CN103007981A - Residual oil catalytic cracking catalyst - Google Patents
Residual oil catalytic cracking catalyst Download PDFInfo
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- CN103007981A CN103007981A CN2011102804649A CN201110280464A CN103007981A CN 103007981 A CN103007981 A CN 103007981A CN 2011102804649 A CN2011102804649 A CN 2011102804649A CN 201110280464 A CN201110280464 A CN 201110280464A CN 103007981 A CN103007981 A CN 103007981A
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Abstract
The present invention relates to a residual oil catalytic cracking catalyst, which comprises, by weight, 15-35% of a REUSY molecular sieve, 5-25% of a silicon-magnesium glue, 0-5% of a MFI structure shape selective molecular sieve, 15-25% of boehmite or diaspore, 2-10% of an inorganic oxide binder, and 20-60% of clay. The catalytic cracking catalyst has characteristics of large matrix specific surface area, suitable acidity, metal nickel and vanadium passivation, excellent heavy oil conversion capacity, and catalytic cracking coke yield reducing.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst, further say the Resid Fcc Catalyst that reduces slurry oil and coke yield about a kind of.
Background technology
Catalytic cracking is the core process device that China's petrol and diesel oil is produced.At present, gasoline, the diesel oil 30% or more of China more than 70% comes catalytic cracking.Carbon residue less than the crude oil of 10 heavy % account for world's crude oil reserve less than 30%, the overwhelming majority in the world oil reserves is the crude oil with poor quality of high carbon residue, high content of beary metal.Along with the external interdependency of China's oil improves constantly, China's catalytic cracking needs further to improve the slag oil cracking ability.
Because the residual oil molecule much larger than the orifice diameter of Y zeolite, can't enter in the molecular sieve pore passage by molecular sieve cracking, thereby the cracking of residual oil molecule need to carry out in stromal surface, and Resid Fcc Catalyst need to have large matrix specific area.
Conventional catalytic cracking catalyst matrix specific area is usually less than 100m
2/ g is many at 70～100m such as the common catalyst substrates specific areas such as catalytic cracking catalyst LBO-16, CGP-C
2/ g.
In order to prepare the catalytic cracking catalyst with large matrix specific area, W. R. Grace ﹠ Co has proposed to adopt the host material with bigger serface silica in CN101636227A, and the catalyst substrates specific area that obtains reaches 182m
2/ g.
CN101745373A reports a kind of assistant for calalytic cracking, it is characterized by two kinds of aluminium oxide that contain stepped pore distribution, and a kind of is macroporous aluminium oxide, and a kind of is little porous aluminum oxide.CN1978593B has reported a kind of catalytic cracking catalyst, it is characterized by catalyst and contains a kind of mesoporous material with structure of similar to thin diaspore, and this mesoporous material is salic, silica and metal oxide, such as magnesia or rare earth oxide etc.CN1322917C has reported a kind of mesoporous silicon aluminum and preparation method thereof, and aluminium all is four-coordination in this mesoporous silicon aluminum.CN1964785A has reported a kind of FCC method of using medium-pore catalyst, this medium-pore catalyst do not contain 10～
The hole, mesopore concentrates on 40～
Summary of the invention
The purpose of this invention is to provide a kind of Resid Fcc Catalyst, this catalyst has large matrix specific area and suitable acidity, can decrease slurry oil yield and coke yield.
A kind of Resid Fcc Catalyst of the present invention, this catalytic cracking catalyst by weight 100%, REUSY molecular sieve by 15～35%, 5～25% silicon magnesium glue, 0～5% MFI structure shape-selective molecular sieve, a diaspore of 15～25,2～10% inorganic oxide binder and 20～60% Clay composition.
A kind of Resid Fcc Catalyst of the present invention, this catalytic cracking catalyst by weight 100%, REUSY molecular sieve by 15～25%, 15～25% silicon magnesium glue, a diaspore of 15～20%, 3～9% aluminium colloidal sol or Ludox, 0～5% MFI structure shape-selective molecular sieve and the kaolin of 25～45 heavy % form.
Described silicon magnesium glue content of magnesia is 10～40% of silicon magnesium glue weight.
Described silicon magnesium glue content of magnesia is preferably 15～35% of silicon magnesium glue weight.
Said silicon magnesium glue fluorine content is 0.1～3% of silicon magnesium glue weight.
Said REUSY molecular sieve rare earth oxide weight content 8～10%, cell parameter 24.55～
Described rare earth oxide is one or both the mixture in lanthana, cerium oxide, the samarium oxide.
Described clay is selected from one or more the mixture in kaolin, galapectite and the sepiolite.
Described inorganic oxide binder is selected from one or more the mixture in aluminium colloidal sol, Ludox, the Alusil.
Catalytic cracking catalyst provided by the invention adds the water making beating via raw material, obtains finished product through spray-drying, roasting again.
Catalytic cracking catalyst provided by the invention, because large matrix specific area, suitable acidity and the function of passive metal nickel and vanadium, can significantly catalytic cracking coke yield, the heavy oil conversion performance that has simultaneously excellence.
The specific embodiment
Embodiment 1
According to the fluorine-containing silicon magnesium glue of United States Patent (USP) 3129189 preparations, the silicon magnesium glue content of magnesia 21.0 heavy % that obtain, fluorine content 2.2 heavy %, specific area 528m
2/ g, pore volume 0.54ml/g.In reactor, add 2000 gram water, under vigorous stirring, add successively again silicon magnesium glue 120 grams and (press the butt note, together lower), 150 gram REUSY (catalyst Chang Ling branch company products, rare earth oxide 9 heavy %), 36 gram aluminium colloidal sols are (in aluminium oxide, aluminium sol alumina content 21 heavy %, catalyst Chang Ling branch company provides), and 96 gram boehmites (in aluminium oxide, alumina content 70 heavy %, Shandong Aluminum Plant's product), 198 gram kaolin (Suzhou China Kaolin Co., Ltd product, igloss 30 heavy %), hydrochloric acid 30 grams of 20 heavy %, stir spray-drying after 30 minutes, 100～150 ℃ of spray-drying exhaust temperatures, then 350～450 ℃ of roastings are 30 minutes, washing, obtain product A after the drying.
Catalyst A specific area (SA) 313m
2/ g, its mesostroma specific area (MSA) 178m
2/ g, content of magnesia 4.1 heavy %, rare earth oxide 2.2 heavy %.
Embodiment 2
According to the fluorine-containing silicon magnesium glue of United States Patent (USP) 3129189 preparations, the silicon magnesium glue content of magnesia 21.0 heavy % that obtain, fluorine content 2.2 heavy %, specific area 528m
2/ g, pore volume 0.54ml/g.In reactor, add 2000 gram water, under vigorous stirring, add successively again silicon magnesium glue 120 grams and (press the butt note, together lower), 150 gram REUSY (catalyst Chang Ling branch company products, rare earth oxide 9 heavy %), 36 gram aluminium colloidal sols are (in aluminium oxide, aluminium sol alumina content 21 heavy %, catalyst Chang Ling branch company provides), and 96 gram boehmites (in aluminium oxide, alumina content 70 heavy %, Shandong Aluminum Plant's product), 198 gram galapectites (Cenxi, Hunan kaolin company product, igloss 30 heavy %), technical hydrochloric acid 30 grams of 20 heavy %, stir spray-drying after 30 minutes, 100～150 ℃ of spray-drying exhaust temperatures, then 350～450 ℃ of roastings are 30 minutes, washing, obtain product B after the drying.
Catalyst B specific area 333m
2/ g, its mesostroma specific area 198m
2/ g, content of magnesia 4.1 heavy %, rare earth oxide 2.2 heavy %.
Embodiment 3
According to the fluorine-containing silicon magnesium glue of United States Patent (USP) 3129189 preparations, the silicon magnesium glue content of magnesia 16.0 heavy % that obtain, fluorine content 2.0 heavy %, specific area 512m
2/ g, pore volume 0.65ml/g.In reactor, add 2000 gram water, under vigorous stirring, add successively again silicon magnesium glue 150 grams and (press the butt note, together lower), 114 gram REUSY (catalyst Chang Ling branch company products, rare earth oxide 9 heavy %), 30 gram aluminium colloidal sols are (in aluminium oxide, aluminium sol alumina content 21 heavy %, catalyst Chang Ling branch company provides), and 90 gram boehmites (in aluminium oxide, alumina content 70 heavy %, Shandong Aluminum Plant's product), 216 gram galapectites (Cenxi, Hunan kaolin company product, igloss 30 heavy %), technical hydrochloric acid 27 grams of 20 heavy %, stir spray-drying after 30 minutes, 100～150 ℃ of spray-drying exhaust temperatures, then 350～450 ℃ of roastings are 30 minutes, washing, obtain products C after the drying.
Catalyst C specific area 319m
2/ g, its mesostroma specific area 217m
2/ g, content of magnesia 4.0 heavy %, rare earth oxide 1.7 heavy %.
Embodiment 4
According to the fluorine-containing silicon magnesium glue of United States Patent (USP) 3129189 preparations, the silicon magnesium glue content of magnesia 16.0 heavy % that obtain, fluorine content 2.0 heavy %, specific area 512m
2/ g, pore volume 0.65ml/g.In reactor, add 2000 gram water, under vigorous stirring, add successively again silicon magnesium glue 132 grams and (press the butt note, together lower), 90 gram REUSY (catalyst Chang Ling branch company products, rare earth oxide 9 heavy %), 30 gram aluminium colloidal sols are (in aluminium oxide, aluminium sol alumina content 21 heavy %, catalyst Chang Ling branch company provides), and 90 gram boehmites (in aluminium oxide, alumina content 70 heavy %, Shandong Aluminum Plant's product), 258 gram galapectites (Cenxi, Hunan kaolin company product, igloss 30 heavy %), technical hydrochloric acid 27 grams of 20 heavy %, stir spray-drying after 30 minutes, 100～150 ℃ of spray-drying exhaust temperatures, then 350～450 ℃ of roastings are 30 minutes, washing, obtain product D after the drying.
Catalyst D specific area 288m
2/ g, its mesostroma specific area 207m
2/ g, content of magnesia 3.4 heavy %, rare earth oxide 1.3 heavy %.
Embodiment 5
According to the fluorine-containing silicon magnesium glue of United States Patent (USP) 3129189 preparations, the silicon magnesium glue content of magnesia 16.0 heavy % that obtain, fluorine content 2.0 heavy %, specific area 512m
2/ g, pore volume 0.65ml/g.In reactor, add 2000 gram water, under vigorous stirring, add successively again silicon magnesium glue 132 grams and (press the butt note, together lower), 90 gram REUSY (catalyst Chang Ling branch company products, rare earth oxide 9 heavy %), 6 gram RPSA molecular sieves (catalyst is built long branch company product), 30 gram aluminium colloidal sols (in aluminium oxide, aluminium sol alumina content 21 heavy %, catalyst Chang Ling branch company provides), 90 gram boehmites are (in aluminium oxide, alumina content 70 heavy %, Shandong Aluminum Plant's product), 252 gram galapectite (Cenxi, Hunan kaolin company products, igloss 30 heavy %), technical hydrochloric acid 27 grams of 20 heavy % stir spray-drying after 30 minutes, 100～150 ℃ of spray-drying exhaust temperatures, then 350～450 ℃ of roastings are 30 minutes, washing, obtain product E after the drying.
Catalyst E specific area 290m
2/ g, its mesostroma specific area 206m
2/ g, content of magnesia 3.4 heavy %, rare earth oxide 1.3 heavy %.
Embodiment 6
According to the fluorine-containing silicon magnesium glue of United States Patent (USP) 3129189 preparations, the silicon magnesium glue content of magnesia 16.0 heavy % that obtain, fluorine content 2.0 heavy %, specific area 512m
2/ g, pore volume 0.65ml/g.In reactor, add 2000 gram water, under vigorous stirring, add successively again silicon magnesium glue 90 grams and (press the butt note, together lower), 120 gram REUSY (catalyst Chang Ling branch company products, rare earth oxide 9 heavy %), 36 gram aluminium colloidal sols are (in aluminium oxide, aluminium sol alumina content 21 heavy %, catalyst Chang Ling branch company provides), and 96 gram boehmites (in aluminium oxide, alumina content 70 heavy %, Shandong Aluminum Plant's product), 258 gram galapectites (Cenxi, Hunan kaolin company product, igloss 30 heavy %), technical hydrochloric acid 30 grams of 20 heavy %, stir spray-drying after 30 minutes, 100～150 ℃ of spray-drying exhaust temperatures, then 350～450 ℃ of roastings are 30 minutes, washing, obtain product F after the drying.
Catalyst F specific area 285m
2/ g, its mesostroma specific area 177m
2/ g, content of magnesia 2.4 heavy %, rare earth oxide 1.8 heavy %.
Comparative Examples
In reactor, add 2000 gram water, under vigorous stirring, add successively again 150 gram REUSY (catalyst Chang Ling branch company products, rare earth oxide 9 heavy %), 36 gram aluminium colloidal sols are (in aluminium oxide, aluminium sol alumina content 21 heavy %, catalyst Chang Ling branch company provides), 96 gram boehmites are (in aluminium oxide, alumina content 70 heavy %, Shandong Aluminum Plant's product), 318 gram kaolin (Suzhou China Kaolin Co., Ltd product, igloss 30 heavy %), technical hydrochloric acid 30 grams of 20 heavy %, stir spray-drying after 30 minutes, 100～150 ℃ of spray-drying exhaust temperatures, then 350～450 ℃ of roastings are 30 minutes, washing, obtain product DB after the drying.
Catalyst DB specific area 211m
2/ g, its mesostroma specific area 76m
2/ g, rare earth oxide 2.2 heavy %.
The physico-chemical property of the auxiliary agent of above-described embodiment and Comparative Examples preparation sees Table 1.
Table 1. specific surface area of catalyst, rare earth oxide and content of magnesia
| The catalyst numbering | RE 2O 3，m％ | MgO，m％ | SA，m 2/g | MSA，m 2/g |
| A | 2.2 | 4.1 | 313 | 178 |
| B | 2.2 | 4.1 | 333 | 198 |
| C | 1.7 | 4.0 | 319 | 217 |
| D | 1.3 | 3.4 | 288 | 207 |
| E | 1.3 | 3.4 | 290 | 206 |
| F | 1.8 | 2.4 | 285 | 177 |
| DB | 2.2 | 0 | 211 | 76 |
Embodiment 8
Present embodiment illustrates the fixed fluidized bed evaluation result of auxiliary agent provided by the invention.
Feedstock oil is long celebrating petrochemical industry decompression residuum, and feedstock oil character sees Table 2
Table 2. feedstock oil character
| Character | Value |
| Density (20 ℃) (kg.m -1) | 933.3 |
| Carbon residue, heavy % | 9.8 |
| Saturated hydrocarbons, heavy % | 50.7 |
| Aromatic hydrocarbons, heavy % | 38.7 |
| Colloid, heavy % | 6.2 |
| Asphalitine, heavy % | 4.4 |
Before the evaluating catalyst through aging 12 hours of 800 ℃, 100% steam, 500 ℃ of reaction temperatures, air speed 30h
-1, oil ratio is 7.0.
Evaluation result sees Table 3.
Table 3
| Catalyst | A | B | C | D | E | F | DB |
| Dry gas | 3.6 | 3.7 | 3.6 | 3.2 | 3.3 | 3.5 | 4.5 |
| Liquefied gas | 13.3 | 13.1 | 12.3 | 12.0 | 14.2 | 12.6 | 13.2 |
| Gasoline | 44.1 | 44.0 | 38.0 | 33.3 | 31.6 | 39.6 | 40.1 |
| Diesel oil | 23.7 | 24.2 | 30.7 | 34.0 | 33.4 | 27.4 | 18.1 |
| Heavy oil | 8.3 | 7.7 | 7.5 | 9.9 | 9.8 | 8.9 | 13.3 |
| Coke | 7.0 | 7.3 | 7.8 | 7.6 | 7.7 | 8.0 | 10.8 |
| Conversion ratio | 68.0 | 68.1 | 61.8 | 56.1 | 56.8 | 63.7 | 68.6 |
| Total liquid is received * | 81.1 | 81.3 | 81.0 | 79.3 | 79.2 | 79.6 | 71.4 |
* total liquid is received and is gasoline+diesel oil+liquefied gas
From the fixed fluidized bed evaluation result that table 3 provides, the catalyst of embodiment preparation is compared with contrast medium, not only can significantly reduce the slurry oil productive rate, and can reduce simultaneously coke yield and dry gas yied.
Claims (8)
1. Resid Fcc Catalyst, it is characterized in that: this catalytic cracking catalyst by weight 100%, REUSY molecular sieve by 15～35%, 5～25% silicon magnesium glue, 0～5% MFI structure shape-selective molecular sieve, a diaspore of 15～25,2～10% inorganic oxide binder and 20～60% Clay composition.
2. Resid Fcc Catalyst, it is characterized in that: this catalytic cracking catalyst by weight 100%, REUSY molecular sieve by 15～25%, 15～25% silicon magnesium glue, a diaspore of 15～20%, 3～9% aluminium colloidal sol or Ludox, 0～5% MFI structure shape-selective molecular sieve and the kaolin of 25～45 heavy % form.
3. according to claim 1,2 described Resid Fcc Catalysts, it is characterized in that: described silicon magnesium glue content of magnesia is 10～40% of silicon magnesium glue weight.
4. according to claim 1,2 described Resid Fcc Catalysts, it is characterized in that: described silicon magnesium glue content of magnesia is 15～35% of silicon magnesium glue weight.
5. according to claim 1,2 described Resid Fcc Catalysts, it is characterized in that: said silicon magnesium glue fluorine content is 0.1～3% of silicon magnesium glue weight.
6. according to claim 1,2 described Resid Fcc Catalysts, it is characterized in that: said REUSY molecular sieve rare earth oxide weight content 8～10%, cell parameter 24.55～
Said rare earth oxide is one or both the mixture in lanthana, cerium oxide, the samarium oxide.
7. according to claim 1,2 Resid Fcc Catalyst, it is characterized in that: described clay is selected from one or more the mixture in kaolin, galapectite and the sepiolite.
8. according to claim 1,2 described Resid Fcc Catalysts, it is characterized in that: described inorganic oxide binder is selected from one or more the mixture in aluminium colloidal sol, Ludox, the Alusil.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107081170A (en) * | 2017-05-08 | 2017-08-22 | 青岛惠城环保科技股份有限公司 | A kind of preparation method of catalytic pyrolysis propylene catalyst |
| CN116212940A (en) * | 2023-03-06 | 2023-06-06 | 青岛惠城环保科技集团股份有限公司 | Preparation method of catalytic cracking catalyst with excellent coke and dry gas selectivity |
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| US3129189A (en) * | 1960-06-08 | 1964-04-14 | Grace W R & Co | Process for preparing a silica-magnesia-fluorine hydrocarbon cracking catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107081170A (en) * | 2017-05-08 | 2017-08-22 | 青岛惠城环保科技股份有限公司 | A kind of preparation method of catalytic pyrolysis propylene catalyst |
| CN116212940A (en) * | 2023-03-06 | 2023-06-06 | 青岛惠城环保科技集团股份有限公司 | Preparation method of catalytic cracking catalyst with excellent coke and dry gas selectivity |
| CN116212940B (en) * | 2023-03-06 | 2024-06-07 | 青岛惠城环保科技集团股份有限公司 | Preparation method of catalytic cracking catalyst with excellent coke and dry gas selectivity |
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Application publication date: 20130403 |