CN1275443A - Catalyst for cracking hydrocarbon containing phosphorus and rareearth and preparation process thereof - Google Patents
Catalyst for cracking hydrocarbon containing phosphorus and rareearth and preparation process thereof Download PDFInfo
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- CN1275443A CN1275443A CN 99107787 CN99107787A CN1275443A CN 1275443 A CN1275443 A CN 1275443A CN 99107787 CN99107787 CN 99107787 CN 99107787 A CN99107787 A CN 99107787A CN 1275443 A CN1275443 A CN 1275443A
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Abstract
The present invention relates to a hydrocarbon cracking catalyst containing phosphorus and rare earth, and said catalyst is formed from a cracking catalyst component containing zeolite and a possivating agent component. The described passivating agent component contains phosphorus compound, rare earth compound and aluminium compound, and in 31PMAS NMR spectral diagram of passivating agent component, there is a sharp peak at the place in which the chemical displacement is 0--10 ppm.. Said catlayst possesses comparatively high resistance to metal contamination, comparatively high catalytic activity, comparatively high gasoline selectivity and comparatively low coke selectivity.
Description
The invention relates to a kind of catalyst and cracking of hydrocarbon that contains molecular sieve and preparation method thereof, more specifically say so about a kind of catalyst and cracking of hydrocarbon that contains molecular sieve, phosphorus and rare earth element and preparation method thereof.
Catalyst and cracking of hydrocarbon of phosphorous and/or rare earth and preparation method thereof can be divided three classes.
The first kind is to contain aluminum phosphate independently or the aluminium oxide-aluminum phosphate component part as matrix or matrix in the catalyst, and independently aluminum phosphate or aluminium oxide-aluminum phosphate component is previously prepared.As US 4,873,211 disclose a kind of material as the Cracking catalyst component, and this material comprises a kind of zeolite and a kind of host material, and this host material is made up of aluminum phosphate basically, has embedded described zeolite in this host material.The general employing of this Cracking catalyst component materials will contain aluminum ions solution and mix with the solution of phosphoric acid, phosphate radical or phosphoric acid hydrogen radical ion, generate precipitation, then Separation of Solid and Liquid, washing, dehydration be prepared.This Cracking catalyst component materials has higher hydrothermal stability.Again for example, EP 215, and 336A1 discloses a kind of aluminum phosphate component as the catalytic cracking catalyst component, and wherein phosphorus is at least 0.8 with the ratio of aluminium, and preferably near 1, and this component has high porosity.
Second class is to handle rare earth containing zeolite with phosphoric acid, phosphorous acid and ammonium salt thereof in catalyst preparation process.For example, EP 0,095, and 364A2 discloses a kind of catalyst, and this catalyst contains a kind of crystal silicon-aluminate zeolite from the clay material preparation, the residue of this clay generation and the phosphorus of effective dose.Described Preparation of catalysts method comprises with a kind of non-alkali metal will carry out ion-exchange by the aluminosilicate zeolite and the residue of the alkali metal containing of clay preparation, with the alkali metal content in the aluminosilicate zeolite that reduces alkali metal containing; Roasting obtains zeolite and clay residue, and, zeolite after the roasting is contacted the sufficiently long time with residue with a kind of medium, make the phosphorus that contains effective dose in the zeolite residue after the roasting, described medium contains a kind of anion, and this anion is selected from the group of being made up of dihydrogen phosphate ions, dihydrogen phosphite radical ion.This catalyst has higher activity.
The 3rd class is after the Preparation of Catalyst moulding of rare-earth-containing molecular sieve, with the phosphorous aqueous solution catalyst is carried out post processing, makes it to flood 0.1～1% heavy phosphorus.For example, CN1,062,750A discloses a kind of Cracking catalyst of phosphorous and hyperastable Y-type RE zeolite, and this catalyst is made up of with the mixture of ZSM-5, the clay of 0～95 heavy %, the high-temperature inorganic oxide of 0～85 heavy % and the phosphorus of 0.1～1 weight % the hyperastable Y-type RE zeolite of 1～40 heavy % or its.Wherein, in rare earth oxide, the content of rare earth in the hyperastable Y-type RE zeolite is 0.5～6.0 heavy %.This Preparation of catalysts method comprises mixes the precursor of zeolite slurry, clay and/or high-temperature inorganic oxide in proportion, spray drying forming behind the homogeneous, then, carry out one or many ion-exchange post processing, filter and drying with the phosphorus-containing compound aqueous solution.This catalyst has higher hydrothermal stability, scuff resistance, activity and selectivity preferably.Again for example, CN1,062,157A discloses catalytic cracking catalyst of a kind of phosphorous and hydrogen Y zeolite and preparation method thereof, this catalyst by 4～50 heavy % be selected from one of HY, HX, REHY, REHX or wherein two or more mixture or one of them form with the mixture of other zeolites, the natural or artificial synthetic clay of 0～80 heavy %, the high temperature resistant phosphorus that contains aluminium inorganic oxide and 0.05～4.0 weight % of 5～95 heavy %.This Preparation of catalysts method comprises that mixture, clay and the high temperature resistant precursor that contains the aluminium inorganic oxide with the faujasite of the pre-exchange degree 0～90% of sodium ion or it and other zeolites is mixed into glue in proportion, spray drying forming behind the homogeneous, through or without washing, carry out one or many ion-exchange post processing with the phosphorus-containing compound aqueous solution, filtration, drying.This catalyst has higher activity stability, scuff resistance and selectivity preferably.
Above-mentioned three class catalyst are purpose to improve activity of such catalysts, selectivity, hydrothermal stability and wearability all.
CN1,067,670A discloses a kind of hydrocarbon cracking catalyzer composite that contains vanadium fixing agent and preparation method thereof, this catalyst is made up of the semi-synthetic or full synthesising cracking catalyst particle of 95～60 heavy % and the vanadium fixing agent particle of 5～40 heavy %, and vanadium fixing agent wherein is made up of the alkali earth metal of 0.1～20 heavy % and/or the aluminium oxide of thulium and surplus.The preparation method of vanadium fixing agent wherein adopts conventional infusion process.This catalyst has good anti-vanadium ability.
US4,919,787 disclose the method for metal in a kind of passivation hydrocarbon raw material, and this method is included under the passivation condition described raw material is contacted with a kind of porous passivator, and described passivator contains rare earth oxide-aluminum oxide-and aluminum phosphate precipitation.
US5,001,096 discloses a kind of catalytic cracking catalyst and preparation method thereof, and described catalyst contains the catalyst cracking particles and the coating on described particle of dispersion, and described coating contains the metal that can catch the described catalytic cracking reaction of influence at least effectively.Coating contains rare earth oxide, aluminum oxide and aluminum phosphate as described.The preparation method of described coating comprises a kind of solution and a kind of aqueous slkali that contains at least a+3 valency aluminium sources, a kind of+3 valency rare earth metals and phosphoric acid of preparation, under the condition that keeps pH value 8～12, above-mentioned two kinds of solution is under agitation mixed.Above-mentioned passivating agent composition is introduced the ability that can improve the preventing from heavy metal pollution of catalyst in the Cracking catalyst.
The purpose of this invention is to provide a kind of new, have the higher preventing from heavy metal pollution performance and the catalytic cracking catalyst of high catalytic activity and better choice more, another object of the present invention provides this Preparation of catalysts method.
Catalyst provided by the invention is made up of a kind of Cracking catalyst component and a kind of passivating agent composition that contains zeolite, and described passivating agent composition contains phosphorus compound, rare earth compound and aluminium compound, described passivating agent composition
31In the P MAS NMR spectrogram, be that 0～-10 ppm place has a spike in chemical shift.
Preparation of catalysts method provided by the invention comprises that the component that composition is contained the Cracking catalyst of zeolite mixes with passivating agent composition, and wherein, described passivating agent composition contains phosphorus compound, rare earth compound and aluminium compound, its
31In the P MAS NMR spectrogram, be 0 in chemical shift～-there is a spike at the 10ppm place, the preparation method of described passivating agent composition is included in room temperature to 100 ℃, to having at least solid to separate out, room temperature to 250 ℃ drying is 300～800 ℃ of products that roasting obtains also with a kind of solution concentration that contains rare-earth compound, aluminium compound and phosphorus compound; The addition of described rare-earth compound, aluminium compound and phosphorus compound makes in the passivating agent composition that obtains, and in oxide, contains the phosphorus of 0.1～80 heavy %, the rare earth of 0.1～80 heavy % and the aluminium of 10～99.8 heavy %.
Described passivating agent composition can also prepare with another method, and this method comprises with containing the solution of rare-earth compound and the solution impregnation aluminium oxide of phosphorus-containing compound, room temperature to 250 ℃ drying and 300～800 ℃ of products that roasting obtains; The consumption of described rare-earth compound, phosphorus compound and aluminium oxide makes in the passivating agent composition that obtains, and in oxide, contains the phosphorus of 0.1～80 heavy %, the rare earth of 0.1～80 heavy % and the aluminium of 10～99.8 heavy %.
According to catalyst provided by the invention, described passivating agent composition
31Exist in the P MAS NMR spectrogram chemical shift be 0～-spike of 10ppm, the position of this spike is preferably-2～-7ppm.The phosphorus in passivating agent composition and the mol ratio of rare earth hour, as, the mol ratio of phosphorus and rare earth less than 1 o'clock, described passivating agent composition
31Basically have only in the P MAS NMR spectrogram chemical shift be 0～-10ppm, be preferably-2～-spike of 7ppm.When the mol ratio of phosphorus in the passivating agent composition and rare earth is big, as the mol ratio of phosphorus and rare earth greater than 1 o'clock, described passivating agent composition
31Remove in the P MAS NMR spectrogram exist chemical shift be 0～-10ppm, be preferably-2～-spike of 7ppm beyond, also exist a chemical shift be-24～-peak of 31ppm.Described chemical shift is-24～-peak of 31ppm is the nuclear magnetic resonance peak of four-coordination phosphorus in the aluminum phosphate (referring to J.Phys.Chem., 92,3965～3970,1988).Described passivating agent composition
31In the P MAS NMR spectrogram, chemical shift is 0～-10ppm, be preferably-2～-spike of 7ppm do not see bibliographical information.By inference, it is likely the nuclear magnetic resonance peak of four-coordination phosphorus in the RE phosphate.
According to catalyst provided by the invention, the content of described passivating agent composition in catalyst is 1～50 heavy %, is preferably 5～30 heavy %.
According to catalyst provided by the invention, in oxide, phosphorous 0.1～80 heavy %, preferred 5～40 heavy % in the described passivating agent composition, rare earth 0.1～80 heavy %, preferred 5～50 heavy %, aluminium 10～99.8 heavy %, preferred 35～85 heavy %.
The phosphorus in the described passivating agent composition and the mol ratio of rare earth can in very large range change, and generally speaking, the mol ratio of phosphorus and rare earth is 0.1～100, is preferably 0.5～50.
Described rare earth is selected from one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium.Wherein, preferred rare earth is selected from lanthanum, cerium or mainly is the mixed rare-earth elements that contains lanthanum and/or cerium.
According to catalyst provided by the invention, the described Cracking catalyst component that contains zeolite generally contains zeolite and matrix.
Wherein, described zeolite is selected from and is commonly used in the natural of catalytic cracking catalyst active component or the artificial synthetic zeolite one or more, as in faujasite, Beta zeolite, modenite, the ZSM-5 zeolite one or more.Preferred zeolite is one or more in X type zeolite, y-type zeolite, overstable gamma zeolite, sealumination modified Y zeolite, Beta zeolite, modenite, the ZSM-5 zeolite.Described zeolite is one or more in the y-type zeolite, overstable gamma zeolite, sealumination modified Y zeolite, Beta zeolite, ZSM-5 zeolite of Hydrogen, ammonium type and/or rare-earth type more preferably.In catalyst provided by the invention, be benchmark with final catalyst, the content of described zeolite can be 5～80 heavy %, is preferably 10～50 heavy %.
Wherein, described matrix is selected from one or more in silica, aluminium oxide, amorphous aluminosilicate, the various clay, is preferably in silica, aluminium oxide, amorphous aluminosilicate, kaolin, the halloysite one or more.In catalyst provided by the invention, the content of described matrix is 10～95 heavy %, is preferably 20～80 heavy %.
Described composition contains the component of Cracking catalyst of zeolite and the mixing of passivating agent composition can be adopted various known methods.
For example, the mixing that contains the component of Cracking catalyst of zeolite and passivating agent composition of described composition can be formed described ratio with the component that contains the Cracking catalyst of zeolite according to catalyst with passivating agent composition and carries out mechanical mixture.
Under the preferable case, described composition contains the method that the mixing of the component of Cracking catalyst of zeolite and passivating agent composition adopts making beating to mix, promptly according to the ratio of each component of catalytic cracking catalyst, various components and/or its precursor and passivating agent composition of the present invention and water are mixed together making beating, drying is also washed described slurries, obtains catalyst provided by the invention.Wherein, described drying can adopt common drying means, also can adopt spray-dired method.
According to Preparation of catalysts method provided by the invention, described rare-earth compound is selected from one or more in water-soluble rare-earth compound, wherein, in preferred nitrate of rare earth element, the halide one or more, more preferred lanthanum nitrate, lanthanum chloride, cerous nitrate, cerium chloride and mainly contain in the chloride of mixed rare-earth elements of lanthanum chloride and cerium chloride one or more.
According to Preparation of catalysts method provided by the invention, described aluminium compound is to contain in the soluble compound of trivalent aluminium ion one or more.Wherein, preferred aluminium compound is one or more in aluminum nitrate, aluminium chloride, the aluminum sulfate.More preferred aluminium compound is aluminum nitrate or aluminium chloride.
According to Preparation of catalysts method provided by the invention, described phosphorus compound is selected from one or more in the titanium pigment compound.Preferred phosphorus compound is selected from one or more in phosphoric acid, the soluble phosphate.Described soluble phosphate is as being selected from alkali-metal phosphate, acid phosphate, subphosphate, one or more in ammonium phosphate, ammonium dihydrogen phosphate (ADP), the diammonium hydrogen phosphate.Preferred phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), the diammonium hydrogen phosphate.
The described temperature that concentrates the solution contain rare-earth compound, aluminium compound and phosphorus compound can be room temperature to 100 ℃, for saving time, is preferably 50～100 ℃.
The temperature of described drying is a room temperature to 250 ℃, is preferably 80～200 ℃.The temperature of roasting can be 300～800 ℃, is preferably 500～750 ℃.
Described aluminium oxide can be various aluminium oxide, as in gama-alumina, η-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, κ-aluminium oxide, ρ-aluminium oxide, the Alpha-alumina one or more.Preferred aluminium oxide is one or more in gama-alumina, η-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, κ-aluminium oxide, the ρ-aluminium oxide.More preferred aluminium oxide is gama-alumina and/or η-aluminium oxide.
Described usefulness contains in the process of solution impregnation aluminium oxide of the solution of rare-earth compound and phosphorus-containing compound, with the process of the solution impregnation aluminium oxide that contains rare-earth compound can be before solution impregnation alumina process with phosphorus-containing compound, carry out afterwards or simultaneously.Flooding can be dry after a kind of solution, also drying not.Under the preferable case, earlier with the solution impregnation aluminium oxide that contains rare-earth compound, drying is not used the solution impregnation aluminium oxide of phosphorus-containing compound again.
The consumption of phosphorus compound, rare earth compound and aluminium compound or aluminium oxide preferably makes in the passivating agent composition that obtains, in oxide, and phosphorous 5～40 heavy %, rare earth 5～50 heavy % and aluminium 35～85 heavy %.
Catalyst provided by the invention has following advantage: catalyst provided by the invention is compared with the prior art catalyst has higher preventing from heavy metal pollution ability, higher catalytic activity, higher gasoline selective and lower coke selectivity.
Fig. 1 is the contained passivating agent composition of catalyst provided by the invention
31P MAS NMR spectrogram;
Fig. 2 is the contained passivating agent composition of catalyst provided by the invention
31P MAS NMR spectrogram;
The reference passivating agent composition that Fig. 3 is made up of phosphorous oxides and aluminium oxide
31P MAS NMR spectrogram;
Fig. 4 is the passivating agent composition of existing phosphorous, aluminium and rare earth compound
31P MAS NMR spectrogram.
The following examples will the present invention is described further.
Example 1
This example illustrates passivating agent composition of the present invention and preparation thereof.
With 100 milliliters of La
2O
3After the aluminum chloride aqueous solution of the lanthanum chloride solution of content 235.0 grams per liters and 655 grams, 40 heavy % mixes, the temperature that keeps mixed solution is at 50 ℃, the ammonium phosphate solution that under condition of stirring, adds 212 grams, 40 heavy % gradually, concentrate this mixed solution to pasty state 50 ℃ of heating, oven dry is after 4 hours in 200 ℃ of air dry ovens, 550 ℃ of roastings 4 hours, obtain passivating agent composition after the grinding, be designated as a.The composition of passivating agent composition a is listed in the table 1, its
31Also list in the table 1 position (chemical displacement value) that the peak occurs in the P MAS NMR spectrogram.Wherein, chlorinity adopts ion-chromatographic determination, and chlorinity is a trace, in table, do not list, down together, no longer repeat specification.Other constituent contents are got by calculating.
31P MAS NMR spectrogram is measured on Bruker AM-300 type superconduction nuclear magnetic resonance spectrometer.
Example 2
This example illustrates passivating agent composition of the present invention and preparation thereof.
Get 100 gram γ-Al
2O
3Powder (boehmite of being produced by Chang Ling oil plant catalyst plant makes through 550 ℃ of roastings 2 hours), 100 milliliters of lanthanum chloride solutions (with example 1) are slowly added wherein, after mixing, add the 100 ml water solution that contain 84.7 gram ammonium phosphate while stirring, with above-mentioned liquid-solid mixture 150 ℃ of dryings 4 hours, 700 ℃ of roastings 3 hours, obtain passivating agent composition after the grinding then, be designated as b.The composition of passivating agent composition b is listed in the table 1.Its
31Also list in the table 1 position (chemical displacement value) that the peak occurs in the P MAS NMR spectrogram
Example 3
This example illustrates passivating agent composition of the present invention and preparation thereof.
Method by example 2 prepares passivating agent composition, and different is with 100 milliliters of La
2O
3The lanthanum chloride solution of content 235.0 grams per liters changes 100 milliliters of La into
2O
3130 grams per liters, CeO
270 grams per liter rare earth chloride solutions, the 100 ml water solution that will contain 84.7 gram ammonium phosphate change the phosphate aqueous solution (proportion is 1.69 grams per milliliters) of 75 milliliter of 85 heavy % into, and baking temperature is 200 ℃, and sintering temperature is 600 ℃, and the passivating agent composition that obtains is designated as c.The composition of passivating agent composition c is listed in the table 1.Its
31Also list in the table 1 position (chemical displacement value) that the peak occurs in the P MAS NMR spectrogram
Example 4
This example illustrates passivating agent composition of the present invention and preparation thereof.
Method by example 2 prepares passivating agent composition, and that different is γ-Al
2O
3Consumption is 200 grams, and the lanthanum chloride solution consumption is 150 milliliters, and ammonium phosphate content is 100 grams in the ammonium phosphate solution, and sintering temperature is 600 ℃, and the passivating agent composition note that obtains is made d.The composition of passivating agent composition d is listed in the table 1.Its
31Also list in the table 1 position (chemical displacement value) that the peak occurs in the P MAS NMR spectrogram
Example 5
This example illustrates passivating agent composition of the present invention and preparation thereof.
Method by example 2 prepares passivating agent composition, and different is that the lanthanum chloride solution consumption is 200 milliliters, and the content of ammonium phosphate is 200 grams in the ammonium phosphate solution, and the consumption of ammonium phosphate solution is 200 milliliters, and the passivating agent composition note that obtains is made e.The composition of passivating agent composition e is listed in the table 1, its
31Also list in the table 1 position (chemical displacement value) that the peak occurs in the P MAS NMR spectrogram.Its
31P MAS NMR spectrogram as shown in Figure 1.
Example 6
This example illustrates passivating agent composition of the present invention and preparation thereof.
Method by example 2 prepares passivating agent composition, and different is that the lanthanum chloride solution consumption is 400 milliliters, and the content of ammonium phosphate is 50 grams in the ammonium phosphate solution, and the consumption of ammonium phosphate solution is 50 milliliters, and the passivating agent composition note that obtains is made f.The composition of passivating agent composition f is listed in the table 1, its
31Also list in the table 1 position (chemical displacement value) that the peak occurs in the P MAS NMR spectrogram.Its
31P MAS NMR spectrogram as shown in Figure 2.
Comparative Examples 1
The preparation method of the reference component of this Comparative Examples explanation compounds containing rare earth and aluminium oxide.
Get 100 gram γ-Al
2O
3Powder (with example 2) slowly adds 100 milliliters of lanthanum chloride solutions (with example 2) wherein, and after mixing, 150 ℃ of dryings 4 hours then 700 ℃ of roastings 3 hours, obtain reference component g after the grinding.La among the reference component g
2O
3Content is listed in the table 1.
Comparative Examples 2
The preparation method of the reference component of this Comparative Examples explanation phosphorus-containing compound and aluminium oxide.
Get 100 gram γ-Al
2O
3Powder (with example 2) adds the 100 ml water solution contain 84.7 gram ammonium phosphate, and 150 ℃ of dryings 4 hours then 700 ℃ of roastings 3 hours, obtain reference component h after the grinding.P among the reference component h
2O
5Content is listed in the table 1, its
31Also list in the table 1 position (chemical displacement value) that the peak occurs in the P MAS NMR spectrogram.Its
31P MAS NMR spectrogram as shown in Figure 3.
Comparative Examples 3
This Comparative Examples explanation prior art contains the preparation method of the reference passivating agent composition of rare earth oxide, aluminum phosphate and aluminium oxide.
According to US5, the method for 001,096 example 3 prepares the reference passivating agent composition.Get 52 gram Al (NO
3)
3.9H
2O is dissolved in the 136 gram deionized waters, is made into aluminum nitrate solution.Get 12 gram La (NO
3)
3.6H
2O is dissolved in the 136 gram deionized waters, is made into lanthanum nitrate hexahydrate.The aluminum nitrate solution and the lanthanum nitrate hexahydrate that are made into are mixed and add 8 phosphoric acid that restrain, form a kind of mixed solution.This mixed solution and the tetramethyl ammonium hydroxide solutions that contain 196 grams, 25 heavy % are added drop-wise in the flask that contains 136 gram deionized waters simultaneously, stir simultaneously, the adding speed of solution makes the pH of slurries in the flask keep 9.0, the pH that contains the slurries of precipitation at last is 9.11, filter, wash, 150 ℃ of dryings 4 hours with 2 liters of deionized waters, 700 ℃ of roastings 3 hours, obtain reference component i after the grinding then.La among the reference component i
2O
3Content and P
2O
5Content is listed in the table 1.Its
31P MAS NMR spectrogram as shown in Figure 4.
Table 1
La
2O
3And CeO
2Total content.
Example 7
This example illustrates catalyst provided by the invention and preparation thereof.
With 35 gram (dry basis) industrial trades mark is the ultrastable (lattice constant is 24.54 dusts) of SRY, the passivating agent composition a of 15 gram examples, 1 preparation, 30 gram (dry basis) kaolin (Suzhou kaolin company product) and 20 gram (dry basis) boehmite gels and 100 gram deionized waters mix making beating, the slurries that obtain are dried down at 120 ℃, the solid product that obtains with the washing of the ammonium sulfate solution of 50 times 0.2 heavy % 3 times, the solid product that obtains with the washing of 50 times deionized water at last, 120 ℃ of oven dry, obtain catalyst provided by the invention, note is made C
1Table 2 has provided C
1Composition.The catalyst composition is got by calculating, and wherein, the part amount of losing because of washing is very little, so washing process is considered as not loss.
Wherein, the preparation method of boehmite gel is, boehmite (production of Chang Ling oil plant catalyst plant) is mixed making beating with deionized water in 1: 10 ratio, be 36% commercially available analysis pure hydrochloric acid again in 1 gram boehmite than the ratio of 0.5 milliliter of hydrochloric acid adding concentration, stirred 2 hours in 80 ℃, be incubated after 2～3 hours, become the boehmite gel.
Example 8～9
Following example illustrates catalyst provided by the invention and preparation thereof.
Method by example 7 prepares catalyst, that different is the passivating agent composition b that the passivating agent composition a of example 1 preparation is changed into example 2 preparations, the consumption of passivating agent composition b is respectively 10 grams and 15 grams, the kaolin consumption is respectively 35 grams and 30 grams, the boehmite amount of gel is 20 grams, obtains catalyst C provided by the invention
2And C
3Table 2 has provided C
2And C
3Composition.
Comparative Examples 4
This Comparative Examples explanation reference catalyst and preparation method thereof.
Prepare catalyst by the method for example 7 and each material consumption, the different passivating agent composition a that just do not add, kaolin consumption 45 restrain, and obtain reference catalyst B
1Reference catalyst B
1Composition list in the table 2.
Comparative Examples 5
This Comparative Examples explanation reference catalyst and preparation method thereof.
Method and each material consumption by example 8 prepare catalyst, and different just changes passivating agent composition b into reference component g, obtains reference catalyst B
2Reference catalyst B
2Composition list in the table 2.
Comparative Examples 6
This Comparative Examples explanation reference catalyst and preparation method thereof.
Method and each material consumption by example 8 prepare catalyst, and different just changes passivating agent composition b into reference component h, obtains reference catalyst B
3Reference catalyst B
3Composition list in the table 2.
Example 10～11
Following example illustrates catalyst provided by the invention and preparation thereof.
Method by example 7 prepares catalyst, that different is the passivating agent composition c that the passivating agent composition a of example 1 preparation is changed into example 3 preparations, the consumption of passivating agent composition c is respectively 5 grams and 15 grams, the kaolin consumption is respectively 40 grams and 30 grams, the boehmite consumption is 20 grams, obtains catalyst C provided by the invention
4And C
5Table 2 has provided C
4And C
5Composition.
Example 12
This example illustrates catalyst provided by the invention and preparation thereof.
Method by example 7 prepares catalyst, and different is that the passivating agent composition d with the passivating agent composition a of example 1 preparation changes example 4 preparations into obtains catalyst C provided by the invention
6Table 2 has provided C
6Composition.
Example 13～14
Following example illustrates catalyst provided by the invention and preparation thereof.
Method by example 7 prepares catalyst, and different is changes ultrastable into rare earth Y type zeolite that the industrial trade mark is SRCY (silica alumina ratio is 6.0, and rare earth oxide content is 14.0 heavy %, wherein La
2O
3Content is 10.0 heavy %, CeO
2Content is 3.0 heavy %, rare earth oxide content beyond lanthanum and the cerium is 1.0 heavy %), the consumption of rare earth Y type zeolite is respectively 30 grams and 25 grams, the passivating agent composition a of example 1 preparation is changed into the passivating agent composition d of example 4 preparations, the consumption of passivating agent composition d is respectively 15 grams and 20 grams, the kaolin consumption is 35 grams, change the boehmite gel into aluminium colloidal sol (salic 12.5 heavy %, the Zhou village catalyst plant is produced), aluminium colloidal sol consumption is 20 grams (dry basis), obtains catalyst C provided by the invention
7And C
8Table 2 has provided C
7And C
8Composition.
Example 15
This example illustrates catalyst provided by the invention and preparation thereof.
Method by example 7 prepares catalyst, different is to change ultrastable into example 13～14 described rare earth Y type zeolites, the passivating agent composition a of example 1 preparation is changed into the passivating agent composition e of example 5 preparations, change the boehmite gel into aluminium colloidal sol (with example 13～14), obtain catalyst C provided by the invention
9Table 2 has provided C
9Composition.
Comparative Examples 7
This Comparative Examples explanation reference catalyst and preparation method thereof.
Method and each material consumption by example 15 prepare catalyst, and different just changes passivating agent composition e into reference component i, obtains reference catalyst B
4Reference catalyst B
4Composition list in the table 2.
Example 16
This example illustrates catalyst provided by the invention and preparation thereof.
Method by example 7 prepares catalyst, different is to change ultrastable into example 13～14 described rare earth Y type zeolites, the passivating agent composition a of example 1 preparation is changed into the passivating agent composition f of example 6 preparations, change the boehmite gel into aluminium colloidal sol (with example 13～14), obtain catalyst C provided by the invention
10Table 2 has provided C
10Composition.
Table 2
Example 17～18
Following example illustrates the catalytic performance of catalyst provided by the invention.
With catalyst C
1Carry out pollution of vanadium with Michele (Mitchell) method (Ind.Eng.Chem., Prod.Res.Dev., 17,209,1980).Promptly at 350 ℃ with catalyst roasting 1 hour, with quantitative aphthenic acids vanadium solution impregnated catalyst C
1, in 150 ℃ of oven dry, 550 ℃ of roastings 4 hours.The catalyst that soaks vanadium after the roasting wore out 4 hours in 100% water vapour atmosphere in 800 ℃, polluted severity to improve.
Estimating the catalyst C that pollutes after vanadium also wears out on the heavy oil microreactor
1Reach the catalyst C after uncontaminated vanadium wears out with same procedure
1Reactivity worth, reaction raw materials is the wax oil (density 0.8916, the heavy % of carbon residue 0.28) of 288～518 ℃ of boiling range scopes, reaction condition is: 500 ℃ of reaction temperatures, agent weight of oil ratio is 5.0, weight (hourly) space velocity (WHSV) 16 hours
-1, catalyst loading amount 5 grams.Reaction result is listed in the table 3.Wherein, product is formed the employing gas chromatographic analysis.
Micro-activity of heavy oil (being conversion ratio)=dry gas yied+liquefied gas yield+C
5～210 ℃ of gasoline yield+coke yields.
Comparative Examples 8～9
The catalytic performance of following Comparative Examples explanation reference catalyst.
The method of pressing example 17～18 is to reference catalyst B
1It is also aging to carry out pollution of vanadium, presses the method evaluation of example 17～18 and pollutes the reference catalyst B that goes up after vanadium also wears out
1And the uncontaminated catalyst B that goes up after vanadium also wears out
1, reaction result is respectively in the table 3.
Table 3
| Example number | 17 | ?18 | Comparative Examples 8 | Comparative Examples 9 |
| The catalyst numbering | C 1 | ?C 1 | ?B 1 | ?B 1 |
| Content of vanadium, ppm | 0 | ?4000 | ?0 | ?4000 |
| Conversion ratio, heavy % | 73.30 | ?66.11 | ?71.56 | ?57.14 |
| Product is formed, heavy % | ||||
| Dry gas | 1.81 | ?2.23 | ?1.74 | ?2.14 |
| Liquefied gas (liquid hydrocarbon) | 15.28 | ?14.40 | ?16.46 | ?10.22 |
| C 5～210 ℃ of gasoline | 45.71 | ?41.78 | ?42.19 | ?34.17 |
| 210～350 ℃ of cuts | 20.61 | ?24.24 | ?19.79 | ?24.77 |
| ＞350 ℃ of cuts | 6.09 | ?9.65 | ?8.65 | ?18.09 |
| Coke | 10.50 | ?7.70 | ?11.17 | ?10.61 |
| Coke/conversion ratio | 0.14 | ?0.12 | ?0.16 | ?0.19 |
Example 19～20
Following example illustrates the catalytic performance of catalyst provided by the invention.
The method of pressing example 17～18 is to catalyst C
3Carry out pollution of vanadium and aging, different is that aging temperature is 760 ℃.Press the method evaluation of example 17～18 and pollute the catalyst C that goes up after vanadium also wears out
3And the uncontaminated catalyst C that goes up after vanadium also wears out
3, different is that agent weight of oil ratio is 3.2, reaction result is listed in the table 4.
Comparative Examples 10～11
The catalytic performance of following Comparative Examples explanation reference catalyst.
The method of pressing example 19～20 is to reference catalyst B
2It is also aging to carry out pollution of vanadium, presses the method evaluation of example 19～20 and pollutes the reference catalyst B that goes up after vanadium also wears out
2And the uncontaminated catalyst B that goes up after vanadium also wears out
2, reaction result is listed in the table 4.
Table 4
| Example number | 19 | ?20 | Comparative Examples 10 | Comparative Examples 11 |
| The catalyst numbering | C 3 | ?C 3 | ?B 2 | ?B 2 |
| Content of vanadium, ppm | 0 | ?4000 | ?0 | ?4000 |
| Conversion ratio, heavy % | 78.25 | ?72.25 | ?73.20 | ?61.30 |
| Product is formed, heavy % | ||||
| Dry gas | 2.96 | ?3.20 | ?1.93 | ?2.34 |
| Liquefied gas (liquid hydrocarbon) | 18.43 | ?18.88 | ?15.28 | ?9.56 |
| C 5～210 ℃ of gasoline | 46.36 | ?41.50 | ?43.55 | ?38.37 |
| 210～350 ℃ of cuts | 14.54 | ?17.70 | ?15.80 | ?23.50 |
| ＞350 ℃ of cuts | 7.21 | ?10.05 | ?11.00 | ?15.20 |
| Coke | 10.5 | ?8.67 | ?12.44 | ?11.03 |
| Coke/conversion ratio | 0.13 | ?0.12 | ?0.17 | ?0.18 |
Example 21～22
The catalytic performance of following Comparative Examples explanation reference catalyst.
The method of pressing example 17～18 is to catalyst C
5Carry out pollution of vanadium and aging, different is that aging temperature is 760 ℃.Press the method evaluation of example 17～18 and pollute the catalyst C that goes up after vanadium also wears out
5And the uncontaminated catalyst C that goes up after vanadium also wears out
5, different is that agent weight of oil ratio is 3.2, reaction result is respectively in the table 5.
Comparative Examples 12～13
The catalytic performance of following Comparative Examples explanation reference catalyst.
The method of pressing example 21～22 is to reference catalyst B
3It is also aging to carry out pollution of vanadium, presses the method evaluation of example 21～22 and pollutes the reference catalyst B that goes up after vanadium also wears out
3And the uncontaminated catalyst B that goes up after vanadium also wears out
3, reaction result is listed in the table 5.
Table 5
| Example number | 21 | ?22 | Comparative Examples 12 | Comparative Examples 13 |
| The catalyst numbering | C 5 | ?C 5 | ?B 3 | ?B 3 |
| Content of vanadium, ppm | ?0 | ?4000 | ?0 | ?4000 |
| Conversion ratio, heavy % | 76.60 | ?70.10 | ?71.65 | ?58.56 |
| Product is formed, heavy % | ||||
| Dry gas | 2.03 | ?1.94 | ?1.67 | ?2.21 |
| Liquefied gas (liquid hydrocarbon) | 20.60 | ?18.02 | ?17.07 | ?11.90 |
| C 5～210 ℃ of gasoline | 44.78 | ?41.03 | ?42.16 | ?35.08 |
| 210～350 ℃ of cuts | 17.00 | ?19.23 | ?19.50 | ?25.33 |
| ＞350 ℃ of cuts | 6.40 | ?10.67 | ?8.85 | ?16.11 |
| Coke | 9.19 | ?9.11 | ?10.75 | ?9.37 |
| Coke/conversion ratio | 0.12 | ?0.13 | ?0.15 | ?0.16 |
Example 23～24
The catalytic performance of following Comparative Examples explanation reference catalyst.
The method of pressing example 17～18 is to catalyst C
9It is also aging to carry out pollution of vanadium, presses the method evaluation of example 17～18 and pollutes the catalyst C that goes up after vanadium also wears out
9And the uncontaminated catalyst C that goes up after vanadium also wears out
9, reaction result is listed in the table 6.
Comparative Examples 14～15
The catalytic performance of following Comparative Examples explanation reference catalyst.
The method of pressing example 23～24 is to reference catalyst B
4It is also aging to carry out pollution of vanadium, presses the method evaluation of example 23～24 and pollutes the reference catalyst B that goes up after vanadium also wears out
4And the uncontaminated catalyst B that goes up after vanadium also wears out
4, reaction result is listed in the table 6.
Table 6
| Example number | 23 | ?24 | Comparative Examples 14 | Comparative Examples 15 |
| The catalyst numbering | C 9 | ?C 9 | ?B 4 | ?B 4 |
| Content of vanadium, ppm | ?0 | ?5000 | ?0 | ?5000 |
| Conversion ratio, heavy % | 73.50 | ?62.34 | ?72.03 | ?56.25 |
| Product is formed, heavy % | ||||
| Dry gas | 2.11 | ?2.52 | ?1.89 | ?3.15 |
| Liquefied gas (liquid hydrocarbon) | 18.97 | ?13.42 | ?16.71 | ?10.08 |
| C 5～210 ℃ of gasoline | 43.60 | ?38.92 | ?42.63 | ?32.89 |
| 210～350 ℃ of cuts | 16.23 | ?21.43 | ?18.90 | ?27.90 |
| ＞350 ℃ of cuts | 10.27 | ?16.23 | ?9.07 | ?15.85 |
| Coke | 8.82 | ?7.48 | ?10.80 | ?10.13 |
| Coke/conversion ratio | 0.12 | ?0.12 | ?0.15 | ?0.18 |
From the result of table 3～6 as can be seen, compared with prior art, catalyst provided by the invention has higher preventing from heavy metal pollution ability, higher catalytic activity, higher gasoline selective and lower coke selectivity.For example:
(1) shown in the result of table 3, under identical reaction condition, do not pollute the micro-activity of heavy oil going up vanadium and pollute the catalyst provided by the invention of going up the 4000ppm vanadium than do not contain passivating agent composition of the present invention not have to pollute go up vanadium and pollution upward the reference catalyst of 4000ppm vanadium improved 2.4% and 15.7% respectively.Behind the 4000ppm vanadium, its micro-activity of heavy oil has only reduced by 9.8% than the catalyst that does not pollute vanadium to catalyst provided by the invention on polluting, and for the reference catalyst that does not contain passivating agent composition, its micro-activity of heavy oil has but reduced by 20.2%.Adopt and to pollute not that gasoline yield is respectively 45.71 heavy % and 41.78 heavy % when going up vanadium and polluting the catalyst provided by the invention of going up the 4000ppm vanadium, the ratio of coke and conversion ratio is respectively 0.14 and 0.12, and adopt do not pollute go up vanadium and pollute go up the 4000ppm vanadium do not contain the reference catalyst of passivating agent composition the time, gasoline yield has only 42.19 and 34.17 respectively, and the ratio of coke and conversion ratio is respectively up to 0.16 and 0.19.
(2) shown in the result of table 4, under identical reaction condition, do not pollute the micro-activity of heavy oil going up vanadium and pollute the catalyst provided by the invention of going up the 4000ppm vanadium and go up vanadium and pollute the reference catalyst that contains the passivating agent composition of forming by lanthanum-oxides and aluminium oxide that goes up the 4000ppm vanadium and do not improved 6.9% and 17.9% respectively than not polluting.Catalyst provided by the invention is behind 4000ppm vanadium in the pollution, its micro-activity of heavy oil has only reduced by 7.7% than the catalyst that does not pollute vanadium, and for the reference catalyst that contains the passivating agent composition of being made up of lanthanum-oxides and aluminium oxide, its micro-activity of heavy oil has but reduced by 16.3%.Adopt and not pollute when going up vanadium and polluting the catalyst provided by the invention of going up the 4000ppm vanadium, gasoline yield is respectively 46.36 heavy % and 41.50 heavy %, the ratio of coke and conversion ratio is respectively 0.13 and 0.12, and adopt do not pollute go up vanadium and pollute go up the 4000ppm vanadium contain the reference catalyst of the passivating agent composition of forming by lanthanum-oxides and aluminium oxide the time, gasoline yield has only 43.55 heavy % and 38.37 heavy % respectively, and the ratio of coke and conversion ratio is respectively up to 0.17 and 0.18.
(3) shown in table 5 result, under identical reaction condition, do not pollute the micro-activity of heavy oil going up vanadium and pollute the catalyst provided by the invention of going up the 4000ppm vanadium and go up vanadium and pollute the reference catalyst that contains the passivating agent composition of forming by phosphorous oxides and aluminium oxide that goes up the 4000ppm vanadium and do not improved 6.9% and 19.7% respectively than not polluting.Catalyst provided by the invention is behind 4000ppm vanadium in the pollution, its micro-activity of heavy oil has only reduced by 8.5% than the catalyst that does not pollute vanadium, and for the reference catalyst that contains the passivating agent composition of being made up of phosphorous oxides and aluminium oxide, its micro-activity of heavy oil has but reduced by 18.3%.Adopt and not pollute when going up vanadium and polluting the catalyst provided by the invention of going up the 4000ppm vanadium, gasoline yield is respectively 44.78 heavy % and 41.03 heavy %, the ratio of coke and conversion ratio is respectively 0.12 and 0.13, and adopt do not pollute go up vanadium and pollute go up the 4000ppm vanadium contain the reference catalyst of the passivating agent composition of forming by phosphorous oxides and aluminium oxide the time, gasoline yield has only 42.16 heavy % and 35.08 heavy % respectively, and the ratio of coke and conversion ratio is respectively up to 0.15 and 0.16.
(4) shown in table 6 result, under identical reaction condition, not polluting the micro-activity of heavy oil of going up vanadium and polluting the catalyst provided by the invention of going up the 5000ppm vanadium goes up vanadium and pollutes the US5 that contains that goes up the 5000ppm vanadium than not polluting, the reference catalyst of 001,096 disclosed passivating agent composition has improved 2% and 10.8% respectively.Catalyst provided by the invention is behind 5000ppm vanadium in the pollution, its micro-activity of heavy oil has only reduced by 15.2% than the catalyst that does not pollute vanadium, and for containing US5,001, the reference catalyst of 096 disclosed passivating agent composition, its micro-activity of heavy oil has but reduced by 21.9%.Adopt and not pollute when going up vanadium and polluting the catalyst provided by the invention of going up the 5000ppm vanadium, gasoline yield is respectively 43.60 heavy % and 38.92 heavy %, the ratio of coke and conversion ratio is respectively 0.12 and 0.12, go up vanadium and pollute the US5 that contains that goes up the 5000ppm vanadium and adopt not pollute, 001, during the reference catalyst of 096 disclosed passivating agent composition, gasoline yield has only 42.63 heavy % and 32.89 heavy % respectively, and the ratio of coke and conversion ratio is respectively up to 0.15 and 0.18.
Claims (40)
1. the hydrocarbon cracking catalyzer of a phosphorous and rare earth, this catalyst is made up of a kind of Cracking catalyst component and a kind of passivating agent composition that contains zeolite, it is characterized in that described passivating agent composition contains phosphorus compound, rare earth compound and aluminium compound, described passivating agent composition
31In the P MAS NMR spectrogram, be 0 in chemical shift～-there is a spike at the 10ppm place.
2. catalyst according to claim 1 is characterized in that, the position of described spike is-2～-7ppm.
3. catalyst according to claim 1 is characterized in that, described passivating agent composition
31Also exist in the PMAS NMR spectrogram chemical shift be-24～-peak of 31ppm.
4. catalyst according to claim 1 is characterized in that, the content of described passivating agent composition in catalyst is 1～50 heavy %.
5. catalyst according to claim 4 is characterized in that, the content of described passivating agent composition in catalyst is 5～30 heavy %.
6. catalyst according to claim 1 is characterized in that, in oxide, and phosphorous 0.1～80 heavy % in the described passivating agent composition, rare earth 0.1～80 heavy %, aluminium 10～99.8 heavy %.
7. catalyst according to claim 6 is characterized in that, phosphorous 5～40 heavy % in the described passivating agent composition, rare earth 5～50 heavy %, aluminium 35～85 heavy %.
8. according to claim 6 or 7 described catalyst, it is characterized in that the phosphorus in the described passivating agent composition and the mol ratio of rare earth are 0.1～100.
9. catalyst according to claim 8 is characterized in that, the phosphorus in the described passivating agent composition and the mol ratio of rare earth are 0.5～50.
10. catalyst according to claim 1 is characterized in that described rare earth is selected from one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium.
11. catalyst according to claim 10 is characterized in that, described rare earth is selected from lanthanum, cerium or mainly is the mixed rare-earth elements that contains lanthanum and/or cerium.
12. catalyst according to claim 1 is characterized in that, the described Cracking catalyst component that contains zeolite contains zeolite and matrix.
13. catalyst according to claim 12 is characterized in that, described zeolite is selected from one or more in faujasite, Beta zeolite, modenite, the ZSM-5 zeolite.
14. catalyst according to claim 13 is characterized in that, described zeolite is selected from one or more in X type zeolite, y-type zeolite, overstable gamma zeolite, sealumination modified Y zeolite, Beta zeolite, modenite, the ZSM-5 zeolite.
15. catalyst according to claim 14 is characterized in that, described zeolite is selected from one or more in the y-type zeolite, overstable gamma zeolite, sealumination modified Y zeolite, Beta zeolite, ZSM-5 zeolite of Hydrogen, ammonium type and/or rare-earth type.
16. catalyst according to claim 12 is characterized in that, is benchmark with final catalyst, the content of described zeolite is 5～80 heavy %.
17. catalyst according to claim 16 is characterized in that, is benchmark with final catalyst, the content of described zeolite is 10～50 heavy %.
18. catalyst according to claim 12 is characterized in that, described matrix is selected from one or more in silica, aluminium oxide, amorphous aluminosilicate, the various clay.
19. catalyst according to claim 18 is characterized in that, described matrix is selected from one or more in silica, aluminium oxide, amorphous aluminosilicate, kaolin, the halloysite.
20. catalyst according to claim 12 is characterized in that, the content of described matrix is 10～95 heavy %.
21. catalyst according to claim 20 is characterized in that, the content of described matrix is 20～80 heavy %.
22. claim 1 Preparation of catalysts method, this method comprises that the component that composition is contained the Cracking catalyst of zeolite mixes with a kind of passivating agent composition, it is characterized in that the preparation method of described passivating agent composition is by following (1) and/or (2) described method preparation; (1) be included in room temperature to 100 ℃, with a kind of solution concentration that contains rare-earth compound, aluminium compound and phosphorus compound to having at least solid to separate out, room temperature to 250 ℃ drying and 300～800 ℃ of products that roasting obtains; The addition of described rare-earth compound, aluminium compound and phosphorus compound makes in the passivating agent composition that obtains, and in oxide, contains the phosphorus of 0.1～80 heavy %, the rare earth of 0.1～80 heavy % and the aluminium of 10～99.8 heavy %; (2) comprise with containing the solution of rare-earth compound and the solution impregnation aluminium oxide of phosphorus-containing compound, room temperature to 250 ℃ drying and 300～800 ℃ of products that roasting obtains; The consumption of described rare-earth compound, phosphorus compound and aluminium oxide makes in the passivating agent composition that obtains, and in oxide, contains the phosphorus of 0.1～80 heavy %, the rare earth of 0.1～40 heavy % and the aluminium of 10～99.8 heavy %.
23. method according to claim 22 is characterized in that, described composition contains the method that the mixing of the component of Cracking catalyst of zeolite and passivating agent composition adopts making beating to mix.
24. method according to claim 22 is characterized in that, described rare-earth compound is selected from one or more in water-soluble rare-earth compound.
25. method according to claim 24 is characterized in that, described rare-earth compound is selected from one or more in nitrate of rare earth element, the halide.
26. method according to claim 25 is characterized in that, described rare-earth compound is selected from lanthanum nitrate, lanthanum chloride, cerous nitrate, cerium chloride and mainly contains in the chloride of mixed rare-earth elements of lanthanum chloride and cerium chloride one or more.
27. method according to claim 22 is characterized in that, described aluminium compound is selected from one or more in the soluble aluminum compound that contains trivalent aluminium ion.
28. method according to claim 27 is characterized in that, described aluminium compound is selected from one or more in aluminum nitrate, aluminium chloride, the aluminum sulfate.
29. method according to claim 28 is characterized in that, described aluminium compound is selected from aluminum nitrate or aluminium chloride.
30. method according to claim 22 is characterized in that, described phosphorus compound is selected from one or more in the titanium pigment compound.
31. method according to claim 30 is characterized in that, described phosphorus compound is selected from one or more in phosphoric acid, the soluble phosphate.
32. method according to claim 31 is characterized in that, described soluble phosphate is selected from alkali-metal phosphate, acid phosphate, subphosphate, one or more in ammonium phosphate, ammonium dihydrogen phosphate (ADP), the diammonium hydrogen phosphate.
33. method according to claim 31 is characterized in that, described phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), the diammonium hydrogen phosphate.
34. method according to claim 22 is characterized in that, the described temperature that concentrates the solution that contains rare-earth compound, aluminium compound and phosphorus compound is 50～100 ℃.
35. method according to claim 22 is characterized in that, the temperature of described drying is a room temperature to 250 ℃, and the temperature of roasting is 300～800 ℃.
36. method according to claim 35 is characterized in that, the temperature of described drying is 80～200 ℃, and the temperature of roasting is 500～750 ℃.
37. method according to claim 22 is characterized in that, described aluminium oxide is selected from one or more in gama-alumina, η-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, κ-aluminium oxide, ρ-aluminium oxide, the Alpha-alumina.
38., it is characterized in that described aluminium oxide is selected from one or more in gama-alumina, η-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, κ-aluminium oxide, the ρ-aluminium oxide according to the described method of claim 37.
39., it is characterized in that described aluminium oxide is selected from gama-alumina and/or η-aluminium oxide according to the described method of claim 38.
40. method according to claim 22 is characterized in that the consumption of phosphorus compound, rare earth compound and aluminium compound or aluminium oxide makes in the passivating agent composition that obtains, in oxide, and phosphorous 5～40 heavy %, rare earth 5～50 heavy % and 35～85 heavy %.
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| CN 99107787 CN1112246C (en) | 1999-05-28 | 1999-05-28 | Catalyst for cracking hydrocarbon containing phosphorus and rareearth and preparation process thereof |
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| CN 99107787 CN1112246C (en) | 1999-05-28 | 1999-05-28 | Catalyst for cracking hydrocarbon containing phosphorus and rareearth and preparation process thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312039C (en) * | 2004-07-29 | 2007-04-25 | 中国石油化工股份有限公司 | Zeolite containing phosphor and preparation method |
| CN100389170C (en) * | 2004-09-15 | 2008-05-21 | 中国石油化工股份有限公司 | Catalytic cracking aid and its preparing method |
| CN100478420C (en) * | 2004-09-15 | 2009-04-15 | 中国石油化工股份有限公司 | Catalytic cracking aid and its preparing method |
| CN100478421C (en) * | 2004-08-31 | 2009-04-15 | 中国石油化工股份有限公司 | Catalytic cracking adjuvant and its preparing method |
| CN100486700C (en) * | 2004-07-29 | 2009-05-13 | 中国石油化工股份有限公司 | Hydrogenant cracking catalyst containing zeolite, and preparation method |
| CN102925241A (en) * | 2012-11-27 | 2013-02-13 | 中国环境科学研究院 | Method and device for preparing household garbage derived fuel |
-
1999
- 1999-05-28 CN CN 99107787 patent/CN1112246C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312039C (en) * | 2004-07-29 | 2007-04-25 | 中国石油化工股份有限公司 | Zeolite containing phosphor and preparation method |
| CN100486700C (en) * | 2004-07-29 | 2009-05-13 | 中国石油化工股份有限公司 | Hydrogenant cracking catalyst containing zeolite, and preparation method |
| CN100478421C (en) * | 2004-08-31 | 2009-04-15 | 中国石油化工股份有限公司 | Catalytic cracking adjuvant and its preparing method |
| CN100389170C (en) * | 2004-09-15 | 2008-05-21 | 中国石油化工股份有限公司 | Catalytic cracking aid and its preparing method |
| CN100478420C (en) * | 2004-09-15 | 2009-04-15 | 中国石油化工股份有限公司 | Catalytic cracking aid and its preparing method |
| CN102925241A (en) * | 2012-11-27 | 2013-02-13 | 中国环境科学研究院 | Method and device for preparing household garbage derived fuel |
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|---|---|
| CN1112246C (en) | 2003-06-25 |
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