in the framework of molecular sieve; Its absorption weight ratio to normal hexane and hexanaphthene is 4-5.
D value (* 10
-1Nanometer) I/I
0
11.2±0.2 VS
10.1±0.2 M
9.8±0.2 VW
3.85±0.04 VS
3.81±0.04 S
3.75±0.04 W
3.72±0.04 M
3.65±0.04 M
3.60±0.04 W
2. according to the described molecular sieve of claim 1, it is characterized in that its rare earth in forming from molecular sieve the employed faujasite seeds that contains rare earth when synthetic.
3. according to the described molecular sieve of claim 1, it is characterized in that this molecular sieve exists
27Have the spectrum peak that chemical shift is 55ppm and 39ppm in the Al NMR spectrum,
31Have the spectrum peak of chemical shift in the P NMR spectrum for-29ppm.
4. according to the described molecular sieve of claim 1, it is characterized in that the phosphorus in its composition is evenly distributed in the molecular sieve crystalline phase.
5. the preparation method of claim 1 molecular sieve is characterized in that it comprises the following steps: that the faujusite to contain rare earth is a crystal seed, makes the reactant system of being made up of water glass, aluminium salt, mineral acid and water carry out crystallization; The ion-exchange of gained crystallization product is become the ammonium type; With silicofluoric acid it is carried out dealuminzation; Under water vapor and pyritous atmosphere, it is carried out activation treatment with phosphorus-aluminium activator.
6. according to the described preparation method of claim 5, it is characterized in that said crystallization is is crystal seed in the zeolite that is selected from one of REY, REHY or REX that contains rare earth 2-27%, sodium≤0.7% (all with oxide weight), with crystal seed be evenly dispersed in form by water glass, aluminium salt, mineral acid and water, SiO
2/ Al
2O
3=30-120, Na
2O/Al
2O
3=2-15, H
2O/SiO
2In the colloidal state system of=20-100 (being mol ratio), under 130-200 ℃, leave standstill and finished in 12-60 hour.
7. according to the described preparation method of claim 5, it is characterized in that said ion-exchange be with crystallization product, ammonium sulfate and water according to 1: the weight ratio of 0.2-1.0: 5-20 was carried out under 50-90 ℃ 0.5-2.0 hour.
8. according to the described preparation method of claim 5, it is characterized in that said dealuminzation be with ammonium type crystallization product, silicofluoric acid and water according to 1: the weight ratio of 0.05-0.30: 3-20 40-90 ℃ down reaction finished in 1-5 hour.
9. according to the described preparation method of claim 5, it is characterized in that said activation treatment be with the crystallization product behind the dealuminzation and phosphorus-aluminium activator according to 1.0: the weight ratio of 0.05-0.80 mixes, 90-130 ℃ dry 0.3-6 hour, 350-700 ℃ water vapour atmosphere reaction 0.5-3 hour down.
10. according to the described preparation method of claim 9, it is characterized in that said phosphorus-aluminium activator is according to Al by the aluminium source that is selected from pseudo-boehmite or aluminium hydroxide and phosphoric acid
2O
3: H
3PO
4=1.0: the weight ratio of 0.1-40 is formed.
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| WO2006069535A1 (en) | 2004-12-28 | 2006-07-06 | China Petroleum & Chemical Corporation | A catalyst and a hydrocarbon oil cracking method |
| JP2007509833A (en) * | 2003-10-31 | 2007-04-19 | 中國石油化工股▲分▼有限公司 | MFI molecular molecular sieve containing phosphorus and metal components, and production method and use thereof |
| CN103007986A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration |
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| CN103007986A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration |
| CN103007986B (en) * | 2011-09-22 | 2014-12-31 | 中国石油化工股份有限公司 | Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration |
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