CN103203229A - Preparation method and application of fluidized catalytic cracking catalyst aid - Google Patents
Preparation method and application of fluidized catalytic cracking catalyst aid Download PDFInfo
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- CN103203229A CN103203229A CN2013101103744A CN201310110374A CN103203229A CN 103203229 A CN103203229 A CN 103203229A CN 2013101103744 A CN2013101103744 A CN 2013101103744A CN 201310110374 A CN201310110374 A CN 201310110374A CN 103203229 A CN103203229 A CN 103203229A
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- catalytic cracking
- catalyst
- catalyst aid
- fluidized catalytic
- kaolin microsphere
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Abstract
The invention discloses a preparation method and an application of a fluidized catalytic cracking catalyst aid. The method comprises the following steps of: performing ammonium ion exchange on kaolin microspheres serving as a substrate; treating the kaolin microspheres by using alkaline matters; and finally adding alkaline earth metal oxides such as magnesium, calcium and the like and roasting, thereby obtaining the fluidized catalytic cracking catalyst aid. The synthesized catalyst aid can be used for lowering the carbon deposition quantity and improving the diesel oil production rate during the fluidized catalytic cracking. By utilizing the obtained catalyst aid, the great modification to the existing device is not required; and the low cost is achieved. Most importantly, the obtained catalyst aid can well adapt to heavy oil and can be used for obviously lowering the coke quantity and the diesel fuel increase rate thereof.
Description
Technical field
The present invention relates to a kind of preparation method and application of fluidized catalytic cracking catalyst auxiliary agent, this catalyst promoter can adapt to the catalyzed cracking processing that contains heavy distillate, residual oil on the basis that does not change existing apparatus, coking amount promotes the diesel component yield simultaneously on the reduction catalyst.
Background technology
Catalytic cracking technology occupies very consequence in the petroleum refining industry of China, this has close relationship with crude oil in China character.China overwhelming majority's crude oil all belongs to mink cell focus, is catalytic cracking process so enough capacity to reprocess must be arranged, and could effectively utilize crude oil, and suitable catalytic cracking catalyst is played the part of crucial role in whole process.Simultaneously, exhausted day by day along with some high-quality light petroleum resources from world wide, heavy raw oil is increasing in the shared ratio of catalytic cracking process, this problem the most direct bringing is exactly that cracking process is finished carbon deposition quantity increase on the rear catalyst, makes the thermic load of regenerator strengthen.Moreover, because the economy that diesel oil has, and the maturation of diesel engine technologies that car uses, it is very big to the demand of diesel oil that country is crossed very much by European Union and the U.S. etc., and therefore a lot of oil plants are wanted some diesel oil of producing according to the needs in market more.Conventional flow fluidized catalytic cracking catalytic unit and supporting catalyst thereof are in order to produce gasoline, to hold concurrently and produce diesel oil, therefore need taking some means to reach the purpose of high-yield diesel oil at the beginning of design.Through practice for many years, the means of the high-yield diesel oil that adopts are generally following several now: adopt low activity catalyst, big recycle ratio, low reaction severity, low-conversion etc.
Summary of the invention
The purpose of this invention is to provide a kind of fluidized catalytic cracking catalyst auxiliary agent, be added in the FCC catalyst host according to the certain quality mark, when reducing amount of coke, can improve production of diesel oil.
Another object of the present invention provides a kind of preparation method of fluidized catalytic cracking catalyst auxiliary agent, this method is: kaolin microsphere used alkaline matter to handle before impregnating metal salt precursor body earlier, it is more to make that metals such as magnesium, calcium enter the amount of metal of microsphere surface, dispersion effect is better simultaneously, so that more basic sites to be provided.
A further object of the present invention is the application of the fluidized catalytic cracking catalyst auxiliary agent that provides, and this auxiliary agent is added in fluid catalytic cracking in the FCC catalyst host, can improve production of diesel oil when reducing amount of coke.
The object of the present invention is achieved like this:
A kind of preparation method of fluidized catalytic cracking catalyst auxiliary agent, this method comprises following concrete steps:
Get kaolin microsphere, behind 650～980 ℃ of following roasting 2～6h, with the kaolin microsphere after the roasting as in the alkaline substance solution and 120～185 ℃ of following crystallization 24 hours, filter and take out microballoon, organic matter is removed 450～980 ℃ of following roastings in washing, oven dry back, impregnating metal salting liquid then, oven dry and 450～980 ℃ of following roastings obtains described catalyst promoter; Wherein:
Described alkaline matter is TMAH (TMAOH), TPAOH (TPAOH), tetraethyl ammonium hydroxide (TEAOH), TBAH (TBAOH) or the mixture of any combination wherein;
Described slaine is the nitrate of alkaline-earth metal such as magnesium, calcium or carbonate etc.;
SiO in described alkaline matter and the kaolin microsphere
2Mol ratio be 0.02～0.20;
The mass percent that described slaine accounts for kaolin microsphere is 5%～50%, in order to be 1～5 with the quality of the water of the required adding of slaine wiring solution-forming and the mass ratio of kaolin microsphere.
Auxiliary agent of the present invention is applied in and is added in the fluid catalytic cracking in the FCC catalyst host, can reduce amount of coke and improve production of diesel oil.
The addition that auxiliary agent of the present invention is added in the FCC catalyst host is 1～20% of catalyst host weight.
Kaolin microsphere used in the present invention can contain silicon bonding spray drying forming according to a certain percentage by the former powder of kaolin and water glass solution, Ludox etc., also can buy existing kaolin microsphere on the market, adapts to wide.The microballoon of spray drying forming or commercial kaolin microsphere are through high-temperature roasting, and ammonium ion exchange just can use alkaline matter that it is handled after the roasting again, prepare for introducing alkaline-earth metal such as magnesium, calcium.
Of the present inventionly introduce basic sites at kaolin microsphere, reduced the total acidic site of catalyst, improved the productive rate of diesel oil, simultaneously because the introducing of metals such as magnesium, calcium, can reduce the carbon deposition quantity of catalyst, make the thermic load of regenerator reduce.As catalyst promoter, the present invention does not need conventional device is made very big change, and is with low cost simultaneously, and it is good to the most important thing is simultaneously the adaptability of mink cell focus, and it is obvious to reduce amount of coke and diesel oil thereof increase ratio.
The specific embodiment
Below introduce realization of the present invention and the effect that has in detail by specific embodiment, so that novelty essence of the present invention place to be described better, but but do not constitute restriction to the present invention's practical range.
The evaluation method of catalyst promoter: the catalyst that adds catalyst promoter uses the ACE high level flow fluidized catalytic cracking unit of U.S. Kayser company design to estimate its activity.Main operating condition is: 520 ℃ of reaction temperatures, oil ratio are 5, and the gross mass of catalyst host and auxiliary agent is 9 grams.What feedstock oil and catalyst used is Jinan Refinery FCC apparatus feedstock oil and poising agent thereof.
The rerum natura of Jinan FCC feedstock oil
| Feedstock oil | Jinan FCC |
| Density (20 oC），g/cm 3 | 0.9023 |
| Carbon residue | 3.9 |
| Group composition, wt% | ? |
| Saturated hydrocarbons | 50.62 |
| Aromatic hydrocarbon | 39.51 |
| Colloid | 9.87 |
| Asphalitine | 1.84 |
Embodiment 1
Get the commodity kaolin microsphere, at 830 ℃ of following roasting 2h, take by weighing the microballoon after the 3.003g roasting then, place the TMAOH solution of 1.528 grams, 25 wt%, 175 ℃ of following crystallization 24 hours, the oven dry back was 550 ℃ of following roastings 6 hours, dipping Mg (NO
3)
26H
2The quality of O is 1.170 grams.After 12 hours, oven dry and 900 degrees centigrade of following roastings 2 hours, the sample that obtains is sifted out and is got the 60-400 order and be designated as sample A, adds this auxiliary agent of 10wt% in poising agent, uses the ACE device to estimate, and the result is as follows:
| The catalyst title | Poising agent | Poising agent+sample A |
| Product distributes, wt% | ? | ? |
| Amount of coke | 12.181 | 11.625 |
| Dry gas yied | 2.860 | 2.727 |
| Gasoline yield | 39.459 | 39.526 |
| Diesel yield | 16.140 | 16.330 |
| The liquefied petroleum gas productive rate | 16.583 | 15.684 |
| The mink cell focus productive rate | 12.813 | 14.108 |
Amount of coke has the reduction amount about 0.5 wt% as can be seen from the table, and diesel oil also has the increase about 0.2wt% simultaneously.
Embodiment 2
Similar with embodiment 1, the commodity kaolin microsphere 950 ℃ of following roastings two hours, is got roasting microballoon 3.007 gram, 25 wt% TMAOH solution, 1.512 grams drys and 550 ℃ of following roastings 5 hours adding Mg (NO after 24 hours 175 ℃ of following crystallization
3)
26H
2The quality of O is 1.156 grams, flood after 12 hours, and oven dry was 900 degrees centigrade of following roastings 2 hours, and the sample that obtains sieves and gets the 60-400 order and be designated as sample B, this auxiliary agent of interpolation 10 wt% in poising agent, and the result is as follows after the evaluation of ACE device:
| The catalyst title | Poising agent | Poising agent+sample B |
| Product distributes, wt% | ? | ? |
| Amount of coke | 12.181 | 11.571 |
| Dry gas yied | 2.860 | 2.327 |
| Gasoline yield | 39.459 | 40.203 |
| Diesel yield | 16.140 | 16.373 |
| The liquefied petroleum gas productive rate | 16.583 | 15.581 |
| The mink cell focus productive rate | 12.813 | 13.674 |
Diesel yield increased when also amount of coke reduced as can be seen from table.
Embodiment 3
Take by weighing kaolin microsphere 3.007 grams that it's 2 hours are past 830 ℃ of following roastings, use 1.509 grams, 25 wt% TMAOH to handle, 175 ℃ of following crystallization 24 hours, drying is finished 550 ℃ of following roastings 5 hours, use the original position infusion process to introduce calcium afterwards, the load capacity of calcium nitrate is 20 percent, so add Ca (NO
3)
2 .4H
2The quality of O is 0.883 gram, leave standstill 12 hours after, oven dry back is 550 ℃ of following roastings 5 hours, the sample that the obtains 60-400 order that sieves is labeled as sample C, adds this auxiliary agent of 10 wt% in poising agent, uses the ACE device to estimate, the result is as follows:
| The catalyst title | Poising agent | Poising agent+sample C |
| Product distributes, wt% | ? | ? |
| Amount of coke | 12.047 | 11.827 |
| Dry gas yied | 2.727 | 2.717 |
| Gasoline yield | 41.934 | 41.095 |
| Diesel yield | 16.152 | 16.593 |
| The liquefied petroleum gas productive rate | 15.714 | 15.184 |
| The mink cell focus productive rate | 11.427 | 12.632 |
Amount of coke reduces after adding this auxiliary agent equally as can be seen, and the productive rate of diesel oil has also had raising.
Embodiment 4
Take by weighing 3.004 grams at two hours commodity kaolin microsphere of 830 ℃ of following roastings, place the TEAOH solution of 2.574 gram 25wt%, 175 ℃ of following crystallization 24 hours, the oven dry back was 550 ℃ of following roastings 6 hours, dipping Mg (NO
3)
26H
2The quality of O is 1.392 grams, and the time is 12 hours, and oven dry back is 550 ℃ of following roastings 6 hours, and the sample that obtains is sifted out and got the 60-400 order and be designated as sample D, adds this auxiliary agent of 10 wt% in poising agent, uses the ACE device to estimate, and the result is as follows:
| The catalyst title | Poising agent | Poising agent+sample D |
| Product distributes, wt% | ? | ? |
| Amount of coke | 11.925 | 11.568 |
| Dry gas yied | 2.811 | 2.836 |
| Gasoline yield | 41.639 | 41.507 |
| Diesel yield | 15.602 | 15.749 |
| The liquefied petroleum gas productive rate | 16.581 | 16.379 |
| The mink cell focus productive rate | 11.442 | 11.961 |
Added equally as can be seen after the auxiliary agent, diesel yield increased when carbon deposition quantity reduced.
Comparative Examples 1
Take by weighing 950 ℃ of following roastings and cross 2 hours kaolin microsphere 3.012g, with 1.511 grams, 25 wt% TMAOH solution-treated, 175 ℃ of following crystallization 24 hours, drying was finished 550 ℃ of following roastings.Do not introduce alkali metal, be labeled as sample E, add this auxiliary agent of 10 wt% in poising agent, use the ACE device to estimate, the result is as follows:
| The catalyst title | Poising agent | Poising agent+sample E |
| Product distributes, wt% | ? | ? |
| Amount of coke | 12.229 | 13.173 |
| Dry gas yied | 3.153 | 3.281 |
| Gasoline yield | 40.802 | 40.754 |
| Diesel yield | 15.634 | 15.133 |
| The liquefied petroleum gas productive rate | 16.581 | 16.379 |
| The mink cell focus productive rate | 10.978 | 10.635 |
Under the situation of not introducing alkalinous metal, carbon deposition quantity increases as can be seen, and diesel yield reduces.
Claims (3)
1. the preparation method of a fluidized catalytic cracking catalyst auxiliary agent is characterized in that this method comprises following concrete steps:
Get kaolin microsphere, behind 650～980 ℃ of following roasting 2～6h, with the kaolin microsphere after the roasting as in the alkaline substance solution and 120～185 ℃ of following crystallization 24 hours, filter and take out microballoon, organic matter is removed 450～980 ℃ of following roastings in washing, oven dry back, impregnating metal salting liquid then, oven dry and 450～980 ℃ of following roastings obtains described catalyst promoter; Wherein:
Described alkaline matter is TMAH, TPAOH, tetraethyl ammonium hydroxide, TBAH or the mixture of any combination wherein;
Described slaine is nitrate or the carbonate of magnesium, calcium alkaline-earth metal;
SiO in described alkaline matter and the kaolin microsphere
2Mol ratio be 0.02～0.20;
The mass percent that described slaine accounts for kaolin microsphere is 5%～50%, is 1～5 with the quality of the water of the required adding of slaine wiring solution-forming and the mass ratio of kaolin microsphere.
2. the application of the described catalyst promoter of claim 1 is characterized in that this auxiliary agent is added in the FCC catalyst host in fluid catalytic cracking, the application in reducing amount of coke and raising production of diesel oil.
3. according to the application of the described catalyst promoter of claim 2, it is characterized in that the addition that described catalyst promoter is added in the FCC catalyst host is 1～15% of catalyst host weight.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109694721A (en) * | 2017-10-23 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of macropore kaolinite and its preparation and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872415A (en) * | 2005-05-31 | 2006-12-06 | 北京惠尔三吉绿色化学科技有限公司 | Method for preparing catalytic cracking auxiliary agent of containing ZSM-5 zeolite for productiveness of propylene |
| CN101108734A (en) * | 2006-07-19 | 2008-01-23 | 中国石油大学(北京) | Beta type molecular sieve and method of manufacturing the same |
-
2013
- 2013-04-01 CN CN2013101103744A patent/CN103203229A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872415A (en) * | 2005-05-31 | 2006-12-06 | 北京惠尔三吉绿色化学科技有限公司 | Method for preparing catalytic cracking auxiliary agent of containing ZSM-5 zeolite for productiveness of propylene |
| CN101108734A (en) * | 2006-07-19 | 2008-01-23 | 中国石油大学(北京) | Beta type molecular sieve and method of manufacturing the same |
Non-Patent Citations (1)
| Title |
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| 刘娟娟等: "高岭土的改性及其用于合成分子筛的国内研究进展", 《中外能源》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109694721A (en) * | 2017-10-23 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of macropore kaolinite and its preparation and application |
| CN109694721B (en) * | 2017-10-23 | 2021-01-08 | 中国石油化工股份有限公司 | Macroporous kaolinite and preparation and application thereof |
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Application publication date: 20130717 |