CN100351345C - Method for catalytic cracking petroleum hydrocarbon - Google Patents
Method for catalytic cracking petroleum hydrocarbon Download PDFInfo
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- CN100351345C CN100351345C CNB2004101028119A CN200410102811A CN100351345C CN 100351345 C CN100351345 C CN 100351345C CN B2004101028119 A CNB2004101028119 A CN B2004101028119A CN 200410102811 A CN200410102811 A CN 200410102811A CN 100351345 C CN100351345 C CN 100351345C
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Abstract
The present invention discloses a catalytic cracking method of petroleum hydrocarbons, which comprises: hydrocarbon oil contacts a catalytic mixture containing an auxiliary agent under cracking conditions; cracked products are recovered. The method is characterized in that the auxiliary agent is prepared from 10 to 65 wt% of modified ZSM-5 molecular sieve, 0 to 60 wt% of clay, 15 to 70 wt% of inorganic oxide binding agent (measured by an oxide) and 2 to 25 wt% of phosphorus additive agent (measured by P2O5) which are measured according to a dry basis, wherein the modified ZSM-5 molecular sieve is modified by phosphorus and a metal selected from one of 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 method can be used for greatly improving the concentration of propene in liquid gas while increasing the yield of catalytically cracked liquid gas and improving the octane number of catalytically cracked gasoline.
Description
Technical field
The invention relates to a kind of petroleum hydrocarbon catalytic cracking process, the petroleum hydrocarbon catalytic cracking process of further saying so and adopting auxiliary agent 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
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.
USP5 discloses a kind of ZSM-5 zeolite with the phosphorus modification in 171,921.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.
USP5 discloses 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 472,594.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 and can not only increase the catalytic cracking liquefied gas yield effectively, improve the octane value of catalytically cracked gasoline, can also improve the petroleum hydrocarbon catalytic cracking process of 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 the phosphorus additive of appropriate level, made catalyst aid is applied in the catalytic cracking process of petroleum hydrocarbon, can not only increase the productive rate of catalytic cracking liquefied gas effectively, improve the octane value of catalytically cracked gasoline, can also improve the density of propylene in the catalytic cracking liquefied gas simultaneously greatly.
Petroleum hydrocarbon catalytic cracking process provided by the invention, this method is included under the cracking conditions, hydrocarbon ils is contacted with a kind of catalyst mixture that contains auxiliary agent, reclaim crackate, 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 is in oxide compound, and said phosphorus additive is with P
2O
5Meter.
Catalyst cracking method provided by the invention, described hydrocarbon ils can carry out in various reactors with contacting of described catalyst mixture.Described reactor types can be riser reactor, fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor, and described reactor is a riser reactor under the preferable case.
Described cracking conditions comprises that temperature of reaction is 400-650 ℃, is preferably 420-600 ℃, and agent-oil ratio (weight ratio of catalyzer and hydrocarbon ils) is 1-25, is preferably 3-20.
For fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor, described contact conditions comprises that also weight hourly space velocity is 10～120 hours
-1, be preferably 15～80 hours
-1And for riser reactor, described contact conditions comprises that also the reaction times is 0.5～15 second, is preferably 0.5～10 second.
In the catalyst cracking method provided by the invention, the described catalyst mixture that contains auxiliary agent mainly is made up of cracking catalyst and auxiliary agent, and content separately is conventionally known to one of skill in the art.In general, in this catalyst mixture, the content of cracking catalyst is 70～99 heavy %, be preferably 80～95 heavy %, and the content of auxiliary agent is 1～30 heavy %, be preferably 3～20 heavy %.
In the described catalyst mixture, the kind of cracking catalyst and consist of conventionally known to one of skill in the artly can be various cracking catalyst, as the various cracking catalyst that contain zeolite.
In the described catalyst mixture, auxiliary agent is made up of 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 is in oxide compound, and said phosphorus additive is with P
2O
5Meter.
Described auxiliary agent 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 %.The content of said phosphorus additive does not comprise the content of phosphorus in the modified zsm-5 zeolite in the auxiliary agent 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
In the described auxiliary agent, clay is conventionally known to one of skill in the art, 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.
In the described auxiliary agent, 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, be included in the content of said phosphorus additive.
Described auxiliary agent can adopt any method in the existing cracking catalyst technology of preparing that comprises spray drying forming to prepare by zeolite, clay, inorganic oxide binder, and the present invention has no particular limits it.Wherein 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 described substrate material of inside, duct, zeolite of zeolite.
Described phosphorus compound is 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, the phosphorus aluminium colloidal sol.
In the catalyst cracking method provided by the invention, 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.
In the catalyst cracking method provided by the invention, described catalyst mixture can disposablely use, still, and under the preferable case, with the regeneration of described catalyst mixture and recycle.The regeneration of described catalyst mixture is exactly that with the process that the coke in the catalyst mixture is burnt, this process is to well known to a person skilled in the art general knowledge in oxygen-containing atmosphere (being generally air).For example, in general, described regeneration temperature is 600～770 ℃, preferred 650～730 ℃.When described hydrocarbon ils carries out in fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor with contacting of catalyst mixture, can feed oxygen-containing atmosphere regeneration in position.When described hydrocarbon ils carries out in riser reactor with contacting of catalyst mixture, can directly utilize existing reaction-regeneration system to finish.In " (residual oil complete processing " (Li Chunnian writes, and Sinopec press published in 2002), the 282nd～338 page existing catalytic cracking reaction-regeneration system rapidly and revivifier summarized.
Catalyst cracking method provided by the invention when increasing the catalytic cracking liquefied gas yield and improving the catalytically cracked gasoline octane value, can improve the density of propylene in the liquefied gas greatly.
Embodiment
The following examples will give further instruction 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.
The preparation of used auxiliary agent in embodiment 1～17 explanation method provided by the invention.
Embodiment 1
Get 1.84 kilograms of (butt) A
1, 1.58 kilograms of (butt) kaolin (special-purpose kaolin of the cracking catalyst that kaolin company in Suzhou produces, solid content 78 weighs %) 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, 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 making beating 45 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 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 making beating 45 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 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 making beating 45 minutes, 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 making beating 45 minutes, 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
2O
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 making beating 30 minutes, 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 making beating 45 minutes, 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 making beating 45 minutes, 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 making beating 45 minutes, 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 making beating 30 minutes, 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 making beating 45 minutes, 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 making beating 45 minutes, 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
That uses in this Comparative Examples explanation contrast cracking method only contains modified ZSM-5 (sample A
1), the not preparation of the reference auxiliary agent of phosphor-included additive.
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 making beating 45 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 35 heavy %A
1, 30 heavy % kaolin and 35 heavy %Al
2O
3Reference auxiliary agent CB
1
Comparative Examples 2
The ZRP-5 zeolite that uses in this Comparative Examples explanation contrast cracking method is the preparation of the reference auxiliary agent of active ingredient.
Method by Comparative Examples 1 prepares auxiliary agent, and the ZRP-5 zeolite that is not both with same weight replaces A
1, make and contain 35 heavy %ZRP-5 zeolites, 30 heavy % kaolin and 35 heavy %Al
2O
3Reference auxiliary agent CB
2
Comparative Examples 3
The ZRP-5 zeolite that uses in this Comparative Examples explanation contrast cracking method is the preparation of the reference auxiliary agent of active ingredient, phosphor-included additive.
Method by embodiment 1 prepares auxiliary agent, and the ZRP-5 zeolite that is not both with same weight replaces A
1, make and contain 35 heavy %ZRP-5 zeolites, 30 heavy % kaolin 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
Embodiment 18～34 is an example with the fixed fluidized-bed reactor, and petroleum hydrocarbon catalytic cracking process 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
Comparative Examples 4～7 is an example with the fixed fluidized-bed reactor, and the petroleum hydrocarbon catalytic cracking process 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
1Mixture, CB with industrial FCC equilibrium catalyst
2Mixture and CB with industrial FCC equilibrium catalyst
3Mixture with industrial FCC equilibrium catalyst.Table 3, provided in the control methods catalyst system therefor mixture and formed reaction conditions and reaction result.
From the result of table 3, table 4 and table 5 as can be seen, compare with the method that adopts the reference auxiliary agent, method 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 |
Embodiment 35～41
Embodiment 35～41 is an example with the riser reactor, and petroleum hydrocarbon catalytic cracking process provided by the invention is described.
Respectively with ZJ
1-ZJ
3, ZJ
8, ZJ
9, ZJ
14, ZJ
16Under 800 ℃, 100% steam atmosphere condition, carry out 8 hours burin-in process.Get the ZJ through burin-in process of different amounts respectively
1-ZJ
3, ZJ
8, ZJ
9, ZJ
14, ZJ
16Mix with MLC-500 industry equilibrium catalyst.Catalyst mixture is fed small-sized catalytic cracking riser reactor continuously, feed stock oil and water vapour shown in stock oil shown in the table 2 or the table 2 simultaneously continuously, described decompressed wax oil is contacted with catalyst mixture, catalyzer is separated with reaction product, isolated catalyzer enters revivifier regeneration, and the catalyst recirculation after the regeneration is returned riser reactor.
Table 6 and table 7 have provided the catalyst system therefor mixture and have formed (being percent by weight), reaction conditions and reaction result.
Comparative Examples 8～11
Comparative Examples 8～11 is an example with the riser reactor, and the petroleum hydrocarbon catalytic cracking process that uses the reference auxiliary agent is described.
By the method among the embodiment 35 same stock oil is carried out catalytic cracking, different is that the catalyst system therefor mixture is used 100% industrial FCC equilibrium catalyst, CB respectively
1Mixture, CB with industrial FCC equilibrium catalyst
2Mixture and CB with industrial FCC equilibrium catalyst
3Replace with the mixture of industrial FCC equilibrium catalyst.Table 6 has provided catalyst system therefor mixture composition in the control methods, reaction conditions and reaction result.
The result of table 6 and table 7 further shows, compare with the method for using the reference auxiliary agent, method 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 6
| Example number | Comparative Examples 8 | 35 | Comparative Examples 9 | 36 | Comparative Examples 10 | 37 | Comparative Examples 11 |
| Catalyzer | 100% poiser | 5％ZJ 1+ 95% poiser | 5％CB 1+ 95% poiser | 5％ZJ 2+ 95% poiser | 5％CB 2+ 95% poiser | 5％ZJ 3+ 95% poiser | 5％CB 3+ 95% poiser |
| Reaction times, second | 2.8 | ||||||
| Regeneration temperature, ℃ | 670 | ||||||
| Temperature of reaction, ℃ | 500 | ||||||
| Agent-oil ratio | 5.0 | ||||||
| The water vapour add-on | The 10 weight % that are equivalent to described stock oil | ||||||
| Material balance, heavy % | |||||||
| Dry gas | 1.73 | 1.78 | 1.70 | 1.69 | 1.76 | 1.75 | 1.71 |
| Liquefied gas | 11.95 | 14.71 | 14.27 | 14.84 | 14.03 | 14.34 | 14.23 |
| C 5+ gasoline | 45.71 | 42.61 | 42.57 | 42.65 | 42.80 | 42.70 | 43.16 |
| Diesel oil | 17.09 | 17.31 | 17.83 | 17.15 | 17.88 | 17.37 | 17.28 |
| Heavy oil | 17.49 | 17.58 | 17.53 | 17.65 | 17.51 | 17.79 | 17.61 |
| Coke | 6.03 | 6.01 | 6.10 | 6.02 | 6.02 | 6.05 | 6.01 |
| Transformation efficiency, heavy % | 65.42 | 65.11 | 64.64 | 65.20 | 64.61 | 64.84 | 65.11 |
| Propylene, heavy % | 3.29 | 5.00 | 4.56 | 4.91 | 4.11 | 5.14 | 4.47 |
| 100 * propylene/liquefied gas | 27.55 | 33.98 | 31.96 | 34.62 | 29.27 | 34.25 | 31.40 |
| Gasoline is formed, heavy % | |||||||
| Alkane | 28.76 | 25.78 | 25.16 | 25.4 | 25.41 | 25.90 | 25.37 |
| Alkene | 40.23 | 41.19 | 41.85 | 41.48 | 42.67 | 41.38 | 42.09 |
| Naphthenic hydrocarbon | 8.44 | 8.57 | 8.72 | 8.51 | 8.14 | 8.47 | 8.51 |
| Aromatic hydrocarbons | 22.52 | 24.42 | 24.07 | 24.56 | 23.74 | 24.11 | 23.96 |
| RON (actual measurement) | 87.5 | 89.2 | 89.3 | 89.3 | 89.5 | 89.1 | 89.5 |
| MON (actual measurement) | 77.8 | 79.8 | 79.6 | 79.8 | 79.2 | 79.7 | 79.3 |
Table 7
| Example number | 38 | 39 | 40 | 41 |
| Catalyzer | 10％ZJ 8+ 90% poiser | 3％ZJ 14+ 97% poiser | 5％ZJ 16+ 95% poiser | 15％ZJ 9+ 85% poiser |
| Reaction times, second | 2.5 | 1.5 | 3.5 | 3.0 |
| Regeneration temperature, ℃ | 695 | 670 | 695 | 670 |
| Temperature of reaction, ℃ | 490 | 500 | 510 | 510 |
| Agent-oil ratio | 6 | 4 | 5 | 6.5 |
| Water vapour add-on (the weight % that is equivalent to stock oil) | 10 | 5 | 15 | 0 |
| Material balance, weight % | ||||
| Dry gas | 1.71 | 1.66 | 1.81 | 1.85 |
| Liquefied gas | 19.81 | 15.27 | 16.18 | 21.02 |
| C 5+ gasoline | 39.95 | 40.80 | 43.40 | 39.22 |
| Diesel oil | 16.61 | 18.01 | 15.96 | 16.03 |
| Heavy oil | 15.73 | 18.31 | 16.38 | 15.39 |
| Coke | 6.19 | 5.95 | 6.27 | 6.49 |
| Transformation efficiency, weight % | 67.66 | 63.68 | 67.66 | 68.58 |
| Propylene, weight % | 7.12 | 5.45 | 5.66 | 7.59 |
| 100 * propylene/liquefied gas | 35.92 | 35.72 | 35.01 | 36.12 |
| Gasoline is formed, weight % | ||||
| Alkane | 25.86 | 23.12 | 25.87 | 26.39 |
| Alkene | 37.35 | 43.06 | 39.48 | 35.17 |
| Naphthenic hydrocarbon | 8.48 | 8.57 | 8.06 | 8.64 |
| Aromatic hydrocarbons | 28.31 | 25.22 | 26.56 | 29.78 |
| RON (actual measurement) | 89.0 | 90.0 | 89.2 | 89.0 |
| MON (actual measurement) | 79.9 | 79.8 | 80.1 | 80.3 |
Claims (11)
1. petroleum hydrocarbon catalytic cracking process, be included under the cracking conditions, hydrocarbon ils is contacted with a kind of cracking catalysis agent composition that contains auxiliary agent, reclaim crackate, it is characterized in that described 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 is in oxide compound, and said phosphorus additive is with P
2O
5Meter; Said cracking catalysis agent composition is made up of cracking catalyst and auxiliary agent, and the content that wherein with the mixture weight is the benchmark auxiliary agent is the heavy % of 1-30.
2. according to the method for claim 1, the described process that hydrocarbon ils is contacted with the catalyst mixture that contains auxiliary agent is carried out in fixed-bed reactor, fluidized-bed reactor or moving-burden bed reactor, and temperature of reaction is that 400-650 ℃, agent-oil ratio are that 1-25, weight hourly space velocity are 10-120 hour
-1
3. according to the method for claim 2, temperature of reaction is that 420-600 ℃, agent-oil ratio are that 3-20, weight hourly space velocity are 15-80 hour
-1
4. according to the method for claim 1, the described process that hydrocarbon ils is contacted with the catalyst mixture that contains auxiliary agent is carried out in riser reactor, and described cracking hydrocarbon oil condition comprises that temperature of reaction is 400-650 ℃, and agent-oil ratio is 1-25, and the reaction times is 0.5-15 second.
5. according to the method for claim 4, temperature of reaction is that 420-600 ℃, agent-oil ratio are 3-20, reaction times to be 0.5-10 second.
6. according to the method for claim 1, the content of auxiliary agent is the heavy % of 3-20 in the catalyst mixture.
7. according to the method for claim 1, described auxiliary agent is made up of 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 % in butt.
8. according to the method for claim 1, the anhydrous chemical expression of the modified zsm-5 zeolite described in the auxiliary agent 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
9. according to the method for claim 1 or 8, it is characterized in that described M is Fe.
10. according to the method for 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.
11. according to the method for 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.
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| CN104492474B (en) * | 2015-01-14 | 2017-01-11 | 任丘市华北石油科林环保有限公司 | Catalytic cracking production increasing low carbon olefin auxiliary and preparation method thereof |
| CN106179470A (en) * | 2016-08-08 | 2016-12-07 | 青岛惠城环保科技股份有限公司 | A kind of catalytic cracking improves the preparation method of octane number auxiliary agent |
| CN107868675B (en) * | 2016-09-23 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of method and catalytic cracking inert carrier auxiliary agent of catalytic cracking |
| CN107971032B (en) * | 2016-10-21 | 2019-12-27 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent for improving gasoline octane number barrel and preparation method thereof |
| CN108047051B (en) * | 2017-12-12 | 2020-05-08 | 万华化学集团股份有限公司 | Application and method of compound molecular sieve catalyst in catalytic cracking treatment of aniline tar |
| CN114425432B (en) * | 2020-10-29 | 2023-07-11 | 中国石油化工股份有限公司 | Cracking catalyst, preparation method and application |
| CN114749208B (en) * | 2021-01-11 | 2023-07-14 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
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 |
-
2004
- 2004-12-28 CN CNB2004101028119A patent/CN100351345C/en active Active
Patent 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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