CN1388214A - Prepn of fluid cracking catalyst - Google Patents

Prepn of fluid cracking catalyst Download PDF

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Publication number
CN1388214A
CN1388214A CN 01118436 CN01118436A CN1388214A CN 1388214 A CN1388214 A CN 1388214A CN 01118436 CN01118436 CN 01118436 CN 01118436 A CN01118436 A CN 01118436A CN 1388214 A CN1388214 A CN 1388214A
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heavy
catalyzer
cracking catalyst
add
molecular sieve
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CN1195581C (en
Inventor
邱中红
张万虹
王振波
李才英
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

During the preparation of fluidizing and cracking catalyst, the cracking catalyst component mixture containing alumina from beta-alumina trihydrate and in 1.5-55 wt% of dried and recovered. The catalyst thus prepared has bulk specific weight and pore volume capable of being regulated in a wide range. Compared with catalyst prepared through available technological process, the catalyst of the present invention has differential reaction activity to light oil raised by 2-11 units and differential reaction activity to heavy oil raised by 0.8-12.9 units.

Description

A kind of preparation method of fluid cracking catalyst
The invention relates to a kind of preparation method of fluid cracking catalyst.
Catalytic cracking is an important oil refining process, and catalytic cracking unit is occupied critical role in petroleum refining industry.In recent years,, have higher requirement, promptly have stronger heavy oil macromole cracking ability and better lightweight oil selectivity for cracking catalyst along with improving constantly of stock oil slag-mixing amount.
In order to guarantee the wear strength of fluid cracking catalyst, simultaneously in order to improve its reaction preference, the composite aluminum base binding agent that binding agent used in the prior art mainly contains aluminium sol adhesive, pseudo-boehmite binding agent, comprehensive silicon al binder, be made up of aluminium colloidal sol and pseudo-boehmite etc.
USP4010116 discloses a kind of preparation method of fluidized catalytic cracking catalyst, this method proposes to make binding agent with the pseudo-boehmite of peptization attitude, prepared catalyzer has higher intensity and hydrothermal stability, can be applicable to cracking unit mitigation or harsh regenerative operation condition.Though pseudo-boehmite has certain activity and adhesive property, but the employing of the high silica alumina ratio molecular sieve little along with structure cell, that the acid sites number is few, hydrogen transfer activity is low, the add-on of molecular sieve obviously increases in the catalyzer, adhesive property to binding agent proposes requirements at the higher level, and pseudo-boehmite can not satisfy this requirement fully like this.
The preparation method of the disclosed catalytic cracking catalyst of USP4542118, be to make binding agent with the better aluminium colloidal sol of adhesive property, to improve the abrasion resistance of catalyzer, but, because aluminium colloidal sol itself is inert, with aluminium colloidal sol is that the support of the catalyst cracking activity of adhesive preparation is low, and cracking is macromolecular limited in one's ability, and it can influence the cracking performance of catalyzer as single binding agent.
CN1098130A has disclosed a kind of catalytic cracking catalyst that contains the composite aluminum base binding agent, said composite aluminum base binding agent integrates certain cracking activity of pseudo-boehmite and the sol bonded performance of aluminium is good, green coke is few characteristics, makes catalyzer at aspects such as activity, intensity, yield of light oil significant improvement arranged.
The objective of the invention is on the basis of existing technology, a kind of preparation method of new cracking catalyst is provided, have better heavy oil cracking activity and light oil selectivity through the catalyzer of this method preparation.
The preparation method of fluid cracking catalyst provided by the invention will contain the cracking catalyst component mixture drying of clay, aluminum oxide and molecular sieve, and reclaim the catalyzer make, wherein contain the heavy % of 1.5-55 in this cracking catalyst component, the aluminum oxide of the heavy % of preferred 5-30 from β-alumina trihydrate.
In the preparation method of fluid cracking catalyst provided by the present invention, contain the clay of the heavy % of 20-50 in the said cracking catalyst component, the heavy % of 5-60 is from the aluminum oxide of pseudo-boehmite and/or aluminium colloidal sol, the molecular sieve of the heavy % of 15-50 and with RE 2O 3The rare earth component of the heavy % of meter 0-12.
In preparation method provided by the present invention, said aluminum oxide in the cracking catalyst component, its precursor also has pseudo-boehmite and/or aluminium colloidal sol except β-alumina trihydrate, the mixture of wherein preferred aluminium pseudo-boehmite and aluminium colloidal sol.When aluminum oxide precursor during from the mixture of pseudo-boehmite and aluminium colloidal sol, with Al 2O 3The weight meter under the normal condition, should make the content of pseudo-boehmite be higher than the content of aluminium colloidal sol.
Among the preparation method provided by the invention, said clay is selected from one or more in the catalyzer common clay that comprises kaolin, halloysite, polynite, diatomite, wilkinite, sepiolite, wherein preferred kaolin and/or polynite.
Among the preparation method provided by the invention, said molecular screening one or more in Y zeolite, MFI structure molecular screen, mercerising molecular sieve and beta-molecular sieve; Said Y zeolite is selected from one or more among HY, REY, REHY, USY, REUSY and the DASY.
Among the preparation method provided by the invention, less demanding to β-alumina trihydrate material purity, in containing the hydrated aluminum oxide mixture of different crystalline phases, with Al 2O 3Meter, the heavy % in its content＞60 gets final product.β-alumina trihydrate can add in arbitrary step of the aqueous slurry of preparation catalyst component and/or its precursor, for example all is applicable to the present invention with the process that adds β-alumina trihydrate after pseudo-boehmite and/or aluminium colloidal sol mix after clay slurry forms or at clay slurry.
Among the preparation method provided by the invention, the said catalyst component mixture exsiccant process that will contain can be carried out according to the drying means of routine, as oven dry or spraying drying.In general, said drying temperature can be from room temperature to 800 ℃, and drying temperature commonly used is a room temperature to 650 ℃.
The preparation method of fluid cracking catalyst provided by the invention has following characteristics:
(1) preparation method provided by the invention can some physical properties of regulating catalyst also can keep good abrasion resistance in a big way.For example, bulk density is 0.60～0.80 grams per milliliter, and pore volume is 0.25～0.45 a milliliter/gram, and abrasion index AI was less than 2% hour -1
(2) through the catalyzer of method preparation provided by the invention, compare, have better lightweight oil selectivity and stronger heavy oil macromole cracking ability with the catalyzer that prior art is prepared.For example, light oil microactivity improves 2-11 unit (example 7); Under same reaction temperature and agent-oil ratio cracking conditions, micro-activity of heavy oil improves 0.8-12.9 unit, and during product distributed, the yield of gasoline exceeded 4-12.2 percentage point, and＞330 ℃ heavy oil component has reduced 1.1-10.5 percentage point (example 8).
Following example will the present invention is described further, but not thereby limiting the invention.
In example, each component concentration of catalyzer is got by calculating, and the content of rare earth oxide is meant the part that is deposited on separately in the preparation process on the carrier, does not comprise the content of rare earth in the molecules of active components sieve.
Prepared catalyzer in the example, its bulk density, pore volume and abrasion index adopt " petrochemical complex analytical procedure (RIPP test method) " respectively, and (Yang Cuiding, Gu Kanying compile, 1990, Science Press) middle RIPP31-90, RIPP28-90 that records and narrates and RIPP29-90 method mensuration.
Comparative Examples 1
The explanation of this Comparative Examples is the preparation process of the contrast medium of composite aluminum base binding agent according to the CN1098130A method with pseudo-boehmite and aluminium colloidal sol.
Take by weighing kaolin (dry basis, Suzhou kaolin industry company produces) 100 grams, make kaolin slurry with 430 ml deionized water, 8.5 milliliters of concentrated hydrochloric acids that add 36 heavy %, stirring mixes slurries, add pseudo-boehmite (in aluminum oxide, Shandong Aluminum Plant produces) 50 grams, add aluminium colloidal sol then (in aluminum oxide, Qilu Petrochemical company catalyst plant is produced) 16.7 grams, stir after 0.5 hour, be warming up to 60 ℃, aging 1 hour, at last, adding USY (dry basis, lattice constant are 2.447 nanometers, and Qilu Petrochemical company catalyst plant is produced) 55.6 grams stirs.Above-mentioned slurries 110 ℃ of oven dry down, are obtained comparative catalyst DB1.
Comparative Examples 2
The explanation of this Comparative Examples is the preparation process of the contrast medium of binding agent according to the USP4010116 method with the pseudo-boehmite.
Get kaolin 100 grams, make kaolin slurry with 490 ml deionized water, 14.3 milliliters of concentrated hydrochloric acids that add 36 heavy %, stirring mixes slurries, adds pseudo-boehmite 66.7 grams, stirs after 0.5 hour, be warming up to 60 ℃, aging 1 hour, last, add super stable molecular sieve USY55.6 gram and stir.Above-mentioned slurries 110 ℃ of oven dry down, are obtained comparative catalyst DB2.
Comparative Examples 3
The explanation of this Comparative Examples is the preparation process of the contrast medium of binding agent according to the USP4542118 method with aluminium colloidal sol.
Take by weighing kaolin 100 grams, make kaolin slurry with 230 ml deionized water, add aluminium colloidal sol 66.7 grams, restir added molecular sieve USY55.6 gram and stirs after 0.5 hour.Above-mentioned slurries 110 ℃ of oven dry down, are obtained comparative catalyst DB3.
Example 1
Take by weighing kaolin 88.9 gram, make kaolin slurry, add 4.3 milliliters of the concentrated hydrochloric acids of 36 heavy % with 430 ml deionized water, stirring mixes slurries, add pseudo-boehmite 20 grams, add β-alumina trihydrate (in hydrated aluminum oxide, Shandong Aluminum Plant produces) 30 grams, add aluminium colloidal sol 16.7 grams then, stir after 1 hour, be warming up to 60 ℃, aging 1 hour, at last, adding super stable molecular sieve USY55.6 gram stirs.Above-mentioned slurries 110 ℃ of oven dry down, are obtained adopting the catalyzer C1 of method preparation provided by the invention.
Example 2
Take by weighing kaolin 88.9 grams, make kaolin slurry, add β-alumina trihydrate 50 grams, add aluminium colloidal sol 16.7 grams then, stir after 1 hour with 430 ml deionized water, last, add super stable molecular sieve USY55.6 gram and stir.Above-mentioned slurries 110 ℃ of oven dry down, are obtained adopting the catalyzer C2 of method preparation provided by the invention.
Comparative catalyst DB1, the DB2 of the catalyzer C1 of example 1 and 2 preparations and C2 and Comparative Examples 1,2 and 3 preparations and the composition of DB3 are listed in the table 1.
Table 1
Example number The catalyzer numbering Catalyzer is formed, heavy %
????USY Kaolin Aluminum oxide
Intend thin water Beta-alumina Aluminium colloidal sol
????1 ????C1 ????26.3 ????42.1 ????9.5 ????14.2 ????7.9
????2 ????C2 ????26.3 ????42.1 ????0 ????23.7 ????7.9
Comparative Examples 1 ????DB1 ????25.0 ????45.0 ????22.5 ????0 ????7.5
Comparative Examples 2 ????DB2 ????25.0 ????45.0 ????30.0 ????0 ?????0
Comparative Examples 3 ????DB3 ????25.0 ????45.0 * ????0 ????0 ????30.0
Example 3
Get 3.85 kilograms of kaolin and 0.5 kilogram of (dry basis of polynite, Zhong Xiang county, Hubei iron ore factory produces), add in 16 liters of deionized waters, pulled an oar 2 hours, add 0.5 kilogram of β-alumina trihydrate again, stirred 0.5 hour, then, add 2.0 kilograms of aluminium colloidal sols, continue to stir 0.5 hour, add 700 milliliters of re chlorides, at last, (lattice constant is 2.467 nanometers, and rare earth oxide content is 7.8 heavy % to add 2.5 kilograms in REHY type molecular sieve, Qilu Petrochemical company catalyst plant is produced) and ZSM-5 molecular sieve 0.5 kilogram (silica alumina ratio is 60, Qilu Petrochemical company catalyst plant product) stir.With above-mentioned slurries spraying drying, obtain catalyzer C3.
Example 4
Get 0.5 kilogram of 2.85 kilograms of kaolin and polynite, add in 20 liters of deionized waters, stir after 2 hours, 108 milliliters of concentrated hydrochloric acids that add 36 heavy %, add 0.5 kilogram of pseudo-boehmite, be warming up to 60 ℃, aging after 1 hour, add 1 kilogram of β-alumina trihydrate, slurries are mixed, add 1.5 kilograms of aluminium colloidal sols then, continue to stir after 0.5 hour, add 700 milliliters of re chlorides, add 3 kilograms of rare earth hydrogen Y zeolites and ZSM-5 molecular sieve at last and stir for 0.5 kilogram.With above-mentioned slurries spraying drying, obtain catalyzer C4.
Example 5
Get 0.5 kilogram of 2.35 kilograms of kaolin and polynite, make kaolin slurry with 20 kilograms of deionized waters, add 1 kilogram of β-alumina trihydrate, stir after 1 hour, add 154 milliliters of the concentrated hydrochloric acids of 36 heavy %, add 1 kilogram of pseudo-boehmite, be warming up to 60 ℃, aging after 1 hour, add 1.5 kilograms of aluminium colloidal sols then, add 700 milliliters of re chlorides again, add 3 kilograms of rare earth hydrogen Y zeolites and ZSM-5 molecular sieve at last and stir for 0.5 kilogram.With above-mentioned slurries spraying drying, obtain catalyzer C5.
Example 6
Get 0.5 kilogram of 1.65 kilograms of kaolin and polynite, make kaolin slurry, then, add 700 milliliters of 1.5 kilograms of β-alumina trihydrates and re chlorides with 9 liters of deionized waters; In 10 liters of deionized waters, add 1.2 kilograms of pseudo-boehmites, add 190 milliliters of the concentrated hydrochloric acids of 36 heavy % again, be warming up to 60 ℃, aging 1 hour, add 1.5 kilograms of aluminium colloidal sols then, slurries are mixed.At last 3 kilograms of rare earth hydrogen Y zeolites and 0.5 kilogram of slurries of ZSM-5 molecular sieve and above-mentioned kaolin slurry, binding agent slurries are stirred, spraying drying obtains catalyzer C6 then.
The composition of catalyzer C3, C4, C5 and C6 that example 3,4,5 and 6 is prepared is listed in table 2, and physical properties is listed in table 3.
Table 2
Example The catalyzer numbering Catalyzer is formed, heavy %
??REHY ????+ ??ZSM-5 Kaolin+polynite Aluminum oxide ???RE 2O 3
Intend thin water Beta-alumina Aluminium colloidal sol
????3 ????C3 ????30 ????43.5 ????0 ????5 ????20 ????1.5
????4 ????C4 ????35 ????33.5 ????5 ????10 ????15 ????1.5
????5 ????C5 ????35 ????28.5 ????10 ????10 ????15 ????1.5
????6 ????C6 ????35 ????21.5 ????12 ????15 ????15 ????1.5
Table 3
Example The catalyzer numbering The bulk density grams per milliliter Pore volume milliliter/gram Abrasion index % hour -1
????3 ????C3 ????0.8 ??????0.30 ?????1.1
????4 ????C4 ????0.74 ??????0.36 ?????1.7
????5 ????C5 ????0.68 ??????0.39 ?????1.5
????6 ????C6 ????0.61 ??????0.43 ?????1.8
Example 7
This example illustrates the comparison of the light oil microactivity of the catalyzer C1 of method provided by the invention preparation and C2 and contrast medium DB1, DB2 and DB3.
Light oil microactivity is estimated on the small stationary bed bioreactor.
With prepared catalyzer in 100% water vapour in 800 ℃ aging 4 hours, be broken into diameter again and be 420～841 microns particle.
The catalyzer loading amount is 5.0 grams, and reaction raw materials is that boiling range is that (density 20 ℃ the time is 0.8419 gram per centimeter for 235～337 ℃ straight distillation light diesel oil 3), reaction conditions is 460 ℃ of temperature, weight hourly space velocity is 16 hours -1, agent weight of oil ratio is 3.2.
Light oil microactivity is listed in the table 4.
Table 4
The catalyzer numbering Light oil microactivity
????C1 ????70
????C2 ????73
????DB1 ????65
????DB2 ????68
????DB3 ????62
As can be seen from Table 4, than the catalyzer of prior art for preparing, light oil microactivity has improved 2-11 unit.
Example 8
This example illustrates the comparison of the micro-activity of heavy oil of the catalyzer C1 of method provided by the invention preparation and C2 and contrast medium DB1, DB2 and DB3.
With prepared catalyzer in 100% water vapour in 800 ℃ aging 4 hours, be broken into diameter again and be 420～841 microns particle.
Little anticatalyzer loading amount 4.0 grams of heavy oil, raw material is boiling range 227-475 ℃ a decompressed wax oil, this raw material oil properties is listed table 5 in.
The little anti-condition of heavy oil is: 482 ℃ of temperature of reaction, weight hourly space velocity are 16 hours -1, agent weight of oil ratio is 4.0.
Reaction product is made up of gas chromatographic analysis, forms according to product to calculate micro-activity of heavy oil by following formula.
Micro-activity of heavy oil=(C 5Following gas yield+C 5~ 221 ℃ of gasoline output+coke outputs)/charging total amount * 100%=C 5Following gas yield+C 5~ 221 ℃ of gasoline yield+coke yields.
Reaction product is formed and micro-activity of heavy oil is listed in the table 6.
Table 5
The stock oil title Decompressed wax oil
Density (20 ℃), gram per centimeter 3 ????0.8652
Viscosity, millimeter 2/ second ????14.58
Asphalt content, heavy % ????0.686
Conradson carbon residue, heavy % ????0.04
Boiling range, ℃
Initial boiling point ????227
??????????10％ ????289
??????????50％ ????389
??????????90％ ????446
??????????95％ ????458
Do ????475
Table 6
The catalyzer numbering Micro-activity of heavy oil Product distributes, heavy %
???C 5Following gas ??C 5～221 ℃ of gasoline Coke ??＞330℃
????C1 ????77.4 ????14.0 ????62.1 ????1.30 ????5.20
????C2 ????79.4 ????14.2 ????63.9 ????1.30 ????5.60
????DB1 ????73.2 ????14.6 ????57.2 ????1.40 ????7.20
????DB2 ????76.6 ????16.3 ????58.1 ????2.20 ????6.70
????DB3 ????66.5 ????13.3 ????51.7 ????1.50 ????15.70
As can be seen from Table 6, than the catalyzer of prior art for preparing, the micro-activity of heavy oil of the catalyzer of method preparation provided by the present invention has improved 0.8-12.9 unit, during product distributes, the yield of gasoline exceeds 4-12.2 percentage point, and＞330 ℃ heavy oil component has reduced 1.1-10.5 percentage point.

Claims (7)

1, a kind of preparation method of fluid cracking catalyst, it is the cracking catalyst component mixture drying that will contain clay, aluminum oxide and molecular sieve, and reclaim the catalyzer of making, it is characterized in that containing in this catalyst component the aluminum oxide of the heavy % of 1.5-55 from β-alumina trihydrate.
2, in accordance with the method for claim 1, it is characterized in that containing in the described cracking catalyst component aluminum oxide of the heavy % of 5-30 from β-alumina trihydrate.
3, according to claim 1 or 2 described methods, it is characterized in that containing in the said cracking catalyst component clay of the heavy % of 20-50, the heavy % of 5-60 is from the aluminum oxide of pseudo-boehmite and/or aluminium colloidal sol, the molecular sieve of the heavy % of 15-50 and with RE 2O 3The rare earth component of the heavy % of meter 0-12.
4, in accordance with the method for claim 1, it is characterized in that described clay is selected from one or more in the catalyzer common clay that comprises kaolin, halloysite, polynite, diatomite, wilkinite, sepiolite.
5, in accordance with the method for claim 4, it is characterized in that described clay is kaolin and/or polynite.
6, in accordance with the method for claim 1, it is characterized in that described molecular screening one or more in Y zeolite, MFI structure molecular screen, mercerising molecular sieve and beta-molecular sieve.
7, in accordance with the method for claim 6, it is characterized in that described Y zeolite is selected from one or more among HY, REY, REHY, USY, REUSY or the DASY.
CNB011184361A 2001-05-30 2001-05-30 Prepn of fluid cracking catalyst Expired - Fee Related CN1195581C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006010316A1 (en) * 2004-07-29 2006-02-02 China Petroleum & Chemical Corporation A cracking catalyst for hydrocarbons and its preparation
CN100443181C (en) * 2004-04-29 2008-12-17 中国石油化工股份有限公司 Process for preparing cracking catalyst for hydrocarbons containing molecular sieves
CN100478421C (en) * 2004-08-31 2009-04-15 中国石油化工股份有限公司 Catalytic cracking adjuvant and its preparing method
CN100478420C (en) * 2004-09-15 2009-04-15 中国石油化工股份有限公司 Catalytic cracking aid and its preparing method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100443181C (en) * 2004-04-29 2008-12-17 中国石油化工股份有限公司 Process for preparing cracking catalyst for hydrocarbons containing molecular sieves
WO2006010316A1 (en) * 2004-07-29 2006-02-02 China Petroleum & Chemical Corporation A cracking catalyst for hydrocarbons and its preparation
US9175230B2 (en) 2004-07-29 2015-11-03 China Petroleum & Chemical Corporation Cracking catalyst and a process for preparing the same
CN100478421C (en) * 2004-08-31 2009-04-15 中国石油化工股份有限公司 Catalytic cracking adjuvant and its preparing method
CN100478420C (en) * 2004-09-15 2009-04-15 中国石油化工股份有限公司 Catalytic cracking aid and its preparing method

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