CN102847551B - Cracking aid for improving lower-carbon olefin concentration - Google Patents
Cracking aid for improving lower-carbon olefin concentration Download PDFInfo
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- CN102847551B CN102847551B CN201110180859.1A CN201110180859A CN102847551B CN 102847551 B CN102847551 B CN 102847551B CN 201110180859 A CN201110180859 A CN 201110180859A CN 102847551 B CN102847551 B CN 102847551B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The inventive cracking aid for improving lower-carbon olefin concentration comprises a phosphorus/aluminum inorganic binder containing a first clay, a modified MFI molecular sieve, other inorganic binder, group-VIII metal additive, and optional a second clay. The first inorganic binder comprises aluminum component (as alumina) 15-40 wt%, phosphorus component (as phosphorus pentoxide) 45-80 wt%, and the first clay (on dry basis) 1-40 wt%. The cracking aid is used for catalytic cracking of petroleum hydrocarbons, can increase yield of catalytic cracked liquefied gas and obviously improve lower-carbon olefin (especially propylene) concentration in liquefied gas, and has high heavy oil conversion ability.
Description
Technical field
The present invention relates to a kind of cracking additive that improves catalytic cracking liquefied gas low-carbon alkene concentration.
Background technology
Propylene is important Organic Chemicals.Along with the growth of the acryloyl derivative demands such as polypropylene, the whole world all 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 % by weight or the phosphorous and rare earth of Y-type high-Si zeolite and 75～100 % by weight.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 % by weight (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 2002/0003103 A1.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/A1 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 2002/0049133 A1.The ZSM-5 zeolite that this catalyst contains 30～85 % by weight, the phosphorus of 6～24 % by weight is (with P
2o
5meter), and lower than the Al of 10 % by weight
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 % by weight phosphorus, 0.01～1.0 % by weight iron or 0.01～10 % by weight 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, can improve C
2～C
4the productive rate of alkene and selective, has higher liquefied gas yield.
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) SiO
2, 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 zeolitic material of prior art and catalyst are for catalytic cracking process, and liquid gas propylene concentration is not high, and due to the adding of auxiliary agent, when especially addition is larger, have diluted major catalyst, have weakened the heavy oil conversion performance of carbon monoxide-olefin polymeric.
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 is applied to catalytic cracking, can improve the density of propylene in catalytic cracking liquefied gas.
The invention provides a kind of assistant for calalytic cracking, the butt weight of described auxiliary agent of take is benchmark, contains the modification MFI molecular sieve in butt 10～75 % by weight, with Al
2o
3(containing the Al in the phosphorus aluminium inorganic binder al composition of the first clay
2o
3), P
2o
5(containing the P in the phosphorus aluminium inorganic binder phosphorus component of the first clay
2o
5) 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 binder of oxide 3～30 % by weight, in the second clay of butt 0～60 % by weight with in the VIII family metallic addition of oxide 0.5～15 % 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, its P/Al weight ratio is 1～6; Described modification MFI molecular sieve is phosphorous and the molecular sieve with MFI structure transition metal, and 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, 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.
The present invention also provides a kind of preparation method of assistant for calalytic cracking, comprise modification MFI molecular sieve, the phosphorus aluminium inorganic binder containing the first clay, other inorganic binder mixing, add or do not add the second clay, making beating, the step that is dried and introduces VIII family metallic addition; Wherein, the butt weight of the described phosphorus aluminium inorganic binder containing the first clay of take is benchmark, and the described phosphorus aluminium inorganic binder containing the first clay, contains with Al
2o
3meter 15～40 % by weight components, with P
2o
5the phosphorus component of meter 45～80 % by weight and in butt 1～40 % by weight the first clay, should be that 1～6, pH value is 1～3.5 containing P/Al weight ratio of the phosphorus aluminium inorganic binder of the first clay, and solid content is 15～60 % by weight.
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.The VIII family metal relating in modification MFI molecular sieve is not considered as VIII family metallic addition.
The first described clay is one or more in kaolin, sepiolite, concave convex rod, rectorite, imvite and diatomite.
Described VIIIB family metal is preferably one or more in Fe, Co and Ni, wherein Fe more preferably.
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 in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone.
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 and binder component, for example, be one or more of boehmite, aluminium colloidal sol, silicon-aluminum sol, waterglass and phosphorus aluminium colloidal sol.
In catalyst aid provided by the present invention, can also contain with P
2o
5meter is no more than the phosphorus additive of 25 % by weight, described phosphorus additive is derived from the compound of phosphorus, comprise 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 auxiliary agent, phosphorus additive for example, exists with the form of phosphorus compound (one or more in the oxide of phosphorus, phosphate, phosphite, subphosphate, acid phosphate).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.The amount that does not comprise the phosphorus relating in modification MFI molecular sieve in the content of described phosphorus additive, does not comprise the amount containing the phosphorus relating in the phosphorus aluminium inorganic binder of the first clay yet.
Auxiliary agent provided by the invention, adopting modification MFI molecular sieve phosphorous, transition metal is active component and appropriate argillaceous phosphorus aluminium inorganic binder, prepared auxiliary agent is for catalytic cracking process, can increase and increase significantly catalytic cracking liquefied gas yield, can also improve significantly especially density of propylene of low-carbon alkene in catalytic cracking liquefied gas simultaneously, significantly improve selective for propylene of catalytic cracking reaction process, improve the octane number of catalytically cracked gasoline; Improve the heavy oil conversion performance of carbon monoxide-olefin polymeric, and can reduce dry gas and coke yield.For example, industrial DVR-3 poising agent is 16h at 480 ℃, weight (hourly) space velocity (WHSV)
-1, react under the oil ratio condition that is 5, conversion ratio is 64.91 % by weight, liquefied gas yield is 15.31 % by weight, 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 55 % by weight modified zsm-5 zeolites that contain provided by the invention, 6 % by weight kaolin, 8 % by weight boehmites, 5 % by weight aluminium colloidal sols, 24 % by weight are containing the phosphorus aluminium inorganic binder of rectorite and the auxiliary agent of 2 % by weight iron additives, after mixing with above-mentioned DVR-3 poising agent with the weight ratios of 10: 90, under similarity condition, react, conversion ratio is 66.3 % by weight, liquefied gas yield is 20.65 % by weight, productivity of propylene is 8.06 % by weight, in liquefied gas, density of propylene is 39.03 % by weight, coke selectivity is 9.11 % by weight, dry gas is selectively 2.25 % by weight.
The specific embodiment
In assistant for calalytic cracking provided by the invention, described MFI molecular sieve is preferably ZSM-5, and described transition metal M is preferably Fe, and its anhydrous chemical expression is preferably (0～0.2) Na in oxide weight
2o (0.9～3.5) Al
2o
3(1.5～7) P
2o
5(0.9～10) M
xo
y(82～92) SiO
2.
Assistant for calalytic cracking 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 the phosphorus relating in modification MFI molecular sieve, do not comprise containing the phosphorus relating in the phosphorus aluminium inorganic binder of the first clay yet.
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.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, its P/Al weight ratio is that 2.0～5.0, pH is 1.0～3.5.P/Al weight ratio is in the phosphorus component of P elements with in the weight ratio of the al composition of aluminium element.
Cracking additive provided by the invention, wherein said 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 and binder component, the mixture of one or more in boehmite, aluminium colloidal sol, phosphorus aluminium glue, silicon-aluminum sol, waterglass for example, wherein preferred one or more of boehmite, aluminium colloidal sol, phosphorus aluminium glue.In auxiliary agent, contain except described and for example during phosphorus aluminium colloidal sol, be considered as having introduced phosphorus additive containing other the phosphorous binding agent the phosphorus aluminium inorganic binder of the first clay, the phosphorus content of the content of the phosphorus of its introducing and the introducing of other phosphorus additive is (with P
2o
5meter) sum is no more than 25 % by weight.
In the preparation method of assistant for calalytic cracking provided by the invention, the described phosphorus aluminium compound 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
5meter 45～80 % by weight phosphorus component and take butt 1～40 % by weight its P/Al weight ratio of the first clay as 1.0～6.0, pH be 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 element in phosphoric acid, and Al is in the weight of the aluminium of element 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, preferably 50～75 % by weight P
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 2.0～5.0.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.Described al composition is from described aluminium 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.
In the phosphorus aluminium inorganic binder preparation process that contains the first clay provided by the invention, clay, alumina source, SPA and water are mixed and reacted, do not introduce chlorine, obtain the not chloride phosphorus aluminium inorganic binder that contains the first clay.Due to the introducing of clay, mass transfer, the heat transfer of storeroom not only in preparation process, have been improved, the phosphorus aluminium glue adhesive cures of having avoided the inhomogeneous local moment vigorous reaction heat release overtemperature of material to cause.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.
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, 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.Preferably, water, modification MFI molecular sieve, other inorganic binder and clay are mixed, pull an oar and add the described phosphorus aluminium inorganic binder containing the first clay after 15～60 minutes, this is conducive to improve abrasion resistance properties, the residual oil cracking performance and selective of catalyst.
Assistant for calalytic cracking preparation method provided by the invention, also comprises the step of the slurry dried moulding that described making beating is obtained, and described dry for example spraying is dry, and spray-dired method is known for those skilled in the art, and the present invention does not have specific (special) requirements.
The preparation method of assistant for calalytic cracking provided by the invention, described introducing VIII family metallic addition can add the metallic compound introducing of VIII family in any step before the drying and moulding of auxiliary agent preparation process in slurries, also can after auxiliary agent drying and moulding, by roasting after dipping or chemisorbed VIII family metallic compound, introduce.After drying and moulding, introduce, comprise auxiliary agent with flooding containing the transistion metal compound aqueous solution or chemisorbed processing, then carry out Separation of Solid and Liquid (if necessary), dry and roasting, wherein dry temperature is room temperature to 400 ℃, preferably 100～300 ℃, the temperature of roasting is 400～700 ℃, is preferably 450～650 ℃, roasting time is 0.5～100 hour, is preferably 0.5～10 hour.Preferably, described VIII family metallic addition was introduced before drying and moulding.Described VIII family metallic addition can ShiⅧ family metal inorganic compound and one or more in organic compound, can be soluble in water, can be to be also insoluble in water or water-fast compound.The example of VIII family metallic compound comprises its oxide, hydroxide, chloride, nitrate, sulfate, phosphate and organic compound.Preferred transistion metal compound is selected from one or more in their chloride, nitrate, sulfate and phosphate.
Described transition metal additives 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 host material, can also be present in the inside, duct of zeolite, in the surface and described host material of zeolite, be preferably present in host material simultaneously.Described VIII family metallic addition can their oxide, phosphate, phosphite, subphosphate, the form of acid phosphate exist.
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, is preferably 3～20 % by weight.Described hydrocarbon ils is selected from various petroleum distillates, and 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, agent weight of oil ratio is 1～20, is preferably 3～15.Cracking additive provided by the invention can be used for existing various catalyst cracker, as 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 content of the present invention.
In embodiment, A
1～A
5five modified zsm-5 zeolite samples are prepared by the disclosed method of CN1465527A, and its anhydrous chemical expression is to form with the element of x-ray fluorescence spectrometry molecular sieve, then obtain through converting.
Sample A
1: 0.04Na
2o3.57Al
2o
34.0P
2o
52.4Fe
2o
390.49SiO
2.
Sample A
2: 0.1Na
2o5.3Al
2o
31.5P
2o
51.1Fe
2o
392SiO
2.
Sample A
3: 0.1Na
2o0.94Al
2o
35.1P
2o
510.1Fe
2o
384SiO
2.
Sample A
4: 0.03Na
2o5.1Al
2o
34.8P
2o
53.6Co
2o
386.5SiO
2.
Sample A
5: 0.1Na
2o4.6Al
2o
36.9P
2o
56.4Ni
2o
382SiO
2.
Boehmite is Shandong Aluminum Plant's manufacture product, solid content 60 % by weight; The industrial products that aluminium colloidal sol (the present invention claims again colloidal sol containing chloride and aluminium) is produced for Qilu Petrochemical catalyst plant, Al
2o
3content is 21.5 % by weight; Waterglass is the industrial products that Qilu Petrochemical catalyst plant is produced, SiO
2content 28.9 % by weight, Na
2o content 8.9%; Kaolin is the special-purpose kaolin of Cracking catalyst that Kaolin of Suzhou company produces, solid content 78 % by weight; ZRP-5 zeolite is the industrial products of the conventional MFI structural zeolite of Qilu Petrochemical catalyst plant production, wherein P
2o
52.5 % by weight, degree of crystallinity 85 % by weight, silica alumina ratio 50.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; 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 1～4 preparation the present invention phosphorus aluminium inorganic binder argillaceous used, formula and composition are in Table 1.
Embodiment 1
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 0.03Kg 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 1.
Embodiment 2～4
According to embodiment 1 preparation phosphorus aluminium inorganic binder argillaceous of the present invention.Material proportion is in Table 1.
Comparative example 1
This comparative example is prepared phosphorus aluminium inorganic binder according to existing method.
Phosphorus aluminium colloidal sol 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, slowly 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 inorganic binder.Material proportion is in Table 1.
Embodiment 5
Get molecular sieve-4 A
1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add FeCl
3.6H
2the aqueous solution (the FeCl of O
3concentration 30 % by weight), obtain the slurries that solid content is 30 % by weight, with hydrochloric acid, regulating the pH value of slurries is 3.0, then the 45 minutes kinds of pulling an oar, the phosphorus al binder argillaceous that adds embodiment 2 to provide, stirs 30 minutes, the slurries spraying obtaining is dry, obtain microballoon, by microballoon roasting 1 hour at 500 ℃, make auxiliary agent ZJ
1.Formula is in Table 2.
Embodiment 6
Get molecular sieve-4 A
2, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add Co (NO
3)
26H
2the aqueous solution of O (Co (NO
3)
2concentration 30 % by weight), obtain the slurries that solid content is 30 % by weight, adding hydrochloric acid to regulate the pH value of slurries is 3.0, continue 45 minutes kinds of making beating, then toward the phosphorus al binder argillaceous that adds embodiment 1 to provide in mixed serum, stir 45 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 ℃.
Get 1 kilogram of thus obtained microsphere product (butt), adding 10 kilograms of concentration is in the ammonium dibasic phosphate aqueous solution of 5 % by weight, is warming up to 60 ℃ under stirring, at this temperature, react after 20 minutes, by slurries vacuum filtration, dry, then roasting 2 hours at 500 ℃, makes auxiliary agent ZJ
2.Formula is in Table 2.
Embodiment 7
Get molecular sieve-4 A
3, kaolin, diatomite and boehmite, add decationized Y sieve water and waterglass making beating 120 minutes, adding hydrochloric acid to regulate the pH value of slurries is 3.0, pull an oar 45 minutes, add diammonium hydrogen phosphate solid, then toward the phosphorus aluminium inorganic binder argillaceous that adds embodiment 3 preparations in slurries, stir the slurries that obtain solid content 38 % by weight for 30 minutes, then the slurries spraying obtaining is dry, obtain average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 ℃.
Get the microballoon after gained roasting, with concentration be 1.5 % by weight FeCl
36H
2o aqueous solution is reacted 20 minutes at 60 ℃ of temperature, filters, dry, and then roasting 2 hours at 500 ℃, makes auxiliary agent ZJ
3.Formula is in Table 2.
Embodiment 8
Get molecular sieve-4 A
4, kaolin and boehmite, add decationized Y sieve water making beating 120 minutes, under stirring, add Co (NO
3)
26H
2the aqueous solution of O (Co (NO
3)
2concentration is 30 % by weight), adding hydrochloric acid to regulate the pH value of slurries is 3.0, pull an oar 45 minutes, obtain the slurries of solid content 30 % by weight, then toward the argillaceous phosphorus al binder that adds embodiment 4 preparations in slurries, spraying is dry, obtains average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 ℃, make auxiliary agent ZJ
4.Formula is in Table 2.
Embodiment 9
Get molecular sieve-4 A
5, add decationized Y sieve water making beating 120 minutes, under stirring, add Ni (NO
3)
26H
2the aqueous solution of O (Ni (NO
3)
2concentration 30 % by weight), add hydrochloric acid to make the pH value 3.0 of slurries, pull an oar 45 minutes, obtain the slurries of solid content 30 % by weight, then add the argillaceous phosphorus al binder of embodiment 4 preparation and the phosphorus aluminium glue of comparative example 1 preparation, spraying is dry, obtains average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 ℃, make auxiliary agent ZJ
5.Formula is in Table 2.
Comparative example 2
Get molecular sieve-4 A
1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, obtaining solid content is the slurries of 30 % by weight, by adding hydrochloric acid to regulate the pH value of slurries, is 3.0, continues 45 minutes kinds of making beating, then toward the argillaceous phosphorus al binder that adds embodiment 2 to provide in mixed serum, after stirring, 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 auxiliary agent DB
1.Formula is in Table 3.
Comparative example 3
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 that solid content is 30 % by weight, under stirring, add FeCl
36H
2the aqueous solution (the FeCl of O
3concentration 30 % by weight, lower same), adding hydrochloric acid to regulate the pH value of slurries is 3.0, the 45 minutes kinds of pulling an oar then add diammonium hydrogen phosphate in slurries, stir 30 minutes, obtain the slurries of solid content 30 % by weight, 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 auxiliary agent DB
2.Formula is in Table 3.
Comparative example 4
Get molecular sieve-4 A
1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add FeCl
36H
2the aqueous solution of O, obtains the slurries of solid content 30 % by weight, by adding hydrochloric acid to regulate the pH value of slurries, is 3, continue 45 minutes kinds of making beating, then toward the phosphorus al binder that adds comparative example 1 to provide in slurries, after stirring, spraying is dry, obtains average particulate diameter and be the microballoon of 65 microns.By microballoon roasting 1 hour at 500 ℃, make auxiliary agent DB
3.Formula is in Table 3.
Comparative example 5
Get molecular sieve-4 A 1, kaolin and boehmite, add decationized Y sieve water and the making beating of aluminium colloidal sol 120 minutes, under stirring, add FeCl36H
2the O aqueous solution, adding hydrochloric acid to regulate the pH value of slurries is 3, continues 45 minutes kinds of making beating, after stirring, the slurries spraying obtaining is dried, and obtains average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 ℃, makes auxiliary agent DB
4.Formula is in Table 3.
Comparative example 6
With comparative example 2, different is to replace molecular sieve-4 A with ZRP-5
1, make auxiliary agent DB
5.Formula is in Table 3.
Comparative example 7
Get molecular sieve ZRP-5, kaolin, diatomite and boehmite, add decationized Y sieve water and waterglass making beating 120 minutes, under stirring, add FeCl
36H
2the O aqueous solution, adding hydrochloric acid to regulate the pH value of slurries is 3, and the 45 minutes kinds of then pulling an oar, then add diammonium hydrogen phosphate, stir, and spraying is dried, and obtains average particulate diameter and be the microballoon of 65 microns, by microballoon roasting 1 hour at 500 ℃, makes auxiliary agent DB
6.Formula is in Table 3.
Comparative example 8
Get molecular sieve ZRP-5, kaolin, add decationized Y sieve water and boehmite making beating 120 minutes, adding hydrochloric acid to regulate the pH value of slurries is 3, the 45 minutes kinds of pulling an oar, 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 auxiliary agent DB
7.Formula is in Table 3.
Embodiment 10～16
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
5under 800 ℃, 100% steam atmosphere condition, carry out the burin-in process of 8 hours.Get respectively the ZJ through burin-in process of Different Weight
1-ZJ
5mix with the industrial FCC equilibrium catalyst (the FCC equilibrium catalyst that the industrial trade mark is DVR-3, main character is in Table 4) of Different Weight.Catalyst mixture is packed in the reactor of small fixed flowing bed-tion reacting device, feedstock oil oil shown in his-and-hers watches 5 carries out catalytic cracking (feedstock oil character is in Table 5).Table 6, table 7 have provided used catalyst mixture weight and have formed, reaction condition and reaction result.
Comparative example 9～16
By the method for embodiment 10, same feedstock oil is carried out to catalytic cracking, different is that used catalyst is respectively 100% industrial FCC equilibrium catalyst, DB
1～DB
7mixture with industrial FCC equilibrium catalyst.Table 6, table 7 have provided used catalyst compositions of mixtures, reaction condition and reaction result.
Comparative example 17
According to the method for comparative example 1, prepare phosphorus aluminium colloidal sol, different is, with SB powder and phosphatase reaction, the addition of SB powder is 0.37Kg, and the addition of 85 % by weight phosphoric acid is 2.14Kg, water addition is 4.31Kg, then in the phosphorus aluminium colloidal sol obtaining, add the making beating of 0.52Kg rectorite, obtain the mixture of rectorite and phosphorus aluminium glue, be designated as Dbinder, then with this mixture, replace the Binder 3 in embodiment 7 to obtain auxiliary agent DB8, then according to the method for embodiment 12 to DB
8evaluate, the results are shown in Table 7.
From table 6, table 7, compare with existing auxiliary agent, catalyst aid provided by the invention, there is higher catalytic cracking liquefied gas yield, can improve significantly the density of propylene in catalytic cracking liquefied gas, there is higher productivity of propylene and the conversion ratio of Geng Gao, even when vast scale adds, heavy oil conversion performance is still higher, is unexpectedly also to have higher liquid to receive.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Claims (13)
1. improve an assistant for calalytic cracking for liquid gas propylene concentration, the butt weight of described auxiliary agent of take is benchmark, contains modification MFI molecular sieve in butt 10～75 % by weight, with Al
2o
3, P
2o
5and 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, in the VIII family metallic addition of oxide 0.5～15 % by weight with in the second clay of butt 0～60 % by weight; Wherein, the described phosphorus aluminium inorganic binder butt weight that contains the first clay of take is benchmark, and the described phosphorus aluminium inorganic binder that contains 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 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 M, y represents to meet the required number of oxidation state of described M; Described M is selected from one or more in Fe, Co, Ni, Cu, Mn, Zn, Sn, Bi;
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) in the slurries that obtain to step (1) under stirring, according to the part by weight of P/Al=1～6, add SPA;
(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 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.
3. according to auxiliary agent claimed in claim 1, it is characterized in that, described MFI molecular sieve is ZSM-5.
4. 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 comprises one or more in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and rectorite; Other described inorganic matter binding agent comprises one or more in boehmite, aluminium colloidal sol, silicon-aluminum sol, waterglass and phosphorus aluminium colloidal sol.
5. according to auxiliary agent claimed in claim 1, it is characterized in that, described VIII family metal is one or more in Fe, Co and Ni.
6. according to the auxiliary agent described in claim 1～5 any one, it is characterized in that, described auxiliary agent contains with P
2o
5the phosphorus additive of meter 0～25 % 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 second clay of the modification MFI molecular sieve of 20～60 % by weight, 10～45 % by weight, the VIII family metallic addition of 0.5～15 % by weight, other inorganic binder of 5～25 % by weight and the phosphorus additive of 0～10 % by weight.
8. 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 introduce VIII family metallic addition; Wherein, 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
5meter 45～80 % by weight phosphorus component and in butt 1～40 % by weight the first clay, its P/Al weight ratio is that 1～6, pH value is 1～3.5, solid content is 15～60 % by weight;
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) in the slurries that obtain to step (1) under stirring, according to the part by weight of P/Al=1～6, add SPA;
(3) slurries that step (2) obtained react 15～90 minutes at 50～99 ℃ of temperature.
9. in accordance with the method for claim 8, it is characterized in that, described P/Al weight ratio is 2～5.
10. in accordance with the method for claim 8, 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.
11. according to the method described in claim 8～10 any one, it is characterized in that, the described phosphorus aluminium inorganic binder containing the first clay, and take its butt weight is benchmark, comprises the Al that 15～35 % by weight are derived from described alumina source
2o
3, the P of 50～75 % by weight
2o
5the first clay with 8～35 % by weight.
12. in accordance with the method for claim 8, it is characterized in that, the temperature described in step (3) is 65～90 ℃.
13. according to the method described in claim 8 or 9, it is characterized in that, also comprises the step of introducing phosphorus additive.
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| CN105854927B (en) * | 2016-05-04 | 2018-10-26 | 青岛润乾高新科技有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
| CN107970979B (en) * | 2016-10-21 | 2020-07-03 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent for increasing propylene yield and preparation method thereof |
| CN107970983B (en) * | 2016-10-21 | 2019-12-27 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent for improving gasoline octane number barrel and preparation method thereof |
| CN107970980B (en) * | 2016-10-21 | 2020-07-03 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent for increasing propylene yield and preparation method thereof |
| CN110494217B (en) * | 2017-04-10 | 2022-10-18 | 信实工业公司 | FCC catalyst additive and preparation process thereof |
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| CN101745412A (en) * | 2008-12-08 | 2010-06-23 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
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