CN1112247C - Process for preparing catalyst containing small-grain Y-molecular sieve - Google Patents
Process for preparing catalyst containing small-grain Y-molecular sieve Download PDFInfo
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- CN1112247C CN1112247C CN99112565A CN99112565A CN1112247C CN 1112247 C CN1112247 C CN 1112247C CN 99112565 A CN99112565 A CN 99112565A CN 99112565 A CN99112565 A CN 99112565A CN 1112247 C CN1112247 C CN 1112247C
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Abstract
The present invention relates to a method for preparing a catalytic cracking catalyst using Y type molecular sieves with small crystal particles whose particle diameters are from 200 nm to 800 nm as active components. Compared with catalysts prepared by conventional Y type molecular sieves, the catalyst containing the Y molecular sieves with the small crystal particles has the advantages of higher activity, higher liquid gas yield, higher gasoline yield, higher conversion rate of heavy oil and excellent product selectivity.
Description
That the present invention relates to is catalytic cracking catalyst and the preparation method who contains small crystal grain Y-shaped molecular sieve, specifically, prepares catalytic cracking catalyst with the modification small crystal grain Y-shaped molecular sieve as active component exactly.
At present, the Y zeolite in the common catalytic cracking catalyst, the average grain diameter of its crystal surpasses 1000nm, and the duct is longer, and diffusional resistance is big, easily makes product because of long aromatisation of the time of staying and carbon deposit coking, and cracking activity is low, poor selectivity.The micro channel of small crystal grain molecular sieve shortens, and increase in the activated centre, and the activated centre disperses more, make the big molecule of heavy oil easier to be approaching, and the easy stripping of reaction afterproduct, coke yield descends significantly, therefore, the small crystal grain molecular sieve catalyst shows higher cracking activity and cracking selectivity.
Though the synthetic and application study of small crystal grain molecular sieve is very active, and CA, API and patent database are retrieved, and does not find to prepare as active component with the modification small crystal grain Y-shaped molecular sieve report of catalytic cracking catalyst.
At the shortcoming of big crystal grain molecular sieve catalyst and the advantage that small crystal grain molecular sieve showed, we handle the small crystal grain NaY molecular sieve of suitable particle size range through conventional modification, Y zeolites such as the little crystal grain USY of modification, ReY, ReHY, HY have been obtained respectively, combine with carrier, bonding agent, made the catalytic cracking catalyst that contains small crystal grain Y-shaped molecular sieve.Show that through evaluation the combination property of small crystal grain Y-shaped molecular sieve catalytic cracking catalyst obviously is better than big crystal grain molecular sieve catalyst.
The process that preparation provided by the present invention contains the catalytic cracking catalyst of small crystal grain Y-shaped molecular sieve comprises:
1, the conventional modification of small crystal grain NaY molecular sieve is handled
A is 200nm～800nm with particle diameter, and the NaY molecular sieve that is preferably 500nm～700nm joins and contains ReCl
3Solution in, under 90 ℃～100 ℃ temperature, stirred 1 hour, filter, oven dry, at 650 ℃ of roasting 1h; Repeat said process, make the ReY molecular sieve of modification.
B is 200nm～800nm with particle diameter, and the NaY molecular sieve that is preferably 500nm～700nm joins and contains ReCl
3In the solution of ammonium sulfate, under 90 ℃～100 ℃ temperature, stirred 1 hour, filter, oven dry, at 650 ℃ of roasting 1h; Repeat said process, make the ReHY molecular sieve of modification.
C is 200nm～800nm with particle diameter, and the NaY molecular sieve that is preferably 500nm～700nm joins in the solution of sulfur acid ammonium, stirs 1 hour filtration, oven dry, roasting under 90 ℃～100 ℃ temperature; Repeat said process, make the HY molecular sieve of modification.
D is 200nm～800nm with particle diameter, and the NaY molecular sieve that is preferably 500nm～700nm joins in the solution of sulfur acid ammonium, stirs 1 hour under 90 ℃～100 ℃ temperature, filters, dries, and super stabilizing is handled; Repeat said process, make the USY molecular sieve of modification.
E is 200nm～800nm with particle diameter, and the NaY molecular sieve that is preferably 500nm～700nm joins and contains ReCl
3In the solution of ammonium sulfate, under 90 ℃～100 ℃ temperature, stirred 1 hour, filter, oven dry, super stabilizing is handled; Repeat said process, make the ReUSY molecular sieve of modification.
2, active constituent making beating:
In the little crystal grain Modified Zeolite Y of step 1 preparation one or more are added to the water as the activity of such catalysts component, and 20～80 ℃ of temperature, under best 30～60 ℃, making beating obtains uniform molecular sieve pulp; In molecular sieve pulp, add earth solution and magnesium sulfate, make that rare earth oxide accounts for 1～10% of molecular sieve weight in final catalyst, magnesia accounts for 0.1～5% of molecular sieve weight, adjusting pH value with ammoniacal liquor is 5～6.5, making beating was handled 0.5～1.5 hour, made the active constituent slurries of modification.
3, preparation catalyst matrix slurries
The carrier of catalyst is kaolin, Al
2O
3, in the carclazyte one or more, binding agent is one or more in boehmite, aluminium colloidal sol, Ludox, the silicon-aluminum sol.Carrier, binding agent and water are mixed into slurries, and adjusting pH value with hydrochloric acid is 2～5, is preferably 3～4,30～90 ℃ of temperature, under best 50～80 ℃, static aging 0.5～2.5 hour, best 1～2 hour, makes uniform matrix slurries.
4, Preparation of Catalyst
The slurries that step 2,3 is obtained mix, and carry out spray drying forming.
Catalyst detergent after the moulding, drying promptly get catalyst prod.
The maximum characteristics of prepared catalyst of the present invention are: as the Y zeolite of catalyst activity component, its particle size range is far smaller than the particle diameter of conventional molecular sieve at 200nm～800nm.The activity of small crystal grain Y-shaped molecular sieve catalytic cracking catalyst, liquefied gas yield, gasoline yield, heavy oil transformation rate all are improved, and have shown good product selectivity.
The following examples will be further described the preparation process that contains the small crystal grain Y-shaped molecular sieve catalytic cracking catalyst.
Embodiment
A makes homogeneous slurry with kaolin slurry 850Kg (solid content 35%), boehmite 450Kg (solid content 40%), aluminium colloidal sol 150Kg (aluminium content 11%～12%), 500Kg water, adjusting pH value with hydrochloric acid is 3.5, under 72 ℃ of temperature, burin-in process 1 hour makes matrix component slurries.
B gets the little crystal grain ReHY molecular sieve 250Kg that little crystal grain USY molecular sieve 300Kg that particle diameter is 650nm and particle diameter be 650nm and joins in the 1500Kg water, stirs, and adds earth solution 200Kg (ReCl
350g/l), solid magnesium sulfate 20Kg, adjusting pH value with ammoniacal liquor is 6.0, making beating was handled 1 hour, made modified active component slurries.
C mixes the slurries of A, B preparation, stirs 1 hour, and spray-drying makes catalyst.
After the catalyst detergent that D makes C, the drying, promptly get catalyst prod (C-1).
Comparative Examples
Little crystal grain USY molecular sieve among the embodiment and ReHY molecular sieve equivalent are replaced with conventional USY and the ReHY molecular sieve of producing of industry,, make catalyst prod (C-2) according to the method for preparing catalyst of embodiment.
Table 1 is catalyst C-1 and the evaluation result of C-2 in the riser of laboratory.
Appreciation condition: catalyst loading amount 8Kg, 500 ℃ of reaction temperatures, 675 ℃ of regeneration temperatures, oil inlet quantity 800g/h, time of contact 1.3s, oil ratio 5.
The product of table 1 catalyst distributes
Annotate: 1 light oil=gasoline+diesel oil 2 total liquid receipts=gasoline+diesel oil+liquefied gas
| Catalyst | C-1 | C-2 |
| Dry gas (weight %) | 1.82 | 1.63 |
| Liquefied gas (weight %) | 7.35 | 6.94 |
| Gasoline (weight %) | 44.64 | 40.44 |
| Diesel oil (weight %) | 26.99 | 28.64 |
| Heavy oil (weight %) | 16.26 | 19.97 |
| Light oil (weight %) | 71.63 | 69.09 |
| Total liquid is received (%) | 78.98 | 76.02 |
| Conversion ratio (%) | 83.74 | 80.03 |
3 conversion ratios=(100-heavy oil) %
As can be seen from Table 1, compare with conventional molecular sieve catalyst, contain the catalytic cracking catalyst of small crystal grain Y-shaped molecular sieve: heavy oil reduces, and shows to have high cracking activity; Have better liquid product yield, show and improved its selectivity.
Claims (3)
1, a kind of is the FCC catalyst of active component with the modification small crystal grain Y-shaped molecular sieve, comprise carrier, binding agent, active component, carrier is a kaolin, aluminium oxide, kind in the carclazyte or several, bonding agent is a boehmite, aluminium colloidal sol, Ludox, in the silicon-aluminum sol one or more, it is characterized in that described active component is the active component of modification, comprise modification small crystal grain Y-shaped molecular sieve and rare earth, magnesium salts, oxide in rare earth and magnesium, rare earth oxide weight accounts for 1～10% of modification small crystal grain Y-shaped molecular sieve weight, MgO weight accounts for 0.1～5% of modification small crystal grain Y-shaped molecular sieve weight, the active component of modification is 10～60% of a catalyst weight in the catalyst, and described modification small crystal grain Y-shaped molecular sieve is to be that the particle diameter that the small crystal grain NaY molecular sieve of 200～800nm obtains through modification is the little crystal grain USY of modification of 200～800nm with particle size range, ReY, ReHY, in the Y zeolites such as HY one or more.
2, catalyst according to claim 1, the particle size range that it is characterized in that described small crystal grain NaY molecular sieve is 500～700nm.
3, a kind ofly prepare claim 1 described to be the method for the FCC catalyst of active component with the modification small crystal grain Y-shaped molecular sieve, to it is characterized in that comprising the steps:
(1) is the conventional modification procedure such as small crystal grain NaY molecular sieve process ion-exchange, roasting or super stabilizing processing of 200～800nm with particle size range, obtains Y zeolites such as the little crystal grain USY of modification, ReY, ReHY, HY respectively;
(2) with one or more modification small crystal grain Y-shaped molecular sieves of obtaining in the step (1) as the activity of such catalysts component, and active component and water be mixed into slurries;
(3) slurries that step (2) obtained with rare earth and magnesium salts carry out the modification processing, make that rare earth oxide weight accounts for 1～10% of modification small crystal grain Y-shaped molecular sieve weight in the final catalyst, MgO weight accounts for 0.1～5% of modification small crystal grain Y-shaped molecular sieve weight, obtains the active component slurries of modification;
(4) carrier and bonding agent and water are mixed into slurries, and adjusting pH value with hydrochloric acid is 2～5, and is static aging under 30～90 ℃ temperature, obtains the matrix slurries;
(5) slurries that step (3) and (4) are obtained are mixed into uniform slurries, spray drying forming in proportion;
(6) after the material washing that step (5) is obtained, the drying, promptly obtain catalyst prod.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112565A CN1112247C (en) | 1999-11-17 | 1999-11-17 | Process for preparing catalyst containing small-grain Y-molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112565A CN1112247C (en) | 1999-11-17 | 1999-11-17 | Process for preparing catalyst containing small-grain Y-molecular sieve |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1296860A CN1296860A (en) | 2001-05-30 |
| CN1112247C true CN1112247C (en) | 2003-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99112565A Expired - Fee Related CN1112247C (en) | 1999-11-17 | 1999-11-17 | Process for preparing catalyst containing small-grain Y-molecular sieve |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332765C (en) * | 2004-04-29 | 2007-08-22 | 中国石油化工股份有限公司 | Process for preparing cracking catalyst for hydrocarbons containing molecular sieves |
| CN101284243B (en) * | 2007-04-12 | 2011-04-20 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| 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 |
| CN101745373B (en) * | 2008-11-28 | 2012-05-23 | 中国石油化工股份有限公司 | Catalytic cracking additive |
| CN101745417B (en) * | 2008-11-28 | 2011-12-21 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN102974388B (en) * | 2011-09-06 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
| CN103157506B (en) | 2011-12-15 | 2015-09-23 | 中国石油天然气股份有限公司 | High-light-yield heavy oil catalytic cracking catalyst and preparation method thereof |
| US11053129B2 (en) | 2017-02-21 | 2021-07-06 | China Petroleum & Chemical Corporation | Magnesium modified Y-type molecular sieve, preparation thereof and catalyst comprising the same |
| CN109305686B (en) * | 2017-07-28 | 2020-10-13 | 中国石油天然气股份有限公司 | Preparation method of Y-type molecular sieve |
| CN109569713B (en) * | 2017-09-28 | 2021-12-17 | 中国石油化工股份有限公司 | Catalytic material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1122111A (en) * | 1994-02-09 | 1996-05-08 | 巴西石油公司 | Process for preparing a modified Y-zeolite |
| US5646082A (en) * | 1993-06-24 | 1997-07-08 | Cosmo Research Institute | Crystalline aluminosilicate, process for producing the same, and catalyst employing the same for catalytic cracking of hydrocarbon oil |
-
1999
- 1999-11-17 CN CN99112565A patent/CN1112247C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5646082A (en) * | 1993-06-24 | 1997-07-08 | Cosmo Research Institute | Crystalline aluminosilicate, process for producing the same, and catalyst employing the same for catalytic cracking of hydrocarbon oil |
| CN1122111A (en) * | 1994-02-09 | 1996-05-08 | 巴西石油公司 | Process for preparing a modified Y-zeolite |
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