CN1727444A - Cracking catalyst for hydrocarbon and preparation method - Google Patents
Cracking catalyst for hydrocarbon and preparation method Download PDFInfo
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- CN1727444A CN1727444A CN 200410071117 CN200410071117A CN1727444A CN 1727444 A CN1727444 A CN 1727444A CN 200410071117 CN200410071117 CN 200410071117 CN 200410071117 A CN200410071117 A CN 200410071117A CN 1727444 A CN1727444 A CN 1727444A
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Abstract
A cracking catalyst for hydrocarbon contains the eta-alumina and/or x-alumina or the mixture of said alumina (0.5-50 Wt %) and gamma-alumina (0-50), Y zeolite (10-70), clay (0-75), P (0.1-4) and alkali-earth metal (0.1-4). It has high resistance to heavy metal pollution.
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 poisoning of catalyst 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 value, because environmental requirement needs to reduce the FCC olefin content in gasoline.In order to remedy the loss of the gasoline octane rating 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 catalyzer is by the composite aluminum base al binder of being made up of according to 1: 9 to 9: 1 weight ratio pseudo-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 supersiliceous zeolite and/or HZSM-5 zeolite of 0-10 weight %.
CN1072201A discloses a kind of hydrocarbon conversion catalyst of producing stop bracket gasoline and alkene, this catalyzer 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 stop bracket gasoline of producing, propylene, the hydrocarbon conversion catalyst of butylene, this catalyzer 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 phosphorated hydrocarbon cracking catalyzer, and this catalyzer 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 aluminum 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 aluminum oxide are respectively from pseudo-boehmite and aluminium colloidal sol.This catalyzer 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 Trimethylmethane are rich in a kind of production, this catalyzer 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 type-Y high silicon 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 type-Y high silicon 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 mordenite or ZRP zeolite.
Aluminum oxide is the component that cracking catalyst contains usually.In the prior art, aluminum oxide is many from monohydrate alumina and aluminium colloidal sol, wherein, monohydrate alumina comprises boehmite and pseudo-boehmite, in the roasting process of Preparation of Catalyst, boehmite, pseudo-boehmite and aluminium colloidal sol all change gama-alumina into, and the contained aluminum oxide of the described catalyzer of above-mentioned prior art is gama-alumina.
Aluminum oxide can also be from hibbsite.Alumina trihydrate comprises α-alumina trihydrate, β-alumina trihydrate (or claiming surge aluminium stone) and promise diaspore, and in catalyst preparation process, α-alumina trihydrate is transformed into the x-aluminum oxide, and β-alumina trihydrate then is transformed into η-aluminum oxide.The promise diaspore just exists at occurring in nature, still can't obtain by synthetic.CN1388214 discloses a kind of preparation method of fluid cracking catalyst, this method is to contain the cracking catalyst component mixture drying of clay, aluminum oxide and molecular sieve, contains the aluminum oxide from β-alumina trihydrate of 1.5-55 weight % in the described catalyzer.This catalyzer has stronger heavy oil cracking activity and lightweight 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 catalyzer 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 alumina trihydrate in the cracking catalyst preparation is also arranged,, its purpose just improves the cracking ability of catalyzer, 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 stock oil of heavy metal content such as Ni-V-Fe, in cracking catalyst, introduce aluminum oxide, phosphorus and alkaline-earth metal that alumina trihydrate forms simultaneously, the aluminum oxide that forms of β-alumina trihydrate particularly, be η-aluminum oxide, phosphorus and alkaline-earth metal, produced special synergistic effect, in light oil with high yield, can also improve quality of gasoline, and when the higher hydrocarbon ils of heavy metal content such as catalytic cracking Ni-V-Fe, this catalyzer still has higher cracking activity.
Catalyzer provided by the invention contains aluminum oxide and molecular sieve, contain or do not contain clay, wherein, described aluminum oxide is η-aluminum oxide and/or x-aluminum oxide, or the mixture of η-aluminum oxide and/or x-aluminum oxide and gama-alumina, this catalyzer also contains phosphorus and alkaline-earth metal, with the catalyzer total amount is benchmark, the content of η-aluminum oxide and/or x-aluminum 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 of clay is 0-75 weight %, with P
2O
5Meter, the content of phosphorus is 0.1-4 weight %, and in oxide compound, 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 aluminum compound, molecular sieve and water, contain or slurry dried not argillaceous and roasting, wherein, described aluminum compound is the aluminum compound that can form η-aluminum oxide and/or x-aluminum oxide, or can form the aluminum compound of η-aluminum oxide and/or x-aluminum oxide and can form the mixture of the aluminum compound of gama-alumina, before roasting, also add phosphorus and alkaline earth metal compounds, the consumption of each component makes in the final catalyzer and contains, with the catalyzer total amount is benchmark, 0.5-50 the η-aluminum oxide of weight % and/or x-aluminum 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 compound, the alkaline-earth metal of 0.1-4 weight %, described molecular sieve are y-type zeolite.
Catalyzer 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 contaminations such as nickel, vanadium and iron, catalyzer still has higher cracking activity and higher lightweight oil productive rate, has lower olefin(e) centent and higher aromatic hydrocarbons and isoparaffin content in the gasoline.
Embodiment
According to catalyzer provided by the invention, under the preferable case, the content of η-aluminum oxide and/or x-aluminum 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 compound, 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, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite one or more.Preferred clay is one or more in kaolin, polynite, 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 aluminum compound is the aluminum compound that can form η-aluminum oxide and/or x-aluminum oxide, or can form the aluminum compound of η-aluminum oxide and/or x-aluminum oxide and can form the mixture of the aluminum compound of gama-alumina.
The described aluminum compound that can form η-aluminum oxide and/or x-aluminum oxide can be any in catalyst preparation process, can form the aluminum compound of η-aluminum oxide and/or x-aluminum oxide, be preferably α-alumina trihydrate and/or β-alumina trihydrate, more preferably β-alumina trihydrate.
The described aluminum compound that can form gama-alumina can be any in catalyst preparation process, can form the aluminum compound of gama-alumina, is preferably boehmite, pseudo-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 pickling process substep or introduce phosphorus and alkaline earth metal compound, roasting then together.In the catalyzer 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, phosphoric acid salt, phosphorous acid, phosphite, tetra-sodium, pyrophosphate salt, polymer phosphate, polymeric phosphate, metaphosphoric acid, the metaphosphate one or more, be preferably in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, phosphorous acid, ammonium phosphite, trisodium phosphate, potassium pyrophosphate, tripoly phosphate sodium STPP, Potassium tripolyphosphate, Sodium hexametaphosphate 99, the hexa metaphosphoric acid potassium one or more.One or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate, phosphorous acid, ammonium phosphite, trisodium phosphate, tripoly phosphate sodium STPP, the Sodium hexametaphosphate 99 more preferably.
Described alkaline earth metal compound comprises the compound of various soluble alkaline earth, as in beryllium chloride, magnesium chloride, magnesium nitrate, sal epsom, calcium chloride, nitrocalcite, calcium acetate, strontium chloride, strontium nitrate, strontium acetate, bariumchloride, nitrate of baryta, the barium acetate one or more, be preferably in magnesium chloride, magnesium nitrate, sal epsom, calcium chloride, nitrocalcite, calcium acetate, bariumchloride, nitrate of baryta, the barium acetate one or more.
The consumption of each component makes in the final catalyzer and contains, and is benchmark with the catalyzer total amount, the gama-alumina of the η-aluminum oxide of 0.5-50 weight % and/or x-aluminum 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 compound, the alkaline-earth metal of 0.1-4 weight %.Under the preferable case, the consumption of each component makes η-aluminum oxide and/or the x-aluminum oxide that contains 5-25 weight % in the final catalyzer, 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 compound, 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 exsiccant temperature 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 spraying drying, preferably oven dry or spray-dired method as oven dry.
Catalyzer 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 heavy metal content such as Ni-V-Fe and boiling point thereof petroleum fractions greater than 330 ℃, as normal pressure residual oil, vacuum 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 working conditions of catalyzer provided by the invention is conventional cracking reaction condition, and in general, described cracking conditions comprises that temperature of reaction is 350-700 ℃, is preferably 400-650 ℃, and agent-oil ratio (weight ratio of catalyzer 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-alumina trihydrate is 64 weight % (research institute of Shandong Aluminium Industrial Corp products); The alumina content of pseudo-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 polynite is 80 weight % (Hubei Zhong Xiang county iron ore factory products); The phosphorated 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 silicon oxide and aluminum oxide.
Example 1-6
Following example illustrates Catalysts and its preparation method provided by the invention.
With β-alumina trihydrate or β-alumina trihydrate and pseudo-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 catalyzer C provided by the invention
1-C
6Wherein, preparing catalyzer by the method for example 6, is to replace example 5 described pseudo-boehmites with aluminium colloidal sol, obtains catalyzer C
6The consumption of β-alumina trihydrate and pseudo-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, maturing temperature and time list in the table 6.Catalyzer 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 catalyzer, 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-alumina trihydrate and pseudo-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, maturing 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 x or η-aluminum oxide and preparation method thereof.
Method by example 1 prepares catalyzer, and different is to replace β-alumina trihydrate with pseudo-boehmite, obtains reference catalyst CB
2The consumption of pseudo-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, maturing temperature and time list in the table 6.Reference catalyst CB
2Composition list in the table 7.
Table 1
| Example number | β-alumina trihydrate consumption, kilogram | Pseudo-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 | Polynite | 63.4 |
| 5 | Kaolin | 47.0 |
| 6 | Kaolin | 47.0 |
Table 4
| Example number | The phosphorus compound kind | The phosphorus compound consumption, kilogram |
| 1 | Secondary ammonium phosphate | 1.3 |
| Comparative Examples 1 | - | - |
| Comparative Examples 2 | Secondary ammonium phosphate | 1.3 |
| 2 | Sodium hexametaphosphate 99 | 2.2 |
| 3 | Ammonium phosphate | 4.2 |
| 4 | Ammonium phosphate | 0.7 |
| 5 | Primary ammonium phosphate | 0.8 |
| 6 | Primary ammonium phosphate | 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 | Nitrocalcite | 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 | Drying temperature, ℃ | Maturing 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 catalyzer numbering | η-alumina content, weight % | Gama-alumina content, weight % | Molecular sieve content, weight % | Clay content, weight % | P 2O 5Content, weight % | Alkaline earth metal 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 catalyzer provided by the invention.
Respectively with catalyzer C
1-C
6Carrying out Ni-V-Fe pollutes, promptly flooded 1 hour with the kerosin that contains nickel naphthenate and naphthenic acid 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% water vapour, at the nickel that pollutes 4000ppm on the catalyzer, the vanadium of 1500ppm and the iron of 3000ppm.On the small-sized fluidized bed reaction unit, with the catalyzer C after the above-mentioned pollution
1-C
6, stock oil carries out catalytic cracking shown in the his-and-hers watches 8, and the catalyzer loading amount is 90 grams.Reaction conditions and reaction result are listed in the table 9.
Wherein, transformation efficiency=dry gas yield+yield of liquefied gas+yield of gasoline+coking yield; Lightweight 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 catalyzer, and under same condition, same stock 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 conditions and reaction result are listed in the table 9.
Table 8
| Stock oil | Long residuum |
| 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, ℃ | 0.8977 5.14 1.4884 23.61 13.72 44 97.7 |
| Elementary composition, weight % C H S N | 86.89 12.77 0.13 0.21 |
| Four components, weight % stable hydrocarbon 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 catalyzer numbering | C 1 | CB 1 | CB 2 | C 2 | C 3 | C 4 | C 5 | C 6 |
| Temperature of reaction, ℃ | 510 | 510 | 510 | 460 | 530 | 490 | 500 | 500 |
| Agent-oil ratio | 5.0 | 5.0 | 5.0 | 6.0 | 3.5 | 4.5 | 5.5 | 5.5 |
| Weight hourly space velocity, hour -1 | 26.0 | 26.0 | 26.0 | 30.0 | 28.0 | 24.0 | 24.0 | 24.0 |
| Transformation efficiency, weight % | 71.5 | 68.4 | 66.7 | 77.8 | 74.9 | 72.4 | 73.3 | 72.8 |
| Lightweight 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 stock oil is carried out catalytic cracking, compare with the use reference catalyst, though use catalyzer provided by the invention to pollute the beavy metal impurity of going up high level, transformation efficiency 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 catalyzer contains aluminum oxide and molecular sieve, contain or do not contain clay, it is characterized in that, described aluminum oxide is η-aluminum oxide and/or x-aluminum oxide, or the mixture of η-aluminum oxide and/or x-aluminum oxide and gama-alumina, this catalyzer also contains phosphorus and alkaline-earth metal, with the catalyzer total amount is benchmark, the content of η-aluminum oxide and/or x-aluminum 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 compound, the content of alkaline-earth metal is 0.1-4 weight %, and described molecular sieve is a y-type zeolite.
2. catalyzer according to claim 1 is characterized in that, the content of η-aluminum oxide and/or x-aluminum 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 compound, the content of alkaline-earth metal is 0.2-2.5 weight %.
3. catalyzer 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. catalyzer 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. catalyzer according to claim 1 is characterized in that described alkaline-earth metal is selected from one or more in magnesium, calcium, the barium.
6. catalyzer according to claim 1 and 2, it is characterized in that described clay is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite.
7. claim 1 Preparation of catalysts method, this method comprises and will contain aluminum compound, molecular sieve and water, contain or slurry dried not argillaceous and roasting, it is characterized in that, described aluminum compound is the aluminum compound that can form η-aluminum oxide and/or x-aluminum oxide, or can form the aluminum compound of η-aluminum oxide and/or x-aluminum oxide and can form the mixture of the aluminum compound of gama-alumina, before roasting, also add phosphorus and alkaline earth metal compounds, the consumption of each component makes in the final catalyzer and contains, with the catalyzer total amount is benchmark, 0.5-50 the η-aluminum oxide of weight % and/or x-aluminum 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 compound, 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 aluminum compound that can form η-aluminum oxide and/or x-aluminum oxide is α-alumina trihydrate and/or β-alumina trihydrate; The described aluminum compound that can form gama-alumina is boehmite, pseudo-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, phosphoric acid salt, phosphorous acid, phosphite, tetra-sodium, pyrophosphate salt, 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, primary ammonium phosphate, phosphorous acid, ammonium phosphite, trisodium phosphate, tripoly phosphate sodium STPP, the Sodium hexametaphosphate 99.
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, sal epsom, calcium chloride, nitrocalcite, calcium acetate, bariumchloride, nitrate of baryta, the barium acetate.
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Cited By (4)
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| WO2009000164A1 (en) * | 2007-06-27 | 2008-12-31 | China Petroleum & Chemical Corporation | A catalytic cracking catalyst, its preparation and use |
| WO2013005225A1 (en) * | 2011-07-06 | 2013-01-10 | Reliance Industries Ltd. | Process and composition of catalyst/ additive for reducing fuel gas yield in fluid catalytic cracking (fcc) process |
| CN101573430B (en) * | 2006-12-06 | 2013-09-25 | 哥伦比亚国家石油股份有限公司 | Method for producing vanadium traps by means of impregnation and resulting vanadium trap |
| 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 |
Family Cites Families (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 |
| CN1024504C (en) * | 1991-10-24 | 1994-05-18 | 中国石油化工总公司石油化工科学研究院 | Cracking catalyst containing phosphate and hydrogen Y molecular sieve, and its preparation |
| CN1142019C (en) * | 2000-05-31 | 2004-03-17 | 中国石油化工集团公司 | P-contained cracking catalyst for hydrocarbons and its preparing process |
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| CN101573430B (en) * | 2006-12-06 | 2013-09-25 | 哥伦比亚国家石油股份有限公司 | Method for producing vanadium traps by means of impregnation and resulting vanadium trap |
| WO2009000164A1 (en) * | 2007-06-27 | 2008-12-31 | China Petroleum & Chemical Corporation | A catalytic cracking catalyst, its preparation and use |
| RU2471553C2 (en) * | 2007-06-27 | 2013-01-10 | Чайна Петролеум Энд Кэмикал Корпорэйшн | Catalyst for catalytic cracking, its production and application |
| US9486795B2 (en) | 2007-06-27 | 2016-11-08 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst, its preparation and use |
| WO2013005225A1 (en) * | 2011-07-06 | 2013-01-10 | Reliance Industries Ltd. | Process and composition of catalyst/ additive for reducing fuel gas yield in fluid catalytic cracking (fcc) process |
| CN103703105A (en) * | 2011-07-06 | 2014-04-02 | 瑞来斯实业有限公司 | Process and composition of catalyst/ additive for reducing fuel gas yield in fluid catalytic cracking (FCC) process |
| 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 |
| CN103703105B (en) * | 2011-07-06 | 2016-05-18 | 瑞来斯实业有限公司 | The technique of catalyst/additive and constituent, for reducing the fuel gas yield in fluid catalystic cracking (FCC) process |
| US9783743B2 (en) | 2011-07-06 | 2017-10-10 | Reliance Industries Limited | 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 |
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| CN1311906C (en) | 2007-04-25 |
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