CN1436835A - Catalytic cracking catalyst and its prepn - Google Patents
Catalytic cracking catalyst and its prepn Download PDFInfo
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- CN1436835A CN1436835A CN 02103907 CN02103907A CN1436835A CN 1436835 A CN1436835 A CN 1436835A CN 02103907 CN02103907 CN 02103907 CN 02103907 A CN02103907 A CN 02103907A CN 1436835 A CN1436835 A CN 1436835A
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- aluminium oxide
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Abstract
The catalytic cracking catalyst contains medium and large pore alumina with average pore size not smaller than 3 nm 5-60 wt%, zeolite 5-60 wt%, adhesive 5-40 wt% and clay 5-85 wt%. The preparation process includes mixing the said materials, spraying, roasting, washing and drying. Compared with conventional catalyst, the catalyst has strengthened heavy oil converting capacity, obviously improved gasoline and coke selectivity and strengthened heavy metal nickel resistance.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst, specifically about a kind of catalytic cracking catalyst that contains middle macroporous aluminium oxide.
Background technology
For the refining of petroleum industry, oil transformation efficiency, high gasoline and low coke selectivity are that catalytic cracking unit is produced the target of pursuing all the time at the bottom of the high tower.People make catalytic cracking catalyst adapt to the requirement of above-mentioned target by improving the performance of zeolite and matrix.In long duration in the past, the improvement of zeolite is occupied an leading position always, in recent years, along with the stock oil development of heaviness (＞500 ℃ high boiling component increases), poor qualityization and catalytic cracking process day by day, the effect of matrix seems more and more outstanding, require the matrix of catalyzer to have middle macropore and certain active, thereby improve the ability of cracking mink cell focus; Simultaneously, because heavy metal content such as nickel, vanadium are higher in the heavy oil, require to contain in the matrix certain preventing from heavy metal function ingredients.Middle macroporous aluminium oxide has certain lytic activity as solid acid, adds being expected to reach the purpose of improving catalyzer heavy oit pyrolysis performance in catalyst substrates.
Improvement for matrix, US4,843,052 disclose a kind of acid carclazyte matrix technology of living, with the kaolin fine powder 700～910 ℃ of roastings, react with acidic substance (mainly being hydrochloric acid) then, having made mean pore size is the sour modified kaolin of 2～4 nanometers, and this acid carclazyte of living has active surface and pore distribution preferably, has increased oily cracking ability at the bottom of the tower, improved selectivity, the preventing from heavy metal ability strengthens.US4,836, the temperature of 913 roasting kaolins is brought up to more than 1000 ℃, react with NaOH again, having prepared specific surface is 150～350 meters squared per gram, and pore volume is the alkali modification kaolin of 0.3～1.0 milliliter/gram, adopts this modified kaolin as support of the catalyst, can increase reactive behavior effectively, improve anti-Ni, the V pollutant performance of catalyzer.CN1,186,105A adopts the component of sour modified kaolin as hydrocarbon cracking catalyzer, and anti-pollution of vanadium ability is obviously strengthened.CN1,195,014A 850～920 ℃ of roastings, handles kaolin with inorganic monoprotic acid and diprotic acid, prepared the modified kaolin of pore distribution in 5～20 nanometers, and is very effective to catalytic cracking reaction.
For the application of aluminum oxide in cracking catalyst, US4,010,116, US4,206,085 and CN1,098,130A utilizes sour molten aluminum oxide to have certain adhesive property and active characteristics, adopt the mineral acid treatment aluminum oxide to make the oxidation aluminic acid molten, mix with other catalyst component as binding agent, mixed serum carries out spraying drying, can improve catalyst strength, regulate active.CN1,008,974 and CN1,083,512 provides the technology that adopts phosphorus-containing alumina to prepare catalytic cracking catalyst, and aluminum oxide is handled through phosphide in advance, with the composite catalyzer of making of other component, has improved gasoline selective and preventing from heavy metal pollution ability.
Have lot of advantages though the above patent adopts soda acid modified argil to assign to improve performance such as matrix pore structure as matrix group, have etching apparatus and modified technique complicated problems; The molten aluminum oxide of acid has adhesive property and certain activity preferably, but there be the etching problem of acid to equipment, acid treatment simultaneously makes all or part of fusion in hole of aluminum oxide self, make and help the middle macropore ratio minimizing that the stock oil macromole enters, the catalyst substrates pore structure can not improve, and easily makes cracking reaction coke selectivity variation; Technology with aluminum oxide passes through phosphide Processing of Preparation catalyzer in advance makes complex process.
Summary of the invention
The purpose of this invention is to provide that a kind of technology is fairly simple, pore structure and cracking reaction selectivity improve and have cracking catalyst of certain anti-nickel performance and preparation method thereof.
Catalyzer of the present invention is formed (being benchmark with the catalyst weight) by following component:
(1) macroporous aluminium oxide 5～60% in, best 10～40%;
(2) zeolite 5～60%, and best 15～40%;
(3) binding agent 5～40%, and best 10～20%;
(4) clay 5～85%, and best 10～65%.
In the catalyzer of the present invention, middle macroporous aluminium oxide is meant boehmite, pseudo-boehmite and at the dewatered product below 900 ℃, the aluminum oxide average pore diameter is greater than 3 nanometers.
Zeolite in the catalyzer of the present invention is meant that NaY, NaX are through the various zeolites after the modification, as Y zeolite, the X zeolite of REY, REX, REHY, USY, REUSY and various high silica alumina ratios, ZSM type zeolite, one or more in the β zeolite; Binding agent is meant silica-alumina gel, silicon sol, aluminium colloidal sol, sial complex sol, aluminum phosphate colloidal sol, phosphaljel, sour molten pseudo-boehmite or their mixture in the catalyzer of the present invention; Catalyzer medium clay soil of the present invention is meant that kaolin, wilkinite, polynite, sepiolite etc. can be used as the various clays of catalyst component.
Catalyzer of the present invention can be made by following method: middle macroporous aluminium oxide component is directly mixed in required ratio with other component, fully stirs, and spray shaping behind the homogeneous through overcuring, washing, drying, is made the catalytic cracking catalyst that contains zeolite.In preparation process, also can add phosphide, make catalyzer further improve resistive connection charcoal ability.
Compared with the prior art the present invention has the following advantages: because middle macroporous aluminium oxide component do not need in advance through the molten processing of peracid, thereby simplified Preparation of catalysts technology, avoided the corrosion of acid base pair equipment, simultaneously, catalyst slurry fluid solid content height, single still treatment capacity is big, catalyzer yield height.Middle macroporous aluminium oxide can improve the hole structural property of catalyzer, regulates catalyst activity, and the catalyzer heavy oil conversion performance is strengthened, and gasoline and coke selectivity obviously improve, and the ability of preventing from heavy metal nickel is strengthened.
Embodiment
Following example will the invention will be further described, but do not limit the present invention.
(1) used analysis test method:
1. specific surface: thermal desorption chromatography
2. pore volume: carbon tetrachloride method.
3. total acid content: NH
3-TPD method.
4. acid: the IR spectrography of pyridine adsorption.
5. pore size distribution: adopt Omnisorp 360 full-automatic absorption instrument, sample determination vacuum tightness is less than 01333 pascal, and the sample pretreatment temperature is 350 ℃, 4 hours degassing time.
6. catalyst selectivity: heavy oil micro anti-evaluation.
(2) the used places of origin of raw materials and specification
1. kaolin: China Kaolin Co., Ltd produces, aluminum oxide 42.5 heavy %, quartzy 3.5 heavy %, kaolinite 86 heavy %; Sepiolite: Yi County, Hebei province sepiolite development corporation, Ltd. produces, granularity 0.3mm.
2. aluminium colloidal sol: Catalyst Factory of Lanzhou Petrochemical Company production, Al
2O
3Content 24.56 heavy %, the Al/Cl mol ratio is 1.24; Silicon sol: Dalian Inst of Chemicophysics, Chinese Academy of Sciences produces, SiO
2Content 27.0 heavy %.
3.USY zeolite: self-control, Na
2O content 3.5 heavy %, lattice constant is 2.450～2.456 nanometers; REHY zeolite: Na
2O content 1.2 heavy %, RE
2O
3Content 5.7 heavy %, lattice constant is 2.464 nanometers; REY zeolite: Na
2O content 3.1 heavy %, RE
2O
3Content 15.5 heavy %, lattice constant is 2.472 nanometers; ZSM-5: igloss 3.0 heavy %, silica alumina ratio 300, Fudan University in Shanghai production.USY zeolite, REHY zeolite, REY zeolite are Catalyst Factory of Lanzhou Petrochemical Company production.
4. pseudo-boehmite: alumina content is 65.0 heavy %, specific surface 284 meters squared per gram, and 0.42 milliliter/gram of pore volume, pore size distribution is more concentrated, and average pore diameter is greater than 3 nanometers (seeing accompanying drawing 1), and the Shandong alumina producer is produced; Boehmite: the heavy % of alumina content 84.0, specific surface 46 meters squared per gram, 0.50 milliliter/gram of pore volume, pore radius distributes mainly at 4～60 nanometers (seeing accompanying drawing 1), German Condea inorganic chemical product company industrial goods.
5. ammonium chloride, ammonium phosphate: industrial goods.
Embodiment 1～8
With quantitatively middle macroporous aluminium oxide, zeolite, binding agent, clay, deionized water thorough mixing, stirred spray drying forming behind the homogeneous 2 hours.With thus obtained microsphere 450 ℃ of roastings 0.5 hour.Get 1 kilogram of roasting microballoon, add 10 kilograms of deionized waters and 0.225 kilogram of ammonium chloride, 75 ℃ of following agitator treatings 20 minutes, filter the back and add ammonium phosphate (making the catalyzer phosphorus content is 1.0 heavy %) and 10 kilograms of deionized waters, 75 ℃ of following agitator treatings 10 minutes, filtration drying promptly got the catalyzer of the embodiment of the invention 1～8.Table 1 has provided embodiment 1～8 catalyzer, and each is formed and consumption.
Each forms table 1 embodiment 1～8 catalyzer and consumption
Comparative Examples 1～4
Compare with embodiment 1～8, do not adopt pseudo-boehmite, boehmite when being Preparation of Catalyst, and the kaolin consumption increases.Other treatment condition make the catalyzer of Comparative Examples 1～4 with embodiment 1～8.Table 2 has provided Comparative Examples 1～4 catalyzer, and each is formed and consumption.
Each forms table 2 Comparative Examples 1～4 catalyzer and consumption
Test and evaluation:
(1) embodiment 1,2 gained catalyzer and Comparative Examples 1 gained catalyzer are carried out the pore size distribution analytical test, the pore size distribution test result is seen accompanying drawing 2 and table 3, among the figure, the pore size distribution of embodiment 1 gained catalyzer is a curve A, and the pore size distribution of embodiment 2 gained catalyzer is that the pore size distribution of curve B, Comparative Examples 1 gained catalyzer is curve F.
Table 3 pore size distribution test result
| Catalyzer | Add aluminum oxide | The specific surface meters squared per gram of φ＞2 nanoporouss | Pore volume milliliter/the gram of φ＞2 nanoporouss |
| Embodiment 1 | Pseudo-boehmite | ????48.8 | ????0.124 |
| Embodiment 2 | Boehmite | ????49.8 | ????0.146 |
| Comparative Examples 1 | Do not have | ????41.2 | ????0.117 |
By accompanying drawing 2 and table 3 as seen, embodiment 1, the pore size distribution of 2 gained catalyzer is notch cuttype, more meet the pore structure design requirements of residual oil catalytic cracking catalyzer, (φ＞2 nanometers) specific surface area of macropore in the catalyzer and pore volume are all than Comparative Examples 1 gained catalyzer height, illustrate that the middle macroporous aluminium oxide that adds truly has effect preferably to improving the matrix pore structure, this part hole can make catalyst substrates form open-celled structure, improve the accessibility of reactant and catalyst active center, and improve the stripping performance of catalyzer, thereby help the conversion of heavy oil, help the diffusion of reactant and product molecule simultaneously, reduce carbon deposit.
(2) catalytic performance test of catalyzer: embodiment 1～8 and Comparative Examples 1～4 gained catalyzer in advance after handling 10 hours under 800 ℃, 100% water vapor conditions, are carried out cracking reaction performance evaluation on miniature heavy-oil catalytic agent evaluation device.Reaction raw materials is a tower petrochemical industry wax oil, 482 ℃ of temperature of reaction, air speed 16 hours
-1, agent weight of oil ratio is 3.0, evaluation result is listed in the table 4.
The catalytic performance test of table 4 embodiment 1～8 and Comparative Examples 1～4 gained catalyzer
By the result in the table 4 as seen, compare with forming close reference catalyst, catalyzer gasoline productive rate height provided by the invention, coke yield is low, and heavy oil conversion performance strengthens, and gasoline and coke selectivity obviously improve.
(3) the anti-nickel contamination performance of catalyzer
Nickelous nitrate is dissolved in the distilled water, moves into volumetric flask and be mixed with certain density solution.Pipette a certain amount of nickel solution, be diluted to certain volume, make catalyzer just all moistening; Be impregnated into contaminating fluid on the catalyzer equably, regularly fully stir, placed 16 hours, then 110 ℃ of dryings 4 hours, in 540 ℃ of roastings 4 hours, make embodiment 1,2 gained catalyzer and Comparative Examples 1 gained catalyzer pollute the metallic nickel of 6000 microgram/grams respectively again, on the miniature heavy-oil catalytic agent evaluation device catalyzer after polluting is being estimated, evaluation method is the same, and evaluation result is listed in the table 5.
The little anti-performance of table 5 different catalysts heavy oil
By the result in the table 5 as seen, compare with contaminated Comparative Examples 1 catalyzer, heavy oil conversion rate height, the yield of gasoline height of embodiment 1,2 catalyzer that polluted equally, and coke yield is low, illustrates that catalyzer provided by the invention has anti-preferably nickel performance.
Description of drawings
Fig. 1 is the graph of pore diameter distribution of the used pseudo-boehmite of embodiments of the invention, boehmite, and Fig. 2 is the graph of pore diameter distribution of embodiment 1,2 and Comparative Examples 1 gained catalyzer.
Claims (9)
1. a catalytic cracking catalyst is characterized in that with the catalyst weight being benchmark, and this catalyzer contains middle macroporous aluminium oxide 5～60%, zeolite 5～60%, binding agent 5～40%, the clay 5～85% that average pore diameter is not less than 3 nanometers.
2. catalyzer according to claim 1 is characterized in that with the catalyst weight being benchmark, and this catalyzer contains middle macroporous aluminium oxide 10～40%, zeolite 15～40%, binding agent 10～20%, clay 10～6 5% that average pore diameter is not less than 3 nanometers.
3. catalyzer according to claim 1 and 2, macroporous aluminium oxide is meant that average pore diameter is not less than the boehmite of 3 nanometers, pseudo-boehmite and at the dewatered product below 900 ℃ in it is characterized in that.
4. catalyzer according to claim 1 and 2 is characterized in that zeolite is selected from one or more in faujusite, ZSM type zeolite, the β zeolite.
5. catalyzer according to claim 4 is characterized in that faujusite is meant that NaY, NaX are through the various zeolites after the modification, as Y zeolite, the X zeolite of REY, REX, REHY, USY, REUSY and high silica alumina ratio.
6. catalyzer according to claim 1 and 2 is characterized in that described faujusite is meant that NaY, NaX are through the various zeolites after the modification, as Y zeolite, the X zeolite of REY, REX, REHY, USY, REUSY and high silica alumina ratio.
7. catalyzer according to claim 1 is characterized in that binding agent comprises silica-alumina gel, silicon sol, aluminium colloidal sol, sial complex sol, aluminum phosphate colloidal sol, phosphaljel, sour molten pseudo-boehmite or the mixture between them.
Catalyzer according to claim 1 is characterized in that clay comprises kaolin, wilkinite, polynite, sepiolite.
9. the described Preparation of catalysts method of claim 1 is characterized in that middle macroporous aluminium oxide component and other component are directly mixed back spray shaping in required ratio, passes through roasting, washs, is drying to obtain catalyzer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02103907 CN1209442C (en) | 2002-02-07 | 2002-02-07 | Catalytic cracking catalyst and its prepn |
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|---|---|---|---|
| CN 02103907 CN1209442C (en) | 2002-02-07 | 2002-02-07 | Catalytic cracking catalyst and its prepn |
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| CN1209442C CN1209442C (en) | 2005-07-06 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100377782C (en) * | 2004-09-15 | 2008-04-02 | 中国石油化工股份有限公司 | Hydrocarbon cracking catalyst and its use |
| CN101745373B (en) * | 2008-11-28 | 2012-05-23 | 中国石油化工股份有限公司 | Catalytic cracking additive |
| CN105728014A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN106890664A (en) * | 2015-12-18 | 2017-06-27 | 中国石油天然气股份有限公司 | A kind of preparation method of catalytic cracking catalyst |
| CN106925336A (en) * | 2017-05-08 | 2017-07-07 | 青岛惠城环保科技股份有限公司 | A kind of Resid Fcc Catalyst and preparation method thereof |
| CN107297203A (en) * | 2016-04-14 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of binding agent and its application and catalytic cracking catalyst and preparation method thereof |
| CN107303479A (en) * | 2016-04-19 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of phosphorus Alumina gel and its preparation method and application and catalytic cracking catalyst and preparation method thereof |
| CN107433170A (en) * | 2016-05-26 | 2017-12-05 | 中国石油化工股份有限公司 | Magnalium colloidal sol and its preparation method and application and catalytic cracking catalyst and preparation method thereof |
| US11084024B2 (en) | 2015-08-05 | 2021-08-10 | Petrochina Company Limited | Method for modifying molecular sieve and a catalytic cracking catalyst containing the molecular sieve |
| WO2023056863A1 (en) | 2021-10-09 | 2023-04-13 | 中国石油化工股份有限公司 | Catalytic cracking catalyst having rich mesoporous structure and preparation method therefor |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100377782C (en) * | 2004-09-15 | 2008-04-02 | 中国石油化工股份有限公司 | Hydrocarbon cracking catalyst and its use |
| CN101745373B (en) * | 2008-11-28 | 2012-05-23 | 中国石油化工股份有限公司 | Catalytic cracking additive |
| CN105728014B (en) * | 2014-12-11 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of preparation method of catalytic cracking catalyst |
| CN105728014A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst |
| US11084024B2 (en) | 2015-08-05 | 2021-08-10 | Petrochina Company Limited | Method for modifying molecular sieve and a catalytic cracking catalyst containing the molecular sieve |
| CN106890664A (en) * | 2015-12-18 | 2017-06-27 | 中国石油天然气股份有限公司 | A kind of preparation method of catalytic cracking catalyst |
| CN106890664B (en) * | 2015-12-18 | 2020-06-09 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN107297203B (en) * | 2016-04-14 | 2019-10-25 | 中国石油化工股份有限公司 | A kind of binder and its application and catalytic cracking catalyst and preparation method thereof |
| CN107297203A (en) * | 2016-04-14 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of binding agent and its application and catalytic cracking catalyst and preparation method thereof |
| CN107303479A (en) * | 2016-04-19 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of phosphorus Alumina gel and its preparation method and application and catalytic cracking catalyst and preparation method thereof |
| CN107303479B (en) * | 2016-04-19 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of phosphorus Aluminum sol and its preparation method and application and catalytic cracking catalyst and preparation method thereof |
| CN107433170A (en) * | 2016-05-26 | 2017-12-05 | 中国石油化工股份有限公司 | Magnalium colloidal sol and its preparation method and application and catalytic cracking catalyst and preparation method thereof |
| CN107433170B (en) * | 2016-05-26 | 2019-11-15 | 中国石油化工股份有限公司 | Magnalium colloidal sol and its preparation method and application and catalytic cracking catalyst and preparation method thereof |
| CN106925336A (en) * | 2017-05-08 | 2017-07-07 | 青岛惠城环保科技股份有限公司 | A kind of Resid Fcc Catalyst and preparation method thereof |
| WO2023056863A1 (en) | 2021-10-09 | 2023-04-13 | 中国石油化工股份有限公司 | Catalytic cracking catalyst having rich mesoporous structure and preparation method therefor |
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|---|---|
| CN1209442C (en) | 2005-07-06 |
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