CN1224667C - Velocit cracking method - Google Patents
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- CN1224667C CN1224667C CN 03137908 CN03137908A CN1224667C CN 1224667 C CN1224667 C CN 1224667C CN 03137908 CN03137908 CN 03137908 CN 03137908 A CN03137908 A CN 03137908A CN 1224667 C CN1224667 C CN 1224667C
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Abstract
The present invention relates to a hydrocarbon oil cracking method comprises: a kind of hydrocarbon oil contacts a cracking catalyst under hydrocarbon oil cracking conditions. The catalyst contains a zeolite composition and a substrate material, wherein the zeolite composition contains zeolite, fluorine, a silicon component and phosphorus; the total quantity of the zeolite composition is used as the reference, the content of the zeolite is from 50 to 99.5 wt%, the content of the fluorine is from 0.1 to 10 wt%, the content of SiO2 is from 0.1 to 20 wt%, and the content of P2O5 is from 0.1 to 20 wt%. The method has the advantages of high hydrocarbon oil conversion rate and high octane number of a gasoline product.
Description
Technical field
The invention relates to a kind of cracking method for hydrocarbon oil.
Background technology
Cracking method for hydrocarbon oil is usually included under the cracking hydrocarbon oil condition, and hydrocarbon ils is contacted with a kind of cracking catalyst.Cracking catalyst wherein contains zeolite and a kind of substrate material.Described substrate material is selected from heat-resistant inorganic oxide and/or clay.For the transformation efficiency that improves hydrocarbon ils and/or the character of improving crackate, distribution, often adopt the cracking catalyst that contains a kind of zeolite compositions.For this reason, in the prior art, various zeolite compositions contain the cracking catalyst of zeolite compositions and adopt the cracking method of such catalyzer to emerge in an endless stream.Phosphorous or fluorine-containing zeolite compositions contains the catalyzer of this phosphorous or fluorine-containing zeolite compositions and promptly is wherein example with the cracking method of such catalyzer.
EP 0,397, and 183 disclose a kind of composition, and said composition contains Na
2O content is that 2-5 weight % is through the NaY of ion-exchange zeolite with P
2O
5Meter, the phosphorus of 0.1-4.0 weight %.The preparation method of said composition comprises the NaY zeolite is carried out ion-exchange, obtains Na
2O content be 1-5 weight % through the NaY of ion-exchange zeolite; To reclaim with P through the reactant aqueous solution of the NaY of ion-exchange zeolite and a kind of phosphorus compound
2O
5Meter, phosphorus content is the product that contains y-type zeolite of 0.1-4.0 weight %.Wherein, described phosphorus compound is selected from phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate and SODIUM PHOSPHATE, MONOBASIC.Said composition can form phosphorous overstable gamma zeolite through hydrothermal treatment consists, as the active ingredient of cracking catalyst.
US4,839,319 disclose a kind of catalyzer, and this catalyzer contains a kind of nonzeolite inorganic oxide matrix and a kind of overstable gamma zeolite, and described overstable gamma zeolite makes the compound phosphorus of going up significant quantity of zeolite by contacting time enough with a kind of phosphorus compound.Described phosphorus compound is selected from one group that is made up of phosphoric acid, phosphorous acid, phosphoric acid salt and phosphite.This catalyzer has lower coking yield as hydrocarbon cracking catalyzer.
US5,110,776 disclose a kind of preparation method who contains the zeolite catalysis cracking catalyst, and this method comprises that (a) handles zeolite with a kind of phosphatic aqueous solution, makes Zeolite modifying, obtains a kind of aqueous slurry; (b) described aqueous slurry is directly mixed with a kind of matrix precursor, spraying drying obtains catalyzer.The catalyzer that contains phosphorus-modified zeolite with this method preparation has abrasion resistance preferably, and when the catalytically crack hydrocarbons raw material, the gasoline that obtains has higher octane value.
US4,388,178 disclose a kind of cracking method of petroleum hydrocarbon raw material, and this method is included under the cracking hydrocarbon condition and under 850-950 the temperature, a kind of petroleum hydrocarbon raw material is contacted with a kind of zeolitic cracking catalyst.This catalyzer is made up of y-type zeolite and a kind of silica-alumina matrix of at least 90 weight %, and described catalyzer also contains the fluorine of 0.1-5 weight %.This method can increase the yield of motor spirit and can improve gasoline octane rating.
Summary of the invention
The purpose of this invention is to provide a kind of new have higher hydrocarbon oil conversion rate and the higher cracking method for hydrocarbon oil of gasoline product octane value.
Method provided by the invention is included under the cracking hydrocarbon oil condition, a kind of hydrocarbon ils is contacted with a kind of cracking catalyst, this catalyzer contains a kind of zeolite compositions and a kind of substrate material, and described zeolite compositions contains zeolite and fluorine, wherein, this zeolite compositions also contains silicon components and phosphorus, total amount with zeolite compositions is a benchmark, and the content of zeolite is 50-99.5 weight %, in element fluorine, the content of fluorine is 0.1-10 weight %, with SiO
2Meter, the content of silicon components is 0.1-20 weight %, with P
2O
5Meter, the content of phosphorus is 0.1-20 weight %.
Compared with prior art, method provided by the invention has higher hydrocarbon oil conversion rate, and the octane value of gasoline product is higher.
For example, adopting method provided by the invention, is 28.6 weight % with alumina content, kaolin content is 42.8 weight %, and (with the zeolite compositions is benchmark to zeolite compositions, and the HY zeolite content is 92.4 weight %, in fluorine element, fluorine content is 1.3 weight %, with SiO
2Meter, silicon components content is 2.1 weight %, with P
2O
5Meter, phosphorus content is 4.2 weight %) content be the catalyzer of 28.6 weight % at 800 ℃, after wearing out 4 hours with 100% water vapour, be 482 ℃ in temperature of reaction, weight hourly space velocity is 16 hours
-1, the agent weight of oil is than being under 4 the condition, is that 227-475 ℃ decompressed wax oil carries out catalytic cracking to boiling range, and transformation efficiency is up to 79 weight %, and the research octane number (RON) of gasoline product (RON) is up to 90.3.And adopt other component concentration identical, and just zeolite compositions is respectively the HY zeolite, the HY zeolite content is 98.7 weight %, and in element fluorine, fluorine content is that reference zeolite compositions and the HY zeolite content of 1.3 weight % is 95.8 weight %, with P
2O
5, when phosphorus content was the catalyzer of reference zeolite compositions of 4.2 weight %, transformation efficiency had only 70 weight %, 73 weight % and 74 weight % respectively, and the octane value of gasoline product has only 87.8,88.5 and 88.6 respectively.
Embodiment
According to method provided by the invention, be benchmark with the total amount of described zeolite compositions, the content of zeolite is preferably 70-99 weight %, and in element fluorine, the content of fluorine is preferably 0.1-5 weight %, with SiO
2Meter, the content of silicon components is preferably 0.2-10 weight %, with P
2O
5Meter, phosphorus content is preferably 0.2-15 weight %.
In described zeolite compositions, described fluorine is with the compound of fluorine, as the form existence of fluorochemical and/or silicofluoride.Silicon components is with the compound of silicon, exists as the form of oxide compound, silicate and/or the silicofluoride of silicon.Because the fluorine in the zeolite compositions is easy and the framework aluminum reaction of zeolite, make the zeolite dealuminzation, room after staying dealuminzation on the zeolite, silicon components in the zeolite compositions provided by the invention can be filled up the room of taking out behind the aluminium in preparation process, thereby the part in the silicon components may form the framework silicon of zeolite.Described phosphorus is with phosphorus compound, as the oxide compound and/or the existence of phosphatic form of phosphorus.
Zeolite in the described zeolite compositions is selected from one or more in synthetic and natural macropore, mesopore and the aperture aluminosilicate zeolite.
Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujusite, L zeolite, Beta zeolite, omega zeolite, mordenite, the ZSM-18 zeolite one or more, y-type zeolite particularly contains in the y-type zeolite (abbreviating REY or REHY as), overstable gamma zeolite (abbreviating USY as), the overstable gamma zeolite (abbreviating REUSY as) that contains rare earth, Beta zeolite, mordenite of rare earth one or more.
Described mesopore zeolite is to have greater than the zeolite of 0.56 nanometer less than the cavernous structure of 0.7 nano-rings opening, as have in the zeolite (as the ZSM-5 zeolite, the zeolite of the disclosed MFI of the having structure of CN1194181A) of MFI structure, the zeolite with the MFI structure ZSM-5 zeolite of rare earth (as contain) that contains rare earth, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, the MCM-56 zeolite one or more.
Described pore zeolite refers to have the zeolite less than the cavernous structure of 0.56 nano-rings opening, as ZSM-34 zeolite and/or erionite.
In preferred large pore zeolite of described zeolite and the mesopore zeolite one or more, preferred especially y-type zeolite, contain y-type zeolite, the overstable gamma zeolite of rare earth, the overstable gamma zeolite that contains rare earth, Beta zeolite, have the MFI structure zeolite, contain the zeolite with MFI structure of rare earth, in the mordenite one or more.Sodium oxide content is not particularly limited in the described zeolite, and preferred sodium oxide content is less than 1 weight %.
Described zeolite compositions and the substrate material content in catalyzer is conventional content.In general, with the catalyzer total amount is benchmark, the content of described zeolite compositions is 1-99 weight %, the content of substrate material is 1-99 weight %, and under the preferable case, the content of described zeolite compositions is 10-70 weight %, the content of substrate material is 30-90 weight %, more under the preferable case, the content of described zeolite compositions is 10-60 weight %, and the content of substrate material is 40-90 weight %.
Described substrate material is selected from one or more in the cracking catalyst substrate material commonly used, as in heat-resistant inorganic oxide and the clay one or more.
Described heat-resistant inorganic oxide is selected from as in the heat-resistant inorganic oxide of cracking catalyst matrix components and/or binder component one or more, as in aluminum oxide, silicon oxide, amorphous aluminum silicide, zirconium white, titanium oxide, alkaline earth metal oxide, the boron oxide one or more, one or more in preferred aluminum oxide, silicon oxide and the amorphous aluminum silicide.
Described clay is selected from as in the clay of cracking catalyst matrix components one or more, as in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite one or more, preferred kaolin.
According to embodiment preferred of the present invention, catalyzer of the present invention contains above-mentioned zeolite compositions, the substrate material aluminum oxide, contain or do not contain the substrate material clay, with the catalyzer total amount is benchmark, the content of zeolite compositions is 10-70 weight, and the content of aluminum oxide is 5-60 weight %, and the content of clay is 0-75 weight %.Under the preferable case, the content of zeolite compositions is 10-60 weight %, and alumina content is 10-50 weight %, and clay content is 10-60 weight %.Described clay is preferably kaolin, in preferred macropore of zeolite in the described zeolite compositions and the mesopore zeolite one or more, be preferably y-type zeolite especially, contain y-type zeolite, the overstable gamma zeolite of rare earth, the overstable gamma zeolite that contains rare earth, Beta zeolite, have the MFI structure zeolite, contain the zeolite with MFI structure of rare earth, in the mordenite one or more.
Catalyzer of the present invention can also contain a kind of zeolite that is not included in the above-mentioned zeolite compositions except that containing above-mentioned zeolite compositions and substrate material, be called the independent component zeolite here.Described independent component zeolite is selected from as in the zeolite of active component of cracking catalyst one or more, be preferably in large pore zeolite and the mesopore zeolite one or more, y-type zeolite more preferably, contain y-type zeolite, the overstable gamma zeolite of rare earth, the overstable gamma zeolite that contains rare earth, Beta zeolite, have the MFI structure zeolite, contain the zeolite with MFI structure of rare earth, in the mordenite one or more, particularly have the zeolite of MFI structure and/or contain the zeolite with MFI structure of rare earth.With the catalyzer total amount is benchmark, and the content of described independent component zeolite is 0-40 weight %, is preferably 0-30 weight %.
Preparation of catalysts method of the present invention comprises mixes making beating with zeolite compositions with the precursor and the deionized water of substrate material and/or substrate material, dry, wherein, described zeolite compositions contains zeolite, fluorine, silicon components and phosphorus, total amount with zeolite compositions is a benchmark, and the content of zeolite is 50-99.5 weight %, in element fluorine, the content of fluorine is 0.1-10 weight %, with SiO
2Meter, the content of silicon components is 0.1-20 weight %, with P
2O
5Meter, the content of phosphorus is 0.1-20 weight %; The preparation method of described zeolite compositions comprises zeolite is mixed jointly or step by step with the fluorine cpd aqueous solution, phosphorous compound aqueous solution and silicon compound, or with the fluorine cpd aqueous solution, phosphorous compound aqueous solution, the silicon compound aqueous solution common or step impregnation zeolite, the each mixing or the dipping after drying, roasting or not roasting mix or dipping back roasting for the last time.
Described blended process with zeolite and the fluorine cpd aqueous solution, phosphorous compound aqueous solution and the silicon compound aqueous solution, perhaps can be simultaneously or proceed step by step with the process of the fluorine cpd aqueous solution, the silicon compound aqueous solution and phosphorous compound aqueous solution dipping zeolite, to mixing or the sequencing of dipping is not particularly limited.Under the preferred situation, earlier with zeolite and silicon compound aqueous solution or elder generation's silicon compound aqueous solution dipping zeolite, dry, roasting or not roasting, again zeolite is mixed simultaneously or step by step with the phosphorous compound aqueous solution and the fluorine cpd aqueous solution, perhaps use the phosphorous compound aqueous solution and fluorine cpd aqueous solution while or step impregnation zeolite, mix or the dipping after drying at every turn, roasting or not roasting mix or dipping after drying and roasting for the last time.
Described exsiccant temperature can be preferably 100-250 ℃ from room temperature to 300 ℃, and the temperature of roasting is greater than 300 ℃ to 700 ℃, is preferably 400-650 ℃, and the time of roasting is more than 0.5 hour, is preferably 0.5-20 hour, more preferably 0.5-10 hour.
Described fluorine cpd are selected from one or more in water-soluble fluorine cpd, as hydrogen fluoride, alkali-metal fluorochemical, one or more in the Neutral ammonium fluoride.The concentration of the fluorine cpd aqueous solution can be any possible concentration, as long as mixes afterwards with zeolite or after flooding zeolite, the fluorine that can introduce 0.1-10 weight % in final zeolite compositions gets final product.If the concentration of the fluorine cpd aqueous solution is higher, can only carry out single-steeping or mixing, can introduce the fluorine of q.s.If the fluorine cpd concentration of aqueous solution is lower, then can repeatedly flood or mix, flood or the mixing after drying, to introduce the fluorine of q.s at every turn.
Described phosphorus compound is selected from one or more in water-soluble phosphorus compound, as in phosphoric acid, phosphoric acid salt, phosphorous acid and the phosphite one or more, and one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and the primary ammonium phosphate particularly.The concentration of phosphorous compound aqueous solution can be any possible concentration, as long as mixes afterwards with zeolite or after flooding zeolite, can introduce with P in final zeolite compositions
2O
5Meter, the phosphorus of 0.1-10 weight % gets final product.If the concentration of phosphorous compound aqueous solution is higher, can only carry out mixed once or dipping, just can introduce the phosphorus of q.s.If the concentration of phosphorous compound aqueous solution is lower, then can repeatedly flood or mix, flood or the mixing after drying, to introduce the phosphorus of q.s at every turn.
Described silicon compound is selected from one or more in water-soluble silicon compound, as silicon tetrachloride, tetramethoxy-silicane Si (OCH
3)
4, tetraethoxy-silicane Si (OC
2H
5)
4In one or more.The concentration of the silicon compound aqueous solution can be any possible concentration, as long as after mixing with zeolite or flooding zeolite, can introduce with SiO in final zeolite compositions
2Meter, the silicon components of 0.1-20 weight % gets final product.If the concentration of the silicon compound aqueous solution is higher, can only carry out the silicon components that mixed once or dipping can be introduced q.s.If the concentration of the silicon compound aqueous solution is lower, then can repeatedly mix or flood, until the silicon components of introducing q.s, flood or the mixing after drying at every turn.
The exsiccant method that zeolite compositions is mixed with the precursor of substrate material and/or substrate material after pulling an oar is conventionally known to one of skill in the art.Described drying can adopt existing various exsiccant method, as dry, method such as oven dry, forced air drying, spraying drying, the method for preferably spray drying.The exsiccant temperature can be preferably 50-250 ℃ from room temperature to 300 ℃.If also contain described independent component zeolite in the catalyzer, can when making beating, add in the lump.
When zeolite compositions is mixed making beating with the precursor of substrate material and/or substrate material, the consumption of each component contains final catalyzer, with the catalyzer total amount is benchmark, 1-99 weight %, preferred 10-70 weight %, the more preferably described zeolite compositions of 10-60 weight %, 1-99 weight %, preferred 30-90 weight %, the more preferably substrate material of 40-90 weight %.
Wherein, the precursor of described substrate material refers in catalyst preparation process, can form the material of described substrate material, can be selected from any hydrated aluminum oxide (as pseudo-boehmite), aluminium colloidal sol etc. as the precursor of aluminum oxide.The precursor of silicon oxide can be selected from silicon solution, silicon gel, water glass.The precursor of amorphous aluminum silicide can be selected from silicon-aluminum sol, silica-alumina gel.The precursor of other heat-resistant inorganic oxides can be selected from their oxyhydroxide separately.
Cracking method for hydrocarbon oil provided by the invention can carry out catalytic cracking to various hydrocarbon ils, to produce low-molecular-weight cracked product, particularly produces stop bracket gasoline.Described hydrocarbon ils can be selected from one or more in oil and the cut thereof, and as crude oil, long residuum, vacuum residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, propane is light/in heavily de-oiling, wax tailings and the gelatin liquefaction product one or more.
Method provided by the invention can be carried out in existing various reactors, as carrying out in fixed-bed reactor, fluidized-bed reactor, riser reactor, multi-reaction-area reactor etc.
Described cracking hydrocarbon oil condition is conventional cracking hydrocarbon oil condition, and these conditions are conventionally known to one of skill in the art.In general, described cracking hydrocarbon oil condition comprises that temperature of reaction is 400-600 ℃, is preferably 450-550 ℃, and weight hourly space velocity is 10-120 hour
-1, be preferably 10-80 hour
-1, the agent weight of oil is preferably 3-15 than for 1-20.
The following examples will the present invention will be further described.
Example 1
This example illustrates zeolite compositions of the present invention and preparation method thereof.
(1) (lattice constant is 2.462 nanometers, Na with 10 kilograms of NaY zeolites
2O content is 12.4 weight %, the Zhou village catalyst plant is produced) being 10 weight % with 10 liters of concentration, ammonium sulfate solution mixes, under agitation, carried out ion-exchange 2 hours in 80 ℃, filter, be detected with deionized water wash filter cake to sulfate radical-free ion, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours, (lattice constant is 2.458 nanometers, Na to obtain the HY zeolite
2O content is 0.5 weight %).Wherein, lattice constant adopts X-ray diffraction method to measure Na
2O content adopts aas determination.
(2) with 10 kilograms in the above-mentioned HY zeolite that obtains and 6.5 kilograms of SiCl
4Content is that the silicon tetrachloride aqueous solution of 5 weight % is even, filters, and 120 ℃ of oven dry obtain containing the HY zeolite of silicon components.
(3) be 0.05 mol with 10 kilograms of HY zeolites that contain silicon components that obtain and 30 liters of Neutral ammonium fluoride concentration, ammonium hydrogen phosphate concentration is that the Neutral ammonium fluoride of 0.1 mol and the mixed aqueous solution of ammonium hydrogen phosphate mix, filter, 120 ℃ of oven dry, 550 ℃ of roastings 02 hour obtain zeolite compositions Z1 of the present invention.The composition of Z1 is listed in the table 5.
Wherein, in the zeolite compositions, the content of phosphorus, fluorine, silicon adopts the x-ray fluorescence spectrometry method to measure.
Example 2-7
Following example illustrates zeolite compositions of the present invention and preparation method thereof.
Step by (2) in the example 1 and (3) prepares zeolite compositions, the kind of the kind of different is zeolite and consumption, silicon compound, phosphorus compound, the fluorine cpd aqueous solution is different with consumption, the temperature and time of roasting is also different, obtains zeolite compositions Z2-Z7 of the present invention.Table 1 has provided used zeolite, the source of zeolite, wherein contained components contents and unit cell parameters.Table 2 has provided kind and the consumption and the silicon compound kind of zeolite, the concentration of the silicon compound aqueous solution and consumption.Table 3 has provided the kind of phosphorus compound and fluorine cpd and the concentration and the consumption of the aqueous solution thereof.Table 4 has provided maturing temperature and time.Table 5 has provided the composition of zeolite compositions Z2-Z7.
Comparative Examples 1-2
Following Comparative Examples explanation reference zeolite compositions and preparation method thereof.
Method by example 2 prepares zeolite compositions, different is not with the step of silicon aqueous solution, the fluorine cpd aqueous solution or phosphorous compound aqueous solution with identical type and concentration replaces fluorine cpd and phosphorus compound mixed aqueous solution respectively, the consumption of the fluorine cpd aqueous solution or phosphorous compound aqueous solution is respectively 15 liters and 15 liters, obtains reference zeolite compositions ZB1 and ZB2.The composition of ZB1 and ZB2 is listed in the table 5.
Table 1
| Zeolite type | Lattice constant, nanometer | Na 2O content, weight % | Rare earth oxide content, weight % | The source |
| HY | 2.458 | 0.5 | - | In the example (1) |
| REHY | 2.447 | 0.9 | 3.6 1. | The Zhou village catalyst plant |
| REY | 2.453 | 0.7 | 19.5 2. | The Zhou village catalyst plant |
| USY | 2.440 | 0.82 | - | The Zhou village catalyst plant |
| REUSY | 2.444 | 0.6 | 1.5 3. | The Zhou village catalyst plant |
| Annotate: 1. wherein, lanthanum trioxide content is 2.57 weight %, and cerium oxide content is 0.64 weight %, and other rare earth oxide content is 0.39 weight %.2. wherein, lanthanum trioxide content is 13.7 weight %, and cerium oxide content is 3.4 weight %, and other rare earth oxide content is 2.4 weight %.3. wherein, lanthanum trioxide content is 1.1 weight %, and cerium oxide content is 0.3 weight %.Other rare earth oxide content is 0.1 weight %. | ||||
Table 2
| Example number | Zeolite | The silicon compound aqueous solution | |||
| Kind | Consumption, kilogram | The silicon compound kind | Concentration of aqueous solution, weight % | Amount of aqueous solution used, kilogram | |
| 2 | HY | 10 | SiCl 4 | 6.0 | 18.5 |
| 3 | REHY | 10 | SiCl 4 | 4.0 | 15 |
| 4 | REY | 10 | SiCl 4 | 2.5 | 20 |
| 5 | USY | 10 | SiCl 4 | 8.0 | 16 |
| 6 | REUSY | 10 | SiCl 4 | 3.0 | 22.5 |
| 7 | HY | 10 | Si(OCH 3) 4 | 10 | 25 |
Table 3
| Example number | Fluorine cpd and phosphorus compound mixed aqueous solution | ||||
| The fluorine cpd kind | Fluorine cpd concentration, mol | The phosphorus compound kind | Phosphorus compound concentration, mol | The mixed aqueous solution consumption rises | |
| 2 | NH 4F | 0.5 | NH 4H 2PO 4 | 0.5 | 16.5 |
| 3 | HF | 0.01 | (NH 4) 3PO 4 | 0.05 | 100 |
| 4 | NH 4F | 0.1 | NH 4H 2PO 4 | 0.2 | 30 |
| 5 | NH 4F | 0.4 | (NH 4) 3PO 4 | 0.15 | 20 |
| 6 | NH 4F | 0.2 | (NH 4) 3PO 4 | 0.15 | 22.5 |
| 7 | NH 4F | 1.0 | (NH 4) 3PO 4 | 1.0 | 18 |
Table 4
| Example number | Maturing temperature, ℃ | Roasting time, hour |
| 2 | 480 | 8 |
| 3 | 520 | 3 |
| 4 | 500 | 4 |
| 5 | 530 | 1 |
| 6 | 500 | 2 |
| 7 | 500 | 3 |
Table 5
| Example number | Zeolite compositions | Fluorine content, weight % | SiO 2Content, weight % | P 2O 5Content, weight % | Zeolite type | Zeolite content, weight % |
| 1 | Z1 | 0.14 | 1.1 | 1.2 | HY | 97.56 |
| 2 | Z2 | 1.3 | 2.1 | 4.2 | HY | 92.4 |
| Comparative Examples 1 | ZB1 | 1.3 | - | - | HY | 98.7 |
| Comparative Examples 2 | ZB2 | - | - | 4.2 | HY | 95.8 |
| 3 | Z3 | 0.12 | 1.2 | 3.6 | REHY | 95.08 |
| 4 | Z4 | 0.4 | 1.3 | 3.9 | REY | 94.4 |
| 5 | Z5 | 1.4 | 2.6 | 1.2 | USY | 94.8 |
| 6 | Z6 | 0.26 | 1.9 | 2.0 | REUSY | 95.84 |
| 7 | Z7 | 3.1 | 7.2 | 10.3 | HY | 79.4 |
Example 8-10
Following example illustrates the described Catalysts and its preparation method of method provided by the invention.
(solid content is 25 weight % with zeolite compositions Z1 of the present invention and Z2 and aluminium colloidal sol respectively, the Zhou village catalyst plant is produced) or aluminium colloidal sol and kaolin (solid content is 75 weight %, Suzhou kaolin company produces) and deionized water mixing making beating, be prepared into the slurries that solid content is 25 weight %, spraying drying under 200 ℃ temperature obtains catalyzer C1-C3 provided by the invention.The kind of zeolite compositions and consumption, aluminium colloidal sol, kaolinic consumption are listed in the table 6.The composition of C1-C3 is listed in the table 7.Catalyzer is formed by calculating.
Comparative Examples 3-5
Following Comparative Examples explanation contains cracking catalyst of HY zeolite and reference zeolite compositions and preparation method thereof.
Method by example 10 prepares catalyzer, different is to use HY zeolite, reference zeolite compositions ZB1 and the ZB2 of (1) preparation in the example 1 to replace zeolite compositions Z2 of the present invention, reference catalyst CB1, the CB2 and the CB3 that obtain containing the HY zeolite He contain reference zeolite compositions ZB1 or ZB2 respectively.Each material consumption is listed in the table 6.The composition of reference catalyst CB1-CB3 is listed in the table 7.
Example 11-15
This example illustrates Catalysts and its preparation method provided by the invention.
(solid content is 35 weight % with pseudo-boehmite, the Zhou village catalyst plant is produced) mix with deionized water, be prepared into the slurries that solid content is 30 weight %, adding concentration is the aqueous hydrochloric acid of 36.5 volume %, regulates the pH value to 2.0 of slurries, adds zeolite compositions Z3-Z7 respectively, add aluminium colloidal sol (with example 8) and kaolin (with example 9) again, be prepared into the slurries that solid content is 20 weight %, spraying drying under 200 ℃ temperature obtains catalyzer C4-C8 provided by the invention.The kind of pseudo-boehmite consumption, zeolite compositions and consumption, aluminium colloidal sol consumption and kaolinic consumption are listed in the table 6, and the composition of catalyzer C4-C8 is listed in the table 7.
Table 6
| Example number | Each material consumption, kilogram | The combination of zeolites species | |||
| Pseudo-boehmite | Aluminium colloidal sol | Kaolin | Zeolite compositions | ||
| 8 | - | 12.0 | - | 3.0 | Z1 |
| 9 | - | 12.0 | 6.0 | 3.0 | Z1 |
| 10 | - | 12.0 | 6.0 | 3.0 | Z2 |
| Contrast medium 3 | 12.0 | 6.0 | 3.0 | HY | |
| Contrast medium 4 | 12.0 | 6.0 | 3.0 | ZB1 | |
| Contrast medium 5 | 12.0 | 6.0 | 3.0 | ZB2 | |
| 11 | 4.0 | 3.96 | 2.25 | 1.75 | Z3 |
| 12 | 1.0 | 2.6 | 2.7 | 2.0 | Z4 |
| 13 | 2.0 | 1.2 | 2.7 | 2.0 | Z5 |
| 14 | 2.9 | 6.0 | 7.3 | 2.0 | Z6 |
| 15 | 0.7 | 1.0 | 4.0 | 1.5 | Z7 |
Table 7
| Example number | The catalyzer numbering | The combination of zeolites species | Zeolite compositions content, weight % | Alumina content, weight % | Kaolin content, weight % |
| 8 | C1 | Z1 | 50 | 50 | - |
| 9 | C2 | Z1 | 28.6 | 28.6 | 42.8 |
| 10 | C3 | Z2 | 28.6 | 28.6 | 42.8 |
| Contrast medium 3 | CB1 | HY | 28.6 | 28.6 | 42.8 |
| Contrast medium 4 | CB2 | ZB1 | 28.6 | 28.6 | 42.8 |
| Contrast medium 5 | CB3 | ZB2 | 28.6 | 28.6 | 42.8 |
| 11 | C4 | Z3 | 30 | 41 | 29 |
| 12 | C5 | Z4 | 40 | 20 | 40 |
| 13 | C6 | Z5 | 40 | 20 | 40 |
| 14 | C7 | Z6 | 20 | 25 | 55 |
| 15 | C8 | Z7 | 30 | 10 | 60 |
Example 16-17
This example illustrates the described Catalysts and its preparation method of method provided by the invention.
Intending thin water aluminium (with example 11) with 3 kilograms respectively mixes with 30 kilograms of deionized waters, adding concentration is the aqueous hydrochloric acid of 36.5 volumes, regulate the pH value to 2.0 of slurries, adding 2.5 kilograms of zeolite compositions Z1 and Z5 respectively stirs, (silica alumina ratio is 100 to add 0.25 kilogram of ZSM-5 zeolite more respectively, sodium oxide content is 0.1 weight %, the Zhou village catalyst plant is produced) and 2.5 kilograms of REHY zeolites (specification sees Table 1), 4.8 kilogram and 5.8 kilograms of aluminium colloidal sols (with example 8) and 10 kilograms and 6.7 kilograms of kaolin (with example 9), stir, obtain the slurries that solid content is 29.4 weight %, 200 ℃ of following spraying dryings, get catalyzer C9 of the present invention and C10.The composition of C9 and C10 is listed in and is expressed in 8.
Table 8
| Example number | 16 | 17 |
| The catalyzer numbering | C9 | C10 |
| The combination of zeolites species | Z1 | Z5 |
| Zeolite compositions content, weight % | 20 | 20 |
| Alumina content, weight % | 18 | 20 |
| Kaolin content, weight % | 60 | 40 |
| The REHY zeolite content, weight % | - | 20 |
| The ZSM-5 zeolite content, weight % | 2 | - |
Example 18-27
Following example illustrates method provided by the invention.
The catalyzer C1-C10 of example 8-17 preparation at 800 ℃, was worn out 4 hours with 100% water vapour.On small fixed flowing bed-tion reacting device, with the decompressed wax oil shown in the catalyst cracking table 9 after above-mentioned the wearing out, catalyzer loading amount 90 grams, the granules of catalyst diameter is the 0.18-0.25 millimeter.Reaction conditions and reaction result are respectively among the table 10-11.
Comparative Examples 6-8
The cracking method that contains HY zeolite or reference zeolite compositions is used in following Comparative Examples explanation.
Press the method aging catalyst of example 20 and to same stock oil, carry out catalytic cracking under similarity condition, different is to replace catalyzer C3 with reference catalyst CB1, CB2 and CB3 respectively.Reaction conditions and reaction result are listed in the table 10.
Table 9
| The stock oil title | Decompressed wax oil |
| Proportion (d 4 10), gram per centimeter 3 | 0.8652 |
| Viscosity, millimeter 250 ℃ 100 ℃ of/seconds | 14.58 4.37 |
| Carbon residue content; The % by weight boiling range, ℃ initial boiling point 10% 30% 50% 70% 90% is done | 0.04 227 289 347 389 417 446 475 |
Table 10
| Example number | 18 | 19 | 20 | Comparative Examples 6 | Comparative Examples 7 | Comparative Examples 8 |
| Catalyzer | C1 | C2 | C3 | CB1 | CB2 | CB3 |
| Temperature of reaction, ℃ | 500 | 520 | 482 | 482 | 482 | 482 |
| Weight space velocity, hour -1 | 20 | 16 | 16 | 16 | 16 | 16 |
| Agent weight of oil ratio | 6 | 8 | 4 | 4 | 4 | 4 |
| Transformation efficiency, weight % | 82 | 85 | 79 | 70 | 73 | 74 |
| Product yield, weight % | ||||||
| Dry gas | 2.6 | 3.3 | 2.1 | 1.6 | 1.8 | 1.8 |
| Liquefied gas | 21.4 | 22.5 | 20.8 | 18.9 | 19.2 | 19.7 |
| Gasoline | 50.2 | 51.2 | 48.9 | 44.5 | 45.1 | 45.5 |
| Diesel oil | 11.6 | 9.1 | 11.3 | 16.8 | 14.4 | 13 |
| Heavy oil | 6.4 | 5.9 | 9.7 | 13.2 | 12.6 | 13 |
| Coke | 7.8 | 8.0 | 7.2 | 6.6 | 6.9 | 7.0 |
| RON | 90.7 | 91.2 | 90.3 | 87.8 | 88.5 | 88.6 |
Table 11
| Example number | 21 | 22 | 23 | 24 | 25 | 26 | 27 |
| Catalyzer | C4 | C5 | C6 | C7 | C8 | C9 | C10 |
| Temperature of reaction, ℃ | 492 | 482 | 510 | 482 | 482 | 482 | 482 |
| Weight hourly space velocity, hour -1 | 12 | 16 | 20 | 16 | 16 | 16 | 16 |
| Agent weight of oil ratio | 3 | 4 | 6 | 4 | 4 | 4 | 4 |
| Transformation efficiency, weight % | 78 | 81 | 84 | 76 | 76.5 | 79.7 | 84.3 |
| Product yield, weight % dry gas | 2.1 | 2.5 | 3.0 | 2.0 | 2.0 | 2.2 | 3.2 |
| Liquefied gas | 21.1 | 21.9 | 22.8 | 20.3 | 20.6 | 21 | 22.6 |
| Gasoline | 47.7 | 49 | 50.4 | 46.7 | 46.8 | 49.5 | 50.6 |
| Diesel oil | 11.7 | 9.6 | 9.5 | 11.8 | 11.1 | 11.2 | 9.7 |
| Heavy oil | 10.3 | 9.4 | 6.5 | 12.2 | 12.4 | 9.1 | 6.0 |
| Coke | 7.1 | 7.6 | 7.8 | 7.0 | 7.1 | 7.0 | 7.9 |
| RON | 89.4 | 90.7 | 90.9 | 89.1 | 89.2 | 89.6 | 91.0 |
From the result of table 10 as can be seen, adopt method provided by the invention, transformation efficiency is up to 79 weight %, and Study of Gasoline method octane value RON is up to 90.3.And adopt composition identical, described zeolite compositions is respectively the HY zeolite, and during the method for the reference catalyst of ZB1 and ZB2, transformation efficiency has only 70 weight % respectively, 73 weight % and 74 weight %, Study of Gasoline method octane value RON has only 87.8,88.5 and 88.6 respectively.This illustrates that method provided by the invention has higher hydrocarbon oil conversion rate, and the octane value of the gasoline product that obtains is higher.
Example 28-30
Following example illustrates method provided by the invention.
Carry out catalytic cracking by the method aging catalyst of example 18 and to stock oil, different is that raw materials used oil is the long residuum shown in the table 12, and catalyzer and/or reaction conditions are also different, and catalyst system therefor, reaction conditions and reaction result are listed in the table 13.
Table 12
| The stock oil title | Long residuum |
| Proportion (d 4 10), gram per centimeter 3 | 0.8906 |
| Viscosity, millimeter 280 ℃ of/seconds | 44.18 |
| 100℃ | 24.84 |
| Carbon residue content, weight % | 4.3 |
| Boiling range, ℃ initial boiling point | 282 |
| 10％ | 370 |
| 30％ | 482 |
| 50％ | 553 |
Table 13
| Example number | 28 | 29 | 30 |
| Catalyzer | C2 | C3 | C5 |
| Temperature of reaction, ℃ | 500 | 500 | 500 |
| Weight space velocity, hour -1 | 10 | 10 | 10 |
| Agent weight of oil ratio | 5 | 5 | 5 |
| Transformation efficiency, weight % | 75.2 | 76.1 | 76.8 |
| Product yield, weight % | |||
| Dry gas | 2.1 | 2.2 | 2.3 |
| Liquefied gas | 17.1 | 16.6 | 16.8 |
| Gasoline | 48.7 | 49.9 | 50.2 |
| Diesel oil | 17.3 | 17.0 | 16.5 |
| Heavy oil | 7.5 | 6.9 | 6.7 |
| Coke | 7.3 | 7.4 | 7.5 |
| RON | 88.3 | 89.0 | 89.5 |
Claims (20)
1. cracking method for hydrocarbon oil, this method is included under the cracking hydrocarbon oil condition, and a kind of hydrocarbon ils is contacted with a kind of cracking catalyst, and this catalyzer contains a kind of zeolite compositions and a kind of substrate material, described zeolite compositions contains zeolite and fluorine, it is characterized in that this zeolite compositions also contains silicon components and phosphorus, is benchmark with the total amount of zeolite compositions, the content of zeolite is 50-99.5 weight %, in element fluorine, the content of fluorine is 0.1-10 weight %, with SiO
2Meter, the content of silicon components is 0.1-20 weight %, with P
2O
5Meter, the content of phosphorus is 0.1-20 weight %.
2. method according to claim 1 is characterized in that, the content of described zeolite is 70-99 weight %, and the content of fluorine is 0.1-5 weight %, and the content of silicon components is 0.2-10 weight %, and the content of phosphorus is 0.2-15 weight %.
3. method according to claim 1 and 2 is characterized in that described zeolite is selected from one or more in large pore zeolite and the mesopore zeolite.
4. method according to claim 3, it is characterized in that, described zeolite is selected from y-type zeolite, contains the y-type zeolite of rare earth, overstable gamma zeolite, the overstable gamma zeolite that contains rare earth, Beta zeolite, have the MFI structure zeolite, contain the zeolite with MFI structure of rare earth, in the mordenite one or more.
5. method according to claim 1 is characterized in that, is benchmark with the catalyzer total amount, and the content of described zeolite compositions is 1-99 weight %, and the content of substrate material is 1-99 weight %.
6. method according to claim 5 is characterized in that, the content of described zeolite compositions is 10-70 weight %, and the content of substrate material is 30-90 weight %.
7. catalyzer according to claim 6 is characterized in that, the content of described zeolite compositions is 10-60 weight %, and the content of substrate material is 40-90 weight %.
8. according to claim 1,5,6 or 7 described methods, it is characterized in that described substrate material is selected from one or more in heat-resistant inorganic oxide and the clay.
9. method according to claim 8, it is characterized in that, described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide and the amorphous aluminum silicide, and described clay is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite.
10. method according to claim 5, it is characterized in that, this catalyzer contains described zeolite compositions, substrate material aluminum oxide, contains or does not contain the substrate material clay, with the catalyzer total amount is benchmark, the content of described zeolite compositions is 10-70 weight %, the content of aluminum oxide is 5-60 weight %, and the content of clay is 0-75 weight %.
11. catalyzer according to claim 10 is characterized in that, the content of described zeolite compositions is 10-60 weight %, and the content of aluminum oxide is 10-50 weight %, and the content of clay is 10-60 weight %.
12., it is characterized in that described clay is a kaolin according to claim 10 or 11 described methods.
13., it is characterized in that the zeolite in the described zeolite compositions is selected from one or more in macropore and the mesopore zeolite according to claim 10 or 11 described methods.
14. method according to claim 13, it is characterized in that, the zeolite in the described zeolite compositions is selected from y-type zeolite, contains the y-type zeolite of rare earth, overstable gamma zeolite, the overstable gamma zeolite that contains rare earth, Beta zeolite, have the MFI structure zeolite, contain the zeolite with MFI structure of rare earth, in the mordenite one or more.
15. according to claim 1,5 or 10 described methods, it is characterized in that described catalyzer also contains a kind of independent component zeolite, this independent component zeolite is selected from one or more in macropore and the mesopore zeolite, with the catalyzer total amount is benchmark, and the content of this independent component zeolite is 2-40 weight %.
16. catalyzer according to claim 15 is characterized in that, the content of this independent component zeolite is 2-30 weight %.
17. method according to claim 15, it is characterized in that, this independent component zeolite is selected from y-type zeolite, contains y-type zeolite, the overstable gamma zeolite of rare earth, the overstable gamma zeolite that contains rare earth, Beta zeolite, have the MFI structure zeolite, contain the zeolite with MFI structure of rare earth, in the mordenite one or more.
18. method according to claim 17 is characterized in that, this independent component zeolite is selected from the zeolite with MFI structure and/or contains the zeolite with MFI structure of rare earth.
19. method according to claim 1 is characterized in that, described hydrocarbon ils be selected from crude oil, long residuum, vacuum residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, propane light/in heavily de-oiling, wax tailings and the gelatin liquefaction product one or more.
20. method according to claim 1 is characterized in that, described cracking hydrocarbon oil condition comprises that temperature of reaction is 400-600 ℃, and weight hourly space velocity is 10-120 hour
-1, the agent weight of oil is than being 1-20.
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| CN109304223B (en) * | 2017-07-28 | 2021-05-28 | 中国石油天然气股份有限公司 | Low-coking type catalytic cracking catalyst and preparation method thereof |
| CN108745409B (en) * | 2018-06-05 | 2021-07-02 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst for improving gasoline yield and preparation method thereof |
| CN108786782B (en) * | 2018-06-05 | 2021-07-02 | 中国石油天然气股份有限公司 | Catalytic cracking auxiliary agent for reducing coke yield and preparation method thereof |
| CN108855204B (en) * | 2018-06-05 | 2021-06-01 | 中国石油天然气股份有限公司 | Rare earth-containing medium-large pore silicon-aluminum material and preparation method thereof |
| CN108786901B (en) * | 2018-06-05 | 2021-06-01 | 中国石油天然气股份有限公司 | Heavy metal resistant catalytic cracking catalyst and preparation method thereof |
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