CN103923689B - The method of catalytic cracking sulfur reduction additive and its preparation method and reduction Sulfur Content in Catalytic Cracking Gasoline - Google Patents
The method of catalytic cracking sulfur reduction additive and its preparation method and reduction Sulfur Content in Catalytic Cracking Gasoline Download PDFInfo
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Abstract
The present invention discloses the preparation method of a kind of catalytic cracking sulfur reduction additive, the catalytic cracking sulfur reduction additive obtained by this preparation method and the method using this catalytic cracking sulfur reduction additive reduction Sulfur Content in Catalytic Cracking Gasoline. Catalytic cracking sulfur reduction additive provided by the invention can while reducing content of sulfur in gasoline, it is to increase the receipts rate of catalytically cracked gasoline.
Description
Technical field
The present invention relates to a kind of catalytic cracking sulfur reduction additive, and the preparation method of this catalytic cracking sulfur reduction additive, and use this catalytic cracking sulfur reduction additive to carry out reducing the method for Sulfur Content in Catalytic Cracking Gasoline.
Background technology
Currently, air environmental regulation increasingly stringent. For meeting the laws and regulations requirement to motor vehicle exhaust, the sulphur content significantly reduced in gasoline becomes the important topic that China's oil refining industry faces. Producing in China in the complete processing of petrol and diesel oil, catalytic cracking process is core process process, and the gasoline of China more than 70% and the diesel oil of more than 30% are all from catalytic cracking process. This just makes to reduce the sulphur content in the gasoline of catalytic cracking process acquisition, becomes the top priority of the sulphur content reduced in gasoline.
The method of existing reduction sulfur content of catalytic cracking gasoline comprises use low-sulfur raw material oil (buying sweet crude oil or fcc raw material oil hydrogenating desulfurization), catalytic gasoline hydrogenation desulfurization or adsorption desulfurize, and in catalytic cracking process, use has the catalyzer or auxiliary agent that fall sulfur functional exactly in addition.
It is suitable that stock oil hydrogenating desulfurization is sayed from sweetening effectiveness, but investment is big and hydrogen consumption is high. Catalytic gasoline hydrogenation sweetening effectiveness is also fine, but also there is the problem that investment is big and loss of octane number is big.
Therefore the catalyzer agent with desulfurizing function or auxiliary agent is used to become the method generally adopted at present in catalytic cracking process.
US5376608A discloses a kind of catalytic cracking catalyst compositions. Said composition contains molecular sieve, inorganic oxide carrier and the Lewis acid containing aluminum oxide, and selected Lewis acid comprises the elements such as zinc, copper, nickel, and load is on alumina. Although said composition can reduce sulfur content of catalytic cracking gasoline, but gasoline yield does not improve.
US2011120911A1 discloses a kind of method reducing the sulphur content that catalytically cracked gasoline evaporates point, and the method uses containing molecular sieve, yttrium and a kind of element of being selected from zinc, magnesium and manganese. This method reduce the sulphur content in gasoline, but yield of gasoline reduces.
US6482315B1 discloses a kind of catalytically cracked gasoline that reduces and evaporates a point middle sulphur content method. The assistant for calalytic cracking that the method uses uses the vanadium oxide of alumina load as the active component falling sulphur. Although this auxiliary agent can reduce sulfur content of catalytic cracking gasoline, but itself does not have catalytic cracking activity, and the v element added can cause catalytic cracking catalyst poisoning, affects the reactive behavior of catalyzer host.
US20070249495A1 discloses a kind of sulfur-lowing catalyst reducing sulphur content in catalytically cracked gasoline product. This catalyzer contains the vanadium metal acid compound of carrier and load, and wherein metal is selected from rare earth metal, Zn, Mn, Zr, Al, Mg, Ni and Cu. Although this catalyzer has the effect falling sulphur, but the v element introduced can cause catalytic cracking catalyst poisoning.
As can be seen here, although the existing sulfur prodegradant that can reduce Sulfur Content in Catalytic Cracking Gasoline at present, Sulfur Content in Catalytic Cracking Gasoline can be realized reduce, but adopt existing sulfur prodegradant also can reduce the receipts rate of gasoline simultaneously, what have even also can bring poisoning impact to catalytic cracking catalyst, makes catalytic cracking process produce the decline in benefits of gasoline.
Summary of the invention
Although it is an object of the invention to overcome existing catalytic cracking sulfur reduction additive can reduce the sulphur content in gasoline, but the defect of yield of gasoline can being reduced, it is provided that a kind of catalytic cracking sulfur reduction additive and its preparation method and application.
In order to realize above-mentioned purpose, the present invention provides the preparation method of a kind of catalytic cracking sulfur reduction additive, and the method comprises the following steps: molecular sieve, clay, pseudo-boehmite and Alumina gel are carried out mixing making beating for the first time by (1), obtain the first slurries; (2) described first slurries and titanium-containing compound are carried out second time and mix making beating, obtain the 2nd slurries; (3) described 2nd slurries are dried and roasting successively.
Present invention also offers prepared according to the methods of the invention catalytic cracking sulfur reduction additive.
Present invention also offers a kind of method reducing Sulfur Content in Catalytic Cracking Gasoline, the method comprises: when catalytic cracking reaction, being contacted with hydrocarbon oil containing surphur by catalyzer containing sulfur prodegradant, wherein, described sulfur prodegradant is catalytic cracking sulfur reduction additive provided by the invention.
By technical scheme provided by the invention, in the catalytic cracking reaction process of hydrocarbon oil containing surphur, adopt the catalytic cracking sulfur reduction additive prepared according to method provided by the invention, owing to introducing titanium oxide component, the sulphur content in the gasoline of acquisition can not only be reduced, moreover it is possible to improve the receipts rate of gasoline products. Specifically, it may also be useful to during the cat-1 catalyst reaction of catalytic cracking sulfur reduction additive SAC-1 prepared containing embodiment 1, the sulfur content in gasoline of acquisition is reduced to 261 �� g/g, and yield of gasoline is 43.4%. When using the cat-6 catalyst reaction of the comparative catalyst D1 containing comparative example 1 preparation, the sulfur content in gasoline of acquisition is 310 �� g/g, and yield of gasoline is 42.0%. It thus is seen that adopt the catalytic cracking sulfur reduction additive that preparation method provided by the invention obtains, it is possible to realize reducing content of sulfur in gasoline, improve the goal of the invention of yield of gasoline simultaneously.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Hereinafter the specific embodiment of the present invention is described in detail. Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The present invention provides the preparation method of a kind of catalytic cracking sulfur reduction additive, and the method comprises the following steps:
(1) undertaken molecular sieve, clay, pseudo-boehmite and Alumina gel mixing making beating for the first time, obtain the first slurries;
(2) described first slurries and titanium-containing compound are carried out second time and mix making beating, obtain the 2nd slurries;
(3) described 2nd slurries are dried and roasting successively.
According to the present invention, in step (1), in dry base, relative to described catalytic cracking sulfur reduction additive prepared by 100 weight parts, the consumption of described molecular sieve is 25-45 weight part, it is preferable to 30-40 weight part; The consumption of described clay is 20-60 weight part, it is preferable to 30-40 weight part; The consumption of described pseudo-boehmite is 10-20 weight part, it is preferable to 12-18 weight part; The consumption of described Alumina gel is 2-15 weight part, it is preferable to 4-8 weight part.
In the present invention, refer to by molecular sieve, clay, pseudo-boehmite and Alumina gel respectively after roasting in dry base, in the weight of the calcining matter that each material obtains. Relative to preparation catalytic cracking sulfur reduction additive be relative to the catalytic cracking sulfur reduction additive obtained after roasting.
According to the present invention, described molecular sieve can be the various molecular sieves that this area routine uses. Under preferable case, described molecular sieve contains the REY molecular sieve of more than 50 weight %, it is more preferable to the REY molecular sieve containing more than 80-95 weight %. In described REY molecular sieve, can as 10-20 weight % taking the content of rare earth that rare-earth oxidation thing is counted, it is preferable to 14-18 weight %. Described rare-earth oxidation thing can be one or more in lanthanum trioxide, cerium oxide and Samarium trioxide.
According to the present invention, described molecular sieve can also contain other molecular sieves of 0.1-50 weight %, and other molecular sieves described are at least one being selected from MFI structure molecular sieve, USY molecular sieve and REUSY molecular sieve. Other molecular sieves under preferable case, containing 5-20 weight %.
In the present invention, described clay can be the various clays that this area routine uses, such as can at least one for being selected from kaolin, halloysite, sepiolite, polynite, wilkinite, halloysite, diatomite, saponite, rectorite, attapulgite and hydrotalcite. Under preferable case, described clay is kaolin and/or halloysite.
In the present invention, first time described in step (1) mixes making beating, the making beating method that this area catalyst preparing routine uses can be taked, molecular sieve, clay and pseudo-boehmite such as first can be mixed into the slurries of certain solid content respectively with water, and then successively each slurries and Alumina gel are mixed, obtain the first slurries. The mixing making beating of described first time at 25-40 DEG C of temperature, can carry out in the making beating tank that this area routine uses. The mixing making beating of described first time can complete through stirring for 20-40 minute.
According to the present invention, in step (2), relative to described catalytic cracking sulfur reduction additive prepared by 100 weight parts, the consumption that described titanium-containing compound is counted taking titanium oxide is as 3-20 weight part, it is preferable to 6-10 weight part.
According to the present invention, described titanium-containing compound is used in the described catalytic cracking sulfur reduction additive of preparation to introduce titanium oxide, it is possible to use can realizing the various titanium-containing compounds of this object, it is preferable that in situation, described titanium-containing compound can be organic titanic compound. Further preferably, described titanium-containing compound is at least one in tetrabutyl titanate, titanium sulfate and titanium tetrachloride.
In the present invention, in step (2) before the mixing making beating of described second time, the aqueous solution that described titanium-containing compound and water can first be mixed into described titanium-containing compound, the described titanium-containing compound wherein counted taking titanium elements and the mol ratio of described water can as 1:2-30. Described second time mixing making beating can be the aqueous solution of described first slurries with described titanium-containing compound mix making beating.
In the present invention, described second time mixing making beating temperature can be 25-40 DEG C. The mixing making beating of described second time can complete through stirring for 20-40 minute.
According to the present invention, the drying carried out in step (3) and roasting can take the method for this area routine use. The dry condition with roasting of conventional cracking catalyst as described by CN1727442A, if drying temperature can be room temperature to 200 DEG C, it is preferable to 80-180 DEG C; Maturing temperature can be 200-750 DEG C, it is preferable to 300-600 DEG C; Roasting time is at least 0.1 hour, it is preferable to 0.1-10 hour, it is more preferable to be 0.3-4 hour. The method of described drying can adopt existing various drying means, as dried or spray-dired method.
In the present invention, after step (3), can further include described catalytic cracking sulfur reduction additive roasting obtained carry out washing and drying. The method that this area routine uses can be taked, as can with water washing 0.5-4 hour of 40-90 DEG C; Drying can carry out in pneumatic dryer, and drying temperature can be 100-200 DEG C, and time of drying can be 0.5-3 hour.
Present invention also offers prepared according to the methods of the invention catalytic cracking sulfur reduction additive.
Present invention also offers a kind of method reducing Sulfur Content in Catalytic Cracking Gasoline, the method comprises: when catalytic cracking reaction, being contacted with hydrocarbon oil containing surphur by catalyzer containing sulfur prodegradant, wherein, described sulfur prodegradant is catalytic cracking sulfur reduction additive provided by the invention.
According to the present invention, described catalytic cracking reaction condition can be the condition that this area routine uses, it is preferable that in situation, described catalytic cracking reaction condition comprises: temperature of reaction is 460-540 DEG C, it is more preferable to be 485-500 DEG C; Agent-oil ratio (weight ratio of catalyzer and hydrocarbon ils) is 4-20, it is more preferable to be 6-10.
In the method for reduction Sulfur Content in Catalytic Cracking Gasoline of the present invention, described sulfur prodegradant can mix together with catalytic cracking catalyst, such as, be that 1:3-6 is used in combination with catalytic cracking poiser according to weight ratio. Described hydrocarbon oil containing surphur can be the various raw materials for catalytic cracking reaction, such as, can be at least one in long residuum, vacuum residuum, VGO and hydrogenation tail oil. The described sulphur content containing sulphur oil can be 0.1-1.5 weight %.
The method of reduction Sulfur Content in Catalytic Cracking Gasoline of the present invention can carry out in fluidized-bed reactor and/or riser reactor, it is also possible to carries out in fixed-bed reactor.
Hereinafter will be described the present invention by embodiment.
In following examples, the total pore volume of catalytic cracking sulfur reduction additive and middle hole pore volume, record according to the standard method (compiling see " Petrochemical Engineering Analysis method " (RIPP test method) Yang Cuiding etc., scientific publication society, nineteen ninety publishes) of RIPP151-90.
The abrasion index of catalytic cracking sulfur reduction additive records according to the method for ASTMD5757-00 (2006).
Following examples use raw material condition as follows:
REY molecular sieve, purchased from China Petrochemical Industry's catalyst Co. Chang Ling branch office, trade mark CDY, rare earth oxide content is 16.2 weight %;
USY molecular sieve, purchased from China Petrochemical Industry's catalyst Co. Chang Ling branch office;
ZRP molecular sieve, purchased from Hunan Jian Chang company, silica alumina ratio 120;
Pseudo-boehmite, purchased from Shanxi Aluminium Plant product, alumina content is 60.2 weight %;
Alumina gel, purchased from Hunan Jian Chang company, alumina content is 21.8 weight %;
Halloysite, purchased from Cenxi, Hunan kaolin company, solid content 72.0 weight %;
Kaolin, purchased from China Kaolin Co., Ltd's product, solid content 70.0 weight %;
Tetrabutyl titanate, purchased from company of Beijing Chemical Plant.
Embodiment 1
The present embodiment is for illustration of the preparation method of the catalytic cracking sulfur reduction additive of the present invention.
(1) being that the REY molecular sieve pulp of 30 weight %, 179.4 grams of pseudo-boehmites, 192.7 grams of Alumina gel and 325.0 grams of halloysites add making beating tank by 700.0 grams of solid contents successively, mixing making beating obtains the first slurries A1 for 30 minutes;
(2) carry out mixing making beating 20 minutes with the solution of 280.8 grams of tetrabutyl titanates and 59.0 grams of water formation by the first slurries A1, obtain the 2nd slurries B1;
(3) after the 2nd slurries B1 being carried out spraying dry, roasting successively, hot wash, drier, obtain sulfur prodegradant SAC-1; Spray drying temperature is 450 DEG C; Maturing temperature is 500 DEG C, and roasting time is 1 hour.
Wherein, calculating according to charging capacity and learn, relative to the SAC-1 of 100 weight parts, the content of titanium oxide is 10 weight parts.
Embodiment 2
The present embodiment is for illustration of the preparation method of the catalytic cracking sulfur reduction additive of the present invention.
(1) being that the slurries being made up of 95 weight %REY molecular sieves and 5 weight %USY molecular sieves of 30 weight %, 179.4 grams of pseudo-boehmites, 192.7 grams of Alumina gel and 257.1 grams of kaolin add making beating tank by 700.0 grams of solid contents successively, mixing making beating obtains the first slurries A2 for 30 minutes.
(2) carry out mixing making beating with the solution of 199.8 grams of tetrabutyl titanates and 42.0 grams of water formation by the first slurries A2, after 30 minutes, obtain the 2nd slurries B2.
(3) after the 2nd slurries B2 being carried out spraying dry, roasting successively, hot wash, drier, obtain sulfur prodegradant SAC-2; Spray drying temperature is 450 DEG C; Maturing temperature is 500 DEG C, and roasting time is 1 hour.
Wherein, calculating according to charging capacity and learn, relative to the SAC-2 of 100 weight parts, the content of titanium oxide is 8 weight parts.
Embodiment 3
The present embodiment is for illustration of the preparation method of the catalytic cracking sulfur reduction additive of the present invention.
(1) being that the slurries being made up of 80 weight %REY molecular sieves and 20 weight %ZRP molecular sieves of 30 weight %, 179.4 grams of pseudo-boehmites, 192.7 grams of Alumina gel and 334.3 grams of kaolin add making beating tank by 700.0 grams of concentration successively, mixing making beating obtains the first slurries A3 for 30 minutes.
(2) carry out mixing making beating with the solution of 161.3 grams of tetrabutyl titanates and 33.9 grams of water formation by the first slurries A3, after 20 minutes, obtain the 2nd slurries B3.
(3) after the 2nd slurries B3 being carried out spraying dry, roasting successively, hot wash, drier, obtain sulfur prodegradant SAC-3; Spray drying temperature is 450 DEG C; Maturing temperature is 500 DEG C, and roasting time is 1 hour.
Wherein, calculating according to charging capacity and learn, relative to the SAC-3 of 100 weight parts, the content of titanium oxide is 6 weight parts.
Embodiment 4
According to the method for embodiment 1, the difference is that, substitute 280.8 grams of tetrabutyl titanates and 59.0 grams of water with 631.9 grams of tetrabutyl titanates and 132.7 grams of water. Obtain sulfur prodegradant SAC-4.
Wherein, calculating according to charging capacity and learn, relative to the SAC-4 of 100 weight parts, the content of titanium oxide is 20 weight parts.
Embodiment 5
According to the method for embodiment 1, the difference is that, with 78.2 grams of tetrabutyl titanates and 16.4 grams of water, substitute 280.8 grams of tetrabutyl titanates and 59.0 grams of water. Obtain sulfur prodegradant SAC-5.
Wherein, calculating according to charging capacity and learn, relative to the SAC-5 of 100 weight parts, the content of titanium oxide is 3 weight parts.
Comparative example 1
According to the method for embodiment 1, the difference is that, it does not have step (2), directly carries out step (3) by the first slurries A1, obtains comparative catalyst D1.
Wherein, not containing titanium oxide in comparative catalyst D1.
Test case 1
Measure the catalytic cracking sulfur reduction additive SAC-1 to 5 that above-described embodiment 1-5 and comparative example 1 obtain, and the total pore volume of comparative catalyst D1 and middle hole pore volume; Measure above-described embodiment 1-5 and the catalytic cracking sulfur reduction additive SAC-1 to 5 of comparative example 1 acquisition, and the abrasion index of comparative catalyst D1. Measurement result is as shown in table 1 below.
Table 1
| Catalyzer is numbered | Abrasion index | Total pore volume (ml/g) | Specific surface area (m2/ g) |
| SAC-1 | 1.2 | 0.21 | 287 |
| SAC-2 | 1.5 | 0.21 | 272 |
| SAC-3 | 1.4 | 0.21 | 264 |
| SAC-4 | 1.8 | 0.21 | 278 |
| SAC-5 | 1.0 | 0.21 | 248 |
| D1 | 1.0 | 0.20 | 280 |
Embodiment 6
The present embodiment is for illustration of the method for the reduction Sulfur Content in Catalytic Cracking Gasoline of the present invention.
The catalytic cracking sulfur reduction additive SAC-1 to 5 prepared by above-described embodiment 1-5 is respectively at 800 DEG C, under 100% water vapor aging 17 hours.
Auxiliary agent and poiser (refinery branch office catalysis workshop, Zhong Hai oil refining limited liability company Huizhou) through overaging is mixed to get cat-1, cat-2, cat-3, cat-4, cat-5 by the weight ratio of 20:80.
Poiser and cat-1 to 5 being filled in respectively in fixed fluidized bed device (purchased from the earth company of petrochemical industry Research Institute of Petro-Chemical Engineering of China), amount of fill is 150g; Then, it is 30h temperature of reaction, the weight hourly space velocity of 500 DEG C-1, agent-oil ratio (weight) is when being 7, raw material hydrocarbon ils as shown in table 2 for composition is injected described fixed fluidized bed device and carries out catalytic cracking reaction, and analyze the composition of catalytic cracking reaction product, result is as shown in table 3 below.
Comparative example 2
According to the method for embodiment 6, the difference is that, with the SAC-1 to 5 of comparative catalyst D1 alternate embodiment 1-5, it is mixed to get cat-6 with poiser. Result is as shown in table 3 below.
Table 2
| Raw material hydrocarbon ils | Parameter |
| Density (20 DEG C) (kg m-3) | 933.3 |
| Carbon residue (weight %) | 9.83 |
| Stable hydrocarbon (weight %) | 50.7 |
| Aromatic hydrocarbons (weight %) | 38.7 |
| Colloid (weight %) | 6.2 |
| Bituminous matter (weight %) | 4.4 |
| Sulphur content (weight %) | 0.2758 |
Table 3
By the data of table 3 it may be seen that the sulfur content in gasoline that balance agent reaction obtains is 320 �� g/g, it may also be useful to during cat-6, sulfur content in gasoline is 310 �� g/g, and uses the sulfur content in gasoline reacting acquisition during cat-1 catalyzer to be 261 �� g/g. While realizing falling sulphur object, it may also be useful to the yield of gasoline that cat-1 catalyst reaction obtains is 43.4%, it is possible to than the yield of gasoline 41.7% that balance agent reaction obtains, it is to increase 1.7 percentage points; Than the yield of gasoline 42.0% using cat-6 reaction to obtain, it is to increase 1.4 percentage points.
Therefore, adopt the catalytic cracking sulfur reduction additive that preparation method provided by the invention obtains, it is possible to significantly reduce content of sulfur in gasoline, improve yield of gasoline simultaneously.
Claims (7)
1. a preparation method for catalytic cracking sulfur reduction additive, the method comprises the following steps:
(1) undertaken molecular sieve, clay, pseudo-boehmite and Alumina gel mixing making beating for the first time, obtain the first slurries;
(2) described first slurries and titanium-containing compound are carried out second time and mix making beating, obtain the 2nd slurries;
(3) described 2nd slurries are dried and roasting successively;
In step (1), in dry base, relative to described catalytic cracking sulfur reduction additive prepared by 100 weight parts, the consumption of described molecular sieve is 25-45 weight part, the consumption of described clay is 20-60 weight part, the consumption of described pseudo-boehmite is 10-20 weight part, and the consumption of described Alumina gel is 2-15 weight part;
In step (2), relative to described catalytic cracking sulfur reduction additive prepared by 100 weight parts, the consumption that described titanium-containing compound is counted taking titanium oxide is as 3-20 weight part;
Described molecular sieve contains the REY molecular sieve of more than 50 weight %; Described titanium-containing compound is at least one in tetrabutyl titanate, titanium sulfate and titanium tetrachloride.
2. method according to claim 1, wherein, in step (1), in dry base, relative to described catalytic cracking sulfur reduction additive prepared by 100 weight parts, the consumption of described molecular sieve is 30-40 weight part; The consumption of described clay is 30-40 weight part; The consumption of described pseudo-boehmite is 12-18 weight part; The consumption of described Alumina gel is 4-8 weight part.
3. method according to claim 1, wherein, described molecular sieve also contains other molecular sieves of 0.1-50 weight %, and other molecular sieves described are at least one being selected from MFI structure molecular sieve, USY molecular sieve and REUSY molecular sieve.
4. method according to claim 1, wherein, in step (2), relative to described catalytic cracking sulfur reduction additive prepared by 100 weight parts, the consumption that described titanium-containing compound is counted taking titanium oxide is as 6-10 weight part.
5. the catalytic cracking sulfur reduction additive prepared according to method described in any one in claim 1-4.
6. one kind is reduced the method for Sulfur Content in Catalytic Cracking Gasoline, the method comprises: when catalytic cracking reaction, catalyzer containing sulfur prodegradant is contacted with hydrocarbon oil containing surphur, it is characterised in that, described sulfur prodegradant is catalytic cracking sulfur reduction additive according to claim 5.
7. method according to claim 6, wherein, described catalytic cracking reaction condition comprises: temperature of reaction is 460-540 DEG C, and the weight ratio of catalyzer and hydrocarbon ils is 6-10.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101486925A (en) * | 2008-05-13 | 2009-07-22 | 北京三聚环保新材料股份有限公司 | Stable FCC sulfur reduction additive and FCC desulphurization complexing agent using the same |
| US20110120911A1 (en) * | 2005-02-25 | 2011-05-26 | Ruizhong Hu | Gasoline sulfur reduction catalyst for fluid catalytic cracking process |
| CN102274721A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Desulfurization additive for product obtained by hydrocarbon oil cracking and preparation and application thereof |
| CN102294261A (en) * | 2011-06-24 | 2011-12-28 | 卓润生 | Catalyst suitable for two-stage catalytic cracking reaction, and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110120911A1 (en) * | 2005-02-25 | 2011-05-26 | Ruizhong Hu | Gasoline sulfur reduction catalyst for fluid catalytic cracking process |
| CN101486925A (en) * | 2008-05-13 | 2009-07-22 | 北京三聚环保新材料股份有限公司 | Stable FCC sulfur reduction additive and FCC desulphurization complexing agent using the same |
| CN102274721A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Desulfurization additive for product obtained by hydrocarbon oil cracking and preparation and application thereof |
| CN102294261A (en) * | 2011-06-24 | 2011-12-28 | 卓润生 | Catalyst suitable for two-stage catalytic cracking reaction, and preparation method and application thereof |
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