CN103007988B - Cracking assistant for improving low-carbon olefin concentration - Google Patents
Cracking assistant for improving low-carbon olefin concentration Download PDFInfo
- Publication number
- CN103007988B CN103007988B CN201110284431.1A CN201110284431A CN103007988B CN 103007988 B CN103007988 B CN 103007988B CN 201110284431 A CN201110284431 A CN 201110284431A CN 103007988 B CN103007988 B CN 103007988B
- Authority
- CN
- China
- Prior art keywords
- phosphorus
- weight
- clay
- molecular sieve
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a cracking assistant for improving a low-carbon olefin concentration. The cracking assistant comprises a modified MFI molecular sieve, a first clay-containing phosphor-aluminum inorganic binder and other inorganic binders, and second clay or no second clay. The first clay-containing phosphor-aluminum inorganic binder comprises an aluminum component, a phosphor component and first clay. The modified MFI molecular sieve contains phosphor and one or more of transition metals such as Fe, Co, Ni, Cu, Mn, Zn, Sn and Bi. There is not an absorption peak at the wavelength of 1633cm<-1> in a modified MFI molecular sieve infrared spectra obtained by trimethylpyridine as a probe molecule. The cracking assistant is used for catalytic cracking, can improve a catalytic cracking liquefied gas yield, can improve a yield of a low-carbon olefin such as propylene, can improve a heavy oil conversion capacity of a catalyst composition, and can improve the selectivity of dry gas and coke.
Description
Technical field
The present invention relates to a kind of cracking additive that improves catalytic cracking liquefied gas low-carbon alkene.Relate to furtherly a kind of cracking additive that improves density of propylene in catalytic cracking liquefied gas.
Background technology
Propylene is important Organic Chemicals.Along with the growth of the acryloyl derivative demands such as polypropylene, the whole world increases year by year to the demand of propylene.Fluid catalytic cracking is the important method of producing the low-carbon alkenes such as propylene, in order to increase the productive rate of propylene, adopts that to contain catalyst or the auxiliary agent with MFI structural zeolite be effective technological approaches in catalytic cracking process.
USP3,758,403 are early disclosed in the method for adding ZSM-5 zeolite in catalytic cracking catalyst can improve the octane number of gasoline and increase C
3～C
4the productive rate of alkene.For example, add in containing the conventional catalyst of 10%REY from 1.5,2.5,5 to 10% ZSM-5 zeolite, octane number improves, and the productive rate of low-carbon alkene increases; While using the auxiliary agent that contains ZSM-5 zeolite, also there is same effect.
USP 5,318, proposed to be less than based on a kind of large pore zeolite and silica alumina ratio the hydrocarbon conversion process process of the catalyst that 30 the zeolite with MFI structure forms in 696.This technique is produced high-knock rating gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly propylene.
USP 5,997, disclose a large amount of methods of using shape slective cracking auxiliary agents in heavy charge catalytic cracking process in 728.Said auxiliary agent adds 12～40% ZSM-5 zeolite to form in [amorphous, and system reserve at least 10% makes the ratio of ZSM-5 in catalyst surpass 3%.The method can, when increasing substantially low-carbon alkene, additionally not increase aromatic production and loss gasoline yield.
ZSM-5 zeolite carries out after modification with phosphorus-containing compound, and its cracking activity stability can improve, and reduces the consumption of zeolite.
In CN 1049406C, disclose a kind of phosphorous and rare earth and had the zeolite of MFI structure, it is aRE without hydrochemical compositions
2o
3bNa
2oAl
2o
3cP
2o
5dSiO
2, a=0.01～0.25 wherein, b=0.005～0.02, c=0.2～1.0, d=35～120.This zeolite has excellent hydrothermal activity stability and good selectivity of light olefin when for hydro carbons pyrolytic conversion.
In CN 1034223C, disclose a kind of catalyst for cracking for the production of low-carbon alkene, by the clay of 0～70% (take catalyst weight as benchmark), 5～99% inorganic oxide and 1～50% zeolite, formed.Zeolite is wherein the mixture of the five-membered ring silica-rich zeolite of the REY of 0～25 heavy % or the phosphorous and rare earth of Y-type high-Si zeolite and 75～100 heavy %.This catalyst has take higher hydrothermal activity stability, conversion ratio and the C of catalyst that ZSM-5 zeolite is active component
2 =～C
4 =productive rate.
USP5, discloses the preparation method with the ZSM-5 zeolite catalyst of phosphorus modification in 110,776.Described phosphorus modifying process is that zeolite is dispersed in the phosphorus-containing compound aqueous solution of pH value 2～6, then with matrix making beating, spray drying forming.Gained catalyst does not increase dry gas and coke yield when improving octane number.
USP6, discloses a kind of Cracking catalyst of phosphorous modified ZSM-5 zeolite in 566,293.The preparation of described phosphorous modified ZSM-5 is that zeolite is dispersed in the more than 4.5 phosphorus-containing compound aqueous solution of pH value, makes the phosphorus of zeolite-loaded at least 10 heavy % (with P
2o
5meter), then pull an oar with matrix and other zeolite component, spray drying forming.Gained catalyst has higher productivity of low carbon olefin hydrocarbon.
USP 5,171, disclose a kind of ZSM-5 zeolite with phosphorus modification in 921.This zeolite has 20～60 silica alumina ratio, with phosphorus-containing compound, floods by after 500～700 ℃ of steam treatment, for C
3～C
20hydrocarbon changes into C
2～C
5during the reaction of alkene, the ZSM-5 relatively processing without phosphorus has higher activity.
USP6, discloses a kind of method that improves aperture and mesopore zeolite catalytic activity in 080,303.The method is to process aperture and mesopore zeolite with phosphorus compound, then by the zeolite of processing through phosphorus and AlPO
4gel combination.The method can be improved activity and the hydrothermal stability of aperture and mesopore zeolite.
USP 5,472, disclose the hydrocarbon conversion process process of the catalyst forming based on a kind of large pore zeolite and phosphorous MFI structure mesopore zeolite in 594.This technique is produced high-knock rating gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly C
4/ C
5.
Except ZSM-5 zeolite is carried out, phosphorus modification, also report and introduce phosphorus compound in matrix, can improve selective to low-carbon alkene of catalyst or auxiliary agent.
A kind of catalytic cracking process process that increases productivity of propylene is disclosed in USP 2002/0003103A1.This technical process is except entering at least part of gasoline product in second riser and re-start cracking reaction, in the carbon monoxide-olefin polymeric adopting except containing macropore USY zeolite, the inorganic binder component that also contains the mesopore zeolites such as ZSM-5 and there is cracking performance.Phosphorous in inorganic binder component wherein, its P/Al ratio is 0.1～10.This technical process is increased low carbon olefine output significantly, particularly increases productivity of propylene.
The catalyst of a kind of high zeolite content, high abrasion resistance strength is disclosed in USP 2002/0049133A1.The ZSM-5 zeolite that this catalyst contains 30～85 heavy %, the phosphorus of 6～24 heavy % is (with P
2o
5meter), and lower than the Al of 10 heavy %
2o
3with other components such as clay of surplus, phosphorus is wherein present in matrix.This catalyst, for catalytic cracking process, can increase light olefin, especially productivity of propylene.
Zeolite has following relevant report with metal-modified method and application thereof.For example USP 5,236, disclose the catalyst containing MFI or MEL structural zeolite in 880.Wherein zeolite Shi Jing VIII used family metal, preferably with Ni modification, this zeolite is introduced after Ni, experiences heat or hydrothermal treatment consists at harsh control temperature, makes VIII family metal and aluminium at surface enrichment.Said catalyst can improve octane number while transforming for alkane, increases C
3～C
4the productive rate of alkene.
A kind of catalyst for cracking containing silica-rich zeolite is disclosed in CN 1057408A, there is higher catalytic pyrolysis active, wherein said silica-rich zeolite is ZSM-5, β zeolite or the modenite that contains 0.01～3.0 heavy % phosphorus, 0.01～1.0 heavy % iron or 0.01～10 heavy % aluminium, silica alumina ratio to be greater than to 15 Hydrogen or potassium type ZSM-5 zeolite, β zeolite or modenite be heated to 350～820 ℃, with 0.1～10 hour
-1volume space velocity obtain after passing into the halide solution of aluminium, the halide solution of iron or saline solution of ammonium phosphate.
The MFI structural zeolite that discloses a kind of phosphorous and transition metal in CN 1465527A, the anhydrous chemical expression of this zeolite, counts (0～0.3) Na with the quality of oxide
2o (0.5～5) Al
2o
3(1.3～10) P
2o
5(0.7～15) M
2o
3(70～97) SiO
2, wherein, M is selected from a kind of in transition-metal Fe, Co and Ni.When this zeolite is applied to the catalytic cracking process of petroleum hydrocarbon, although can improve C
2～C
4the productive rate of alkene and selective, have higher liquefied gas yield, but dry gas and coke selectivity are poor, and in liquefied gas, density of propylene is not high.
CN 1611299A discloses a kind of MFI structure molecular screen of phosphorous and metal component, and its anhydrous chemical expression, counts with the weight of oxide: (0～0.3) Na2O (0.5～5.5) Al
2o
3(1.3～10) P
2o
5(0.7～15) M1
xo
y(0.01～5) M2
mo
n(70～97) SiO2, wherein M1 is selected from a kind of in transition-metal Fe, Co and Ni, and M2 is selected from any in Metal Zn, Mn, Ga and Sn.
At present, for most catalytic cracking units, under the prerequisite of identical liquefied gas yield, the density of propylene improving in liquefied gas is the important channel of improving catalytic cracking unit economic benefit, the disclosed propylene additive of prior art is for catalytic cracking process, in liquefied gas, density of propylene is lower, and addition is when larger, can weaken heavy oil conversion performance.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of cracking additive that improves catalytic cracking liquid gas propylene concentration, and this auxiliary agent can improve the density of propylene of catalytic cracking liquefied gas for catalytic cracking, reduces coke and dry gas selective.
The invention provides a kind of assistant for calalytic cracking, the butt weight of described auxiliary agent of take is benchmark, contain modification MFI molecular sieve in butt 10～75 % by weight, with the al composition containing in the phosphorus aluminium inorganic binder of the first clay (with Al
2o
3meter), phosphorus component is (with P
2o
5meter) and the first clay butt weight sum meter 3～30 % by weight containing the phosphorus aluminium inorganic binder of the first clay, in other inorganic binders of oxide 3～30 % by weight with in the second clay of butt 0～60 % by weight; Wherein, the described phosphorus aluminium inorganic binder butt weight containing the first clay of take is benchmark, and the described phosphorus aluminium inorganic binder containing the first clay comprises with Al
2o
3meter 15～40 % by weight al compositions, with P
2o
5the phosphorus component of meter 45～80 % by weight and in the first clay of butt 1～40 % by weight, and its P/Al weight ratio is 1.0～6.0; Described modification MFI molecular sieve, its anhydrous chemical expression, counts with the weight of oxide: (0～0.3) Na
2o (0.5～6) Al
2o
3(1.3～10) P
2o
5(0.7～15) M
xo
y(70～97) SiO
2, x represents the atomicity of described transition metal M, y represents to meet the required number of oxidation state of described transition metal M; Described transition metal M is selected from one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi; The infrared spectrum that described modification MFI molecular sieve obtains as probe molecule with trimethylpyridine is at 1633cm
-1place is without absworption peak.
The present invention also provides a kind of preparation method of assistant for calalytic cracking, comprises modification MFI molecular sieve, the phosphorus aluminium inorganic binder containing the first clay, other inorganic binder mixing, adds or do not add the second clay, making beating, and spraying is dry; Wherein, the described phosphorus aluminium compound inorganic binder containing the first clay, in butt, contains with Al
2o
3meter 15～40 % by weight alumina component, with P
2o
5meter 45～80 % by weight phosphorus component and in butt 1～40 % by weight clay, its P/Al weight ratio is that 1.0～6.0, pH is 1.0～3.5, this binding agent solid content is 15～60 % by weight; Described modification MFI molecular sieve, its anhydrous chemical expression, counts with the weight of oxide: (0～0.3) Na
2o (0.5～6) Al
2o
3(1.3～10) P
2o
5(0.7～15) M
xo
y(70～97) SiO
2, x represents the atomicity of described transition metal M, y represents to meet the required number of oxidation state of described transition metal M; Described transition metal M is one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi preferably, and the infrared spectrum that described modification MFI molecular sieve obtains as probe molecule with trimethylpyridine is at 1633cm
-1place is without absworption peak.
Described modification MFI molecular sieve is phosphorous and the molecular sieve with MFI structure transition metal, and its anhydrous chemical expression is preferably: (0～0.2) Na
2o (0.9～5.5) Al
2o
3(1.5～7) P
2o
5(0.9～10) M
xo
y(82～92) SiO
2.Its surperficial phosphorus content of a kind of described molecular sieve is higher than the body phase phosphorus content of molecular sieve, the ratio that represents the surperficial phosphorus content of molecular sieve and the body phase phosphorus content of molecular sieve with the distribution D of phosphorus, the distribution D of its phosphorus meets D > 1, be generally and be greater than 1～9: 1, more preferably (1.05～9): 1, wherein D=P (
s)/ P
(C), described P
(S)represent to adopt zeolite crystal that TEM-EDX method characterizes from edge 1/10th the phosphorus content to center, P
(C)the phosphorus content that represents zeolite crystal center.Described MFI structure molecular screen, carries out IR Characterization with trimethylpyridine as probe, and its spectrogram is at 1633cm
-1place is without absworption peak.With trimethylpyridine, as probe, carrying out IR Characterization is existing method, and its process is as follows: by sample compressing tablet, the original position pond that is placed in infrared spectrometer seals, and at 450 ℃, is evacuated down to 10
-3pa, roasting 1.5h, is cooled to room temperature; Then the trimethylpyridine steam importing to original position pond, maintains adsorption equilibrium 30min, takes the photograph spectrum.Described MFI molecular sieve is preferably one or more in ZMS-5, ZSM-8 and ZSM-11, more preferably ZSM-5 molecular sieve.MFI molecular sieve is also referred to as MFI structure molecular screen or have MFI structure molecular screen.
The first described clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and diatomite.
The second described clay is selected from one or more that well known to a person skilled in the art in clay, for example be selected from one or more in kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, rectorite, diatomite, galapectite, saponite, boron-moisten soil and hydrotalcite, be preferably one or more the mixture in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and rectorite.
Cracking additive provided by the invention, also contains other inorganic binder except described phosphorus aluminium inorganic binder argillaceous.Described other inorganic binder is selected from one or more in the inorganic oxide that is customarily used in assistant for calalytic cracking or catalyst substrates or binder component, can be derived from one or more in boehmite, aluminium colloidal sol, phosphorus aluminium glue, silicon-aluminum sol, waterglass, wherein one or more in preferred boehmite, aluminium colloidal sol, phosphorus aluminium glue.
In catalyst aid provided by the present invention, can also contain with P
2o
5the phosphorus additive of meter 0～15 % by weight, the compound that described phosphorus additive is selected from phosphorus comprises the inorganic compound of phosphorus and one or more in organic compound, can be soluble in water, also can be to be insoluble in water or water-fast phosphorus compound, for example, be selected from the oxide, phosphoric acid, phosphate, phosphite, hypophosphites, subphosphate, acid phosphate of phosphorus and one or more in phosphorous organic compound.Preferred phosphorus compound is one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate and phosphorus aluminium colloidal sol.In resulting catalyst, phosphorus additive exists with the form of phosphorus compound (as the oxide of phosphorus, phosphate, phosphite, subphosphate, acid phosphate).In auxiliary agent, contain except described containing other the phosphorous binding agent the phosphorus aluminium inorganic binder of the first clay for example during phosphorus aluminium colloidal sol, the phosphorus of other described inorganic phosphor-contained binding agent introducing is considered as phosphorus additive.The total content of the phosphorus that phosphorus additive is introduced is no more than 15 % by weight.Described phosphorus additive may reside in any position that may exist of auxiliary agent, as may reside in the inside, duct of zeolite, the surface of zeolite, may reside in described host material, can also be present in the inside, duct of zeolite, in the surface and described host material of zeolite simultaneously.Described phosphorus additive does not comprise modification MFI molecular sieve and contains the phosphorus relating in the phosphorus aluminium inorganic binder of the first clay.
Assistant for calalytic cracking provided by the invention, there is good anti-wear performance and Catalytic Cracking Performance, for heavy oil catalytic cracking reaction process, can increase RFCC liquefied gas yield, improve significantly especially density of propylene of low-carbon alkene concentration in catalytic cracking liquefied gas, the selective height of propylene, coke and dry gas selectively low, and can improve heavy oil conversion performance, and improve the octane number of gasoline, improve light oil productive rate.Compare with existing auxiliary agent, there is higher heavy oil transformation active, higher Propylene Selectivity and liquid gas propylene concentration, better coke and dry gas are selective, are unexpectedly also to have higher liquid to receive.For example, industrial MLC-500 poising agent is 16h at 480 ℃, weight (hourly) space velocity (WHSV)
-1, react under the oil ratio condition that is 5, liquefied gas yield is 15.31 % by weight, heavy oil yield is 15.78 % by weight, it is 76.69 % by weight that liquid is received, productivity of propylene is 4.76 % by weight, in liquefied gas, density of propylene is 31.09 % by weight, and coke selectivity is 9.34 % by weight, and dry gas is selectively 2.26 % by weight.And the 50 % by weight modified zsm-5 zeolites that contain provided by the invention, 12 % by weight kaolin, 24 % by weight are containing the phosphorus aluminium inorganic binder of the first clay, 8 % by weight boehmites, the auxiliary agent of 6 % by weight aluminium colloidal sols, after mixing with above-mentioned MLC-500 poising agent with the weight ratios of 10: 90, under similarity condition, react, liquefied gas yield is 22.65 % by weight, heavy oil yield is 14.81 % by weight, it is 77.64 % by weight that liquid is received, productivity of propylene is 9.32 % by weight, in liquefied gas, density of propylene is 41.15 % by weight, coke selectivity is 8.98 % by weight, dry gas is selectively 2.17 % by weight.
Accompanying drawing explanation
Fig. 1 is the TEM-EDS spectrogram of the ZSM-5 molecular sieve of the phosphorus that obtains of the embodiment of the present invention 1 and comparative example 1 and iron modification.
Fig. 2 is the trimethylpyridine absorption infrared spectrum of the ZSM-5 molecular sieve of the phosphorus that obtains of the embodiment of the present invention 1 and comparative example 1 and iron modification modification, the spectrogram of the molecular sieve that figure center line 1 obtains for comparative example 1, the infrared spectrum of the phosphorus that line 2 obtains for embodiment 1 and the ZSM-5 molecular sieve of iron modification modification.
The specific embodiment
Cracking additive provided by the present invention, preferably include 8～25 % by weight containing the phosphorus aluminium inorganic binder of the first clay, the modification MFI molecular sieve of 20～60 % by weight, the clay of 10～45 % by weight, the phosphorus additive of other inorganic binder of 5～25 % by weight and 0～10 % by weight.In the content of wherein said phosphorus additive, do not comprise modification MFI molecular sieve and contain the phosphorus amount relating in the phosphorus aluminium inorganic binder of the first clay.
Under preferable case, described the first clay containing in the phosphorus aluminium inorganic binder of the first clay comprises rectorite, and more preferably the first described clay is rectorite.Take butt weight as benchmark, and the described phosphorus aluminium compound binding agent containing the first clay contains with Al
2o
3the al composition of meter 15～35 % by weight, with P
2o
5the phosphorus component of meter 50～75 % by weight and in the first clay of butt 8～35 % by weight, and not chloride, and it is 1.0～3.5 that its P/Al weight ratio is preferably 2.0～5.0, pH.
In the preparation method of assistant for calalytic cracking provided by the invention, the described phosphorus aluminium inorganic binder containing the first clay, take its butt weight is benchmark, contains with Al
2o
3meter 15～40 % by weight al compositions, with P
2o
5the phosphorus component of meter 45～80 % by weight and in the first clay of butt 1～40 % by weight, its P/Al weight ratio is that 1.0～6.0, pH is 1.0～3.5, this binding agent solid content is 15～60 % by weight.The described phosphorus aluminium compound inorganic binder preparation method containing the first clay comprises:
(1) alumina source, the first clay and water making beating are dispersed into the slurries that solid content is 8～45 % by weight; Described alumina source is can be by the aluminium hydroxide of sour peptization and/or aluminium oxide, in the first clay of butt and with Al
2o
3the weight ratio of the alumina source of meter is 1～40: 15～40;
(2) stir in the lower slurries that obtain toward step (1) and add SPA according to the part by weight of P/Al=1～6; In wherein said P/Al, P is the weight of the phosphorus in simple substance in phosphoric acid, and Al is in the weight of the aluminium of simple substance in alumina source;
(3) slurries that step (2) obtained react 15～90 minutes at 50～99 ℃ of temperature.
Wherein, the consumption of alumina source, SPA and the first clay, makes the resulting phosphorus aluminium inorganic binder that contains the first clay, and take its butt weight is benchmark, comprises: 15～40 % by weight preferably 15～35 % by weight are derived from the Al of described alumina source
2o
3, 45～80 % by weight are 50～75 % by weight P preferably
2o
5, 1～40 % by weight is the first clay of 8～35 % by weight preferably; Described P/Al weight ratio is preferably 1.2～6.0, and more preferably 2～5.Alumina source is one or more in ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and boehmite, and described al composition is derived from described alumina source.The first described clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and diatomite, is preferably rectorite.Its concentration of described SPA is 60～98 % by weight, more preferably 75～90 % by weight.The charging rate of phosphoric acid be preferably 0.01-0.10Kg phosphoric acid/minute/Kg alumina source, more preferably 0.03-0.07Kg phosphoric acid/minute/Kg alumina source.
The inorganic binder of described phosphorous aluminium compound is due to the introducing of clay, mass transfer, the heat transfer of storeroom not only in preparation process, have been improved, the adhesive cures of having avoided the inhomogeneous local moment vigorous reaction heat release overtemperature of material to cause, can regulate more neatly the pH value of binding agent, obtain the binding agent of high solids content, and do not need high temperature depolymerization, the step such as concentrated, preparation method is simple.The adhesive property of resulting binding agent is with not introduce phosphorus al binder prepared by clay mitigation suitable; And the method introduces clay, especially there is the rectorite of layer structure, improved the heavy oil conversion performance of carbon monoxide-olefin polymeric, the auxiliary agent that makes to obtain has better selective.
Described modification MFI molecular sieve (MFI molecular sieve is also referred to as having MFI structure molecular screen or MFI structure molecular screen), comprise phosphorus and transition metal, can prepare by the following method: the method is included in the molecular sieve with MFI structure of ammonium exchange and introduces phosphorus and transition metal, described phosphorus divides two parts to introduce, part phosphorus is introduced after introducing transition metal, and a part of phosphorus before introducing transition metal or introduce with transition metal simultaneously in addition.Resulting its anhydrous chemical expression of modification MFI molecular sieve, counts with the weight of oxide: (0～0.3) Na
2o (0.5～6) Al
2o
3(1.3～10) P
2o
5(0.7～15) M
xo
y(70～97) SiO
2, x represents the atomicity of described transition metal M, y represents to meet the required number of oxidation state of described transition metal M; Described transition metal M is one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi preferably.
In described modification MFI molecular sieve preparation method, in the molecular sieve with MFI structure of ammonium exchange, introduce phosphorus and transition metal, wherein phosphorus divides two parts to introduce, a part is to introduce after transition metal is all introduced after transition metal is introduced, and a part before before transition metal has been introduced, introducing introduces transition metal or introduce with transition metal simultaneously in addition.The phosphorus that described transition metal is introduced after introducing accounts for 10～90% of total phosphorus introduction volume in molecular sieve, preferably 25～50%, described transition metal is introduced (before introducing transition metal or introduce with transition metal) simultaneously phosphorus before having introduced accounts for introduces 10～90% of total phosphorus in molecular sieve, and preferably 50～75%; The phosphorus that transition metal is introduced after introducing and the atomic molar of introducing transition metal in molecular sieve are 0.25～10: 1 than the mol ratio of phosphorus atoms and metallic atom (take), are preferably 0.5～2.5: 1; Before introducing transition metal or with the transition metal phosphorus of introducing and the atomic molar ratio of introducing transition metal in molecular sieve simultaneously, be preferably 0.5～4.0: 1.Every a part of phosphorus can be introduced one or more times.
The MFI structure molecular screen of described ammonium exchange, it is ammonium type MFI structure molecular screen and/or Hydrogen MFI structure molecular screen, can by by the sodium type molecular sieve with MFI structure according to molecular sieve: ammonium salt: H
2o=1: (0.1～1): the method that the weight ratio of (5～10) is filtered exchange 0.3～1 hour at room temperature to 100 ℃ after obtains, the filter cake after wherein filtering can roasting or not roasting.The MFI structure molecular screen sodium oxide content of described ammonium exchange is not preferably higher than 0.2 % by weight.Described Hydrogen MFI structure molecular screen can, by the roasting of ammonium type MFI structure molecular screen is obtained, also can exchange sodium type MFI structure molecular screen with acid and obtain.Described ammonium salt is water miscible ammonium salt, can be conventional inorganic ammonium salt, for example, can be one of ammonium chloride, ammonium sulfate or ammonium nitrate or their mixture.Described MFI structure molecular screen, can be ZSM-5, ZSM-8 and ZSM-11, wherein preferred ZSM-5.
The preparation method of described modification MFI molecular sieve, preferably, by the sodium type molecular sieve with MFI structure according to molecular sieve: ammonium salt: H
2o=1: (0.1～1): the weight ratio of (5～10) is filtered after room temperature (common 15～30 ℃) exchanges 0.3～1 hour to 100 ℃, with phosphorus-containing compound solution and the solution that contains transistion metal compound, molecular sieve is flooded to modification again, wherein by phosphorus-containing compound solution impregnation, at least carry out twice, and after transistion metal compound dipping, carry out at least one times; Preferably, phosphorus-containing compound solution impregnation is carried out at twice, for the first time containing carry out before transistion metal compound solution impregnation or with containing transistion metal compound solution, flood simultaneously; Be to carry out after completing containing transistion metal compound solution impregnation for the second time, flood for the second time by dry, calcination process, obtain product.Described phosphorus-containing compound can be selected from one or more of phosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) or ammonium phosphate.Described transistion metal compound is selected from the water soluble salt of described transition metal, and described water soluble salt is selected from a kind of in sulfate, nitrate, chlorate.
Preferably, describedly by the process that phosphorus-containing compound solution and the solution that contains transistion metal compound flood modification to molecular sieve, carry out in the following way:
Filter cake after ammonium exchange is mixed in room temperature to 95 ℃ with the part phosphorus-containing compound of amount of calculation and the mixed impregnant liquor of metal-containing compound, after dry or dry, in temperature, be roasting under the condition of 400～800 ℃, mix in room temperature to 95 ℃ with remaining phosphorus-containing compound maceration extract again, dry, in 400～800 ℃ of roasting temperatures.Described dry for example oven dry.
In the modification MFI structure molecular screen preparation method of phosphorous and transition metal provided by the invention, described calcination process process can be also to carry out under water vapour atmosphere.
The modification MFI molecular sieve that described modification MFI molecular sieve preparation method obtains, its anhydrous chemical expression, counts with the weight of oxide: (0～0.3) Na
2o (0.5～6) Al
2o
3(1.3～10) P
2o
5(0.7～15) M
xo
y(70～97) SiO
2, be preferably: (0～0.2) Na
2o (0.9～5.5) Al
2o
3(1.5～7) P
2o
5(0.9～10) M
xo
y(82～92) SiO
2, x represents the atomicity of described transition metal M, y represents to meet the required number of oxidation state of described transition metal M.Described transition metal M is one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi preferably.The MFI structure molecular screen rich surface phosphorus of resulting phosphorous and transition metal, its surperficial phosphorus content is greater than its body phase phosphorus content, and the distribution D of its phosphorus is greater than 1, is preferably 1.05～9, and more preferably 1: 1.15～9; It carries out IR Characterization with trimethylpyridine as probe molecule, in infrared spectrum at 1633cm
-1place, without L acid characteristic absorption peak, shows that outer surface does not have L acid substantially, and outer surface metal center is covered by phosphorus.
The preparation method of assistant for calalytic cracking provided by the invention, described by modification MFI molecular sieve, the phosphorus aluminium inorganic binder containing the first clay, other inorganic binder mixing, making beating, its reinforced order does not have specific (special) requirements, for example the phosphorus aluminium inorganic binder containing the first clay, other inorganic binder (can omit relevant addition step when not containing other inorganic binder time), modification MFI molecular sieve, the second clay can be mixed to (can omit relevant addition step when not containing the second clay time) making beating
Assistant for calalytic cracking preparation method provided by the invention, also comprises the spray-dired step of the slurries that described making beating is obtained.Spray-dired method is known for those skilled in the art, and the present invention does not have specific (special) requirements.
While containing phosphorus additive in auxiliary agent, one of its introducing mode of described phosphorus additive is following method or the combination of several method, but is not limited to these methods:
1, before spray drying forming, in slurries, add phosphorus compound;
2, by other inorganic binder, be incorporated in auxiliary agent, when containing phosphorus aluminium colloidal sol in inorganic oxide binder, after roasting, in auxiliary agent, both brought phosphorus into, phosphorus aluminium colloidal sol can play the effect of host material and binding agent again, and this part phosphorus also belongs to phosphorus additive of the present invention;
3, after auxiliary agent spray drying forming through dipping or chemisorbed phosphorus compound, through Separation of Solid and Liquid (if necessary), dry and roasting process introducing, wherein said dry temperature is room temperature to 400 ℃, preferably 100～300 ℃, the temperature of roasting is 400～700 ℃, be preferably 450～650 ℃, roasting time is 0.5～100 hour, is preferably 0.5～10 hour.
Cracking additive provided by the invention is applicable to hydrocarbon oil catalytic cracking.During for catalytic cracking process, can in catalyst cracker, add separately, after also can mixing with Cracking catalyst, use.Generally, auxiliary agent provided by the invention accounts for 1～30 % by weight of FCC catalyst and catalyst mixture total amount provided by the invention, be preferably 3～20 % by weight, described hydrocarbon ils is selected from various petroleum distillates, as crude oil, reduced crude, decompression residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, propane is light/one or more in heavily de-oiling, wax tailings and coal liquefaction products.Described hydrocarbon ils can contain the beavy metal impurities such as nickel, vanadium and sulphur, nitrogen impurity, and as the content of sulphur can be up to 3.0 % by weight, the content of nitrogen can be up to 2.0 % by weight, and the content of the metal impurities such as vanadium, nickel is up to 3000ppm.
Cracking additive provided by the invention is for catalytic cracking process, and cracking hydrocarbon oil condition is conventional catalytic cracking condition.In general, this cracking hydrocarbon oil condition comprises that reaction temperature is 400～600 ℃, is preferably 450～550 ℃, and weight (hourly) space velocity (WHSV) is 10～120 hours
-1, be preferably 10～80 hours
-1, oil ratio (weight ratio) is 1～20, is preferably 3～15.Cracking additive provided by the invention can be used for existing various catalyst cracker, for example fixed bed reactors, fluidized-bed reactor, riser reactor, multi-reaction-area reactor.
The following examples will be further described the present invention, but not thereby limit the present invention.
Part material used is as follows: boehmite is Shandong Aluminium Industrial Corp's manufacture product, solid content 60 % by weight; Aluminium colloidal sol is the industrial products that catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, Al
2o
3content is 21.5 % by weight; Waterglass is the industrial products that catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, SiO
2content 28.9 % by weight, Na
2o content 8.9 % by weight; Kaolin is the special-purpose kaolin of Cracking catalyst that Kaolin of Suzhou company produces, solid content 78 % by weight; Rectorite: Hebei Zhongxiang Mingliu Rectorite Development Co., Ltd., quartz sand < 3.5 % by weight, Al
2o
339.0 % by weight, Fe
2o
32.0 % by weight, Na
2o 0.03 % by weight, solid content 77 % by weight; ZRP-5 zeolite is the industrial products of the conventional MFI structural zeolite of catalyst asphalt in Shenli Refinery of China Petrochemical Industry production, wherein P
2o
52.5 % by weight, degree of crystallinity 85 % by weight, silica alumina ratio (SiO
2/ Al
2o
3, mol ratio, lower same) 50.SB aluminium hydrate powder: German Condex company produces, Al
2o
3content 75 % by weight; Gamma oxidation aluminium powder: German Condex company produces, Al
2o
3content 95 % by weight.Hydrochloric acid: chemical pure, concentration 36～38 % by weight, Beijing Chemical Plant produces.
Embodiment 1～5 preparation the present invention molecular sieve used; Comparative example 1～5 preparation contrast molecular sieve.The chemical composition of molecular sieve is in Table 1.
Embodiment 1
By 5kg NH
4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO
2/ Al
2o
3=50),, after 90 ℃ of exchange 0.5h, filter to obtain filter cake; By 0.56kg H
3pO
4(concentration 85 % by weight) and 0.81kgFe (NO
3)
39H
2o is dissolved in 9kg water, by this maceration extract and filter cake hybrid infusion, oven dry, 550 ℃ of calcination process 2 hours, obtains flooding for the first time rear sample; By 0.34kg H
3pO
4(concentration 85 % by weight) are dissolved in 9kg water, by sample mix dipping after this maceration extract and above-mentioned dipping for the first time, dry, 550 ℃ of calcination process 2 hours, obtain modification MFI molecular sieve of the present invention, be designated as A
1.It is 0.08Na that elementary analytical chemistry forms (quality)
2o3.0Al
2o
35.4P
2o
51.5Fe
2o
389.3SiO
2.The phosphorus of introducing for the second time accounts for 38%.The distribution D of phosphorus is 1.48.
Comparative example 1
By the method for CN1425567A, prepare phosphorous and transition metal and there is the molecular sieve of MFI structure.
By 5kg NH
4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO
2/ Al
2o
3=50),, after 90 ℃ of exchange 0.5h, filter to obtain filter cake; By 0.9kg H
3pO
4(concentration 85 % by weight) and 0.81kgFe (NO
3)
39H
2o is dissolved in 90g water, dries with filter cake hybrid infusion; Gained sample, 550 ℃ of calcination process 2 hours, obtains contrast molecular sieve, is designated as B
1.Elementary analytical chemistry consists of 0.08Na
2o3.0Al
2o
35.4P
2o
51.5Fe
2o
389.3SiO
2.The distribution D of phosphorus is: 1.48
Embodiment 2
By 5kg NH
4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry of China Petrochemical Industry produces, and has amine method synthetic, SiO
2/ Al
2o
3=50),, after 90 ℃ of exchange 0.5h, filter to obtain filter cake; By 0.61kg H
3pO
4(concentration 85 % by weight) and 3kg Co (NO
3)
26H
2o is dissolved in 9kg water obtaining maceration extract, by this maceration extract and filter cake hybrid infusion, oven dry, 550 ℃ of roastings 2 hours, obtains sample; By 0.32kgH
3pO
4(concentration 85 % by weight) are dissolved in 9kg water obtaining maceration extract, by this maceration extract and above-mentioned sample mix dipping, oven dry, 550 ℃ of calcination process 2 hours, obtain modification MFI molecular sieve of the present invention, are designated as A
2.Elementary analytical chemistry consists of 0.11Na
2o2.8Al
2o
35.5P
2o
58.6Co
2o
383SiO
2, the phosphorus of introducing for the second time accounts for 34%, and the distribution D of phosphorus is 1.32.
Comparative example 2
By 5kg NH
4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO
2/ Al
2o
3=50),, after 90 ℃ of exchange 0.5h, filter to obtain filter cake; By 0.93kgH
3pO
4(concentration 85 % by weight) and 3kgCo (NO
3)
26H
2o is dissolved in 9kg water, by this maceration extract and the even hybrid infusion of filter cake, oven dry; Gained sample, 550 ℃ of calcination process 2 hours, obtains contrast molecular sieve, is designated as B
2.Elementary analytical chemistry consists of 0.11Na
2o2.8Al
2o
35.5P
2o
58.6Co
2o
383SiO
2.
Embodiment 3
By 5kg NH
4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO
2/ Al
2o
3=50),, after 90 ℃ of exchange 0.5h, filter to obtain filter cake; By 0.15kg H
3pO
4(concentration 85 % by weight) and 0.38kgNi (NO
3)
26H
2o is dissolved in 9kg water, by this maceration extract and the even hybrid infusion of filter cake, oven dry, 550 ℃ of calcination process 2 hours, impregnated sample for the first time; By 0.1kg H
3pO
4(concentration 85 % by weight) are dissolved in 9kg water, by this maceration extract and the above-mentioned hybrid infusion of impregnated sample for the first time, oven dry, 550 ℃ of calcination process 2 hours, obtain modification MFI molecular sieve of the present invention, are designated as A
3.Elementary analytical chemistry consists of 0.1Na
2o3.2Al
2o
31.5P
2o
51.0NiO94.2SiO
2, the phosphorus of introducing for the second time accounts for 40%, and the distribution D of phosphorus is 1.15.
Comparative example 3
By 5kg NH
4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (Shandong catalyst branch company produces, and has amine method synthetic, SiO
2/ Al
2o
3=50),, after 90 ℃ of exchange 0.5h, filter to obtain filter cake; Add 0.25kg H
3pO
4(concentration 85 % by weight) and 0.38kgNi (NO
3)
26H
2o dissolves in 9kg water, by this maceration extract and filter cake hybrid infusion, oven dry; Gained sample, 550 ℃ of calcination process 2 hours, obtains modification MFI molecular sieve, is designated as B
3.Elementary analytical chemistry consists of 0.1Na
2o3.2Al
2o
31.5P
2o
51.0NiO94.2SiO
2.
Embodiment 4
By 5kg NH
4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO
2/ Al
2o
3=50),, after 90 ℃ of exchange 0.5h, filter to obtain filter cake; By 0.39kg H
3pO
4(concentration 85 % by weight) and 0.332KgMn (NO
3)
2be dissolved in 9kg water, this maceration extract and filter cake hybrid infusion, oven dry, 550 ℃ of roastings are obtained to sample Y4 for 2 hours; By 0.16kg H
3pO
4(concentration 85 % by weight) are dissolved in 9kg water, by this maceration extract and above-mentioned sample Y4 hybrid infusion, oven dry, 550 ℃ of roastings 2 hours, obtain molecular sieve of the present invention, are designated as A
4.Elementary analytical chemistry consists of 0.12Na
2o3.0Al
2o
33.5P
2o
56.0Mn
2o
387.4SiO
2.The phosphorus of introducing for the second time accounts for 29%.The distribution D of phosphorus is 3.48.
Comparative example 4
By 5kgNH
4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO
2/ Al
2o
3=50),, after 90 ℃ of exchange 0.5h, filter to obtain filter cake; By 0.55kg H
3pO
4(concentration 85 % by weight) and 0.332kgMn (NO
3)
2be dissolved in 9kg water, by this maceration extract and filter cake hybrid infusion, oven dry; Gained sample, 550 ℃ of roastings 2 hours, obtains modification MFI molecular sieve, is designated as B
4.Elementary analytical chemistry consists of 0.12Na
2o3.0Al
2o
33.5P
2o
56.0Mn
2o
387.4SiO
2.
Embodiment 5
By 5kg NH
4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces, and has amine method synthetic, SiO
2/ Al
2o
3=50),, after 90 ℃ of exchange 0.5h, filter to obtain filter cake; By 0.31kg H
3pO
4(concentration 85 % by weight), 0.82kgFe (NO
3)
39H
2o and 0.22kgBi (NO
3)
35H
2o dissolves in 9kg water, and this maceration extract and filter cake hybrid infusion, oven dry, 550 ℃ of calcination process are obtained to impregnated sample for the first time for 2 hours; Add 0.21kgH
3pO
4(concentration 85 % by weight) dissolve in 9kg water, by this maceration extract and the above-mentioned hybrid infusion of impregnated sample for the first time, oven dry, 550 ℃ of roastings 2 hours, obtain phosphorus of the present invention and transition metal modified MFI molecular sieve, are designated as A
5.Elementary analytical chemistry consists of 0.1Na
2o3.1Al
2o
33.1P
2o
51.6Fe
2o
31.0Bi
2o
391.1SiO
2.Also can be expressed as 0.1Na
2o3.1Al
2o
33.1P
2o
52.6M
2o
391.1SiO
2, wherein the calculating atomic weight of M is 82.9.The phosphorus of introducing for the second time accounts for 40%.The distribution D of phosphorus is 2.43.
Comparative example 5
By 5kg NH
4cl is dissolved in 100kg water, and to adding 10kg (butt) crystallization product ZSM-5 molecular sieve in this solution, (Shandong catalyst branch company produces, and has amine method synthetic, SiO
2/ Al
2o
3=50),, after 90 ℃ of exchange 0.5h, filter to obtain filter cake; Add 0.52kg H
3pO
4(concentration 85 % by weight) and 0.82kgFe (NO
3)
39H
2o, 0.22kg Bi (NO
3)
35H
2o dissolves in 9kg water, by this maceration extract and filter cake hybrid infusion, oven dry; Gained sample, 550 ℃ of calcination process 2 hours, obtains modified molecular screen, is designated as B
5.Elementary analytical chemistry consists of 0.1Na
2o3.1Al
2o
33.1P
2o
51.6Fe
2o
31.0Bi
2o
391.1SiO
2.Also can be expressed as 0.1Na
2o3.1Al
2o
33.1P
2o
52.6M
2o
391.1SiO
2, wherein the calculating atomic weight of M is 82.9.
Table 1
Embodiment 6
The sample that embodiment 1～5 and comparative example 1 are made with TEM-EDS to Fe
2o
3and P
2o
5distribution characterize.The TEM-EDS of embodiment 1 and comparative example 1 the results are shown in Figure 1.
The IR Characterization of embodiment 1～5 and comparative example 1～5 gained molecular sieve the results are shown in Table 1.The infrared spectrum of embodiment 1 and comparative example 1 is shown in Fig. 2.
As can be seen from Figure 1, the sample that comparative example 1 makes, Fe
2o
3and P
2o
5in body phase and surface, be equally distributed, the sample that embodiment 1 makes, Fe
2o
3in body phase and surface, be equally distributed, and P
2o
5at surface enrichment.
Embodiment 7～10 preparation the present invention phosphorus aluminium inorganic binder argillaceous used, formula and composition are in Table 2.
Embodiment 7
This example is prepared phosphorus aluminium inorganic binder argillaceous of the present invention.
0.74 kilogram of boehmite (is contained to Al
2o
30.45 kilogram), 0.39 kilogram of rectorite (0.30 kilogram of butt) and 1.6 kilograms of decationizing water making beating 30 minutes, under stirring, in slurries, add 2.03 kilograms of SPAs (mass concentration 85%), phosphoric acid add speed be 0.04Kg phosphoric acid/minute/Kg alumina source, be warming up to 70 ℃, then at this temperature, react 45 minutes, make phosphorus aluminium inorganic binder argillaceous.Material proportion is in Table 2.
Embodiment 8～10
Example 8～10 preparation phosphorus aluminium inorganic binder argillaceous of the present invention, its preparation method is referring to embodiment 7.Material proportion is in Table 2.
Comparative example 6
This comparative example is prepared comparative example of the present invention phosphorus aluminium glue used (phosphorus aluminium colloidal sol).
Phosphorus aluminium glue preparation: by 0.66 kilogram of boehmite (0.44 kilogram of butt) and 1.75 kilograms of decationizing water making beating 30 minutes, under stirring, in slurries, add 2.6 kilograms of SPAs (chemical pure, phosphoric acid 85 % by weight), be warming up to 70 ℃, then at this temperature, react 45 minutes, obtain phosphorus aluminium glue (phosphorus al binder).Material proportion is in Table 2.
Embodiment 11～18 preparation auxiliary agent provided by the present invention.Auxiliary formula is in Table 3, and preparation process is described below:
Embodiment 11
Get molecular sieve-4 A
1, kaolin and boehmite, add decationized Y sieve water and and aluminium colloidal sol making beating 120 minutes, obtain the slurries of solid content 30 % by weight, add hydrochloric acid to regulate the pH value 3.0 of slurries, then continue making beating 45 minutes, then the phosphorus aluminium inorganic binder argillaceous (Binder2) that adds embodiment 8 preparations, stir after 30 minutes, the slurries spraying obtaining is dry, obtain microballoon, by microballoon roasting 1 hour at 500 ℃, make ZJ
1, its proportioning is in Table 3.
Table 2
Embodiment 12
Get molecular sieve-4 A
1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3.0, continue making beating 45 minutes, then toward the phosphorus aluminium inorganic binder argillaceous (Binder1) that wherein adds embodiment 7 preparations.The slurries that obtain, 500 ℃ of dry gas inlet temperatures, are sprayed under the condition that exhaust temperature is 180 ℃ dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 ℃.
Get thus obtained microsphere product, add ammonium dibasic phosphate aqueous solution, be warming up to 60 ℃ under stirring, react after 20 minutes at this temperature, by slurries vacuum filtration, dry, then roasting 2 hours at 500 ℃, makes auxiliary agent ZJ
2.Auxiliary agent proportioning is in Table 3.
Embodiment 13
Get molecular sieve-4 A
1with boehmite, kaolin, diatomite, add decationized Y sieve water and waterglass making beating 120 minutes, obtain the slurries of solid content 35 % by weight, add hydrochloric acid to make the pH value 3 of slurries, then pull an oar 45 minutes, to the phosphorus aluminium inorganic binder argillaceous (Binder 3) that adds embodiment 9 preparations in mixed serum, stir 30 minutes, the slurries spraying obtaining is dry, obtain microballoon, by microballoon roasting 1 hour at 500 ℃, obtain auxiliary agent ZJ
3, its proportioning is in Table 3.
Embodiment 14
Get molecular sieve-4 A
1with boehmite, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 38 % by weight, add hydrochloric acid to make the pH value 3.0 of slurries, then pull an oar 45 minutes, then in mixed serum, add the phosphorus aluminium inorganic binder argillaceous (Binder 4) of embodiment 10 preparations and the phosphorus al binder that comparative example 6 provides, stir 30 minutes.The slurries that obtain, 500 ℃ of dry air inlet temperatures, are sprayed under the condition that exhaust temperature is 180 ℃ dry, obtain average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 ℃, obtain auxiliary agent ZJ
4, its proportioning is in Table 3.
Embodiment 15
Get molecular sieve-4 A
2with boehmite, kaolin, add decationized Y sieve water making beating 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3, then pull an oar 45 minutes, then toward the phosphorus al binder argillaceous (Binder 1) that adds embodiment 7 preparations in slurries, stir 30 minutes.The slurries spraying obtaining is dry, obtain microballoon.By microballoon roasting 1 hour at 500 ℃, obtain auxiliary agent ZJ
5, auxiliary agent proportioning is in Table 3.
Embodiment 16
Get molecular sieve-4 A
3, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3, continues making beating 45 minutes, then the phosphorus aluminium inorganic binder argillaceous (Binder 2) that adds embodiment 8 preparations, and after diammonium hydrogen phosphate solid stirs, the slurries spraying obtaining is dry, obtain microballoon, by microballoon roasting 1 hour at 400 ℃, make auxiliary agent ZJ
6.Proportioning is in Table 3.
Embodiment 17
Get molecular sieve-4 A
4with boehmite, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, with hydrochloric acid, regulating the pH value of slurries is 3.0, then continues making beating 45 minutes, the phosphorus aluminium inorganic binder argillaceous (Binder 3) that adds embodiment 9 preparations, stir 30 minutes, the slurries spraying obtaining is dry, obtain microballoon, by microballoon roasting 1 hour at 500 ℃, make auxiliary agent ZJ
7.Auxiliary agent proportioning is in Table 3.
Embodiment 18
Get molecular sieve-4 A
5, kaolin soil and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to make the pH value of slurries is 3, continues making beating 30 minutes, the phosphorus aluminium inorganic binder argillaceous (Binder 3) that adds embodiment 9 preparations, pull an oar again 30 minutes, then that the slurries spraying obtaining is dry, obtain, by microballoon roasting 1 hour at 500 ℃, make auxiliary agent ZJ
8.Auxiliary agent proportioning is in Table 3.
Comparative example 7
Get A
1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, under stirring, adding concentration is the hydrochloric acid of 36 % by weight, and the pH value that makes slurries is 3.0, then pulls an oar 45 minutes, the slurries spraying obtaining is dry, obtain average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 ℃, make reference auxiliary agent DB
1.Reference auxiliary agent proportioning is in Table 4.
Comparative example 8
Get A
1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, under stirring, add hydrochloric acid, by hydrochloric acid content, control the pH value 3.0 of slurries, mixture was continued to making beating after 45 minutes, the phosphorus al binder that adds comparative example 6 to make, then stir 30 minutes, by the slurries that obtain 500 ℃ of inlet temperatures, under the condition that exhaust temperature is 180 ℃, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 ℃, make reference auxiliary agent DB
2.Reference auxiliary agent proportioning is in Table 4.
Comparative example 9
Method by embodiment 11 is prepared auxiliary agent, is not both and uses molecular sieve B
1replace A
1, make reference auxiliary agent DB
3.Reference auxiliary agent proportioning is in Table 4.
Comparative example 10
By the method for comparative example 7 is prepared to auxiliary agent, be not both with molecular sieve ZRP-5 and replace A
1, make reference auxiliary agent DB
4.Reference auxiliary agent proportioning is in Table 4.
Comparative example 11
By the method for embodiment 15 is prepared to auxiliary agent, be not both and use molecular sieve B
2replace A
2, make reference auxiliary agent DB
5.Reference auxiliary agent proportioning is in Table 4.
Comparative example 12
Get molecular sieve B
3, kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, by adding hydrochloric acid to regulate the pH value 3.0 of slurries, then continue making beating 30 minutes, add diammonium hydrogen phosphate, pull an oar again 30 minutes, then by the slurries that obtain 500 ℃ of inlet temperatures, under the condition that exhaust temperature is 180 ℃, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 ℃, make auxiliary agent DB
6.Reference auxiliary agent proportioning is in Table 4.
Comparative example 13
Get molecular sieve B
4and kaolin, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3.0, and the phosphorus al binder argillaceous that adds embodiment 9 to provide is provided 30 minutes, pull an oar 45 minutes, then by the slurries that obtain 500 ℃ of dry air inlet temperatures, under the condition that exhaust temperature is 180 ℃, spray dry, obtain average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 ℃, obtain reference auxiliary agent DB
7.Reference auxiliary agent proportioning is in Table 4.
Comparative example 14
Get molecular sieve B
5, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtain the slurries of solid content 30 % by weight, by adding hydrochloric acid to make the pH value 3.0 of slurries, pull an oar 45 minutes, then that the slurries spraying obtaining is dry, obtain microballoon, make reference auxiliary agent DB
8.Reference auxiliary agent proportioning is in Table 4.
Embodiment 19～26
The following examples be take fixed fluidized-bed reactor as example, and the cracking reaction effect of cracking additive provided by the invention is described.
Respectively by 30 grams of ZJ
1-ZJ
8under 800 ℃, 100% steam atmosphere condition, carry out the burin-in process of 12 hours.Get the ZJ through burin-in process of different amounts
1-ZJ
8mix respectively from the industrial FCC equilibrium catalyst (the FCC equilibrium catalyst that the industrial trade mark is MLC-500, main character is in Table 5) of different amounts.Catalyst mixture is packed in the reactor of small fixed flowing bed-tion reacting device, feedstock oil oil shown in his-and-hers watches 6 carries out catalytic cracking (feedstock oil character is in Table 6).Table 7, table 8 have provided used catalyst mixture weight and have formed, reaction condition and reaction result.
Comparative example 15～23
Comparative example below be take fixed fluidized-bed reactor as example, and the situation of using reference auxiliary agent is described.
By the method in embodiment 19, same feedstock oil is carried out to catalytic cracking, different is that used catalyst is respectively 100% industrial FCC equilibrium catalyst, DB
1～DB
8mixture with industrial FCC equilibrium catalyst.Table 7, table 8 have provided used catalyst mixture weight and have formed, reaction condition and reaction result.
From table 7 and table 8, can find out, compare with auxiliary agent prepared by existing method, catalyst aid provided by the invention, there is higher catalytic cracking liquefied gas yield, density of propylene in catalytic cracking liquefied gas is higher, coke and dry gas selective better, heavy oil conversion performance is higher, is unexpectedly also to have higher liquid to receive.
Table 5
Table 6
Claims (18)
1. improve an assistant for calalytic cracking for density of propylene, contain modification MFI molecular sieve in butt 10～75 % by weight, in the phosphorus aluminium inorganic binder containing the first clay of al composition, phosphorus component and the first clay butt weight sum 3～30 % by weight, in other inorganic binders of oxide 3～30 % by weight with in the second clay of butt 0～60 % by weight; Wherein, the described phosphorus aluminium inorganic binder butt weight containing the first clay of take is benchmark, and the described phosphorus aluminium inorganic binder containing the first clay comprises with Al
2o
3meter 15～40 % by weight al compositions, with P
2o
5the phosphorus component of meter 45～80 % by weight and in the first clay of butt 1～40 % by weight, and its P/Al weight ratio is 1～6; Described modification MFI molecular sieve, its anhydrous chemical expression, counts with the weight of oxide: (0～0.3) Na
2o (0.5～6) Al
2o
3(1.3～10) P
2o
5(0.7～15) M
xo
y(70～97) SiO
2x represents the atomicity of described transition metal M, y represents to meet the required number of oxidation state of described transition metal M, described transition metal M is one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi preferably, and the infrared spectrum that described modification MFI molecular sieve obtains as probe molecule with trimethylpyridine is at 1633cm
-1place is without absworption peak; The described phosphorus aluminium inorganic binder preparation method who contains the first clay comprises:
(1) alumina source, the first clay and water making beating are dispersed into the slurries that solid content is 8～45 % by weight; Described alumina source is can be by the aluminium hydroxide of sour peptization and/or aluminium oxide, in the first clay of butt and with Al
2o
3the weight ratio of the alumina source of meter is 1～40: 15～40;
(2) stir in the lower slurries that obtain toward step (1) and add SPA according to the part by weight of P/Al=1～6;
(3) slurries that step (2) obtained react 15～90 minutes at 50～99 ℃ of temperature.
2. according to auxiliary agent claimed in claim 1, it is characterized in that, described modification MFI molecular sieve rich surface phosphorus, the distribution D of its phosphorus is greater than 1, wherein D=P
(S)/ P
(C), described P
(S)represent to adopt zeolite crystal that TEM-EDX method characterizes from edge 1/10th the phosphorus content to center, P
(C)the phosphorus content that represents zeolite crystal center.
3. according to auxiliary agent claimed in claim 2, it is characterized in that, the distribution D of described modification MFI molecular sieve phosphorus is 1.15～9: 1.
4. according to the auxiliary agent described in claim 1,2 or 3, it is characterized in that, described its anhydrous chemical expression of modification MFI molecular sieve is: (0～0.2) Na
2o (0.9～5.5) Al
2o
3(1.5～7) P
2o
5(0.9～10) M
xo
y(82～92) SiO
2.
5. according to auxiliary agent claimed in claim 1, it is characterized in that, described MFI molecular sieve is one or more in ZSM-5, ZSM-8 or ZSM-11.
6. according to auxiliary agent claimed in claim 1, it is characterized in that, described auxiliary agent contains with P
2o
5meter is no more than the phosphorus additive of 15 % by weight.
7. according to auxiliary agent claimed in claim 6, it is characterized in that, this auxiliary agent comprise 8～25 % by weight containing the phosphorus aluminium inorganic binder of the first clay, the described modification MFI molecular sieve of 20～60 % by weight, the second clay of 10～45 % by weight, the phosphorus additive of other inorganic binder of 5～25 % by weight and 0～10 % by weight.
8. according to auxiliary agent claimed in claim 1, it is characterized in that, the first described clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and diatomite; Described the second clay is one or more in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and rectorite; Other described inorganic matter binding agent is one or more in boehmite, aluminium colloidal sol, silicon-aluminum sol, waterglass and phosphorus aluminium colloidal sol.
9. a preparation method for assistant for calalytic cracking, comprises modification MFI molecular sieve, the phosphorus aluminium inorganic binder containing the first clay, other inorganic binder mixing, adds or do not add the second clay, making beating, and spraying is dry; Wherein, the described phosphorus aluminium inorganic binder containing the first clay, take its butt weight is benchmark, containing with Al
2o
3meter 15～40 % by weight al compositions, with P
2o
5the phosphorus component of meter 45～80 % by weight and in the first clay of butt 1～40 % by weight, its P/Al weight ratio is that 1～6, pH is 1～3.5, this binding agent solid content is 15～60 % by weight; Described modification MFI molecular sieve, its anhydrous chemical expression, counts with the weight of oxide: (0～0.3) Na
2o (0.5～6) Al
2o
3(1.3～10) P
2o
5(0.7～15) M
xo
y(70～97) SiO
2, x represents the atomicity of described transition metal M, y represents to meet the required number of oxidation state of described transition metal M; Described transition metal M is one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi preferably; The infrared spectrum that described modification MFI molecular sieve obtains as probe molecule with trimethylpyridine is at 1633cm
-1place is without absworption peak;
The described phosphorus aluminium inorganic binder preparation method containing the first clay comprises:
(1) alumina source, the first clay and water making beating are dispersed into the slurries that solid content is 8～45 % by weight; Described alumina source is can be by the aluminium hydroxide of sour peptization and/or aluminium oxide, in the first clay of butt and with Al
2o
3the weight ratio of the alumina source of meter is 1～40: 15～40;
(2) stir in the lower slurries that obtain toward step (1) and add SPA according to the part by weight of P/Al=1～6;
(3) slurries that step (2) obtained react 15～90 minutes at 50～99 ℃ of temperature.
10. in accordance with the method for claim 9, it is characterized in that, the described phosphorus aluminium inorganic binder containing the first clay, take its butt weight is benchmark, comprises the Al that 15～35 % by weight are derived from described alumina source
2o
3, 50～75 % by weight P
2o
5the first clay with 8～35 % by weight.
11. according to the method described in claim 9 or 10, it is characterized in that, described P/Al weight ratio is 2～5.
12. in accordance with the method for claim 9, it is characterized in that, described alumina source is one or more in ρ-aluminium oxide, χ-aluminium oxide, η-aluminium oxide, gama-alumina, κ-aluminium oxide, δ-aluminium oxide, θ-aluminium oxide, gibbsite, surge aluminium stone, promise diaspore, diaspore, boehmite and boehmite; The first described clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and diatomite.
13. in accordance with the method for claim 9, it is characterized in that, the temperature described in step (3) is 65～90 ℃.
14. in accordance with the method for claim 9, it is characterized in that, the preparation method of described modification MFI molecular sieve, be included in the molecular sieve with MFI structure of ammonium exchange and introduce phosphorus and transition metal, wherein, described phosphorus divides two parts to introduce, and a part of phosphorus is introduced after transition metal is introduced, and a part of phosphorus before introducing transition metal or introduce with transition metal simultaneously in addition; The anhydrous chemical expression of described modification MFI molecular sieve, counts with the weight of oxide: (0～0.3) Na
2o (0.5～6) Al
2o
3(1.3～10) P
2o
5(0.7～15) M
xo
y(70～97) SiO
2, x represents the atomicity of described transition metal M, and y represents to meet the required number of oxidation state of described transition metal M, and described transition metal M is selected from one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi.
15. in accordance with the method for claim 14, it is characterized in that, in the preparation method of described modification MFI molecular sieve, the phosphorus that transition metal is introduced after introducing accounts for 10～90% of total phosphorus in molecular sieve.
16. according to the method described in claims 14 or 15, it is characterized in that, in the phosphorus that transition metal is introduced after introducing and molecular sieve, the mol ratio of transition metal is 0.25～10: 1.
17. in accordance with the method for claim 16, it is characterized in that, described phosphorus and the transition metal introduced in the molecular sieve with MFI structure of ammonium exchange comprise with phosphorus-containing compound solution and the solution that contains transistion metal compound described molecular sieve flooded to modification, is then dried, 400～800 ℃ of roastings; Wherein phosphorus-containing compound solution impregnation is at least carried out twice.
18. in accordance with the method for claim 17, it is characterized in that, described with phosphorus-containing compound solution and the solution that contains transistion metal compound, described molecular sieve flooded to modification and comprise: the filter cake after ammonium exchange is mixed with the part phosphorus-containing compound that comprises amount of calculation and the solution of metal-containing compound, after dry or dry, at 400～800 ℃ of roasting temperatures, then mix with the solution of remaining phosphorus-containing compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110284431.1A CN103007988B (en) | 2011-09-22 | 2011-09-22 | Cracking assistant for improving low-carbon olefin concentration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110284431.1A CN103007988B (en) | 2011-09-22 | 2011-09-22 | Cracking assistant for improving low-carbon olefin concentration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103007988A CN103007988A (en) | 2013-04-03 |
| CN103007988B true CN103007988B (en) | 2014-08-20 |
Family
ID=47957420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110284431.1A Active CN103007988B (en) | 2011-09-22 | 2011-09-22 | Cracking assistant for improving low-carbon olefin concentration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103007988B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479361A (en) * | 2019-09-03 | 2019-11-22 | 四川润和催化新材料股份有限公司 | A kind of drop slurry oil and the auxiliary agent of low-carbon olefines high-output and the preparation method and application thereof |
| CN114505093B (en) * | 2020-10-28 | 2023-08-08 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent and preparation method and application thereof |
| CN112371167B (en) * | 2020-10-16 | 2022-09-30 | 中科合成油内蒙古有限公司 | Catalyst for producing high-octane component gasoline and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal |
| CN1727443A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Cracking catalyst and its application |
| CN1796496A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Cracking auxiliary agent for raising density of propylene |
| CN101385983A (en) * | 2007-09-12 | 2009-03-18 | 中国石油化工股份有限公司 | Heavy oil catalytic cracking catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI383039B (en) * | 2007-08-09 | 2013-01-21 | China Petrochemical Technology Co Ltd | A catalytic conversion method |
-
2011
- 2011-09-22 CN CN201110284431.1A patent/CN103007988B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal |
| CN1727443A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Cracking catalyst and its application |
| CN1796496A (en) * | 2004-12-28 | 2006-07-05 | 中国石油化工股份有限公司 | Cracking auxiliary agent for raising density of propylene |
| CN101385983A (en) * | 2007-09-12 | 2009-03-18 | 中国石油化工股份有限公司 | Heavy oil catalytic cracking catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103007988A (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103007990B (en) | Cracking assistant for improving low-carbon olefin concentration | |
| CN103007989B (en) | Cracking assistant for improving low-carbon olefin concentration | |
| CN102847551B (en) | Cracking aid for improving lower-carbon olefin concentration | |
| CN103785456B (en) | A kind of cracking additive improving low-carbon olefin concentration | |
| CN100389174C (en) | Cracking auxiliary agent for raising density of propylene | |
| CN103007986B (en) | Cracking auxiliary agent for improving catalytic cracking low-carbon olefin concentration | |
| CN102452669B (en) | MFI structure molecular sieve containing phosphorus and transition metal as well as its preparation method | |
| CN103785458B (en) | A kind of cracking additive improving low-carbon olefin concentration | |
| CN105013525B (en) | A kind of assistant for calalytic cracking for improving low-carbon olefin concentration and preparation method thereof | |
| CN100537030C (en) | Catalytic cracking additive for promoting liquid gas propylene concentration | |
| CN102847552B (en) | Cracking aid for improving lower-carbon olefin concentration | |
| CN107971003A (en) | It is a kind of to contain phosphorous and assistant for calalytic cracking of Beta molecular sieves of carried metal and preparation method thereof | |
| CN107970999A (en) | A kind of assistant for calalytic cracking containing phosphorous Beta molecular sieves and preparation method thereof | |
| CN104998681B (en) | A kind of assistant for calalytic cracking for improving low-carbon olefin concentration and preparation method thereof | |
| CN103007988B (en) | Cracking assistant for improving low-carbon olefin concentration | |
| CN103007991B (en) | Cracking assistant for improving low-carbon olefin concentration | |
| CN103785457B (en) | A kind of cracking additive improving low-carbon olefin concentration | |
| CN103007993B (en) | Cracking assistant for improving low-carbon olefin concentration | |
| CN107971000A (en) | A kind of assistant for calalytic cracking containing phosphorous Beta molecular sieves and preparation method thereof | |
| CN103785455B (en) | A kind of cracking additive improving catalytic cracking low-carbon olefin concentration | |
| CN103007992B (en) | Cracking assistant for improving low-carbon olefin concentration | |
| CN100497530C (en) | Method for cracking hydrocarbon oil | |
| CN100389175C (en) | Catalytic auxiliary agent for raising density of propylene in catalytic cracking liquefied gas | |
| CN100389176C (en) | Cracking auxiliary agent for increasing production of propylene | |
| CN104998677B (en) | A kind of assistant for calalytic cracking for improving low-carbon olefin concentration and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |