CN100363466C - Catalytic cracking auxiliary agent - Google Patents
Catalytic cracking auxiliary agent Download PDFInfo
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- CN100363466C CN100363466C CNB2004101028123A CN200410102812A CN100363466C CN 100363466 C CN100363466 C CN 100363466C CN B2004101028123 A CNB2004101028123 A CN B2004101028123A CN 200410102812 A CN200410102812 A CN 200410102812A CN 100363466 C CN100363466 C CN 100363466C
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Abstract
The present invention discloses a catalytic cracking auxiliary agent containing 10 to 65 wt% of modified ZSM-5 molecular sieve, 15 to 60 wt% of two kinds of zeolite, 15 to 70 wt% of inorganic oxide binding agent and 2 to 25 wt% of phosphorus additive agent which are measured by dry basis, wherein the modified ZSM-5 molecular sieve is modified by phosphorus and a metal selected from Fe, Co or Ni, the anhydrous chemical expression of the modified ZSM-5 molecular sieve, which is measured by oxides, is (0 to 0.3)Na2O. (0.5 to 5)Al2O3. (1.3 to 10)P2O5. (0.7 to 15)MxOy. (70 to 97)SiO2, x represents the atom number of M, and y represents a number meeting the requirements of an oxidation state of M; the two kinds of zeolite are mordenite and clinoptilolite, and the weight ratio of the mordenite to the clinoptilolite is from 1:99 to 99:1; both the binding agent and the phosphorus additive agent are measured by oxides. The auxiliary agent applied to the catalytic cracking process of petroleum hydrocarbons can obviously improve the concentration of propene in liquid gas while improving the yield of catalytically cracked liquid gas.
Description
Technical field
The invention relates to a kind of assistant for calalytic cracking, the auxiliary agent of further saying so and improving density of propylene in the catalytic cracking liquefied gas about a kind of.
Background technology
Propylene is important Organic Chemicals, and along with increasing rapidly of derivative demands such as polypropylene, the whole world is also all increasing year by year to the demand of propylene.Fluid catalytic cracking is to produce one of important production technique of light olefin and propylene.For most of catalytic cracking unit, for increasing light olefin yield and propylene, it is the otherwise effective technique approach that employing contains catalyzer or auxiliary agent with MFI structural zeolite.
USP3,758,403 early are disclosed in the method for adding the ZSM-5 zeolite in the catalytic cracking catalyst can improve the octane value of gasoline and increase C
3～C
4The productive rate of alkene.For example, add in containing the conventional catalyst of 10%REY behind 1.5,2.5,5 to 10% ZSM-5 zeolite, gasoline octane rating improves, the gain in yield of low-carbon alkene; Use also has same effect when containing the auxiliary agent of ZSM-5 zeolite.
USP 5,318, proposed the hydrocarbon conversion process process of the catalyzer formed less than 30 the zeolite with MFI structure based on a kind of large pore zeolite and silica alumina ratio in 696.This technology is produced stop bracket 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 the shape slective cracking auxiliary agents in the heavy feed stock catalytic cracking process in 728.Said auxiliary agent is made up of the ZSM-5 zeolite that adds 12～40% in the [amorphous, and system's reserve at least 10% makes the ratio of ZSM-5 in catalyzer surpass 3%.This method can additionally not increase aromatic production and loss gasoline yield when increasing substantially low-carbon alkene.
After the ZSM-5 zeolite carried out modification with P contained compound, its cracking activity stability can improve, and reduced the consumption of zeolite.
The zeolite that discloses a kind of phosphorous and rare earth among the CN 1049406C and had the MFI structure, its anhydrous chemical constitution 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 has excellent hydrothermal activity stability and good selectivity of light olefin when being used for the hydro carbons pyrolytic conversion.
Disclose a kind of catalyst for cracking that is used to produce low-carbon alkene among the CN 1034223C, formed by the clay of 0～70% (is benchmark with the catalyst weight), 5～99% inorganic oxide and 1～50% zeolite.Zeolite wherein is the mixture of the five-ring supersiliceous zeolite of the REY of 0～25 heavy % or the phosphorous and rare earth that type-Y high silicon zeolite and 75～100 weighs %.It is higher hydro-thermal activity stability, transformation efficiency and the C of catalyzer of active ingredient with the ZSM-5 zeolite that this catalyzer has
2 =～C
4 =Productive rate.
USP5 discloses the preparation method with the ZSM-5 zeolite catalyst of phosphorus modification in 110,776.Said phosphorus modifying process is that zeolite is dispersed in the P contained compound aqueous solution of pH value 2～6, then with matrix making beating, spray drying forming.The gained catalyzer does not increase dry gas and coke yield when improving gasoline octane rating.
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 P contained compound aqueous solution of pH value more than 4.5, and the phosphorus that makes zeolite-loaded at least 10 heavy % is (with P
20
5Meter), pull an oar spray drying forming with matrix and other zeolite component then.The gained catalyzer has higher productivity of low carbon olefin hydrocarbon.
USP 5,171, disclose a kind of ZSM-5 zeolite with the phosphorus modification in 921.This zeolite has 20～60 silica alumina ratio, with P contained compound dipping after after 500～700 ℃ of steam-treated, be used for C
3～C
20Hydrocarbon changes into C
2～C
5During the reaction of alkene, the ZSM-5 that handles without phosphorus has higher activity relatively.
USP6 discloses a kind of method that improves aperture and mesopore zeolite catalytic activity in 080,303.This method is to handle aperture and mesopore zeolite with phosphorus compound, then the zeolite and the AlPO that will handle through phosphorus
4The gel combination.This method can be improved the activity and the hydrothermal stability of aperture and mesopore zeolite.
USP 5,472, disclose the hydrocarbon conversion process process of the catalyzer of forming based on a kind of large pore zeolite and phosphorated MFI structure mesopore zeolite in 594.This technology is produced stop bracket gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly C
4/ C
5
Also report and in matrix, introduce phosphorus compound the phosphorus modification except the ZSM-5 zeolite is carried out, can improve catalyzer or auxiliary agent selectivity low-carbon alkene.
A kind of catalytic cracking process process that increases productivity of propylene is disclosed among USP 2002/0003103 A1.This technological process is carried out the cracking reaction near small part gasoline product enters second riser tube again, in the catalyst composition that is adopted except containing macropore USY zeolite, the mineral binder bond component that also contains mesopore zeolites such as ZSM-5 and have cracking performance.Phosphorous in the mineral binder bond component wherein, its P/Al ratio is 0.1～10.This technological process is increased low carbon olefine output significantly, particularly increases productivity of propylene.
The catalyzer of a kind of high zeolite content, high abrasion resistance strength is disclosed among USP 2002/0049133 A1.This catalyzer 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
3With other components such as clay of surplus, phosphorus wherein is present in the matrix.This catalyzer is used 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 catalyzer that contains MFI or MEL structural zeolite in 880.Wherein used zeolite is through VIII family metal, preferably with the Ni modification, and after this zeolite was introduced Ni, heat or hydrothermal treatment consists under the controlled temperature of experience harshness made VIII family metal and aluminium at surface enrichment.Said catalyzer is used for can improving gasoline octane rating when alkane transforms, and increases C
3～C
4The productive rate of alkene.
A kind of catalyst for cracking that contains supersiliceous zeolite is disclosed among the CN 1057408A, has higher catalytic pyrolysis activity, wherein said supersiliceous zeolite is ZSM-5, β zeolite or the mordenite 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 mordenite, 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 compound
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 catalyzer are used for catalytic cracking process, though can increase the productive rate of low-carbon alkene effectively, improve the octane value of catalytically cracked gasoline product, but the selectivity for propylene in the catalytic cracking reaction process is not very high, thereby the amplitude that improves density of propylene in the liquefied gas is limited.
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 of propylene enhancing, this auxiliary agent is applied in the catalytic cracking process, can not only increase the catalytic cracking liquefied gas yield effectively, improve the octane value of catalytically cracked gasoline, can also improve the density of propylene in the catalytic cracking liquefied gas simultaneously greatly.
The inventor finds, with disclosed phosphorous and modified zsm-5 zeolite transition metal among the CN 1465527A is active component, introduce mordenite and clinoptilolite and replace conventional clay composition, and further introduce an amount of phosphorus additive, prepared cracking additive is applied to can reach purpose of the present invention in the catalytic cracking process of petroleum hydrocarbon.
Catalyst aid provided by the present invention is by butt, contain the modified zsm-5 zeolite of 10～65 heavy %, the zeolite of 15～60 heavy %, the inorganic oxide binder of 15～70 heavy % and the phosphorus additive of 2～25 heavy %, wherein said modified zsm-5 zeolite is through phosphorus and be selected from the metal-modified of one of Fe, Co or Ni, its anhydrous chemical expression is counted (0～0.3) Na with oxide compound
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 to satisfy the required number of M oxidation state, and said zeolite is that part by weight is 1: 99～99: 1 mordenite and a clinoptilolite, and said binding agent and phosphorus additive are all in oxide compound.
Auxiliary agent provided by the invention is by butt, preferred group becomes the modified zsm-5 zeolite of 20～50 heavy %, the zeolite of 20～40 heavy %, the inorganic oxide binder of 25～50 heavy % and the phosphorus additive of 5～15 heavy %, and said zeolite is the mixture of mordenite and clinoptilolite.In the auxiliary agent provided by the invention, said phosphorus additive and content thereof do not comprise the phosphorus in the modified zsm-5 zeolite.
In the auxiliary agent provided by the invention, said modified zsm-5 zeolite, its anhydrous chemical expression is preferably (0～0.2) Na
2O (0.9～3.5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(82～92) SiO
2
In the auxiliary agent provided by the invention, said zeolite is the mixture of mordenite and clinoptilolite, the two part by weight is preferably 30: 70～and 90: 10, more preferably part by weight is 50: 50～80: 20.
The natural zeolite raw material also can be taken from the source of said mordenite and clinoptilolite, for example originate from the natural mineral that is rich in mordenite and clinoptilolite of Jimusar County, Xinjiang natural zeolite ore, product after pulverizing, pulp, washing, obtain through acid and inorganic ammonium salt processing, wherein the part by weight of mordenite and clinoptilolite is about 70: 30, and chemical constitution is referring to table 1.The general treating processes of said natural zeolite raw material is that the natural zeolite raw material is carried out mechanical disintegration earlier, be dispersed into the slurries of certain solid content then with the making beating of decationized Y sieve water, stir adding acid and inorganic ammonium salt down, rise to certain temperature and react certain hour, filter then, wash; Repeating step is handled for several times in the same way, until most of Na, the K, the accompanying impurities components such as Mg, Ca that remove wherein.
Table 1
| Material | Form heavy % | ||||||
| SiO 2 | Al 2O 3 | Na 2O | CaO | MgO | K 2O | Fe 2O 3 | |
| The natural zeolite raw material | 74.2 | 14.0 | 4.6 | 2.4 | 0.78 | 0.98 | 1.8 |
| After acid and inorganic ammonium salt are handled | 78.3 | 16.7 | 0.6 | 0.8 | 0.7 | 0.6 | 2.3 |
Auxiliary agent provided by the invention, wherein said inorganic oxide binder is selected from as in the inorganic oxide of auxiliary agent matrix and binder component one or more, one or more the mixture that can comprise pseudo-boehmite, aluminium colloidal sol, silicon-aluminum sol, water glass and phosphorus aluminium colloidal sol, the mixture of one or more in wherein preferred pseudo-boehmite, aluminium colloidal sol or the phosphorus aluminium colloidal sol.When containing phosphorus aluminium colloidal sol in the auxiliary agent, in the phosphorus aluminium colloidal sol content of phosphorus in Vanadium Pentoxide in FLAKES, calculate and be included in the said phosphorus additive.
Auxiliary agent provided by the invention, described phosphorus additive exists with the form of phosphorus compound (as oxide compound, phosphoric acid salt, phosphite, subphosphate, the acid phosphate of phosphorus).
Auxiliary agent provided by the invention can be adopted any method in the existing cracking catalyst technology of preparing that comprises spray drying forming to prepare by ZSM-5 molecular sieve, mordenite, clinoptilolite and the inorganic oxide binder of modification, the present invention has no particular limits it.
Said phosphorus additive can adopt the combination of one of following method or several method, introduces in the auxiliary agent but be not limited to these methods:
1, when handling mordenite and clinoptilolite, introduces with phosphorus compound, such as adopting phosphoric acid and/or phosphorous acid, or adopt Secondary ammonium phosphate, primary ammonium phosphate, ammonium phosphate, ammonium phosphite, dihydrogen phosphite ammonium etc. to handle mordenite and clinoptilolite as inorganic ammonium salt as sour reagent;
2, before the auxiliary agent spray drying forming, in slurries, add phosphorus compound;
3, 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 substrate material and binding agent again;
4, after the auxiliary agent spray drying forming through the dipping or the chemisorption phosphorus compound, introduce through solid-liquid separation (if necessary), drying and roasting process, said exsiccant temperature is a room temperature to 400 ℃, preferred 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.
Therefore, said phosphorus additive may reside in any position that may exist of auxiliary agent, as may reside in the inside, duct of molecular sieve, the surface of molecular sieve, may reside in the described substrate material, can also be present in simultaneously in the surface and described substrate material of inside, duct, molecular sieve of molecular sieve.
Auxiliary agent provided by the invention, phosphorus compound described in its preparation method are selected from the various mineral compound of phosphorus and in the organic compound one or more.Described phosphorus compound can be soluble in water, also can be to be insoluble in water or water-fast phosphorus compound.The embodiment of phosphorus compound comprises oxide compound, phosphoric acid, phosphoric acid salt, phosphite, hypophosphite, phosphorated organic compound of phosphorus etc.Preferred phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, aluminum phosphate and the phosphorus aluminium colloidal sol.
When auxiliary agent provided by the invention is used for catalytic cracking process, can in catalyst cracker, add separately, also can mix the back with cracking catalyst and use.Generally speaking, auxiliary agent provided by the invention accounts for 1～25 weight % of FCC catalyzer and catalyst mixture gross weight provided by the invention, is preferably 3～15 weight %.
Auxiliary agent provided by the invention can be used for the processing of various hydrocarbon ils, described hydrocarbon ils is selected from various petroleum fractionss, as crude oil, long residuum, vacuum residuum, normal pressure wax oil, decompressed wax oil, straight-run gas oil, propane is light/in heavily de-oiling, wax tailings and the gelatin liquefaction product one or more.Described hydrocarbon ils can contain beavy metal impurity such as nickel, vanadium and sulphur, nitrogen impurity, can be as the content of sulphur up to 3.0 heavy %, and the content of nitrogen can be up to 2.0 heavy %, and the content of metallic impurity such as vanadium, nickel is up to 3000ppm.
Auxiliary agent provided by the invention is used for catalytic cracking process, and the cracking hydrocarbon oil condition is conventional catalytic cracking condition.In general, this cracking hydrocarbon oil condition comprises that temperature of reaction is 400～600 ℃, is preferably 450～550 ℃, and weight hourly space velocity is 10～120 hours
-1, be preferably 10～80 hours
-1, agent weight of oil ratio is 1～20, is preferably 3～15.
Auxiliary agent provided by the invention can be used for existing various catalyst cracker, as carrying out in fixed-bed reactor, fluidized-bed reactor, riser reactor, multi-reaction-area reactor etc.
In the auxiliary agent provided by the present invention owing to introduced the natural zeolite component that comprises mordenite and clinoptilolite, and further introduced an amount of phosphorus additive, obviously improved in the catalytic cracking reaction process selectivity, thereby improved the density of propylene in the catalytic cracking liquefied gas significantly for propylene.
Embodiment
The following examples will illustrate further to the present invention, but content not thereby limiting the invention.
In embodiment and the Comparative Examples, A
1～A
8Eight modified zsm-5 zeolite samples are by the disclosed method preparation of CN1465527A, and its anhydrous chemical expression is use the x-ray fluorescence spectrometry molecular sieve elementary composition, 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
2O5.0Al
2O
32.0P
2O
50.9Fe
2O
392SiO
2
Sample A
3: 0.1Na
2O5.3Al
2O
31.5P
2O
51.1Fe
2O
392SiO
2
Sample A
4: 0.03Na
2O2.2Al
2O
34.9P
2O
52.1Fe
2O
390.8SiO
2
Sample A
5: 0.1Na
2O0.94Al
2O
35.1P
2O
510.1Fe
2O
384SiO
2
Sample A
6: 0.03Na
2O5.1Al
2O
34.8P
2O
53.6Co
2O
386.5SiO
2
Sample A
7: 0.1Na
2O4.6Al
2O
36.9P
2O
56.4Ni
2O
382SiO
2
Sample A
8: 0.1Na
2O5.2Al
2O
34.5P
2O
52.0Ni
2O
388.2SiO
2
Among the embodiment, pseudo-boehmite is Shandong Aluminum Plant's manufacture product, solid content 60 heavy %.The Industrial products that aluminium colloidal sol is produced for the Qilu Petrochemical catalyst plant, Al
2O
3Content is 21.5 heavy %.The Industrial products that water glass is produced for the Qilu Petrochemical catalyst plant, SiO
2Content 28.9 heavy %, Na
2O content 8.9%.Kaolin is the special-purpose kaolin of cracking catalyst that Suzhou kaolin company produces, solid content 78 heavy %.
The ZRP-5 zeolite is the Industrial products of the conventional MFI structural zeolite of Qilu Petrochemical catalyst plant production, wherein P
2O
52.5 heavy %, degree of crystallinity 85 heavy %, silica alumina ratio 50.Mordenite is the Industrial products that Catalyst Factory, Nankai Univ is produced, and wherein degree of crystallinity 90 weighs %, silica alumina ratio 12.Clinoptilolite is the Industrial products that Catalyst Factory, Nankai Univ is produced, and wherein degree of crystallinity 90 weighs %, silica alumina ratio 8.
The preparation of embodiment 1～19 explanation assistant for calalytic cracking provided by the invention.
Embodiment 1
Get 1.84 kilograms of (butt) A
1, 1.11 kilograms of (butt) mordenites, 0.47 kilogram of (butt) clinoptilolite and 0.98 kilogram of (butt) pseudo-boehmite (technical grade, Shandong Aluminum Plant produces, solid content 60 heavy %), (the Qilu Petrochemical catalyst plant is produced to add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols, solid content 21.5 heavy %) making beating is 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating.Then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying 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 %Al, 22.12 heavy % mordenites, 9.48 heavy % clinoptilolites and 31.6 heavy %Al
2O
3Microballoon.
Get 1 kilogram of thus obtained microsphere product (butt), add 10 liters of decationized Y sieve water and 100 gram Secondary ammonium phosphates, stir be warming up to down 60 ℃ and react 20 minutes after, vacuum filtration, drying then in 500 ℃ of following roastings 2 hours, make and contain 35 weight %A
1, 21 heavy % mordenites, 9 heavy % clinoptilolites and 30 heavy %Al
2O
3With 5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
1
Embodiment 2
3.5 kilograms of (butt) mordenites and 1.5 kilograms of (butt) clinoptilolites stirrings are carried out saturated dipping with 1.5 liters of aqueous solution that contain 0.97 kilogram of Secondary ammonium phosphate down, left standstill 12 hours, the oven dry back was in 550 ℃ of following roastings 2 hours, and obtaining phosphorus modification and phosphorus content is that 10 heavy % are (with P
2O
5Meter) the mordenite and the mixture of clinoptilolite.
Method by embodiment 1 prepares auxiliary agent, is not both the zeolite mixture replacement of zeolite with the above-mentioned phosphorus modification of same weight, makes to contain 35 heavy %A
1, 18.9 heavy % mordenites, 8.1 heavy % clinoptilolites and 30 heavy %Al
2O
3, and the auxiliary agent ZJ of 8 heavy % phosphorus additives
2
Embodiment 3
Get 1.94 kilograms of (butt) A
1, 1.11 kilograms of (butt) natural zeolites (originate from Jimusar County, Xinjiang natural zeolite ore, handle through pickling and ammonium, wherein the part by weight of mordenite and clinoptilolite is 70: 30, character sees Table 1) and 1.34 kilograms of (butt) pseudo-boehmites, add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating, then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying 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 38.9 heavy %A
1, 22.2 heavy % natural zeolites and 38.9 heavy %Al
2O
3Microballoon.
Get 1 kilogram of thus obtained microsphere product (butt), add 10 liters of decationized Y sieve water and 210 gram Secondary ammonium 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, 20 heavy % natural zeolites, 35 heavy %Al
2O
3With 10 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
3
Embodiment 4
Phosphorus aluminium colloidal sol preparation: with 1.05 kilograms of pseudo-boehmites (butt) and 3.35 kilograms of decationizing water making beating 30 minutes, stir down and in slurries, add 4.9 kilograms of strong phosphoric acid (chemical pure, phosphoric acid 85 heavy %), be warming up to 70 ℃, under this temperature, reacted 45 minutes then, promptly make water white phosphorus aluminium colloidal sol.P wherein
2O
530.6 weight %, Al
2O
310.5 weight %, PH=1.7.
Get 1.75 kilograms of (butt) A
1, 1.4 kilograms of (butt) mordenites, 0.6 kilogram of (butt) clinoptilolite, add 4.2 kilograms of decationized Y sieve water and 3.48 kilograms of aluminium colloidal sols making beating 120 minutes, in mixed serum, add 1.22 kilograms of phosphorus aluminium colloidal sols then, after stirring, with the slurries that obtain 500 ℃ of temperature ins, carry out spraying 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, 28 heavy % mordenites, 12 heavy % clinoptilolites, 17.5 heavy %Al
2O
3With 7.5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
4
Embodiment 5
Get ZJ
41 kilogram of auxiliary agent (butt) adds 10 liters of decationized Y sieve water and 157 gram Secondary ammonium 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, 26 heavy % mordenites, 11 heavy % clinoptilolites, 16.2 heavy %Al
2O
3With 14.42 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
5
Embodiment 6
Get 1.75 kilograms of (butt) A
1(the Qilu Petrochemical catalyst plant is produced, SiO for zeolite, 1.05 kilograms of (butt) mordenites, 0.45 kilogram of (butt) clinoptilolite and 4.33 kg of water glass
2Content 28.9 heavy %, Na
2O content 8.9%), add 5 kilograms of decationized Y sieve water making beating 120 minutes, stir and add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.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 temperature ins, carry out spraying drying under the condition that exhaust temperature is 180 ℃, obtain average particulate diameter and be 65 microns microballoon.With microballoon in 500 ℃ 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
1Zeolite, 21 heavy % mordenites, 9 heavy % clinoptilolites, 2.5 heavy %Al
2O
3, 25 heavy %SiO
2With 7.5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
6
Embodiment 7
Get 2.25 kilograms of (butt) A
1, 0.7 kilogram of (butt) mordenite, 0.3 kilogram of (butt) clinoptilolite, add 4.2 kilograms of decationized Y sieve water and 5.8 kilograms of aluminium colloidal sols making beating 120 minutes, in mixed serum, add 1.22 kilograms of phosphorus aluminium colloidal sols then, after stirring, with the slurries that obtain 500 ℃ of temperature ins, carry out spraying 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 45 heavy %A
1, 14 heavy % mordenites, 6 heavy % clinoptilolites, 27.5 heavy %Al
2O
3With 7.5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
7
Embodiment 8
Get 1.05 kilograms of (butt) A
1, 1.66 kilograms of (butt) mordenites, 0.71 kilogram of (butt) clinoptilolite and 0.98 kilogram of (butt) pseudo-boehmite, (the Qilu Petrochemical catalyst plant is produced to add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols, solid content 21.5 heavy %) making beating is 120 minutes, stir and to add the hydrochloric acid that concentration is 36 heavy % down, the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating.Then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying 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 21.05 heavy %A
1, 33.16 heavy % mordenites, 14.21 heavy % clinoptilolites and 31.58 heavy %Al
2O
3Microballoon.
Get 1 kilogram of thus obtained microsphere product (butt), add 10 liters of decationized Y sieve water and 100 gram Secondary ammonium phosphates, stir be warming up to down 60 ℃ and react 20 minutes after, vacuum filtration, drying then in 500 ℃ of following roastings 2 hours, make and contain 20 weight %A
1, 31.5 heavy % mordenites, 13.5 heavy % clinoptilolites, 30 heavy %Al
2O
3With 5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
8
Embodiment 9
Method by embodiment 1 prepares auxiliary agent, and not being both the mordenite consumption and being 0.8 kilogram, clinoptilolite consumption is 0.8 kilogram, makes to contain 35 heavy %A
1, 15 heavy % mordenites, 15 heavy % clinoptilolites, 30 heavy %Al
2O
3Auxiliary agent ZJ with 5 heavy % phosphorus additives
9
Embodiment 10
Method by embodiment 1 prepares auxiliary agent, is not both with 1.32 kilograms of A
2Replace A
1, the mordenite consumption is that 1.05 kilograms, clinoptilolite consumption are 1.05 kilograms, makes to contain 25 heavy %A
2, 20 heavy % mordenites, 20 heavy % clinoptilolites, 30 heavy %Al
2O
3Auxiliary agent ZJ with 5 heavy % phosphorus additives
10
Embodiment 11
Method by embodiment 1 prepares auxiliary agent, is not both with 2.11 kilograms of A
3Replace A
1, the mordenite consumption is that 1.18 kilograms, clinoptilolite consumption are 0.39 kilogram, makes to contain 40 heavy %A
3, 22.5 heavy % mordenites, 7.5 heavy % clinoptilolites, 25 heavy %Al
2O
3Auxiliary agent ZJ with 5 heavy % phosphorus additives
11
Embodiment 12
Method by embodiment 3 prepares auxiliary agent, is not both with 2.22 kilograms of A
4Replace A
1, replace natural zeolite with 0.67 kilogram of mordenite and 0.17 kilogram of clinoptilolite, make and contain 40 heavy %A
4, 12 heavy % mordenites, 3 heavy % clinoptilolites, 35 heavy %Al
2O
3Auxiliary agent ZJ with 10 heavy % phosphorus additives
12
Embodiment 13
Method by embodiment 1 prepares auxiliary agent, is not both with 1.58 kilograms of A
5Replace A
1, the mordenite consumption is that 1.11 kilograms, clinoptilolite consumption are 0.47 kilogram, makes to contain 30 heavy %A
5, 21 heavy % mordenites, 9 heavy % clinoptilolites, 35 heavy %Al
2O
3Auxiliary agent ZJ with 5 heavy % phosphorus additives
13
Embodiment 14
Method by embodiment 4 prepares auxiliary agent, is not both with 1.5 kilograms of A
6Replace A
1, the mordenite consumption is that 1.05 kilograms, clinoptilolite consumption are 0.45 kilogram, makes to contain 30 heavy %A
6, 21 heavy % mordenites, 9 heavy % clinoptilolites, 35 heavy %Al
2O
3Auxiliary agent ZJ with 7.5 heavy % phosphorus additives
14
Embodiment 15
Method by embodiment 3 prepares auxiliary agent, is not both with 1.39 kilograms of A
7Replace A
1, replace natural zeolite with 1.17 kilograms of mordenites and 0.5 kilogram of clinoptilolite, make and contain 25 heavy %A
7, 21 heavy % mordenites, 9 heavy % clinoptilolites, 35 heavy %Al
2O
3Auxiliary agent ZJ with 10 heavy % phosphorus additives
15
Embodiment 16
Method by embodiment 1 prepares auxiliary agent, is not both with 1.58 kilograms of A
8Replace A
1, the mordenite consumption is that 1.11 kilograms, clinoptilolite consumption are 0.47 kilogram, makes to contain 30 heavy %A
8, 21 heavy % mordenites, 9 heavy % clinoptilolites, 35 heavy %Al
2O
3Auxiliary agent ZJ with 5 heavy % phosphorus additives
16
Embodiment 17
Method by embodiment 1 prepares auxiliary agent, is not both with 1.84 kilograms of A
3Replace A
1, the mordenite consumption is that 1.11 kilograms, clinoptilolite consumption are 0.47 kilogram, makes to contain 35 heavy %A
3, 21 heavy % mordenites, 9 heavy % clinoptilolites, 30 heavy %Al
2O
3Auxiliary agent ZJ with 5 heavy % phosphorus additives
17
Embodiment 18
Method by embodiment 1 prepares auxiliary agent, is not both with 1.84 kilograms of A
6Replace A
1, the mordenite consumption is that 1.11 kilograms, clinoptilolite consumption are 0.47 kilogram, makes to contain 35 heavy %A
6, 21 heavy % mordenites, 9 heavy % clinoptilolites, 30 heavy %Al
2O
3Auxiliary agent ZJ with 5 heavy % phosphorus additives
18
Embodiment 19
Method by embodiment 1 prepares auxiliary agent, is not both with 1.84 kilograms of A
8Replace A
1, the mordenite consumption is that 1.11 kilograms, clinoptilolite consumption are 0.47 kilogram, makes to contain 35 heavy %A
8, 21 heavy % mordenites, 9 heavy % clinoptilolites, 30 heavy %Al
2O
3Auxiliary agent ZJ with 5 heavy % phosphorus additives
19
Comparative Examples 1
The explanation of this Comparative Examples only contains modified zsm-5 zeolite (sample A
1) the preparation of reference auxiliary agent.
Get 1.75 kilograms of (butt) A
1, (kaolin company in Suzhou produces 1.5 kilograms of (butt) kaolin, solid content 78 weighs %) and 1.15 kilograms of (butt) pseudo-boehmite (technical grades, Shandong Aluminum Plant produces, solid content 60 heavy %), (the Qilu Petrochemical catalyst plant is produced to add 7.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols, the heavy % of solid content 21.5) making beating is 120 minutes, stirs to add the hydrochloric acid that concentration is 36 heavy % down, and the consumption of hydrochloric acid makes the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating.Then with the slurries that obtain 500 ℃ of temperature ins, carry out spraying 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
1
Comparative Examples 2
The explanation of this Comparative Examples contains modified zsm-5 zeolite (sample A
1) and the preparation of the reference auxiliary agent of phosphorus additive.
Method by embodiment 1 prepares auxiliary agent, and the kaolin (kaolin company in Suzhou produces, solid content 78 heavy %) that is not both with same weight replaces mordenite and clinoptilolite, makes to contain 35 heavy %A
1, 30 heavy % kaolin and 30 heavy %Al
2O
3, and the reference auxiliary agent CB of the phosphorus additive of 5 heavy %
2
Comparative Examples 3
Present embodiment explanation ZRP-5 zeolite is as the reference auxiliary agent and the preparation thereof of active ingredient.
Method by Comparative Examples 1 prepares auxiliary agent, is not both ZRP-5 zeolite (the conventional MFI structural zeolite Industrial products that the Qilu Petrochemical catalyst plant is produced, wherein P with same weight
2O
52.5 heavy %, silica alumina ratio 50) replaces A1, make and contain 35 heavy %ZRP-5 zeolites, 30 heavy % kaolin and 35 heavy %Al
2O
3Reference auxiliary agent CB
3
Comparative Examples 4
Present embodiment explanation ZRP-5 zeolite is as active ingredient and the reference auxiliary agent and the preparation thereof of phosphorus additive are arranged.
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 with 5 heavy % phosphorus additives
4
Comparative Examples 5
The explanation of this Comparative Examples contains modified zsm-5 zeolite (sample A
1) and the preparation of the reference auxiliary agent of mordenite.
Method by Comparative Examples 1 prepares auxiliary agent, and different is to use the mordenite of identical weight to replace kaolin, makes to contain 35 heavy %A
1,, 30 heavy % mordenites and 35 heavy %Al
2O
3Reference auxiliary agent CB
5
Comparative Examples 6
The explanation of this Comparative Examples contains modified zsm-5 zeolite (sample A
1) and the preparation of the reference auxiliary agent of clinoptilolite.
Method by Comparative Examples 1 prepares auxiliary agent, and different is to use the clinoptilolite of identical weight to replace kaolin, makes to contain 35 heavy %A
1,, 30 heavy % clinoptilolites and 35 heavy %Al
2O
3Reference auxiliary agent CB
6
Embodiment 20～38
The following examples are example with the fixed fluidized-bed reactor, and the reaction effect of assistant for calalytic cracking provided by the invention is described.
Respectively with 30 gram ZJ
1-ZJ
19Under 800 ℃, 100% steam atmosphere condition, carry out 8 hours burin-in process.Get the ZJ through burin-in process of different amounts
1-ZJ
8Mix with the industrial FCC equilibrium catalyst (the industrial trade mark is the FCC equilibrium catalyst of MLC-500, and main character sees Table 2) of different amounts.Catalyst mixture is packed in the reactor of small fixed flowing bed-tion reacting device, and stock oil oil shown in the his-and-hers watches 3 carries out catalytic cracking (stock oil character sees Table 3).Table 4, table 5 and table 6 have provided the catalyst system therefor mixture and have formed reaction conditions and reaction result.
Comparative Examples 7～13
These Comparative Examples are example with the fixed fluidized-bed reactor, and the reaction effect that uses the reference auxiliary agent is described.
By the method among the embodiment 20 same stock oil is carried out catalytic cracking, different is that catalyst system therefor is respectively 100% industrial FCC equilibrium catalyst and CB
1～CB
6Mixture with industrial FCC equilibrium catalyst.The table 4 used composition that contains the catalyst mixture that contrasts auxiliary agent, reaction conditions and reaction result.
Table 2
| Project | Industry equilibrium catalyst MLC-500 |
| Metal content, ppm Ni/V Fe/Sb Ca | 9386/1665 6503/2673 1714 |
| Little index alive | 60 |
Table 3
| The stock oil title | The defeated wax oil of pipe is mixed residual oil |
| Density (20 ℃), gram per centimeter 3Viscosity (100 ℃), millimeter 2/ second zero pour, ℃ carbon residue, weight % | 0.9070 10.41 40 3.1 |
| Elementary composition, weight % C/H S/N | 86.39/12.53 0.8/0.29 |
| Four components, weight % stable hydrocarbon aromatic hydrocarbons gum asphalt | 56.8 24.2 18.2 0.8 |
| Metal content, ppm V/Ni Fe/Cu Na boiling range, ℃ initial boiling point/5% 10%/20% 30%/40% 50%/60% 70%/80% | 0.8/7.0 7.8/0.1 2.6 241/309 343/387 413/432 450/466 493/535 |
As can be seen from Table 4, compare with the reference auxiliary agent, catalyst aid provided by the invention can not only increase the catalytic cracking liquefied gas yield effectively, improves the octane value of catalytically cracked gasoline, can also significantly improve the density of propylene in the catalytic cracking liquefied gas simultaneously.
Table 4
| The embodiment numbering | Comparative Examples 7 | Comparative Examples 8 | Comparative Examples 9 | Comparative Examples 10 | Comparative Examples 11 | Comparative Examples 12 | Comparative Examples 13 | 20 | 21 |
| Catalyzer | 100% poiser | 10％CB 1+ 90% poiser | 10％CB 2+ 90% poiser | 10％CB 3+ 90% poiser | 10％CB 4+ 90% poiser | 10％CB 5+ 90% poiser | 10％CB 6+ 90% poiser | 10％ZJ 1+ 90% poiser | 10％ZJ 2+ 90% poiser |
| Temperature of reaction, ℃ | 500 | 500 | 500 | 500 | 500 | 500 | 500 | 500 | 500 |
| Air speed, hour -1 | 16 | 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 | 5.92 |
| Water vapour (to stock oil), heavy % | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Productive rate, heavy % | |||||||||
| Dry gas | 1.60 | 1.60 | 1.55 | 1.70 | 1.56 | 1.50 | 1.51 | 1.58 | 1.52 |
| Liquefied gas | 18.04 | 21.03 | 20.85 | 21.37 | 20.76 | 21.56 | 20.83 | 22.04 | 21.94 |
| C 5 +Gasoline | 43.13 | 39.88 | 39.39 | 39.55 | 39.78 | 39.95 | 39.84 | 40.01 | 38.90 |
| Diesel oil | 17.17 | 17.04 | 17.97 | 17.10 | 17.11 | 17.17 | 17.67 | 16.96 | 17.72 |
| Heavy oil | 13.61 | 14.34 | 14.38 | 13.77 | 14.60 | 13.40 | 13.88 | 13.83 | 14.50 |
| Coke | 6.45 | 6.12 | 5.87 | 6.51 | 6.19 | 6.42 | 6.27 | 5.58 | 5.42 |
| Transformation efficiency, heavy % | 69.23 | 68.62 | 67.65 | 69.13 | 68.30 | 69.43 | 67.65 | 69.21 | 67.77 |
| Liquid is received, heavy % | 78.34 | 77.95 | 78.21 | 78.02 | 77.65 | 78.68 | 78.21 | 79.02 | 78.57 |
| Propylene, heavy % | 5.07 | 6.65 | 7.12 | 6.45 | 6.67 | 6.88 | 6.58 | 7.77 | 7.81 |
| Propylene/liquefied gas | 28.13 | 31.64 | 34.18 | 30.16 | 32.12 | 31.89 | 31.58 | 35.26 | 35.61 |
| Gasoline is formed, heavy % | |||||||||
| Alkane | 33.59 | 30.56 | 31.06 | 29.69 | 29.78 | 29.61 | 31.16 | 28.56 | 27.99 |
| Alkene | 23.89 | 24.54 | 24.64 | 25.4 | 24.93 | 25.48 | 24.54 | 25.17 | 25.45 |
| Naphthenic hydrocarbon | 8.26 | 8.26 | 8.45 | 8.2 | 8.50 | 8.25 | 8.43 | 8.27 | 8.00 |
| Aromatic hydrocarbons | 34.08 | 36.38 | 35.6 | 36.48 | 36.44 | 36.43 | 35.62 | 37.68 | 38.29 |
| RON (chromatography) | 87.1 | 88.9 | 89.1 | 89.2 | 89.0 | 89.2 | 89.1 | 89.5 | 90.4 |
| MON (chromatography) | 82.0 | 82.7 | 82.7 | 82.7 | 82.7 | 82.7 | 82.7 | 82.7 | 83.0 |
Table 5
| The embodiment numbering | 22 | 23 | 24 | 25 | 26 | 27 | 28 | 29 |
| Catalyzer | 10％ZJ 3+ 90% poiser | 10％ZJ 4+ 90% poiser | 12％ZJ 5+ 88% poiser | 10％ZJ 6+ 90% poiser | 8％ZJ 7+ 92% poiser | 15％ZJ 8+ 85% poiser | 10％ZJ 9+ 90% poiser | 12％ZJ 10+ 88% poiser |
| Temperature of reaction, ℃ | 500 | 500 | 500 | 500 | 500 | 500 | 500 | 500 |
| Weight hourly space velocity, 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 |
| Water vapour (to stock oil), heavy % | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Material balance, heavy % | ||||||||
| Dry gas | 1.62 | 1.63 | 1.68 | 1.48 | 1.71 | 1.68 | 1.60 | 1.68 |
| Liquefied gas | 23.68 | 23.95 | 24.23 | 22.54 | 22.02 | 23.85 | 23.45 | 23.14 |
| C 5 +Gasoline | 38.51 | 37.96 | 37.35 | 40.60 | 40.07 | 38.13 | 38.30 | 38.14 |
| Diesel oil | 17.03 | 17.46 | 16.79 | 17.40 | 16.91 | 17.49 | 17.12 | 17.45 |
| Heavy oil | 13.73 | 12.94 | 13.94 | 12.46 | 13.53 | 12.84 | 13.92 | 14.06 |
| Coke | 5.43 | 6.06 | 6.01 | 5.53 | 5.76 | 6.01 | 5.61 | 5.53 |
| Transformation efficiency, heavy % | 69.24 | 69.59 | 69.27 | 70.14 | 69.56 | 69.67 | 68.96 | 68.49 |
| Liquid is received, heavy % | 79.22 | 79.37 | 78.37 | 80.54 | 79.00 | 79.47 | 78.87 | 78.73 |
| Propylene, heavy % | 8.41 | 8.40 | 8.61 | 7.95 | 7.71 | 8.55 | 8.28 | 8.15 |
| Propylene/liquefied gas | 35.52 | 35.08 | 35.52 | 35.26 | 35.03 | 35.86 | 35.32 | 35.21 |
| Gasoline is formed, heavy % | ||||||||
| Alkane | 26.62 | 29.65 | 27.07 | 31.66 | 25.98 | 29.35 | 26.52 | 31.18 |
| Alkene | 25.08 | 24.66 | 25.88 | 24.54 | 26.07 | 24.96 | 25.18 | 24.82 |
| Naphthenic hydrocarbon | 8.25 | 8.13 | 8.3 | 8.45 | 7.54 | 8.12 | 8.01 | 8.64 |
| Aromatic hydrocarbons | 38.00 | 37.33 | 38.49 | 35.10 | 40.15 | 37.34 | 38.24 | 35.11 |
| RON-GC (chromatography) | 89.7 | 89.1 | 90.0 | 89.1 | 90.6 | 89.2 | 89.6 | 89.2 |
| MON-GC (chromatography) | 82.7 | 82.7 | 82.9 | 82.7 | 82.8 | 82.8 | 82.6 | 82.8 |
Table 6
| The embodiment numbering | 30 | 31 | 32 | 33 | 34 | 35 | 36 | 37 | 38 |
| Catalyzer | 4％ZJ 11+ 96% poiser | 6％ZJ 12+ 90% poiser | 15％ZJ 13+ 85% poiser | 10％ZJ 14+ 90% poiser | 12％ZJ 15+ 88% poiser | 10％ZJ 16+ 90% poiser | 10％ZJ 17+ 90% poiser | 10％ZJ 18+ 90% poiser | 8％ZJ 19+ 92% poiser |
| Temperature of reaction, ℃ | 520 | 500 | 520 | 490 | 510 | 490 | 500 | 520 | 510 |
| Air speed, hour -1 | 10 | 20 | 10 | 16 | 16 | 20 | 16 | 10 | 10 |
| Agent weight of oil ratio | 5.92 | 7.0 | 5.92 | 6.5 | 5.0 | 5.92 | 5.92 | 4.5 | 6.5 |
| Water vapour (to stock oil), heavy % | 5 | 5 | 5 | 5 | 10 | 10 | 10 | 10 | 10 |
| Liquefied gas | 22.14 | 22.93 | 21.85 | 22.37 | 22.74 | 22.91 | 24.23 | 21.84 | 22.54 |
| Propylene, heavy % | 7.78 | 8.17 | 7.69 | 8.00 | 7.98 | 8.13 | 8.69 | 7.66 | 7.94 |
| Propylene/liquefied gas | 35.13 | 35.64 | 35.18 | 35.76 | 35.11 | 35.49 | 35.88 | 35.06 | 35.21 |
| Gasoline olefin, heavy % | 23.87 | 24.51 | 24.63 | 25.41 | 24.91 | 25.42 | 24.51 | 25.37 | 25.12 |
| RON (chromatography) | 89.6 | 88.9 | 89.2 | 89.2 | 89.4 | 89.3 | 89.3 | 89.4 | 90.1 |
| MON (chromatography) | 82.5 | 82.8 | 82.6 | 82.7 | 82.8 | 82.6 | 82.7 | 82.6 | 82.9 |
From table 5 and table 6 also as can be seen, catalyst aid provided by the invention can not only increase the catalytic cracking liquefied gas yield effectively, improves the octane value of catalytically cracked gasoline, can also significantly improve the density of propylene in the catalytic cracking liquefied gas simultaneously.
Claims (8)
1. assistant for calalytic cracking, this auxiliary agent is by butt, contain the modified zsm-5 zeolite of 10～65 heavy %, the zeolite of 15～60 heavy %, the inorganic oxide binder of 15～70 heavy % and the phosphorus additive of 2～25 heavy %, wherein said modified zsm-5 zeolite is through phosphorus and the metal M modification that is selected from one of Fe, Co or Ni, its anhydrous chemical expression is counted (0～0.3) Na with oxide compound
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 to satisfy the required number of M oxidation state; Said zeolite is that part by weight is 1: 99～99: 1 mordenite and a clinoptilolite; Said binding agent and phosphorus additive are all in oxide compound.
2. according to the auxiliary agent of claim 1, it consists of the modified zsm-5 zeolite of 20～50 heavy %, the zeolite of 20～40 heavy %, the inorganic oxide binder of 20～50 heavy % and the phosphorus additive of 5～15 heavy %.
3. according to the auxiliary agent of claim 1, wherein the anhydrous chemical expression of modified zsm-5 zeolite is counted (0～0.2) Na with oxide compound
2O (0.9～3.5) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
2O
3(82～92) SiO
2
4. according to the auxiliary agent of claim 1, it is characterized in that described M is Fe.
5. according to the auxiliary agent of claim 1, the part by weight of described mordenite and clinoptilolite is 30: 70～90: 10.
6. according to the auxiliary agent of claim 5, described part by weight is 50: 50～80: 20.
7. according to the auxiliary agent of claim 1, described inorganic oxide binder is selected from one or more the mixture in pseudo-boehmite, aluminium colloidal sol, silicon-aluminum sol, water glass and the phosphorus aluminium colloidal sol.
8. according to the auxiliary agent of claim 7, described inorganic oxide binder is selected from one or more the mixture in pseudo-boehmite, aluminium colloidal sol and the phosphorus aluminium colloidal sol.
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888378A (en) * | 1997-03-18 | 1999-03-30 | Mobile Oil Corporation | Catalytic cracking process |
| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888378A (en) * | 1997-03-18 | 1999-03-30 | Mobile Oil Corporation | Catalytic cracking process |
| CN1465527A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal |
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