CN1143666A - Cracking catalyst for producing isomeric olefine and gasoline with high yield - Google Patents
Cracking catalyst for producing isomeric olefine and gasoline with high yield Download PDFInfo
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Abstract
A cracking catalyst for high outputs of isomeric olefin and high-octane gasoline is prepared from Al-base compound adhesive (5-70%), clay (5-65%) and mixed zeolite (23-50%) and is suitable for catalytic cracking of different raw oils such as wax oil, residual oil, high-V raw oil, etc. The total output rate of isobutylene and isopentene is up to 10.11-13.73 Wt.% and the output rate is 41.5-48.5 Wt.% for gasoline, 95.6-96.4 for RON and 80.5-81.3 for MON.
Description
The present invention is on a kind of Cracking catalyst, specifically.It is on a kind of Cracking catalyst that light isoolefins and high-knock rating gasoline are produced for catalytic cracking petroleum hydrocarbons.
With the development of petrochemical industry, catalytic cracking process is not only to provide the important means of light-end products, while being also to provide a kind of processing mode of the basic organic chemical industry raw material such as alkene.Require there are the oxygenatedchemicals such as certain oxygen content, MTBE, TAME will to be gradually added into gasoline due to readjusting for gasoline formulation, in gasoline.Used as the raw material-isobutene and iso-amylene of MTBE, TAME, its demand will increasingly increase.Therefore.It is required that Cracking catalyst improves to some extent to the selectivity of isomeric olefine.Common catalytic cracking is only producing based on light oil, although also by-product liquefied gas.But yield is seldom, 10 weight below % of feedstock oil are only accounted for, the wherein yield of isobutene and iso-amylene is just less, only accounts for 5 weight % of raw material or so.
In order to improve octane number and olefin yield, people had once made a large amount of effort, such as CN 1072201A, CN 1093101A, CN 1098130A and CN 1085825A etc..But during catalytic cracking, the research for improving gasoline production and octane number and increasing isomeric olefine yield aspects is still rare.For example in NPRA meetings in 1992, the result of study of U.S. W.R.Grace companies Davison Chemicals Divisions report shows, ZSM-5 is added in OCTACAT catalyst and is conducive to high yield of isobutene, iso-amylene, but the yield of gasoline is but decreased.
The Cracking catalyst of a kind of high yield of isobutene and iso-amylene is disclosed in CN 1103105A, is made up of 5~25% modified HZSM-5,1~5% silicon HZSM-5 high, 5~20%USY zeolites, 1~5% β zeolites, four kinds of active components and 30~60% natural clays and 15~30% inorganic oxides as carrier.Use the catalyst, although it is 81~82 that RON can reach 93~94, MON, but gasoline yield is 36.84~45.09%, and the gross production rate of isobutene and iso-amylene is only 9.40~10.61%.
A kind of catalysis conversion method of low-carbon olefines high-output is disclosed in CN 1102431A, which use the catalyst being made up of 0~70% clay, 5~90% inorganic oxides and 10~35% zeolites, active component is three kinds of the five-membered ring silica-rich zeolite by 0~75% Y-type high-Si zeolite and 0~25% y-type zeolite containing rare earth and 25~100% phosphorous and rare earth into being grouped into.Using the catalyst, the gross production rate of isobutene and iso-amylene reaches as high as 13%, and now gasoline yield is 26~43%.
A kind of producing in high-yield olefin catalyst disclosed in CN 1099788A, is made up of the y-type zeolite of 20~80% semi-synthetic carriers being made up of kaolin and al binder and 10~50% lattice constants≤2.450nm, 2~40% modified ZSM-5 zeolites, beta-zeolite and its mixture.Use the catalyst, although the gross production rate of isobutene and iso-amylene is up to 10~13%, but gasoline yield is only 35~42%.
In sum, existing Cracking catalyst can not keep gasoline production and octane number higher while isomeric olefine yield is improved.
In addition, disclosing a kind of composite aluminum base binding agent in CN 1098130A, the binding agent improves the wearability and coke selectivity of semi-synthetic carrier Cracking catalyst.
The purpose of the present invention is that a kind of new catalyst is provided on the basis of above-mentioned prior art, and it can improve isobutene and iso-amylene yield, and gasoline production and octane number can be made to maintain higher level again.
The catalyst that the present invention is provided has following composition (being counted on the basis of catalyst weight)：5~70% by boehmite and Alumina gel according to 1: 9 to 9: 1 weight than the composite aluminum base binding agent, 5~65% clay and 23~50% zeolite that constitute, described zeolite be 15~82% y-type zeolite and surplus phosphorus content (with P2O5Meter) it is the silica-rich zeolite containing rare-earth five-membered ring of 0~10 weight % and/or the mixture of HZSM-5 zeolites, wherein when silica-rich zeolite containing rare-earth five-membered ring and the described HZSM-5 zeolites that described phosphorus content is 0~10 weight % simultaneously in the presence of, phosphorus content is that the content of silica-rich zeolite containing rare-earth five-membered ring of 0~10 weight % is no more than 65%.
In this catalyst clay used be natural or synthetic, through or without various chemistry and/or physical methods treatment, be typically used as the various clays of cracking catalyst carrier.Such as kaolin, halloysite.
Y-type zeolite used is content of rare earth (with RE in this catalyst2O3Meter) be 0~5 heavy %, lattice constant ＜ 2.455nm y-type zeolite and/or REHY zeolites.Described content of rare earth be 0~5 heavy %, lattice constant ＜ 2.455nm y-type zeolite through chemistry and/or physical method stabilization processes obtain, the ultrastable for for example being obtained with hydro-thermal method, the Y-type high-Si zeolite obtained with liquid phase method or vapor phase method aluminium-eliminating and silicon-replenishing.The content of rare earth of described REHY zeolites is (with RE2O3Meter) it is 2~16 heavy %.
Phosphorus content used is (with P in this catalyst2O5Meter) it is that 0~10 silica-rich zeolite containing rare-earth five-membered ring (hereinafter referred to as ZRP zeolites) for weighing % is by USP5,232, prepared by the method disclosed in 675, i.e. with waterglass, aluminum phosphate, inorganic acid as raw material, with REY or REHY zeolites as crystal seed, crystallization 12~60 hours at 130~200 DEG C, obtain final product not phosphorous silica-rich zeolite containing rare-earth five-membered ring；
The five-membered ring silica-rich zeolite containing rare earth of above-mentioned gained is such as carried out into pre- exchange treatment with ammonium ion makes its sodium content (with Na2O is counted) no more than 0.1 heavy % is down to, it is Al by composition2O3∶P2O5=1: 1~3 aluminum phosphate colloid is according to P2O5: the weight ratio of zeolite (butt)=1: 5~99 is well mixed with the zeolite, is calcined 5~6 hours in the presence of 300~600 DEG C, 10~100% water vapours, you can obtain phosphorous and rare-earth five-membered ring silica-rich zeolite.
The preparation method of catalyst that the present invention is provided is as follows：
(1) zeolite aqueous slurry is prepared：Zeolite is mixed with decationized Y sieve water, untill glue is milled to granularity less than 6 μm；
(2) catalyst carrier slurries are prepared：Decationized Y sieve water, binding agent are well mixed with clay, the slurries that solid content is 10~50 weight % are configured to, stirred, in standing aging 0~2 hour at 20~80 DEG C,
(3) above-mentioned zeolite aqueous slurry is added in catalyst carrier slurries, and mixed, homogeneous, spray drying；
(4) it is calcined or is optionally washed and dried with ammonium hydroxide and/or ammonium phosphate solution.
The advantage of catalyst that the present invention is provided is：
1. applicable raw materials wide ranges.Can be used for the feedstock oil of various properties, such as wax oil, residual oil, the catalytic cracking of content of vanadium feedstock oil high.For example on middle scale riser device, the catalyst that the present invention is provided is the feedstock oil of 5.2ppm for content of vanadium, can still make the gross production rate of isobutene and iso-amylene up to 10.74%, C5 +Gasoline production is up to 46.30 heavy %；
2. cracking conversion rate is high, C3 =~C5 =Yield and isobutene, iso-amylene yield are high, and gasoline production and octane number are high.For example on heavy oil microreactor, under identical appreciation condition, the present invention provide catalyst than single binding agent and the catalyst without y-type zeolite high conversion rate, C3 =~C5 =Total olefin is high, the gross production rate of isobutene and iso-amylene is high, gasoline production is high；Under the same conditions, catalyst of the present invention also than ZRP zeolite contents high catalyst conversion ratio and gasoline production it is high.
It is in a word in the range of 76.4~87.0 weight % in conversion ratio, the catalyst that the present invention is provided can make gasoline production reach 41.5~48.5 heavy % while the gross production rate of isobutene and iso-amylene reaches 10.11~13.73%, and octane number is higher, up to 95.6~96.4, motor octane number (MON) is up to 80.5~813 for research octane number (RON) (RON).
The present invention is further described below by way of embodiment, but these embodiments should not be construed as any limitation on the scope of the present invention.
(1) place of production raw materials used in the embodiment of the present invention, specification are as follows：
1. Alumina gel：Qilu Petrochemical Company's catalyst plant industrial products, containing Al2O321.6 weights %；
2. kaolin：Hard paste porcelain God in charge of the Earth department industrial products, the heavy % of solid content 78.6；
3. boehmite：Shandong Aluminum Plant's industrial products, the heavy % of solid content 34.2；
4.DASY zeolites：Qilu Petrochemical Company's catalyst plant industrial products, are the y-type zeolites being made of hydrothermal dealumination method, and lattice constant is 2.445nm；
5.ZRP zeolites：Qilu Petrochemical Company's catalyst plant industrial products, Na2The heavy % of O ＜ 1；
6.REDASY zeolites：Qilu Petrochemical Company's catalyst plant industrial products, are the y-type zeolites being made of re chloride exchange, hydrothermal dealumination method, and lattice constant is 2.452nm；
7.HZSM-5 zeolites：The commercial industrial product of silica alumina ratio 60；
8.REHY zeolites：Qilu Petrochemical Company's catalyst plant industrial products, content of rare earth is (with RE2O3Meter) it is 6.1 heavy %.
(2) method and condition of the evaluation catalyst for being used in the embodiment of the present invention：
1. the condition of catalyst is evaluated on heavy oil microreactor：
Reaction temperature is 520 DEG C, weight space velocity 16h-1, 4 grams of catalyst sample consumption.Catalyst sample evaluate before in advance through normal pressure, 800 DEG C, 100% steam treatment 8 hours.The performance for testing raw materials used oily A is as follows：
2. the condition of catalyst is evaluated on small-sized cyclic catalytic cracking device (ARCO)：
Reaction temperature is 520 DEG C, oil ratio 8.0, the heavy % of atomized water 5.0.Catalyst sample evaluate before in advance through normal pressure, 790 DEG C, 100% steam treatment 10 hours.The performance for testing raw materials used oily B is as follows：
3. the condition of catalyst is evaluated on middle scale riser device：
Reaction temperature is 530 DEG C, reaction pressure 127KPa.Catalyst sample evaluate before in advance through normal pressure, 790 DEG C, 100% steam treatment 4 hours.The performance of experiment feedstock oil C and D used is as follows：
Embodiment 1~2
The preparation of the catalyst that the present invention is provided and its cracking performance evaluated on heavy oil microreactor.
83 kilograms of Alumina gels, 103 kilograms of kaolin are added to the water mixing, stir, add 9.5 kilograms of boehmites, it is aging 2 hours at 62 DEG C, carrier pulp is obtained, 3.6 kilograms of DASY zeolites, 2.8 kilograms of ZRP zeolites (phosphorous 8 heavy %) are taken respectively to be added to the water, it is well mixed with colloid mill, that is, zeolite slurry is obtained.Then carrier pulp is mixed with zeolite slurry, through homogeneous, spray drying forming, roasting obtains catalyst sample A of the invention.
152.8 kilograms of Alumina gels, 98 kilograms of kaolin are added to the water mixing, 643 kilograms of boehmites are added, stirred, that is, carrier pulp is obtained.58.4 kilograms of REDASY zeolites are taken respectively and 34 kilograms of HZSM-5 zeolites are added to the water, it is well mixed with colloid mill, that is, zeolite slurry is obtained.Then carrier pulp is mixed with zeolite slurry, through homogeneous, spray drying forming, washing, drying, that is, obtains catalyst sample B of the invention.
[comparative example 1] comparative example provides being prepared by CN 1093101A methods describeds, the semi-synthetic carrier with Alumina gel as binding agent, the Cracking catalyst with clay as matrix, with ZRP zeolites (phosphorous 8 heavy %) as active component：16.7 kilograms of Alumina gels, 10.3 kilograms of kaolin are added to the water mixing, are uniformly mixed, that is, carrier pulp is obtained.6.5 kilograms of ZRP zeolites (phosphorous 8 heavy %) are taken to be added to the water, it is well mixed with colloid mill, that is, zeolite slurry is obtained.Carrier pulp is mixed with zeolite slurry, through homogeneous, spray drying forming, that is, comparative sample 1 is obtained.
[comparative example 2] replaces ZRP zeolites with HZSM-5 zeolites, according to the raw material dosage and preparation method of comparative example 1, comparative sample 2 is obtained.
The composition of aforementioned four sample is listed in table 1.Evaluation result to above-mentioned sample on heavy oil microreactor is listed in Table 2 below.
From the heavy oil micro anti-evaluation result of table 2：Under identical appreciation condition, compared with comparative catalyst of the catalyst of the present invention with single binding agent and without y-type zeolite, high conversion rate,Total olefin it is high, the gross production rate of isobutene and iso-amylene is high, and gasoline production reaches 42.7 weight more than %, and the performance of catalyst of the present invention is substantially better than comparative sample 1 and 2.
Table 1
Table 2
Embodiment 3~6
The preparation of the catalyst that the present invention is provided and its cracking performance evaluated on heavy oil microreactor.
6.9 kilograms of Alumina gels, 7.6 kilograms of kaolin are added to the water mixing, are stirred, add 7.9 kilograms of boehmites, be well mixed, it is aging 1.5 hours at 65 DEG C, that is, carrier pulp is obtained.3.0 kilograms of DASY zeolites, 0.15 kilogram of HZSM-5 zeolite and 1.7 kilograms of ZRP zeolites are taken respectively to be added to the water, it is well mixed with colloid mill, that is, zeolite slurry is obtained.The step of according to embodiment 2, carries out operation and catalyst sample C of the invention is obtained.
In addition to ageing time is 2 hours, according to above-mentioned preparation method, catalyst sample D of the invention is obtained with 125 kilograms of Alumina gels, 91.6 kilograms of kaolin, 52.6 kilograms of boehmites and 28.7 kilograms of REDASY zeolites, 9.5 kilograms of REHY zeolites and 27.8 kilograms of HZSM-5 zeolites.
6.7 kilograms of Alumina gels and 8.5 kilograms of kaolin are added to the water mixing, add 8.9 kilograms of boehmites, stir, carrier pulp is obtained, 1.9 kilograms of ZRP zeolites, 1.5 kilograms of HZSM-5 zeolites and 3.8 kilograms of REDASY zeolites are taken respectively to be added to the water, it is well mixed with colloid mill, that is, zeolite slurry is obtained.Catalyst sample E of the invention is obtained by the preparation method operation of embodiment 1.
93 kilograms of Alumina gels and 9.4 kilograms of kaolin are mixed, stir, add 11.7 kilograms of boehmites, it is well mixed, it is aging 2 hours at 62 DEG C, that is, carrier pulp is obtained, 1.2 kilograms of ZRP zeolites, 1.4 kilograms of HZSM-5 zeolites, 0.6 kilogram of REHY zeolite and 3.6 kilograms of REDASY zeolites are taken respectively to be added to the water, it is well mixed with colloid mill, that is, zeolite slurry is obtained.Preparation method operation according to embodiment 2 obtains catalyst sample F of the invention.
[comparative example 3] comparative example provides the semi-synthetic carrier with Alumina gel and boehmite as binding agent, the Cracking catalyst with clay as matrix, with zeolite as active component：In addition to replacing the consumption of 3.0 kilograms of DASY zeolites and wherein ZRP zeolites with 33 kilograms of REDASY zeolites in zeolite component and being changed into 1.5 kilograms, the preparation method fully according to catalyst C in embodiment 3 is obtained comparative sample 3.
The composition of above-mentioned five kinds of samples is listed in table 3.Evaluation result to above-mentioned sample on heavy oil microreactor is listed in table 4.
From the heavy oil micro anti-evaluation result of table 4：Under identical appreciation condition, catalyst of the present invention compares with the comparative sample 3 of ZRP zeolite contents high, and the alkene and isomeric olefine yield of the two are all higher, but the conversion ratio and gasoline production of comparative sample 3 are relatively low.The gasoline production of catalyst of the present invention can reach 41.5~48.5 heavy %, hence it is evident that higher than the gasoline production of comparative sample 3.
Table 3
Table 4
Embodiment 7
The preparation of the catalyst that the present invention is provided and its cracking performance evaluated on small-sized cyclic catalytic cracking device.
3.5 kilograms of Alumina gels, 6.7 kilograms of kaolin are added to the water mixing, stir, add 13.2 kilograms of boehmites, it is well mixed, it is aging 2 hours at 62 DEG C, obtain final product carrier pulp, 1.5 kilograms of DASY zeolites are taken respectively and 3.1 kilograms of HZSM-5 zeolites are added to the water, it is well mixed with colloid mill, that is, zeolite slurry is obtained, then obtain catalyst sample G of the invention according to the preparation method operation of embodiment 2.
The composition of above-mentioned sample is listed in table 5.Evaluation result to above-mentioned sample on small-sized cyclic catalytic cracking device is listed in table 6.
As seen from Table 6.The characteristics of evaluation results of the catalyst G of the present invention on ARCO devices has same with above catalyst A~F, isobutene yield reaches 4.68~4.77 heavy %, the gross production rate of isobutene and iso-amylene is up to 12.75~12.87 heavy %, gasoline production may also reach up 42.28~43.34 heavy %, RON reaches 96.1, MON and reaches 80.5.
Table 5
Table 6
Embodiment 8
The preparation of the catalyst that the present invention is provided and its cracking performance evaluated on middle scale riser device.
125.0 kilograms of Alumina gels, 91.6 kilograms of kaolin are added to the water mixing, are stirred, add 52.6 kilograms of boehmites, be well mixed, it is aging 1.5 hours at 60 DEG C, that is, carrier pulp is obtained.27.9 kilograms of ZRP zeolites (phosphorous 2 heavy %), 38.2 kilograms of REDASY zeolites are taken respectively to be added to the water, it is well mixed with colloid mill, that is, zeolite slurry is obtained.Then catalyst sample H of the invention is obtained by the preparation method operation of embodiment 2.
The composition of above-mentioned sample is listed in table 7.Table 8 is listed in the evaluation result of above-mentioned sample on middle scale riser device, using feedstock oil C.
As seen from Table 8.Catalyst sample H of the invention can make gasoline yield in the case of 45.56%, make the gross production rate of isobutene and iso-amylene up to 12.88%.
Embodiment 9
The preparation of the catalyst that the present invention is provided and its cracking performance evaluated on middle scale riser device.
131.9 kilograms of Alumina gels, 103.9 kilograms of kaolin are added to the water mixing, are stirred, add 55.6 kilograms of boehmites, be well mixed, it is aging 1 hour at 65 DEG C, that is, carrier pulp is obtained.23.5 kilograms of HZSM-5 zeolites, 16.0 kilograms of REHY zeolites and 24.2 kilograms of REDASY zeolites are taken respectively to be added to the water, it is well mixed with colloid mill, that is, zeolite slurry is obtained.Then catalyst sample I of the invention is obtained according to the preparation method operation of embodiment 2.
The composition of above-mentioned sample is listed in table 7.Table 8 is listed in the evaluation result of above-mentioned sample on middle scale riser device, using feedstock oil D.
As seen from Table 8, when the content of vanadium in feedstock oil D is 5.2ppm, the isobutene and iso-amylene gross production rate of catalyst I of the present invention are up to 10.11 heavy %, C5Gasoline production is up to 46.30 heavy %.
Table 7
Table 8
Claims (10)
1. a kind of Cracking catalyst for producing isomeric olefine, it is characterized in that what it was made up of according to 1: 9 to 9: 1 weight boehmite and Alumina gel (based on the basis of catalyst weight) 5~70% than the composite aluminum base binding agent, 5~65% clay and 23~50% zeolite that constitute, described zeolite be 15~82% y-type zeolite and surplus phosphorus content (with P2O5Meter) be the silica-rich zeolite containing rare-earth five-membered ring of 0~10 weight % and/or the mixture of HZSM-5 zeolites, when silica-rich zeolite containing rare-earth five-membered ring and HZSM-5 zeolites simultaneously in the presence of, the content of silica-rich zeolite containing rare-earth five-membered ring is no more than 65%.
2. according to the catalyst described in claim 1, it is characterised in that described clay is natural or synthetic, through or without various chemistry and/or physical methods treatment, be typically used as the various clays of cracking catalyst carrier.
3. according to the catalyst described in claim 2, it is characterised in that described clay is kaolin, halloysite.
4. according to the catalyst described in claim 1, it is characterised in that described y-type zeolite is content of rare earth (with RE2O3Meter) be 0~5 heavy %, lattice constant ＜ 2.455nm y-type zeolite and/or REHY zeolites.
5. according to the catalyst described in claim 4, it is characterised in that described content of rare earth is (with RE2O3Meter) it is that 0~5 heavy %, the y-type zeolite of lattice constant ＜ 2.455nm are obtained through chemistry and/or physical method stabilization processes, including the ultrastable obtained with hydro-thermal method, the Y-type high-Si zeolite that is obtained with liquid phase method or vapor phase method aluminium-eliminating and silicon-replenishing.
6. according to the catalyst described in claim 4, it is characterised in that the content of rare earth of described REHY zeolites is (with RE2O3Meter) it is 2~16 heavy %.
7. according to the catalyst described in claim 1, it is characterised in that described phosphorous silica-rich zeolite containing rare-earth five-membered ring is processed obtained in silica-rich zeolite containing rare-earth five-membered ring with aluminum phosphate.
8. according to the catalyst described in claim 1 or 7, it is characterised in that with waterglass, aluminum phosphate, inorganic acid as raw material, with REY or REHY zeolites as crystal seed, at 130~200 DEG C, crystallization is made described silica-rich zeolite containing rare-earth five-membered ring for 12~60 hours.
9. according to the catalyst described in claim 7, it is characterised in that the method that described being processed with aluminum phosphate contains rare-earth five-membered ring silica-rich zeolite is as follows：Zeolite is carried out into pre- exchange treatment with ammonium ion makes its sodium content (with Na2O is counted) no more than 0.1 heavy % is down to, it is Al by composition2O3∶P2O5=1: 1~3 aluminum phosphate colloid is according to P2O5: the weight ratio of zeolite (butt)=1: 5~99 is well mixed with the zeolite, is calcined 5~6 hours in the presence of 300~600 DEG C, 10~100% water vapours.
10. catalyst described in claim 1 is used to produce light isoolefins and high-knock rating gasoline including the catalytic cracking petroleum hydrocarbons including wax oil, residual oil and content of vanadium feedstock oil high.
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| Application Number | Priority Date | Filing Date | Title |
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| CN96100782A CN1055301C (en) | 1996-02-08 | 1996-02-08 | Cracking catalyst for producing isomeric olefine and gasoline with high yield |
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| CN96100782A CN1055301C (en) | 1996-02-08 | 1996-02-08 | Cracking catalyst for producing isomeric olefine and gasoline with high yield |
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| CN1143666A true CN1143666A (en) | 1997-02-26 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008028343A1 (en) | 2006-08-31 | 2008-03-13 | China Petroleum & Chemical Corporation | A process for catalytic converting hydrocarbons |
| WO2008034299A1 (en) | 2006-08-31 | 2008-03-27 | China Petroleum & Chemical Corporation | A catalyst for converting hydrocarbons |
| CN101829592B (en) * | 2009-03-10 | 2012-07-18 | 中国石油天然气股份有限公司 | Preparation method of fluidizing, catalyzing and cracking catalyst with high solid content |
| CN105728028A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Catalyst for highly-producing olefin isomer and high-octane gasoline |
Families Citing this family (1)
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030287C (en) * | 1992-10-22 | 1995-11-22 | 中国石油化工总公司 | Hydrocarbon conversion catalyst for preparation of high-quality gasoline, propene and butene |
| CN1034223C (en) * | 1993-03-29 | 1997-03-12 | 中国石油化工总公司 | Cracking catalyst for processing low-carbon olefines |
| CN1034718C (en) * | 1993-07-29 | 1997-04-30 | 中国石油化工总公司 | Cracking catalyst and preparing process thereof |
| CN1034586C (en) * | 1993-11-05 | 1997-04-16 | 中国石油化工总公司 | Catalytic conversion method of low-carbon olefines high-output |
-
1996
- 1996-02-08 CN CN96100782A patent/CN1055301C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008028343A1 (en) | 2006-08-31 | 2008-03-13 | China Petroleum & Chemical Corporation | A process for catalytic converting hydrocarbons |
| WO2008034299A1 (en) | 2006-08-31 | 2008-03-27 | China Petroleum & Chemical Corporation | A catalyst for converting hydrocarbons |
| US8716163B2 (en) | 2006-08-31 | 2014-05-06 | China Petroleum & Chemical Corporation | Hydrocarbon conversion catalyst |
| US8900445B2 (en) | 2006-08-31 | 2014-12-02 | China Petroleum & Chemical Corporation | Process for the catalytic conversion of hydrocarbons |
| CN101829592B (en) * | 2009-03-10 | 2012-07-18 | 中国石油天然气股份有限公司 | Preparation method of fluidizing, catalyzing and cracking catalyst with high solid content |
| CN105728028A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Catalyst for highly-producing olefin isomer and high-octane gasoline |
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| CN1055301C (en) | 2000-08-09 |
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