CN1796497A - Catalytic auxiliary agent for raising density of propylene in catalytic cracking liquefied gas - Google Patents
Catalytic auxiliary agent for raising density of propylene in catalytic cracking liquefied gas Download PDFInfo
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- CN1796497A CN1796497A CN 200410102814 CN200410102814A CN1796497A CN 1796497 A CN1796497 A CN 1796497A CN 200410102814 CN200410102814 CN 200410102814 CN 200410102814 A CN200410102814 A CN 200410102814A CN 1796497 A CN1796497 A CN 1796497A
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Abstract
This invention describes a pyrolysis assistant for increasing the propylene concentration in the catalytic pyrolytic liquefied gas, which, measured on dry basis, comprises 10-65 wt.% of modified ZSM-5 molecular sieve, 0-60 wt.% of clay, 15-70 wt.% of inorganic oxide binder and 2-25 wt.% of phosphorus additive, wherein the said ZSM-5 molecular sieve is modified with phosphorus and a metal selected from ferrum, cobalt or nickel, whose anhydrous chemical formulation is (0-0.3)Na2O.(0.5-5)Al2O3.(1.3-10)P2O5.(0.7-15)MxOy.(70-97)SiO2, wherein x represents the molecular number of M and y represents the number needed for the oxidation state of M. The said binder and phosphorus additive are both measured by their oxides. The process of this invention can increase the yield of the catalytic pyrolytic liquefied gas, the octane number of the catalytic pyrolytic gasoline, as well as the propylene concentration in the liquefied gas.
Description
Technical field
The invention relates to a kind of catalyst aid, further say so about a kind of ZSM-5 of containing molecular sieve, be used for improving the catalyst aid of catalytic cracking liquefied gas density of propylene.
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
2O
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 the USP 2002/0003103A1.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 the USP 2002/0049133A1.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 catalyst aid that improves density of propylene in the catalytic cracking liquefied gas, 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 modification MFI structural zeolite transition metal among the CN 1465527A is active component, 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.
Therefore, the catalyst aid of raising density of propylene provided by the present invention, it is characterized in that this auxiliary agent is by butt, form by the inorganic oxide binder of the clay of the modified zsm-5 zeolite of 10～65 heavy %, 0～60 heavy %, 15～70 heavy % with the phosphorus additives 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, counts (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 binding agent and phosphorus additive are all in oxide compound.
Catalyst aid provided by the present invention is by butt, and preferred group becomes the modified zsm-5 zeolite of 20～50 heavy %, the clay of 10～45 heavy %, the inorganic oxide binder of 25～50 heavy % and the phosphorus additive of 5～15 heavy %.Said phosphorus additive does not comprise the content of phosphorus in the modified zsm-5 zeolite in the catalyst aid provided by the invention.
Under the preferable case, described modified zsm-5 zeolite is through phosphorus and Fe modification, and its anhydrous chemical expression 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
xO
y(82～92) SiO
2
Catalyst aid provided by the present invention, wherein said clay is conventionally known to one of skill in the art, the present invention has no particular limits it, can be selected from one or more the mixture that comprises in kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, the tired clay material that takes off stone, diatomite, halloysite, saponite, boron-moisten soil, hydrotalcite, wherein preferred kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired one or more the mixture that takes off in the stone.
Catalyst aid provided by the present invention, wherein said inorganic oxide binder is selected from as in the inorganic oxide of auxiliary agent matrix and binder component one or more, they are conventionally known to one of skill in the art, the present invention has no particular limits it, one or more the mixture that comprises pseudo-boehmite, aluminium colloidal sol, silicon-aluminum sol, water glass, phosphorus aluminium colloidal sol, the mixture of one or more in wherein preferred pseudo-boehmite, aluminium colloidal sol and 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 in the content that is included into said phosphorus additive.
Catalyst aid provided by the present invention can be by zeolite, clay, inorganic oxide binder, and phosphorus additive adopts any method in the existing cracking catalyst technology of preparing comprise spray drying forming to prepare, and 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, 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 substrate 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 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, described phosphorus additive may reside in any position that may exist of auxiliary agent, as may reside in the inside, duct of zeolite, the surface of zeolite, and may reside in the described substrate material, can also be present in simultaneously in the surface and substrate material of inside, duct, zeolite of zeolite.
Catalyst aid provided by the present invention, described phosphorus compound 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 example 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 catalyst aid 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 heavy % of FCC catalyzer and agent mixture gross weight provided by the invention, is preferably 3～15 heavy %.
Catalyst aid 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.
Catalyst aid 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.
Catalyst aid 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 catalyst aid provided by the present invention owing to adopt phosphorous and modified zsm-5 zeolite transition metal is an active component, further introduced simultaneously 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 greatly for propylene.
Embodiment
The following examples will give further instruction to the present invention, but be not therefore and restriction the present 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.
The preparation process of embodiment 1～17 explanation catalyst aid provided by the invention.
Embodiment 1
Get 1.84 kilograms of (butt) A
1, 1.58 kilograms of (butt) kaolin and 0.98 kilogram of (butt) pseudo-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 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 %A
1, 31.6 heavy % kaolin 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, 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, 30 heavy % kaolin, 30 heavy %Al
2O
3With 5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
1
Embodiment 2
Get 1.94 kilograms of (butt) A
1With 2.46 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 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 38.89 heavy %A
1With 61.11 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, 55 heavy %Al
2O
3With 10 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
2
Embodiment 3
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, 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, 1.5 kilograms of (butt) kaolin and 0.65 kilogram of (butt) pseudo-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 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.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) auxiliary agent ZJ
3
Embodiment 4
Get ZJ
31 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, 27.75 heavy % kaolin, 25.44 heavy %Al
2O
3With 14.43 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
4
Embodiment 5
Get 1.75 kilograms of (butt) A
1, 1.5 kilograms of (butt) kaolin and 4.33 kg of water glass, 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 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, 30 heavy % kaolin, 2.5 heavy %Al
2O
3, 25 heavy %SiO
2With 7.5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
5
Embodiment 6
Method by embodiment 3 prepares auxiliary agent, is not both A
1Weight be 2.25 kilograms (butts), kaolinic weight is 1 kilogram (butt), makes to contain 45 heavy %A
1, 20 heavy % kaolin, 27.5 heavy %Al
20
3Do not comprise in the modification MFI zeolite phosphorous 7.5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
6
Embodiment 7
Get 1 kilogram of (butt) A
1, 2.25 kilograms of (butt) kaolin and 0.9 kilogram of (butt) pseudo-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 the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, adds 465 gram Secondary ammonium phosphates, pulled an oar again 30 minutes, 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 20 heavy %A
1, 45 heavy % kaolin, 30 heavy %Al
2O
3With 5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
7
Embodiment 8
Get 1.5 kilograms of (butt) A
2, 1.5 kilograms of (butt) kaolin and 0.9 kilogram of (butt) pseudo-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 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.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 30 heavy %A
2, 30 heavy % kaolin, 32.5 heavy %Al
2O
3With 7.5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
8
Embodiment 9
Get 1.5 kilograms of (butt) A
3, 1.5 kilograms of (butt) kaolin and 0.9 kilogram of (butt) pseudo-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 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.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 25 heavy %A
3, 35 heavy % kaolin, 32.5 heavy %Al
2O
3With 7.5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
9
Embodiment 10
Method by embodiment 1 prepares auxiliary agent, is not both with 1.84 kilograms of (butt) A
4Substitute A
1, make and contain 35 heavy %A
4, 30 heavy % kaolin, 30 heavy %Al
2O
3With 5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
10
Embodiment 11
Get 3 kilograms of (butt) A
5With 0.9 kilogram of (butt) pseudo-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 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.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 60 heavy %A
5, 32.5 heavy %Al
2O
3With 7.5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
11
Embodiment 12
Get 2 kilograms of (butt) A
6, 1 kilogram of (butt) kaolin and 0.9 kilogram of (butt) pseudo-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 the pH value 3.0 of slurries.Mixture is continued 30 fens kinds of making beating, adds 870 gram Secondary ammonium phosphates, pulled an oar again 30 minutes, 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 40 heavy %A
6, 20 heavy % kaolin, 30 heavy %Al
2O
3With 10 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
12
Embodiment 13
Get 2.5 kilograms of (butt) A
7, 0.5 kilogram of (butt) kaolin and 0.9 kilogram of (butt) pseudo-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 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.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 50 heavy %A
7, 10 heavy % kaolin, 32.5 heavy %Al
2O
3With 7.5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
13
Embodiment 14
Get 2.5 kilograms of (butt) A
8, 0.5 kilogram of (butt) kaolin and 0.9 kilogram of (butt) pseudo-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 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.Microballoon in 500 ℃ of following roastings 1 hour, is made and contains 50 heavy %A
8, 10 heavy % kaolin, 32.5 heavy %Al
2O
3With 7.5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
14
Embodiment 15
Method by embodiment 1 prepares auxiliary agent, is not both with 1.84 kilograms of (butt) A
6Substitute A
1, make and contain 35 heavy %A
3, 30 heavy % kaolin, 30 heavy %Al
2O
3With 5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
15
Embodiment 16
Method by embodiment 1 prepares auxiliary agent, is not both with 1.84 kilograms of (butt) A
6Substitute A
1, make and contain 35 heavy %A
6, 30 heavy % kaolin, 30 heavy %Al
2O
3With 5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
16
Embodiment 17
Method by embodiment 1 prepares auxiliary agent, is not both with 1.84 kilograms of (butt) A
8Substitute A
1, make and contain 35 heavy %A
8, 30 heavy % kaolin, 30 heavy %Al
2O
3With 5 heavy % phosphorus additives (with P
2O
5Meter) auxiliary agent ZJ
16
Comparative Examples 1
The explanation of this Comparative Examples only contains modified ZSM-5 (sample A
1), the not reference auxiliary agent and the preparation thereof of phosphor-included additive.
Get 1.75 kilograms of (butt) A
1, 1.5 kilograms of (butt) kaolin and 1.15 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 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 35 heavy %A
1, 30 heavy % kaolin and 35 heavy %Al
2O
3Reference auxiliary agent CB
1
Comparative Examples 2
This Comparative Examples illustrates reference auxiliary agent and the preparation thereof that conventional ZRP-5 zeolite is an 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) replacement A
1, make and contain 35 heavy %ZRP-5 zeolites, 30 heavy % kaolin and 35 heavy %Al
2O
3Reference auxiliary agent CB
2
Comparative Examples 3
This Comparative Examples illustrates reference auxiliary agent and the preparation thereof that conventional ZRP-5 zeolite is active ingredient, phosphor-included additive.
Method by embodiment 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
3Do not comprise in the ZRP-5 zeolite the reference auxiliary agent CB of phosphorous 5 heavy % phosphorus additives
3
Embodiment 18～34
The following examples are example with the fixed fluidized-bed reactor, and the effect of catalyst aid provided by the invention is described.
Respectively with 30 gram ZJ
1-ZJ
17Under 800 ℃, 100% steam atmosphere condition, carry out 8 hours burin-in process.Get the ZJ through burin-in process of different amounts
1-ZJ
17Mix 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 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 2 carries out catalytic cracking (stock oil character sees Table 2).Table 3, table 4 and table 5 have provided the catalyst system therefor mixture and have formed reaction conditions and reaction result.
Comparative Examples 4～7
Following Comparative Examples is an 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 18 same stock oil is carried out catalytic cracking, different is that catalyst system therefor is respectively 100% industrial FCC equilibrium catalyst, CB
1～CB
3Mixture with industrial FCC equilibrium catalyst.Table 3 has provided the catalyst system therefor mixture and has formed reaction conditions and reaction result.
From table 3, table 4 and table 5 result 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 value of catalytically cracked gasoline, can also obviously improve the density of propylene in the catalytic cracking liquefied gas simultaneously.
Table 1
| Project | Industry equilibrium catalyst MLC-500 |
| Metal content, ppm Ni/V Fe/Sb Ca | 9386/1665 6503/2673 1714 |
| Little index alive | 60 |
Table 2
| 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 |
| Tenor; 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 |
Table 3
| The embodiment numbering | Comparative Examples 4 | 18 | Comparative Examples 5 | Comparative Examples 5 | 19 | 20 | Comparative Examples 7 |
| Catalyzer | 100% poiser | 10％ZJ 1+ 90% poiser | 10％CB 1+ 90% poiser | 10％CB 2+ 90% poiser | 10％ZJ 2+ 90% poiser | 10％ZJ 3+ 90% poiser | 10％CB 3+ 90% poiser |
| Temperature of reaction, ℃ | 500 | 500 | 500 | 500 | 500 | 500 | 500 |
| Weight hourly space velocity, hour -1 | 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 |
| Water vapour add-on (being equivalent to the stock oil percent by weight) | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Material balance, weight %: | |||||||
| Dry gas | 1.60 | 1.55 | 1.60 | 1.70 | 1.52 | 1.47 | 1.56 |
| Liquefied gas | 18.04 | 20.85 | 21.03 | 21.37 | 21.94 | 20.58 | 20.76 |
| C 5 +Gasoline | 43.13 | 39.39 | 39.88 | 39.55 | 38.90 | 40.09 | 39.78 |
| Diesel oil | 17.17 | 17.97 | 17.04 | 17.10 | 17.72 | 17.46 | 17.11 |
| Heavy oil | 13.61 | 14.38 | 14.34 | 13.77 | 14.50 | 14.83 | 14.60 |
| Coke | 6.45 | 5.87 | 6.12 | 6.51 | 5.42 | 5.57 | 6.19 |
| Transformation efficiency, weight % | 69.23 | 67.65 | 68.62 | 69.13 | 67.77 | 67.71 | 68.30 |
| Liquid is received, weight % | 78.34 | 78.21 | 77.95 | 78.02 | 78.57 | 78.13 | 77.65 |
| Propylene, weight % | 5.07 | 7.12 | 6.65 | 6.45 | 7.64 | 7.14 | 6.67 |
| 100 * propylene/liquefied gas | 28.13 | 34.18 | 31.64 | 30.16 | 34.81 | 34.69 | 32.12 |
| Gasoline is formed, weight % | |||||||
| Alkane | 33.59 | 31.06 | 30.56 | 29.69 | 30.99 | 31.33 | 29.78 |
| Alkene | 23.89 | 24.64 | 24.54 | 25.4 | 24.45 | 24.86 | 24.93 |
| Naphthenic hydrocarbon | 8.26 | 8.45 | 8.26 | 8.2 | 8.00 | 7.98 | 8.5 |
| Aromatic hydrocarbons | 34.08 | 35.6 | 36.38 | 36.48 | 36.29 | 35.66 | 36.44 |
| RON (chromatography) | 87.1 | 89.1 | 88.9 | 89.2 | 89.6 | 89.8 | 89.0 |
| MON (chromatography) | 82.0 | 82.7 | 82.7 | 82.7 | 82.7 | 82.7 | 82.7 |
Table 4
| The embodiment numbering | 21 | 22 | 23 | 24 | 25 | 26 | 27 | 28 |
| Catalyzer | 12％ZJ 4+ 88% poiser | 10％ZJ 5+ 90% poiser | 8％ZJ 6+ 92% poiser | 18％ZJ 7+ 82% poiser | 10％ZJ 8+ 90% poiser | 15％ZJ 9+ 85% poiser | 12％ZJ 10+ 88% poiser | 6％ZJ 11+ 94% poiser |
| Reaction conditions | ||||||||
| 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 add-on (being equivalent to the stock oil percent by weight) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Liquefied gas, weight % | 21.33 | 21.63 | 22.04 | 22.68 | 20.92 | 21.36 | 20.86 | 20.91 |
| Propylene, weight % | 7.38 | 7.39 | 7.68 | 7.72 | 7.14 | 7.27 | 7.09 | 7.12 |
| 100 * propylene/liquefied gas | 34.61 | 34.15 | 34.84 | 34.02 | 34.15 | 34.02 | 34.01 | 34.05 |
| Gasoline olefin, weight % | 24.43 | 24.23 | 24.17 | 26.08 | 24.38 | 25.62 | 24.02 | 24.00 |
| RON-GC (chromatography) | 89.6 | 89.3 | 89.5 | 89.7 | 89.6 | 89.8 | 89.4 | 89.3 |
| MON-GC (chromatography) | 82.7 | 82.4 | 82.7 | 82.7 | 82.5 | 82.7 | 87.3 | 87.2 |
Table 5
| The embodiment numbering | 29 | 30 | 31 | 32 | 33 | 34 |
| Catalyzer | 6％ZJ 12+ 94% poiser | 4％ZJ 13+ 96% poiser | 4％ZJ 14+ 96% poiser | 10％ZJ 15+ 90% poiser | 12％ZJ 16+ 88% poiser | 8％ZJ 17+ 92% poiser |
| Reaction conditions | ||||||
| Temperature of reaction, ℃ | 520 | 520 | 490 | 510 | 490 | 500 |
| Weight hourly space velocity, hour -1 | 20 | 10 | 30 | 10 | 20 | 16 |
| Agent weight of oil ratio | 5.92 | 5.92 | 7.0 | 4.0 | 5.92 | 5.0 |
| Water vapour add-on (being equivalent to the stock oil percent by weight) | 5 | 5 | 5 | 10 | 10 | 10 |
| Liquefied gas, weight % | 21.31 | 21.75 | 22.12 | 21.18 | 22.14 | 20.83 |
| Propylene, weight % | 7.30 | 7.43 | 7.57 | 7.27 | 7.65 | 7.13 |
| 100 * propylene/liquefied gas | 34.25 | 34.17 | 34.24 | 34.32 | 34.56 | 34.25 |
| Gasoline olefin, weight % | 24.83 | 24.08 | 24.07 | 26.13 | 25.84 | 24.32 |
| RON-GC (chromatography) | 89.6 | 89.3 | 89.3 | 89.8 | 89.6 | 89.8 |
| MON-GC (chromatography) | 82.7 | 82.4 | 82.6 | 82.8 | 82.6 | 82.4 |
Claims (7)
1. catalyst aid that improves density of propylene in the catalytic cracking liquefied gas, it is characterized in that this auxiliary agent is by butt, form by the modified zsm-5 zeolite of 10～65 heavy %, the clay of 0～60 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, counts (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 binding agent and phosphorus additive are all in oxide compound.
2. according to the auxiliary agent of claim 1, described modified zsm-5 zeolite, its anhydrous chemical expression 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
xO
y(82～92) SiO
2
3. according to the auxiliary agent of claim 2, be characterised in that M wherein is Fe.
4. according to the auxiliary agent of claim 1, form by the modified zsm-5 zeolite of 20～50 heavy %, the clay of 20～50 heavy %, the inorganic oxide binder of 25～50 heavy % and the phosphorus additive of 5～15 heavy % by butt.
5. according to the auxiliary agent of claim 1, described clay is selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and the tired mixture that takes off in the stone one or more.
6. according to the auxiliary agent of claim 1, described inorganic oxide binder is selected from one or more mixture of pseudo-boehmite, aluminium colloidal sol, silicon-aluminum sol, water glass and phosphorus aluminium colloidal sol.
7. according to the auxiliary agent of claim 6, said 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049292B (en) * | 2009-10-27 | 2012-11-14 | 中国石油化工股份有限公司 | Methanol-to-gasoline catalyst and methanol-to-gasoline method |
| CN102847552A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Cracking aid for improving lower-carbon olefin concentration |
| CN101550352B (en) * | 2008-04-03 | 2013-01-09 | 中国石油化工股份有限公司 | Aromatizatian catalytic material and preparation method thereof |
| CN103007990A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN103007991A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5236880A (en) * | 1989-12-11 | 1993-08-17 | W. R. Grace & Co.-Conn. | Catalyst for cracking of paraffinic feedstocks |
| US20020049133A1 (en) * | 1999-03-02 | 2002-04-25 | Michael S. Ziebarth | High zeolite content and attrition resistant catalyst, methods for preparing the same and catalyzed processes therewith |
| CN1176020C (en) * | 2002-06-27 | 2004-11-17 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and transition metal |
-
2004
- 2004-12-28 CN CNB2004101028142A patent/CN100389175C/en active Active
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| CN101550352B (en) * | 2008-04-03 | 2013-01-09 | 中国石油化工股份有限公司 | Aromatizatian catalytic material and preparation method thereof |
| CN102049292B (en) * | 2009-10-27 | 2012-11-14 | 中国石油化工股份有限公司 | Methanol-to-gasoline catalyst and methanol-to-gasoline method |
| CN102847552A (en) * | 2011-06-30 | 2013-01-02 | 中国石油化工股份有限公司 | Cracking aid for improving lower-carbon olefin concentration |
| CN102847552B (en) * | 2011-06-30 | 2014-05-28 | 中国石油化工股份有限公司 | Cracking aid for improving lower-carbon olefin concentration |
| CN103007990A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN103007991A (en) * | 2011-09-22 | 2013-04-03 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN103007990B (en) * | 2011-09-22 | 2014-12-03 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN103007991B (en) * | 2011-09-22 | 2014-12-31 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN111760588A (en) * | 2020-07-10 | 2020-10-13 | 山西腾茂科技有限公司 | Yield-increasing propylene catalytic cracking auxiliary agent |
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