CN100510014C - Cracking catalyst for preparing high-quality gasoline, and preparing method thereof - Google Patents
Cracking catalyst for preparing high-quality gasoline, and preparing method thereof Download PDFInfo
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- CN100510014C CN100510014C CNB200510004963XA CN200510004963A CN100510014C CN 100510014 C CN100510014 C CN 100510014C CN B200510004963X A CNB200510004963X A CN B200510004963XA CN 200510004963 A CN200510004963 A CN 200510004963A CN 100510014 C CN100510014 C CN 100510014C
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Abstract
A cracking catalyst for preparing high quality of gas oil includes Al2O and molecular sieves and clays may be included in it or not, in which, said Al2O is eta or chi one or a mixture of eta-Al2O and/or chi-Al2O with gamma-Al2O, said catalyst also includes P and rare earth metal, taking the gross of the catalyst as the primary, the content of eta-Al2O or chi-Al2O is 0.5-50weight%, the gamma-Al2O is 0-50%, the clay is 0-75%, counting it in P<SUB>2</SUB>0<SUB>5</SUB>, content of P is 0.1-8% and in oxide, the rare earth metal is 2-6%, the molecular sieve is 10-70%, which is Y-type zeolite.
Description
Technical field
The invention relates to a kind of hydrocarbon cracking catalyzer and preparation method thereof.
Background technology
The heaviness tendency of catalytically cracked stock is serious day by day, and this just requires cracking catalyst and cracking technology to have stronger cracking ability, to reach the purpose of light oil with high yield (gasoline and diesel oil) and liquefied gas.
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 the weight ratio of 1:9 to 9:1 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 made up of the full synthesis carrier of ZSM-5, the REY of 10-40 weight % 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, 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 hydrocarbon conversion catalyst of producing stop bracket gasoline, propylene and 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, still, uses this catalyzer to fail to improve the quality of catalytic cracking diesel oil.
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 χ-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.
Summary of the invention
The purpose of this invention is to provide a kind of cracking catalyst of producing high-quality gasoline, use in the cracked product of this catalyzer, the olefin(e) centent of gasoline is lower, and aromatic hydrocarbons and isoparaffin content are higher.
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 cracking catalyst, and to gasoline in the cracked product and not influence of diesel quality.The present inventor is surprised to find that, in cracking catalyst, introduce the aluminum oxide that phosphorus and alumina trihydrate form simultaneously, particularly the aluminum oxide of β-alumina trihydrate formation is η-aluminum oxide, has produced special synergistic effect, can significantly improve quality of gasoline in the cracked product.
Catalyzer provided by the invention 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 χ-aluminum oxide, or the mixture of η-aluminum oxide and/or χ-aluminum oxide and gama-alumina, this catalyzer also contains phosphorus and rare earth metal, with the catalyzer total amount is benchmark, and the content of η-aluminum oxide and/or χ-aluminum oxide is 0.5-50 weight %, and the content of gama-alumina is 0-50 weight %, the content of clay is 0-75 weight %, with P
2O
5Meter, the content of phosphorus is 0.1-8 weight %, and in oxide compound, the content of rare earth metal is 2-6 weight %, and the content of molecular sieve is 10-70 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, it is characterized in that, described aluminum compound is the aluminum compound that can form the aluminum compound of η-aluminum oxide and/or can form χ-aluminum oxide, or can form the aluminum compound of η-aluminum oxide and/or can form the aluminum compound of χ-aluminum oxide and can form the mixture of the aluminum compound of gama-alumina, before roasting, also add phosphorus compound and rare earth compound, the consumption of each component makes in the final catalyzer and contains, with the catalyzer total amount is benchmark, 0.5-50 η-aluminum oxide of weight % and/or χ-aluminum oxide, the gama-alumina of 0-50 weight %, the clay of 0-75 weight % is with P
2O
5Meter, the phosphorus of 0.1-8 weight %, in oxide compound, the rare earth metal of 2-6 weight %, the molecular sieve of 10-70 weight %, described molecular sieve are y-type zeolite.
Catalyzer provided by the invention has improved the quality of gasoline in the cracked product significantly, shows, gasoline has lower olefin(e) centent and higher aromatic hydrocarbons and isoparaffin content.
Embodiment
According to catalyzer provided by the invention, under the preferable case, the content of η-aluminum oxide and/or χ-aluminum oxide is 20-45 weight %, and the content of gama-alumina is 0-40 weight %, and the content of clay is 0-55 weight %, with P
2O
5Meter, the content of phosphorus is 0.5-5 weight %, and in oxide compound, the content of rare earth metal is 2-4.5 weight %, and the content of molecular sieve is 20-50 weight %, and described molecular sieve is a y-type zeolite.
Described molecular screening one or more in the overstable gamma zeolite of HY zeolite, rare earth HY zeolite, rare earth exchanged Y zeolite, overstable gamma zeolite, modification, its middle-weight rare earths HY zeolite also can phosphorous and/or iron, rare earth exchanged Y zeolite also can phosphorous and/or iron, and the overstable gamma zeolite of modification also can contain one or more in rare earth, phosphorus, the iron.Preferred molecular screening from rare earth exchanged Y zeolite, the overstable gamma zeolite of phosphorous and/or iron, contain one or more the overstable gamma zeolite of modification in rare earth, phosphorus, the iron.
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 the aluminum compound of η-aluminum oxide and/or can form χ-aluminum oxide, or can form the aluminum compound of η-aluminum oxide and/or can form the aluminum compound of χ-aluminum oxide and can form the mixture of the aluminum compound of gama-alumina.
The described aluminum compound that can form η-aluminum oxide can be any in catalyst preparation process, can form the aluminum compound of η-aluminum oxide, is preferably β-alumina trihydrate; The aluminum compound that can form χ-aluminum oxide can be any in catalyst preparation process, can form the aluminum compound of χ-aluminum oxide, is preferably α-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 selected from boehmite, pseudo-boehmite, the aluminium colloidal sol one or more.
Described phosphorus compound and rare earth 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 rare earth compound, roasting then together.In the catalyzer of the present invention, the content of described phosphorus and rare earth metal does not comprise phosphorus and the rare earth metal that molecular sieve contained originally.
Described phosphorus compound comprises the compound of various phosphorus, as one or more in phosphoric acid, phosphoric acid salt, phosphorous acid, phosphite, tetra-sodium, pyrophosphate salt, polymer phosphate, polymeric phosphate, metaphosphoric acid, the metaphosphate, be preferably in phosphoric acid, ammonium phosphate, Secondary ammonium 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, Secondary ammonium phosphate, primary ammonium phosphate, phosphorous acid, ammonium phosphite, trisodium phosphate, tripoly phosphate sodium STPP, the Sodium hexametaphosphate 99 more preferably.
Described rare earth compound comprises the compound of various soluble ree metals, as in rare earth chloride, the rare earth nitrate one or more, is preferably rare earth chloride.
The consumption of each component makes in the final catalyzer and contains, and is benchmark with the catalyzer total amount, the gama-alumina of η-aluminum oxide of 0.5-50 weight % and/or χ-aluminum oxide, 0-50 weight %, and the clay of 0-75 weight % is with P
2O
5Meter, the phosphorus of 0.1-8 weight %, in oxide compound, the rare earth metal of 2-6 weight %, the molecular sieve of 10-70 weight %, described molecular sieve are y-type zeolite.Under the preferable case, the consumption of each component makes in the final catalyzer and contains, and is benchmark with the catalyzer total amount, and the content of η-aluminum oxide and/or χ-aluminum oxide is 20-45 weight %, the content of gama-alumina is 0-40 weight %, the content of clay is 0-55 weight %, and in P2O5, the content of phosphorus is 0.5-5 weight %, in oxide compound, the content of rare earth metal is 2-4.5 weight %, and the content of molecular sieve is 20-50 weight %, and described molecular sieve is a y-type zeolite.
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 as dry, dry, spraying drying, preferably the oven dry or spray-dired method.
Catalyzer provided by the invention is applicable to oil and various cut thereof is carried out catalytic cracking, be particularly suitable for oil and boiling point petroleum fractions greater than 330 ℃, as normal pressure residual oil, vacuum residuum, decompressed wax oil, normal pressure wax oil, straight-run gas oil, propane light/in heavy deasphalted oil and the wax tailings one or more 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.
Catalyzer provided by the invention has improved the quality of gasoline in the cracked product significantly, shows, gasoline has lower olefin(e) centent and higher aromatic hydrocarbons and isoparaffin content.
The following examples will the present invention will be further described, but therefore do not limit the present invention.
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).
In the example, used kaolinic solid content 76 weight % (China Kaolin Co., Ltd's product); The solid content of polynite is 80 weight % (Zhongxiang City, Hubei iron ore factory products).
In the example, used REHY zeolite be a kind of y-type zeolite that contains rare earth (content of rare earth oxide is 8.4 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 3.7 weight %, and silica alumina ratio is 5.6, and lattice constant is 2.461nm, and the Shandong catalyst plant is produced); 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 lattice constant is 2.468nm, and the Shandong catalyst plant is produced); The MOY zeolite be a kind of phosphorous and rare earth y-type zeolite (content of rare earth oxide is 8.0 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 1.3 weight %, and in element phosphor, phosphorus content is 1.1 weight %, and silica alumina ratio is 5.6, and lattice constant is 2.460nm, 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 lattice constant is 2.446nm, 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 lattice constant is 2.447nm, and the Shandong catalyst plant is produced).Above-mentioned silica alumina ratio all refers to the mol ratio of silicon oxide and aluminum oxide.
In the example, used phosphorated compound is a chemical pure; Re chloride (prepared in laboratory, the concentration of rare earth oxide are 219 grams per liters, wherein, and La
2O
3Account for rare earth oxide 53.2%, CeO
2Account for rare earth oxide 13.0%, Pr
6O
11Account for rare earth oxide 13.0%, Nd
2O
3Account for 20.8% of rare earth oxide, the solid rare earth chloride is produced by Inner Mongol Baotou rare earth factory).
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, rare earth 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 the kind of the kind of the consumption of β-alumina trihydrate and pseudo-boehmite, the kind of clay and consumption, molecular sieve and consumption, phosphorus compound and consumption, re chloride is 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 rare earth metal and preparation method thereof.
Method by example 1 prepares catalyzer, and different is not add phosphorus compound and rare earth metal solution, and the consumption difference of clay gets reference catalyst CB
1The kind of the consumption of β-alumina trihydrate and pseudo-boehmite, the kind of clay and consumption, molecular sieve and consumption are listed in respectively among the table 1-4.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 χ-aluminum oxide 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 the kind of the kind of the consumption of pseudo-boehmite, the kind of clay and consumption, molecular sieve and consumption, phosphorus compound and consumption, re chloride is 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 | 51.6 | - |
| Comparative Examples 1 | 51.6 | - |
| Comparative Examples 2 | - | 53.2 |
| 2 | 34.4 | 25.8 |
| 3 | 64.1 | 38.7 |
| 4 | 31.3 | 9.7 |
| 5 | 46.9 | 24.2 |
| 6 | 46.9 | /69.4 |
Table 2
| Example number | The molecular sieve kind | The molecular sieve consumption, kilogram |
| 1 | MOY+REY | 20+5 |
| Comparative Examples 1 | MOY+REY | 20+5 |
| Comparative Examples 2 | MOY+REY | 20+5 |
| 2 | DASY0.0 | 48 |
| 3 | MOY+DASY2.0 | 15+18 |
| 4 | REY | 20.1 |
| 5 | REHY | 30 |
| 6 | REHY | 30 |
Table 3
| Example number | Clay types | The clay consumption, kilogram |
| 1 | Kaolin | 48.0 |
| Comparative Examples 1 | Kaolin | 55.3 |
| Comparative Examples 2 | Kaolin | 48.0 |
| 2 | Kaolin | 9.6 |
| 3 | - | - |
| 4 | Polynite | 63.0 |
| 5 | Kaolin | 27.9 |
| 6 | Kaolin | 27.9 |
Table 4
| Example number | The phosphorus compound kind | The phosphorus compound consumption, kilogram |
| 1 | Secondary ammonium phosphate | 2.8 |
| Comparative Examples 1 | - | - |
| Comparative Examples 2 | Secondary ammonium phosphate | 2.8 |
| 2 | Sodium hexametaphosphate 99 | 6.5 |
| 3 | Ammonium phosphate | 4.2 |
| 4 | Ammonium phosphate | 1.3 |
| 5 | Primary ammonium phosphate | 1.6 |
| 6 | Primary ammonium phosphate | 1.6 |
Table 5
| Example number | The re chloride consumption rises |
| 1 | 18.3 |
| Comparative Examples 1 | 0 |
| Comparative Examples 2 | 18.3 |
| 2 | 10.0 |
| 3 | 11.4 |
| 4 | 13.2 |
| 5 | 12.8 |
| 6 | 12.8 |
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 | 1 | Comparative Examples 1 | Comparative Examples 2 | 2 | 3 | 4 | 5 | 6 |
| The catalyzer numbering | C1 | CB1 | CB2 | C2 | C3 | C4 | C5 | C6 |
| Form weight % | ||||||||
| η-aluminum oxide | 33.0 | 33.0 | 0 | 22.0 | 41.0 | 20.0 | 30.0 | 30.0 |
| Gama-alumina | 0 | 0 | 33.0 | 16.0 | 21.5 | 6.0 | 15.0 | 15.0 |
| Molecular sieve | 25.0 | 25.0 | 25.0 | 48.0 | 33.0 | 20.1 | 30.0 | 30.0 |
| Clay | 36.5 | 42.0 | 36.5 | 7.3 | 0 | 50.4 | 21.2 | 21.2 |
| P 2O 5 | 1.5 | 0 | 1.5 | 4.5 | 2.0 | 0.6 | 1.0 | 1.0 |
| RE 2O 3 | 4.0 | 0 | 4.0 | 2.2 | 2.5 | 2.9 | 2.8 | 2.8 |
Example 7-12
Following example illustrates the catalytic performance of catalyzer provided by the invention.
Respectively with catalyzer C
1-C
6At 800 ℃, wore out 8 hours with 100% water vapour.On the small-sized fluidized bed reaction unit, with the catalyzer C after above-mentioned the wearing out
1-C
6Stock 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=gas recovery ratio+yield of gasoline+coking 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 gas comprises liquefied gas and dry gas, and wherein 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 wears out to catalyzer, and under same condition, same stock oil is carried out catalytic cracking, and that different is the reference catalyst CB that catalyst system therefor is respectively Comparative Examples 1 and Comparative Examples 2 preparations
1And CB
2, reaction conditions and reaction result are listed in the table 9.
Table 8
| Stock oil | The mixing oil of decompressed wax oil and vacuum residuum |
| Density (20 ℃), gram per centimeter 3 | 0.9158 |
| Carbon residue, weight % | 3.0 |
| Refractive power (70 ℃) | 1.4974 |
| Viscosity (100 ℃), millimeter 2/ second | 26.69 |
| Zero pour, ℃ | 40 |
| Aniline point, ℃ | 95.8 |
| Elementary composition, weight % | |
| C | 85.98 |
| H | 12.86 |
| S | 0.55 |
| N | 0.18 |
| Four components, weight % | |
| Stable hydrocarbon | 61.6 |
| Aromatic hydrocarbons | 21.7 |
| Colloid | 16.5 |
| Bituminous matter | 0.2 |
| Boiling range, ℃ | |
| Initial boiling point | 243 |
| 5％ | 294 |
| 10％ | 316 |
| 30％ | 395 |
| 50％ | 429 |
| 70％ | 473 |
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, ℃ | 490 | 490 | 490 | 460 | 510 | 530 | 500 | 500 |
| Agent-oil ratio | 5.0 | 5.0 | 5.0 | 3.5 | 4.0 | 6.0 | 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 % | 75.9 | 72.2 | 71.4 | 83.5 | 79.4 | 75.6 | 78.3 | 78.0 |
| Product is formed, weight % | ||||||||
| Gas | 15.7 | 13.9 | 14.1 | 15.8 | 16.3 | 16.2 | 16.7 | 17.0 |
| Gasoline | 55.2 | 51.1 | 49.9 | 61.6 | 57.8 | 54.5 | 56.2 | 55.7 |
| Diesel oil | 14.2 | 11.5 | 11.3 | 12.2 | 13.5 | 13.8 | 13.8 | 13.6 |
| Coke | 5.0 | 7.2 | 7.4 | 6.1 | 5.3 | 4.9 | 5.4 | 5.3 |
| Unconverted heavy oil | 9.9 | 16.3 | 17.3 | 4.3 | 7.1 | 10.6 | 7.9 | 8.4 |
| Gasoline is formed, weight % | ||||||||
| Alkene | 23.1 | 32.5 | 33.0 | 19.4 | 21.8 | 23.5 | 22.6 | 22.9 |
| Aromatic hydrocarbons | 30.3 | 27.7 | 26.2 | 33.0 | 32.7 | 31.3 | 31.7 | 31.2 |
| Isoparaffin | 32.6 | 25.5 | 25.2 | 35.2 | 32.4 | 31.5 | 31.6 | 31.5 |
From the result of table 9 as can be seen, compare, use catalyzer provided by the invention that same stock oil is carried out catalytic cracking with using reference catalyst, transformation efficiency significantly improves, and, reduced olefin content in gasoline significantly, improved aromatic hydrocarbons and the isoparaffin content in the gasoline.This explanation, catalyzer provided by the invention not only has higher cracking activity and gasoline yield, and, improved the quality of gasoline in the cracked product significantly.
Claims (10)
1, a kind of cracking catalyst of producing high-quality gasoline, 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 χ-aluminum oxide, or the mixture of η-aluminum oxide and/or χ-aluminum oxide and gama-alumina, this catalyzer also contains phosphorus and rare earth metal, with the catalyzer total amount is benchmark, the content of η-aluminum oxide and/or χ-aluminum oxide is 0.5-50 weight %, the content of gama-alumina is 0-50 weight %, and the content of clay is 0-75 weight %, with P
2O
5Meter, the content of phosphorus is 0.1-8 weight %, and in oxide compound, the content of rare earth metal is 2.2-6 weight %, and the content of molecular sieve is 10-70 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 χ-aluminum oxide is 20-45 weight %, and the content of gama-alumina is 0-40 weight %, and the content of clay is 0-55 weight %, with P
2O
5Meter, the content of phosphorus is 0.5-5 weight %, and in oxide compound, the content of rare earth metal is 2.2-4.5 weight %, and the content of molecular sieve is 20-50 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 HY zeolite, rare earth HY zeolite, rare earth exchanged Y zeolite, overstable gamma zeolite, modification.
4, catalyzer according to claim 3 is characterized in that the phosphorous and/or iron of described rare earth HY zeolite, the phosphorous and/or iron of described rare earth exchanged Y zeolite, and the overstable gamma zeolite of modification contains one or more in rare earth, phosphorus, the iron.
5, catalyzer according to claim 1 and 2 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.
6, a kind of method for preparing the described catalyzer of claim 1, 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 the aluminum compound of η-aluminum oxide and/or can form χ-aluminum oxide, or can form the aluminum compound of η-aluminum oxide and/or can form the aluminum compound of χ-aluminum oxide and can form the mixture of the aluminum compound of gama-alumina, before roasting, also add phosphorus compound and rare earth compound, the consumption of each component makes in the final catalyzer and contains, with the catalyzer total amount is benchmark, 0.5-50 η-aluminum oxide of weight % and/or χ-aluminum oxide, the gama-alumina of 0-50 weight %, the clay of 0-75 weight % is with P
2O
5Meter, the phosphorus of 0.1-8 weight %, in oxide compound, the rare earth metal of 2.2-6 weight %, the molecular sieve of 10-70 weight %, described molecular sieve are y-type zeolite.
7, method according to claim 6, it is characterized in that the described aluminum compound that can form η-aluminum oxide is β-alumina trihydrate, the aluminum compound that can form χ-aluminum oxide is α-alumina trihydrate, and the aluminum compound that can form gama-alumina is selected from one or more in boehmite, pseudo-boehmite, the aluminium colloidal sol.
8, method according to claim 6 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.
9, require described method according to right 8, it is characterized in that, described phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, Secondary ammonium phosphate, primary ammonium phosphate, phosphorous acid, ammonium phosphite, trisodium phosphate, tripoly phosphate sodium STPP, the Sodium hexametaphosphate 99.
10, method according to claim 6 is characterized in that, described rare earth compound is selected from one or more in rare earth chloride, the rare earth nitrate.
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| CNB200510004963XA CN100510014C (en) | 2005-01-31 | 2005-01-31 | Cracking catalyst for preparing high-quality gasoline, and preparing method thereof |
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| CNB200510004963XA CN100510014C (en) | 2005-01-31 | 2005-01-31 | Cracking catalyst for preparing high-quality gasoline, and preparing method thereof |
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| CN100510014C true CN100510014C (en) | 2009-07-08 |
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| TWI277648B (en) | 2004-07-29 | 2007-04-01 | China Petrochemical Technology | A cracking catalyst for hydrocarbons and its preparation |
| CN100389177C (en) * | 2005-01-31 | 2008-05-21 | 中国石油化工股份有限公司 | Heavy-oil catalytic-cracking catalyst and preparing method |
| WO2009089681A1 (en) | 2007-12-20 | 2009-07-23 | China Petroleum & Chemical Corporation | Improved integrated process for hydrogenation and catalytic cracking of hydrocarbon oil |
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