CN100338186C - Petroleum hydrocarbon cracking catalyst - Google Patents
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- CN100338186C CN100338186C CNB2005100681687A CN200510068168A CN100338186C CN 100338186 C CN100338186 C CN 100338186C CN B2005100681687 A CNB2005100681687 A CN B2005100681687A CN 200510068168 A CN200510068168 A CN 200510068168A CN 100338186 C CN100338186 C CN 100338186C
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Abstract
The present invention relates to a petroleum hydrocarbon cracking catalyst which comprises 10 to 50 wt% of Y-type zeolite, 10 to 40 wt% of phosphorus and rare earth modified natural zeolite, 10 to 40 wt% of clay and 10 to 30 wt% of inorganic oxide, wherein the natural zeolite is natural zeolite in which mordenite is used as a main crystal phase accompanied with a clinoptilolite crystal phase; the phosphorus content in the modified natural zeolite, which is measured by P2O5, is from 0.5 to 15 mass%, and the rare earth content measured by RE2O3 is from 0.5 to 10 wt%. The catalyst for a heavy oil cracking reaction has the advantages of high heavy oil cracking capability, high content of liquefied gas in products, and low olefine content and high isoalkane content in a produced gasoline fraction.
Description
Technical field
The present invention is a kind of catalyst for cracking petroleum hydrocarbons, specifically, be a kind of be that raw material is produced the catalyzer that is rich in isoparaffin gasoline by cracking reaction with the mink cell focus.
Background technology
Along with the increasingly stringent of environmental protection requirement, gasoline develops into reformulated gasoline from white gasoline.In the standard of reformulated gasoline, require the vapour pressure and the benzene content of restriction gasoline on the one hand, on the other hand, also will progressively limit the content of olefin component.As requiring the content of gasoline component alkene below 20 volume % in the world fuel oil standard II class gasoline standard.China on July 1st, 2002 requires that the content of alkene is lower than 35 volume % in the gasoline component in the gasoline standard that carry out in Beijing, Shanghai, three big cities, Guangzhou.China's gasoline quality standard from now on also will further limit the content of alkene in the gasoline.
Catalytic cracking is to produce one of major technique of motor spirit component, and its gasoline yield can reach more than the 50 quality %, and catalytically cracked gasoline is the main blend component of motor spirit.In China, catalytically cracked gasoline accounts for more than 80% of motor spirit blend component.Since the 1980s, the unleaded catalytic cracking technology that forces of motor spirit develops to the direction of producing stop bracket gasoline.For this reason, wide variation have taken place in the processing condition of catalytic cracking and catalyst type.At process aspect, mainly be to improve temperature of reaction, shorten the reaction times, improve the reaction severity, suppressed cracking reaction, improve the contact efficiency of riser tube bottom oil gas and catalyzer; Aspect catalyzer, developed super steady Y (USY) type zeolite in conjunction with the catalyzer of inert base or active matrix and the composite catalyst that contains dissimilar zeolites.
Though catalytic cracking technology has been obtained above-mentioned progress, satisfied the requirement of unleaded gasoline, improved the octane value of gasoline, but no matter be by changing processing condition, also being to use the new zeolite catalyzer, all is the octane value that increases gasoline with the olefin(e) centent in the raising gasoline component.This and reformulated gasoline differ greatly to the requirement of olefin(e) centent.
CN1179461A discloses a kind of cracking catalyst that contains natural zeolite.This catalyzer is the natural zeolite that contains mordenite and clinoptilolite by the ZSM-5 zeolite of the y-type zeolite of 5～45 heavy %, 0～15 heavy %, 40～70 heavy %, and the inorganic oxide binder of surplus is formed.Natural zeolite in this catalyzer does not carry out modification, just it is used as a kind of catalyst substrates.Thereby the hydrogen transfer reaction activity of this catalyzer is lower, can reduce coke yield, but in the crackate low-carbon alkene especially the content of low-carbon (LC) isomeric olefine is higher.
Because octane value height, the susceptibility of isoparaffin are low, are ideal gasoline blend components.Therefore, reducing the more satisfactory approach of catalytic cracking gasoline olefine content is the novel cracking catalytic that can increase the gasoline isoparaffin content by using, in catalytic cracking process, make olefin component through isomerization reaction and hydrogen transfer reactions as much as possible, change into the higher isoparaffin component of octane value.
CN1354223A discloses the catalytic cracking catalyst that isoparaffin gasoline is rich in a kind of production.This catalyzer is by being that the clay of 0～70 heavy % of benchmark, the inorganic oxide of 5～90 heavy % and the zeolite of 1～50 heavy % are formed with the catalyst weight, and described zeolite is the mixture of the high-silicon Y-Zeolite of two kinds of different content of rare earth, wherein with RE
2O
3The content of rare earth of meter is that the silica alumina ratio of 8～20 heavy % is that 5～15 high-silicon Y-Zeolite content is 25～75 heavy %, with RE
2O
3The content of rare earth of meter is that the silica alumina ratio of 2～7 heavy % is that the content of 16～50 high-silicon Y-Zeolite is 25～75 heavy %.This catalyzer gained crackate is based on gasoline, and liquefied gas output is not high.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst for cracking petroleum hydrocarbons, this catalyzer has heavy oil macromole cracking ability preferably, yield of light oil height in the crackate, and olefin(e) centent is low in the gasoline component, the isoparaffin content height.
Catalyst for cracking petroleum hydrocarbons provided by the invention, comprise the y-type zeolite of 10～50 quality %, phosphorus and rare earth modified natural zeolite, the clay of 10～40 quality % and the inorganic oxide of 10～30 quality % of 10～40 quality %, described natural zeolite is for the mordenite being principal crystalline phase and with the natural zeolite of clinoptilolite crystalline phase, in the modified natural zeolite with P
2O
5The phosphorus content of meter is 0.5～15 quality %, with RE
2O
3The content of rare earth of meter is 0.5～10 quality %.
The present invention adds rare earth in the natural zeolite that with the mordenite is principal crystalline phase and phosphorus carries out modification, to improve the pore structure of natural zeolite, improves the lightweight oil productive rate, and reduces the olefin(e) centent of gasoline.Cracking catalyst with modified natural zeolite preparation of the present invention not only has heavy oil cracking ability preferably, and lightweight oil productive rate height in the crackate, and olefin(e) centent is low in the gasoline product that obtains, and isoparaffin content obviously increases.
Embodiment
The present invention's preparation earlier adds the active ingredient y-type zeolite again with phosphorus and rare earth modified natural zeolite in this modified zeolite, clay and inorganic oxide are made cracking catalyst.Owing to the existence of modifying element, its pore passage structure changes in the described modified natural zeolite, and the aperture dwindles, when therefore catalyzer prepared therefrom was used for cracking reaction, the light component yield increased, and particularly liquefied gas output increases, olefin(e) centent reduces in the gained gasoline, and isoparaffin content increases.
The MFI type zeolite that also further contains 0.3～1.5 quality % in the catalyzer of the present invention, the described preferred ZSM-5 of MFI type zeolite or contain the ZSM-5 of modifying element, as phosphorated ZSM-5, contain the ZSM-5 of rare earth or the ZSM-5 of phosphorous and rare earth, the preparation method of described modified ZSM-5 sees CN1020269C, CN1059133C, CN1027632C, CN1049406C.The silicon oxide of ZSM-5 and the mol ratio of aluminum oxide are 20～500, preferred 20～120.
The preferred hyperastable Y-type RE of y-type zeolite in the described catalyzer (REUSY), Rare Earth Y (REY) or both mixtures.If when hyperastable Y-type RE and Rare Earth Y mixture, hyperastable Y-type RE content wherein is 80～85 quality %, and Rare Earth Y content is 15～20 quality %.
In the described modified natural zeolite with P
2O
5Preferred 2.0～6.0 quality % of phosphorus content of meter are with RE
2O
3Preferred 2.0～5.0 quality % of content of rare earth of meter.The X-ray diffraction of described natural zeolite (XRD) spectrogram is referring to CN1179461A.
The preferred kaolin of described clay, sepiolite, attapulgite, montmorillonite or tired stone, the more preferably kaolin of taking off.Preferred 20～40 quality % of the content of catalyzer medium clay soil.
Described inorganic oxide is a binding agent, preferred aluminum oxide, silicon-dioxide or the mixture of the two, more preferably aluminum oxide.
The preferred mishmetal of the rare earth that contains in each component in the described catalyzer.The kind of mishmetal is not limit, and the major metal component that it contains is a lanthanum, is selected from the metal constituent element of lanthanide series metal simultaneously with other one to multiple kind.
Modified natural prepare zeolite method of the present invention is: with natural zeolite or to make solid content through pretreated natural zeolite be 1～40 quality %, the slurries of preferred 10～30 quality %, in slurries, add P contained compound and fully react, add rare earth compound solution again and continue reaction for some time.The temperature of reacting behind described adding P contained compound and the rare earth compound is 35～95 ℃, preferred 50～70 ℃, and 0.5～10 hour reaction times, preferred 1～4 hour.With gained mixture drying, roasting, make the natural zeolite of modification then.Maturing temperature in the above-mentioned preparation process is 300～800 ℃, and preferred 400～650 ℃, suitable roasting time is 0.5～10 hour, preferred 1～2 hour.
Described natural zeolite is obtained after step process such as pulverizing, pulp and washing by the natural mineral that is rich in mordenite and clinoptilolite.The natural zeolite that obtains can be directly used in preparation modified natural zeolite, preferably carries out modification again through pre-treatment.
The pretreatment process of natural zeolite is: with decationized Y sieve water described natural zeolite making beating being dispersed into solid content is 1～40 quality %, the slurries of preferred 10～30 quality %, stir and add mineral acid down, 35～95 ℃, preferred 50～70 ℃ of reaction for some time, the suitable reaction times is 0.5～10 hour, preferred 1～4 hour.Filter then, wash, make the slurries of accompanying impurities such as removing most of Na, K, Mg, Ca.Adding P contained compound and rare earth compound can make the modified natural zeolite in these slurries.
Mineral acid described in the aforesaid method is selected from hydrochloric acid, nitric acid or sulfuric acid, but does not comprise phosphoric acid.
The used P contained compound of preparation modified natural zeolite is selected from one or more in phosphoric acid, phosphorous acid, phosphoric anhydride, Secondary ammonium phosphate, primary ammonium phosphate, ammonium phosphate, ammonium phosphite, dihydrogen phosphite ammonium, the aluminum phosphate, or the mixture of phosphoric acid and ammoniacal liquor, preferably phosphoric acid.
Catalyzer of the present invention is applicable to that heavy oil cracking produces the various technological processs of light component and distillate.The temperature of reaction that application the present invention carries out heavy oil cracking is 460～600 ℃, and agent-oil ratio is 2～12: 1 during reaction.
Further specify the present invention below by example, but the present invention is not limited to this.
Natural zeolite described in the example is the natural mineral that is rich in mordenite and association clinoptilolite that originates from Jimusar County, Xinjiang natural zeolite ore, the product that after pulverizing, pulp, washing, obtains, its chemical constitution sees Table 1, and the chemical constitution of table 1 mesolite is by x-ray fluorescence spectrometry.
Example 1
Prepare modified natural zeolite of the present invention.
(1) natural zeolite pre-treatment: in a stirring tank, add 150 kilograms of decationized Y sieve water and 10 kilograms of (butt) natural zeolites, dispersed with stirring 30 minutes, the technical hydrochloric acid of 2.2 liter of 10.2 mol of adding is warming up to 65 ℃ of reactions 1.5 hours.The gained mixture is filtered, and with the decationized Y sieve water washing of 50 times of filter cake dry basises three times, obtaining solid content is the natural zeolite slurries of 25 quality %.
(2) prepare the modified natural zeolite: get 24 kilograms of natural zeolite slurries, stirring the 450 gram concentration of adding down is the phosphoric acid of 85 quality %, and 65 ℃ were reacted 45 minutes.The chlorination mishmetal that to add 0.6 liter of concentration again be 200 grams per liters (technical grade, Shanghai allosaurus rare earth company limited produces) solution continues reaction 45 minutes.With 120 ℃ of dryings of gained mixture 24 hours, 450 ℃ of roastings 1 hour made modified natural zeolite a, and its chemical constitution sees Table 1.
Example 2
Method by example 1 prepares modified natural zeolite b, and different is (2) step to add 1.2 liters of chlorination mixed rare earth solutions that concentration is 200 grams per liters, and the chemical constitution of the modified natural zeolite b that makes sees Table 1.
Example 3
Prepare cracking catalyst of the present invention.
Get 1.6 kilograms of (butt) modified natural zeolite a, 2.4 (kaolin company in Suzhou produces kilogram (butt) kaolin, solid content 78 quality %), add 15 kilograms of decationized Y sieve water making beating 90 minutes, add 1.2 kilograms of (butt) pseudo-boehmites again and continue making beating 45 minutes.Add concentration and be 0.22 liter of the hydrochloric acid of 36 quality %, after stirring, 60 ℃ aging 1 hour.(the Qilu Petrochemical catalyst plant is produced will to contain 2.4 kilograms of (butt) hyperastable Y-type REs (REUSY) zeolite, commodity are called DM-4) solid content be that (the Qilu Petrochemical catalyst plant is produced for the mixed serum of 30 quality % and 1.86 kg aluminium colloidal sols, solid content 21.5 quality %) join in the said mixture, after making beating mixes, spray drying forming.Getting 1 kilogram of moulding after product (butt), add 10 kilograms in decationized Y sieve water and 30 gram ammonium chlorides, is the hydrochloric acid adjusting slurry pH value to 3.0 of 2.0 quality % with concentration, stirring is warming up to 60 ℃, wash 20 minutes after-filtration, will wash the after product drying, the composition of the catalyst A that makes sees Table 2.
Example 4
Method by example 3 prepares catalyst B, and different is to add modified natural zeolite b to replace modified natural zeolite a, and the composition of catalyst B sees Table 2.
Example 5
Method by example 3 prepares catalyzer C, different is with modified natural zeolite a, kaolin and pseudo-boehmite making beating, and 60 ℃ aging after, adding the solid content that contains 2 kilograms of REUSY and 0.4 kilogram of Rare Earth Y (REY) zeolite (production of Qilu Petrochemical catalyst plant) is the mixed serum of 30 quality %, and the composition of the catalyzer C that makes sees Table 2.
Example 6
Method by example 3 prepares catalyzer D, different is with modified natural zeolite b, kaolin and pseudo-boehmite making beating, and 60 ℃ aging after, adding the solid content that contains 2 kilograms of REUSY and 0.4 kilogram of rare earth exchanged Y zeolite is the mixed serum of 30 quality %, the composition of the catalyzer D that makes sees Table 2.
Example 7
Method by example 3 prepares catalyzer E, and different is with modified natural zeolite a, kaolin and pseudo-boehmite making beating, and 60 ℃ aging after, add and contain 2 kilograms of REUSY, 0.4 kilogram of rare earth exchanged Y zeolite and 0.08 kilogram of ZSM-5 zeolite (SiO
2/ Al
2O
335) solid content is the mixed serum of 30 quality %, and the composition of the catalyzer E that makes sees Table 2.
Example 8
Method by example 3 prepares catalyzer F, and different is with modified natural zeolite b, kaolin and pseudo-boehmite making beating, and 60 ℃ aging after, add and contain 2 kilograms of REUSY, 0.4 kilogram of rare earth exchanged Y zeolite and 0.08 kilogram of ZSM-5 zeolite (SiO
2/ Al
2O
335) solid content is the mixed serum of 30 quality %, and the composition of the catalyzer F that makes sees Table 2.
Example 9
Method by example 3 prepares catalyzer G, and different is with modified natural zeolite a, kaolin and pseudo-boehmite making beating, and 60 ℃ aging after, (the Qilu Petrochemical catalyst plant is produced, SiO to add the phosphorous ZSM-5 zeolite that contains 2.4 kilograms of REUSY and 0.08 kilogram
2/ Al
2O
335) solid content is the mixed serum of 30 quality %, and the composition of the catalyzer G that makes sees Table 2.
Comparative Examples 1
Method by example 3 prepares comparative catalyst M, and different is not add the modified natural zeolite in the preparation process, but pulls an oar with 4.0 kilograms Suzhou kaolin and 1.2 kilograms pseudo-boehmite, and the composition of the catalyzer M that makes sees Table 2.
Comparative Examples 2
The preparation CN1179461A example 2 described comparative catalyst N that contain without the natural zeolite of modification.
Method by example 3 prepares comparative catalyst N, and different is replaces wherein modified natural zeolite a and kaolin with 4.0 kilograms natural zeolite, and the composition of the comparative catalyst N that makes sees Table 2.
Comparative Examples 3
Method by CN1179461A example 1 prepares comparative catalyst K, but does not contain ZSM-5 in the catalyzer.
Method by example 3 prepares comparative catalyst K, and different is to add 1.6 kilograms natural zeolite and 2.4 kilograms kaolin making beating, again by follow-up step operation, until spray drying forming.Get 1 kilogram of the product (butt) after the moulding, add 10 kilograms of making beating of decationized Y sieve water, add concentration and be 45 milliliters of phosphoric acid 37 grams of 85 quality % and ammoniacal liquor that concentration is 25 quality %, pulled an oar 30 minutes for 60 ℃, cross filtered product and add decationized Y sieve water 3000 grams, add industrial ammonium chloride 30 grams again, pulled an oar 30 minutes for 60 ℃, filter after drying, make comparative catalyst K, its composition sees Table 2.
Example 10～19
The catalytic performance of following example explanation catalyzer of the present invention.
With the preparation cracking catalyst through 800 ℃, 100% steam aging 12 hours is estimated on the fixed fluidized bed device of small-sized FCC, estimates raw materials used oil nature and sees Table 3, evaluation result sees Table 4.
As known from Table 4, catalyzer of the present invention is compared with the comparative catalyst, has higher heavy oil cracking ability, and transformation efficiency is higher, liquefied gas and C in the product
5Yield of gasoline is all higher, and olefin(e) centent is lower in the gasoline product that obtains, and isoparaffin content obviously improves, and gasoline octane rating and REUSY are that the comparative catalyst M of active ingredient compares, and obviously do not descend.
Table 1
| Zeolite | Form quality % | |||||||||
| SiO 2 | Al 2O 3 | Na 2O | CaO | MgO | K 2O | Fe 2O 3 | RE 2O 3 | P 2O 5 | Cl - | |
| Natural zeolite | 74.2 | 14.0 | 4.6 | 2.4 | 0.78 | 0.98 | 1.8 | Trace | Trace | 1.2 |
| Modified natural zeolite a | 75.0 | 14.0 | 0.6 | 1.3 | 0.6 | 0.5 | 1.3 | 2.0 | 4.2 | 0.5 |
| Modified natural zeolite b | 74.0 | 13.5 | 0.5 | 1.0 | 0.6 | 0.5 | 1.3 | 4.0 | 4.0 | 0.6 |
Table 2
| Instance number | The catalyzer numbering | Catalyzer is formed, quality % | |||||||
| REUSY | REY | Natural zeolite | Kaolin | Aluminum oxide | ZSM-5 | P 2O 5 | |||
| Numbering | Content | ||||||||
| 3 | A | 30 | - | a | 20 | 30 | 20 | - | - |
| 4 | B | 30 | - | b | 20 | 30 | 20 | - | - |
| 5 | C | 25 | 5 | a | 20 | 30 | 20 | - | - |
| 6 | D | 25 | 5 | b | 20 | 30 | 20 | - | - |
| 7 | E | 25 | 5 | a | 20 | 29 | 20 | 1.0 | - |
| 8 | F | 25 | 5 | b | 20 | 29 | 20 | 1.0 | - |
| 9 | G | 30 | - | a | 20 | 29 | 20 | Phosphorous ZSM-5 1.0 | - |
| Comparative Examples 1 | M | 30 | - | - | 50 | 20 | - | - | |
| Comparative Examples 2 | N | 30 | - | Unmodified | 50 | - | 20 | - | - |
| Comparative Examples 3 | K | 30 | - | Unmodified | 20 | 28 | 20 | - | 2.0 |
Table 3
| Project | Index |
| Density (20 ℃), g/cm 3Viscosity (100 ℃), mm 2/ s zero pour, ℃ carbon residue, m% | 0.8906 24.84 43 4.3 |
| Elementary composition, m% C/H S/N | 86.54/13.03 0.13/0.3 |
| Four components, m% stable hydrocarbon aromatic hydrocarbons gum asphalt | 51.2 29.7 18.3 0.8 |
| Boiling range, ℃ fore-running～5% 10%～30% 50%～70% 90%～95% | 282～351 370～482 553～- - |
Table 3
| Instance number | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | Example 15 | Example 16 | Example 17 | Example 18 | Example 19 |
| The catalyzer numbering | M | N | K | A | B | C | D | E | F | G |
| Little index alive (800 ℃ 12 hours) | 64 | 64 | 62 | 67 | 67 | 68 | 68 | 68 | 68 | 67 |
| The reaction conditions temperature of reaction, ℃ weight space velocity, hr -1The agent-oil ratio water injection rate, m% | 500 10 6 10 | 500 10 6 10 | 500 10 6 10 | 500 10 6 10 | 500 10 6 10 | 500 10 6 10 | 500 10 6 10 | 500 10 6 10 | 500 10 6 10 | 500 10 6 10 |
| Material balance, m% dry gas liquefied gas C 5Gasoline, diesel heavy oil coke | 2.26 19.38 50.99 11.28 6.46 9.64 | 2.32 19.95 51.82 10.42 5.76 9.73 | 2.01 19.12 50.28 12.58 6.89 9.12 | 2.87 20.59 51.88 9.76 4.33 10.47 | 2.66 20.60 51.46 10.24 4.73 10.31 | 2.33 20.23 54.20 9.58 4.68 8.98 | 2.84 20.58 54.11 8.50 4.13 9.85 | 3.02 22.66 52.09 8.10 3.93 10.21 | 2.65 23.04 49.93 9.56 4.51 10.31 | 2.62 23.08 51.04 9.24 4.16 9.87 |
| Transformation efficiency, m% | 82.27 | 83.82 | 80.53 | 85.81 | 85.03 | 85.74 | 87.37 | 87.98 | 85.93 | 86.60 |
| Gasoline+diesel oil, m% | 62.27 | 62.24 | 62.86 | 61.64 | 61.77 | 63.78 | 62.61 | 60.19 | 59.49 | 60.28 |
| Gasoline is formed olefin isomerization alkane N-alkanes naphthenic hydrocarbon aromatic hydrocarbons | 24.64 33.85 5.74 7.43 28.35 | 26.74 35.53 5.67 7.24 24.83 | 27.89 34.77 5.04 7.68 24.62 | 19.56 43.03 6.49 6.32 24.60 | 18.06 43.81 6.42 6.31 26.42 | 15.99 45.23 5.68 6.56 26.52 | 14.45 45.82 6.49 6.25 26.96 | 16.03 46.97 6.31 6.47 24.22 | 15.82 43.59 5.61 6.62 28.34 | 20.58 42.49 5.86 6.87 24.21 |
| Gasoline RON* | 87.5 | 88.1 | 88.6 | 87.3 | 87.6 | 87.2 | 87.7 | 87.2 | 87.9 | 87.5 |
RON: research octane number (RON)
Claims (9)
1, a kind of catalyst for cracking petroleum hydrocarbons, comprise the y-type zeolite of 10～50 quality %, phosphorus and rare earth modified natural zeolite, the clay of 10～40 quality % and the inorganic oxide of 10～30 quality % of 10～40 quality %, described natural zeolite is for the mordenite being principal crystalline phase and with the natural zeolite of clinoptilolite crystalline phase, in the modified natural zeolite with P
2O
5The phosphorus content of meter is 0.5～15 quality %, with RE
2O
3The content of rare earth of meter is 0.5～10 quality %.
2,, it is characterized in that also further containing in the described catalyzer MFI type zeolite of 0.3～1.5 quality % according to the described catalyzer of claim 1.
3,, it is characterized in that described MFI type zeolite is selected from ZSM-5, phosphorous ZSM-5, contains the ZSM-5 of rare earth ZSM-5 or phosphorous and rare earth according to the described catalyzer of claim 2.
4,, it is characterized in that described y-type zeolite is selected from hyperastable Y-type RE, Rare Earth Y or both mixtures according to the described catalyzer of claim 1.
5,, it is characterized in that described y-type zeolite is made up of the hyperastable Y-type RE of 80～85 quality % and the Rare Earth Y of 15～20 quality % according to the described catalyzer of claim 4.
6,, it is characterized in that in the described modified natural zeolite with P according to the described catalyzer of claim 1
2O
5The phosphorus content of meter is 2.0～6.0 quality %, with RE
2O
3The content of rare earth of meter is 2.0～5.0 quality %.
7, according to the described catalyzer of claim 1, it is characterized in that described clay is selected from kaolin, sepiolite, attapulgite, montmorillonite or tiredly takes off stone, clay content is 20～40 quality %.
8,, it is characterized in that described inorganic oxide is aluminum oxide, silicon-dioxide or the mixture of the two according to the described catalyzer of claim 1.
9,, it is characterized in that described rare earth is a mishmetal according to the described catalyzer of claim 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5191131A (en) * | 1988-12-05 | 1993-03-02 | Research Association For Utilization Of Light Oil | Process for preparation of lower aliphatic hydrocarbons |
| CN1055302C (en) * | 1996-10-11 | 2000-08-09 | 中国石油化工总公司 | Cracking catalyst containing natural zeolite |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5191131A (en) * | 1988-12-05 | 1993-03-02 | Research Association For Utilization Of Light Oil | Process for preparation of lower aliphatic hydrocarbons |
| CN1055302C (en) * | 1996-10-11 | 2000-08-09 | 中国石油化工总公司 | Cracking catalyst containing natural zeolite |
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