CN1088407C

CN1088407C - Zeolite containing phosphorus and its preparing process

Info

Publication number: CN1088407C
Application number: CN98117286A
Authority: CN
Inventors: 腾祖光; 田辉平; 张剑秋; 张蔚琳; 范中碧
Original assignee: Sinopec Petrochemical Research Institute; China Petrochemical Corp
Current assignee: Sinopec Petrochemical Research Institute; China Petrochemical Corp
Priority date: 1998-08-14
Filing date: 1998-08-14
Publication date: 2002-07-31
Anticipated expiration: 2018-08-14
Also published as: CN1245087A

Abstract

The present invention relates to phosphorus-containing zeolite which contains 90 to 99.9 wt% of aluminosilicate zeolite and 0.1 to 10 wt% of phosphorus measured by P2O5. In the 31 P MAS-NMR spectrum of the zeolite, the percentage of the peak area of peak whose chemical shifts is-0.05 +/-0.2 ppm is not larger than 80% of that of total peak are, and the percentage of the sum of the peak areas of peaks whose chemical shifts are-14.05 +/-0.2 ppm,-20.05 +/-0.2 ppm and-26.80 +/-0.2 ppm is not smaller than 20% of that of the total peak area. Compared with the existing phosphorus-containing zeolite, the zeolite has the properties of high hydrocarbon conversion activity, high selectivity to diesel oil and good resistance to heavy metals, such as vanadium, nickel, etc.

Description

A kind of P-contained zeolite and preparation method thereof

The invention relates to a kind of phosphorus containing molecular sieve and preparation method thereof, more particularly, is about a kind of phosphorous aluminosilicate zeolite and preparation method thereof.

Phosphorus is introduced the catalytic performance that can improve zeolite in the aluminosilicate zeolite.

US4,839,319 disclose a kind of catalyst, this catalyst contains a kind of nonzeolite inorganic oxide matrix and a kind of overstable gamma zeolite, described zeolite is handled with phosphorus compound in advance, and described phosphorus compound is selected from one group that is made up of phosphoric acid, phosphorous acid, phosphate, phosphite and their mixture.Described process with phosphorus-containing compound processing zeolite is carried out in liquid phase medium (as water), and the PH of liquid phase medium is 2-8, and the concentration of phosphorus-containing compound is the heavy % of 0.05-5.Compare with not phosphorous catalyst, this catalyst in use has lower coke and gas yield.

EP0,397,183 have disclosed a kind of composition and method of making the same, said composition contain after the ion-exchange of the heavy % of a kind of sodium oxide content 2-5 the NaY zeolite and with P ₂O ₅Meter, the phosphorus of the heavy % of 0.1-4.0.The preparation method of this P-contained Y-zeolite comprises a kind of NaY zeolite carried out ion-exchange and washing, obtains the y-type zeolite after the exchange of the heavy % of a kind of sodium oxide content 1-5; The reactant aqueous solution of the y-type zeolite after the exchange and a kind of phosphorus-containing compound is also reclaimed with P ₂O ₅Meter, the P-contained Y-zeolite of the heavy % of phosphorus content 0.1-4.0.This P-contained Y-zeolite combines the catalyst made the catalytic cracking of hydro carbons is had extra high catalytic activity and gasoline selective preferably with inorganic oxide matrix such as silica, aluminium oxide, Alusil and clays.

US5,110,776 disclose a kind of preparation method who contains the catalytic cracking catalyst of zeolite, this method comprises that handling zeolite with phosphorous aqueous acid carries out modification to zeolite, form a kind of aqueous mixture that contains phosphorus-modified zeolite, the aqueous mixture that directly this is contained phosphorus-modified zeolite mixes with the precursor of matrix, forms a kind of slurries, with described slurries spray-drying, be prepared into catalyst.Described zeolite comprises X, Y, USY, REX, REY, RE-USY, ZSM-5, ZSM-22 etc.Catalyst with the preparation of this method carries out catalytic cracking to oil or residual oil, and the octane number of gasoline is improved, and this catalyst slurry wear resistance preferably.

US5,378,670 disclose a kind of preparation method of P-contained zeolite/molecular sieve, and this method comprises that (a) carries out ion-exchange and washing with na-pretreated zeolite/molecular sieve, obtains zeolite/molecular sieve of the heavy % of a kind of sodium oxide content 1-5; (b) handle the product that (a) obtains with a kind of aqueous solution of phosphorus-containing compound, obtain a kind of P ₂O ₅Meter, P-contained zeolite/molecular sieve of the heavy % of phosphorus content 0.5-1.5; (c) product that heating (b) obtains under steam atmosphere; (d) product that (c) obtained further reacts with a kind of phosphorus compound, obtains a kind of a kind of P that obtains ₂O ₅Meter, P-contained zeolite/molecular sieve of the heavy % of phosphorus content 2-7.Described zeolite/molecular sieve can be the Y zeolite,, ZSM-5 zeolite, BETA zeolite,, modenite, phosphate aluminium molecular sieve (as SAPO) etc.The phosphorous USY zeolite of being engaged in being equipped with this method system combines the catalyst made the catalytic cracking of hydro carbons is had extra high catalytic activity with inorganic oxide matrix such as silica, aluminium oxide, Alusil and clays.

The oxygenatedchemicals of phosphorus and aluminium has two kinds of amorphous and crystallization shapes, wherein, the phosphorus in general and 1-2 the aluminium coordination of the phosphorus in the amorphous compound, the crystallization shape compound can with two, three or four aluminium coordinations.In phosphorus in the amorphous compound, the crystallization shape compound with the phosphorus of two aluminium coordinations, exist respectively with the phosphorus of three aluminium coordinations and with the phosphorus of four aluminium coordinations ³¹Characteristic peak appears on the P MAS-NMR spectrogram, its chemical shift be respectively 0 ± 3ppm ,-14 ± 3ppm ,-20 ± 3ppm and-27 ± 3ppm.In above-mentioned zeolite, the molecular sieve, the phosphorus in the SAPO molecular sieve existed with the form of the phosphorus oxygen tetrahedron phosphorus of four aluminium coordinations (promptly with), phosphorus contained in all the other aluminosilicate zeolites all existed with amorphous form.

The purpose of this invention is to provide a kind of new phosphorous aluminosilicate zeolite and preparation method thereof.

P-contained zeolite provided by the invention contains the aluminosilicate zeolite of the heavy % of 85-99.9 and with P ₂O ₅Meter, the phosphorus of the heavy % of 0.1-15, this zeolite ³¹In the P MAS-NMR spectrogram, chemical shift is not more than 80% for the percentage that the peak area at-0.05 ± 0.2ppm peak accounts for total peak area, chemical shift be-14.05 ± 0.2ppm ,-peak area at 20.05 ± 0.2ppm and-26.80 ± 0.2ppm peak is not less than 20% with the percentage that accounts for total peak area.

The preparation method of P-contained zeolite provided by the invention comprises phosphorus-containing compound is directly mixed by the weight ratio of 0.1-40 with zeolite, and, in confined conditions, in 50-550 ℃ of heating at least 0.1 hour, spend product that deionised water obtains to there not being acid ion, reclaim P-contained zeolite.

According to zeolite provided by the invention, under the preferable case, this zeolite has following feature ³¹P MAS-NMR spectrogram:

Chemical shift, ppm	Each peak area accounts for the percentage of total peak area
Chemical shift, ppm		-0.05±0.1	1-70
-14.05±0.1	10-50	-0.05±0.1	1-70
-14.05±0.1	10-50	-20.05±0.1	10-70
-26.80±0.1	0-50	-20.05±0.1	10-70

According to zeolite provided by the invention, more under the preferable case, this zeolite has following feature ³¹P MAS-NMR spectrogram:

Chemical shift, ppm	The relative size of each peak area
Chemical shift, ppm	The relative size of each peak area	-0.05±0.1	5-50
-14.05±0.1	20-50	-0.05±0.1	5-50
-14.05±0.1	20-50	-20.05±0.1	10-50
-26.80±0.1	0-25	-20.05±0.1	10-50

According to zeolite provided by the invention, with P ₂O ₅Meter, the content of phosphorus are the heavy % of 0.1-15, the heavy % of preferred 0.1-10.

Described zeolite can be to have in the zeolite of existing aluminosilicate zeolite structure one or more, described zeolite can be the zeolite with macroporous structure, as has a faujasite, the Beta zeolite, the zeolite of omega zeolite structure, described zeolite also can be the zeolite with central hole structure, as has a modenite, the ZSM-5 zeolite, the ZSM-11 zeolite, the ZSM-22 zeolite, the ZSM-23 zeolite, the ZSM-35 zeolite, the ZSM-48 zeolite, the isostructural zeolite of ZSM-57 zeolite, described zeolite can also be the zeolite with small structure, as has the Erionite zeolite, the zeolite that ZSM-34 is zeolite structured.Described zeolite preferably have the faujasite structure zeolite, have mordenite structure zeolite, have in the zeolite structured zeolite of ZSM-5 one or more, more preferably have the y-type zeolite structure zeolite, have mordenite structure zeolite, have in the zeolite structured zeolite of ZSM-5 one or more.

Generally speaking, the cation-bit of P-contained zeolite provided by the invention is occupied by in sodium ion, ammonium ion, the hydrogen ion one or more.Before or after introducing phosphorus, by the ion-exchange of routine, sodium ion wherein, ammonium ion, hydrogen ion can all or part ofly be replaced by other ion with P-contained zeolite provided by the invention.

According to embodiment preferred of the present invention, described P-contained zeolite provided by the invention is HY zeolite, rare-earth type Y zeolite REY, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, rare-earth type overstable gamma zeolite REUSY, the dealuminium Y type beta stone with faujasite structure and has in the zeolite structured zeolite of ZSM-5 one or more.

According to prepare zeolite method provided by the invention, described phosphorus-containing compound is selected from one or more in the oxide of phosphoric acid, phosphorous acid, phosphate, phosphite, phosphorus, one or more in preferably phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate, sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, phosphorus pentoxide, the diphosphorus trioxide.More in preferably phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate, phosphorus pentoxide, the diphosphorus trioxide one or more.

Described raw material zeolite can be one or more in the aluminosilicate zeolite, described raw material zeolite can be a large pore zeolite, as faujasite, Beta zeolite, omega zeolite, as described in the raw material zeolite also can be mesopore zeolite, as modenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-48 zeolite, ZSM-57 zeolite etc., described raw material zeolite can also be a pore zeolite, as Erionite zeolite, ZSM-34 zeolite etc.In the preferred faujasite of described raw material zeolite, the ZSM-5 zeolite one or more.In more preferred y-type zeolite, the ZSM-5 zeolite one or more.

Generally speaking, the cation-bit of the described raw material zeolite of method provided by the invention is occupied by in sodium ion, ammonium ion, the hydrogen ion one or more.But by conventional ion-exchange, sodium ion wherein, ammonium ion, hydrogen ion all or part of by zeolite that other ion replaced also can and also usually as the raw materials used zeolite of method provided by the invention.

According to embodiment preferred of the present invention, described raw material zeolite is selected from HY zeolite, rare-earth type Y zeolite REY, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, rare-earth type overstable gamma zeolite REUSY, dealuminium Y type beta stone and has in the zeolite structured zeolite of ZSM-5 one or more.

The weight ratio of described phosphorus-containing compound and raw material zeolite is 0.1-40, preferred 0.1-20, more preferred 0.1-15.

Described heating-up temperature is 50-550 ℃, preferred 80-500 ℃.Heat time heating time is greater than 0.1 hour, and preferred 0.5-24 hour, more preferred 0.5-10 hour.

P-contained zeolite provided by the invention has the feature of the prior art of being different from ³¹P MAS-NMR spectrogram is a kind of new zeolite.This P-contained zeolite has high thermal stability and crystallization reservation degree.For example, the P that contains provided by the invention ₂O ₅1.7 the lattice avalanche temperature of the y-type zeolite of heavy % is 1056 ℃, and the lattice avalanche temperature of corresponding not phosphorous y-type zeolite has only 1018 ℃, has only 1038 ℃ with the lattice avalanche temperature of the y-type zeolite that contains same quantity phosphorus of art methods preparation.P-contained zeolite provided by the invention can be used alone as adsorbent, and can directly be used as hydrocarbon conversion catalyst, P-contained zeolite provided by the invention can also with the catalyst carrier of routine and or binding agent, as silica, aluminium oxide, silica-alumina, clay is (as kaolin, halloysite, sepiolite, imvite, bentonite), zirconia, one or more combinations in the magnesia etc., or introduce various catalyst components, as IIA family, IIB family, IIIA family, IIIB family, IVA family, IVB family, VA family, VB family, VIA family, group vib, VIIA family, VIIB family, in the VIII family component one or more, again with said catalyst carrier and or binding agent combine and is prepared into the conversions of various hydrocarbon, as catalytic cracking, hydrocracking, hydrofinishing, hydrodesulfurization, hydrodenitrogeneration, HDM, isomerization, alkylation, catalyst such as disproportionation.

P-contained zeolite provided by the invention is particularly suitable for the active component as catalytic cracking catalyst, and have higher activity, to the performance of heavy metals such as diesel oil selectivity and anti-vanadium, nickel.For example, will contain the P of containing provided by the invention ₂O ₅1.7 the catalyst of the y-type zeolite 30 heavy % of heavy % is after 800 ℃ of 100% steam wore out 4 hours, in 482 ℃ of reaction temperatures, weight (hourly) space velocity (WHSV) 16 hours ^-1The agent weight of oil is than under 4 the condition, as the boiling range scope is the catalytic cracking catalyst of 227-475 ℃ decompressed wax oil, conversion ratio is 68 heavy %, gasoline yield is 50.8 heavy %, diesel yield is 25.6 heavy %, handle through similarity condition with the catalyst of the P-contained zeolite of prior art for preparing and will contain same weight, under similarity condition, be used as the catalytic cracking catalyst of same feedstock oil, conversion ratio has only 63 heavy %, and gasoline yield has only 44.5 heavy %, and diesel yield has only 23.4 heavy %. that above-mentioned catalyst is used nickel contamination respectively, make in the catalyst behind the nickeliferous 985ppm, estimate their catalytic performance under similarity condition, when active component was a P-contained zeolite provided by the invention, conversion ratio was 65 heavy %, gasoline yield is 43.6 heavy %, diesel yield is 24.0 heavy %, and when active component was the P-contained zeolite of prior art for preparing, conversion ratio had only 59 heavy %, gasoline yield has only 39.4 heavy %, and diesel yield has only 18.9 heavy %.Above-mentioned catalyst is used nickel and pollution of vanadium respectively, after making nickeliferous 985ppm in the catalyst, vanadium 2050ppm, estimate their catalytic performance under similarity condition, when active component was a P-contained zeolite provided by the invention, conversion ratio was 62 heavy %, gasoline yield is 40.6 heavy %, diesel yield is 20.0 heavy %, and when active component was the P-contained zeolite of prior art for preparing, conversion ratio had only 54 heavy %, gasoline yield has only 36.6 heavy %, and diesel yield has only 17.8 heavy %.

Preparation method provided by the invention adopts zeolite and phosphorus-containing compound is directly mixed, and the method for roasting is in confined conditions prepared a kind of new P-contained zeolite, has advantage simple to operate, the equipment of saved the dissolving of requisite solution in the prior art, depositing, the P-contained zeolite that is prepared into have the low characteristics of cost.

The following examples will the present invention is described further.But it is not thereby limiting the invention.

Embodiment 1

The preparation of P-contained zeolite provided by the invention.

(1) with the NaY zeolite of 3 kilograms of (dry basis) lattice constant 2.470 nanometers (sodium oxide content 14 heavy %, the Zhou village catalyst plant is produced) be that the edta solution of 1 mol mixes with 3 liters, concentration, stirring reaction is 6 hours under reflux state, filter, wash back spray-drying under 500 ℃ of temperature, 550 ℃ of roastings are 3 hours in Muffle furnace, then, with 6 liters, concentration (the NH of 5 heavy % with the gained solid product ₄) ₂SO ₄The aqueous solution carried out ion-exchange 0.5 hour, filtered, and spent the deionised water filter cake to there not being acid group, and drying obtains lattice constant 2.468 nanometers, silica alumina ratio 8.6, the dealuminium Y type beta stone of sodium oxide content 0.8 heavy %.The lattice avalanche temperature of this dealuminium Y type beta stone is 1018 ℃.

(2) with dealuminzation Y zeolite and 25 kilograms of (NH of 2.5 kilograms of (dry basis) above-mentioned preparations ₄) ₂HPO ₄Fully mix, be enclosed within the autoclave pressure, added thermal response 2 hours, reaction temperature is 150 ℃, and product, drying with 20 times of deionized water washings obtain obtain phosphorous y-type zeolite Z ₁Table 1 has provided Z ₁Composition, lattice constant, crystallization reservation degree and lattice avalanche temperature.Table 2 has provided Z ₁ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the P MAS-NMR spectrogram.

Wherein, the mensuration of zeolite composition is carried out 550 ℃ of roastings zeolite after 4 hours.Sodium oxide content, alumina content, silica content and P ₂O ₅Content all adopts x-ray fluorescence spectrometry.Lattice constant and crystallization reservation degree adopt x-ray diffraction method to measure, and lattice avalanche temperature adopts differential thermal (DTA) method to measure.The chemical shift at each peak and each peak area account for the percentage of total peak area on BrukerDMX-300 type NMR, with H in the spectrogram ₃PO ₄For reference sample is measured.

Comparative Examples 1

The preparation of reference P-contained zeolite.

With 3 liters of NaY zeolite (specification is with example 1) addings, the concentration of 3 kilograms of (dry basis) lattice constant 2.470 nanometers is in the edta solution of mol, stirring reaction is 6 hours under reflux state, filter, wash back spray-drying under 500 ℃ of temperature, 550 ℃ of roastings are 3 hours in Muffle furnace, then, with (the NH of gained solid product with 6 liters, concentration 5 heavy % ₄) ₂SO ₄The aqueous solution carried out ion-exchange 0.5 hour, filtered, and spent the deionised water filter cake to there not being acid group, and drying obtains lattice constant 2.468nm, silica alumina ratio 8.6, the dealuminium Y type beta stone of sodium oxide content 0.8 heavy %.

Dealuminzation Y type type zeolite and 4.0 liters of (NH that concentration is 4N with 2.5 kilograms of (dry basis) above-mentioned preparations ₄) ₂HPO ₄Solution mixes, and in 150 ℃ of dryings 2 hours, the solid product that obtains washed with 20 times of deionized waters in air, and drying obtains reference P-contained zeolite B ₁Table 1 has provided B ₁Composition, lattice constant, crystallization reservation degree and lattice avalanche temperature.Table 2 has provided B ₁ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the P MAS-NMR spectrogram.

Table 1

Example number		1	Comparative Examples 1
Example number		1	Comparative Examples 1	The zeolite numbering		Z ₁	B ₁
Zeolite is formed, heavy %	Na ₂O	0.3	0.6	The zeolite numbering		Z ₁	B ₁
	Na ₂O	0.3	0.6	Al ₂O ₃	14.6	14.2
	SiO ₂	83.4	83.5	Al ₂O ₃	14.6	14.2
	SiO ₂	83.4	83.5	P ₂O ₅	1.7	1.7
	Lattice constant, nanometer		2.448	P ₂O ₅	1.7	1.7	2.447
Crystallization reservation degree, %	Lattice constant, nanometer		2.448		80	78	2.447
Crystallization reservation degree, %	Lattice avalanche temperature, ℃		1056		80	78	1038

Table 2

Example number		1	Comparative Examples 1
Example number		1	Comparative Examples 1	The zeolite numbering		Z ₁	B ₁
		Each peak area accounts for the percentage of total peak area		The zeolite numbering		Z ₁	B ₁
				Chemical shift, ppm	-0.06	11.8	100
-14.08	29.4	0			-0.06	11.8	100
-14.08	29.4	0	-20.06		41.2	0
-26.86	17.6	0	-20.06		41.2	0

Embodiment 2

The preparation of P-contained zeolite provided by the invention.

With the NaY zeolite (specification is with example 1) of 3 kilograms of (dry basis) lattice constant 2.470 nanometers and 6 liters, ammonium sulfate concentrations is that the ammonium sulfate of 1 mol, pH=4.5 mixes with the mixed solution of sulfuric acid, carried out ion-exchange 1 hour at 75 ℃, filter, spend the deionised water solid product to there not being acid ion.Ion exchange process carries out twice altogether.

With the solid product drying that obtains.(concentration is greater than 99.5 heavy % to take by weighing 2.5 kilograms of above-mentioned solid products that obtain and 25 kilograms of phosphorous acid, the auxiliary reagent factory, Shenyang produces) mix, in 300 ℃ of roastings 0.5 hour, product, drying with 20 times of deionized water washings obtain got P-contained zeolite Z provided by the invention in confined conditions ₂Table 3 has provided Z ₂Composition, lattice constant, crystallization reservation degree and lattice avalanche temperature.Table 4 has provided Z ₂ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the P MAS-NMR spectrogram.

Comparative Examples 2-3

The preparation of reference P-contained zeolite.

Press US5, the method for 378,670 examples 1 prepares P/Na, H, the NH4Y zeolite, different is that the phosphoric acid consumption is US5,1.7 times of 378,670 examples, 1 consumption, the P/Na for preparing, H, the NH4Y zeolite be numbered B ₂Press US5, the method for 378,670 examples 1 is prepared P/Na, H, and the NH4Y zeolite, different is that the phosphoric acid consumption is US5, prepares the P/USY zeolite by the method for the example 2 again for 1.7 times of 378,670 examples, 1 consumption, it is numbered B ₃Table 3 has provided B ₂, B ₃Composition, lattice constant, crystallization reservation degree and lattice avalanche temperature,

Table 3

Example number		2
Example number		2	The zeolite numbering		Z ₂
Zeolite is formed, heavy %	Na ₂O	0.3	The zeolite numbering		Z ₂
	Na ₂O	0.3	Al ₂O ₃	14.5
	SiO ₂	83.7	Al ₂O ₃	14.5
	SiO ₂	83.7	P ₂O ₅	1.5
	Lattice constant, nanometer		P ₂O ₅	1.5	2.448
Crystallization reservation degree, %	Lattice constant, nanometer			70	2.448
Crystallization reservation degree, %	Lattice avalanche temperature, ℃			70	1049

Table 4

Example number		2	Comparative Examples 2	Comparative Examples 3
Example number		2	Comparative Examples 2	Comparative Examples 3	The zeolite numbering		Z ₂	B ₂	B ₃
		Each peak area accounts for the percentage of total peak area			The zeolite numbering		Z ₂	B ₂	B ₃
					Chemical shift, ppm	-0.05	9.3	100	100
-14.03	31.3	0	0			-0.05	9.3	100	100
-14.03	31.3	0	0	-20.08		44.7	0	0
-26.55	14.7	0	0	-20.08		44.7	0	0

Embodiment 3

The preparation of P-contained zeolite provided by the invention.

Method by example 1 prepares P-contained Y-zeolite, different just (NH ₄) ₂HPO ₄Consumption is 15 kilograms, and reaction temperature is 500 ℃, and the reaction time is 4 hours, obtains phosphorous y-type zeolite Z ₃Table 5 has provided Z ₃Composition, lattice constant, crystallization reservation degree and lattice avalanche temperature.Table 6 has provided Z ₃ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the P MAS-NMR spectrogram.

Table 5

Example number		3
Example number		3	The zeolite numbering		Z ₃
Zeolite is formed, heavy %	Na ₂O	0.2	The zeolite numbering		Z ₃
	Na ₂O	0.2	Al ₂O ₃	13.3
	SiO ₂	82.3	Al ₂O ₃	13.3
	SiO ₂	82.3	P ₂O ₅	4.2
	Lattice constant, nanometer		P ₂O ₅	4.2	2.440
Crystallization reservation degree, %	Lattice constant, nanometer			68	2.440
Crystallization reservation degree, %	Lattice avalanche temperature, ℃			68	1058

Table 6

Example number		3
Example number		3	The zeolite numbering		Z ₃
		Each peak area accounts for the percentage of total peak area	The zeolite numbering		Z ₃
			Chemical shift, ppm	-0.05	12.5
-14.07	27.5			-0.05	12.5
-14.07	27.5	-20.06		41.7
-26.88	18.3	-20.06		41.7

Embodiment 4

The preparation of P-contained zeolite provided by the invention.

Method by example 1 prepares P-contained Y-zeolite, and different is with (NH ₄) H ₂PO ₄Replace (NH ₄) ₂HPO ₄, (NH ₄) H ₂PO ₄Consumption be 25 kilograms, obtain phosphorous y-type zeolite Z ₄Table 7 has provided Z ₄Composition, lattice constant, crystallization reservation degree and lattice avalanche temperature.Table 8 has provided Z ₄ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the PMAS-NMR spectrogram.

Table 7

Example number		4
Example number		4	The zeolite numbering		Z ₄
Zeolite is formed, heavy %	Na ₂O	0.3	The zeolite numbering		Z ₄
	Na ₂O	0.3	Al ₂O ₃	14.5
	SiO ₂	83.4	Al ₂O ₃	14.5
	SiO ₂	83.4	P ₂O ₅	1.8
	Lattice constant, nanometer		P ₂O ₅	1.8	2.448
Crystallization reservation degree, %	Lattice constant, nanometer			78	2.448
Crystallization reservation degree, %	Lattice avalanche temperature, ℃			78	1058

Table 8

Example number		4
Example number		4	The zeolite numbering		Z ₄
		Each peak area accounts for the percentage of total peak area	The zeolite numbering		Z ₄
			Chemical shift, ppm	-0.08	11.7
-14.10	29.4			-0.08	11.7
-14.10	29.4	-20.08		41.7
-26.86	17.2	-20.08		41.7

Embodiment 5

The preparation of P-contained zeolite provided by the invention.

Prepare P-contained Y-zeolite by (2) described method in the example 1, the different HY zeolites of just using (produce by the Zhou village catalyst plant, sodium oxide content is 0.68 heavy %, lattice constant is 2.468 nanometers, and silica alumina ratio is 5.0) replace dealuminium Y type beta stone, phosphorus-containing compound is an ammonium dihydrogen phosphate (ADP), the consumption of ammonium dihydrogen phosphate (ADP) is 15 kilograms, 250 ℃ of reaction temperatures in 2 hours reaction time, obtain phosphorous y-type zeolite Z ₅Table 9 has provided Z ₅Composition, lattice constant, crystallization reservation degree and lattice avalanche temperature.Table 10 has provided Z ₅ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the P MAS-NMR spectrogram.

Table 9

Example number		5
Example number		5	The zeolite numbering		Z ₅
Zeolite is formed, heavy %	Na ₂O	0.3	The zeolite numbering		Z ₅
	Na ₂O	0.3	Al ₂O ₃	14.5
	SiO ₂	83.2	Al ₂O ₃	14.5
	SiO ₂	83.2	P ₂O ₅	2.0
	Lattice constant, nanometer		P ₂O ₅	2.0	2.448
Crystallization reservation degree, %	Lattice constant, nanometer			83	2.448
Crystallization reservation degree, %	Lattice avalanche temperature, ℃			83	1050

Table 10

Example number		5
Example number		5	The zeolite numbering		Z ₅
		Each peak area accounts for the percentage of total peak area	The zeolite numbering		Z ₅
			Chemical shift, ppm	-0.05	12.1
-14.08	31.1			-0.05	12.1
-14.08	31.1	-20.07		41.1
-26.90	15.7	-20.07		41.1

Embodiment 6-8

The preparation of P-contained zeolite provided by the invention.

Prepare P-contained Y-zeolite by (2) described method in the example 1, the different overstable gamma zeolites of just using (produce by the Zhou village catalyst plant, sodium oxide content is 0.87 heavy %, lattice constant is 2.442 nanometers, and silica alumina ratio is 6.8) replace dealuminium Y type beta stone, phosphorus-containing compound is an ammonium phosphate, the consumption of ammonium phosphate is respectively 15 kilograms, 25 kilograms and 2.5 kilograms, reaction temperature is respectively 150 ℃, 500 ℃ and 140 ℃, and the reaction time was respectively 2 hours, 4 hours and 2 hours, obtains phosphorous USY zeolite Z ₆, Z ₇And Z ₈Table 11 has provided Z ₆, Z ₇And Z ₈Composition, lattice constant, crystallization reservation degree and lattice avalanche temperature.Table 12 has provided Z ₆, Z ₇And Z ₈ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the P MAS-NMR spectrogram.

Table 11

Example number		6	7	8
Example number		6	7	8	The zeolite numbering		Z ₆	Z ₇	Z ₈
Zeolite is formed, heavy %	Na ₂O	0.4	0.2	0.8	The zeolite numbering		Z ₆	Z ₇	Z ₈
	Na ₂O	0.4	0.2	0.8	Al ₂O ₃	11.5	10.8	10.7
	SiO ₂	86.1	81.0	88.3	Al ₂O ₃	11.5	10.8	10.7
	SiO ₂	86.1	81.0	88.3	P ₂O ₅	2.0	8.0	0.2
	Lattice constant, nanometer		2.438	2.434	P ₂O ₅	2.0	8.0	0.2	2.440
Crystallization reservation degree, %	Lattice constant, nanometer		2.438	2.434		80	63	88	2.440
Crystallization reservation degree, %	Lattice avalanche temperature, ℃		1046	1058		80	63	88	1035

Table 12

Example number		6	7	8
Example number		6	7	8	The zeolite numbering		Z ₆	Z ₇	Z ₈
		Each peak area accounts for the percentage of total peak area			The zeolite numbering		Z ₆	Z ₇	Z ₈
					Chemical shift, ppm	-0.05	45.5	42.0	48.8
-14.06	29.0	30.7	25.0			-0.05	45.5	42.0	48.8
-14.06	29.0	30.7	25.0	-20.07		18.2	20.7	15.0
-26.83	7.3	6.6	11.2	-20.07		18.2	20.7	15.0

Embodiment 9-10

The preparation of P-contained zeolite provided by the invention.

Prepare P-contained Y-zeolite by (2) described method in the example 1, the different rare earth exchanged Y zeolites of just using respectively (produce, and sodium oxide content is 1.6 heavy % by the Zhou village catalyst plant, lattice constant is 2.452 nanometers, silica alumina ratio is 5.4, and rare earth oxide content is 19.5 heavy %, La in the rare earth oxide ₂O ₃With CeO ₂Weight ratio be 4.08) replace dealuminium Y type beta stone, the ammonium hydrogen phosphate consumption is respectively 5 kilograms and 25 kilograms, obtains phosphorous REY zeolite Z ₉And Z ₁₀Table 13 has provided Z ₉And Z ₁₀Composition, lattice constant, crystallization reservation degree and lattice avalanche temperature.Table 14 has provided Z ₉And Z ₁₀ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the P MAS-NMR spectrogram.

Table 13

Example number		9	10
Example number		9	10	The zeolite numbering		Z ₉	Z ₁₀
Zeolite is formed, heavy %	Na ₂O	0.6	0.3	The zeolite numbering		Z ₉	Z ₁₀
	Na ₂O	0.6	0.3	Al ₂O ₃	12.6	11.7
	SiO ₂	66.1	66.6	Al ₂O ₃	12.6	11.7
	SiO ₂	66.1	66.6	Rare earth oxide content	19.5	19.4
	P ₂O ₅	1.2	2.0	Rare earth oxide content	19.5	19.4
	P ₂O ₅	1.2	2.0	Lattice constant, nanometer		2.450	2.448
Crystallization reservation degree, %		88	85	Lattice constant, nanometer		2.450	2.448
Crystallization reservation degree, %		88	85	Lattice avalanche temperature, ℃		1036	1028

Table 14

Example number		9	10
Example number		9	10	The zeolite numbering		Z ₉	Z ₁₀
		Each peak area accounts for the percentage of total peak area		The zeolite numbering		Z ₉	Z ₁₀
				Chemical shift, ppm	-0.04	42.5	50.0
-14.01	37.5	33.3			-0.04	42.5	50.0
-14.01	37.5	33.3	-20.03		12.5	16.7
-26.76	7.5	0	-20.03		12.5	16.7

Embodiment 11-12

The preparation of P-contained zeolite provided by the invention.

Prepare P-contained Y-zeolite by (2) described method in the example 1, the different hyperastable Y-type RE zeolites of just using respectively (produce, and sodium oxide content is 1.2 heavy % by the Zhou village catalyst plant, lattice constant is 2.444 nanometers, silica alumina ratio is 6.8, and rare earth oxide content is 1.5 heavy %, La in the rare earth oxide ₂O ₃With CeO ₂Weight ratio be 4.08) replace dealuminium Y type beta stone, the ammonium hydrogen phosphate consumption is respectively 20 kilograms and 5 kilograms, obtains phosphorous REUSY zeolite Z ₁₁And Z ₁₂Table 15 has provided Z ₁₁And Z ₁₂Composition, lattice constant, crystallization reservation degree and lattice avalanche temperature.Table 16 has provided Z ₁₁And Z ₁₂ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the P MAS-NMR spectrogram.

Table 15

Example number		11	12
Example number		11	12	The zeolite numbering		Z ₁₁	Z ₁₂
Zeolite is formed, heavy %	Na ₂O	0.3	0.8	The zeolite numbering		Z ₁₁	Z ₁₂
	Na ₂O	0.3	0.8	Al ₂O ₃	10.9	12.0
	SiO ₂	81.3	85.2	Al ₂O ₃	10.9	12.0
	SiO ₂	81.3	85.2	Rare earth oxide content	1.5	1.6
	P ₂O ₅	2.0	0.4	Rare earth oxide content	1.5	1.6
	P ₂O ₅	2.0	0.4	Lattice constant, nanometer		2.441	2.443
Crystallization reservation degree, %		80	88	Lattice constant, nanometer		2.441	2.443
Crystallization reservation degree, %		80	88	Lattice avalanche temperature, ℃		1044	1039

Table 16

Example number		11	12
Example number		11	12	The zeolite numbering		Z ₁₁	Z ₁₂
		Each peak area accounts for the percentage of total peak area		The zeolite numbering		Z ₁₁	Z ₁₂
				Chemical shift, ppm	-0.06	45.2	47.0
-14.07	38.8	42.4			-0.06	45.2	47.0
-14.07	38.8	42.4	-20.08		13.7	10.6
-26.85	2.3	0	-20.08		13.7	10.6

Embodiment 13

The preparation of P-contained zeolite provided by the invention.

Prepare P-contained Y-zeolite by (2) described method in the example 1, the different rare earth HY zeolites of just using respectively (produce, and sodium oxide content is 4.5 heavy % by the Zhou village catalyst plant, lattice constant is 2.448 nanometers, silica alumina ratio is 5.6, and rare earth oxide content is 3.6 heavy %, La in the rare earth oxide ₂O ₃With CeO ₂Weight ratio be 4.08) to replace dealuminium Y type beta stone, ammonium hydrogen phosphate consumption be 15 grams, obtains phosphorous REHY zeolite Z ₁₃Table 17 has provided Z ₁₃Composition, lattice constant, crystallization reservation degree and lattice avalanche temperature.Table 18 has provided Z ₁₃ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the P MAS-NMR spectrogram.

Table 17

Example number		13
Example number		13	The zeolite numbering		Z ₁₃
Zeolite is formed, heavy %	Na ₂O	0.3	The zeolite numbering		Z ₁₃
	Na ₂O	0.3	Al ₂O ₃	11.1
	SiO ₂	82.9	Al ₂O ₃	11.1
	SiO ₂	82.9	Rare earth oxide content	3.7
	P ₂O ₅	2.0	Rare earth oxide content	3.7
	P ₂O ₅	2.0	Lattice constant, nanometer		2.442
Crystallization reservation degree, %		80	Lattice constant, nanometer		2.442
Crystallization reservation degree, %		80	Lattice avalanche temperature, ℃		1053

Table 18

Example number		13
Example number		13	The zeolite numbering		Z ₁₃
		Each peak area accounts for the percentage of total peak area	The zeolite numbering		Z ₁₃
			Chemical shift, ppm	-0.05	44.0
-14.03	36.0			-0.05	44.0
-14.03	36.0	-20.05		16.0
-26.80	4.0	-20.05		16.0

Embodiment 14

The preparation of P-contained zeolite provided by the invention.

Prepare P-contained zeolite by (2) described method in the example 1, different just replaces dealuminium Y type beta stone with modenite (sodium oxide content is less than 0.1 heavy %, and silica alumina ratio is 15.6), and 250 ℃ of reaction temperatures in 2 hours reaction time, obtain phosphorous modenite Z ₁₄Table 19 has provided Z ₁₄Composition.Table 20 has provided Z ₁₄ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the P MAS-NMR spectrogram.

Table 19

Example number		14
Example number		14	The zeolite numbering		Z ₁₄
Zeolite is formed, heavy %	Na ₂O	Trace	The zeolite numbering		Z ₁₄
	Na ₂O	Trace	Al ₂O ₃	15.5
	SiO ₂	83.4	Al ₂O ₃	15.5
	SiO ₂	83.4	P ₂O ₅	1.1

Table 20

Example number		14
Example number		14	The zeolite numbering		Z ₁₄
		Each peak area accounts for the percentage of total peak area	The zeolite numbering		Z ₁₄
			Chemical shift, ppm	-0.07	10.9
-14.10	52.7			-0.07	10.9
-14.10	52.7	-20.11		30.9
-27.04	5.5	-20.11		30.9

Embodiment 15

The preparation of P-contained zeolite provided by the invention.

Prepare P-contained zeolite by (2) described method in the example 1, different just replaces dealuminium Y type beta stone with ZSM-5 zeolite (sodium oxide content is less than the heavy % of 0.1 heavy %, and silica alumina ratio is 90), and 250 ℃ of reaction temperatures in 2 hours reaction time, obtain phosphorous ZSM-5 zeolite Z ₁₅Table 21 has provided Z ₁₅Composition.Table 22 has provided Z ₁₅ ³¹The chemical shift at each peak and each peak area account for the percentage of total peak area in the P MAS-NMR spectrogram.

Table 21

Example number		15
Example number		15	The zeolite numbering		Z ₁₅
Zeolite is formed, heavy %	Na ₂O	Trace	The zeolite numbering		Z ₁₅
	Na ₂O	Trace	Al ₂O ₃	3.4
	SiO ₂	96.3	Al ₂O ₃	3.4
	SiO ₂	96.3	P ₂O ₅	0.3

Table 22

Example number		15
Example number		15	The zeolite numbering		Z ₁₅
		Each peak area accounts for the percentage of total peak area	The zeolite numbering		Z ₁₅
			Chemical shift, ppm	-	-
-14.05	70.0			-	-
-14.05	70.0	-20.08		30.0
-	-	-20.08		30.0

Example 16

This example illustrates the catalytic performance of P-contained zeolite provided by the invention.

P-contained Y-zeolite Z with 2.4 kilograms of (dry basis) embodiment, 1 preparation ₁, 9.6 kilograms of solid contents are Ludox (Zhou village catalyst plant product), 4.8 kilograms of kaolin (dry basises of 25 heavy %, Suzhou mining company produces) and the deionized water that is equivalent to aforementioned substances gross weight 50% fully mix the back spray-drying, and then be the 5 heavy (NH of % with 160 liters of concentration ₄) ₂SO ₄The aqueous solution carries out ion-exchange 0 under 95 ℃.5 hours, filter, washing leaching cake is not to there being acid group, in 120 ℃ of dryings, and in 800 ℃ with aging 4 hours of 100% steam, obtain containing the catalyst C of P-contained zeolite 30 heavy % provided by the invention, silica 30 heavy %, kaolin 40 heavy % ₁

With boiling range is 227-475 ℃ decompressed wax oil, estimates its catalytic performance, 482 ℃ of reaction temperatures, weight (hourly) space velocity (WHSV) 16 hours on the small stationary bed bioreactor ^-1, the agent weight of oil is than 4, and feedstock oil character is listed in the table 23, and evaluation result is listed in the table 24.Wherein, product content adopts gas chromatographic analysis.

Comparative Examples 4

The catalytic performance of this Comparative Examples explanation reference P-contained zeolite.

Press example 8 preparation catalyst, just the P-contained Y-zeolite Z that embodiment 1 is prepared ₁Change the P-contained Y-zeolite B of Comparative Examples 1 preparation into ₁, get reference catalyst C _1AEstimate C with the method identical with example 8 _1AActivity, evaluation result is listed in the table 24.

Table 23

Proportion d ₄ ²⁰, gram per centimeter ³Viscosity, millimeter ²/ second 50 ℃ of 100 ℃ of carbon residues; Heavy % boiling range, ℃ initial boiling point 10% 30% 50% 70% 90% is done

0.8652 14.58 4.37 0.04 227 289 347 389 417 446 475

Table 24

Example number	16	Comparative Examples 4
Example number	16	Comparative Examples 4	The catalyst numbering	C ₁	C _1A
Conversion ratio, heavy %	68	63	The catalyst numbering	C ₁	C _1A
Conversion ratio, heavy %	68	63	Productive rate, heavy %
Dry gas	1.5	1.7	Productive rate, heavy %
Dry gas	1.5	1.7	Liquefied gas	13.7	14.5
Gasoline	50.8	44.5	Liquefied gas	13.7	14.5
Gasoline	50.8	44.5	Diesel oil	25.6	23.4
Heavy oil	6.4	13.6	Diesel oil	25.6	23.4
Heavy oil	6.4	13.6	Coke	2.0	2.3

Embodiment 17-18

P-contained Y-zeolite Z with 2.4 kilograms of (thousand basic weights) embodiment, 1 preparation ₁, 6.4 kilograms of solid contents are 25 heavy % Ludox, 4.7 kilograms of solid contents are that boehmite (Shandong Aluminum Plant's products), 2.44 kilograms of (dry basis) kaolin of 35 heavy % and the deionized water that is equivalent to aforementioned substances gross weight 50% fully mix the back spray-drying, and then are (the NH of 5 weight % with 160 liters of concentration ₄) ₂SO ₄The aqueous solution carries out ion-exchange 0.5 hour under 95 ℃, filter, washing leaching cake is to there not being acid group, is that the 1 mixed rare earth chlorides solution that weighs % mixes with the filter cake that obtains with 80 liters of concentration, carried out ion-exchange 0.5 hour in 95 ℃, filter, washing leaching cake is to there not being acid group, in 120 ℃ of dryings, obtain containing the heavily catalyst of % rare earth oxides of P-contained zeolite 30 heavy % provided by the invention and silica, kaolin aluminium oxide, 2.5.

The above-mentioned catalyst that obtains is carried out Ni pollution and Ni+V pollution as follows respectively, obtain containing the catalyst C that is polluted by Ni of Ni985ppm ₂With the catalyst C that is polluted by Ni and V that contains Ni985ppm, V2050ppm ₃:

The method that Ni pollutes: take by weighing 0.5 kg catalyst, 220 ℃ of heating 1 hour, 660 ℃ of heating 3 hours were the sour nickel solution impregnated catalyst of pentamethylene 2 hours of 0.5 heavy % then with 49.3 gram Ni ion concentrations.The catalyst that will soak Ni is 200 ℃ of heating 1 hour, and 770 ℃ of heating 1 hour were handled 5 hours under 800 ℃, 80% water vapour, 20% air, normal pressure at last.

Ni+V pollutes: take by weighing 0.5 kg catalyst, 220 ℃ of heating 1 hour, 660 ℃ of heating 3 hours were 0.5 heavy % with 49.3 gram Ni ion concentrations then, and V concentration is the mixed solution impregnated catalyst 2 hours of the pentamethylene acid nickel of 1.05 heavy % and the sour vanadium of pentamethylene.The catalyst that will soak Ni and V is 200 ℃ of heating 1 hour, and 770 ℃ of heating 1 hour were handled 5 hours under 770 ℃, 80% water vapour, 20% air, normal pressure at last.

With the described decompressed wax oil of table 23 is raw material, estimates C on the small stationary bed bioreactor ₂And C ₃Catalytic performance, 482 ℃ of reaction temperatures, weight (hourly) space velocity (WHSV) 16 hours ^-1, the agent weight of oil is than 4, and the result lists in respectively in table 25 and 26.

Comparative Examples 5

The method preparation of pressing example 17-18 is the P-contained Y-zeolite Z with embodiment 1 preparation by the catalyst of nickel and nickel and pollution of vanadium ₁Change the P-contained Y-zeolite B of Comparative Examples 1 preparation into ₁, must contain the reference catalyst C that is polluted by Ni of Ni985ppm _2AWith the reference catalyst C that is polluted by Ni and V that contains Ni985ppm, V2050ppm _3AEstimate C with the method identical with example 17-18 _2AAnd C _3AActivity, the result lists in respectively in table 25 and 26.

Table 25

Example number	17	Comparative Examples 5
Example number	17	Comparative Examples 5	The catalyst numbering	C ₂	C _2A
Conversion ratio, heavy %	65	59	The catalyst numbering	C ₂	C _2A
Conversion ratio, heavy %	65	59	Productive rate, heavy %
Dry gas	1.5	1.6	Productive rate, heavy %
Dry gas	1.5	1.6	Gas macerates	16.9	13.8
Gasoline	43.6	39.4	Gas macerates	16.9	13.8
Gasoline	43.6	39.4	Diesel oil	24.0	18.9
Heavy oil	12.0	22.1	Diesel oil	24.0	18.9
Heavy oil	12.0	22.1	Coke	3.0	4.2

Table 26

Example number	18	Comparative Examples 6
Example number	18	Comparative Examples 6	The catalyst numbering	C ₃	C _3A
Conversion ratio, heavy %	62	54	The catalyst numbering	C ₃	C _3A
Conversion ratio, heavy %	62	54	Productive rate, heavy %
Dry gas	1.6	1.5	Productive rate, heavy %
Dry gas	1.6	1.5	Liquefied gas	16.4	12.3
Gasoline	40.6	36.6	Liquefied gas	16.4	12.3
Gasoline	40.6	36.6	Diesel oil	20.0	17.8
Heavy oil	18.0	28.2	Diesel oil	20.0	17.8
Heavy oil	18.0	28.2	Coke	3.4	3.6

Claims

1. P-contained zeolite is characterized in that this zeolite contains the aluminosilicate zeolite of the heavy % of 85-99.9 and with P ₂O ₅Meter, the phosphorus of the heavy % of 0.1-15, this zeolite ³¹In the P MAS-NMR spectrogram, chemical shift is not more than 80% for the percentage that the peak area at-0.05 ± 0.2ppm peak accounts for total peak area, chemical shift be-14.05 ± 0.2ppm ,-20.05 ± 0.2ppm ,-peak area at 26.80 ± 0.2ppm peak and the percentage that accounts for total peak area is not less than 20%.

2. according to the described zeolite of claim 1, it is characterized in that this zeolite has following feature ³¹P MAS-NMR spectrogram:

Chemical shift, each peak area of ppm accounts for the percentage of total peak area

-0.05±0.1 1-70

-14.05±0.1 10-50

-20.05±0.1 10-70

-26.80±0.1 0-50

3. according to the described zeolite of claim 2, it is characterized in that described zeolite has following feature ³¹The PMAS-NMR spectrogram:

Chemical shift, the relative size of each peak area of ppm

-0.05±0.1 5-50

-14.05±0.1 20-50

-20.05±0.1 10-50

-26.80±0.1 0-25

4. according to the described zeolite of claim 1, it is characterized in that, with P ₂O ₅Meter, the content of phosphorus are the heavy % of 0.1-10.

5. according to each described zeolite among the claim 1-4, it is characterized in that described zeolite is selected from one or more in the zeolite with existing aluminosilicate zeolite structure.

6. according to the described zeolite of claim 5, it is characterized in that described zeolite is zeolite with faujasite structure, has the zeolite of mordenite structure or have the zeolite structured zeolite of ZSM-5.

7. according to the described zeolite of claim 6, it is characterized in that described zeolite is the zeolite with y-type zeolite structure.

8. according to the described zeolite of claim 7, it is characterized in that described zeolite is selected from one or more in phosphorous HY zeolite, rare-earth type Y zeolite REY, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, rare-earth type overstable gamma zeolite REUSY, the dealuminium Y type beta stone.

9. claim 1 prepare zeolite method, it is characterized in that this method comprises directly mixes phosphorus-containing compound with the weight ratio of raw material zeolite 0.1-40, and in confined conditions in 50-550 ℃ of heating at least 0.1 hour, spend product that deionised water obtains to there not being acid ion, reclaim P-contained zeolite.

10. according to the described method of claim 9, it is characterized in that described phosphorus-containing compound is selected from one or more in the oxide of phosphoric acid, phosphorous acid, phosphate, phosphite, phosphorus.

11., it is characterized in that described phosphorus-containing compound is selected from phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate, phosphorus pentoxide, the diphosphorus trioxide one or more according to the described method of claim 10.

12., it is characterized in that described raw material zeolite is selected from y-type zeolite, modenite or ZSM-5 zeolite according to the described method of claim 9.

13., it is characterized in that described raw material zeolite is selected from y-type zeolite according to the described method of claim 12.

14., it is characterized in that described raw material zeolite is selected from one or more in HY zeolite, rare-earth type Y zeolite REY, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, rare-earth type overstable gamma zeolite REUSY, the dealuminium Y type beta stone according to the described method of claim 13.

15. according to the described method of claim 9, the weight ratio that it is characterized in that described phosphorus-containing compound and raw material zeolite is 0.1-15.

16. according to the described method of claim 9, it is characterized in that described heating-up temperature is 80-500 ℃, be 0.5-10 hour heat time heating time.