CN1311906C - Cracking catalyst for hydrocarbon and preparation method - Google Patents
Cracking catalyst for hydrocarbon and preparation method Download PDFInfo
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- CN1311906C CN1311906C CNB2004100711175A CN200410071117A CN1311906C CN 1311906 C CN1311906 C CN 1311906C CN B2004100711175 A CNB2004100711175 A CN B2004100711175A CN 200410071117 A CN200410071117 A CN 200410071117A CN 1311906 C CN1311906 C CN 1311906C
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Abstract
The present invention relates to a cracking catalyst for hydrocarbon, which comprises aluminum oxide and molecular sieves and contains or does not contain clay. The present invention is characterized in that the aluminum oxide is eta-aluminum oxide and/or chi-aluminum oxide or a mixture of the eta-aluminum oxide and/or the chi-aluminum oxide with gamma-aluminum oxide. The catalyst also contains phosphorus and alkaline earth metals. Taking the total weight of the catalyst as a reference, the catalyst is prepared from 0.5 to 50 wt% of the eta-aluminum oxide and/or the chi-aluminum oxide, 0 to 50 wt% of the gamma-aluminum oxide, 10 to 70 wt% of the molecular sieve; 0 to 75 wt% of the clay, 0.1 to 4 wt% of the phosphorus measured by P2O5, and 0.1 to 4 wt% of the alkaline earth metals measured by oxide; the molecular sieves are Y-type zeolite. The catalyst has strong heavy metal pollution resistance; when the catalyst is used for catalyzing hydrocarbon oil, the quality of gasoline in cracked products is increased.
Description
Technical field
The invention relates to a kind of hydrocarbon cracking catalyzer and preparation method thereof.
Background technology
The heaviness of catalytically cracked stock and poor qualityization tendency are serious day by day, contained metal pollutants such as Ni-V-Fe can be deposited on the catalyst surface in the raw material, cause the catalyst poisoning inactivation, thereby make the selectivity variation, yield of light oil descends, and hydrogen and coke yield rise.This just requires Cracking catalyst and cracking technology to have stronger preventing from heavy metal pollution ability, to reach the purpose of light oil with high yield (gasoline and diesel oil).
For catalytically cracked gasoline, alkene, aromatic hydrocarbons and isoparaffin are the main contributors of octane number, because environmental requirement needs to reduce the FCC olefin content in gasoline.In order to remedy the loss of the octane number that causes because of olefin(e) centent decline, need to increase the content of isoparaffin, aromatic hydrocarbons in the gasoline, this just need develop to produce has than low olefin-content the hydrocarbon cracking catalyzer of higher aromatic hydrocarbons and isoparaffin content gasoline and cracking technology.
CN1055301C discloses the Cracking catalyst of a kind of voluminous isomeric olefine and gasoline, this catalyst is by the composite aluminum base al binder of being made up of according to 1: 9 to 9: 1 weight ratio boehmite and aluminium colloidal sol of 5-70 weight %, the molecular sieve of the clay of 5-65 weight % and 23-50 weight % is formed, and described molecular sieve is that the phosphorus content of the y-type zeolite of 15-82 weight % and surplus is (with P
2O
5Meter) is the mixture that contains rare-earth five-membered ring silica-rich zeolite and/or HZSM-5 zeolite of 0-10 weight %.
CN1072201A discloses a kind of hydrocarbon conversion catalyst of producing high-knock rating gasoline and alkene, this catalyst is by the ZSM-5 of 10-40 weight %, the full synthesis carrier of REY and three kinds of zeolites of high silicon Y and surplus or the semi-synthetic carrier that contains 10-40 weight % silicon and/or al binder are formed, wherein, it is 3-50 weight % that ZSM-5 divides the content of zeolite, the content of REY and the high-silicon Y-Zeolite 12-75 weight % that respectively does for oneself.
CN1085825A discloses a kind of high-knock rating gasoline of producing, propylene, the hydrocarbon conversion catalyst of butylene, this catalyst is by the ZRP zeolite of 10-40 weight %, the full synthesis carrier of REY and three kinds of zeolites of high silicon Y and surplus or the semi-synthetic carrier that contains 10-40 weight % silicon and/or al binder are formed, wherein, the content of ZRP zeolite is 3-50 weight %, the content of REY and the high-silicon Y-Zeolite 12-75 weight % that respectively does for oneself.
CN1325940A discloses a kind of phosphorous hydrocarbon cracking catalyzer, and this catalyst is by y-type zeolite or y-type zeolite and MFI structural zeolite and/or the Beta zeolite of 10-60 weight %, the clay of 0-75 weight %, and two kinds of aluminium oxide of 10-60 weight % are with P
2O
5Meter, the phosphorus of 0.1-7.0 weight % and with RE
2O
3Meter, the rare earth of 0-20 weight % is formed.Described two kinds of aluminium oxide are respectively from boehmite and aluminium colloidal sol.This catalyst has high ability of residuum conversion, and olefin(e) centent is lower in the product gasoline.
CN1354224A discloses the catalytic cracking catalyst that isoparaffin gasoline, propylene and iso-butane are rich in a kind of production, this catalyst is by the clay of 0-70 weight %, the molecular sieve of the inorganic oxide of 5-90 weight % and 1-50 weight % is formed, molecular sieve wherein for the silica alumina ratio of (1) 20-75 weight % be 5-15, with RE
2O
3The silica alumina ratio of Y-type high-Si zeolite and (2) the 20-75 weight % of the content of rare earth 8-20 weight % of meter is 16-50, with RE
2O
3The Y-type high-Si zeolite of the content of rare earth 2-7 weight % of meter and the β zeolite of (3) 1-50 weight % or the mixture of modenite or ZRP zeolite.
Aluminium oxide is the component that Cracking catalyst contains usually.In the prior art, aluminium oxide is many from monohydrate alumina and aluminium colloidal sol, wherein, monohydrate alumina comprises boehmite and boehmite, in the roasting process of Preparation of Catalyst, boehmite, boehmite and aluminium colloidal sol all change gama-alumina into, and the contained aluminium oxide of the described catalyst of above-mentioned prior art is gama-alumina.
Aluminium oxide can also be from hibbsite.Gibbsite comprises α-gibbsite, β-gibbsite (or claiming surge aluminium stone) and promise diaspore, and in catalyst preparation process, α-gibbsite is transformed into χ-aluminium oxide, and β-gibbsite then is transformed into η-aluminium oxide.The promise diaspore just exists at occurring in nature, still can't be by artificial synthetic obtaining.CN1388214 discloses a kind of preparation method of fluid cracking catalyst, this method is to contain the Cracking catalyst component mixture drying of clay, aluminium oxide and molecular sieve, contains the aluminium oxide from β-gibbsite of 1.5-55 weight % in the described catalyst.This catalyst has stronger heavy oil cracking activity and light oil selectivity preferably, but but can not reduce olefin content in gasoline, and the ability of preventing from heavy metal pollution is also not enough.
Summary of the invention
The purpose of this invention is to provide a kind of new hydrocarbon cracking catalyzer, this catalyst has the ability of stronger preventing from heavy metal pollution, uses this catalyst hydrocarbon ils, and in the cracked product, the olefin(e) centent of gasoline is lower.
In the prior art, though the example of introducing gibbsite in the Cracking catalyst preparation is also arranged,, its purpose just improves the cracking ability of catalyst, and to not influence of the quality of gasoline in the cracked product.The present inventor is surprised to find that, even for the higher feedstock oil of content of beary metal such as Ni-V-Fe, in Cracking catalyst, introduce aluminium oxide, phosphorus and alkaline-earth metal that gibbsite forms simultaneously, the aluminium oxide that forms of β-gibbsite particularly, be η-aluminium oxide, phosphorus and alkaline-earth metal, produced special cooperative effect, in light oil with high yield, can also improve quality of gasoline, and when the higher hydrocarbon ils of content of beary metal such as catalytic cracking Ni-V-Fe, this catalyst still has higher cracking activity.
Catalyst provided by the invention contains aluminium oxide and molecular sieve, contain or do not contain clay, wherein, described aluminium oxide is η-aluminium oxide and/or χ-aluminium oxide, or the mixture of η-aluminium oxide and/or χ-aluminium oxide and gama-alumina, this catalyst also contains phosphorus and alkaline-earth metal, with the catalyst total amount is benchmark, the content of η-aluminium oxide and/or χ-aluminium oxide is 0.5-50 weight %, the content of gama-alumina is 0-50 weight %, the content of molecular sieve is 10-70 weight %, and the content that is stained with is 0-75 weight %, with P
2O
5Meter, the content of phosphorus is 0.1-4 weight %, and in oxide, the content of alkaline-earth metal is 0.1-4 weight %, and described molecular sieve is a y-type zeolite.
Preparation of catalysts method provided by the invention comprises and will contain aluminium compound, molecular sieve and water, contain or slurry dried not argillaceous and roasting, wherein, described aluminium compound is the aluminium compound that can form η-aluminium oxide and/or χ-aluminium oxide, or can form the aluminium compound of η-aluminium oxide and/or χ-aluminium oxide and can form the mixture of the aluminium compound of gama-alumina, before roasting, also add phosphorus and alkaline earth metal compounds, the consumption of each component makes in the final catalyst and contains, with the catalyst total amount is benchmark, 0.5-50 η-aluminium oxide of weight % and/or χ-aluminium oxide, the gama-alumina of 0-50 weight %, the molecular sieve of 10-70 weight %, the clay of 0-75 weight % is with P
2O
5Meter, the phosphorus of 0.1-4 weight %, in oxide, the alkaline-earth metal of 0.1-4 weight %, described molecular sieve are y-type zeolite.
Catalyst provided by the invention has the ability of stronger preventing from heavy metal pollution, uses this catalyst hydrocarbon ils, and in the cracked product, quality of gasoline is improved.Show, during with the catalyst cracking hydrocarbon ils provided by the invention after the heavy metal pollutions such as nickel, vanadium and iron, catalyst still has higher cracking activity and higher light oil productive rate, has lower olefin(e) centent and higher aromatic hydrocarbons and isoparaffin content in the gasoline.
The specific embodiment
According to catalyst provided by the invention, under the preferable case, the content of η-aluminium oxide and/or χ-aluminium oxide is 5-25 weight %, and the content of gama-alumina is 0-40 weight %, and the content of molecular sieve is 20-50 weight %, and the content of clay is 0-60 weight %, with P
2O
5Meter, the content of phosphorus is 0.2-3 weight %, in oxide, the content of alkaline-earth metal is 0.2-2.5 weight %.
Wherein, described molecular screening is from y-type zeolite, as in the overstable gamma zeolite of the y-type zeolite of HY zeolite, phosphorous, iron and/or rare earth, overstable gamma zeolite, phosphorous, iron and/or rare earth one or more, be preferably in the overstable gamma zeolite of the y-type zeolite, overstable gamma zeolite of phosphorous, iron and/or rare earth, phosphorous, iron and/or rare earth one or more.
Described alkaline-earth metal is selected from one or more in beryllium, magnesium, calcium, strontium, the barium, is preferably in magnesium, calcium, the barium one or more.
Described clay is selected from as in the clay of active component of cracking catalyst one or more, as in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite one or more.Preferred clay is one or more in kaolin, imvite, diatomite, rectorite, sepiolite, the attapulgite.These clays are conventionally known to one of skill in the art.
According to Preparation of catalysts method provided by the invention, described aluminium compound is the aluminium compound that can form η-aluminium oxide and/or χ-aluminium oxide, or can form the aluminium compound of η-aluminium oxide and/or χ-aluminium oxide and can form the mixture of the aluminium compound of gama-alumina.
The described aluminium compound that can form η-aluminium oxide and/or χ-aluminium oxide can be any in catalyst preparation process, can form the aluminium compound of η-aluminium oxide and/or χ-aluminium oxide, be preferably α-gibbsite and/or β-gibbsite, more preferably β-gibbsite.
The described aluminium compound that can form gama-alumina can be any in catalyst preparation process, can form the aluminium compound of gama-alumina, is preferably boehmite, boehmite and/or aluminium colloidal sol.
Described phosphorus and alkaline earth metal compound can add by the arbitrary steps before roasting, as joining aluminum contained compound, molecular sieve and water, contain or slurries not argillaceous in, also can be earlier with aluminum contained compound, molecular sieve and water, contain or slurry dried not argillaceous, again with infusion process substep or introduce phosphorus and alkaline earth metal compound, roasting then together.In the catalyst of the present invention, the content of described phosphorus does not comprise the phosphorus that molecular sieve contained originally.
Described phosphorus compound comprises the compound of various phosphorus, as in phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric acid, pyrophosphate, polymer phosphate, polymeric phosphate, metaphosphoric acid, the metaphosphate one or more, be preferably in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphorous acid, ammonium phosphite, sodium pyrophosphate, potassium pyrophosphate, sodium phosphate trimer, PTPP, calgon, the hexa metaphosphoric acid potassium one or more.One or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphorous acid, ammonium phosphite, sodium pyrophosphate, sodium phosphate trimer, the calgon more preferably.
Described alkaline earth metal compound comprises the compound of various soluble alkaline earth, as in beryllium chloride, magnesium chloride, magnesium nitrate, magnesium sulfate, calcium chloride, calcium nitrate, calcium acetate, strontium chloride, strontium nitrate, strontium acetate, barium chloride, barium nitrate, the barium acetate one or more, be preferably in magnesium chloride, magnesium nitrate, magnesium sulfate, calcium chloride, calcium nitrate, calcium acetate, barium chloride, barium nitrate, the barium acetate one or more.
The consumption of each component makes in the final catalyst and contains, and is benchmark with the catalyst total amount, the gama-alumina of η-aluminium oxide of 0.5-50 weight % and/or χ-aluminium oxide, 0-50 weight %, and the molecular sieve of 10-70 weight %, the clay of 0-75 weight % is with P
2O
5Meter, the phosphorus of 0.1-4 weight %, in oxide, the alkaline-earth metal of 0.1-4 weight %.Under the preferable case, the consumption of each component makes η-aluminium oxide and/or the χ-aluminium oxide that contains 5-25 weight % in the final catalyst, the gama-alumina of 0-40 weight %, and the molecular sieve of 20-50 weight %, the clay of 0-60 weight % is with P
2O
5Meter, the phosphorus of 0.2-3 weight %, in oxide, the alkaline-earth metal of 0.2-2.5 weight %.
The condition of described drying and roasting is the Cracking catalyst drying of routine and the condition of roasting, as the temperature of drying is room temperature-200 ℃, be preferably 80-180 ℃, the temperature of roasting is greater than 200 to 750 ℃, be preferably 300-600 ℃, the time of roasting was at least 0.1 hour, was preferably 0.1-10 hour, more preferably 0.3-4 hour.Described drying means can adopt existing various drying means,, dries spray-drying, preferably oven dry or spray-dired method as oven dry.
Catalyst provided by the invention is applicable to oil and various cut thereof is carried out catalytic cracking, be specially adapted to the higher oil of content of beary metal such as Ni-V-Fe and boiling point thereof petroleum distillate greater than 330 ℃, as normal pressure residual oil, decompression residuum, decompressed wax oil, the normal pressure wax oil, straight-run gas oil, propane is light/and heavily one or more in de-oiling and the wax tailings carry out catalytic cracking, to produce premium-type gasoline.
The service condition of catalyst provided by the invention is conventional cracking reaction condition, and in general, described cracking conditions comprises that reaction temperature is 350-700 ℃, is preferably 400-650 ℃, and oil ratio (weight ratio of catalyst and hydrocarbon ils) is 1-20, is preferably 2-15.
The following examples will the present invention will be further described.
In the example, the alumina content of used β-gibbsite is 64 weight % (research institute of Shandong Aluminium Industrial Corp products); The alumina content of boehmite is 62 weight % (Shandong Aluminium Industrial Corp's products); The alumina content of aluminium colloidal sol is 21.6 weight % (Shandong catalyst plant products); Kaolinic solid content 76 weight % (China Kaolin Co., Ltd's product); The solid content of imvite is 80 weight % (Hubei Zhong Xiang county iron ore factory products); Phosphorous compound is a chemical pure; The compound of alkaline including earth metal is a chemical pure; The REY zeolite be a kind of y-type zeolite that contains rare earth (content of rare earth oxide is 18.5 weight %, wherein, La
2O
3Account for 53.2 weight %, the CeO of rare earth oxide
2Account for 13.0 weight %, the Pr of rare earth oxide
6O
11Account for 13.0 weight %, the Nd of rare earth oxide
2O
3Account for 20.8 weight % of rare earth oxide, Na
2O content is 1.6 weight %, and silica alumina ratio is 5.4, and the Shandong catalyst plant is produced); DASY
0.0Zeolite is a kind of overstable gamma zeolite (Na
2O content is 1.0 weight %, and silica alumina ratio is 6.8, and the Shandong catalyst plant is produced); DASY
2.0Zeolite be a kind of overstable gamma zeolite that contains rare earth (content of rare earth oxide is 1.8 weight %, wherein, La
2O
3Account for 53.2 weight %, the CeO of rare earth oxide
2Account for 13.0 weight %, the Pr of rare earth oxide
6O
11Account for 13.0 weight %, the Nd of rare earth oxide
2O
3Account for 20.8 weight % of rare earth oxide, Na
2O content is 1.2 weight %, and silica alumina ratio is 6.8, and the Shandong catalyst plant is produced); The DM-4 zeolite be a kind of overstable gamma zeolite that contains rare earth (content of rare earth oxide is 3.4 weight %, wherein, La
2O
3Account for 53.2 weight %, the CeO of rare earth oxide
2Account for 13.0 weight %, the Pr of rare earth oxide
6O
11Account for 13.0 weight %, the Nd of rare earth oxide
2O
3Account for 20.8 weight % of rare earth oxide, Na
2O content is 2.1 weight %, and silica alumina ratio is 6.2, and the Shandong catalyst plant is produced).Above-mentioned silica alumina ratio all refers to the mol ratio of silica and aluminium oxide.
Example 1-6
Following example illustrates Catalysts and its preparation method provided by the invention.
With β-gibbsite or β-gibbsite and boehmite, molecular sieve, phosphorus compound and water (also having clay sometimes) mixing making beating, the slurries that obtain are spray dried to particle and the roasting that diameter is the 40-150 micron, obtain catalyst C provided by the invention
1-C
6Wherein, preparing catalyst by the method for example 6, is to replace example 5 described boehmites with aluminium colloidal sol, obtains catalyst C
6The consumption of β-gibbsite and boehmite, the kind of clay and consumption, the kind of the kind of molecular sieve and consumption, phosphorus compound, alkaline earth metal compound and consumption are listed in respectively among the table 1-5.Spray-dired temperature, sintering temperature and time list in the table 6.Catalyst C
1-C
6Composition list in the table 7.
Comparative Examples 1
This Comparative Examples illustrates reference catalyst of not phosphorous and alkaline-earth metal and preparation method thereof.
Method by example 1 prepares catalyst, and different is not add phosphorus and alkaline earth metal compound, and the consumption difference of clay gets reference catalyst CB
1The consumption of β-gibbsite and boehmite, the kind of clay and consumption, the kind of molecular sieve and consumption are listed in respectively among the table 1-3.Spray-dired temperature, sintering temperature and time list in the table 6.Reference catalyst CB
1Composition list in the table 7.
Comparative Examples 2
The explanation of this Comparative Examples does not contain reference catalyst of χ or η-aluminium oxide and preparation method thereof.
Method by example 1 prepares catalyst, and different is to replace β-gibbsite with boehmite, obtains reference catalyst CB
2The consumption of boehmite, the kind of clay and consumption, the kind of the kind of molecular sieve and consumption, phosphorus and alkaline earth metal compound and consumption are listed in respectively among the table 1-5.Spray-dired temperature, sintering temperature and time list in the table 6.Reference catalyst CB
2Composition list in the table 7.
Table 1
| Example number | β-gibbsite consumption, kilogram | Boehmite/aluminium colloidal sol consumption, kilogram |
| 1 | 34.4 | - |
| Comparative Examples 1 | 34.4 | - |
| Comparative Examples 2 | - | 35.5/0 |
| 2 | 31.3 | 25.8/0 |
| 3 | 39.1 | 54.8/0 |
| 4 | 15.6 | 29.0/0 |
| 5 | 23.4 | 29.0/0 |
| 6 | 23.4 | 0/83.3 |
Table 2
| Example number | The molecular sieve kind | The molecular sieve consumption, kilogram |
| 1 | DASY 0.0+REY | 20+5 |
| Comparative Examples 1 | DASY 0.0+REY | 20+5 |
| Comparative Examples 2 | DASY 0.0+REY | 20+5 |
| 2 | DASY 2.0 | 48 |
| 3 | DASY 0.0+REY | 26.6+12 |
| 4 | REY | 20 |
| 5 | DM-4 | 30 |
| 6 | DM-4 | 30 |
Table 3
| Example number | Clay types | The clay consumption, kilogram |
| 1 | Kaolin | 67.2 |
| Comparative Examples 1 | Kaolin | 69.7 |
| Comparative Examples 2 | Kaolin | 67.2 |
| 2 | Kaolin | 16.8 |
| 3 | - | |
| 4 | Imvite | 63.4 |
| 5 | Kaolin | 47.0 |
| 6 | Kaolin | 47.0 |
Table 4
| Example number | The phosphorus compound kind | The phosphorus compound consumption, kilogram |
| 1 | Diammonium hydrogen phosphate | 1.3 |
| Comparative Examples 1 | - | - |
| Comparative Examples 2 | Diammonium hydrogen phosphate | 1.3 |
| 2 | Calgon | 2.2 |
| 3 | Ammonium phosphate | 4.2 |
| 4 | Ammonium phosphate | 0.7 |
| 5 | Ammonium dihydrogen phosphate (ADP) | 0.8 |
| 6 | Ammonium dihydrogen phosphate (ADP) | 0.8 |
Table 5
| Example number | The alkaline earth metal compound kind | The alkaline earth metal compound consumption, kilogram |
| 1 | Magnesium dichloride hexahydrate | 6.1 |
| Comparative Examples 1 | - | - |
| Comparative Examples 2 | Magnesium dichloride hexahydrate | 6.1 |
| 2 | Bitter salt | 10.5 |
| 3 | Calcium nitrate | 1.1 |
| 4 | Calcium diacetate monohydrate | 3.1 |
| 5 | One hydration barium acetate | 1.4 |
| 6 | One hydration barium acetate | 1.4 |
Table 6
| Example number | Baking temperature, ℃ | Sintering temperature, ℃ | Roasting time, hour |
| 1 | 110 | 500 | 1 |
| Comparative Examples 1 | 110 | 500 | 1 |
| Comparative Examples 2 | 110 | 500 | 1 |
| 2 | 120 | 350 | 3.5 |
| 3 | 120 | 600 | 0.5 |
| 4 | 120 | 450 | 0.8 |
| 5 | 160 | 550 | 1.5 |
| 6 | 90 | 550 | 1.5 |
Table 7
| Example number | The catalyst numbering | η-alumina content, weight % | Gama-alumina content, weight % | Molecular sieve content, weight % | Clay content, weight % | P 2O 5Content, weight % | Alkaline earth oxide | |
| Kind | Content, weight % | |||||||
| 1 | C 1 | 22.0 | 0 | 25.0 | 51.1 | 0.7 | Magnesium | 1.2 |
| Comparative Examples 1 | CB 1 | 22.0 | 0 | 25.0 | 53.0 | 0 | 0 | |
| Comparative Examples 2 | CB 2 | 0 | 22.0 | 25.0 | 51.1 | 0.7 | Magnesium | 1.2 |
| 2 | C 2 | 20.0 | 16.0 | 48.0 | 12.8 | 1.5 | Magnesium | 1.7 |
| 3 | C 3 | 25.0 | 34.0 | 38.6 | 0 | 2.0 | Calcium | 0.4 |
| 4 | C 4 | 10.0 | 18.0 | 20.0 | 50.7 | 0.3 | Calcium | 1.0 |
| 5 | C 5 | 15.0 | 18.0 | 30.0 | 35.7 | 0.5 | Barium | 0.8 |
| 6 | C 6 | 15.0 | 18.0 | 30.0 | 35.7 | 0.5 | Barium | 0.8 |
Example 7-12
Following example illustrates the catalytic performance of catalyst provided by the invention.
Respectively with catalyst C
1-C
6Carrying out Ni-V-Fe pollutes, promptly flooded 1 hour with the kerosin that contains nickel naphthenate and aphthenic acids vanadium, 120 ℃ of oven dry, used the ferric chloride in aqueous solution impregnated catalyst then 1 hour, 120 ℃ of oven dry, 550 ℃ of roastings 4 hours, at last at 800 ℃, wore out 8 hours with 100% steam, at the nickel that pollutes 4000ppm on the catalyst, the vanadium of 1500ppm and the iron of 3000ppm.On the small-sized fluidized bed reaction unit, with the catalyst C after the above-mentioned pollution
1-C
6, feedstock oil carries out catalytic cracking shown in the his-and-hers watches 8, and the catalyst loading amount is 90 grams.Reaction condition and reaction result are listed in the table 9.
Wherein, conversion ratio=dry gas yield+yield of liquefied gas+yield of gasoline+coking yield; Light oil=yield of gasoline+diesel yield.Gasoline is meant that boiling range is C
5-221 ℃ cut, diesel oil are meant that boiling range is 221-343 ℃ a cut, and liquefied gas is meant C
3-C
4Cut, dry gas is H
2-C
2Cut.
Comparative Examples 3-4
The catalytic performance of following Comparative Examples explanation reference catalyst.
Method by example 7 is polluted catalyst, and under same condition, same feedstock oil is carried out catalytic cracking, and that different is reference catalyst CB1 and the CB2 that catalyst system therefor is respectively Comparative Examples 1 and Comparative Examples 2 preparations, and reaction condition and reaction result are listed in the table 9.
Table 8
| Feedstock oil density (20 ℃), gram per centimeter 3Carbon residue, weight % refractive power (70 ℃) viscosity (80 ℃), millimeter 2/ second viscosity (100 ℃), millimeter 2/ second condensation point, ℃ aniline point, ℃ | Reduced crude |
| 0.8977 5.14 1.4884 23.61 13.72 44 97.7 | |
| Element is formed, weight % C H S N | 86.89 12.77 0.13 0.21 |
| Four components, weight % saturated hydrocarbons aromatic hydrocarbons gum asphalt | 62.7 23.0 12.7 1.6 |
| Boiling range, ℃ initial boiling point/5% 10%/30% 50%/60% | 283/350 374/432 477/511 |
| Characterization factor | 12.3 |
Table 9
| Example number | 7 | Comparative Examples 3 | Comparative Examples 4 | 8 | 9 | 10 | 11 | 12 |
| The catalyst numbering | C 1 | CB 1 | CB 2 | C 2 | C 3 | C 4 | C 5 | C 6 |
| Reaction temperature, ℃ | 510 | 510 | 510 | 460 | 530 | 490 | 500 | 500 |
| Oil ratio | 5.0 | 5.0 | 5.0 | 6.0 | 3.5 | 4.5 | 5.5 | 5.5 |
| Weight (hourly) space velocity (WHSV), hour -1 | 26.0 | 26.0 | 26.0 | 30.0 | 28.0 | 24.0 | 24.0 | 24.0 |
| Conversion ratio, weight % | 71.5 | 68.4 | 66.7 | 77.8 | 74.9 | 72.4 | 73.3 | 72.8 |
| Light oil, weight % | 63.0 | 59.0 | 57.1 | 66.2 | 64.7 | 64.2 | 65.8 | 65.5 |
| Product is formed, weight % | ||||||||
| Dry gas | 2.1 | 1.4 | 1.3 | 1.7 | 1.9 | 1.0 | 1.5 | 1.2 |
| Liquefied gas | 15.9 | 14.2 | 13.2 | 16.3 | 15.8 | 16.1 | 16.0 | 16.5 |
| Gasoline | 48.8 | 45.2 | 44.0 | 53.5 | 51.2 | 49.5 | 50.6 | 50.0 |
| Diesel oil | 14.2 | 13.8 | 13.1 | 12.7 | 13.5 | 14.7 | 15.2 | 15.5 |
| Coke | 4.7 | 7.6 | 8.2 | 6.3 | 6.0 | 5.8 | 5.2 | 5.1 |
| Unconverted heavy oil | 14.3 | 17.8 | 20.2 | 9.5 | 11.6 | 12.9 | 11.5 | 11.7 |
| Gasoline is formed, weight % alkene aromatic hydrocarbons isoparaffin | 32.5 27.2 24.4 | 35.6 25.4 23.8 | 36.7 23.2 23.5 | 27.3 30.4 26.1 | 29.2 27.4 27.0 | 31.6 29.3 23.4 | 29.7 28.6 27.2 | 30.3 27.9 26.5 |
From the result of table 9 as can be seen, same feedstock oil is carried out catalytic cracking, compare with the use reference catalyst, though use catalyst provided by the invention to pollute the beavy metal impurity of going up high level, conversion ratio and yield of light oil all are improved largely, and, reduced olefin content in gasoline significantly, improved aromatic hydrocarbons and the isoparaffin content in the gasoline.
Claims (11)
1. hydrocarbon cracking catalyzer, this catalyst contains aluminium oxide and molecular sieve, contain or do not contain clay, it is characterized in that, described aluminium oxide is η-aluminium oxide and/or χ-aluminium oxide, or the mixture of η-aluminium oxide and/or χ-aluminium oxide and gama-alumina, this catalyst also contains phosphorus and alkaline-earth metal, with the catalyst total amount is benchmark, the content of η-aluminium oxide and/or χ-aluminium oxide is 0.5-50 weight %, and the content of gama-alumina is 0-50 weight %, and the content of molecular sieve is 10-70 weight %, the content of clay is 0-75 weight %, with P
2O
5Meter, the content of phosphorus is 0.1-4 weight %, and in oxide, the content of alkaline-earth metal is 0.1-4 weight %, and described molecular sieve is a y-type zeolite.
2. catalyst according to claim 1 is characterized in that, the content of η-aluminium oxide and/or χ-aluminium oxide is 5-25 weight %, the content of gama-alumina is 0-40 weight %, the content of molecular sieve is 20-50 weight %, and the content of clay is 0-60 weight %, with P
2O
5Meter, the content of phosphorus is 0.2-3 weight %, in oxide, the content of alkaline-earth metal is 0.2-2.5 weight %.
3. catalyst according to claim 1 and 2 is characterized in that, described molecular screening one or more in the overstable gamma zeolite of the y-type zeolite of HY zeolite, phosphorous, iron and/or rare earth, overstable gamma zeolite, phosphorous, iron and/or rare earth.
4. catalyst according to claim 3 is characterized in that, described molecular screening one or more in the overstable gamma zeolite of the y-type zeolite of phosphorous, iron and/or rare earth, overstable gamma zeolite, phosphorous, iron and/or rare earth.
5. catalyst according to claim 1 is characterized in that described alkaline-earth metal is selected from one or more in magnesium, calcium, the barium.
6. catalyst according to claim 1 and 2, it is characterized in that described clay is selected from one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the bentonite.
7. claim 1 Preparation of catalysts method, this method comprises and will contain aluminium compound, molecular sieve and water, contain or slurry dried not argillaceous and roasting, it is characterized in that, described aluminium compound is the aluminium compound that can form η-aluminium oxide and/or χ-aluminium oxide, or can form the aluminium compound of η-aluminium oxide and/or χ-aluminium oxide and can form the mixture of the aluminium compound of gama-alumina, before roasting, also add phosphorus and alkaline earth metal compounds, the consumption of each component makes in the final catalyst and contains, with the catalyst total amount is benchmark, 0.5-50 η-aluminium oxide of weight % and/or χ-aluminium oxide, the gama-alumina of 0-50 weight %, the molecular sieve of 10-70 weight %, the clay of 0-75 weight % is with P
2O
5Meter, the phosphorus of 0.1-4 weight %, in oxide, the alkaline-earth metal of 0.1-4 weight %, described molecular sieve are y-type zeolite.
8. method according to claim 7 is characterized in that, the described aluminium compound that can form η-aluminium oxide and/or χ-aluminium oxide is α-gibbsite and/or β-gibbsite; The described aluminium compound that can form gama-alumina is boehmite, boehmite and/or aluminium colloidal sol.
9. method according to claim 7 is characterized in that described phosphorus compound is selected from one or more in phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric acid, pyrophosphate, polymer phosphate, polymeric phosphate, metaphosphoric acid, the metaphosphate.
10. method according to claim 9 is characterized in that described phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), phosphorous acid, ammonium phosphite, sodium pyrophosphate, sodium phosphate trimer, the calgon.
11. method according to claim 7 is characterized in that, described alkaline earth metal compound is selected from one or more in magnesium chloride, magnesium nitrate, magnesium sulfate, calcium chloride, calcium nitrate, calcium acetate, barium chloride, barium nitrate, the barium acetate.
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| CNB2004100711175A CN1311906C (en) | 2004-07-29 | 2004-07-29 | Cracking catalyst for hydrocarbon and preparation method |
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| CO5930068A1 (en) * | 2006-12-06 | 2008-06-27 | Ecopetrol Sa | PRODUCTION PROCESS OF VANADIUM TRAPS BY IMPREGNATION AND VANADIUM TRAP PRODUCED BY SUCH PROCESS |
| 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 |
| EP2729553A4 (en) * | 2011-07-06 | 2015-04-29 | Reliance Ind Ltd | Process and composition of catalyst/ additive for reducing fuel gas yield in fluid catalytic cracking (fcc) process |
| RU2761921C2 (en) * | 2019-11-11 | 2021-12-14 | Общество с ограниченной ответственностью «Научно-производственное объединение 2К - процессинг» | Method for obtaining multifunctional nano-disperse catalytic system based on native chelate complexes of metals under conditions of thermolysis of hydrocarbon raw materials |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4810369A (en) * | 1987-05-07 | 1989-03-07 | Union Oil Company Of California | Process for the catalytic cracking of feedstocks containing high levels of nitrogen |
| CN1062157A (en) * | 1991-10-24 | 1992-06-24 | 中国石油化工总公司石油化工科学研究院 | The cracking catalyst and the preparation of phosphorous and hydrogen Y molecular sieve |
| CN1325940A (en) * | 2000-05-31 | 2001-12-12 | 中国石油化工集团公司 | P-contained cracking catalyst for hydrocarbons and its preparing process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4810369A (en) * | 1987-05-07 | 1989-03-07 | Union Oil Company Of California | Process for the catalytic cracking of feedstocks containing high levels of nitrogen |
| CN1062157A (en) * | 1991-10-24 | 1992-06-24 | 中国石油化工总公司石油化工科学研究院 | The cracking catalyst and the preparation of phosphorous and hydrogen Y molecular sieve |
| CN1325940A (en) * | 2000-05-31 | 2001-12-12 | 中国石油化工集团公司 | P-contained cracking catalyst for hydrocarbons and its preparing process |
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