CN1322924C - Cracking catalyst for hydrocarbon and preparation method - Google Patents
Cracking catalyst for hydrocarbon and preparation method Download PDFInfo
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- CN1322924C CN1322924C CNB200410071118XA CN200410071118A CN1322924C CN 1322924 C CN1322924 C CN 1322924C CN B200410071118X A CNB200410071118X A CN B200410071118XA CN 200410071118 A CN200410071118 A CN 200410071118A CN 1322924 C CN1322924 C CN 1322924C
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Abstract
The present invention relates to a cracking catalyst for hydrocarbon, which comprises aluminum oxide and a molecular sieve and contains or does not contain clay, wherein 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. 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, 0 to 75 wt% of the clay, 0.1 to 8 wt% of the phosphorus measured by P2O5, and 10 to 70 wt% of the molecular sieve. The molecular sieve is a zeolite mixture which comprises 30 to 90 wt% of Y-type zeolite and 10 to 70 wt% of zeolite with an MFI structure and uses the total weight of the zeolite mixture as a reference. The catalyst obviously increases the quality of gasoline and liquefied gas in cracked products.
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 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.
Moreover, low-carbon alkene and iso-butane contained in the liquefied gas that catalytic cracking obtains are basic Organic Chemicals, at present, supply falls short of demand for low-carbon alkene (particularly propylene) and iso-butane, and in the liquefied gas product of existing Cracking catalyst and explained hereafter, the low-carbon alkene (particularly propylene) and the content of iso-butane are lower, and therefore, Cracking catalyst and the cracking technology that has higher low-carbon alkene (particularly propylene) and iso-butane in the liquefied gas in a kind of crackate also is badly in need of developing in market.
CN1042201C discloses a kind of voluminous C
3-C
5The Cracking catalyst of alkene, this catalyst is by the y-type zeolite of 10-50 weight %, lattice constant≤2.45 nanometers, and 2-40 weight % is selected from P, RE, the ZSM-5 zeolite of H modification, the semi-synthetic carrier of the kaolin of 20-80 weight % and al binder is formed.
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 the y-type zeolite of 10-60 weight % and zeolite and/or the Beta zeolite with MFI structure, 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, still, uses this catalyst can not improve the content of low-carbon alkene and iso-butane in the liquefied gas.
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.Hibbsite comprises α-gibbsite, β-gibbsite (or claiming surge aluminium stone) and promise diaspore, and in catalyst preparation process, α-gibbsite is transformed into the x-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, can not improve the content of low-carbon alkene and iso-butane in the liquefied gas.
Summary of the invention
The purpose of this invention is to provide a kind of new hydrocarbon cracking catalyzer, use this catalyst cracking hydrocarbon ils, in the cracked product, the olefin(e) centent of gasoline is lower, and has higher low-carbon alkene and iso-butane content in the liquefied gas.
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 Cracking catalyst, and the quality of gasoline in the cracked product and liquefied gas is not influenced.The present inventor is surprised to find that, in Cracking catalyst, introduce aluminium oxide and the phosphorus that gibbsite forms simultaneously, the aluminium oxide that forms of β-gibbsite particularly, be η-aluminium oxide and phosphorus, produce special cooperative effect, can significantly improve the gasoline in the cracked product and the quality of liquefied gas.
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 x-aluminium oxide, or the mixture of η-aluminium oxide and/or x-aluminium oxide and gama-alumina, this catalyst also contains phosphorus, with the catalyst total amount is benchmark, and the content of η-aluminium oxide and/or x-aluminium 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 %, the content of molecular sieve is 10-70 weight %, described molecular sieve is the zeolite mixture that contains y-type zeolite and have the zeolite of MFI structure, with described zeolite mixture total amount is benchmark, the content of y-type zeolite is 30-90 weight %, and the content with zeolite of MFI structure is 10-70 weight %.
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 x-aluminium oxide, or can form the aluminium compound of η-aluminium oxide and/or x-aluminium oxide and can form the mixture of the aluminium compound of gama-alumina, the compound that before roasting, also adds phosphorus, the consumption of each component makes in the final catalyst and contains, with the catalyst total amount is benchmark, 0.5-50 the η-aluminium oxide of weight % and/or x-aluminium oxide, the gama-alumina of 0-50 weight %, the clay of 0-75 weight % is with P
2O
5Meter, 0.1-8 the phosphorus of weight %, the molecular sieve of 10-70 weight %, described molecular sieve is the zeolite mixture that contains y-type zeolite and have the zeolite of MFI structure, with described zeolite mixture total amount is benchmark, the content of y-type zeolite is 30-90 weight %, and the content with zeolite of MFI structure is 10-70 weight %.
Catalyst provided by the invention has improved the gasoline in the cracked product and the quality of liquefied gas significantly, show, have lower olefin(e) centent and higher aromatic hydrocarbons and isoparaffin content in the gasoline, have the content of higher low-carbon alkene, particularly propylene and iso-butane in the liquefied gas.
The specific embodiment
According to catalyst provided by the invention, under the preferable case, the content of η-aluminium oxide and/or x-aluminium 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 %, the content of molecular sieve is 20-50 weight %.
Described molecular sieve is the zeolite mixture that contains y-type zeolite and have the zeolite of MFI structure, is benchmark with described zeolite mixture total amount, and the content of y-type zeolite is 30-90 weight %, and the content with zeolite of MFI structure is 10-70 weight %.Under the preferable case, be benchmark with described zeolite mixture total amount, y-type zeolite content is 40-85 weight %, and the content with zeolite of MFI structure is 15-60 weight %.Described contain y-type zeolite and have in the zeolite mixture of zeolite of MFI structure can also optionally contain the Beta zeolite, be benchmark with described zeolite mixture total amount, the content of Beta zeolite is 0-30 weight %, is preferably 0-20 weight %.
Described y-type zeolite is selected from one or more in the overstable gamma zeolite of the y-type zeolite, overstable gamma zeolite of HY zeolite, phosphorous, iron and/or rare earth, phosphorous, iron and/or rare earth.The zeolite of the described MFI of having structure is selected from ZSM-5, (this zeolite is the zeolite with MFI structure that is similar to the phosphorous and/or rare earth of ZSM-5 for ZSM-5 zeolite, the ZRP zeolite of phosphorous and/or rare earth, the Shandong catalyst plant is produced, and is the zeolite of ZRP-1 and/or ZRP-5 as the industrial trade mark) in 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 x-aluminium oxide, or can form the aluminium compound of η-aluminium oxide and/or x-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 x-aluminium oxide can be any in catalyst preparation process, can form the aluminium compound of η-aluminium oxide and/or x-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 compound can add by the arbitrary steps before roasting, as joining aluminium 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, introduce phosphorus compound with infusion process again, then roasting.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 one or more in phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric acid, pyrophosphate, polymer phosphate, polymeric phosphate, metaphosphoric acid, the metaphosphate, 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.
The consumption of each component makes in the final catalyst and contains, and is benchmark with the catalyst total amount, the gama-alumina of the η-aluminium oxide of 0.5-50 weight % and/or x-aluminium oxide, 0-50 weight %, and the clay of 0-75 weight % is with P
2O
5Meter, the phosphorus of 0.1-8 weight %, the molecular sieve of 10-70 weight %.In the described molecular sieve, the y-type zeolite of 30-90 weight %, the zeolite of 10-70 weight % with MFI structure.Under the preferable case, the consumption of each component makes η-aluminium oxide and/or the x-aluminium oxide that contains 20-45 weight % in the final catalyst, the gama-alumina of 0-40 weight %, and the clay of 0-55 weight % is with P
2O
5Meter, the phosphorus of 0.5-5 weight %, the molecular sieve of 20-50 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 particularly suitable for oil and boiling point 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 and liquefied gas.
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 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 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 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 ZSM-5 zeolite is a kind of zeolite (Na with MFI structure
2O content is 0.2 weight %, and silica alumina ratio is 60, and the Shandong catalyst plant is produced); The ZRP-1 zeolite is a kind of zeolite (Na with MFI structure of phosphorous and rare earth
2O content 0.1 weight %, silica alumina ratio is 30, the content of rare earth oxide is 1.7 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, in element phosphor, phosphorus content is 1.9 weight %, and the Shandong catalyst plant is produced), the Na of Beta zeolite
2O content is 3.2 weight %, and silica alumina ratio is 28, 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 (or aluminium colloidal sol), the kind of clay and consumption, the kind of the kind of molecular sieve and consumption, phosphorus compound and consumption are listed in respectively among the table 1-4.Spray-dired temperature, sintering temperature and time list in the table 5.Catalyst C
1-C
6Composition list in the table 6.
Comparative Examples 1
Reference catalyst that the explanation of this Comparative Examples is not phosphorous and preparation method thereof.
Method by example 1 prepares catalyst, and different is not add phosphorus 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 1-4.Spray-dired temperature, sintering temperature and time list in the table 5.Reference catalyst CB
1Composition list in the table 6.
Comparative Examples 2
The explanation of this Comparative Examples does not contain reference catalyst of x 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 compound and consumption are listed in respectively among the table 1-4.Spray-dired temperature, sintering temperature and time list in the table 5.Reference catalyst CB
2Composition list in the table 6.
Table 1
| Example number | β-gibbsite consumption, kilogram | Boehmite/aluminium colloidal sol consumption, kilogram |
| 1 | 59.4 | - |
| Comparative Examples 1 | 59.4 | - |
| Comparative Examples 2 | - | 61.3/0 |
| 2 | 34.4 | 25.8/0 |
| 3 | 64.1 | 38.7/0 |
| 4 | 31.3 | 9.7/0 |
| 5 | 39.1 | 24.2/0 |
| 6 | 39.1 | 0/69.4 |
Table 2
| Example number | The molecular sieve kind | The molecular sieve consumption, kilogram |
| 1 | REHY+ZRP-1 | 25+5 |
| Comparative Examples 1 | REHY+ZRP-1 | 25+5 |
| Comparative Examples 2 | REHY+ZRP-1 | 25+5 |
| 2 | DASY 2.0+Beta+ZRP-1 | 30+8+10 |
| 3 | MOY+ZSM-5+ZRP-1 | 16+12+5 |
| 4 | MOY+ZSM-5 | 14+9 |
| 5 | REHY+DASY 0.0+ZSM-5 | 10+18+7 |
| 6 | REHY+DASY 0.0+ZSM-5 | 10+18+7 |
Table 3
| Example number | Clay types | The clay consumption, kilogram |
| 1 | Kaolin | 40.1 |
| Comparative Examples 1 | Kaolin | 42.1 |
| Comparative Examples 2 | Kaolin | 40.1 |
| 2 | Kaolin | 12.5 |
| 3 | - | - |
| 4 | Imvite | 63.0 |
| 5 | Kaolin | 31.6 |
| 6 | Kaolin | 31.6 |
Table 4
| Example number | The phosphorus compound kind | The phosphorus compound consumption, kilogram |
| 1 | Diammonium hydrogen phosphate | 2.8 |
| Comparative Examples 1 | - | - |
| Comparative Examples 2 | Diammonium hydrogen phosphate | 2.8 |
| 2 | Calgon | 6.5 |
| 3 | Ammonium phosphate | 4.2 |
| 4 | Ammonium phosphate | 1.3 |
| 5 | Ammonium dihydrogen phosphate (ADP) | 1.6 |
| 6 | Ammonium dihydrogen phosphate (ADP) | 1.6 |
Table 5
| 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 6
| Example number | The catalyst numbering | η-alumina content, weight % | Gama-alumina content, weight % | Molecular sieve content, weight % | Clay content, weight % | P 2O 5Content, weight % |
| 1 | C 1 | 38.0 | 0 | 30.0 | 30.5 | 1.5 |
| Comparative Examples 1 | CB 1 | 38.0 | 0 | 30.0 | 32.0 | 0 |
| Comparative Examples 2 | CB 2 | 0 | 38.0 | 30.0 | 30.5 | 1.5 |
| 2 | C 2 | 22.0 | 16.0 | 48.0 | 9.5 | 4.5 |
| 3 | C 3 | 41.0 | 24.0 | 33.0 | 0 | 2.0 |
| 4 | C 4 | 20.0 | 6.0 | 23.0 | 50.4 | 0.6 |
| 5 | C 5 | 25.0 | 15.0 | 35.0 | 24.0 | 1.0 |
| 6 | C 6 | 25.0 | 15.0 | 35.0 | 24.0 | 1.0 |
Example 7-12
Following example illustrates the catalytic performance of catalyst provided by the invention.
Respectively with catalyst C
1-C
6At 800 ℃, wore out 8 hours with 100% steam.On miniature fluidized bed reaction, with the catalyst C after above-mentioned the wearing out
1-C
6Feedstock oil carries out catalytic cracking shown in the his-and-hers watches 7, and the catalyst loading amount is 9 grams.Reaction condition and reaction result are listed in the table 8.
Wherein, conversion ratio=dry gas yield+yield of liquefied gas+yield of gasoline+coking yield; Total liquid receipts=yield of liquefied gas+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 wears out to 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 8.
Table 7
| Feedstock oil | The miscella of decompressed wax oil and decompression residuum |
| Density (20 ℃), gram per centimeter 3 | 0.9044 |
| Refractive power (20 ℃) | 1.5217 |
| Viscosity (100 ℃), millimeter 2/ second | 9.96 |
| Freezing point, ℃ | 40 |
| Aniline point, ℃ | 95.8 |
| Element is formed, weight % C H S N | 85.98 12.86 0.55 0.18 |
| Carbon residue, weight % | 3.0 |
| Boiling range, ℃ initial boiling point 5% 10% 30% 50% 70% 90% | 243 294 316 395 429 473 - |
Table 8
| 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 | 465 | 520 | 530 | 500 | 500 |
| Oil ratio | 5.0 | 5.0 | 5.0 | 4.5 | 3.5 | 6 | 4.5 | 4.5 |
| Weight (hourly) space velocity (WHSV), hour -1 | 16.0 | 16.0 | 16.0 | 15.5 | 18.2 | 14.3 | 12.0 | 16.2 |
| Conversion ratio, weight % | 76.5 | 72.2 | 71.3 | 77.4 | 75.3 | 74.2 | 75.6 | 74.7 |
| Product is formed, weight % | ||||||||
| Dry gas | 2.3 | 1.6 | 2.1 | 0.9 | 2.7 | 3.3 | 1.8 | 1.1 |
| Liquefied gas | 22.5 | 21.3 | 20.4 | 28.8 | 28.1 | 24.7 | 23.6 | 23.1 |
| Gasoline | 43.5 | 39.0 | 37.8 | 40.3 | 36.5 | 37.7 | 42.4 | 41.9 |
| Diesel oil | 14.4 | 11.9 | 12.4 | 14.1 | 14.2 | 13.0 | 13.8 | 13.1 |
| Coke | 8.2 | 10.3 | 11.0 | 7.4 | 8.0 | 8.5 | 7.8 | 8.6 |
| Unconverted heavy oil | 9.1 | 15.9 | 16.3 | 8.5 | 10.5 | 12.8 | 10.6 | 12.2 |
| Gasoline is formed, weight % alkene aromatic hydrocarbons isoparaffin | 29.0 28.2 26.5 | 34.1 25.5 24.2 | 34.9 24.7 23.3 | 30.4 27.5 28.2 | 32.2 26.2 27.2 | 32.8 27.0 25.8 | 30.8 28.1 26.5 | 31.3 26.5 26.8 |
| Liquefied gas character propylene content, weight % butene content, weight % iso-butane content, weight % | 7.4 6.7 4.9 | 6.5 5.9 4.6 | 5.8 5.6 4.1 | 9.1 9.7 5.5 | 10.4 11.7 4.8 | 8.7 8.5 4.8 | 7.2 6.8 5.6 | 7.0 7.5 4.8 |
From the result of table 8 as can be seen, compare with the use reference catalyst, use catalyst provided by the invention that same feedstock oil is carried out catalytic cracking, reduced olefin content in gasoline significantly, improved aromatic hydrocarbons and the isoparaffin content in the gasoline, low-carbon alkene in the liquefied gas (particularly third is rare) and iso-butane content significantly improve.This explanation, catalyst provided by the invention have improved the gasoline in the cracked product and the quality of liquefied gas significantly.
Claims (12)
1. hydrocarbon cracking catalyzer, this catalyst contains aluminium oxide and molecular sieve, contains or does not contain clay, it is characterized in that, described aluminium oxide is η-aluminium oxide and/or x-aluminium oxide, or the mixture of η-aluminium oxide and/or x-aluminium oxide and gama-alumina, this catalyst also contains phosphorus, is benchmark with the catalyst total amount, the content of η-aluminium oxide and/or x-aluminium 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 %, the content of molecular sieve is 10-70 weight %, described molecular sieve is the zeolite mixture that contains y-type zeolite and have the zeolite of MFI structure, with described zeolite mixture total amount is benchmark, the content of y-type zeolite is 30-90 weight %, and the content with zeolite of MFI structure is 10-70 weight %.
2. catalyst according to claim 1 is characterized in that, the content of η-aluminium oxide and/or x-aluminium 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 %, the content of molecular sieve is 20-50 weight %.
3. catalyst according to claim 1 is characterized in that, is benchmark with described zeolite mixture total amount, and y-type zeolite content is 40-85 weight %, and the content with zeolite of MFI structure is 15-60 weight %.
4. according to claim 1 or 3 described catalyst, it is characterized in that, also contain the Beta zeolite in the described zeolite mixture, is benchmark with described zeolite mixture total amount, and the content of Beta zeolite is 0-30 weight %.
5. catalyst according to claim 4 is characterized in that, is benchmark with described zeolite mixture total amount, and the content of Beta zeolite is 0-20 weight %.
6. according to claim 1 or 3 described catalyst, it is characterized in that described y-type zeolite is selected from one or more in the overstable gamma zeolite of the y-type zeolite, overstable gamma zeolite of HY zeolite, phosphorous, iron and/or rare earth, phosphorous, iron and/or rare earth.
7. according to claim 1 or 3 described catalyst, be characterised in that altogether the zeolite of the described MFI of having structure is selected from ZSM-5, the ZSM-5 zeolite of phosphorous and/or rare earth, in the ZRP zeolite one or more.
8. 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.
9. 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 x-aluminium oxide, or can form the aluminium compound of η-aluminium oxide and/or x-aluminium oxide and can form the mixture of the aluminium compound of gama-alumina, the compound that before roasting, also adds phosphorus, the consumption of each component makes in the final catalyst and contains, with the catalyst total amount is benchmark, 0.5-50 the η-aluminium oxide of weight % and/or x-aluminium oxide, the gama-alumina of 0-50 weight %, the clay of 0-75 weight % is with P
2O
5Meter, 0.1-8 the phosphorus of weight %, the molecular sieve of 10-70 weight %, described molecular sieve is the zeolite mixture that contains y-type zeolite and have the zeolite of MFI structure, with described zeolite mixture total amount is benchmark, the content of y-type zeolite is 30-90 weight %, and the content with zeolite of MFI structure is 10-70 weight %.
10. method according to claim 9 is characterized in that, the described aluminium compound that can form η-aluminium oxide and/or x-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.
11. method according to claim 9 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.
12. method according to claim 8 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.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410071118XA CN1322924C (en) | 2004-07-29 | 2004-07-29 | Cracking catalyst for hydrocarbon and preparation method |
| TW094122857A TWI277648B (en) | 2004-07-29 | 2005-07-06 | A cracking catalyst for hydrocarbons and its preparation |
| BRPI0512684-3A BRPI0512684A (en) | 2004-07-29 | 2005-07-14 | process cracking catalyst to manufacture the same |
| PCT/CN2005/001042 WO2006010316A1 (en) | 2004-07-29 | 2005-07-14 | A cracking catalyst for hydrocarbons and its preparation |
| US11/658,831 US9175230B2 (en) | 2004-07-29 | 2005-07-14 | Cracking catalyst and a process for preparing the same |
| RU2007107495/04A RU2367518C2 (en) | 2004-07-29 | 2005-07-14 | Cracking catalyst and preparation method thereof |
| EP05766932.7A EP1795259B1 (en) | 2004-07-29 | 2005-07-14 | A cracking catalyst for hydrocarbons and its preparation |
| JP2007522900A JP4828532B2 (en) | 2004-07-29 | 2005-07-14 | Cracking catalyst and method for producing the same |
| KR1020077003466A KR101183564B1 (en) | 2004-07-29 | 2005-07-14 | A cracking catalyst for hydrocarbons and its preparation |
| SA5260221A SA05260221B1 (en) | 2004-07-29 | 2005-07-18 | Cracking catalyst and process for its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410071118XA CN1322924C (en) | 2004-07-29 | 2004-07-29 | Cracking catalyst for hydrocarbon and preparation method |
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| CN1727445A CN1727445A (en) | 2006-02-01 |
| CN1322924C true CN1322924C (en) | 2007-06-27 |
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| SA (1) | SA05260221B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9175230B2 (en) | 2004-07-29 | 2015-11-03 | China Petroleum & Chemical Corporation | Cracking catalyst and a process for preparing the same |
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|---|---|---|---|---|
| RU2548362C2 (en) | 2009-06-25 | 2015-04-20 | Чайна Петролеум & Кемикал Корпорейшн | Catalyst for catalytic cracking and method of increasing catalyst selectivity (versions) |
| JP5919587B2 (en) * | 2010-01-20 | 2016-05-18 | Ｊｘエネルギー株式会社 | Catalyst for producing monocyclic aromatic hydrocarbon and method for producing monocyclic aromatic hydrocarbon |
| CN102019200B (en) * | 2010-04-13 | 2013-01-16 | 卓润生 | High-activity catalytic pyrolysis catalyst and preparation method thereof |
| AU2013284234B2 (en) | 2012-06-27 | 2018-03-01 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst containing modified Y type molecular sieve and preparation method therefor |
| KR102109395B1 (en) | 2012-09-14 | 2020-05-28 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor |
| WO2015057841A1 (en) * | 2013-10-15 | 2015-04-23 | Basf Corporation | Mesoporous fcc catalysts with excellent attrition resistance |
| MY195283A (en) | 2017-02-21 | 2023-01-12 | Sinopec Res Inst Petroleum | Magnesium Modified Y-Type Molecular Sieve, Preparation Thereof and Catalyst Comprising the same |
| RU2755891C2 (en) | 2017-02-22 | 2021-09-22 | Чайна Петролеум Энд Кемикал Корпорейшен | Catalytic cracking catalyst and its preparation |
| CN108452838B (en) * | 2017-02-22 | 2020-06-16 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
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|---|---|---|---|---|
| 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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2004
- 2004-07-29 CN CNB200410071118XA patent/CN1322924C/en active Active
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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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9175230B2 (en) | 2004-07-29 | 2015-11-03 | China Petroleum & Chemical Corporation | Cracking catalyst and a process for preparing the same |
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| SA05260221B1 (en) | 2008-06-04 |
| CN1727445A (en) | 2006-02-01 |
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