CN103084205B - Anti-basic nitrogen liquefied gas yield increase cracking catalyst and preparation method thereof - Google Patents

Abstract

The invention relates to an anti-basic nitrogen liquefied gas yield increase cracking catalyst and a preparation method thereof. The catalyst comprises a cracking activity component, a mesoporous silicon-aluminum material, an adhesive and clay, wherein the cracking activity component comprises a Y type molecular sieve and a molecular sieve having an MFI structure, the Y type molecular sieve comprises a first Y type molecular sieve, rare earth content in the first Y type molecular sieve is 8-23 wt% (calculated as rare earth oxide), iron content in the first Y type molecular sieve is 0.1-3.0 wt% (calculated as Fe2O3), copper content in the first Y type molecular sieve is 0-3.0 wt% (calculated as CuO), phosphorus content in the first Y type molecular sieve is 0-2.0 wt% (calculated as P2O5), and sodium oxide content in the first Y type molecular sieve is 0.1-2.5 wt%. The catalyst preparation method comprises: carrying out pulping on a cracking activity component, a mesoporous silicon-aluminum material, an adhesive and clay, and carrying out spray drying, washing, filtering and drying. With application of the catalyst in catalytic cracking of basic nitrogen-containing feed stock, high conversion rate and high liquefied gas yield are provided.

Description

Cracking catalyst of a kind of alkali resistant nitrogen fecund liquefied gas and preparation method thereof

Technical field

The present invention relates to a kind of catalytic cracking catalyst, relate to furtherly a kind of Cracking catalyst of voluminous liquefied gas of alkali resistant nitrogen.

Background technology

Catalytic cracking (FCC) is important crude oil secondary processing process, occupies very important status in petroleum refining industry.In catalytic cracking process, heavy end as vacuum distillate or more the residual oil of heavy constituent under catalyst exists, react, be converted into the high value added products such as liquefied gas, gasoline, diesel oil, in this process, conventionally need to use the catalysis material with high cracking activity.Micro-pore zeolite catalysis material, owing to having good shape selective catalysis performance and very high cracking reaction activity, is widely used in petroleum refining and processing industry.Along with the requirement, particularly crude oil of the aspect of exhaustion and environmental protection etc. day by day of petroleum resources becomes heavy growth trend and the market wilderness demand to light-end products increasingly, in PETROLEUM PROCESSING industry, more and more pay attention to the deep processing to heavy oil and residual oil.

Recently, along with heaviness day by day, the in poor quality of catalytically cracked stock, mixing the inferior raw materials such as refining wax tailings (CGO) has become the important channel that refinery expands catalytically cracked material source and enhancing efficiency by relying on tapping internal latent power.Compare with straight-run gas oil, wax tailings is the fcc raw material inferior that a kind of nitrogen content, arene content and gum level are higher, saturated hydrocarbon content is lower, the refining of mixing that increases wax tailings has a strong impact on the normal operating of catalytic cracking unit than regular meeting, cause conversion ratio to reduce, and product distributes and obviously worsens.Research shows, nitride in wax tailings especially basic nitrogen compound (nitrogen-atoms is wherein called alkali nitrogen) is the immediate cause that causes this consequence, basic nitrogen compound is owing to containing lone pair electrons, there is very strong absorption and complex performance, therefore be easy to catalyst on acid centre interact, cause the activity decline of catalyst.And nitrogen-containing compound is easier to be adsorbed on the acid centre of catalyst than polycyclic aromatic hydrocarbon, easily form coking point, promote green coke, nitrogen-containing compound can be regarded as the coke precursor that is easier to absorption.

Overcome in the problem that basic nitrogen compound causes catalyst activity reduction, the process means that the method for taking at present is for example mentioned in CN1088246A, US7744745 and US5660716, and the complexing of mentioning in US4846962 removes the method for basic nitrogen compound etc.

Overcoming the most economical effective method that basic nitrogen compound causes catalyst activity reduction is Cracking catalyst or the auxiliary agent that uses alkali resistance nitrogen compound in catalytic cracking process.But existing Cracking catalyst is active low for still existing containing alkali nitrogen raw material, the problem that product distributes and degenerates, and do not find to relate to the Cracking catalyst of alkali resistant nitrogen fecund liquefied gas.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of catalytic cracking catalyst of alkali resistant nitrogen fecund liquefied gas, this catalytic cracking catalyst for example,, for higher feedstock oil (basic n content is the feedstock oil of the about 900-2000 μ g/g) catalytic cracking of basic nitrogen compound content, has higher conversion ratio and yield of liquefied gas.

The invention provides a kind of catalytic cracking catalyst of alkali resistant nitrogen fecund liquefied gas, this catalytic cracking catalyst contains 10-70 % by weight cracking activity constituent element, 1-20 % by weight mesoporous silica-alumina materials, the clay of 10-70 % by weight and 10-60 % by weight binding agent, wherein, described cracking activity constituent element comprises the Y zeolite of 70-85 % by weight and the MFI structure molecular screen of 15-30 % by weight, described Y zeolite comprises the first Y zeolite, wherein, the first described Y zeolite is for using rare earth, iron, copper, the Y zeolite of phosphorus modification, molecular sieve Rare-Earth Content is counted 8-23 % by weight with rare earth oxide, iron content is with Fe ₂o ₃count 0.1-3.0 % by weight, copper content is counted 0-3.0 % by weight with CuO, and phosphorus content is with P ₂o ₅count 0-2.0 % by weight, sodium oxide content is 0.1-2.5 % by weight.

In the gross weight of described cracking activity constituent element, the Y zeolite that described cracking activity constituent element contains 70-85 % by weight and the MFI structure molecular screen of 15-30 % by weight; The gross weight of described Y zeolite of take is benchmark, described Y zeolite comprises other Y zeolite of 20-100 % by weight the first Y zeolite and 0-80 % by weight, other described Y zeolite is the second Y zeolite and/or the 3rd Y zeolite, wherein said the second Y zeolite is the DASY molecular sieve containing rare earth, and its content of rare earth is preferably 1.5-3 % by weight; In described the 3rd Y zeolite, take the content of rare earth of rare earth oxide as 12-16 % by weight, with P ₂o ₅the phosphorus content of meter is 0.5-7 % by weight, this molecular sieve ³¹in P MAS NMR spectrum, the percentage that the peak area that chemical shift is-14 ± 2ppm and-23 ± 2ppm resonance signal accounts for total peak area is greater than 85%, this molecular sieve ²⁷in Al MAS NMR spectrum, chemical shift is that the percentage that the peak area of 0 ± 2ppm resonance signal accounts for total peak area is greater than 20%.

Described cracking activity constituent element contains the first Y zeolite, and described the first Y zeolite is for containing rare earth, iron or iron and copper, containing or not phosphorous Y zeolite, and content of rare earth is counted 8-23 % by weight with rare earth oxide, and iron content is with Fe ₂o ₃count 0.1-3.0 % by weight, copper content is counted 0-3.0 % by weight with CuO, and phosphorus content is with P ₂o ₅count 0-2.0 % by weight, sodium oxide content is 0.1-2.5 % by weight.

Described the first Y zeolite can be through following process by Y zeolite modification preparation, and its process comprises: take NaY molecular sieve as raw material, through rare earth exchanged and roasting, obtain " one hands over a roasting " RENaY; Again with rare earth compound, iron compound, copper-containing substance, phosphorus containg substances, with or do not react with ammonium salt, obtain the Y molecular sieve product with rare earth and the modification of iron/copper/phosphorus, be described modified Y molecular sieve active component.

Wherein, the process of described acquisition " hand over a roasting " RENaY is well known to those skilled in the art, normally by NaY and rare earth compound at NaY: RE ₂o ₃=1: 0.10-0.25 (weight ratio), pH=2.0-4.5, processes 0.3-1.5 hour under exchange temperature 25-100 ℃ condition, filters, washing, filter cake is at 400-850 ℃, and under 0-100% water vapour, roasting obtains for 0.3 hour above.Further described acquisition is according to object product composition by the process of the Y molecular sieve product of rare earth and the modification of iron/copper/phosphorus, by RENaY and rare earth compound, iron content, cupric, phosphorous material, is with or without in the situation of ammonium salt, according to NaY: RE ₂o ₃: Fe ₂o ₃/ CuO: P ₂o ₅: ammonium salt=1: 0.02-0.15: 0.001-0.05: 0-0.04: 0-0.5 (weight ratio), pH=2.0-4.5, reaction at 20-100 ℃, more after filtration, the process of washing.

Described MFI structure molecular screen can be the first MFI structure molecular screen and/or the 2nd MFI structure molecular screen, wherein,

In a described MFI structure molecular screen, take oxide molar ratio computing without hydrochemical compositions expression formula, be (0.01-025) RE ₂o ₃(0.005-0.02) Na ₂oAl ₂o ₃(0.2-1.0) P ₂o ₅(35-120) SiO ₂, this molecular sieve is 4-5 to the absorption weight ratio of n-hexane and cyclohexane;

Described the 2nd MFI structure molecular screen take oxide weight than without hydrochemical compositions expression formula, be (0-03) Na ₂o (0.5-5.5) Al ₂o ₃(1.3-10) P ₂o ₅(0.7-15) M1 _xo _y(0.01-5) M2 _mo _n(70-97) SiO ₂, wherein, M1 is Fe, Co or Ni, and x represents the atomicity of M1, and y represents to meet the number of M1 oxidation state requisite oxygen, and M2 is selected from Zn, Mn, Ga or Sn, and m represents the atomicity of M2, and n represents to meet the number of M2 oxidation state requisite oxygen.

The present invention also provides a kind of preparation method of catalytic cracking catalyst of described alkali resistant nitrogen fecund liquefied gas, and the method comprises:

By cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent mixing making beating, then spray successively and be dried, wash, filter and be dried.

The anti-catalytic cracking catalyst that falls nitrogen fecund liquefied gas provided by the present invention is specially adapted to RFCC, particularly, when basic nitrogen compound content in feedstock oil is higher, for example basic n content is about 900-2000 μ g/g, the anti-catalytic cracking catalyst that falls nitrogen fecund liquefied gas provided by the invention can show higher catalytic cracking activity in the process of RFCC, can obtain higher conversion ratio, obtain higher yield of liquefied gas.

The specific embodiment

The catalytic cracking catalyst of alkali resistant nitrogen fecund liquefied gas provided by the invention, contain cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, wherein, the Y zeolite that described cracking activity constituent element contains a kind of modification (being the first Y zeolite of the present invention), this is rare earth, iron, copper, phosphorus modification for molecular sieve, molecular sieve Rare-Earth Content is counted 8-23 % by weight with rare earth oxide, and iron content is with Fe ₂o ₃count 0.1-3.0 % by weight, copper content is counted 0-3.0 % by weight with CuO, and phosphorus content is with P ₂o ₅count 0-2.0 % by weight, sodium oxide content is 0.1-2.5 % by weight.

Preferably, the first described Y zeolite Rare-Earth Content is counted 10-20 % by weight with rare earth oxide, and iron content is with Fe ₂o ₃count 0.5-2.5 % by weight, copper content is counted 0.2-1.5 % by weight with CuO, and phosphorus content is with P ₂o ₅count 0-1.0 % by weight.

More preferably, the first described Y zeolite Rare-Earth Content is counted 14-20 % by weight with rare earth oxide, and iron content is with Fe ₂o ₃count 0.6-1.0 % by weight, copper content is counted 0.5-1.2 % by weight with CuO, and phosphorus content is with P ₂o ₅count 0-1.0 % by weight, sodium oxide content is 0.1-2.0 % by weight.

Described the first Y zeolite is prepared Y zeolite modification through following process, and its process comprises: take NaY molecular sieve as raw material, through rare earth exchanged and roasting, obtain " one hands over a roasting " RENaY; Again with rare earth compound, iron compound, copper-containing substance, phosphorus containg substances, with or do not react with ammonium salt, obtain the Y molecular sieve product with rare earth and the modification of iron/copper/phosphorus, be the first described Y zeolite.

Wherein, the process of described " one hands over a roasting " RENaY is well known to those skilled in the art, normally by NaY and rare earth compound at NaY: RE ₂o ₃=1: 0.10-0.25 (weight ratio), pH=2.0-4.5, processes 0.3-1.5 hour under exchange temperature 25-100 ℃ condition, filters, washing, filter cake is at 400-850 ℃, and under 0-100% water vapour, roasting obtains for 0.3 hour above.Further, the process of described acquisition the first Y zeolite (using the Y molecular sieve of rare earth, iron, copper, phosphorus modification) product, is according to object product composition, by RENaY and rare earth compound, iron content, cupric, phosphorous material, be with or without in the situation of ammonium salt, according to NaY: RE ₂o ₃: Fe ₂o ₃/ CuO: P ₂o ₅: ammonium salt=1: 0.02-0.15: 0.001-0.05: 0-0.04: 0-0.5 (weight ratio), pH=2.0-4.5, reaction at 20-100 ℃, more after filtration, the process of washing.

In above-mentioned modifying process, described rare earth compound is rare earth chloride or nitric acid rare earth or sulfuric acid rare earth, preferably rare earth chloride.Can be single rare earth element, can be also the mixture of different rare earth element.

Described iron compound can be selected from the salt of different valence state iron, as one or more in iron chloride, frerrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate.

Described copper-containing substance can be selected from the salt of different valence state copper, as one or more in copper chloride, stannous chloride, copper nitrate, cuprous nitrate, copper sulphate.

Described phosphorus containg substances is selected from phosphoric acid or its esters, as one or more the mixture in ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate.

Described ammonium salt is selected from one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, carbonic hydroammonium, ammonium hydrogen sulfate, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, wherein preferred ammonium chloride and/or ammonium sulfate.

The first described Y zeolite, in the situation that content of rare earth is suitable, compares with conventional rare-earth Y molecular sieve, has higher acid amount and especially has higher outer surface acid amount.By the acid amount characterizing method of absorption tributyl phosphoxide and absorption trimethyl phosphorous oxide, after this Modified Zeolite Y absorption tributyl phosphoxide (TBPO, dynamically diameter 0.82nm) ³¹the molecular sieve acid amount that P MAS NMR measures is 1.400-4.500mmolg ^-1, because the molecule dynamic diameter of TBPO is 0.82nm, be greater than molecular sieve pore passage size, do not enter in molecular sieve pore passage, so its sign is the outer surface acid amount of molecular sieve; And after this Modified Zeolite Y absorption trimethyl phosphorous oxide (TMPO) ³¹the molecular sieve acid amount that P MAS NMR measures is 2.300-6.600mmolg ^-1, because the dynamic diameter of TMPO molecule is 0.55nm, can enter into the duct of molecular sieve, so its sign is the body acid amount mutually of molecular sieve.

The first Y zeolite of the present invention, by take NaY as raw material, has introduced higher content of rare earth through twice rare earth exchanged, has improved the activity stability of molecular sieve; The effect of adjustment of acidity center intensity and density has been played in the introducing of iron/copper/phosphorus, simultaneously because distributing, iron and/or copper ion electron outside nucleus there is d unoccupied orbital, be conducive to form complex compound and selective absorption basic nitrogen compound with the nitrogen-atoms containing lone pair electrons, alleviate the toxic action of alkali nitrogen to molecular sieve acid site, and the first described Y zeolite has more outer surface acid amount, this is conducive to it and effectively resists the toxic action of alkali nitrogen macromolecule to molecular sieve acid site as active component, makes resulting Modified Zeolite Y show excellent alkali resistant nitrogen performance.Thereby be conducive to catalyst provided by the invention and there is significant alkali resistant nitrogen performance.

For the catalytic cracking catalyst that improves alkali resistant nitrogen of the present invention fecund liquefied gas carries out the catalytic cracking activity in the process of catalytic cracking at the heavy oil higher to basic nitrogen compound content, to obtain the conversion ratio improving, and raising is converted into mink cell focus the activity of liquefied gas, to improve yield of liquefied gas, under preferable case, in the gross weight of described cracking activity constituent element, the MFI structure molecular screen component of the Y zeolite component that described cracking activity constituent element contains 70-85 % by weight and 15-30 % by weight.In the present invention, the part by weight of the Y zeolite component in described cracking activity constituent element and MFI structure molecular screen component is all in butt.

Active component of the present invention comprises Y zeolite, described Y zeolite can also comprise other molecular sieve except the first described Y zeolite, the gross weight of Y zeolite of take is benchmark, and described Y zeolite comprises the first Y zeolite of 20～100 % by weight and other Y zeolite of 0-80 % by weight.Other described Y zeolite can be the second Y zeolite and/or the 3rd Y zeolite, and described the second Y zeolite is the DASY molecular sieve containing rare earth, and the described DASY molecular sieve containing rare earth is for the hydro-thermal super stable molecular sieve containing rare earth, wherein with RE ₂o ₃the content of rare earth of (rare earth oxide) meter is preferably 1.5-3.0 % by weight.The described DASY molecular sieve containing rare earth can be various commercially available prod, for example, can be the DASY2.0 molecular sieve purchased from catalyst asphalt in Shenli Refinery of China Petrochemical Industry.

In described the 3rd Y zeolite, take the content of rare earth of rare earth oxide as 12-16 % by weight, with P ₂o ₅the phosphorus content of meter is 0.5-7 % by weight, in the 31P MAS NMR spectrum of this molecular sieve, the percentage that the peak area that chemical shift is-14 ± 2ppm and-23 ± 2ppm resonance signal accounts for total peak area is greater than 85%, in the 27Al MAS NMR spectrum of molecular sieve, chemical shift is that the percentage that the peak area of 0 ± 2ppm resonance signal accounts for total peak area is greater than 20%.

Under preferable case, in described the 3rd Y zeolite with P ₂o ₅the phosphorus content of meter is 1-3 % by weight.

Under preferable case, described the 3rd Y zeolite ³¹in P MAS NMR spectrum, the percentage that the peak area that chemical shift is-14 ± 2ppm and-23 ± 2ppm resonance signal accounts for total peak area is greater than 90%.Under preferable case, the lattice constant of described the 3rd Y zeolite is

In the present invention, what described the 3rd Y zeolite can be prepared according to existing method obtains, and concrete preparation method can be with reference to patent application CN101088917A, particularly embodiment 1-4 wherein.

In the present invention, a described MFI structure molecular screen is 4-5 to the absorption weight ratio of n-hexane and cyclohexane, and with the molar ratio computing of oxide, it without hydrochemical compositions expression formula is: (0.01-0.25) RE ₂o ₃(0.005-0.02) Na ₂oAl ₂o ₃(0.2-1.0) P ₂o ₅(35-120) SiO ₂.

The x-ray diffraction spectra data of a described MFI structure molecular screen are as shown in table 1 below, and in table, the represented relative intensity of each symbol value is as follows, in following table 1, and 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

In a described MFI structure molecular screen, rare earth is included in molecular sieve intracrystalline.The faujasite seeds containing rare earth that rare earth is used during from Zeolite synthesis.

In a described MFI structure molecular screen, the aluminum chemistry of phosphorus in framework of molecular sieve is combined, and this molecular sieve exists ²⁷in Al NMR spectrum, have corresponding to Al (4Si) coordination spectrum peak (being that Al is derived from by oxygen and four Si atoms formation tetrahedral structures), that chemical shift is 55ppm, and have corresponding to Al (4P) coordination spectrum peak (being that Al atom forms tetrahedral structures by oxygen and four P atoms), that chemical shift is 39ppm; This molecular sieve exists ³¹in P NMR spectrum, have corresponding to P (4Al) coordination and (exist PO ₄tetrahedron and adjacent AlO ₄tetrahedral interaction), chemical shift is-the spectrum peak of 29ppm.

In the preferred case, the phosphorus in a described MFI structure molecular screen is uniformly distributed in molecular sieve crystalline phase.The analysis result of transmission electron microscope-energy dispersion spectrum (TEM-EDS) shows that the phosphorus content during phosphorus content in any single crystal grain and molecule sieve nest are is mutually close.

A described MFI structure molecular screen is 4-5 to the absorption weight ratio of n-hexane and cyclohexane, at adsorption temp, is that 40 ℃, adsorption time are 3 hours, Adsorption Phase pressure P/P ₀under the condition of=0.20-0.25, this molecular sieve to the adsorbance of n-hexane be 98-105 milligram/gram, to the adsorbance of cyclohexane be 20-25 milligram/gram.P wherein ₀for saturated vapor pressure.

In the present invention, a described MFI structure molecular screen can prepare according to existing method, and concrete preparation method can be with reference to patent application CN1147420A, particularly embodiment 1-6 wherein.

In the present invention, described the 2nd MFI structure molecular screen take oxide weight than without hydrochemical compositions expression formula, be (0-0.3) Na ₂o (0.5-5.5) Al ₂o ₃(1.3-10) P ₂o ₅(0.7-15) M1 _xo _y(0.01-5) M2 _mo _n(70-97) SiO ₂, wherein, M1 is Fe, Co or Ni, and x represents the atomicity of M1, and y represents to meet the number of M1 oxidation state requisite oxygen, and M2 is selected from Zn, Mn, Ga or Sn, and m represents the atomicity of M2, and n represents to meet the number of M2 oxidation state requisite oxygen.

In the preferred case, described the 2nd MFI structure molecular screen is counted (0-0.2) Na with oxide weight ratio ₂o (0.9-5.0) Al ₂o ₃(1.5-7) P ₂o ₅(0.9-10) M1 _xo _y(0.5-2) M2 _mo _n(82-92) SiO ₂.

In the preferred case, M1 is Fe, and M2 is Zn.

In the present invention, described the 2nd MFI structure molecular screen can prepare according to existing method, and concrete preparation method also can be with reference to patent application CN1611299A, particularly embodiment 1-11 wherein.

In the present invention, described clay can be the conventional various clays that use in catalytic cracking catalyst, for example can be for being selected from one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.

In the present invention, described binding agent can be the conventional various binding agents that use in catalytic cracking catalyst, for example, can, for being selected from one or more in Ludox, aluminium colloidal sol and boehmite, be preferably the double aluminium binder of aluminium colloidal sol and boehmite.

In the catalytic cracking catalyst of alkali resistant nitrogen provided by the invention, also contain mesoporous silica-alumina materials, preferably, described mesoporous silica-alumina materials has the phase structure of boehmite, and the anhydrous chemical expression of oxide weight of take is (0-0.3) Na ₂o (40-90) Al ₂o ₃(10-60) SiO ₂, its average pore size is 8-20nm, and most probable aperture is 5-15nm, and specific area is 200-400m ²/ g, pore volume is 0.5-2.0ml/g; More preferably, its average pore size is 10-20nm, and most probable aperture is 10-15nm, and specific area is 200-400m ²/ g, pore volume is 1.0-2.0ml/g.Described mesoporous silica-alumina materials can be made by following methods, and the method comprises: by during aluminium source and aqueous slkali are at room temperature to 85 ℃ and plastic, plastic terminal pH is 7-11; Then according to SiO ₂: Al ₂o ₃=1: weight ratio (0.6-9) adds silicon source, aging 1-10 hour at room temperature to 90 ℃, then filter, filter gained filter cake through ammonium exchange, make sodium oxide content be no more than 0.3 % by weight, roasting 1-20 hour obtains mesoporous silica-alumina materials at dry at 100-150 ℃, 350-650 ℃ again, this material can be directly used in Kaolinite Preparation of Catalyst, or the mesoporous silica-alumina materials under the condition of room temperature to 80 ℃, sour aluminum ratio 0.1-0.3, above-mentioned roasting being obtained contacts 0.5-3 hour and obtains acid-treated mesoporous silica-alumina materials for the preparation of Cracking catalyst with inorganic acid.Described aluminium source can be conventional various aluminium source of using, this area, and described aluminium source for example can be for being selected from one or more in aluminum nitrate, aluminum sulfate or aluminium chloride.Described silicon source can be conventional various silicon source of using, this area, and described silicon source can be for example at least one in silica gel, waterglass, sodium metasilicate, silicon tetraethyl, silica, Ludox and silicon gel.Described aqueous slkali can be the conventional various aqueous slkalis that use in this area, for example, can be one or more in ammoniacal liquor, potassium hydroxide solution, sodium aluminate solution and sodium hydroxide solution.Described mesoporous silica-alumina materials and preparation method thereof can be referring to CN1565733A or CN 1854258A, for example the embodiment 1～9 of CN 1854258A.

According to the catalytic cracking catalyst of alkali resistant nitrogen fecund liquefied gas provided by the invention, the butt weight of described catalytic cracking catalyst of take is benchmark, it is 10-70 % by weight that described cracking activity constituent element be take the content of butt, it is 1-20 % by weight that described mesoporous silica-alumina materials be take the content of butt, it is 10-60 % by weight that described binding agent be take the content of butt, it is 10-70 % by weight that described clay be take the content of butt, in preferred situation, the butt weight of described catalytic cracking catalyst of take is benchmark, it is 10-45 % by weight that described cracking activity constituent element be take the content of butt, it is 2-15 % by weight that described mesoporous silica-alumina materials be take the content of butt, it is 20-40 % by weight that described clay be take the content of butt, it is 20-50 % by weight that described binding agent be take the content of butt.

The present invention also provides a kind of preparation method of catalytic cracking catalyst of described alkali resistant nitrogen fecund liquefied gas, and the method comprises the following steps:

(1) take NaY molecular sieve as raw material, through rare earth exchanged and roasting, obtain " one hands over a roasting " RENaY; Again with rare earth compound, iron compound, copper-containing substance, phosphorus containg substances, with or do not react with ammonium salt, obtain the Y molecular sieve product with rare earth and the modification of iron/copper/phosphorus, be the first Y molecular sieve active component of the present invention;

Wherein, the process of described " one hands over a roasting " RENaY is well known to those skilled in the art, normally by NaY and rare earth compound at NaY: RE ₂o ₃=1: 0.10-0.25 (weight ratio), pH=2.0-4.5, processes 0.3-1.5 hour under exchange temperature 25-100 ℃ condition, filters, washing, filter cake is at 400-850 ℃, and under 0-100% water vapour, roasting obtains for 0.3 hour above.Further described acquisition is according to object product composition by the process of the Y molecular sieve product of rare earth and the modification of iron/copper/phosphorus, by RENaY and rare earth compound, iron content, cupric, phosphorous material, is with or without in the situation of ammonium salt, according to NaY: RE ₂o ₃: Fe ₂o ₃/ CuO: P ₂o ₅: ammonium salt=1: 0.02-0.15: 0.001-0.05: 0-0.04: 0-0.5 (weight ratio), pH=2.0-4.5, reaction at 20-100 ℃, more after filtration, the process of washing.

(2) by cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent mixing making beating, then spray successively and be dried, wash, filter and be dried, wherein, described cracking activity constituent element contains Y zeolite component and MFI structure molecular screen component;

Described Y zeolite component comprises the first described Y zeolite, or comprise the first described Y zeolite and other Y zeolite, described other Y zeolite is preferably the second Y zeolite and/or the 3rd Y zeolite, described MFI structure molecular screen component is a MFI structure molecular screen and/or the 2nd MFI structure molecular screen, wherein

Described the second Y zeolite is the DASY molecular sieve containing rare earth;

In described the 3rd Y zeolite, take the content of rare earth of rare earth oxide as 12-16 % by weight, with P ₂o ₅the phosphorus content of meter is 0.5-7 % by weight, this molecular sieve ³¹in P MAS NMR spectrum, the percentage that the peak area that chemical shift is-14 ± 2ppm and-23 ± 2ppm resonance signal accounts for total peak area is greater than 85%, this molecular sieve ²⁷in Al MAS NMR spectrum, chemical shift is that the percentage that the peak area of 0 ± 2ppm resonance signal accounts for total peak area is greater than 20%;

In a described MFI structure molecular screen, take oxide molar ratio computing without hydrochemical compositions expression formula, be (0.01-0.25) RE ₂o ₃(0.005-0.02) Na ₂oAl ₂o ₃(0.2-1.0) P ₂o ₅(35-120) SiO ₂, this molecular sieve is 4-5 to the absorption weight ratio of n-hexane and cyclohexane;

Described the 2nd MFI structure molecular screen take oxide weight than without hydrochemical compositions expression formula, be (0-0.3) Na ₂o (0.5-5.5) Al ₂o ₃(13-10) P ₂o ₅(0.7-15) M1 _xo _y(0.01-5) M2 _mo _n(70-97) SiO ₂, wherein, M1 is Fe, Co or Ni, and x represents the atomicity of M1, and y represents to meet the number of M1 oxidation state requisite oxygen, and M2 is selected from Zn, Mn, Ga or Sn, and m represents the atomicity of M2, and n represents to meet the number of M2 oxidation state requisite oxygen.

According to the catalytic cracking catalyst preparation method of alkali resistant nitrogen fecund liquefied gas provided by the invention, in step (2), by described cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent mix making beating, and follow-up spraying is dry, washing, filter and be dried, the implementation method of these operations all can adopt conventional method to implement, their specific implementation method is for example at patent application CN1916166A, CN1362472A, CN1727442A, CN1132898C, in CN1727445A and CN1098130A, there is detailed description, here introduce in the lump in the present invention with for referencial use.

According to described method provided by the invention, in step (2), in butt, the weight ratio of the addition of described cracking activity constituent element, described mesoporous silica-alumina materials, described clay and described binding agent can be (10-70): (1-20): (10-70): (10-60), be preferably (10-45): (2-15): (20-40): (20-50).Described cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent all with describe above identical.

The invention will be further described by the following examples.

In the following Examples and Comparative Examples,

Mesoporous silica-alumina materials makes (SH-SA-1) according to the method for embodiment 1 in CN 1854258A;

The second Y zeolite is DASY2.0 molecular sieve, by catalyst asphalt in Shenli Refinery of China Petrochemical Industry, is produced;

The 3rd Y zeolite makes according to the method for embodiment 1 in patent application CN101088917A;

The one MFI structure molecular screen makes according to the method for embodiment 1 in patent application CN1147420A;

The 2nd MFI structure molecular screen makes according to the method for embodiment 1 in patent application CN1611299A;

Aluminium colloidal sol is produced by catalyst asphalt in Shenli Refinery of China Petrochemical Industry, Al ₂o ₃content is 21.5 % by weight;

Kaolin is purchased from Suzhou China Kaolin Co., Ltd;

Boehmite is purchased from Shandong Aluminum Plant;

Embodiment 1

The present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.

(1) preparation of Modified Zeolite Y

In reactor, add that (Chang Ling catalyst plant provides, degree of crystallinity 86%, framework si-al ratio (SiO in 5.0 kilograms of NaY molecular sieves of butt ₂/ Al ₂o ₃mol ratio) 5.2) (Shandong catalyst plant provides, RE and 4 kilograms of deionized waters, under high degree of agitation state, slowly to add the re chloride of 4.0 liters ₂o ₃content 222.5 grams per liters), with 4 % by weight watery hydrochloric acid regulation system pH=3.5, be warming up at 90 ℃ and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours under 650 ℃, 100% water vapour atmosphere, makes " one hands over a roasting " rare earth sodium Y, and note is modified molecular screen ABY-1A.

Get 2.0 kilograms of modified molecular screen ABY-1A butts and put into reactor, add 1.6 kilograms of deionized waters, under high degree of agitation state, slowly add the re chloride (RE of 0.50 liter ₂o ₃content 222.5 grams per liters), 135 grams of Fe (NO ₃) ₃9H ₂o, 55 grams of CuCl ₂2H ₂o solid and 48.6 grams of ammonium dihydrogen phosphate (ADP)s, with 4% watery hydrochloric acid regulation system pH=3.5, be warming up to 90 ℃ and stir 1 hour, filter, and washing, dry, make the first Y zeolite of the present invention, note is ABY-1.

It is 16.1 % by weight that fluorescence method (XRF) records rare earth oxide content in ABY-1 sample, and sodium oxide content is 1.6 % by weight, and iron oxide content is 0.75 % by weight, and cupric oxide content is 0.69 % by weight, and phosphorus pentoxide content is 0.83 % by weight.

31P MAS NMR analysis result: B acid 3.712mmolg after sample absorption trimethyl phosphorous oxide (TMPO) ^-1, L acid 0.638mmolg ^-1, add up to 4.350mmolg ^-1.

31P MAS NMR analysis result: B acid 2.054mmolg after sample absorption tributyl phosphoxide (TBPO) ^-1, L acid 0.582mmolg ^-1, add up to 2.636mmolg ^-1.

(2) preparation of catalytic cracking catalyst

The boehmite of 19 weight portions in butt is mixed to making beating with deionized water, and be the hydrochloric acid peptization of 36 % by weight to adding concentration in the slurries that obtain, acid aluminum ratio (described 36 % by weight hydrochloric acid with take the boehmite weight ratio of butt) is 0.20, be warming up to 65 ℃ of acidifyings 1 hour, add respectively the kaolinic slurries of 28 weight portion that contain in butt, in the aluminium colloidal sol of 9 weight portions of butt and in the slurries of the mesoporous silica-alumina materials of 8 weight portions of butt, stir 20 minutes, add wherein more afterwards described the first Y zeolite ABY-1 in 23 weight portions of butt, in the described second Y zeolite DASY2.0 of 5 weight portions of butt with in the mixed serum of a MFI structure molecular screen of 8 weight portions of butt, stir the slurries that obtain solid content 30 % by weight for 30 minutes, then spraying is dried and makes microspherical catalyst.By the roasting 1 hour at 500 ℃ of this microspherical catalyst, then at 60 ℃ with (NH ₄) ₂sO ₄washing ((NH ₄) ₂sO ₄: microspherical catalyst: H ₂o=0.05: 1: 10) to Na ₂o content is less than 0.25 % by weight, finally uses deionized water drip washing, after filtration, at 110 ℃, dries, and obtains catalytic cracking catalyst C1.

Embodiment 2-7

The present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.

According to the method for embodiment 1, prepare catalytic cracking catalyst respectively, difference is, in step (2), mesoporous silica-alumina materials, kaolin, described the first Y zeolite ABY-1, described the second Y zeolite DASY2.0, described the 3rd Y zeolite, a described MFI structure molecular screen, described the 2nd MFI structure molecular screen, the inventory in butt of boehmite and aluminium colloidal sol is as shown in table 2 below respectively, to there is the situation of different kinds of molecules sieve in formula, all the form with molecular sieve mixed serum adds, wherein the inventory of each component is all in weight portion, thereby make respectively catalytic cracking catalyst C2-C7.

Table 2

Comparative example 1

(1) this comparative example is the REY preparing according to method described in patent CN1733362.

In reactor, add 3.5 kilograms of NaY molecular sieves of butt (Chang Ling catalyst plant provides, degree of crystallinity 86%, framework si-al ratio 5.2) and 20 kilograms of deionized waters, then (Shandong catalyst plant provides, RE to add wherein the re chloride of 1.46 liters ₂o ₃content 222.5 grams per liters), stir at 60 ℃ after 5 minutes with hydrochloric acid regulation system pH=3.5-5.5, continue to stir after 1 hour, add 0.4 kilogram of ammoniacal liquor, stir filtration washing after 5 minutes, be dried into roaster, when weight space velocity 0.2 ^-1lower 600 ℃ of roastings of water vapour 1.5 hours, then in molecular sieve: ammonium chloride: water=1: for the ratio of 0.1: 10,90 ℃ of ammonium chloride solutions washings are 10 minutes, dryly obtain contrasting molecular sieve DBY.

It is 16.2 % by weight that fluorescence method (XRF) records rare earth oxide content in DBY sample, and sodium oxide content is 1.6 % by weight.

After sample absorption trimethyl phosphorous oxide (TMPO) ³¹p MAS NMR analysis result: B acid 3.657mmolg ^-1, L acid 0.574mmolg ^-1, add up to 4.231mmolg ^-1.

After sample absorption tributyl phosphoxide (TBPO) ³¹p MAS NMR analysis result: B acid 1.700mmolg ^-1, L acid 0.567mmolg ^-1, add up to 2.267mmolg ^-1.

(2) preparation of catalytic cracking catalyst

According to the method for step (2) in embodiment 2, prepare catalytic cracking catalyst, difference is with described DBY, to replace described the first Y zeolite ABY-1, thereby make catalytic cracking catalyst DC1.

Comparative example 2-3

According to the method for comparative example 1, prepare catalytic cracking catalyst respectively, difference is, in step (2), the inventory in butt of mesoporous silica-alumina materials, kaolin, DBY molecular sieve, described the second Y zeolite DASY2.0, described the 3rd Y zeolite, a described MFI structure molecular screen, described the 2nd MFI structure molecular screen, boehmite and aluminium colloidal sol is as shown in table 3 below respectively, wherein the inventory of each component is all in weight portion, thereby makes respectively catalytic cracking catalyst DC2-DC3.

Table 3

Embodiment 8

The present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.

According to the method for embodiment 3, prepare catalytic cracking catalyst, be designated as C8, difference is that the preparation method of Modified Zeolite Y is:

In reactor, add that (Chang Ling catalyst plant provides in 5.0 kilograms of NaY molecular sieves of butt, degree of crystallinity 86%, framework si-al ratio 5.2) and 4 kilograms of deionized waters, (Shandong catalyst plant provides, RE under high degree of agitation state, slowly to add the re chloride of 5.12 liters ₂o ₃content 222.5 grams per liters), with 4% watery hydrochloric acid regulation system pH=3.5, be warming up at 90 ℃ and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours under 650 ℃, 100% water vapour atmosphere, makes " one hands over a roasting " rare earth sodium Y, and note is modified molecular screen ABY-2A.

Get 2.0 kilograms of modified molecular screen ABY-2A butts and put into reactor, add 1.6 kilograms of deionized waters, under high degree of agitation state, slowly add the re chloride of 1.44 liters, 210 grams of Fe (NO ₃) ₃9H ₂o solid, with 4 % by weight watery hydrochloric acid regulation system pH=3.5, is warming up to 90 ℃ and stirs 1 hour, filters, and washing, dry, make the first Y zeolite of the present invention, note is ABY-2.

It is 21.2 % by weight that fluorescence method (XRF) records rare earth oxide content in ABY-2 sample, and sodium oxide content is 1.3 % by weight, and iron oxide content is 2.4 % by weight.

After sample absorption trimethyl phosphorous oxide (TMPO) ³¹p MAS NMR analysis result: B acid 5.210mmolg ^-1, L acid 1.078mmolg ^-1, add up to 6.288mmolg ^-1.

After sample absorption tributyl phosphoxide (TBPO) ³¹p MAS NMR analysis result: B acid 3.159mmolg ^-1, L acid 1.063mmolg ^-1, add up to 4.222mmolg ^-1.

Embodiment 9

The present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.

According to the method for embodiment 3, prepare catalytic cracking catalyst, be designated as C9, difference is that the preparation method of Modified Zeolite Y is:

(Chang Ling catalyst plant provides in reactor, to add 5.0 kilograms of NaY molecular sieves of butt, degree of crystallinity 86%, framework si-al ratio 5.2) and 4 kilograms of deionized waters, (Shandong catalyst plant provides, RE under high degree of agitation state, slowly to add the re chloride of 4.32 liters ₂o ₃content 222.5 grams per liters), with 4% watery hydrochloric acid regulation system pH=3.5, be warming up at 90 ℃ and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours at 550 ℃, makes " one hands over a roasting " rare earth sodium Y, and note is modified molecular screen ABY-5A.

Get 2.0 kilograms of modified molecular screen ABY-5A butts and put into reactor, add 1.6 kilograms of deionized waters, under high degree of agitation state, slowly add the rare earth chloride of 0.55 liter, 40 grams of Fe (NO ₃) ₃9H ₂o solid, 110 grams of CuCl ₂2H ₂o solid, 100 grams of ammonium chlorides, with 4 % by weight watery hydrochloric acid regulation system pH=3.5, are warming up to 90 ℃ and stir 1 hour, filter, washing, dry, make modified Y molecular sieve of the present invention, note is ABY-5.

It is 19.6 % by weight that fluorescence method (XRF) records rare earth oxide content in ABY-5 sample, and sodium oxide content is 1.5 heavy % by weight, and iron oxide content is 0.29 % by weight, and cupric oxide content is 1.48 % by weight.

After sample absorption trimethyl phosphorous oxide (TMPO) ³¹p MAS NMR analysis result: B acid 4.471mmolg ^-1, L acid 0.863mmolg ^-1, add up to 5.334mmolg ^-1.

After sample absorption tributyl phosphoxide (TBPO) ³¹p MAS NMR analysis result: B acid 2.163mmolg ^-1, L acid 0.683mmolg ^-1, add up to 2.846mmolg ^-1.

Embodiment 10

The present embodiment is used for illustrating described catalytic cracking catalyst provided by the invention.

According to the method for embodiment 3, prepare catalytic cracking catalyst, be designated as C10, difference is that the preparation method of Modified Zeolite Y is:

(Chang Ling catalyst plant provides in reactor, to add 5.0 kilograms of NaY molecular sieves of butt, degree of crystallinity 86%, framework si-al ratio 5.2) and 4 kilograms of deionized waters, (Shandong catalyst plant provides, RE under high degree of agitation state, slowly to add the re chloride of 5.10 liters ₂o ₃content 222.5 grams per liters), with 4% watery hydrochloric acid regulation system pH=3.5, be warming up at 90 ℃ and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours under 650 ℃, 100% water vapour atmosphere, makes " one hands over a roasting " rare earth sodium Y, and note is modified molecular screen ABY-4A.

Get 2.0 kilograms of modified molecular screen ABY-4A butts and put into reactor, add 1.6 kilograms of deionized waters, under high degree of agitation state, slowly add re chloride, 135 grams of Fe (NO3) of 1.50 liters ₃9H ₂o and 55 grams of CuCl ₂2H ₂o solid, with 4% (quality) watery hydrochloric acid regulation system pH=3.5, is warming up to 90 ℃ and stirs 1 hour, filters, and washing, dry, make the first Y zeolite of the present invention, note is ABY-4.

It is 22.5 % by weight that fluorescence method (XRF) records rare earth oxide content in ABY-4 sample, and sodium oxide content is 1.1 % by weight, and iron oxide content is 0.79 % by weight, and cupric oxide content is 0.73 % by weight.

After sample absorption trimethyl phosphorous oxide (TMPO) ³¹p MAS NMR analysis result: B acid 5.317mmolg ^-1, L acid 1.181mmolg ^-1, add up to 6.498mmolg ^-1.

After sample absorption tributyl phosphoxide (TBPO) ³¹p MAS NMR analysis result: B acid 3.265mmolg ^-1, L acid 1.097mmolg ^-1, add up to 4.362mmolg ^-1.

Test case 1

By above-mentioned catalytic cracking catalyst C1-C10 and DC1-DC3 under 800 ℃, 100% water vapour condition aging 8 hours respectively, be filled in afterwards the reactivity worth of evaluating catalytic cracking catalyst in small fixed flowing bed ACE device (purchased from U.S. KTI company), amount of fill is 9g.Then, in reaction temperature, be that 530 ℃, weight (hourly) space velocity (WHSV) are 10h ^-1, under oil ratio (weight) condition that is 6, using the catalytic mixing oil shown in table 4 as feedstock oil, inject described small fixed flowing bed ACE device and carry out catalytic cracking reaction.The composition of analytical reactions product, and calculate conversion ratio according to following formula, result is as shown in table 5 below:

Table 4

Table 5

In above-mentioned table 5, by by embodiment 2 and comparative example 1, embodiment 3 and comparative example 2, and embodiment 5 compares respectively and can find out with comparative example 3, described catalytic cracking catalyst of the present invention shows relatively high catalytic cracking activity in the feedstock oil higher to basic n content carries out the process of catalytic cracking processing, higher conversion ratio can be obtained, particularly higher yield of liquefied gas can be obtained.

Embodiment 11

Method Kaolinite Preparation of Catalyst according to embodiment 5, is designated as C11, and different is that the first Y zeolite preparation method used is as follows:

(Chang Ling catalyst plant provides in reactor, to add 5.0 kilograms of NaY molecular sieves of butt, degree of crystallinity 86%, framework si-al ratio 5.2) and 4 kilograms of deionized waters, (Shandong catalyst plant provides, RE under high degree of agitation state, slowly to add the re chloride of 4.20 liters ₂o ₃content 222.5 grams per liters), with 4% watery hydrochloric acid regulation system pH=3.5, be warming up at 90 ℃ and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours at 550 ℃, makes " one hands over a roasting " rare earth sodium Y, and note is modified molecular screen ABY-11A.

Get 2.0 kilograms of modified molecular screen ABY-11A butts and put into reactor, add 1.6 kilograms of deionized waters, under high degree of agitation state, slowly add the rare earth chloride of 0.48 liter, 125 grams of Fe (NO ₃) ₃9H ₂o solid, 100 grams of ammonium chlorides, with 4% watery hydrochloric acid regulation system pH=3.5, are warming up to 90 ℃ and stir 1 hour, filter, washing, dry, make modified Y molecular sieve of the present invention, note is ABY-11.

It is 17.1 % by weight that fluorescence method (XRF) records rare earth oxide content in ABY-11 sample, and sodium oxide content is 1.7 % by weight, and iron oxide content is 0.84 % by weight.

After sample absorption trimethyl phosphorous oxide (TMPO) ³¹p MAS NMR analysis result: B acid 4.399mmolg ^-1, L acid 0.756mmolg ^-1, add up to 5.155mmolg ^-1.

After sample absorption tributyl phosphoxide (TBPO) ³¹p MAS NMR analysis result: B acid 2.100mmolg ^-1, L acid 0.658mmolg ^-1, add up to 2.758mmolg ^-1.

Embodiment 12

Method Kaolinite Preparation of Catalyst according to embodiment 2, is designated as C12, and different is that the first Y zeolite preparation method used is as follows:

(Chang Ling catalyst plant provides in reactor, to add 5.0 kilograms of NaY molecular sieves of butt, degree of crystallinity 86%, framework si-al ratio 5.2) and 2 kilograms of deionized waters, (Shandong catalyst plant provides, RE under high degree of agitation state, slowly to add the re chloride of 3.16 liters ₂o ₃content 222.5 grams per liters), with 4% watery hydrochloric acid regulation system pH=3.5, be warming up at 90 ℃ and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours under 650 ℃, 100% water vapour atmosphere, makes " one hands over a roasting " rare earth sodium Y, and note is modified molecular screen ABY-12A.

Get 2.0 kilograms of modified molecular screen ABY-12A butts and put into reactor, add 1.6 kilograms of deionized waters, under high degree of agitation state, slowly add the rare earth chloride of 1.48 liters, 15 grams of Fe (NO ₃) ₃9H ₂o solid, 90 grams of CuCl ₂2H ₂o solid, with 4% watery hydrochloric acid regulation system pH=3.5, is warming up to 90 ℃ and stirs 1 hour, filters, and washing, dry, make modified Y molecular sieve of the present invention, note is ABY-12.

It is 18.3 % by weight that fluorescence method (XRF) records rare earth oxide content in ABY-12 sample, and sodium oxide content is 1.3 % by weight, and iron oxide content is 0.13 % by weight, and cupric oxide content is 1.03 % by weight.

After sample absorption trimethyl phosphorous oxide (TMPO) ³¹p MAS NMR analysis result: B acid 4.459mmolg ^-1, L acid 0.859mmolg ^-1, add up to 5.318mmolg ^-1.

After sample absorption tributyl phosphoxide (TBPO) ³¹p MAS NMR analysis result: B acid 2.151mmolg ^-1, L acid 0.672mmolg ^-1, add up to 2.823mmolg ^-1.

Embodiment 13

(Chang Ling catalyst plant provides in reactor, to add 5.0 kilograms of NaY molecular sieves of butt, degree of crystallinity 86%, framework si-al ratio 5.2) and 4 kilograms of deionized waters, (Shandong catalyst plant provides, RE under high degree of agitation state, slowly to add the re chloride of 2.50 liters ₂o ₃content 222.5 grams per liters), with 4% watery hydrochloric acid regulation system pH=3.5, be warming up at 90 ℃ and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours at 550 ℃, makes " one hands over a roasting " rare earth sodium, and note is modified molecular screen ABY-13A.

Get 2.0 kilograms of modified molecular screen ABY-13A butts and put into reactor, add 1.6 kilograms of deionized waters, under high degree of agitation state, slowly add the rare earth chloride of 0.48 liter, 80 grams of Fe (NO ₃) ₃9H ₂o solid, 100 grams of ammonium chlorides, with 4% watery hydrochloric acid regulation system pH=3.5, are warming up to 90 ℃ and stir 1 hour, filter, washing, dry, make modified Y molecular sieve of the present invention, note is ABY-13.

It is 10.2 % by weight that fluorescence method (XRF) records rare earth oxide content in ABY-13 sample, and sodium oxide content is 2.3 % by weight, and iron oxide content is 0.53 % by weight.

After sample absorption trimethyl phosphorous oxide (TMPO) ³¹p MAS NMR analysis result: B acid 2.370mmolg ^-1, L acid 0.223mmolg ^-1, add up to 2.593mmolg ^-1.

After sample absorption tributyl phosphoxide (TBPO) ³¹p MAS NMR analysis result: B acid 1.025mmolg ^-1, L acid 0.218mmolg ^-1, add up to 1.243mmolg ^-1.

Comparative example 4

Get 2.0 kilograms of modified molecular screen ABY-13A butts and put into reactor, add 1.6 kilograms of deionized waters, under high degree of agitation state, slowly add the rare earth chloride of 0.48 liter, 100 grams of ammonium chlorides, with 4% watery hydrochloric acid regulation system pH=3.5, being warming up to 90 ℃ stirs 1 hour, filter, washing, dry, make contrast molecular sieve, note is DBY-8.

It is 10.2 % by weight that fluorescence method (XRF) records rare earth oxide content in DBY-8 sample, and sodium oxide content is 2.3 % by weight.

After comparative sample absorption trimethyl phosphorous oxide (TMPO) ³¹p MAS NMR analysis result: B acid 2.311mmolg ^-1, L acid 0.235mmolg ^-1, add up to 2.546mmolg ^-1.

After comparative sample absorption tributyl phosphoxide (TBPO) ³¹p MAS NMR analysis result: B acid 0.934mmolg ^-1, L acid 0.209mmolg ^-1, add up to 1.143mmolg ^-1.

Test case 2

By DBY-8 and 2-3 NH of ABY-13 process ₄cl exchange, makes Na ₂o content is down to below 0.3 % by weight, again after 800 ℃/17h, 100% steam aging for evaluating light oil microactivity, referring to < < Petrochemical Engineering Analysis method (RIPP method) > >, Science Press, nineteen ninety.In standard light diesel fuel raw material, do not add or add after the basic nitrogen compound 2-methylquinoline of 1200 μ g/g, the micro-activity of sample is listed in table 6.

Table 6

Claims (11)

1. a Cracking catalyst for alkali resistant nitrogen fecund liquefied gas, comprising:

The cracking activity constituent element of 10-70 % by weight, 1-20 % by weight mesoporous silica-alumina materials, the binding agent of 10-60 % by weight and the clay of 10-70 % by weight, wherein, described cracking activity constituent element comprises the Y zeolite of 70-85 % by weight and the MFI structure molecular screen of 15-30 % by weight, described Y zeolite comprises the first Y zeolite, wherein, the first described Y zeolite is the Y zeolite with rare earth, iron, copper, phosphorus modification, the first described molecular sieve Rare-Earth Content is counted 8-23 % by weight with rare earth oxide, and iron content is with Fe ₂o ₃count 0.1-3.0 % by weight, copper content is counted 0-3.0 % by weight with CuO, and phosphorus content is with P ₂o ₅count 0-2.0 % by weight, sodium oxide content is 0.1-2.5 % by weight; After the first described Y zeolite absorption tributyl phosphoxide ³¹the molecular sieve acid amount that P MAS NMR measures is 1.400-4.500mmolg ^-1, after its absorption trimethyl phosphorous oxide ³¹the molecular sieve acid amount that P MAS NMR measures is 2.300-6.600mmolg ^-1.

2. according to the Cracking catalyst of alkali resistant nitrogen fecund liquefied gas claimed in claim 1, it is characterized in that, the first described Y zeolite Rare-Earth Content is counted 10-20 % by weight with rare earth oxide, and iron content is with Fe ₂o ₃count 0.5-2.5 % by weight, copper content is counted 0.2-1.5 % by weight with CuO, and phosphorus content is with P ₂o ₅count 0-1.0 % by weight.

3. according to the Cracking catalyst of alkali resistant nitrogen fecund liquefied gas claimed in claim 1, it is characterized in that, the first described Y zeolite Rare-Earth Content is counted 14-20 % by weight with rare earth oxide, and iron content is with Fe ₂o ₃count 0.6-1.0 % by weight, copper content is counted 0.5-1.2 % by weight with CuO, and phosphorus content is with P ₂o ₅count 0-1.0 % by weight, sodium oxide content is 0.1-2.0 % by weight.

4. according to the Cracking catalyst of alkali resistant nitrogen fecund liquefied gas claimed in claim 1, it is characterized in that, the first described Y zeolite is obtained by the method that comprises following preparation process: take NaY molecular sieve as raw material, through rare earth exchanged and roasting, obtain " one hands over a roasting " RENaY, then with rare earth compound, iron compound, copper-containing substance, phosphorus containg substances, with or do not react with ammonium salt.

5. according to the Cracking catalyst of alkali resistant nitrogen claimed in claim 4 fecund liquefied gas, it is characterized in that, the process of described acquisition " hands over a roasting " RENaY is at NaY: RE by NaY molecular sieve and rare earth compound ₂o ₃=1: the weight ratio of 0.10-0.25, pH value=2.0-4.5, processes 0.3-1.5 hour under exchange temperature 25-100 ℃ condition, filters, washing, filter cake is at 400-850 ℃, and under 0-100% water vapour, roasting is more than 0.3 hour; Described again with rare earth compound, iron compound, copper-containing substance, phosphorus containg substances, with or the process of not reacting with ammonium salt be by RENaY and rare earth compound, iron content, cupric, phosphorous material, be with or without in the situation of ammonium salt, according to NaY: RE ₂o ₃: Fe ₂o ₃/ CuO: P ₂o ₅: the weight ratio of ammonium salt=1: 0.02-0.15: 0.001-0.05: 0-0.04: 0-0.5, pH=2.0-4.5, reaction at 20-100 ℃, more after filtration, washing.

6. according to the Cracking catalyst of alkali resistant nitrogen claimed in claim 1 fecund liquefied gas, it is characterized in that, described Y zeolite comprises the first Y zeolite described in 20-100 % by weight and the second Y zeolite and/or the 3rd Y zeolite of 0-80 % by weight; The second described Y zeolite is DASY molecular sieve, take the content of rare earth of rare earth oxide as 12-16 % by weight, with P in the 3rd described Y zeolite ₂o ₅the phosphorus content of meter is 0.5-7 % by weight, this molecular sieve ³¹in P MAS NMR spectrum, the percentage that the peak area that chemical shift is-14 ± 2ppm and-23 ± 2ppm resonance signal accounts for total peak area is greater than 85%, molecular sieve ²⁷in Al MAS NMR spectrum, chemical shift is that the percentage that the peak area of 0 ± 2ppm resonance signal accounts for total peak area is greater than 20%.

7. according to the Cracking catalyst of alkali resistant nitrogen fecund liquefied gas claimed in claim 6, it is characterized in that, described the 3rd Y zeolite ³¹in P MAS NMR spectrum, the percentage that the peak area that chemical shift is-14 ± 2ppm and-23 ± 2ppm resonance signal accounts for total peak area is greater than 90%, and lattice constant is

8. according to the Cracking catalyst of alkali resistant nitrogen fecund liquefied gas claimed in claim 1, it is characterized in that, described MFI structure molecular screen is a MFI structure molecular screen and/or the 2nd MFI structure molecular screen, a described MFI structure molecular screen, take oxide molar ratio computing without hydrochemical compositions expression formula, be (0.01-0.25) RE ₂o ₃(0.005-0.02) Na ₂oAl ₂o ₃(0.2-1.0) P ₂o ₅(35-120) SiO ₂, this molecular sieve is 4-5 to the absorption weight ratio of n-hexane and cyclohexane; Described the 2nd MFI structure molecular screen take oxide weight than without hydrochemical compositions expression formula, be (0-0.3) Na ₂o (0.5-5.5) Al ₂o ₃(1.3-10) P ₂o ₅(0.7-15) M1 _xo _y(0.01-5) M2 _mo _n(70-97) SiO ₂, wherein, M1 is Fe, Co or Ni, and x represents the atomicity of M1, and y represents to meet the number of M1 oxidation state requisite oxygen, and M2 is selected from Zn, Mn, Ga or Sn, and m represents the atomicity of M2, and n represents to meet the number of M2 oxidation state requisite oxygen.

9. according to the Cracking catalyst of alkali resistant nitrogen claimed in claim 1 fecund liquefied gas, it is characterized in that, described mesoporous silica-alumina materials has the phase structure of boehmite, and the anhydrous chemical expression of oxide weight of take is (0-0.3) Na ₂o (40-90) Al ₂o ₃(10-60) SiO ₂, its average pore size is 8-20nm, and most probable aperture is 5-15nm, and specific area is 200-400m ²/ g, pore volume is 0.5-2.0ml/g.

10. according to the Cracking catalyst of alkali resistant nitrogen fecund liquefied gas claimed in claim 1, it is characterized in that, it is 10-45 % by weight that described cracking activity constituent element be take the content of butt, it is 2-15 % by weight that described mesoporous silica-alumina materials be take the content of butt, it is 15-40 % by weight that described clay be take the content of butt, and it is 20-50 % by weight that described binding agent be take the content of butt.

The preparation method of the Cracking catalyst of the alkali resistant nitrogen fecund liquefied gas described in 11. claim 1-10 any one, comprises that spraying is dry by cracking activity constituent element, mesoporous material, clay and binding agent making beating, and washing is filtered and dry step.