CN103084199B

CN103084199B - Anti-basic nitrogen olefin reduction cracking catalyst and preparation method thereof

Info

Publication number: CN103084199B
Application number: CN201110332264.3A
Authority: CN
Inventors: 许明德; 朱玉霞; 罗一斌; 邓景辉; 杨雪; 王维家; 任飞; 欧阳颖; 郑金玉; 张萍
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2011-10-28
Filing date: 2011-10-28
Publication date: 2014-12-03
Anticipated expiration: 2031-10-28
Also published as: CN103084199A

Abstract

The invention relates to an anti-basic nitrogen olefin reduction 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 first Y type molecular sieve and a second 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), sodium oxide content in the first Y type molecular sieve is 0.1-2.5 wt%, and the second Y type molecular sieve is a phosphorus and rare earth modified molecular sieve. The catalyst preparation method comprises: preparing a slurry comprising a cracking activity component, a mesoporous silicon-aluminum material, an adhesive and clay, and carrying out spray drying, washing and drying. With application of the catalyst in catalytic cracking of high basic nitrogen content hydrocarbon oil, high conversion rate and low gasoline olefin content are provided.

Description

Cracking of olefins Catalysts and its preparation method falls in a kind of alkali resistant nitrogen

Technical field

The present invention relates to a kind of catalytic cracking catalyst, relate to furtherly a kind of Cracking catalyst of reduction content of olefin in gasoline 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 heavy constituent residual oil catalyst exist under 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 become 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 of expansion catalytically cracked material source, refinery and enhancing efficiency by relying on tapping internal latent power.Compared 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, increase mixing of wax tailings and refine the normal operating that has a strong impact on catalytic cracking unit than regular meeting, cause conversion ratio to reduce, 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 catalyst activity decline.And nitrogen-containing compound is easier to be adsorbed on than polycyclic aromatic hydrocarbon on the acid centre of catalyst, easily form coking point, promote green coke, nitrogen-containing compound can be regarded as the coke precursor that is easier to absorption.

Processing is containing method for example CN1088246A, the US7744745 of alkali nitride raw material and the processing method of the disclosed change feeding manner of US5660716.

Another processing is the Cracking catalyst that uses alkali resistance nitrogen compound containing the method for basic nitrogen compound feedstock oil.But existing Cracking catalyst is for containing the catalytic cracking of alkali nitrogen feedstock oil, exist active low, the product problem degenerating that distributes, and discovery relates to alkali resistant nitrogen and fall the Cracking catalyst of alkene.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of alkali resistant nitrogen falls the catalytic cracking catalyst of alkene, 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 lower content of olefin in gasoline.

The invention provides the catalytic cracking catalyst that alkene falls in a kind of alkali resistant nitrogen, the clay that this catalytic cracking catalyst contains 10-70 % by weight cracking activity constituent element, 1-20 % by weight mesoporous silica-alumina materials, 10-70 % by weight and 10-60 % by weight binding agent, described cracking activity constituent element comprises the first Y zeolite of 15-85 % by weight and the second Y zeolite of 15-85 % by weight; Described the first Y zeolite is that this molecular sieve Rare-Earth Content is counted 8-23 % by weight with rare earth oxide with the Y zeolite of rare earth, iron, copper, phosphorus modification, 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, and the second described Y zeolite is phosphorus and rare earth modified Y zeolite.

The present invention also provides a kind of described alkali resistant nitrogen to fall the preparation method of the catalytic cracking catalyst of alkene, 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.

Described cracking activity constituent element contains the first Y zeolite, and described the first Y zeolite is containing rare earth, iron or iron and copper, contains or not phosphorous Y zeolite, and its 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 obtain Y zeolite modification through following process, and its process comprises: taking 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 the first Y zeolite.

Wherein, the process of described acquisition " 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 value=2.0-4.5, processes 0.3-1.5 hour under exchange temperature 25-100 DEG C condition, filters, washing, filter cake is at 400-850 DEG C, and under 0-100% water vapour, roasting obtains for 0.3 hour above.Further, the described process of the Y zeolite product of rare earth, iron, copper, phosphorus modification for acquisition is according to object product composition, by RENaY and rare earth compound, iron content, cupric, phosphorous material, is with or without in the situation of ammonium salt, according to RENaY: 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 DEG C, more after filtration, the process of washing.

The catalytic cracking catalyst that alkene falls in alkali resistant nitrogen provided by the present invention is specially adapted to RFCC, particularly, in the time that the basic nitrogen compound content in feedstock oil is higher, for example basic n content is 900-2000 μ g/g, described catalytic cracking catalyst of the present invention can show higher catalytic cracking activity in the process of RFCC, can obtain higher conversion ratio, obtain higher yield of gasoline, and olefin(e) centent in gasoline is lower.

Detailed description of the invention

The catalytic cracking catalyst of alkene falls in alkali resistant nitrogen provided by the invention, contain cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent, wherein, described cracking activity constituent element contains a kind of Y zeolite with rare earth, iron, copper, phosphorus modification modification (being the first Y zeolite of the present invention), this 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: taking 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 with i.e. described the first Y zeolite of the Y molecular sieve product of rare earth and the modification of iron/copper/phosphorus.

Wherein, the process of described acquisition " 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 DEG C condition, filters, washing, filter cake is at 400-850 DEG C, 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 and 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 DEG C, 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, compared 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, therefore 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, therefore its sign is the body acid amount mutually of molecular sieve.

The first described Y zeolite, by taking 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 containing the nitrogen-atoms of lone pair electrons forms complex compound, selective absorption basic nitrogen compound alleviates the toxic action of alkali nitrogen to molecular sieve acid site; And Modified Zeolite Y has more outer surface acid amount, and this is conducive to it and effectively resists the toxic action of alkali nitrogen macromolecule to molecular sieve acid site as active component, thereby shows excellent alkali resistant nitrogen performance.Thereby make catalyst provided by the invention there is significant alkali resistant nitrogen performance.

Described cracking activity constituent element contains the second Y zeolite, the phosphorous and rare earth of this second Y zeolite, and it can be made by the method comprising the following steps:

(a) NaY molecular sieve is carried out to rare earth ion exchanged and ammonium ion exchange, make the Na of molecular sieve ₂o content is 1-5 % by weight, RE ₂o ₃content is 2-20 % by weight, then by products therefrom in roaster under 100% water vapour atmosphere, at 450-700 DEG C roasting 0.5-4 hour;

(b) by step (a) gained molecular sieve, inorganic ammonium salt, titanium pigment compound and deionized water according to the molecular sieve in butt: total ammonium salt: P ₂o ₅: water=1: (0.1-1): (0.002-0.1): weight ratio (5-40) is mixed making beating evenly, these slurries are warmed up to 40-100 DEG C and stir 0.5-5 hour, filter and wash with water;

(c) by step (b) products therefrom roasting 0.5-5 hour under 350-700 DEG C and 100% water vapour atmosphere.

In the present invention, the concrete preparation process of described the second Y zeolite can be with reference to CN1353086A, particularly embodiment 1-8 wherein.

Can also comprise the 3rd Y zeolite in active component of the present invention, described the 3rd Y zeolite is the DASY molecular sieve containing rare earth, and the described DASY molecular sieve containing rare earth is rare earth modified hydro-thermal super stable molecular sieve, 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.Taking the butt weight of active component as benchmark, taking the content of described the 3rd Y zeolite of butt as 0-30 % by weight.In the present invention, the part by weight of each component in described cracking activity constituent element is all in butt.

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 present invention, preferably, described mesoporous silica-alumina materials has the phase structure of boehmite, and its anhydrous chemical expression taking oxide weight 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; 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 DEG C 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 DEG C, 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 at dry at 100-150 DEG C, 350-650 DEG C, obtains mesoporous silica-alumina materials again, and this mesoporous silica-alumina materials can be directly used in Kaolinite Preparation of Catalyst; Or the mesoporous silica-alumina materials under the condition of room temperature to 80 DEG C, 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 with inorganic acid, by this acid-treated mesoporous silica-alumina materials for the preparation of catalyst.Described aluminium source can be the conventional various aluminium source using, this area, and described aluminium source can be for example one or more in aluminum nitrate, aluminum sulfate or aluminium chloride.Described silicon source can be the conventional various silicon source 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 with reference to CN1565733A or CN1854258A.

The catalytic cracking catalyst of alkene falls according to alkali resistant nitrogen provided by the invention, taking the butt weight of described catalytic cracking catalyst as benchmark, described cracking activity constituent element is taking the content of butt as 10-70 % by weight, described mesoporous silica-alumina materials is taking the content of butt as 1-20 % by weight, described binding agent is taking the content of butt as 10-60 % by weight, described clay is taking the content of butt as 10-70 % by weight, in preferred situation, taking the butt weight of described catalytic cracking catalyst as benchmark, described cracking activity constituent element is taking the content of butt as 10-45 % by weight, described mesoporous silica-alumina materials is taking the content of butt as 2-15 % by weight, described clay is taking the content of butt as 20-40 % by weight, described binding agent is taking the content of butt as 20-50 % by weight.

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

(1), taking 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 first Y zeolite active component;

Wherein, the process of described acquisition " 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 DEG C condition, filters, washing, filter cake is at 400-850 DEG C, 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 DEG C, more after filtration, the process of washing.

(2) cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent are mixed to making beating, then spray successively and be dried, wash, filter and be dried, wherein, described cracking activity constituent element contains the first described Y zeolite and the second described Y zeolite, or also contains the 3rd described Y zeolite.

The preparation method of the catalytic cracking catalyst of alkene falls according to described alkali resistant nitrogen 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.

The preparation method of the catalytic cracking catalyst of alkene falls according to described alkali resistant nitrogen 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 above describe 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.

Phosphorous and Y zeolite rare earth makes according to the method for embodiment in CN1353086A 1;

DASY2.0 molecular sieve is produced by catalyst asphalt in Shenli Refinery of China Petrochemical Industry;

Aluminium colloidal sol is produced (Al by catalyst asphalt in Shenli Refinery of China Petrochemical Industry 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) and 4 kilograms of deionized waters, (Shandong catalyst plant provides, RE under high degree of agitation state, slowly to add the re chloride of 4.0 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 DEG C and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours under 650 DEG C, 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 % by weight watery hydrochloric acid regulation system pH=3.5, be warming up to 90 DEG C 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.

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

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

(2) preparation of catalytic cracking catalyst

The boehmite of 20 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 (hydrochloric acid of described 36 % by weight with weight ratio) taking the boehmite of butt is as 0.20, be warming up to 65 DEG C of acidifyings 1 hour, add respectively the kaolinic slurries of 27 weight portion in butt, in the aluminium colloidal sol of 8 weight portions of butt and in the slurries of the mesoporous silica-alumina materials of 5 weight portions of butt, stir 20 minutes, add wherein more afterwards in the ABY-1 of 16 weight portions of butt and the mixed serum of the Y zeolite of described phosphorous and rare earth of 22 weight portions and the DASY2.0 molecular sieve of 2 weight portions, stirring obtains the slurries of solid content 30 % by weight, then the dry microspherical catalyst of making of spraying.By the roasting 1 hour at 500 DEG C of this microspherical catalyst, then at 60 DEG C 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 DEG C, dries, and obtains catalytic cracking catalyst C1.

Embodiment 2-7

Prepare catalytic cracking catalyst according to the method for embodiment 1 respectively, difference is, in step (2), mesoporous silica-alumina materials, kaolin, described Modified Zeolite Y (the first Y zeolite), the described inventory in the butt phosphorous and Y zeolite (the second Y zeolite) of rare earth, described DASY2.0 molecular sieve, boehmite and aluminium colloidal sol are distinguished as shown in table 1 below, the inventory of each component is all in weight portion, thereby makes respectively catalytic cracking catalyst C2-C7.

Table 1

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), at 60 DEG C, stir 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, 600 DEG C of roastings 1.5 hours under-1 water vapour in the time of weight space velocity 0.2, then in molecular sieve: ammonium chloride: water=1: for the ratio of 0.1: 10,90 DEG C of ammonium chloride solutions wash 10 minutes, are dried and 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

Prepare catalytic cracking catalyst according to the method for step (2) in embodiment 1, difference is, replaces described Modified Zeolite Y ABY-1 with described DBY, thereby makes catalytic cracking catalyst DC1.

Comparative example 2-3

Prepare catalytic cracking catalyst according to the method for comparative example 1 respectively, difference is, in step (2), mesoporous silica-alumina materials, kaolin, DBY type molecular sieve, the described phosphorous and Y zeolite of rare earth, described DASY2.0 molecular sieve, boehmite, aluminium colloidal sol are as shown in table 2 below respectively in the inventory of butt, wherein, the inventory of each component is all in weight portion, thereby makes respectively catalytic cracking catalyst DC2-DC3.

Table 2

Embodiment 8

Prepare catalytic cracking catalyst according to the method for embodiment 2, 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 (concentration of hydrochloric acid is mass concentration, lower same) regulation system pH=3.5, be warming up at 90 DEG C and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours under 650 DEG C, 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% watery hydrochloric acid regulation system pH=3.5, is warming up to 90 DEG C 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

Prepare catalytic cracking catalyst according to the method for embodiment 2, 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% (quality) watery hydrochloric acid regulation system pH=3.5, be warming up at 90 DEG C and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours at 550 DEG C, 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% watery hydrochloric acid regulation system pH=3.5, are warming up to 90 DEG C 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

Prepare catalytic cracking catalyst according to the method for embodiment 2, 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 DEG C and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours under 650 DEG C, 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 the re chloride of 1.50 liters, 135 grams of Fe (NO ₃) ₃9H ₂o and 55 grams of CuCl ₂2H ₂o solid, with 4% watery hydrochloric acid regulation system pH=3.5, is warming up to 90 DEG C 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

Respectively by above-mentioned catalytic cracking catalyst C1-C10 and DC1-DC3, under 800 DEG C, the condition of 100% water vapour aging 8 hours, be filled in afterwards the reactivity worth of evaluating catalytic cracking catalyst in small fixed flowing bed ACE device (purchased from KTI company of the U.S.), amount of fill is 9g.Then be, that 510 DEG C, weight (hourly) space velocity (WHSV) are 12h in reaction temperature ^-1, under oil ratio (weight) condition that is 6, using the catalytic mixing oil shown in table 3 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 4 below.

According to the olefin(e) centent in the methods analyst gasoline of ASTM D6293-98, result is as shown in table 4 below.

Table 3

Table 4

From table 4, catalytic cracking catalyst provided by the invention shows relatively high RFCC activity in to the process of RFCC processing, can obtain higher conversion ratio, and can obtain the gasoline that olefin(e) centent is lower, there is higher gasoline yield.

Embodiment 11

According to the method Kaolinite Preparation of Catalyst of embodiment 5, be designated as C11, 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 DEG C and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours at 550 DEG C, 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 DEG C 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

According to the method Kaolinite Preparation of Catalyst of embodiment 2, be designated as C12, 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 DEG C and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours under 650 DEG C, 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 DEG C 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 DEG C and stir 1.5 hours, filter, washing, dry; Then roasting 2 hours at 550 DEG C, 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 DEG C 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) ³¹pMAS 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 DEG C 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, then after 800 DEG C/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 5.

Table 5

Claims

1. the Cracking catalyst of alkene falls in an alkali resistant nitrogen, comprise: cracking activity constituent element, 1-20 % by weight mesoporous silica-alumina materials, the binding agent of 10-60 % by weight and the clay of 10-70 % by weight of 10-70 % by weight, wherein, described cracking activity constituent element comprises the first Y zeolite of 15-85 % by weight and the second Y zeolite of 15-85 % by weight; Wherein, the first described Y zeolite is that the first described molecular sieve Rare-Earth Content is counted 8-23 % by weight with rare earth oxide with the Y zeolite of rare earth, iron, copper, phosphorus modification, 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; The second described Y zeolite is phosphorus and rare earth modified Y zeolite, and the first described Y zeolite, after absorption tributyl phosphoxide ³¹the molecular sieve acid amount that p MAS NMR measures is 1.400-4.500mmolg ^-1, after absorption trimethyl phosphorous oxide ³¹the molecular sieve acid amount that PMAS NMR measures is 2.300-6.600mmolg ^-1.

2. the Cracking catalyst of falling alkene according to alkali resistant nitrogen claimed in claim 1, 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. the Cracking catalyst of falling alkene according to alkali resistant nitrogen claimed in claim 1, 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. the Cracking catalyst of alkene is fallen according to alkali resistant nitrogen claimed in claim 1, it is characterized in that, the first described Y zeolite prepares Y zeolite modification through following process, this process comprises: taking NaY molecular sieve as raw material, through rare earth exchanged and roasting, obtain " one hand over one roasting " RENaY, then with rare earth compound, iron compound, copper-containing substance, phosphorus containg substances, with or do not react with ammonium salt.

5. the Cracking catalyst of falling alkene according to alkali resistant nitrogen claimed in claim 4, 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=2.0-4.5, processes 0.3-1.5 hour under exchange temperature 25-100 DEG C condition, filters, washing, filter cake is at 400-850 DEG C, 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 DEG C, more after filtration, washing.

6. the Cracking catalyst of falling alkene according to alkali resistant nitrogen claimed in claim 1, is characterized in that, the second described Y zeolite is made by the method comprising the following steps:

(a) NaY molecular sieve is carried out to rare earth ion exchanged and ammonium ion exchange, make the Na of molecular sieve ₂o content is 1-5 % by weight, RE ₂o ₃content is 2-20 % by weight, then by products therefrom in roaster at 100% water vapour atmosphere, 450-700 DEG C roasting 0.5-4 hour;

7. the Cracking catalyst of falling alkene according to alkali resistant nitrogen claimed in claim 1, is characterized in that, described mesoporous silica-alumina materials has the phase structure of boehmite, taking the anhydrous chemical expression of oxide weight as (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.

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

9. the Cracking catalyst of falling alkene according to alkali resistant nitrogen claimed in claim 1, is characterized in that, described active component also comprises the 3rd Y zeolite, and the 3rd described Y zeolite is the DASY molecular sieve containing rare earth.

10. the preparation method of the Cracking catalyst of alkene falls in the alkali resistant nitrogen described in claim 1-9 any one, comprises that spraying is dry by cracking activity constituent element, mesoporous silica-alumina materials, clay and binding agent making beating, and washing is filtered and dry step.