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CN1796494A - Method for cracking hydrocarbon oil - Google Patents

Method for cracking hydrocarbon oil Download PDF

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Publication number
CN1796494A
CN1796494A CN 200410102810 CN200410102810A CN1796494A CN 1796494 A CN1796494 A CN 1796494A CN 200410102810 CN200410102810 CN 200410102810 CN 200410102810 A CN200410102810 A CN 200410102810A CN 1796494 A CN1796494 A CN 1796494A
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China
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weight
heavy
phosphorus
auxiliary agent
additives
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CN 200410102810
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CN100497530C (en
Inventor
舒兴田
田辉平
蒋文斌
朱玉霞
罗一斌
唐立文
陈蓓艳
宋海涛
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CNB2004101028104A priority Critical patent/CN100497530C/en
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to AU2005321726A priority patent/AU2005321726B2/en
Priority to KR1020077017616A priority patent/KR101229756B1/en
Priority to JP2007548676A priority patent/JP5053098B2/en
Priority to RU2007129273/04A priority patent/RU2397811C2/en
Priority to PCT/CN2005/002338 priority patent/WO2006069535A1/en
Priority to EP05824020A priority patent/EP1867388A4/en
Priority to US11/813,056 priority patent/US20080308455A1/en
Priority to SG200908623-2A priority patent/SG158176A1/en
Publication of CN1796494A publication Critical patent/CN1796494A/en
Application granted granted Critical
Publication of CN100497530C publication Critical patent/CN100497530C/en
Priority to US12/813,110 priority patent/US20100311569A1/en
Priority to US13/565,145 priority patent/US8658024B2/en
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Abstract

本发明公开了一种烃油裂化方法，该方法包括在烃油裂化条件下，将烃油与一种含有助剂的催化剂混合物接触，然后回收裂化产物，所述助剂按干基计由10～65重％的改性ZSM－5分子筛、0～60重％的粘土、15～60重％的无机氧化物粘结剂、0.5～15重％的选自VIIIB族金属中的一种或几种的金属添加剂和2～25重％的磷添加剂组成，其中，所说的改性ZSM－5分子筛经磷和选自Fe、Co或Ni之一的金属改性，其无水化学表达式，以氧化物计为(0～0.3)Na2O·(0.5～5)Al2O3·(1.3～10)P2O5·(0.7～15)MxOy·(70～97)SiO2，x表示M的原子数，y表示满足M氧化态所需的一个数，所说的金属添加剂以氧化物计，磷添加剂以五氧化二磷计。该方法在增加催化裂化液化气产率和提高催化裂化汽油辛烷值的同时，可显著地提高液化气中的丙烯浓度。The invention discloses a hydrocarbon oil cracking method, which comprises the steps of contacting the hydrocarbon oil with a catalyst mixture containing an auxiliary agent under the condition of hydrocarbon oil cracking, and then recovering the cracked product. The auxiliary agent consists of 10 ~65% by weight of modified ZSM-5 molecular sieve, 0~60% by weight of clay, 15~60% by weight of inorganic oxide binder, 0.5~15% by weight of one or more selected from group VIIIB metals A metal additive and 2 to 25% by weight of a phosphorus additive, wherein the modified ZSM-5 molecular sieve is modified by phosphorus and a metal selected from Fe, Co or Ni, and its anhydrous chemical expression is, Calculated as oxide (0~0.3)Na 2 O·(0.5~5)Al 2 O 3 ·(1.3~10)P 2 O 5 ·(0.7~15)M x O y ·(70~97)SiO 2 , x represents the number of atoms of M, y represents a number required to satisfy the oxidation state of M, said metal additives are calculated as oxides, and phosphorus additives are calculated as phosphorus pentoxide. The method can significantly increase the propylene concentration in the liquefied gas while increasing the yield of the catalytic cracking liquefied gas and the octane number of the catalytic cracking gasoline.

Description

A kind of cracking method for hydrocarbon oil
Technical field
The invention relates to a kind of cracking method for hydrocarbon oil, the cracking method for hydrocarbon oil of further saying so and improving density of propylene in the catalytic cracking liquefied gas about a kind of.
Background technology
Propylene is important Organic Chemicals, and along with increasing rapidly of derivative demands such as polypropylene, the whole world is also all increasing year by year to the demand of propylene.Fluid catalytic cracking is to produce one of important production technique of light olefin and propylene.For most of catalytic cracking unit, for increasing light olefin yield and propylene, it is the otherwise effective technique approach that employing contains catalyzer or auxiliary agent with MFI structural zeolite.
USP3,758,403 early are disclosed in the method for adding the ZSM-5 zeolite in the catalytic cracking catalyst can improve the octane value of gasoline and increase C 3～C 4The productive rate of alkene.For example, add in containing the conventional catalyst of 10%REY behind 1.5,2.5,5 to 10% ZSM-5 zeolite, gasoline octane rating improves, the gain in yield of low-carbon alkene; Use also has same effect when containing the auxiliary agent of ZSM-5 zeolite.
USP 5,318, proposed the hydrocarbon conversion process process of the catalyzer formed less than 30 the zeolite with MFI structure based on a kind of large pore zeolite and silica alumina ratio in 696.This technology is produced stop bracket gasoline by improved catalytic cracking process, and increased low carbon olefine output, particularly propylene.
USP 5,997, disclose a large amount of methods of using the shape slective cracking auxiliary agents in the heavy feed stock catalytic cracking process in 728.Said auxiliary agent is made up of the ZSM-5 zeolite that adds 12～40% in the [amorphous, and system's reserve at least 10% makes the ratio of ZSM-5 in catalyzer surpass 3%.This method can additionally not increase aromatic production and loss gasoline yield when increasing substantially low-carbon alkene.
After the ZSM-5 zeolite carried out modification with P contained compound, its cracking activity stability can improve, and reduced the consumption of zeolite.
The zeolite that discloses a kind of phosphorous and rare earth among the CN 1049406C and had the MFI structure, its anhydrous chemical constitution is aRE 2O 3BNa 2OAl 2O 3CP 2O 5DSiO 2, a=0.01～0.25 wherein, b=0.005～0.02, c=0.2～1.0, d=35～120.This zeolite has excellent hydrothermal activity stability and good selectivity of light olefin when being used for the hydro carbons pyrolytic conversion.
Disclose a kind of catalyst for cracking that is used to produce low-carbon alkene among the CN 1034223C, formed by the clay of 0～70% (is benchmark with the catalyst weight), 5～99% inorganic oxide and 1～50% zeolite.Zeolite wherein is the mixture of the five-ring supersiliceous zeolite of the REY of 0～25 heavy % or the phosphorous and rare earth that type-Y high silicon zeolite and 75～100 weighs %.It is higher hydro-thermal activity stability, transformation efficiency and the C of catalyzer of active ingredient with the ZSM-5 zeolite that this catalyzer has 2 =～C 4 =Productive rate.
USP5 discloses the preparation method with the ZSM-5 zeolite catalyst of phosphorus modification in 110,776.Said phosphorus modifying process is that zeolite is dispersed in the P contained compound aqueous solution of pH value 2～6, then with matrix making beating, spray drying forming.The gained catalyzer does not increase dry gas and coke yield when improving gasoline octane rating.
USP6 discloses a kind of cracking catalyst of phosphorous modified ZSM-5 zeolite in 566,293.The preparation of said phosphorous modified ZSM-5 is that zeolite is dispersed in the P contained compound aqueous solution of pH value more than 4.5, and the phosphorus that makes zeolite-loaded at least 10 heavy % is (with P 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 and can not only increase the catalytic cracking liquefied gas yield effectively, improve the octane value of catalytically cracked gasoline, can also improve the cracking method for hydrocarbon oil of the density of propylene in the catalytic cracking liquefied gas simultaneously significantly.
The inventor finds, with disclosed phosphorous and modification MFI structural zeolite transition metal among the CN 1465527A is active component, further introducing an amount of transition metal additives is applied in the cracking method of hydrocarbon ils with an amount of made catalyst aid of phosphorus additive, 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 significantly.
Therefore, cracking method for hydrocarbon oil provided by the invention is under the cracking hydrocarbon oil condition, hydrocarbon ils is contacted with a kind of catalyst mixture that contains auxiliary agent, reclaim crackate then, described auxiliary agent is by the modified zsm-5 zeolite of butt by 10～65 heavy %, the clay of 0～60 heavy %, the inorganic oxide binder of 15～60 heavy %, 0.5～15 heavy % be selected from one or more metal additives in the VIIIB family metal and the phosphorus additive of 2～25 heavy % is formed, wherein, said modified zsm-5 zeolite is through phosphorus and be selected from Fe, one of Co or Ni's is metal-modified, its anhydrous chemical expression is counted (0～0.3) Na with oxide compound 2O (0.5～5) Al 2O 3(1.3～10) P 2O 5(0.7～15) M xO y(70～97) SiO 2, x represents the atomicity of M, and y represents to satisfy the required number of M oxidation state, and said metal additive is in oxide compound, and phosphorus additive is in Vanadium Pentoxide in FLAKES.
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 contact conditions comprises that the contact temperature is 400～650 ℃, is preferably 420～600 ℃ that 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 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.
Said auxiliary agent is by butt weight, preferred group become clay, 25～50 heavy % of modified zsm-5 zeolite, 10～45 heavy % of 20～50 heavy % inorganic oxide binder, 1～10 heavy % be selected from one or more metal additives in the VIIIB family metal and the phosphorus additive of 5～15 heavy %, the content of wherein said VIIIB family's metal additive and phosphorus additive does not comprise the content of transition metal and phosphorus in the ZSM-5 molecular sieve of modification.
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
Under the preferable case, said VIIIB family metal is selected from one or more among Fe, Co and the Ni, wherein more preferably Fe.
Described 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.
Described 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 the content that is included into said phosphorus additive.
Said 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.
Described VIIIB group 4 transition metal additive exists with their oxide compound, phosphoric acid salt, phosphite, subphosphate, the form of acid phosphate.
The various mineral compound of described transition metal and in the organic compound one or more can be soluble in water, also can be to be insoluble in water or water-fast compound.The example of transistion metal compound comprises oxide compound, oxyhydroxide, muriate, nitrate, vitriol, the phosphoric acid salt of transistion metal compound, organic compound of transition metal etc.Preferred transistion metal compound is selected from one or more in their muriate, nitrate, vitriol and the phosphoric acid salt.
VIIIB group 4 transition metal additive preferably adds transistion metal compound in the slurries in any step before the spray drying forming of auxiliary agent preparation process and introduces; Can certainly after the auxiliary agent spray drying forming, introduce by roasting behind dipping or the chemisorption transistion metal compound, comprise that the transistion metal compound aqueous solution floods or chemisorption is handled with containing with auxiliary agent, carry out solid-liquid separation (if necessary), drying and roasting then, wherein the 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 transition metal additives may reside in any position that may exist of auxiliary agent, as may reside in the inside, duct of zeolite, the surface of zeolite, may reside in the substrate material, can also be present in simultaneously in the surface and described substrate material of inside, duct, zeolite of zeolite, preferably be present in the substrate material.
Phosphorus additive exists with the form of phosphorus compound (as oxide compound, phosphoric acid salt, phosphite, subphosphate, the acid phosphate of phosphorus) in the said auxiliary agent.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.
Thereby, 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.
Said auxiliary agent, phosphorus compound described in its preparation method are selected from the various mineral compound of phosphorus and in the organic compound one or more.Described phosphorus compound can be soluble in water, also can be to be insoluble in water or water-fast phosphorus compound.The 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.
In the cracking method provided by the invention, described hydrocarbon ils is selected from various petroleum fractionss, and 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 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, Sinopec press 2002 publish), the 282nd～338 page existing catalytic cracking reaction-regeneration system rapidly and revivifier summarized.
Method provided by the invention, because the auxiliary agent that adopts is active component and adds an amount of VIIIB group 4 transition metal additive and an amount of phosphorus additive with phosphorous and modified zsm-5 zeolite transition metal, can improve in the catalytic cracking reaction process selectivity, thereby improve the density of propylene in the catalytic cracking liquefied gas significantly for propylene.
Embodiment
The following examples will be further described 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
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 said auxiliary agent in embodiment 1～19 explanation method provided by the invention.
Embodiment 1
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, 1.4 kilograms of (butt) kaolin and 0.65 kilogram of (butt) pseudo-boehmite, add 6.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 100 gram Fe 2O 3), 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, 28 heavy % kaolin, 27.5 heavy %Al 2O 3, 2.0 heavy %Fe additives are (with Fe 2O 3Meter) and 7.5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 1
Embodiment 2
Get 1.84 kilograms of (butt) A 1, 1.33 kilograms of (butt) kaolin and 0.98 kilogram of (butt) 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 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 250 gram Fe 2O 3), 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, 26.6 heavy % kaolin and 31.6 heavy %Al 2O 3With 5.0 heavy %Fe additives (with Fe 2O 3Meter) microballoon.
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, 25.3 heavy % kaolin, 30 heavy %Al 2O 3, 4.7 heavy %Fe additives are (with Fe 2O 3Meter), 5 heavy % phosphorus additives are (with P 2O 5Meter) auxiliary agent ZJ 2
Embodiment 3
Get 1.94 kilograms of (butt) A 1With 1.91 kilograms of (butt) 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 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 550 gram Fe 2O 3), 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 38.8 heavy %Al, 50.2 heavy %Al 2O 3With 11 heavy %Fe additives (with Fe 2O 3Meter) microballoon.
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, 45.1 heavy %Al 2O 3, 9.9 heavy %Fe additives are (with Fe 2O 3Meter) and 10 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 3
Embodiment 4
The preparation method is with embodiment 1, and different is, the kaolin consumption is 1.25 kilograms (butts), and with 1 liter of Co (NO 3) 2.6H 2The O aqueous solution (containing 250 gram CoO) replaces FeCl 3.6H 2The O aqueous solution makes and contains 35 heavy %A 1, 25 heavy % kaolin, 27.5 heavy %Al 2O 3, 5 heavy %Co additives (in CoO) and 7.5 weight % phosphorus additives are (with P 2O 5Meter) auxiliary agent ZJ 4
Embodiment 5
The preparation method is with embodiment 1, and different is, the kaolin consumption is 1.25 kilograms (butts), and with 1 liter of Ni (NO 3) 2.6H 2The O aqueous solution (containing 250 gram NiO) replaces FeCl 3.6H 2The O aqueous solution makes and contains 35 heavy %A 1, 25 heavy % kaolin, 27.5 heavy %Al 2O 3, 5 heavy %Ni additives (in NiO) and do not comprise in the modification MFI zeolite phosphorous 7.5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 5
Embodiment 6
Get ZJ 11 kilogram of auxiliary agent (butt) adds 10 liters of decationized Y sieve water and 157 gram 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, 25.9 heavy % kaolin, 25.4 heavy %Al 2O 3, 1.85 heavy %Fe additives are (with Fe 2O 3Meter) and 14.47 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 6
Embodiment 7
Get 1.75 kilograms of (butt) A 1, 1 kilogram of (butt) kaolin and 3.46 kg of water glass, add 5 kilograms of decationized Y sieve water making beating 120 minutes, stir and add 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 750 gram Fe 2O 3), 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, 20 heavy % kaolin, 2.5 heavy %Al 2O 3, 20 heavy %SiO 2, 15 heavy %Fe additives are (with Fe 2O 3Meter) and 7.5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 7
Embodiment 8
Method by embodiment 1 prepares auxiliary agent, is not both A 1Weight be 2.25 kilograms (butts), kaolinic weight is 0.9 kilogram (butt), makes to contain 45 heavy %A 1, 18 heavy % kaolin, 27.5 heavy %Al 2O 3, 2 heavy %Fe additives are (with Fe 2O 3Meter) and 7.5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 8
Embodiment 9
Get 1 kilogram of (butt) A 1, 1.85 kilograms of (butt) kaolin and 0.9 kilogram of (butt) 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 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 400 gram Fe 2O 3), the consumption of pH value 3.0 hydrochloric acid of slurries 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, 37 heavy % kaolin, 30 heavy %Al 2O 3, 8 heavy %Fe additives are (with Fe 2O 3Meter) and 5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 9
Embodiment 10
Method by embodiment 9 prepares auxiliary agent, is not both the A with identical weight 2Replace A 1, make and contain 20 heavy %A 2, 37 heavy % kaolin, 30 heavy %Al 2O 3, 8 heavy %Fe additives are (with Fe 2O 3Meter) and 5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 10
Embodiment 11
Get 1.25 kilograms of (butt) A 3, 1 kilogram of (butt) kaolin and 1.65 kilograms of (butt) 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 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 250 gram Fe 2O 3), the consumption of pH value 3.0 hydrochloric acid of slurries 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 25 heavy %A 3, 20 heavy % kaolin, 45 heavy %Al 2O 3, 5 heavy %Fe additives are (with Fe 2O 3Meter) and 5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 11
Embodiment 12
Get 2 kilograms of (butt) A 4, 0.75 kilogram of (butt) kaolin and 1.15 kilograms of (butt) 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 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 250 gram Fe 2O 3), the consumption of pH value 3.0 hydrochloric acid of slurries 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 40 heavy %A 4, 15 heavy % kaolin, 35 heavy %Al 2O 3, 5 heavy %Fe additives are (with Fe 2O 3Meter) and 5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 12
Embodiment 13
Get 2.89 kilograms of (butt) A 5With 1.4 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 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 105.5 gram Fe 2O 3), 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 57.89 heavy %A 8, 40 heavy %Al 2O 3With 2.11 heavy %Fe additives (with Fe 2O 3Meter) microballoon.
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 55 heavy %A then in 500 ℃ of following roastings 2 hours 5, 38 heavy %Al 2O 3, 2 heavy % FeAdditive is (with Fe 2O 3Meter) and 5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 13
Embodiment 14
Get 1.5 kilograms of (butt) A 6, 1.5 kilograms of (butt) kaolin and 0.9 kilogram of (butt) pseudo-boehmite, add 6.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 125 gram Fe 2O 3), 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 6, 30 heavy % kaolin, 30 heavy %Al 2O 3, 2.5 heavy %Fe additives are (with Fe 2O 3Meter) and 7.5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 1
Embodiment 15
Get 1.25 kilograms of (butt) A 7, 1 kilogram of (butt) kaolin and 1.65 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 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 250 gram Fe 2O 3), the consumption of pH value 3.0 hydrochloric acid of slurries 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 25 heavy %A 7, 20 heavy % kaolin, 45 heavy %Al 2O 3, 5 heavy %Fe additives are (with Fe 2O 3Meter) and 5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 15
Embodiment 16
Get 2.5 kilograms of (butt) A 8With 1.63 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 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 270 gram Fe 2O 3), 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 50 heavy %A 8, 44.6 heavy %Al 2O 3With 5.4 heavy %Fe additives (with Fe 2O 3Meter) microballoon.
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 45 heavy %A then in 500 ℃ of following roastings 2 hours 8, 40.1 heavy %Al 2O 3, 4.9 heavy %Fe additives are (with Fe 2O 3Meter) and 10 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 16
Embodiment 17
Method by embodiment 1 prepares auxiliary agent, is not both the A with identical weight 3Replace A 1, make and contain 35 heavy %A 3, 28 heavy % kaolin, 27.5 heavy %Al 2O 3, 2.0 heavy %Fe additives are (with Fe 2O 3Meter) and 7.5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 17
Embodiment 18
Method by embodiment 1 prepares auxiliary agent, is not both the A with identical weight 6Replace A 1, make and contain 35 heavy %A 6, 28 heavy % kaolin, 27.5 heavy %Al 2O 3, 2.0 heavy %Fe additives are (with Fe 2O 3Meter) and 7.5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 18
Embodiment 19
Method by embodiment 1 prepares auxiliary agent, is not both the A with identical weight 8Replace A 1, make and contain 35 heavy %A 8, 28 heavy % kaolin, 27.5 heavy %Al 2O 3, 2.0 heavy %Fe additives are (with Fe 2O 3Meter) and 7.5 weight % phosphorus additives (with P 2O 5Meter) auxiliary agent ZJ 19
The preparation of the reference auxiliary agent that uses in Comparative Examples 1～5 explanation control methods.
Comparative Examples 1
The explanation of this Comparative Examples contains modified zsm-5 zeolite (sample A 1), phosphorus additive, do not contain the preparation of the reference auxiliary agent of VIIIB metal additive.
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) reference auxiliary agent CB 1
Comparative Examples 2
The explanation of this Comparative Examples contains modified zsm-5 zeolite (sample A 1), do not contain the preparation of the reference auxiliary agent of VIIIB metal additive and phosphorus 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 2
Comparative Examples 3
This Comparative Examples illustrates the preparation of the reference auxiliary agent of conventional ZRP-5 zeolite.
Method by Comparative Examples 2 prepares auxiliary agent, and the ZRP-5 zeolite that is not both with same weight replaces A 1, make and contain 35 heavy %ZRP-5 zeolites, 30 heavy % kaolin and 35 heavy %Al 2O 3Reference auxiliary agent CB 3
Comparative Examples 4
This Comparative Examples illustrates the preparation of the reference auxiliary agent of conventional ZRP-5 zeolite and phosphorus additive.
Method by embodiment 1 prepares auxiliary agent, and the ZRP-5 zeolite that is not both with same weight replaces A 1, make and contain 35 heavy %ZRP-5 zeolites, 30 heavy % kaolin and 35 heavy %Al 2O 3Do not comprise in the ZRP-5 zeolite the reference auxiliary agent CB of phosphorous 5 heavy % phosphorus additives 4
Comparative Examples 5
The explanation of this Comparative Examples is with modified zsm-5 zeolite (sample A 1), the VIIIB metal additive, and the not preparation of the reference auxiliary agent of phosphor-included additive.
Get 1.75 kilograms of (butt) A 1, 1.5 kilograms of (butt) kaolin and 0.9 kilogram of (butt) pseudo-boehmite, add 6.2 kilograms of decationized Y sieve water and 2.79 kilograms of aluminium colloidal sols making beating 120 minutes, stir and add 1 liter of FeCl down 3.6H 2The aqueous solution of O (wherein contains 250 gram Fe 2O 3), the pH value 3.0 of slurries.Mixture is continued 45 fens kinds of making beating, the slurries that obtain 500 ℃ of temperature ins, are carried 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, 30 heavy %Al 2O 3, 5 heavy %Fe additives are (with Fe 2O 3Meter) reference auxiliary agent CB 5
Embodiment 20～38
Method provided by the invention in embodiment 20～38 explanation fixed fluidized-bed reactors.
Respectively with 30 gram ZJ 1-ZJ 19Under 800 ℃, 100% steam atmosphere condition, carry out 8 hours burin-in process.Get the ZJ through burin-in process of different amounts 1-ZJ 19Mix 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 6～11
The control methods of Comparative Examples 6～11 explanation fixed fluidized-bed reactors.
By the method among the embodiment 20 same stock oil is carried out catalytic cracking, different is that catalyst system therefor is respectively 100% industrial FCC equilibrium catalyst, CB 1～CB 5Mixture with industrial FCC equilibrium catalyst.Table 3 has provided catalyst system therefor mixture composition in the control methods, reaction conditions and reaction result.
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
From table 3, table 4 and table 5 as can be seen, 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 improve the density of propylene in the catalytic cracking liquefied gas simultaneously significantly.
Table 3
The embodiment numbering Comparative Examples 6 20 Comparative Examples 7 21 Comparative Examples 8 Comparative Examples 9 Comparative Examples 10 Comparative Examples 11
Catalyzer 100% poiser 10％ZJ 1+ 90% poiser 10％CB 1+ 90% poiser 10％ZJ 2+ 90% poiser 10％CB 2+ 90% poiser 10％CB 3+ 90% poiser 10％CB 4+ 90% poiser 10％CB 4+ 90% poiser
Temperature of reaction, ℃ 500 500 500 500 500 500 500 500
Air speed, hour -1 16 16 16 16 16 16 16 16
Agent weight of oil ratio 5.92 5.92 5.92 5.92 5.92 5.92 5.92 5.92
Water vapour (to stock oil), heavy % 0 0 0 0 0 0 0 0
Material balance, heavy %:
Dry gas 1.60 1.59 1.47 1.58 1.70 1.60 1.56 2.10
Liquefied gas 18.04 23.21 20.58 23.54 21.37 21.03 20.76 21.29
C 5 +Gasoline 43.13 37.30 40.09 38.36 39.55 39.88 39.78 38.60
Diesel oil 17.17 17.84 17.46 17.63 17.10 17.04 17.11 17.18
Heavy oil 13.61 13.96 14.83 13.25 13.77 14.34 14.60 13.82
Coke 6.45 6.10 5.57 5.64 6.51 6.12 6.19 7.01
Transformation efficiency, heavy % 69.23 68.20 67.71 69.11 69.13 68.62 68.30 69.00
Liquid is received, heavy % 78.34 78.36 78.13 79.53 78.02 77.95 77.65 77.07
Propylene, heavy % 5.07 8.41 7.14 8.57 6.87 6.65 6.77 6.91
Propylene/liquefied gas 28.13 36.23 34.69 36.41 32.16 31.64 32.62 32.47
Gasoline is formed, heavy %
Alkane 33.59 26.39 31.33 26.10 29.69 30.56 29.78 29.58
Alkene 23.89 26.35 24.86 25.27 25.4 24.54 24.93 25.51
Naphthenic hydrocarbon 8.26 8.99 7.98 9.22 8.2 8.26 8.5 8.33
Aromatic hydrocarbons 34.08 38.27 35.66 39.39 36.48 36.38 36.44 36.35
RON (chromatography) 87.1 89.4 89.8 89.5 89.2 88.9 89.0 89.4
MON (chromatography) 82.0 82.6 82.7 82.6 82.7 82.7 82.7 82.8
Table 4
The embodiment numbering 22 23 24 25 26 77 28 29
Catalyzer 10％ZJ 3+ 90% poiser 10％ZJ 4+ 90% poiser 10％ZJ 5+ 90% poiser 12％ZJ 6+ 88% poiser 10％ZJ 7+ 90% poiser 8％ZJ 8+ 92% poiser 15％ZJ 9+ 85% poiser 15％ZJ 10+ 85% poiser
Temperature of reaction, ℃ 500 500 500 500 500 500 500 500
Air speed, hour -1 16 16 16 16 16 16 16 16
Agent weight of oil ratio 5.92 5.92 5.92 5.92 5.92 5.92 5.92 5.92
Water vapour (to stock oil), heavy % 0 0 0 0 0 0 0 0
Material balance, heavy %:
Dry gas 1.60 1.62 1.45 1.56 1.52 1.41 1.69 1.71
Liquefied gas 23.46 24.22 23.58 25.28 22.18 22.26 24.49 23.73
C 5 +Gasoline 38.54 38.75 37.61 36.65 39.78 39.26 35.50 36.16
Diesel oil 17.49 16.89 17.82 17.31 17.38 17.67 18.55 18.29
Heavy oil 13.14 12.45 13.89 13.41 13.39 13.59 13.59 14.02
Coke 5.77 6.06 5.65 5.79 5.74 5.80 6.19 6.09
Transformation efficiency, heavy % 69.37 70.66 68.29 69.28 69.23 68.74 67.87 67.69
Liquid is received, heavy % 79.48 79.86 79.01 79.24 79.35 79.20 78.54 78.18
Propylene, heavy % 8.47 8.66 8.44 9.12 8.07 7.90 9.05 8.53
Propylene/liquefied gas 36.11 35.74 35.79 36.09 36.39 35.49 36.94 35.94
Gasoline is formed, heavy %
Alkane 25.85 25.06 24.87 26.37 26.85 24.26 28.07 28.36
Alkene 23.22 26.1 26.93 26.08 23.73 23.92 27.19 27.20
Naphthenic hydrocarbon 8.62 8.64 8.85 8.53 8.63 8.54 8.66 8.28
Aromatic hydrocarbons 42.14 40 39.36 39.02 40.67 41.23 36.09 36.17
RON-GC (chromatography) 90.0 89.9 89.5 89.6 89.9 89.5 89.7 89.6
MON-GC (chromatography) 82.7 82.8 82.6 82.8 82.8 82.7 82.7 82.5
Table 5
The embodiment numbering 30 31 32 33 34 35 36 37 38
Catalyzer 12％ZJ 11+ 88% poiser 10％ZJ 12+ 90% poiser 6％ZJ 13+ 94% poiser 10％ZJ 14+ 90% poiser 12％ZJ 15+ 88% poiser 4％ZJ 16+ 96% poiser 8％ZJ 17+ 92% poiser 8％ZJ 18+ 92% poiser 6％ZJ 19+ 92% poiser
Temperature of reaction, ℃ 500 500 510 500 490 520 490 500 520
Air speed, hour -1 16 16 10 16 20 10 20 30 10
Agent weight of oil ratio 5.0 4.5 7.0 5.92 5.0 6.5 5.5 7.0 6.5
Water vapour (to stock oil), heavy % 5 5 5 5 5 10 10 10 10
Liquefied gas, heavy % 23.41 23.06 24.62 22.78 23.78 22.38 22.56 24.19 23.56
Propylene, heavy % 8.41 8.33 9.03 8.15 8.58 7.99 8.06 8.79 8.49
Propylene/liquefied gas 35.91 36.12 36.68 35.79 36.09 35.70 35.71 36.34 36.04
Gasoline olefin, heavy % 23.82 23.42 26.1 26.91 26.18 23.61 23.81 27.25 27.81
RON-GC (chromatography) 90.1 90.1 89.9 89.7 89.6 89.8 89.5 89.8 89.7
MON-GC (chromatography) 82.8 82.5 82.8 82.6 82.7 82.7 82.6 82.8 82.7
Example 39-47
Method provided by the invention in embodiment 39～47 explanation riser reactors.
Respectively with ZJ 1-ZJ 5, ZJ 10, ZJ 11, 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 5, ZJ 10, ZJ 11, 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 12-16
In the Comparative Examples 12-16 explanation riser reactor, the control methods of using the reference auxiliary agent is described.
By the method among the embodiment 39 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, CB with industrial FCC equilibrium catalyst 3Mixture and CB with industrial FCC equilibrium catalyst 4Replace 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.
Table 6 and table 7 result further show, compare with the control methods of 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
The embodiment numbering Comparative Examples 12 39 Comparative Examples 13 40 Comparative Examples 14 41 Comparative Examples 15 Comparative Examples 16
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 5％CB 4+ 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, weight %
Dry gas 1.73 1.61 1.78 1.68 1.70 1.65 1.76 1.71
Liquefied gas 11.95 17.23 14.71 17.03 14.27 16.97 14.03 14.23
C 5+ gasoline 45.71 40.29 42.61 40.46 42.57 41.25 42.80 43.16
Diesel oil 17.09 17.14 17.31 17.30 17.83 17.18 17.88 17.28
Heavy oil 17.49 17.78 17.58 17.57 17.53 16.94 17.51 17.61
Coke 6.03 5.95 6.01 5.96 6.10 6.01 6.02 6.01
Transformation efficiency, weight % 65.42 65.08 65.11 65.13 64.64 65.88 64.61 65.11
Propylene, weight % 3.29 6.49 5.00 6.60 4.56 6.30 4.11 4.47
100 * propylene/liquefied gas 27.55 37.65 33.98 38.76 31.96 37.13 29.27 31.40
Gasoline is formed, weight %
Alkane 28.76 23.62 25.78 24.26 25.16 25.58 25.41 25.37
Alkene 40.23 41.56 41.19 40.37 41.85 40.07 42.67 42.09
Naphthenic hydrocarbon 8.44 8.13 8.57 8.86 8.72 8.12 8.14 8.51
Aromatic hydrocarbons 22.52 26.39 24.42 26.48 24.07 25.93 23.74 23.96
RON (actual measurement) 87.5 90.1 89.2 90.1 89.3 90.0 89.5 89.5
MON (actual measurement) 77.8 80.1 79.8 80.2 79.6 80.0 79.2 79.3
Table 7
The embodiment numbering 42 43 44 45 46 47
Catalyzer 5％ZJ 4+ 95% poiser 5％ZJ 5+ 95% poiser 12％ZJ 11+ 88% poiser 8％ZJ 14+ 92% poiser 3％ZJ 16+ 97% poiser 15％ZJ 10+ 85% poiser
Reaction times, second 2.5 2.8 1.5 3.5 3.0 3.0
Regeneration temperature, ℃ 695 670 670 695 670 670
Temperature of reaction, ℃ 490 500 500 510 515 495
Agent-oil ratio 6 5.0 4 5.5 5 6.5
Water vapour add-on (the weight % that is equivalent to stock oil) 10 10 5 15 0 10
Material balance, weight %
Dry gas 1.69 1.63 1.71 1.70 1.82 1.89
Liquefied gas 18.75 17.01 21.18 19.15 15.83 22.07
C 5 +Gasoline 39.28 40.36 35.17 40.73 42.41 35.31
Diesel oil 17.37 17.25 17.91 15.79 17.23 16.98
Heavy oil 16.71 17.84 18.01 16.52 16.70 17.53
Coke 6.20 5.91 6.02 6.11 6.01 6.22
Transformation efficiency, weight % 65.92 64.91 64.08 67.69 66.07 65.49
Propylene, weight % 7.10 6.32 8.40 7.29 5.85 8.44
100 * propylene/liquefied gas 37.87 37.15 39.68 38.05 36.98 38.25
Gasoline is formed, weight %
Alkane 27.61 24.31 23.16 26.46 24.31 27.51
Alkene 36.00 40.37 43.23 37.85 40.27 34.97
Naphthenic hydrocarbon 8.11 8.86 8.06 8.06 8.65 8.45
Aromatic hydrocarbons 28.28 26.42 25.52 27.63 26.74 29.06
RON (actual measurement) 90.1 90.1 90.5 89.2 90.1 90.1
MON (actual measurement) 80.0 80.2 80.4 80.4 79.8 80.4

Claims (15)

1.一种烃油裂化方法，其特征在于在烃油裂化条件下，将烃油与一种含有助剂的催化剂混合物接触，然后回收裂化产物，所述助剂按干基计由10～65重％的改性ZSM-5分子筛、0～60重％的粘土、15～60重％的无机氧化物粘结剂、0.5～15重％的选自VIIIB族金属中的一种或几种的金属添加剂和2～25重％的磷添加剂组成，其中，所说的改性ZSM-5分子筛经磷和选自Fe、Co或Ni之一的金属改性，其无水化学表达式，以氧化物计为(0～0.3)Na2O·(0.5～5)Al2O3·(1.3～10)P2O5·(0.7～15)MxOy·(70～97)SiO2，x表示M的原子数，y表示满足M氧化态所需的一个数，所说的金属添加剂以氧化物计，磷添加剂以五氧化二磷计。1. A method for cracking hydrocarbon oil, characterized in that under hydrocarbon oil cracking conditions, hydrocarbon oil is contacted with a catalyst mixture containing an auxiliary agent, and then the cracked product is recovered, and the auxiliary agent is calculated by 10 to 65% on a dry basis. % by weight of modified ZSM-5 molecular sieve, 0-60% by weight of clay, 15-60% by weight of inorganic oxide binder, 0.5-15% by weight of one or more metals selected from group VIIIB Metal additives and 2 to 25% by weight of phosphorus additives, wherein the modified ZSM-5 molecular sieve is modified by phosphorus and a metal selected from Fe, Co or Ni, and its anhydrous chemical expression is oxidized (0~0.3)Na 2 O·(0.5~5)Al 2 O 3 ·(1.3~10)P 2 O 5 ·(0.7~15)M x O y ·(70~97)SiO 2 , x represents the number of atoms of M, y represents a number required to satisfy the oxidation state of M, said metal additives are calculated as oxides, and phosphorus additives are calculated as phosphorus pentoxide. 2.按照权利要求1的方法，所述将烃油与含助剂的催化剂混合物接触的过程在固定床反应器、流化床反应器或移动床反应器中进行，反应温度为400～650℃、剂油比为1～25、重时空速为10～120小时-1。2. according to the method for claim 1, the described process that hydrocarbon oil is contacted with the catalyst mixture containing promoter is carried out in fixed bed reactor, fluidized bed reactor or moving bed reactor, and reaction temperature is 400～650 ℃ , The agent-oil ratio is 1-25, and the weight hourly space velocity is 10-120 hours -1 . 3.按照权利要求2的方法，反应温度为420～600℃、剂油比为3～20、重时空速为15～80小时-1。3. The method according to claim 2, wherein the reaction temperature is 420-600° C., the agent-oil ratio is 3-20, and the weight hourly space velocity is 15-80 hours −1 . 4.按照权利要求1的方法，所述将烃油与含助剂的催化剂混合物接触的过程在提升管反应器中进行，所述烃油裂化条件包括反应温度为400～650℃，剂油比为1～25，反应时间为0.5～15秒。4. according to the method for claim 1, the described process that hydrocarbon oil is contacted with the catalyst mixture containing promoter is carried out in riser reactor, and described hydrocarbon oil cracking condition comprises that reaction temperature is 400～650 ℃, agent-oil ratio 1 to 25, and the reaction time is 0.5 to 15 seconds. 5.按照权利要求4的方法，反应温度为420～600℃、剂油比为3～20、反应时间为0.5～10秒。5. according to the method for claim 4, reaction temperature is 420～600 ℃, agent-oil ratio is 3～20, and reaction time is 0.5～10 seconds. 6.按照权利要求1的方法，所述催化剂混合物中助剂的含量为1～30重量％。6. The method according to claim 1, wherein the content of the auxiliary agent in the catalyst mixture is 1 to 30% by weight. 7.按照权利要求6的方法，助剂的含量为3～20重量％。7. The method according to claim 6, the content of the auxiliary agent is 3-20% by weight. 8.按照权利要求1的方法，所述助剂组成为20～50重％的改性ZSM-5分子筛、10～45重％的粘土、25～50重％的无机氧化物粘结剂、1～10重％的选自VIIIB族金属中的一种或几种金属添加剂和5～15重％的磷添加剂8. according to the method for claim 1, described auxiliary agent is composed of the modified ZSM-5 molecular sieve of 20～50 weight %, the clay of 10～45 weight %, the inorganic oxide binding agent of 25～50 weight %, 1 ~10% by weight of one or more metal additives selected from Group VIIIB metals and 5-15% by weight of phosphorus additives 9.按照权利要求1的方法，所述改性ZSM-5分子筛的无水化学表达式，以氧化物计为(0～0.2)Na2O·(0.9～3.5)Al2O3·(1.5～7)P2O5·(0.9～10)MxOy·(82～92)SiO2。9. According to the method of claim 1, the anhydrous chemical expression of the modified ZSM-5 molecular sieve is (0～ 0.2 ) Na2O ·(0.9～3.5) Al2O3 ·(1.5 ~7)P 2 O 5 ·(0.9~10)M x O y ·(82~92)SiO 2 . 10.按照权利要求1或9的方法，其特征在于所述M为Fe。10. Process according to claim 1 or 9, characterized in that said M is Fe. 11.按照权利要求1的方法，所述VIIIB族金属选自Fe、Co和Ni中的一种或几种。11. The method according to claim 1, wherein said group VIIIB metal is selected from one or more of Fe, Co and Ni. 12.按照权利要求11的方法，所述VIIIB族金属为Fe。12. The method according to claim 11, said Group VIIIB metal being Fe. 13.按照权利要求1的方法，所述粘土选自高岭土、偏高岭土、硅藻土、海泡石、凹凸棒石、蒙脱石和累脱石中一种或几种的混合物。13. The method according to claim 1, wherein said clay is selected from the group consisting of one or more mixtures of kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and protonite. 14.按照权利要求1的方法，所述无机氧化物粘结剂选自拟薄水铝石、铝溶胶、硅铝溶胶、水玻璃和磷铝溶胶的一种或几种的混合物。14. The method according to claim 1, wherein the inorganic oxide binder is selected from one or more mixtures of pseudo-boehmite, alumina sol, silica-alumina sol, water glass and phosphoralumina sol. 15.按照权利要求14的方法，所述的无机氧化物粘结剂为拟薄水铝石、铝溶胶和磷铝溶胶中的一种或几种的混合物。15. The method according to claim 14, wherein the inorganic oxide binder is one or a mixture of pseudo-boehmite, aluminum sol and phosphoraluminum sol.
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JP2007548676A JP5053098B2 (en) 2004-12-28 2005-12-28 Catalyst and method for cracking hydrocarbons
RU2007129273/04A RU2397811C2 (en) 2004-12-28 2005-12-28 Cracking catalyst and method of cracking hydrocarbons using said catalyst
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US12/813,110 US20100311569A1 (en) 2004-12-28 2010-06-10 Catalyst and a method for cracking hydrocarbons
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