CN101147876A - Catalytic cracking additive for promoting liquid gas propylene concentration - Google Patents
Catalytic cracking additive for promoting liquid gas propylene concentration Download PDFInfo
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- CN101147876A CN101147876A CNA2006101132342A CN200610113234A CN101147876A CN 101147876 A CN101147876 A CN 101147876A CN A2006101132342 A CNA2006101132342 A CN A2006101132342A CN 200610113234 A CN200610113234 A CN 200610113234A CN 101147876 A CN101147876 A CN 101147876A
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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
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Abstract
The present invention relates to a catalyst promoter for raising catalytic cracked liquefied gas propene concentration. Said catalyst promoter composition contains (by wt%) 10-65% of MFI structural zeolite, 0-20% of non-MFI structural zeolite, 0-60% of clay, 15-60% of inorganic oxide adhesive, 0.5-15% of copper additive (CuO) and 2-25% of phosphorus additive (P2O3). Said catalyst promoter can be used in the catalytic cracking process of petroleum hydrocarbon, at the same time of raising catalytic cracked liquefied gas yield and raising catalytic cracked gasoline octane number, it can obviously raise propene concentration in liquefied gas.
Description
Technical field
The present invention relates to a kind of assistant for calalytic cracking that improves density of propylene in the catalytic cracking liquefied gas.
Background technology
Propylene is important Organic Chemicals, and along with increasing rapidly of derivative demands such as polypropylene, the whole world is also increasing year by year to the demand of propylene.Fluid catalytic cracking is to produce one of important production technology of light olefin and propylene.Most of catalytic cracking units adopt to contain catalyst or auxiliary agent increasing light olefin yield and the propylene with MFI structural zeolite.
USP3,758,403 are disclosed in the catalytic cracking catalyst and add the auxiliary agent that ZSM-5 zeolite or use contain the ZSM-5 zeolite and can improve the octane number of gasoline and increase C
3～C
4The productive rate of alkene.For example, in the conventional catalyst that contains 10 heavy %REY, add the ZSM-5 zeolite of 1.5,2.5,5 or 10 heavy % after, octane number improves, the productive rate of low-carbon alkene increases.
USP 5,318,696 have proposed the hydrocarbon conversion process process of the catalyst formed less than 30 the zeolite with MFI structure based on a kind of large pore zeolite and silica alumina ratio, and this technology is produced high-knock rating gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly propylene.
USP 5,997, and 728 disclose to utilize and contain the method that the assistant for calalytic cracking of selecting the shape zeolite carries out the heavy charge catalytic cracking.Described auxiliary agent is formed by the ZSM-5 zeolites that add 12～40 heavy % in the [amorphous, is at least 10 heavy % in the reserve of catalytic cracking system, and makes the ratio of ZSM-5 in catalyst be not less than 3 weight %.The method can additionally not increase aromatics yield and loss gasoline yield when increasing substantially productivity of low carbon olefin hydrocarbon.
After containing the catalyst usefulness phosphorus modification of ZSM-5 zeolite, cracking activity and stability can improve.
The zeolite that CN 1049406C discloses a kind of phosphorous and rare earth and had the MFI structure, its anhydrous chemical composition is aRE
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 is used for the hydro carbons pyrolytic conversion and has excellent hydrothermal activity stability and good selectivity of light olefin.
CN 1034223C discloses a kind of catalyst for cracking that is used to produce low-carbon alkene, clay by 0～70%, 5～99% inorganic oxide and 1～50% zeolite are formed, and described zeolite is the mixture of five-membered ring silica-rich zeolite of the phosphorous and rare earth of the REY of 0～25 heavy % or Y-type high-Si zeolite and 75～100 heavy %.It is higher hydro-thermal activity stability, conversion ratio and the C of catalyst of active component with the ZSM-5 zeolite that this catalyst has
2 =～C
4 =Productive rate.
USP5,110,776 disclose the Preparation of catalysts method of the ZSM-5 zeolite of phosphorous modification.This method is dispersed in zeolite in the phosphorus-containing compound aqueous solution of pH value 2～6, mixes making beating, spray drying forming then with matrix.The 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 said phosphorous modified ZSM-5 is that zeolite is dispersed in the phosphorus-containing compound aqueous solution of pH value more than 4.5, and the phosphorus that makes zeolite-loaded at least 10 heavy % is (with P
2O
5Meter), pull an oar spray drying forming with matrix and non-MFI structural zeolite component then.The gained catalyst is used for catalytic cracking and has higher productivity of low carbon olefin hydrocarbon.
USP 5,171, disclose a kind of improved C in 921
3～C
20Hydrocarbon changes into C
2～C
5Olefins process.This method catalyst system therefor contains the ZSM-5 zeolite, and described zeolite surface silica alumina ratio is 20～60, and phosphorus content is 0.1～10 heavy %, and introduces phosphorus after 500～700 ℃ of steam treatment.
USP6 discloses a kind of method that improves aperture and mesopore zeolite catalytic activity in 080,303.This method is handled aperture and mesopore zeolite with phosphorus compound, then the zeolite and the AlPO that will handle through phosphorus
4The gel combination.This method can improve activity and the hydrothermal stability that contains described zeolite catalyst.
USP 5,472, disclose the FCC process of the catalyst of forming based on a kind of large pore zeolite and phosphorous MFI structure mesopore zeolite in 594.This process can improve C
4, C
5The productive rate of alkene and the loss of minimizing gasoline.
A kind of catalytic cracking process process that increases productivity of propylene is disclosed among the USP 2002/0003103A1.The near small part gasoline product of this technical process is introduced in second riser and is carried out cracking reaction again, the inorganic phosphor-contained binder component that contains macropore USY zeolite, mesopore ZSM-5 zeolite in the catalyst that is adopted and have cracking performance.
A kind of high zeolite content of the FCC of being used for process raising productivity of low carbon olefin hydrocarbon, the catalyst of high abrasion resistance strength are disclosed among the USP 2002/0049133A1.This catalyst contains the ZSM-5 zeolite of 30～85 heavy %, and the phosphorus of 6～24 heavy % is (with P
2O
5Count), and the Al that is lower than 10 heavy %
2O
3This catalyst is particularly suited for improving the productive rate of ethene.
Zeolite is with the metal-modified increased low carbon olefine output that also can be used for.
A kind of catalyst for cracking with greater catalytic lytic activity that contains silica-rich zeolite is disclosed among the CN 1057408A, 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, be that silica alumina ratio is heated to 350～820 ℃ greater than 15 Hydrogen or potassium type ZSM-5 zeolite, β zeolite or modenite, with 0.1～10 hour
-1Volume space velocity obtain after feeding the halide solution of halide solution, iron of aluminium or saline solution of ammonium phosphate.
Disclose a kind of MFI structural zeolite of phosphorous and transition metal among the CN 1465527A, the anhydrous chemical expression of this zeolite is counted (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 among transition-metal Fe, Co and the 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 selectivity have higher liquefied gas yield.
At present, for the overwhelming majority's catalytic cracking unit, under the prerequisite of identical liquefied gas yield, the density of propylene that improves in the liquefied gas is the important channel of improving the catalytic cracking unit economic benefit.Disclosed zeolitic material of prior art and catalyst are used for catalytic cracking process, though can increase the productive rate of low-carbon alkene effectively, improve the octane number of catalytically cracked gasoline product, but the selectivity for propylene in the catalytic cracking reaction process is lower, thereby the concentration of propylene is lower in the liquefied gas.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of assistant for calalytic cracking that improves the catalytic cracking liquid gas propylene concentration, this auxiliary agent is used for catalytic cracking process, can increase the catalytic cracking liquefied gas yield, improve the density of propylene in the catalytic cracking liquefied gas, improve the octane number of catalytically cracked gasoline.
The inventor finds, with the MFI structural zeolite is active component, further introduce an amount of copper additives and an amount of phosphorus additive, prepared catalyst aid is applied in the catalytic cracking process of petroleum hydrocarbon, can improve the density of propylene in the catalytic cracking liquefied gas significantly.
The invention provides a kind of assistant for calalytic cracking that improves liquid gas propylene concentration, weight with auxiliary agent is benchmark, contains the clay of non-MFI structural zeolite, 0～60 heavy % of MFI structural zeolite, 0～20 heavy % of 10 heavy %～65 heavy %, in the inorganic oxide binder of oxide 15 heavy %～60 heavy %, in the copper additives of the heavy % in CuO 0.5 heavy %～15 with P
2O
5Count the phosphorus additive of the heavy % in 2 heavy %～25.
Catalyst aid provided by the present invention can improve the selectivity of catalytic cracking reaction for propylene significantly, thereby improves the density of propylene in the catalytic cracking liquefied gas significantly.For example, with copper content of the present invention is 2 heavy %, phosphorus content is that 7.5 heavy %, ZSM-5 zeolite content are 35 heavy %, kaolin content is 28%, and boehmite content is 27.5 heavy % auxiliary agents with 10: 90 weight ratio and trade names is that the industrial poising agent of MLC-500 mixes, and is that to mix residual oil be raw material for 0.907 the defeated cured oil of pipe with proportion, in small fixed flowing bed, 500 ℃ of temperature, agent weight of oil ratio is 5.92, air speed is 16h
-1Condition under react, the productive rate of propylene is 9.1 heavy %, the concentration of propylene is 37.5 heavy % in the liquefied gas; And be that 7.5 heavy %, ZSM-5 zeolite content are 35 heavy % with phosphorus content, kaolin content is 30%, boehmite content be 27.5 heavy % not the auxiliary agent of cupric under same condition, carry out catalytic cracking reaction, the productive rate of propylene is 7.1 heavy %, the concentration of propylene is 34.7 heavy % in the liquefied gas.
The specific embodiment
The present invention is a benchmark with the weight of auxiliary agent, preferably contains the clay of non-MFI structural zeolite, the 10 heavy %～45 heavy % of MFI structural zeolite, 0～10 heavy % of 20 heavy %～50 heavy %, in the inorganic oxide binder of oxide 25 heavy %～50 heavy %, in the copper additives of the heavy % in cupric oxide 1 heavy %～15 with P
2O
5Count the phosphorus additive of the heavy % in 5 heavy %～15.
MFI structural zeolite of the present invention is selected from one or more in ZSM-5 zeolite, ZRP zeolite and their modifier, be preferably the modification MFI structural zeolite of disclosed phosphorous and transition metal among the CN 1465527A, be that the ZSM-5 zeolite is through phosphorus and the metal-modified zeolite that is selected from one of Fe, Co or Ni, its anhydrous chemical expression is counted (0～0.3) Na with oxide
2O (0.5～5) 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, and y represents the atomicity of O, and M is a kind of among Fe, Co or the Ni; The anhydrous chemical expression of more preferably described MFI structural zeolite is counted (0～0.2) Na with oxide
2O (0.9～3.5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(82～92) SiO
2
Non-MFI structural zeolite of the present invention is selected from one or more in the habitual zeolite of catalytic cracking catalyst preparation, one or more in preferred y-type zeolite, β zeolite or the modenite zeolite.Described y-type zeolite is selected from the y-type zeolite, overstable gamma zeolite of y-type zeolite, rare earth and the phosphorus modification of rare earth modified y-type zeolite, phosphorus modification, in the rare earth modified overstable gamma zeolite one or more.
Clay of the present invention is as well known to those skilled in the art, have no particular limits, for example described clay is kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, tires out one or more that take off stone, diatomite, galapectite, saponite, boron-moisten soil or hydrotalcite.Preferred kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tiredly take off in the stone one or more.
Described inorganic oxide binder is selected from one or more in the inorganic oxide that is commonly used for catalytic cracking catalyst or auxiliary agent matrix and binder component, one or more of boehmite, aluminium colloidal sol, silicon-aluminum sol, waterglass or phosphorus aluminium colloidal sol for example, one or more of preferred boehmite, aluminium colloidal sol or phosphorus aluminium colloidal sol.When containing phosphorus aluminium colloidal sol in the auxiliary agent, the phosphorus of being introduced by phosphorus aluminium colloidal sol is considered as phosphorus additive.
Assistant for calalytic cracking of the present invention can be by in existing production of cracking catalyst, increase to introduce the step preparation of copper additives and phosphorus additive and roasting, for example described preparation method comprise with zeolite, clay, inorganic oxide binder mixings making beating, spray-drying, before spray-drying slurry preparation any step or after spray-drying, introduce the step of copper additives and phosphorus additive and roasting by the mode of flooding (or chemisorbed).The introducing order of copper and phosphorus does not require, and can introduce simultaneously, can introduce respectively yet.If after spray-drying, introduce copper or phosphorus additive by the mode of dipping or chemisorbed, also should comprise after the introducing with described auxiliary agent separate with maceration extract or adsorption liquid, dry step, wherein Gan Zao temperature is a room temperature to 400 ℃, preferred 100 ℃～300 ℃.The temperature of described roasting is 400 ℃～700 ℃, is preferably 450 ℃～650 ℃, and roasting time is 0.5 hour～100 hours, is preferably 0.5 hour～10 hours.
If copper additives was introduced before the spray drying forming of auxiliary agent preparation process, can introduce by in various slurries, adding copper-containing compound.Copper-containing compound is selected from the inorganic compound of copper and in the organic compound one or more, for example oxide of copper, hydroxide, chloride, nitrate, sulfate, phosphate, organic compound; In chloride, nitrate, sulfate and the phosphate that preferred copper-containing compound is a copper one or more.If copper additives is introduced after the spray drying forming of auxiliary agent preparation process, flood or chemisorbed with the copper-containing compound aqueous solution after the slurries spray-drying, Separation of Solid and Liquid (if necessary), drying and roasting then, wherein Gan Zao temperature is a room temperature to 400 ℃, preferred 100 ℃～300 ℃, the temperature of roasting is 400 ℃～700 ℃, is preferably 450 ℃～650 ℃, roasting time is 0.5 hour～100 hours, is preferably 0.5 hour～10 hours.
The introducing of described phosphorus additive can be adopted the combination of one of following method or several method, but is not limited to these methods:
1, before the auxiliary agent spray drying forming, in slurries, adds phosphorus compound;
2, be incorporated in the auxiliary agent by inorganic oxide binder, when containing phosphorus aluminium colloidal sol in the inorganic oxide binder, both brought phosphorus after the roasting in the auxiliary agent 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 the auxiliary agent spray drying forming through the dipping or the chemisorbed phosphorus compound, again through Separation of Solid and Liquid (if necessary), drying and roasting, the temperature of described drying is a room temperature to 400 ℃, be preferably 100 ℃～300 ℃, the temperature of roasting is 400 ℃～700 ℃, be preferably 450 ℃～650 ℃, roasting time is 0.5 hour～100 hours, is preferably 0.5 hour～10 hours.
Phosphorus compound of the present invention is selected from the various inorganic compounds of phosphorus and in the organic compound one or more.Described phosphorus compound is one or more of the oxide, phosphoric acid, phosphate, phosphite, hypophosphites of phosphorus or phosphorous organic compound.Preferred phosphorus compound is one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate or the phosphorus aluminium colloidal sol.
If phosphorus additive and copper additives are introduced simultaneously, when before spray-drying, introducing, join in the slurries copper compound mixed, makes slurries or wiring solution-forming with phosphorus compound after; When after spray-drying, introducing, flood or chemisorbed with the solution of copper-containing compound and phosphorus compound.
In the auxiliary agent provided by the present invention, described copper additives exists with the form of its oxide, phosphate, phosphite, subphosphate, acid phosphate, can be present in any position that may exist of auxiliary agent, for example in the surface of the inside, duct of zeolite, zeolite, the host material or be present in simultaneously in the surface and host material of inside, duct, zeolite of zeolite.Copper additives preferably is present in the host material, and at this moment, the preparation method added copper-containing compound in slurries before the auxiliary agent spray drying forming, makes its elder generation and aluminium oxide or phosphorus-containing compound association reaction.Can detect copper-containing compound species in the matrix by xrd method.
Described phosphorus additive exists with the form of phosphorus compound (oxide, phosphate, phosphite, subphosphate, acid phosphate), may reside in any position that may exist of auxiliary agent, as may reside in the surface, host material of inside, duct, the zeolite of zeolite or be present in simultaneously zeolite inside, duct, zeolite the surface and as described in the host material.
The phosphorus that phosphorus additive of the present invention is included in phosphorus that the phosphorus compound that adds in the slurries introduces, phosphorus that inorganic oxide binder is introduced, introduces by dipping or chemisorbed mode.If contain phosphorus in the employed molecular sieve, then the phosphorus of introducing by molecular sieve is not considered as the alleged phosphorus additive of the present invention.
When catalyst aid provided by the invention is used for catalytic cracking process, can in catalyst cracker, add (such as catalyst) separately, also can mix the back with Cracking catalyst and use as the DCC device.During as auxiliary agent, auxiliary agent provided by the invention accounts for the heavy % in 1 heavy %～25 of FCC catalyst and agent mixture total amount provided by the invention, is preferably the heavy % in 3 heavy %～15.
Catalyst aid provided by the invention is used for catalytic cracking process, and the cracking hydrocarbon oil condition is conventional catalytic cracking condition.Comprise that reaction temperature is 400 ℃～600 ℃, be preferably 450 ℃～550 ℃, weight (hourly) space velocity (WHSV) is 10 hours
-1～120 hours
-1, be preferably 10 hours
-1～80 hours
-1, agent weight of oil ratio is 1～20, is preferably 3～15.
Catalyst aid 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.
Catalyst aid provided by the invention can be used for the processing of various hydrocarbon ils, 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/in heavily de-oiling, wax tailings and the coal liquefaction product one or more.Described hydrocarbon ils can contain beavy metal impurity such as nickel, vanadium and sulphur, nitrogen impurity, and the permission content of described impurity, the content of sulphur are no more than 3.0 heavy %, and the content of nitrogen is no more than 2.0 heavy %, and the weight content of metal impurities such as vanadium, nickel is no more than 3000ppm.
The following examples will the invention will be further described, but not thereby limiting the invention.
In embodiment and the Comparative Examples, A
1～A
6Six modified ZSM-5 zeolite samples are by the disclosed method preparation of CN 1465527A, and its anhydrous chemical expression is to form with the element of x-ray fluorescence spectrometry zeolite, obtains through conversion again.
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: 0.03Na
2O2.2Al
2O
34.9P
2O
52.1Fe
2O
390.8SiO
2
Sample A
4: 0.1Na
2O0.94Al
2O
35.1P
2O
510.1Fe
2O
384SiO
2
Sample A
5: 0.03Na
2O5.1Al
2O
34.8P
2O
53.6Co
2O
386.5SiO
2
Sample A
6: 0.1Na
2O5.2Al
2O
34.5P
2O
52.0Ni
2O
388.2SiO
2
Boehmite is Shandong Aluminum Plant's manufacture product, solid content 60 heavy %; Aluminium colloidal sol is the industrial products that China Petrochemical Industry's Shandong catalyst plant is produced, Al
2O
3Content is 21.5 heavy %; Waterglass is the industrial products that China Petrochemical Industry's Shandong catalyst plant is produced, SiO
2Content 28.9 heavy %, Na
2O content 8.9 heavy %; Kaolin is the special-purpose kaolin of Cracking catalyst that Suzhou kaolin company produces, solid content 78 heavy %; The ZRP-1 zeolite is the industrial products of the conventional MFI structural zeolite of Shandong catalyst plant production, wherein P
2O
52.6 heavy %, degree of crystallinity 87 heavy %, silica alumina ratio 25; The ZRP-5 zeolite is the industrial products of the conventional MFI structural zeolite of Shandong catalyst plant production, wherein P
2O
52.5 heavy %, degree of crystallinity 85 heavy %, silica alumina ratio 50.The DASY-2 zeolite is the industrial products of the overstable gamma zeolite that contains rare earth of Shandong catalyst plant production, wherein RE
2O
3Content 1.8 heavy %, Na
2O content 0.9 heavy %, relative crystallinity 55 heavy %, lattice constant a
0Be 2.454nm.
The preparation of embodiment 1～15 explanation catalyst aid provided by the invention.
Embodiment 1
Phosphorus aluminium colloidal sol preparation: 1.05 kilograms of boehmites (butt) are mixed making beating 30 minutes with 3.35 kilograms of decationizing water, stir down and in slurries, add 4.9 kilograms of SPA (chemical pures, phosphoric acid 85 heavy %), be warming up to 70 ℃, under this temperature, reacted 45 minutes then, make water white phosphorus aluminium colloidal sol.P wherein
2O
5Content be 30.6 heavy %, Al
2O
3Content is 10.5 heavy %, pH=1.7.
Get 1.75 kilograms of (butt) A
1, 1.4 kilograms of (butt) kaolin and 0.65 kilogram of (butt) boehmite, mix making beating 120 minutes with 6.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols, stir and add 1 liter of CuCl down
2.2H
2The aqueous solution of O (wherein containing 100 gram CuO), the pH value of regulating slurries with hydrochloric acid is 3.0.Mixture is continued 45 fens kinds of making beating, add 1.22 kilograms of phosphorus aluminium colloidal sols then in the mixed serum, after stirring, with the slurries that obtain 500 ℃ of inlet temperatures, spray-drying under the condition that exhaust temperature is 180 ℃ obtains average particulate diameter and is 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
1, 28 heavy % kaolin, 27.5 heavy %Al
2O
3, 2.0 heavy %Cu additives (in CuO) and 7.5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
1
Embodiment 2
Get 1.84 kilograms of (butt) A
1, 1.33 kilograms of (butt) kaolin and 0.98 kilogram of (butt) boehmite, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of Cu (NO down
3)
2.6H
2The aqueous solution of O (wherein containing 250 gram CuO), the pH value of regulating slurries with hydrochloric acid is 2.8.Mixture is continued 45 fens kinds of making beating, then with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 36.8 heavy %A
1, 26.6 heavy % kaolin, 31.6 heavy %Al
2O
3Microballoon with 5.0 heavy %Cu additives (in CuO).
Get 1 kilogram of thus obtained microsphere product (butt), add 10 liters of decationized Y sieve water and 100 gram diammonium hydrogen phosphates, be warming up to 60 ℃ under stirring, after reacting 20 minutes under this temperature, with slurries vacuum filtration, drying,, make and contain 35 heavy %A then in 500 ℃ of following roastings 2 hours
1, 25.3 heavy % kaolin, 30 heavy %Al
2O
3, 4.7 heavy %Cu additives (in CuO) and 5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
2
Embodiment 3
Get 1.94 kilograms of (butt) A
1With 1.91 kilograms of (butt) boehmites, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of CuCl down
2.2H
2The aqueous solution of O (wherein containing 550 gram CuO), the pH value of regulating slurries with hydrochloric acid is 2.5.Mixture is continued 45 fens kinds of making beating, then with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 38.8 heavy %A
1, 50.2 heavy %Al
2O
3Microballoon with 11 heavy %Cu additives (in CuO).
Get 1 kilogram of thus obtained microsphere product (butt), add 10 liters of decationized Y sieve water and 210 gram diammonium hydrogen phosphates, be warming up to 60 ℃ under stirring, after reacting 20 minutes under this temperature, with slurries vacuum filtration, drying,, make and contain 35 heavy %A then in 500 ℃ of following roastings 2 hours
1, 45.1 heavy %Al
2O
3, 9.9 heavy %Cu additives (in CuO) and 10 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
3
Embodiment 4
The preparation method is with embodiment 1, and different is to use the ZRP-1 zeolite of same amount to replace A
1Zeolite makes and contains 35 heavy %ZRP-1,28 heavy % kaolin, 27.5 heavy %Al
2O
3, 2 heavy %Cu additives (in CuO) and 7.5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
4
Embodiment 5
The preparation method is with embodiment 1, and different is to use the ZRP-5 zeolite of same amount to replace A
1Zeolite makes and contains 35 heavy %ZRP-5,28 heavy % kaolin, 27.5 heavy %Al
2O
3, 2 heavy %Cu additives (in CuO) and 7.5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
5
Embodiment 6
Get ZJ
11 kilogram of auxiliary agent (butt) adds 10 liters of decationized Y sieve water and 157 gram diammonium hydrogen phosphates, stirs down and is warming up to 60 ℃, in reaction under this temperature after 20 minutes, with slurries vacuum filtration, drying, then in 500 ℃ of following roastings 2 hours, makes and contains 32.38 weight %A
1, 25.9 heavy % kaolin, 25.4 heavy %Al
2O
3, 1.85 heavy %Cu additives (in CuO) and 14.47 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
6
Embodiment 7
Get 1.75 kilograms of (butt) A
1, 1 kilogram of (butt) kaolin and 3.46 kg of water glass, add 5 kilograms of decationized Y sieve water making beating 120 minutes, stir and add 1 liter of CuCl down
2.2H
2The aqueous solution of O (wherein containing 750 gram CuO), the pH value of regulating slurries with hydrochloric acid is 3.0.Mixture is continued 45 fens kinds of making beating, add 1.22 kilograms of phosphorus aluminium colloidal sols then in the mixed serum, after stirring, with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.With microballoon in 400 ℃ of following roastings 1 hour.
Get 1 kilogram of the microballoon (butt) after the above-mentioned roasting, add 10 liters of decationized Y sieve water and 100 gram ammonium chlorides, stir down and be warming up to 60 ℃, after washing 20 minutes under this temperature, the slurries vacuum filtration.By above identical method filter cake is relaundered once, under 120 ℃ of temperature, dry, make and contain 35 heavy %A
1, 20 heavy % kaolin, 2.5 heavy %Al
2O
3, 20 heavy %SiO
2, 15 heavy %Cu additives (in CuO) and 7.5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
7
Embodiment 8
Method by embodiment 1 prepares auxiliary agent, is not both A
1Weight be 2.25 kilograms (butts), kaolinic weight is 0.9 kilogram (butt), makes to contain 45 heavy %A
1, 18 heavy % kaolin, 27.5 heavy %Al
2O
3, 2 heavy %Cu additives (in CuO) and 7.5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
8
Embodiment 9
Get 1 kilogram of (butt) A
1, 1.85 kilograms of (butt) kaolin and 0.9 kilogram of (butt) boehmite, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of CuCl down
2.2H
2The aqueous solution of O (wherein containing 400 gram CuO), the pH value of regulating slurries with hydrochloric acid is 2.6.Mixture is continued 30 fens kinds of making beating, adds 465 gram diammonium hydrogen phosphates, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 20 heavy %A
1, 37 heavy % kaolin, 30 heavy %Al
2O
3, 8 heavy %Cu additives (in CuO) and 5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
9
Embodiment 10
Method by embodiment 9 prepares auxiliary agent, is not both the A with identical weight
2Replace A
1, make and contain 20 heavy %A
2, 37 heavy % kaolin, 30 heavy %Al
2O
3, 8 heavy %Cu additives (in CuO) and 5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
10
Embodiment 11
Get 1.25 kilograms of (butt) A
3, 1 kilogram of (butt) kaolin and 1.65 kilograms of (butt) boehmites, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of CuCl down
2.2H
2The aqueous solution of O (wherein containing 250 gram CuO), the pH value of regulating slurries with hydrochloric acid is 2.8.Mixture is continued 30 fens kinds of making beating, adds 465 gram diammonium hydrogen phosphates, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 25 heavy %A
3, 20 heavy % kaolin, 45 heavy %Al
2O
3, 5 heavy %Cu additives (in CuO) and 5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
11
Embodiment 12
Get 2 kilograms of (butt) A
4, 0.75 kilogram of (butt) kaolin and 1.15 kilograms of (butt) boehmites, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of CuCl down
2.2H
2The aqueous solution of O (wherein containing 250 gram CuO), the pH value of regulating slurries with hydrochloric acid is 3.0.Mixture is continued 30 fens kinds of making beating, adds 465 gram diammonium hydrogen phosphates, pulled an oar again 30 minutes, then with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 40 heavy %A
4, 15 heavy % kaolin, 35 heavy %Al
2O
3, 5 heavy %Cu additives (in CuO) and 5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
12
Embodiment 13
Get 2.89 kilograms of (butt) A
5With 1.4 kilograms of (butt) boehmites, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of CuCl down
2.2H
2The aqueous solution of O (wherein containing 105.5 gram CuO), the pH value of regulating slurries with hydrochloric acid is 3.0.Mixture is continued 45 fens kinds of making beating, then with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 57.89 heavy %A
8, 40 heavy %Al
2O
3Microballoon with 2.11 heavy %Cu additives (in CuO).
Get 1 kilogram of thus obtained microsphere product (butt), add 10 liters of decationized Y sieve water and 210 gram diammonium hydrogen phosphates, be warming up to 60 ℃ under stirring, after reacting 20 minutes under this temperature, with slurries vacuum filtration, drying,, make and contain 55 heavy %A then in 500 ℃ of following roastings 2 hours
5, 38 heavy %Al
2O
3, 2 heavy %Cu additives (in CuO) and 5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
13
Embodiment 14
Get 1.5 kilograms of (butt) A
6, 1.5 kilograms of (butt) kaolin and 0.9 kilogram of (butt) boehmite, add 6.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of CuCl down
2.2H
2The aqueous solution of O (wherein containing 125 gram CuO), the pH value of regulating slurries with hydrochloric acid is 3.0.Mixture is continued 45 fens kinds of making beating, add 1.22 kilograms of phosphorus aluminium colloidal sols then in the mixed serum, after stirring, with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 30 heavy %A
6, 30 heavy % kaolin, 30 heavy %Al
2O
3, 2.5 heavy %Cu additives (in CuO) and 7.5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
14
Embodiment 15
Get 1.75 kilograms of (butt) A
1, 0.5 kilogram of (butt) DASY-2,0.9 kilogram of (butt) kaolin and 0.65 kilogram of (butt) boehmite, mix making beating 120 minutes with 6.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols, stir and add 1 liter of CuCl down
2.2H
2The aqueous solution of O (wherein containing 100 gram CuO), the pH value 3.0 of regulating slurries with hydrochloric acid.Mixture is continued 45 fens kinds of making beating, add 1.22 kilograms of phosphorus aluminium colloidal sols then in the mixed serum, after stirring, with the slurries that obtain 500 ℃ of inlet temperatures, spray-drying under the condition that exhaust temperature is 180 ℃ obtains average particulate diameter and is 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
1, 10 heavy %DASY-2,18 heavy % kaolin, 27.5 heavy %Al
2O
3, 2.0 heavy %Cu additives (in CuO) and 7.5 weight % phosphorus additives are (with P
2O
5Meter) auxiliary agent ZJ
15
Comparative Examples 1
The explanation of this Comparative Examples contains A
1, phosphorus additive, do not contain the preparation of the reference auxiliary agent of copper additives.
Get 1.75 kilograms of (butt) A
1, 1.5 kilograms of (butt) kaolin and 0.65 kilogram of (butt) boehmite, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes that the pH value of slurries is 3.0.Mixture is continued 45 fens kinds of making beating, add 1.22 kilograms of phosphorus aluminium colloidal sols then in the mixed serum, after stirring, with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
1, 30 heavy % kaolin, 27.5 heavy %Al
2O
3With 7.5 heavy % phosphorus additives (with P
2O
5Meter) reference auxiliary agent CB
1
Comparative Examples 2
The explanation of this Comparative Examples contains A
1, do not contain the reference auxiliary agent and the preparation thereof of copper additives and phosphorus additive.
Get 1.75 kilograms of (butt) A
1, 1.5 kilograms of (butt) kaolin and 1.15 kilograms of (butt) boehmites, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes that the pH value of slurries is 3.0.Mixture is continued 45 fens kinds of making beating.Then with the slurries that obtain 500 ℃ of inlet temperatures, carry out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
1, 30 heavy % kaolin and 35 heavy %Al
2O
3Reference auxiliary agent CB
2
Comparative Examples 3
The explanation of this Comparative Examples only contains the preparation of the reference auxiliary agent of conventional ZRP-5 zeolite.
Method by Comparative Examples 2 prepares auxiliary agent, and the ZRP-5 zeolite that is not both with same weight replaces A
1, make and contain 35 heavy %ZRP-5 zeolites, 30 heavy % kaolin and 35 heavy %Al
2O
3Reference auxiliary agent CB
3
Comparative Examples 4
The explanation of this Comparative Examples contains the preparation of the reference auxiliary agent of conventional ZRP-5 zeolite and phosphorus additive.
Method by embodiment 1 prepares auxiliary agent, and the ZRP-5 zeolite that is not both with same weight replaces A
1, make and contain 35 heavy %ZRP-5 zeolites, 30 heavy % kaolin, 35 heavy %Al
2O
3Reference auxiliary agent CB with 5 heavy % phosphorus additives (do not comprise in the ZRP-5 zeolite phosphorous)
4
Comparative Examples 5
The explanation of this Comparative Examples contains A
1, copper additives, and the not preparation of the reference auxiliary agent of phosphor-included additive.
Get 1.75 kilograms of (butt) A
1, 1.5 kilograms of (butt) kaolin and 0.9 kilogram of (butt) boehmite, add 6.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of CuCl down
2.2H
2The aqueous solution of O (wherein containing 250 gram CuO), the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating, the slurries that obtain 500 ℃ of inlet temperatures, are carried out spray-drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 35 heavy %A
1, 30 heavy % kaolin, 30 heavy %Al
2O
3, 5 heavy %Cu additives (in CuO) reference auxiliary agent CB
5
Embodiment 16～30
The following examples are example with the fixed fluidized-bed reactor, and the cracking reaction effect of catalyst aid provided by the invention is described.
Respectively with 30 gram ZJ
1-ZJ
15Under 800 ℃, 100% steam atmosphere condition, carry out 8 hours burin-in process.Get the ZJ through burin-in process of Different Weight
1-ZJ
15Mix with the industrial FCC equilibrium catalyst (the industrial trade mark is the FCC equilibrium catalyst of MLC-500, and main character sees Table 1) of Different Weight.Catalyst mixture is packed in the reactor of small fixed flowing bed-tion reacting device, and feedstock oil carries out catalytic cracking shown in the his-and-hers watches 2.Table 3, table 4 and table 5 provide the catalyst system therefor mixture and form reaction condition and reaction result.
Comparative Examples 6～11
Following Comparative Examples is an example with the fixed fluidized-bed reactor, and the situation of using the reference auxiliary agent is described.
By the method among the embodiment 15 same feedstock oil is carried out catalytic cracking, different is that catalyst system therefor is respectively 100% industrial FCC equilibrium catalyst, CB
1～CB
5Mixture with industrial FCC equilibrium catalyst.Table 3 has provided the catalyst system therefor mixture and has formed reaction condition and reaction result.
From table 3, table 4 and table 5 as can be seen, compare with the reference auxiliary agent, catalyst aid provided by the invention can not only increase the catalytic cracking liquefied gas yield effectively, improve the octane number of catalytically cracked gasoline, can also improve the density of propylene in the catalytic cracking liquefied gas simultaneously significantly.
Table 1
| Project | Industry equilibrium catalyst MLC-500 |
| Tenor, mg/Kg Ni V Fe Sb Ca | 9386 1665 6503 2673 1714 |
| Little index alive | 60 |
Table 2
| The feedstock oil title | The defeated wax oil of pipe is mixed residual oil |
| Density (20 ℃), gram per centimeter 3Viscosity (100 ℃), millimeter 2/ second freezing point, ℃ carbon residue, heavy % | 0.9070 10.41 40 3.1 |
| Element is formed, heavy % C H S N | 86.39 12.53 0.8 0.29 |
| Four components, heavy % saturated hydrocarbons aromatic hydrocarbons gum asphalt | 56.8 24.2 18.2 0.8 |
| Tenor, mg/Kg V Ni Fe Cu Na boiling range, ℃ initial boiling point 10% 20% 30% 40% 50% 60% 70% 80% | 0.8 7.0 7.8 0.1 2.6 241 343 387 413 432 450 466 493 535 |
Table 3
| The embodiment numbering | Comparative Examples 6 | 16 | Comparative Examples 7 | 17 | Comparative Examples 8 | Comparative Examples 9 | Comparative Examples 10 | Comparative Examples 11 |
| Catalyst | 100% poising agent | 10％ZJ 1+ 90% poising agent | 10％CB 1+ 90% poising agent | 10％ZJ 2+ 90% poising agent | 10％CB 2+ 90% poising agent | 10％CB 3+ 90% poising agent | 10％CB 4+ 90% poising agent | 10％CB 5+ 90% poising agent |
| Reaction temperature, ℃ | 500 | 500 | 500 | 500 | 500 | 500 | 500 | 500 |
| Air speed, hour -1 | 16 | 16 | 16 | 16 | 16 | 16 | 16 | 16 |
| Agent weight of oil ratio | 5.92 | 5.92 | 5.92 | 5.92 | 5.92 | 5.92 | 5.92 | 5.92 |
| Steam (with respect to feedstock oil), heavy % | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Material balance, heavy %: | ||||||||
| Dry gas | 1.60 | 1.62 | 1.47 | 1.60 | 1.70 | 1.60 | 1.56 | 2.52 |
| Liquefied gas | 18.04 | 24.26 | 20.58 | 24.57 | 21.37 | 21.03 | 20.76 | 21.34 |
| C 5 +Gasoline | 43.13 | 36.19 | 40.09 | 37.13 | 39.55 | 39.88 | 39.78 | 37.64 |
| Diesel oil | 17.17 | 17.71 | 17.46 | 17.61 | 17.10 | 17.04 | 17.11 | 17.35 |
| Heavy oil | 13.61 | 13.85 | 14.83 | 13.22 | 13.77 | 14.34 | 14.60 | 13.31 |
| Coke | 6.45 | 6.37 | 5.57 | 5.87 | 6.51 | 6.12 | 6.19 | 7.84 |
| Conversion ratio, heavy % | 69.23 | 68.44 | 67.71 | 69.17 | 69.13 | 68.62 | 68.30 | 69.34 |
| Propylene, heavy % | 5.07 | 9.10 | 7.14 | 9.32 | 6.87 | 6.65 | 6.77 | 6.97 |
| Propylene/liquefied gas, heavy % | 28.13 | 37.52 | 34.69 | 37.93 | 32.16 | 31.64 | 32.62 | 32.65 |
| Gasoline is formed, heavy % | ||||||||
| Alkane | 33.59 | 26.17 | 31.33 | 26.08 | 29.69 | 30.56 | 29.78 | 29.56 |
| Alkene | 23.89 | 26.57 | 24.86 | 25.09 | 25.4 | 24.54 | 24.93 | 25.49 |
| Cycloalkane | 8.26 | 8.80 | 7.98 | 9.28 | 8.2 | 8.26 | 8.5 | 8.02 |
| Aromatic hydrocarbons | 34.08 | 38.46 | 35.66 | 39.53 | 36.48 | 36.38 | 36.44 | 36.91 |
| RON (chromatography) | 87.1 | 89.8 | 89.8 | 89.7 | 89.2 | 88.9 | 89.0 | 89.3 |
| MON (chromatography) | 82.0 | 82.7 | 82.7 | 82.7 | 82.7 | 82.7 | 82.7 | 82.7 |
Table 4
| The embodiment numbering | 18 | 19 | 20 | 21 | 22 | 23 |
| Catalyst | 10％ZJ 3+ 90% poising agent | 10％ZJ 4+ 90% poising agent | 10％ZJ 5+ 90% poising agent | 12％ZJ 6+ 88% poising agent | 10％ZJ 7+ 90% poising agent | 8％ZJ 8+ 92% poising agent |
| Reaction temperature, ℃ | 500 | 500 | 500 | 500 | 500 | 500 |
| Air speed, hour -1 | 16 | 16 | 16 | 16 | 16 | 16 |
| Agent weight of oil ratio | 5.92 | 5.92 | 5.92 | 5.92 | 5.92 | 5.92 |
| Steam (to feedstock oil), heavy % | 0 | 0 | 0 | 0 | 0 | 0 |
| Material balance, heavy %: | ||||||
| Dry gas | 1.72 | 1.68 | 1.66 | 1.73 | 1.72 | 1.71 |
| Liquefied gas | 24.16 | 24.02 | 24.12 | 25.27 | 25.18 | 24.29 |
| C 5 +Gasoline | 37.59 | 38.78 | 36.63 | 36.06 | 36.28 | 36.90 |
| Diesel oil | 17.52 | 16.92 | 17.85 | 17.30 | 17.33 | 17.60 |
| Heavy oil | 13.11 | 12.41 | 13.80 | 13.70 | 13.35 | 13.50 |
| Coke | 5.90 | 6.19 | 5.94 | 5.94 | 6.14 | 6.00 |
| Conversion ratio, heavy % | 69.37 | 70.67 | 68.35 | 69.00 | 69.32 | 68.90 |
| Propylene, heavy % | 9.04 | 8.91 | 8.98 | 9.61 | 9.47 | 9.27 |
| Propylene/liquefied gas, heavy % | 37.43 | 37.10 | 37.25 | 38.01 | 37.59 | 38.15 |
| Gasoline is formed, heavy % | ||||||
| Alkane | 24.86 | 25.05 | 24.35 | 26.16 | 26.63 | 24.92 |
| Alkene | 24.21 | 26.11 | 26.81 | 26.29 | 23.51 | 23.26 |
| Cycloalkane | 8.65 | 8.60 | 8.97 | 8.31 | 8.85 | 8.23 |
| Aromatic hydrocarbons | 42.11 | 40.04 | 39.88 | 39.24 | 40.89 | 41.54 |
| RON-GC (chromatography) | 90.0 | 89.8 | 89.7 | 89.7 | 89.8 | 89.9 |
| MON-GC (chromatography) | 82.8 | 82.7 | 82.8 | 82.7 | 82.8 | 82.8 |
Table 5
| The embodiment numbering | 24 | 25 | 26 | 27 | 28 | 29 | 30 |
| Catalyst | 15％ZJ 9+ 85% poising agent | 15％ZJ 10+ 85% poising agent | 12％ZJ 11+ 88% poising agent | 10％ZJ 12+ 90% poising agent | 6％ZJ 13+ 94% poising agent | 10％ZJ 14+ 90% poising agent | 10％ZJ 15+ 90% poising agent |
| Reaction temperature, ℃ | 500 | 500 | 500 | 500 | 510 | 500 | 500 |
| Air speed, hour -1 | 16 | 16 | 16 | 16 | 10 | 16 | 16 |
| Agent weight of oil ratio | 5.92 | 5.92 | 5.0 | 4.5 | 7.0 | 5.92 | 5.92 |
| Steam (to feedstock oil), heavy % | 0 | 0 | 5 | 5 | 5 | 5 | 0 |
| Liquefied gas, heavy % | 24.09 | 24.75 | 24.47 | 23.86 | 25.62 | 23.78 | 24.65 |
| Propylene, heavy % | 9.12 | 9.41 | 9.33 | 8.99 | 9.89 | 8.99 | 9.2 |
| Propylene/liquefied gas, heavy % | 37.84 | 38.04 | 38.11 | 37.69 | 38.60 | 37.79 | 37.32 |
| Gasoline olefin, heavy % | 27.64 | 27.29 | 23.95 | 23.97 | 26.52 | 26.41 | 23.39 |
| RON-GC (chromatography) | 90.0 | 89.9 | 90.1 | 90.2 | 89.9 | 89.9 | 89.6 |
| MON-GC (chromatography) | 82.8 | 82.7 | 82.9 | 82.8 | 82.8 | 82.8 | 82.5 |
Claims (10)
1. assistant for calalytic cracking that improves liquid gas propylene concentration, weight with auxiliary agent is benchmark, contains the clay of non-MFI structural zeolite, 0～60 heavy % of MFI structural zeolite, 0～20 heavy % of 10 heavy %～65 heavy %, in the inorganic oxide binder of oxide 15 heavy %～60 heavy %, in the copper additives of the heavy % in CuO 0.5 heavy %～15 with P
2O
5Count the phosphorus additive of the heavy % in 2 heavy %～25.
2. according to the described auxiliary agent of claim 1, it is characterized in that described auxiliary agent contains the MFI structural zeolite of 20 heavy %～50 heavy %, the non-MFI structural zeolite of 0～10 heavy %, the clay of 10 heavy %～45 heavy %, the inorganic oxide binder of 25 heavy %～50 heavy %, the copper additives of 1 heavy %～15 heavy % and the phosphorus additive of the heavy % in 5 heavy %～15 to be formed.
3. according to the described auxiliary agent of claim 1, it is characterized in that described MFI structural zeolite is one or more in ZSM-5 zeolite, ZRP zeolite and their modifier.
4. according to the described auxiliary agent of claim 3, it is characterized in that described MFI structural zeolite is the ZSM-5 zeolite through phosphorus and is selected from the metal-modified zeolite of one of Fe, Co or Ni that its anhydrous chemical expression is counted (0～0.3) Na with oxide mass
2O (0.5～5) 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 the atomicity of O.
5. according to the described auxiliary agent of claim 4, it is characterized in that the anhydrous chemical expression of described MFI structural zeolite is counted (0～0.2) Na with oxide
2O (0.9～3.5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(82～92) SiO
2
6. according to the described auxiliary agent of claim 1, it is characterized in that described non-MFI structural zeolite is one or more of y-type zeolite, β zeolite, modenite.
7. according to the described auxiliary agent of claim 6, it is characterized in that described y-type zeolite is one or more of the y-type zeolite, overstable gamma zeolite of y-type zeolite, rare earth and the phosphorus modification of rare earth modified y-type zeolite, phosphorus modification or rare earth modified overstable gamma zeolite.
8. according to the described auxiliary agent of claim 1, it is characterized in that described clay is selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite or tiredly takes off in the stone one or more.
9. according to the described auxiliary agent of claim 1, it is characterized in that described inorganic oxide binder is selected from one or more of boehmite, aluminium colloidal sol, silicon-aluminum sol, waterglass or phosphorus aluminium colloidal sol.
10. according to the described auxiliary agent of claim 9, it is characterized in that described inorganic oxide binder is selected from one or more in boehmite, aluminium colloidal sol or the phosphorus aluminium colloidal sol.
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