CN1124892C - Catalytic cracking catalyst for producing gaosline richly-containing paraffinic hydrocarbon, propylene and isobutane - Google Patents
Catalytic cracking catalyst for producing gaosline richly-containing paraffinic hydrocarbon, propylene and isobutane Download PDFInfo
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- CN1124892C CN1124892C CN 00132748 CN00132748A CN1124892C CN 1124892 C CN1124892 C CN 1124892C CN 00132748 CN00132748 CN 00132748 CN 00132748 A CN00132748 A CN 00132748A CN 1124892 C CN1124892 C CN 1124892C
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Abstract
The present invention relates to a catalytic cracking catalyst for producing isoalkane-enriched gasoline, propene and isobutane, which is prepared from 0 to 70 wt% of clay, 5 to 90 wt% of inorganic oxide and 1 to 50 wt% of zeolite by using the catalyst weight as the reference, wherein the zeolite is a mixture of 20 to 75 wt% of high-silicon Y zeolite (1), 20 to 75 wt% of high-silicon Y zeolite (2) and 1 to 50 wt% of beta zeolite or mordenite or ZRP zeolite (3) by using the zeolite weight as the reference; the silica alumina ratio of the high-silicon Y zeolite (1) is from 5 to 15, and the rare earth content measured by RE2O3 is from 8 to 20 wt%; the silica alumina ratio of the high-silicon Y zeolite (2) is from 16 to 50, and the rare earth content measured by RE2O3 is from 2 to 7 wt%. The content of isoalkane in the gasoline can be improved by using the catalyst, and simultaneously the yield of propene and the yield of isobutane are increased.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst, more particularly, is a kind of catalyzer that isoparaffin gasoline, propylene and Trimethylmethane are rich in petroleum hydrocarbon cracking production that is used for.
Background technology
The y-type zeolite that uses the earliest the beginning of the sixties is through the REY of rare earth exchanged zeolite.REY zeolite silica alumina ratio is less than 5, and content of rare earth is with RE
2O
3Meter is not less than 17 heavy % (it is heavy to account for zeolite), acid site density height, and the hydrogen transference performance is strong, and alkene and naphthene content are low in the gasoline, cause gasoline octane rating to descend, and have to the additive of tetraethyllead as boosting of octane rating.However, y-type zeolite is the main active component of heavy petroleum hydrocarbon fluid catalytic cracking (FCC) catalyst system therefor always.
U.S.'s cancellation leaded up gasoline in 1975 has occurred replacing the cracking catalyst of REY zeolite as active component with super steady Y (USY) zeolite.USY is a kind of high-silicon Y-Zeolite that the y-type zeolite framework dealumination is made by the hydrothermal treatment consists method, and the silica alumina ratio of this zeolite generally between 5～1O, does not contain or contain a small amount of rare earth.Because the framework si-al ratio of USY improves, acid site density reduces, its hydrogen transference performance weakens.Thereby the olefin(e) centent of gasoline increases, octane value improves.As USP4,242,237 disclose a kind of cracking catalyst that is used to produce stop bracket gasoline, and its active ingredient comprises that the heavy % in a kind of content of rare earth＜1.15 is (with RE
2O
3Meter, it is heavy to account for zeolite) USY zeolite and the another kind of pore zeolite that comprises erionite, mordenite, A zeolite, chabazite and offretite.USP4,259,212 disclose a kind of cracking catalyst that contains the USY zeolite, and the heavy % in the content of rare earth of its USY zeolite＜1.15 is (with RE
2O
3Meter, it is heavy to account for zeolite), lattice constant＜24.41 .The used USY zeolite of above-mentioned two pieces of patents all is to contain a spot of rare earth.
The ZSM-5 class was selected the type zeolite and was begun to be applied to the FCC catalyzer beginning of the eighties, in order to improve the octane value of gasoline.USP4 discloses in 309,280, can directly add in the FCC apparatus accounting for the HZSM-5 zeolite that catalyzer weighs 0.01～1 heavy %.USP3,758,083 disclosed the two ratio be 1: 30～3: 1, with ZSM-5 zeolite and large pore zeolite (as the X type, the Y type) be the catalyzer of active ingredient, be intended to improve the octane value of product gasoline, make C simultaneously
3 =+ C
4 =Gain in yield.The effect of ZSM-5 in FCC is actually optionally that octane value in the gasoline fraction is low straight chain hydrocarbon and is cracked into low-carbon alkene, and with part low-carbon alkene aromizing, the octane value of gasoline is improved.Therefore, the application of ZSM-5 can cause the increase of alkene in the gasoline, aromaticity content inevitably.
It is strict day by day to begin environmental requirement the nineties, and the U.S. has proposed the reformulated gasoline scheme, and to alkene in the gasoline and aromatic hydrocarbons, especially the content of benzene limits, and requires in the gasoline a certain amount of oxygenatedchemicals to be arranged.Methyl tertiary butyl ether (MTBE) and tert pentyl methyl ether (TAME) are considered to meet the high-octane rating interpolation component of above-mentioned requirements.Iso-butylene and isopentene are respectively the raw materials of producing MTBE and TAME.Therefore, the oil refining worker has carried out the research work of high yield of isobutene and isopentene.The catalytic cracking catalyst of volume increase iso-butylene and isopentene when being disclosed in production gasoline as ZL94114963.3, ZL94107496.USP5,702,589 is that FCC process and etherification procedure are combined, the etherificate distillation zone is introduced in the logistics that contains n-butene and positive amylene and iso-butylene and isopentene from the FCC reaction zone, then unconverted n-butene and positive amylene are separated from the etherificate distillation zone, be mixed into reaction zone with the FCC raw material, at 0～6atm, contact greater than 500 ZSM-5 with silica alumina ratio under 425～650 ℃ of temperature of reaction, part n-butene and positive amylene change into iso-butylene and isopentene.Though ether compound has advantage, because it can not biological degradation, in case leak can polluted underground water for basin, therefore, its consumption reduces, may soon will forbidding.
As everyone knows, isoparaffin, especially C
4～C
6The low-carbon (LC) isoparaffin, octane value height, susceptibility are low, have ideal volatility and clean burning, are the desirable blend components of gasoline.Isoparaffin can be by low-carbon alkene and alkane alkylation or the isomerization by generate longer-chain hydrocarbons make the general dual-function catalyst that adopts the acidic matrix carried noble metal in these reactions.Existing a lot of report about this respect research work.
FCC is the important process of producing gasoline, though in the FCC process isomerization reaction is arranged, its proportion is less, is not the principal reaction type.If can promote the generation of the isomerization reaction in the FCC process, then help to improve the content of isoparaffin in the FCC gasoline products, can provide new technical support for the production of the reformulated gasoline of compliance with environmental protection requirements.
The isomerization of straight-chain paraffin in catalytic cracking process is actually the skeletal isomerization process that the first cracking of macromolecule hydrocarbon generates alkene.The straight-chain paraffin skeletal isomerization needs stronger acid sites.Though participating in the molecule of isomerization reaction is straight chain, the skeletal isomerization of straight-chain molecule will be undertaken by cyclopropyl carbonium ion intermediate, thereby occupies certain space, so large pore zeolite helps the side chain isomerization reaction of straight chain hydrocarbon.Skeletal isomerization is unimolecular reaction basically, and the zeolite of high silica alumina ratio helps the generation of side chain hydro carbons.Because the reactivity worth maximum of isomery hydro carbons is so the low zeolite of silica alumina ratio can make the isomery hydro carbons cracking again of generation.But silica alumina ratio is too high, not only the acid site of zeolite very little, and strong acid center also begins to lose, and causes the total conversion rate of reaction process to descend.RE
2O
3Also rather important for zeolite, the existence of zeolite middle-weight rare earths element has not only increased the strong acid center of zeolite, has also increased the hydrogen transfer reactions of process, makes that the isomeric olefine of generation is very fast to be saturated to isoparaffin through hydrogen transference.
High-silicon Y-Zeolite is very many as the patent documentation of catalyst activity constituent element.As USP4,880,787 have disclosed a kind of silicon-aluminum containing than being that 5～100 USY and restricted index are 1～12 zeolite catalyst, contain aluminium and rare earth element in its carrier, and content of rare earth is 0.01～10 heavy % of catalyzer.This kind catalyzer is mainly used in coke and the gas yield that increases FCC gasoline and distillate productive rate and reduce the FCC process.When the silica alumina ratio of USY was very high, activity of such catalysts was low, needed reaction severity height, and temperature of reaction is up to 649 ℃, and the liquid air speed is little of 0.1h
-1Even it is lower.
USP5,055,437 has disclosed a kind of FCC catalyzer, and this catalyzer is the mixture of following three kinds of components: A) sealumination modified Y zeolite is an active ingredient, contains the high alumina carried catalyst of rare earth, and its effect is that the cracking of macromole petroleum hydrocarbon is generated less alkane and alkene; B) HZSM-5 is added on the carrier as alkane selective cracking and isomerization auxiliary agent; C) gallium ZSM-5 is as the aromizing auxiliary agent.
The patent documentation of above-mentioned relevant USY zeolite catalyst, how wide no matter the scope of silica alumina ratio has, all only relate to the y-type zeolite of a certain silica alumina ratio, and prepared catalyzer can't satisfy the requirement to the FCC gasoline quality well.
Summary of the invention
The objective of the invention is on the basis of above-mentioned prior art, a kind of new catalyst is provided, this catalyzer can be taken into account cracking reaction and isomerization reaction well, makes the gasoline products of catalytic cracking be rich in isoparaffin, increases production the propylene and the Trimethylmethane of high added value simultaneously.
Catalyzer provided by the invention is made up of the zeolite of 0～70 heavy % clay that with the catalyst weight is benchmark, 5～90 heavy % inorganic oxides and 1～50 heavy %, zeolite wherein be with zeolite weight be the silica alumina ratio of (1) 20～75 heavy % of benchmark be 5～15, with RE
2O
3The content of rare earth of meter be the silica alumina ratio of high-silicon Y-Zeolite and (2) 20～75 heavy % of 8～20 heavy % be 16～50, with RE
2O
3The content of rare earth of meter is high-silicon Y-Zeolite and the β zeolite of (3) 1～50 heavy % or the mixture of mordenite or ZRP zeolite of 2～7 heavy %.
The silica alumina ratio of preferred (1) 30～65 heavy % of zeolite in this catalyzer is 5～15, with RE
2O
3The content of rare earth of meter be the silica alumina ratio of high-silicon Y-Zeolite and (2) 30～65 heavy % of 8～20 heavy % be 16～50, with RE
2O
3The content of rare earth of meter is high-silicon Y-Zeolite and the β zeolite of (3) 5～40 heavy % or the mixture of mordenite or ZRP zeolite of 2～7 heavy %.
Clay in this catalyzer can be natural or synthetic, through or without various chemistry and/or physical treatment, usually as the various clays of cracking catalyst carrier, as kaolin, halloysite etc.
Inorganic oxide in this catalyzer is selected from unformed SiO
2Al
2O
3, Al
2O
3Or SiO
2
High-silicon Y-Zeolite in this catalyzer is handled with chemistry and/or physical method and is obtained, stabilization y-type zeolite, as hydrothermal method, acidic treatment, gas phase or liquid phase aluminium-eliminating and silicon-replenishing method, SiCl
4The type-Y high silicon zeolite that obtains after the processing such as method.
β zeolite among the present invention can make according to any disclosed technology, and preferred manufacturing procedure is: be the silicon source with silica gel, pseudo-boehmite is the aluminium source, adds crystal seed in the NaOH aqueous solution, carries out crystallization then in crystallizing kettle.Concrete working method can be referring to CN1154342A.
ZRP (trade names) zeolite is a kind of five-ring supersiliceous zeolite of phosphorous and rare earth element, this zeolite with P
2O
5The phosphorus content of meter is 2～20 heavy %, is preferably 2～10 heavy %; With RE
2O
3The content of rare earth of meter is 2～10 heavy %.This zeolite is to be handled through aluminum phosphate by the five-ring supersiliceous zeolite that contains rare earth to make.The described rare-earth five-membered ring supersiliceous zeolite that contains is to be raw material with water glass, aluminum phosphate and mineral acid, be crystal seed with REY or REHY zeolite, makes in 12～60 hours at 130～200 ℃ of following crystallizations, and concrete working method is referring to CN1058382A.It is as follows with the method for aluminum phosphate processing that this contains the rare-earth five-membered ring supersiliceous zeolite: zeolite is exchanged processing in advance with ammonium ion make its content (with Na
2O meter) reduces to and be not more than 0.1 heavy %, will consist of Al
2O
3: P
2O
5=1: 1～3 aluminum phosphate colloid is according to P
2O
5: weight ratio and this zeolite of zeolite (butt)=1: 5～99 mix, and have roasting down 0.5～6 hour in 300～600 ℃, 10～100% water vapour.Concrete working method is referring to CN1053918C.
The mordenite that the present invention adopts can make according to any disclosed technology.
Preparation of catalysts method provided by the invention is as follows: with the precursor of inorganic oxide, as aluminium colloidal sol, pseudo-boehmite, silicon sol or its mixture and silicon-aluminum sol or gel mix by preset blending ratio with clay, with decationized Y sieve water it is mixed with the slurries that solid content is 10～50 heavy %, stir, use the mineral acid example hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, PH transfers to 2～4 with slurries, keep this pH value, under 20～80 ℃, left standstill aging 0～2 hour, reduce to the zeolite that adds predetermined amount behind the normal temperature, homogeneous, spraying drying, the flush away free sodium ion, the dry finished product that gets.
Catalyzer of the present invention is because two kinds of high-silicon Y-Zeolites having adopted Different Silicon aluminum ratio and different content of rare earth as main active ingredient, help the cracking reaction of heavy petroleum hydrocarbon in the FCC process and the isomerization reaction of the intermediate product that generated.In order to increase the isomerization reaction in the FCC process, the present invention has adopted silica alumina ratio at 16～50 high-silicon Y-Zeolite.The acid site intensity height of this high-silicon Y-Zeolite can effectively suppress the cracking reaction again of the low-carbon (LC) isomeric hydrocarbon that generated.But weak point is that the cracking performance of its macromole hydrocarbon is relatively poor, and the total conversion rate of reaction process descends, and makes the first set reaction product that can carry out secondary reactions such as isomerization reduce.For this reason, the present invention has adopted another kind of silica alumina ratio than the former low slightly high-silicon Y-Zeolite simultaneously, and its silica alumina ratio is 5～15, to strengthen the macromolecular cracking ability of heavy oil.In addition, because the present invention has also adopted a certain amount of β zeolite or mordenite or ZRP zeolite, with propylene enhancing, the contour value-added product of Trimethylmethane.By test as can be known, catalyzer provided by the invention is under identical transformation efficiency, iso-pentane and isohexane productivity ratio prior art increase by 37～43% and 30～42% respectively in the gasoline, and the productivity ratio latter of propylene increases about 2.5 percentage points, and the Trimethylmethane productivity ratio latter increases about 1.5 percentage points.
Embodiment
The following examples will be further specified the present invention, but not thereby limiting the invention.
Evaluating catalyst test among the embodiment is carried out on heavy oil microreactor, and temperature of reaction is 480 ℃, and agent-oil ratio 3.2 is during weight space velocity 16
-1, 70 seconds oil-feed time.Catalyst sample is in advance through 800 ℃, 100% steam treatment 4 hours, and its Intake Quantity is so that transformation efficiency is controlled at about 75% is as the criterion.Stock oil is the grand celebration wax oil, and its character sees Table 1.
Table 1
| Density, d 4 20Boiling range, ℃ condensation point, ℃ kinematic viscosity, mm 2/ s, 100 ℃ of group compositions, heavy % stable hydrocarbon aromatic hydrocarbon | 0.8564 350～500 42 4.6 86.6 13.4 |
Embodiment 1～2
The explanation of this example the invention provides Preparation of catalysts and reactivity worth thereof.
Embodiment 1～2nd, is active ingredient with supersiliceous zeolite Y1, Y2 and β zeolite or mordenite, is that matrix, pseudo-boehmite are binding agent with kaolin, prepares catalyzer provided by the invention.
Wherein, supersiliceous zeolite Y1 uses NH
4Y is through the preparation of hydrothermal treatment consists and rare earth ion exchanged and get, and its silica alumina ratio is 12.8, with RE
2O
3The content of rare earth of meter is 8.5 heavy % (accounting for zeolite).Supersiliceous zeolite Y2 is through SiCl with NaY
4The sample of gas phase treatment and rare earth ion exchanged preparation, its silica alumina ratio is 18, with RE
2O
3The content of rare earth of meter is 4 heavy %.The β zeolite is according to disclosed method preparation among the CN1154342A.Mordenite is according to disclosed method preparation among the CN1147479A.
With 4300 gram decationized Y sieve water 960 gram halloysites are pulled an oar, add 781 gram pseudo-boehmite and 144ml hydrochloric acid again, stir, left standstill aging 1 hour at 60 ℃, keeping slurries PH is 2～4, reduces to normal temperature, add the preprepared zeolite slurry that contains 300 gram Y1 (butt), 300 gram Y2 (butt), 200 gram β zeolites (butt) and 2000 gram chemical water again, stir spray drying forming, the flush away Na that dissociates
+, the dry catalyzer sample A that gets.
With 4300 gram decationized Y sieve water 960 gram halloysites are pulled an oar, add 781 gram pseudo-boehmite and 144ml hydrochloric acid again, stir, left standstill aging 1 hour at 60 ℃, keeping slurries PH is 2～4, reduces to normal temperature, add the preprepared zeolite slurry that contains 300 gram Y1 (butt), 300 gram Y2 (butt), 200 gram mordenites (butt) and 2000 gram chemical water again, stir spray drying forming, the flush away Na that dissociates
+, the dry catalyzer sample B that gets.
Table 2 and table 3 have been listed composition and their evaluation results on heavy oil microreactor of catalyzer sample A and B respectively.
[Comparative Examples 1] is 5.5 with silica alumina ratio, with RE
2O
3The content of rare earth of meter is that the REY type zeolites of 20 heavy % replace employed zeolite in the catalyzer of the present invention, makes contrast sample 1 according to the preparation method of catalyzer sample A and B.For the purpose of contrast, the composition of this contrast sample and the evaluation result on heavy oil microreactor thereof are also listed table 2 and table 3 respectively in.
As shown in Table 3, the iso-pentane of catalyst A, B, isohexane productive rate and propylene and Trimethylmethane productive rate contrast sample 1 and all are significantly improved, and coke and the dry gas yied of catalyst A, B are also low than the latter, illustrate that the product selectivity of catalyst A, B is better.
Table 2
| Project | Catalyst A | Catalyst B | Contrast sample 1 |
| Form heavy % kaolin Al 2O 3Supersiliceous zeolite Y1 supersiliceous zeolite Y2 β zeolite mordenite REY | 35 25 15 15 10 | 35 25 15 15 10 | 45 30 25 |
Table 3
*The productive rate of single hydrocarbon component is to calculate benchmark with the raw material weight in the reacted gas
*The productive rate of single hydrocarbon component serves as to calculate benchmark with gasoline weight in the gasoline
Embodiment 3
This example illustrates Preparation of catalysts provided by the invention and reactivity worth thereof.
Supersiliceous zeolite Y1, Y2 are same as the previously described embodiments.The ZRP zeolite is the product of Zhou village, Shandong catalyst plant, and silica alumina ratio is 30, with RE
2O
3The content of rare earth of meter is 2.0 heavy %.
With 4300 gram decationized Y sieve water 960 gram halloysites are pulled an oar, add 781 gram pseudo-boehmite and 144ml hydrochloric acid again, stir, left standstill aging 1 hour at 60 ℃, keeping slurries PH is 2～4, reduces to normal temperature, add the preprepared zeolite slurry that contains 300 gram Y1 (butt), 300 gram Y2 (butt), 200 gram ZRP zeolites (butt) and 2000 gram chemical water again, stir spraying drying, the flush away Na that dissociates
+, the dry catalyzer sample C that gets.Table 4 and table 5 have been listed the composition of catalyzer sample C and the evaluation result on heavy oil microreactor thereof respectively.
[contrast sample 2] replaces employed zeolite in the example 3 with the mixture of the Y1 zeolite that accounts for catalyst weight 20% and the ZRP zeolite that accounts for catalyst weight 20%, makes contrast sample 2 according to the preparation method of catalyzer sample C.
[contrast sample 3] with the silica alumina ratio of hydrothermal treatment consists method preparation be 10.7, content of rare earth is (with RE
2O
3Meter) is that the DASY zeolite of 1 heavy % replaces employed zeolite in the example 3, makes contrast sample 3 according to the preparation method of catalyzer sample C.
For the purpose of contrast, also list composition and their evaluation results on heavy oil microreactor of contrast sample 2 and contrast sample 3 in table 4 and table 5 respectively.
As shown in Table 5, compare with contrast sample 2 and contrast sample 3, amylene and hexene content are low in the catalyzer sample C gasoline, and iso-pentane and isohexane content are higher; The propylene content comparison of catalyzer sample C is hanged down 5.92 percentage points than sample 2, but comparison is higher 1.26 percentage points than sample 3; Its Trimethylmethane content comparison is higher 1.4 percentage points than sample 2, compares higher 1.72 percentage points than sample 3.By above-mentioned contrast as can be known, catalyzer sample C can also increase production a certain amount of propylene and Trimethylmethane when the high-quality gasoline of isoparaffin is rich in production.
Table 4
Table 5
*The productive rate of single hydrocarbon component is to calculate benchmark with the raw material weight in the reacted gas
*The productive rate of single hydrocarbon component serves as to calculate benchmark with gasoline weight in the gasoline
| Catalyzer | C | Contrast sample 2 | Contrast sample 3 |
| Form heavy % kaolin Al 2O 3Supersiliceous zeolite Y1 supersiliceous zeolite Y2 ZRP zeolite DASY | 35 25 15 10 15 | 35 25 20 20 | 35 25 40 |
| Catalyzer | C | Contrast sample 2 | Contrast sample 3 |
| Transformation efficiency, the % reacted gas, heavy % is wherein *C 3 ＝C 4 ＝iC 4 0Gasoline (C 5～220 ℃), heavy % is wherein **C 5 ＝C 6 ＝iC 5 0iC 6 0Benzene toluene dimethylbenzene trimethylbenzene diesel oil (221～330 ℃), heavy % heavy oil (＞330 ℃), heavy % coke, heavy % adds up to | 76.35 17.35 5.15 2.90 5.26 53.40 3.88 3.20 8.40 11.92 0.23 1.98 5.00 4.60 12.45 11.20 5.60 100.00 | 73.39 25.49 11.07 8.17 3.86 44.24 14.30 8.61 7.89 10.01 0.46 1.78 4.72 5.64 14.56 12.05 3.66 100.00 | 73.58 12.62 3.89 2.89 3.54 56.97 6.36 4.90 7.15 11.29 0.18 1.53 3.91 4.95 16.18 10.24 3.99 100.00 |
Claims (6)
1, a kind ofly is used to produce the catalytic cracking catalyst that is rich in isoparaffin gasoline, propylene and Trimethylmethane, it is characterized in that it is made up of the zeolite of 0～70 heavy % clay that with the catalyst weight is benchmark, 5～90 heavy % inorganic oxides and 1～50 heavy %, zeolite wherein be with zeolite weight be the silica alumina ratio of (1) 20～75 heavy % of benchmark be 5～15, with RE
2O
3The content of rare earth of meter be the silica alumina ratio of high-silicon Y-Zeolite and (2) 20～75 heavy % of 8～20 heavy % be 16～50, with RE
2O
3The content of rare earth of meter is high-silicon Y-Zeolite and the β zeolite of (3) 1～50 heavy % or the mixture of mordenite or ZRP zeolite of 2～7 heavy %.
2,, it is characterized in that described clay is selected from kaolin and/or halloysite according to the catalyzer of claim 1.
3,, it is characterized in that described inorganic oxide is selected from unformed SiO according to the catalyzer of claim 1
2Al
2O
3, Al
2O
3And/or SiO
2
4, according to the catalyzer of claim 1, it is characterized in that described high-silicon Y-Zeolite handle with chemistry and/or physical method obtain, stabilization y-type zeolite.
5, according to the catalyzer of claim 1, it is characterized in that described β zeolite is is the silicon source with silica gel, pseudo-boehmite is the aluminium source, adds crystal seed in the NaOH aqueous solution, carries out in crystallizing kettle then that crystallization makes.
6,, it is characterized in that described ZRP zeolite is with P according to the catalyzer of claim 1
2O
5The phosphorus content of meter is 2～20 heavy %, with RE
2O
3The content of rare earth of meter is the five-ring supersiliceous zeolite of 2～10 heavy %, and this zeolite is with water glass, and aluminum phosphate and mineral acid are raw material, are crystal seed with REY or REHY zeolite, make in 12～60 hours at 130～200 ℃ of following crystallizations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00132748 CN1124892C (en) | 2000-11-17 | 2000-11-17 | Catalytic cracking catalyst for producing gaosline richly-containing paraffinic hydrocarbon, propylene and isobutane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00132748 CN1124892C (en) | 2000-11-17 | 2000-11-17 | Catalytic cracking catalyst for producing gaosline richly-containing paraffinic hydrocarbon, propylene and isobutane |
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| CN1124892C true CN1124892C (en) | 2003-10-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI277648B (en) | 2004-07-29 | 2007-04-01 | China Petrochemical Technology | A cracking catalyst for hydrocarbons and its preparation |
| CN100378196C (en) * | 2005-04-29 | 2008-04-02 | 中国石油化工股份有限公司 | Petroleum hydrocarbon cracking catalytic method |
| CN101134172B (en) | 2006-08-31 | 2010-10-27 | 中国石油化工股份有限公司 | Hydrocarbons conversion catalyzer |
| CN101134913B (en) | 2006-08-31 | 2011-05-18 | 中国石油化工股份有限公司 | Hydrocarbons catalytic conversion method |
| CN101332433B (en) | 2007-06-27 | 2011-07-20 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and use thereof |
| US9227181B2 (en) | 2011-09-13 | 2016-01-05 | Basf Corporation | Catalyst to increase propylene yields from a fluid catalytic cracking unit |
| WO2015075565A1 (en) * | 2013-11-21 | 2015-05-28 | Indian Oil Corporation Limited | Hydrocarbon cracking catalyst and process for producing light olefins |
| CN109694726B (en) * | 2017-10-24 | 2021-07-09 | 中国石油化工股份有限公司 | Catalytic conversion method for increasing yield of propylene and light aromatic hydrocarbon |
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