CN103566962B - A kind of multi-functional catalyst composition - Google Patents

A kind of multi-functional catalyst composition Download PDF

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CN103566962B
CN103566962B CN201210262943.2A CN201210262943A CN103566962B CN 103566962 B CN103566962 B CN 103566962B CN 201210262943 A CN201210262943 A CN 201210262943A CN 103566962 B CN103566962 B CN 103566962B
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weight
potassium
catalyst composition
mesoporous silica
alumina materials
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CN103566962A (en
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杨雪
王子军
朱玉霞
陈振宇
张书红
罗一斌
汪燮卿
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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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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

A kind of multi-functional catalyst composition, by weight percentage, described catalyst composition comprises: 1% ~ 50% mesoporous silica-alumina materials, 1% ~ 40% gasification reactivity component, 1% ~ 60% cracking activity component, 0% ~ 70% clay and 5% ~ 97% heat-resistant inorganic oxide matrix, wherein, described mesoporous silica-alumina materials has the phase structure of boehmite, taking the anhydrous chemical expression of oxide weight as (0-0.3) Na2O·（40-90）Al2O3·（10-60）SiO2, specific area is 200-400m2/ g, pore volume is 0.5 ~ 2.0mL/g, and average pore size is 8 ~ 20nm, and most probable aperture is 5 ~ 15nm. This catalyst composition can reduce the gasification temperature that cracking hydrocarbon oil gasification transforms.

Description

A kind of multi-functional catalyst composition
Technical field
The present invention relates to a kind of catalysis of the coke gasification anabolic process for petroleum hydrocarbon cracking process and cracking generationComposition, in particular, relates to one and utilizes thermal cracking and/or catalytic cracking process processing to process petroleum hydrocarbon raw material production gentlyMatter fuel, the coke gasification simultaneously under gasifying agent participates in, process being produced is many merits of the process of hydrogen or synthesis gasCan catalyst composition.
Background technology
At present, when catalyzed cracking processing heavy, inferior feedstock oil, catalytic cracking process itself and catalyst have been proposed to chooseWar, the processing of inferior heavy oil on-catalytic, comprises that delayed coking, fluid coking, flexicoking etc. come into one's own day by day. But coking workSkill exists the high and low quality coke of coke yield to be difficult to the problem of utilizing, and delayed coking can produce a large amount of low value-added stoneOil coke, therefore petroleum resources are not efficiently utilized.
The coke part burning that the fluid coking of Exxon Neftegas Limited's exploitation and flexicoking technique produce provides and isSystem heat, remainder adopts air or oxygen, steam etc. to produce and have certain low heat value in high temperature (900 DEG C of left and right) gasificationCoal gas. This technique adopts high-temperature gasification on the one hand, and energy consumption is higher, on the other hand CO and H in institute's producing coal gas2Content lower,Calorific value is lower, and its added value is also very low.
, feedstock oil that colloid/asphalt content less higher containing saturated hydrocarbons is the good raw material of catalytic cracking, adopts traditionCatalyzed cracking processing mode in producing liquefied gas, gasoline, diesel oil, also produce a certain amount of coke, this part coke existsIn regenerative system, burning provides the heat for maintaining the certain reaction temperature of system. In regenerative system, passing into a certain amount of water steamsGas as gasifying agent can be in burning by-product part CO, H2, this part synthesis gas can be used for doing Fischer-Tropsch through processingSynthetic unstripped gas.
Add catalyst can reduce the activation energy of gasification reaction in gasification, reduce gasification temperature, reduce gasifying agentAddition, adjust the composition of synthesis gas. Alkali and alkaline earth metal ions is conventional gasifying catalyst, in Cracking catalyst, addsAdd the gasification that a certain amount of alkali and alkaline earth metal ions can promote deposit coke on catalyst. Public in CN200810246526.2Cloth a kind of alkali metal containing of cracking and gasification function and catalyst of alkaline-earth metal of having concurrently, this catalyst is containing 35% ~ 60% planBoehmite, 2% ~ 10% aluminium colloidal sol, 20% ~ 49.5% kaolin, 5% ~ 30% the alkali metal in oxide and alkaline earth goldBelong to, this catalyst has the optimization function of the distribution of cracking hydrocarbon oil product and gasification reaction available gas productive rate.In CN200910078392.2, announce a kind of coke transfer agent, comprised 50% ~ 80% kaolin, 10% ~ 39.5% binding agentWith 10% ~ 30% alkali and alkaline earth metal ions in oxide, the wherein mass ratio of boehmite and aluminium colloidal sol in binding agentFor (1.2 ~ 6): 1, the atomic ratio of alkali and alkaline earth metal ions is (0.05 ~ 0.8): 1, this catalyst is urged catalysis heavy crudeChange the cracking gasification of catalytic coke simultaneously. CN200910143623.3 has announced a kind of inferior heavy oil cracking and gasifying catalyst, bagDraw together carrier, binding agent, gasification reactivity component and cracking activity component, wherein gasification reactivity component is alkali and alkaline earth metal ions,Taking catalyst total amount as benchmark, oxide content is 2% ~ 30%, the atomic ratio of alkali metal and alkaline-earth metal be (0.05 ~1.1): 1, cracking activity component is the shape-selective molecular sieve of silica alumina ratio between 20 ~ 200.
The gasification temperature of above-mentioned existing catalyst is higher, all carries out gasification reaction at 860 DEG C, for urging of alkali metal containingFormed material, under high-temperature water heat condition, in catalyst alkali-metal loss more serious, for coming containing the catalyst of molecular sieveSay, in the high-temperature water thermal environment more than 800 DEG C, the rapid avalanche of framework of molecular sieve can occur, activity reduces rapidly.
Summary of the invention
The technical problem to be solved in the present invention is to provide one and is applicable to petroleum hydrocarbon cracking conversion and promotes coke gasificationCatalyst composition, to overcome the in use high problem of gasification temperature of prior art catalyst composition.
The invention provides a kind of for processing the cracking gasification catalyst composition of petroleum hydrocarbon, with described cracking gasification catalysis groupThe butt weight of compound is benchmark, and according to weight percent meter, described catalyst composition comprises mesoporous in butt 1% ~ 50%Silica-alumina material, in the cracking activity component of butt 1% ~ 60%, in 1% ~ 40% gasification reactivity component of butt, in butt0% ~ 70% clay and in 5% ~ 97% heat-resistant inorganic oxide matrix of butt; Wherein, described mesoporous silica-alumina materialsThere is the phase structure of boehmite, taking the anhydrous chemical expression of oxide weight as (0-0.3) Na2O·（40-90）Al2O3·（10-60）SiO2, specific area is 200-400m2/ g, pore volume is 0.5 ~ 2.0mL/g, average pore size is 8 ~ 20nm,Can several apertures be 5 ~ 15nm.
The present invention also provides a kind of preparation method of described composition, comprise by mesoporous silica-alumina materials, cracking activity component,Gasification reactivity component, clay and heat-resistant inorganic oxide matrix mix making beating, and spraying is dried the step with roasting.
Described mesoporous silica-alumina materials (the present invention is also called for short mesoporous material) can be according to the side announcing in CN1565733ALegal system is standby, comprises the following steps: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, the pH value of plastic terminal is 7-11; Then according to SiO2:Al2O3=1:(0.6-9) weight ratio add silicon source, aging 1-10 hour at room temperature to 90 DEG C, willGained solid sediment carries out ion-exchange with ammonium, makes the content that contains sodium oxide molybdena in the mesoporous silica-alumina materials of sodium not higher than 0.2%Weight, wherein mesoporous silica-alumina materials (butt): ammonium salt: H2O=1：（0.1-1）：（10-30）。
Described mesoporous silica-alumina materials is acid-treated mesoporous silica-alumina materials preferably, can by according to the method described above for example according toCN1261217C(CN1565733A) mesoporous silica-alumina materials that prepared by claim 1 ~ 6 or the disclosed method of embodiment 1-5 is usedAcid treatment obtains, and its processing method is is 1:5-30:0.03-0.3 by mesoporous silica-alumina materials, water and inorganic acid according to weight ratioRatio is mixed, and contacts at least 0.2 hour, preferably 0.2 ~ 10 hour.
Preferred, described mesoporous silica-alumina materials is acid-treated mesoporous silica-alumina materials, this acid-treated mesoporous Si-AlMaterial is made by the method comprising the following steps: the mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, starchedLiquid, then gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, make in described mesoporous silica-alumina materialsSodium oxide content not higher than 0.2 % by weight, wherein, the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acidWeight ratio is 1:5-30:0.03-0.3. The described mesoporous silica-alumina materials without ion-exchange can be prepared by the following method: willAluminium source and aqueous slkali at room temperature to 85 DEG C in and plastic, the pH value of plastic terminal is 7-11; Then according to SiO2:Al2O3=1:The weight ratio of 0.6-9 adds silicon source, and aging 1-10 hour at room temperature to 90 DEG C, obtains colloid admixture, by described colloidMixture filters the sediment (filter cake) obtaining and is the described mesoporous silica-alumina materials without ion-exchange, or by above-mentioned filtrationAfter the drying precipitate obtaining and/or roasting, obtain product and be the described mesoporous silica-alumina materials without ion-exchange, or willDescribed colloid admixture is dry/or roasting after the product that obtains be the described mesoporous silica-alumina materials without ion-exchange. InstituteStating room temperature and can be 5 ~ 40 DEG C, for example, can be 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C or 35 DEG C.
Described gasification reactivity component comprises at least one of alkali metal and/or alkali earth metal. Described gasOne or more in the optional material that contains alkali metal and/or alkali earth metal certainly of change active component, for example, be selected fromPotassium hydroxide, potash, potassium oxide, potassium nitrate, potassium sulfate, potassium dihydrogen phosphate, potassic feldspar, green bean rock, alunite, trachyte,Potassium-bearing shale, phosphorus potassium ore, containing potassium siltstone, have the principal phase of XRD shown in Fig. 1 peak the chloride containing potassium material, alkaline-earth metal,One or more in the phosphate of the nitrate of alkaline-earth metal, the sulfate of alkaline-earth metal, alkaline-earth metal, described alkaline earth goldGenus is one or more in beryllium, magnesium, calcium, strontium, barium.
Preferably, described gasification reactivity component comprises potassium, contains or alkali-free earth metal; Oxygen in described gasification reactivity componentThe content of changing potassium is 2 % by weight ~ 100 % by weight, and the content of alkaline earth oxide is 0-98 % by weight, preferred, described potassium oxideContent can be 10 % by weight ~ 90 % by weight, the mol ratio of alkaline earth oxide and potassium oxide is 1:9 ~ 1:0.2. Described gasChange active component and can be selected from potassium hydroxide, potash, potassium oxide, potassium nitrate, potassium sulfate, potassium dihydrogen phosphate, potassic feldspar, mung beanRock, alunite, trachyte, potassium-bearing shale, phosphorus potassium ore, containing potassium siltstone, have the principal phase of XRD shown in Fig. 1 peak containing potassium materialIn one or more, or also comprise nitrate, the alkaline-earth metal of chloride, the alkaline-earth metal of alkaline-earth metal sulfate,One or more in the phosphate of alkaline-earth metal; In order to solve the serious problem of potassium lost, described is excellent containing potassium active componentElect as have the principal phase of XRD shown in Fig. 1 peak containing potassium material. Employing have the principal phase of XRD shown in Fig. 1 peak containing potassium material as gasificationActive component, can further improve the gasification efficiency of catalyst composition, reduces the loss of potassium, and can improve catalyst compositionCracking activity.
The described potassium material that contains with the principal phase of XRD shown in Fig. 1 peak comprises potassium oxide, alkaline earth oxide and sialComponent, wherein, comprises 8 % by weight ~ 40 % by weight potassium oxides, alkaline earth oxide and potassium oxide mol ratio 1:9 ~ 1:0.2, all the otherFor sial component, SiO2/Al2O3Mol ratio be 1:10 ~ 10:1. Preferably, the described potassium that contains with the principal phase of XRD shown in Fig. 1 peakIn material, the content of potassium oxide is 10 % by weight ~ 30 % by weight, taking the content of butt sial component as 40 % by weight ~ 89 % by weight,Alkaline earth oxide and potassium oxide mol ratio 1:5 ~ 1:0.5, SiO2/Al2O3Mol ratio be 1:3 ~ 3:1.
The peak of XRD principal phase shown in the described Fig. 1 of having containing 2 θ angles, principal phase peak in the XRD thing phasor of potassium material be respectively 21 °,29 ° and 35 °.
Can preparing according to following steps containing potassium material of the peak of XRD principal phase shown in the described Fig. 1 of having: potassium-containing compound, alkaline earthMetallic compound and sial component are beaten into wet feed, be then dried into siccative, then obtain after roasting, sintering temperature be 900 DEG C ~1150 DEG C, roasting time 1 ~ 10h; Described potassium-containing compound is to be selected from one in potassium oxide, potassium hydroxide, potash, potassium nitrateKind or several, described alkaline earth metal compound is for being selected from alkaline earth oxide, alkaline earth metal carbonate, alkaline earth nitrateIn one or more. Described sial component preferably includes the crystal aluminosilicate mineral with layer structure. Described sial groupDivide and can be selected from kaolin, imvite, rectorite, attapulgite, sepiolite, illite, diatomite, aluminium colloidal sol, LudoxOne or more, wherein aluminium colloidal sol, Ludox do not use separately.
Described cracking activity constituent element can be selected from Y zeolite, have the one in molecular sieve, the beta-molecular sieve of MFI structureOr multiple. Described Y zeolite is for example one or more in REY, REUSY, USY, HY, REHY. Described MFI dividesSon sieve is for example one or more in ZSM-5, ZRP, ZSP. Described beta-molecular sieve can be phosphorus or metal-modified pointSon sieve.
Described clay can be the conventional clay in this area for example, described clay can be selected from kaolin, sepiolite,One or more in attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil, hydrotalcite; More preferablyFor being selected from one or more in kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone.
Cracking gasification catalyst composition provided by the invention contains except described mesoporous silica-alumina materials, cracking activity groupPoint, heat-resistant inorganic oxide matrix beyond gasification reactivity component, clay, the kind of described heat-resistant inorganic oxide is without specialRequirement, can be the conventional heat-resistant inorganic oxide matrix in this area, be preferably aluminium oxide, silica, titanium oxide, magnesia,One or more in zirconia, thorium oxide and beryllium oxide and their predecessor. Described heat-resistant inorganic oxide forerunnerOne or more in thing for example aluminium colloidal sol, Ludox, phosphorus aluminium glue, boehmite, silicon-aluminum sol. Described heat-resisting inorganic oxideThing matrix can add with heat-resistant inorganic oxide precursor in the preparation at catalyst composition, then passes through roasting, heat-resisting inorganicOxide precursor transforms and generates heat-resistant inorganic oxide, also can first be prepared into heat-resisting inorganic oxygen with heat-resistant inorganic oxide precursorCompound, then in the preparation process of catalyst composition, the form with heat-resistant inorganic oxide adds. Wherein the temperature of roasting is logicalOften, lower than 800 DEG C, be generally 400 ~ 750 DEG C. When described heat-resistant inorganic oxide matrix has attachment function, conventionally also becomeBinding agent, for example, binding agent can be one or more in aluminium colloidal sol, Ludox, boehmite, phosphorus aluminium glue.
Cracking gasification catalyst composition provided by the invention can also contain gold while being used for residual oil cracking-gasification group technologyBelong to trapping agent, by butt, the content of described metal traps is no more than 20 % by weight of catalyst composition, and preferably, this metal is caughtCollection agent is free on outside described mesoporous silica-alumina materials. Invention to the kind of described metal traps without particular/special requirement, can be for catchingCollection V, Ni, Fe, Ca etc. pollute the conventional metal traps of the component of metal, and under preferable case, described metal traps is oxygenChange the precursor of rare earth and/or rare earth oxide. More preferably in situation, the precursor metal traps of described rare earth oxide is chlorinationOne or more in rare earth, carbonated rare earth and rare earth hydrate. Wherein, rare earth element can be lanthanum, cerium, praseodymium, neodymium, promethium, samariumWith one or more in europium. In the present invention, the mode of entrance of metal agent for capturing can be in mesoporous silica-alumina materials, gasification reactivity groupPoint, clay mixes when making beating and introduces with ionic species or complex form. If introduce heat-resisting nothing in carbon monoxide-olefin polymericMachine oxide, can also be deposited on metal traps in described inorganic oxide in advance by coprecipitation. This metal trappingAgent can be with mesoporous silica-alumina materials in same particle, also can be in different particles.
The preparation method of described catalyst composition provided by the invention, the method generally includes following steps:
(1) prepare mesoporous silica-alumina materials;
Described mesoporous silica-alumina materials can be by following A) ~ C) either method preparation:
A) according to the method for the announcement of claim 1 ~ 6 in CN1565733A or CN1261217C or embodiment 1 ~ 5The mesoporous silica-alumina materials that preparation is described;
B) will be according to A) mesoporous silica-alumina materials prepared of described method is according to mesoporous silica-alumina materials, water and inorganic acid=1:5-The weight ratio of 30:0.03-0.3 is mixed, and contacts at least 0.2 hour described mesoporous silica-alumina materials of preparation;
C) will mix making beating with water, obtain slurries without the mesoporous silica-alumina materials of ammonium exchange, then by gained slurries and inorganicAcid contact at least 0.2 hour at room temperature to 100 DEG C, obtains sodium oxide content not higher than the mesoporous silica-alumina materials of 0.2 % by weight,Wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:5-30:0.03-0.3; This is excellentIn the preparation process of the mesoporous silica-alumina materials of choosing, without carrying out ammonium exchange, can not produce ammonia nitrogen waste water, make this catalyst compositionPreparation process relatively environmental protection and cost lower. In addition, in the preparation process of described mesoporous silica-alumina materials, only need to use oneInferior inorganic acid carries out ion-exchange can obtain the mesoporous silica-alumina materials of sodium oxide content lower than 0.2 % by weight, thereby has reduced lifeProduce cost and improved production efficiency;
(2) by the described mesoporous silica-alumina materials obtaining in step (1), cracking activity component, gasification reactivity component, clay,Heat-resistant inorganic oxide matrix and water mix making beating, then spray be dried, roasting 2 ~ 10h at 400 ~ 799 DEG C. Preferably, the described mesoporous silica-alumina materials obtaining in step (1), gasification reactivity component are mixed to making beating and obtain the first slurries, by crackingActive component, clay, binding agent mixes making beating, obtains the second slurries, then the first slurries and the second slurries is mixed to making beating, thenSpray dry, at 500 ~ 800 DEG C roasting 2 ~ 10h.
Gasification reactivity component described in step (2) comprises alkali metal and/or alkaline-earth metal, is preferably the thing that comprises potassiumMatter, this material contains or alkali-free earth metal. Described containing potassium material for example potassium hydroxide, potash, potassium oxide, potassium nitrate, sulphurAcid potassium, potassium dihydrogen phosphate, potassic feldspar, green bean rock, alunite, trachyte, potassium-bearing shale, phosphorus potassium ore, containing potassium siltstone, haveThe principal phase of XRD shown in Fig. 1 peak containing one or more in potassium material. In the time that described gasification reactivity component contains alkaline-earth metalWait, can add the compound of alkaline-earth metal, the chloride of for example alkaline-earth metal, sulfate, nitrate, carbonate, oxide,One or more in hydroxide, described alkaline-earth metal is one or more in beryllium, magnesium, calcium, strontium, barium, preferably calcium and/Or magnesium. Described preferably have the principal phase of XRD shown in Fig. 1 peak containing potassium material, it can be prepared according to following steps: containing potassium chemical combinationThing, alkaline earth metal compound and sial component are beaten into wet feed, are then dried into siccative, then obtain after roasting, sintering temperatureBe 800 DEG C ~ 1150 DEG C, roasting time 1 ~ 10h; Described potassium-containing compound is for being selected from potassium oxide, potassium hydroxide, potash, nitric acidOne or more in potassium, described alkaline earth metal compound is for being selected from alkaline earth oxide, alkaline earth metal carbonate, alkaline earth goldOne or more in genus nitrobacter can be for example calcium oxide, calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, magnesia, carbonOne or more in acid magnesium, magnesium chloride, magnesium nitrate, magnesium sulfate. Silica and alumina molar ratio in described sial componentFor 1:10 ~ 10:1, be preferably 1:3 ~ 3:1. Described sial component contains silicon and aluminium element, can be selected from clay, silica, oxygenOne or more in SiClx precursor, aluminium oxide, alumina precursor, are preferably clay. Described in preparation, there is XRD master shown in Fig. 1Containing in potassium substance process of phase peak, after being mixed with alkaline-earth metal and/or alkaline components, sial component obtains institute through roastingThe gasification reactivity component of stating, and then with mesoporous silica-alumina materials, cracking activity component, clay, heat-resistant inorganic oxide and waterMix making beating.
In cracking provided by the invention gasification catalyst composition preparation method, described clay can be commonly used for this areaClay, under preferable case, can be selected from kaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, soapOne or more in stone, boron-moisten soil, hydrotalcite; More preferably be selected from kaolin, diatomite, sepiolite, attapulgite, illiteracy de-One or more in stone and tired de-stone.
In cracking gasification catalyst composition preparation process provided by the invention, add heat-resistant inorganic oxide matrix, describedHeat-resistant inorganic oxide matrix can be heat-resistant inorganic oxide precursor and/or heat-resistant inorganic oxide. Described is heat-resisting inorganicThe kind of oxide, without particular/special requirement, can be the conventional heat-resistant inorganic oxide in this area, be preferably aluminium oxide, silica,One or more in titanium oxide, magnesia, zirconia, thorium oxide and beryllium oxide. Heat-resistant inorganic oxide or heat-resisting inorganic oxygenCompound precursor is commonly referred to binding agent when having adhesive property, described binding agent, and for example aluminium colloidal sol, Ludox, plan are thinOne or more in diaspore, phosphorus aluminium glue. In preparation process, can add heat-resistant inorganic oxide precursor, then through roastingBurn, heat-resistant inorganic oxide precursor conversion is heat-resistant inorganic oxide, also can first be prepared into heat-resistant inorganic oxide precursorHeat-resistant inorganic oxide, then in the preparation process of catalyst composition, the form with heat-resistant inorganic oxide adds.
In cracking provided by the invention gasification catalyst composition preparation method, by mesoporous silica-alumina materials, gasification reactivity component,The order that clay, heat-resistant inorganic oxide matrix mix making beating does not have particular/special requirement, for example, described raw material can be made respectivelyStandby slurries, then mix prepared slurries; Can first mesoporous silica-alumina materials be mixed with clay, and then with other componentMix making beating; Or gasification reactivity component is mixed to making beating with clay, and then mix making beating with other component.
In the time that catalyst composition of the present invention contains metal traps, in the present invention, the introducing mode of metal agent for capturing canIn the time that mesoporous silica-alumina materials, gasification reactivity component, cracking activity component, clay mix making beating with ionic species or complex compound shapeFormula is introduced, and also the form with precipitation after above-mentioned several component spray drying formings can introduced. If in catalyst combinationIn thing, introduce heat-resistant inorganic oxide matrix, can also in advance metal traps be deposited on to described inorganic oxygen by coprecipitationIn compound. Under preferable case, by butt, the content of described metal traps is no more than 20 % by weight of catalyst composition. ThisBright to the kind of described metal traps without particular/special requirement, can pollute for trapping V, Ni, Fe, Ca etc. component conventional of metalsMetal traps, under preferable case, described metal traps is the precursor of rare earth oxide and/or rare earth oxide. More preferably feelingsUnder condition, the precursor of described rare earth oxide is one or more in rare earth chloride, carbonated rare earth and rare earth hydrate. Wherein,Rare earth element can be one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium.
Catalyst composition provided by the invention, by using described mesoporous material, can reduce gasification temperature; Can beUnder low gasification temperature, obtain the higher intensity of making charcoal, obtain higher density of hydrogen. By mesoporous silica-alumina materials and gasification reactivityComponent is carried out effective combination and can greatly improve the coke gasification efficiency of catalyst; The inventor finds unexpectedly simultaneously, usesThe mesoporous silica-alumina materials without ion-exchange of preparing in CN1565733A mixes making beating with water, obtains slurries, then with inorganic acidMix, the mesoporous silica-alumina materials making at least 0.2 hour this ad hoc approach of room temperature to 100 DEG C exchange replaces conventional ammonium to hand overChange or catalyst composition that mesoporous silica-alumina materials that method for removing Na that ammonium exchange and inorganic acid combine obtains makes, have betterCatalytic coke vaporization ability, reduce gasification temperature, improve yield of light oil. Catalyst composition of the present invention is for heavy crudeWhen cracking-gasification integral process of hydrocarbon, gasification result is good, and gasification temperature is low, has such as heavy oil transformation of stronger petroleum hydrocarbonAbility. Especially when described gasification reactivity component be have the principal phase of XRD shown in Fig. 1 peak containing potassium material, not only gasification resultGood, gasification temperature is low, and has stronger hydrocarbon oil conversion ability, and gasification reactivity component runs off few.
Brief description of the drawings
Fig. 1 is the XRD thing phasor containing potassium active component of the present invention.
Fig. 2 is that the X-ray of the mesoporous silica-alumina materials that obtains of mesoporous silica-alumina materials of the present invention and traditional ammonium switching method spreads outPenetrate collection of illustrative plates, wherein, curve 1 is the spectrum of the mesoporous silica-alumina materials obtaining through twice ammonium exchange processing described in CN1565733ALine, curve 2 is spectral lines of the mesoporous silica-alumina materials that obtains of Preparation Example 4.
Detailed description of the invention
Provided by the invention for processing the cracking gasification catalyst composition of heavy petroleum hydrocarbon, this catalytic cracking composition containsThere are mesoporous silica-alumina materials, cracking activity component, gasification reactivity component, clay, heat-resistant inorganic oxide matrix, with butt weight hundredProportion by subtraction meter, described catalyst composition comprises: 1% ~ 50% mesoporous silica-alumina materials in butt, 1% ~ 60% cracking in butt is livedProperty component, 1% ~ 40% gasification reactivity component in butt, resistance in butt of 0% ~ 70% clay in butt and 5% ~ 97%Hot inorganic oxide matrix; Preferably, by weight percentage, described catalyst composition comprises: 2 % by weight ~ 60 % by weight are mesoporousSilica-alumina material, the gasification reactivity component of 5 % by weight ~ 40 % by weight, the cracking activity component of 5 ~ 50 % by weight, 0 % by weight ~ 60 % by weightClay and the heat-resistant inorganic oxide matrix of 10 % by weight ~ 70 % by weight. More preferably, described catalyst composition comprises: 5 % by weight ~30 % by weight mesoporous silica-alumina materials, the gasification reactivity component of 10 % by weight ~ 35 % by weight, the cracking activity component of 10 ~ 35 % by weight, 5The heat-resistant inorganic oxide matrix of the clay of % by weight ~ 45 % by weight and 10 % by weight ~ 40 % by weight.
Wherein, described mesoporous silica-alumina materials can, according to the method preparation of announcing in CN1565733A, specifically comprise following stepRapid: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, the pH value of plastic terminal is 7-11; Then according to SiO2:Al2O3The weight ratio of=1:0.6-9 adds silicon source, and aging 1-10 hour at room temperature to 90 DEG C, by gained solid sediment ammoniumCarry out ion-exchange, make the content that contains sodium oxide molybdena in the mesoporous silica-alumina materials of sodium not higher than 0.2% weight, wherein mesoporous Si-AlMaterial (butt): ammonium salt: H2O=1：（0.1-1）：（10-30）。
Mesoporous silica-alumina materials obtained above, preferably through peracid treatment, described acid treatment comprises mesoporous by after ammonium exchangeSilica-alumina material and inorganic acid contact at least 0.2 hour at room temperature to 100 DEG C, and the temperature of described contact is 30-80 DEG C, is preferably40-70 DEG C; The time of contact is 0.2-2 hour, is preferably 0.3-1.5 hour, more preferably 0.5-1 hour.
Described mesoporous silica-alumina materials is acid-treated mesoporous silica-alumina materials preferably, more preferably, and described acid-treated JieHole silica-alumina material is made by the method comprising the following steps: the mesoporous silica-alumina materials without ion-exchange is mixed with water making beating,Obtain slurries, then gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, make described mesoporous Si-AlSodium oxide content in material is higher than 0.2 % by weight, wherein, and the described mesoporous silica-alumina materials without ion-exchange, water and nothingThe weight ratio of machine acid is 1:5-30:0.03-0.3. In order better to realize object of the present invention, under preferable case, described withoutThe weight ratio of the mesoporous silica-alumina materials of ion-exchange and water and inorganic acid is 1:6-20:0.05-0.2, is further preferably 1:8-15:0.07-0.16. The present invention is to the kind of described inorganic acid without particular/special requirement, and conventional inorganic acid all can be realized the present inventionObject, under preferable case, the inorganic acid using is selected from one or more in sulfuric acid, hydrochloric acid and nitric acid. The present invention is to instituteState mode that slurries contact with inorganic acid without particular/special requirement, they can be mixed with random order, for example can be by inorganic acidJoin in slurries and mix, also slurries can be joined in inorganic acid and mix, wherein, preferred hybrid mode isInorganic acid is joined in slurries and mixed. In the present invention, the condition that described slurries contact with inorganic acid can be conventionalIon-exchange condition. For the present invention, under preferable case, the temperature of described contact is 30-80 DEG C, is preferably 40-70 DEG C; ContactTime be 0.2-2 hour, be preferably 0.3-1.5 hour, more preferably 0.5-1 hour. Described mesoporous without ion-exchangeThe weight ratio of silica-alumina material and water and inorganic acid is 1:6-20:0.05-0.2, is further preferably 1:8-15:0.07-0.16.
In the present invention, in the weight ratio of the mesoporous silica-alumina materials without ion-exchange, water and inorganic acid, described withoutThe mesoporous silica-alumina materials weight of ion-exchange is the weight in butt. In the present invention, refer to 800 in the weight of buttDEG C condition under the weight of roasting after 1 hour.
In the present invention, described mesoporous silica-alumina materials preferably has boehmite crystal phase structure, its x-ray diffraction patternSpectrum is as shown in the curve 2 of Fig. 2. And, in described mesoporous silica-alumina materials, in the anhydrous chemical expression of oxide weightFor: (0-0.2) Na2O·（40-90）Al2O3·（10-60）SiO2。
In the present invention, the described silica-alumina material without ion-exchange can be the sediment obtaining after filtering, and also canBe dried and/or roasting after the mesoporous silica-alumina materials that obtains.
A kind of described silica-alumina material preparation method without ion-exchange: by aluminium source and aqueous slkali at room temperature to 85 DEG CIn and plastic, the pH value of plastic terminal is 7-11; Then according to SiO2:Al2O3The weight ratio of=1:0.6-9 adds silicon source, in chamberTemperature, to aging 1-10 hour at 90 DEG C, is then filtered and is precipitated thing (filter cake). The sediment that this filtration obtains can be used as notThrough the silica-alumina material of ion-exchange, or be dried and/or roasting after as the described silica-alumina material without ion-exchange.
In the preparation process of mesoporous silica-alumina materials of the present invention, described aluminium source can be in the preparation technology of mesoporous silica-alumina materialsThe conventional various aluminium source using, for example can be for being selected from one or more in aluminum nitrate, aluminum sulfate or aluminium chloride.
In the preparation process of mesoporous silica-alumina materials of the present invention, described silicon source can be in the preparation technology of mesoporous silica-alumina materialsThe conventional various sial that use can be for example that silica gel, waterglass, sodium metasilicate, silicon tetraethyl, silica, Ludox and silicon are solidifyingAt least one in glue.
In the preparation process of mesoporous silica-alumina materials of the present invention, described aqueous slkali can be the aqueous slkali of various routines, for exampleCan be one or more in ammoniacal liquor, potassium hydroxide solution, sodium aluminate solution and sodium hydroxide solution.
According to the present invention, although described aluminium source, silicon source and aqueous slkali can be fitted separately from the above-mentioned material of enumeratingLocal selection, but in common described aluminium source, aqueous slkali and silicon source, having at least a kind of is the raw material containing sodium, thereby ensures soThe described mesoporous silica-alumina materials without ion-exchange of preparation has the meso-hole structure of appropriate size. One according to the present invention is excellentChoosing embodiment, described aluminium source is selected from one or more in aluminum nitrate, aluminum sulfate and aluminium chloride, described alkali be selected from ammoniacal liquor,One or more in potassium hydroxide, NaOH and sodium metaaluminate, described silicon source is selected from waterglass, sodium metasilicate, silicon tetraethylWith one or more in silica, and in aluminium source, alkali and silicon source wherein, have at least a kind of for containing sodium raw materials.
In the present invention, described without in the mesoporous silica-alumina materials of ion-exchange taking the sodium content of sodium oxide molybdena as 0.5-15% by weight. And in described catalyst composition of the present invention, the institute of preparing without the mesoporous silica-alumina materials of ion-exchange described in adoptingIn the preferred mesoporous silica-alumina materials of stating, be generally below 0.2 % by weight in the sodium content of sodium oxide molybdena.
Provided by the invention for processing the cracking gasification catalyst composition of petroleum hydrocarbon, preferred, described gasification is livedProperty component comprise potassium, containing or alkali-free earth metal, taking the weight of described gasification reactivity component as benchmark, in oxide weight,In described gasification reactivity component, the content of potassium oxide is 2 ~ 100 % by weight, and the content of alkaline-earth metal is 0-98 % by weight. Described gasChanging active component can be any active component containing potassium, contains or alkali-free earth metal, containing such as hydrogen-oxygen of potassium active componentChange potassium, potash, potassium nitrate, potassium sulfate, potassium dihydrogen phosphate, potassic feldspar, green bean rock, alunite, trachyte, potassium-bearing shale, phosphorusPotassium ore, containing potassium siltstone, have the principal phase of XRD shown in Fig. 1 peak containing one or more in potassium material. Wherein, preferred toolHave the principal phase of XRD shown in Fig. 1 peak containing potassium material, in oxide, wherein the content of potassium is 8 % by weight ~ 40 % by weight.
The present invention has preparing according to following steps containing potassium material of the principal phase of XRD shown in Fig. 1 peak: potassium-containing compound, alkaline earthMetallic compound and sial component are beaten into wet feed, be then dried into siccative, then obtain after roasting, sintering temperature be 800 DEG C ~1150 DEG C, roasting time 1 ~ 10h; In order better to realize object of the present invention, the active higher gasification reactivity component of preparation, excellentUnder selection condition, sintering temperature is 900 DEG C ~ 1100 DEG C, and roasting time is 2 ~ 8h. The present invention to described preparation containing described in potassium materialThe making beating mode of pulling an oar by potassium-containing compound, alkaline earth metal compound and sial component, can be by them to appoint without particular/special requirementMeaning order is mixed, for example, three kinds of materials can be pulled an oar respectively, and then three kinds of slurries are mixed to making beating, also can be by three kinds of thingsThe first mechanical mixture of matter, adding a certain amount of deionized water making beating, and the solid content of controlling slurries is 15% ~ 50%.
Preparation described in the present invention have the principal phase of XRD shown in Fig. 1 peak containing in potassium substance process, described containing potassium chemical combinationOne or more in the optional autoxidation potassium of thing, potassium hydroxide, potash, potassium nitrate, described alkaline earth metal compound can be selected fromOne or more in alkaline earth oxide, alkaline earth metal carbonate, alkaline earth nitrate. Described in the present invention, there is Fig. 1Shown in XRD principal phase peak containing in the preparation of potassium gasification substance active component, described sial component can be selected from any layerThe crystal aluminosilicate mineral of shape structure, as kaolin, imvite, rectorite, attapulgite, illite, sepiolite and diatomOne or more in soil, aluminium colloidal sol, Ludox.
The preparation method of described catalyst composition provided by the invention, one preferred embodiment, comprises the following steps:
(1) mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtain slurries, then by gained slurries and nothingMachine acid contact at least 0.2 hour at room temperature to 100 DEG C, obtains sodium oxide content not higher than the mesoporous silicon aluminium of 0.2 % by weightMaterial, wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:5-30:0.03-0.3;
(2) potassium-containing compound, alkaline earth metal compound and sial component are mixed to making beating, be then dried into siccative, then800 DEG C ~ 1150 DEG C preferably 900 DEG C ~ 1100 DEG C roastings, roasting time 1 ~ 10h, obtains the gasification reactivity component containing potassium after roasting;The wherein alkaline earth metal compound of alkaline earth oxide meter and mol ratio 1:9 ~ 1:0.2 in the potassium-containing compound of potassium oxideBe for example 1:5 ~ 1:0.5, SiO2/Al2O3Mol ratio be that 1:10 ~ 10:1 is for example for 1:3 ~ 3:1, with the gas containing potassium being obtainedChanging the butt weight of active component is benchmark, obtain containing in the gasification reactivity component of potassium taking the potassium content of potassium oxide as 8% by weight ~ 40 % by weight;
(3) the described mesoporous silica-alumina materials obtaining in step (1) and step (2) are obtained containing potassium gasification reactivity component withClay, cracking activity component, heat-resistant inorganic oxide matrix mix making beating, dry, the roasting at 400 ~ 800 DEG C of then sprayingBurn 2 ~ 10h; Wherein press butt weighing scale, described mesoporous silica-alumina materials, gasification reactivity component, cracking activity component, clay andThe consumption of heat-resistant inorganic oxide matrix makes obtained catalyst composition comprise 1% ~ 50% described mesoporous silica-alumina materials, 1%~ 40% described gasification reactivity component, 1% ~ 60% described cracking activity component, 0% ~ 70% described clay and 5% ~ 97% instituteState heat-resistant inorganic oxide matrix. Wherein, described clay can be the conventional clay in this area, under preferable case, and Ke YixuanIn kaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil, hydrotalcite oneKind or multiple; More preferably be selected from a kind of or many in kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stoneKind; In the time that heat-resistant inorganic oxide matrix has adhesive property, be binding agent, described binding agent can be that this area is normalWith binding agent, in preferred situation, can select a kind of or many in aluminium colloidal sol, Ludox, boehmite, phosphorus aluminium glueKind. Under preferable case, in described slurries, also can add acid to carry out acidifying, the one in described acid for example hydrochloric acid, nitric acid, sulfuric acidOr multiple. Preferably, the described mesoporous silica-alumina materials obtaining in step (1), gasification reactivity component are mixed to making beating and obtain firstSlurries, by cracking activity component, clay, binding agent mixes making beating, obtains the second slurries, then by the first slurries and the second slurriesMix making beating, then spray be dried, at 400 ~ 800 DEG C of preferred roasting 2 ~ 10h at 450 ~ 750 DEG C.
The preparation method of described catalyst composition provided by the invention, described preferred embodiment in, only to catalysis groupThe preparation method of compound is described, and is no longer repeated in this description with the identical technical characterictic in product. In step (1),In the weight ratio of the mesoporous silica-alumina materials without ion-exchange, water and inorganic acid, the described mesoporous Si-Al without ion-exchangeMaterial weight is the weight in butt. In the present invention, refer to that in the weight of butt roasting 1 is little under the condition of 800 DEG CTime after weight. According to method of the present invention, the present invention is to the kind of described inorganic acid without particular/special requirement, and conventional is inorganicAcid all can realize object of the present invention, under preferable case, the inorganic acid using be selected from a kind of in sulfuric acid, hydrochloric acid and nitric acid orMultiple. In order better to realize object of the present invention, under preferable case, the described mesoporous silica-alumina materials without ion-exchange and waterWith the weight ratio of inorganic acid be 1:6-20:0.05-0.2, be further preferably 1:8-15:0.07-0.16. Gained slurries and nothingThe mode of machine acid contact, without particular/special requirement, can be mixed them with random order, for example, inorganic acid can be joined to slurriesIn mix, also slurries can be joined in inorganic acid and mix, wherein, preferred hybrid mode is for to add inorganic acidEnter in slurries and mix. The condition that described slurries are contacted with inorganic acid can be conventional ion-exchange condition. PreferablyIn situation, the temperature of described contact is 30-80 DEG C, is preferably 40-70 DEG C; The time of contact is 0.2-2 hour, is preferably 0.3-1.5 hours, more preferably 0.5-1 hour.
According to the preparation method of catalyst composition provided by the invention, described one preferred embodiment in, in step(1), in, the described mesoporous silica-alumina materials without ion-exchange can be for this area conventional various be without any ion-exchangeMesoporous silica-alumina materials. The described mesoporous silica-alumina materials without ion-exchange can prepare according to conventional method, its preparationMethod for example can comprise: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, plastic endpoint pH is 7-11; ThenAccording to SiO2:Al2O3The weight ratio of=1:0.6-9 adds silicon source, and aging 1-10 hour at room temperature to 90 DEG C, then carried outFilter. In the present invention, the sial sediment obtaining after described filtration can directly be used as the described mesoporous silicon without ion-exchangeAluminum, also can be dried and/or roasting after as the described mesoporous silica-alumina materials without ion-exchange. Described aluminiumSource, silicon source and aqueous slkali all with above describe identical.
Described inorganic oxide matrix is exist and/or can obtain described inorganic oxide with oxide formPrecursors of inorganic oxides. The kind of described heat-resistant inorganic oxide, in aforementioned detailed description, does not repeat them here.
The present invention also provides a kind of using method of described catalyst composition, and this using method comprises the steps:
(1) petroleum hydrocarbon contacts and carries out cracking reaction with catalyst composition provided by the invention in cracking unit, and reaction is flowed outThing obtains gas, gasoline fraction, diesel oil distillate, wax oil cut after separating and has deposited the catalyst composition of coke; Described stoneOne in petroleum hydrocarbon for example AGO (atmospheric gas oil), vacuum gas oil (VGO), decompression residuum, reduced crude, To Propane Deasphalting Oil, wax tailingsOr multiple. For example reaction temperature of described reaction condition is 450 ~ 700 temperature, and reaction weight (hourly) space velocity (WHSV) is 0.1 ~ 500h-1, oil ratio(weight ratio of catalyst composition and petroleum hydrocarbon) is 0.1 ~ 100.
(2) deposition of step (1) gained the catalyst composition of coke (band charcoal catalyst composition) enter gasification unit, logicalCross control gasification condition, the charcoal on described catalyst composition and gasifying agent reaction generate is rich in CO and H2Gas, obtain simultaneouslyThe catalyst composition of holomorphosis or half regeneration catalyzing composition, described half regeneration catalyzing composition, at regeneration unit, is havingUnder the condition that oxygen exists, make residual charcoal generation completing combustion on described catalyst composition, obtain holomorphosis catalyst composition;Described gasification condition can be with reference to existing gasification process, gasification condition for example: gasification temperature is 650 ~ 890 DEG C, and gasification temperature canTo be 650 ~ 860 DEG C or 680 ~ 750 DEG C, gasifying agent can comprise the steam of 70 ~ 100 volume % and the oxygen of 0 ~ 30 volume %Gas, for example gasifying agent comprise be greater than 0 and be less than or equal to the oxygen of 20 volume % and be more than or equal to 80 and the water of little 100 volume % steamGas; The time of staying of gasifying agent can be 0.5 ~ 600 second.
(3) the holomorphosis catalyst composition of step (2) gained carries heat and turns back to the described cracking unit of step (1)Recycle.
Above-mentioned steps (2) preferably, by controlling regeneration condition, is gasificated into coke on catalyst composition to be rich in CO and H2GasWhen body, obtain half regeneration catalyzing composition, coke layer remaining on composition can not be subject to entering of gasifying agent by guard catalystOne step is destroyed, and reduces the loss of gasification reactivity component and the inactivation at cracking activity center. In described half regenerative compositions, coke containsAmount is 0.3 ~ 1%
The following examples will be further described the present invention, but not thereby limiting the invention.
In an embodiment with comparative example in:
Aluminium colloidal sol provides (Al by catalyst asphalt in Shenli Refinery of China Petrochemical Industry2O3Content is 21.5 % by weight), kaolin is by ChinaSuzhou provides (solid content is 80 % by weight), and boehmite provides (solid content is 65.8 % by weight) by Shandong Aluminum Plant. DASY-2.0 molecular sieves are produced by catalyst asphalt in Shenli Refinery of China Petrochemical Industry, are designated as Y-1; REY molecular sieve has China Petrochemical Industry's catalyst Shandong point public affairsDepartment produces, and is designated as Y-2; Ultra-steady Y molecular sieve containing magnesium makes according to the method for embodiment in CN1297018A 1, is designated as Y-3; ContainThe Y zeolite of phosphorus and rare earth, according to the method preparation of embodiment in CN1353086A 1, is designated as Y-4; A kind of the super steady of rare earth that containMolecular sieve, according to the method preparation that in CN1958452A patent, embodiment 1 announces, is designated as Y-5; MFI molecular sieve according toIn CN1147420, the method for embodiment 1 makes, and is designated as Y-6. In comparative example and embodiment, chemical reagent used is not dated especially, its specification is chemical pure.
In each embodiment, K in product2O、Na2O、Al2O3、SiO2Content with x-ray fluorescence method measure (can be referring to " stoneOiling work point analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publishes).
Preparation Example 1 ~ 3 is for illustrating the preparation method of the present invention's mesoporous silica-alumina materials used.
Preparation Example 1
The preparation method of embodiment 2 mesoporous materials of announcing according to CN1565733A prepares mesoporous material SA-2.
Preparation Example 2
The preparation method of embodiment 3 mesoporous materials of announcing according to CN1565733A prepares mesoporous material SA-3, then by HClSolution (concentration is 10 % by weight) is by SA-3(butt): the weight ratio of HCl=1:0.09 is mixed with SA-3, contacts 40 points at 50 DEG CClock, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, is designated as SAS-3.
Preparation Example 3
The preparation method of embodiment 4 mesoporous materials of announcing according to CN1565733A prepares mesoporous material SA-4.
Preparation Example 4 ~ 6 is for illustrating the preferably preparation method of mesoporous silica-alumina materials of the present invention.
Preparation Example 4
The mesoporous silica-alumina materials SA-of embodiment 2 in the basic and CN1565733A of the preparation process of mesoporous silica-alumina materials SSA-22 is identical, just adopts sour exchange process to substitute ammonium exchange process wherein. By the intermediate sedimentation thing of SA-2, i.e. aging filtrationAfter sial sediment, mix making beating with water by the weight ratio of 1:10, then by HCl solution (concentration is 10 % by weight) by sedimentThe weight ratio of (butt): HCl=1:0.12 joins in above-mentioned slurries, contacts 40 minutes at 55 DEG C, after filtration, dry and roastingAfter burning, obtain mesoporous silica-alumina materials, be designated as SSA-2. This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 2; ItsElementary analysis weight chemical composition is 0.1Na2O·58.9Al2O3·40.9SiO2。
Preparation Example 5
The mesoporous silica-alumina materials SA-of embodiment 3 in the basic and CN1565733A of the preparation process of mesoporous silica-alumina materials SSA-33 is identical, just adopts sour exchange process to substitute ammonium exchange process wherein. By the intermediate sedimentation thing of SA-3, i.e. aging filtrationAfter sial sediment, mix making beating with water by the weight ratio of 1:12, then by HCl solution (concentration is 10 % by weight) by sedimentThe weight ratio of (butt): HCl=1:0.09 joins in above-mentioned slurries, contacts 40 minutes at 50 DEG C, after filtration, dry and roastingAfter burning, obtain mesoporous silica-alumina materials, be designated as SSA-3. This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 2; ItsElementary analysis weight chemical composition is 0.09Na2O·73.9Al2O3·25.9SiO2。
Preparation Example 6
The mesoporous silica-alumina materials SA-of embodiment 4 in the basic and CN1565733A of the preparation process of mesoporous silica-alumina materials SSA-44 is identical, just adopts sour exchange process to substitute ammonium exchange process wherein. By the intermediate sedimentation thing of SA-4, i.e. aging filtrationAfter sial sediment, mix making beating with water by the weight ratio of 1:12, then by HCl solution (concentration is 10 % by weight) by sedimentThe weight ratio of (butt): HCl=1:0.14 joins in above-mentioned slurries, contacts 30 minutes at 60 DEG C, after filtration, dry and roastingAfter burning, obtain mesoporous silica-alumina materials, be designated as SSA-4. This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 2; ItsElementary analysis weight chemical composition is 0.06Na2O·73.8Al2O3·26.0SiO2。
Preparation Example 7 ~ 11 is for illustrating the gasification reactivity component at XRD principal phase peak shown in the present invention Fig. 1 of having usedPreparation method.
Preparation Example 7
Take in 1776 grams of kaolin of butt, 210 grams of K2O and 14 grams of CaO, mix three and add appropriate deionizationWater, makes slurry solid content 15% ~ 50%, stirs at least 20 minutes, dry, then roasting 4 hours at 1000 DEG C, makes containing potassium gasChange active component K-1, wherein K2O content is 10.5%, CaO/K2The mol ratio of O is 1/9, SiO2/Al2O3Mol ratio be 2, K-1 has the XRD principal phase peak shown in Fig. 1.
Preparation Example 8 ~ 12
Method preparation according to embodiment 7 contains potassium material as gasification reactivity component, adjusts ingredient proportion, and preparation is containing potassium gasChange active component K-2, K-3, K-4, K-5, K-6, specifically feed intake in table 1. What embodiment 7 ~ 12 was prepared all has containing potassium materialXRD feature principal phase peak shown in Fig. 1 (principal phase peak 2 θ are respectively 21 °, 29 °, 35 °)
Table 1
Preparation Example 13 ~ 21 is for illustrating the preparation method of the present invention's catalyst composition used.
Preparation Example 13
The boehmite of 15 weight portions in butt is mixed to making beating with deionized water, and add in the slurries that obtainEnter the hydrochloric acid that concentration is 36 % by weight, sour aluminum ratio (described 36 % by weight hydrochloric acid with Al2O3The weight ratio of the boehmite of meter) be0.2, be warmed up to 65 DEG C of acidifyings 1 hour, obtain slurries. By the kaolin in 20 parts of butts (Suzhou carclazyte), in butt 10The aluminium colloidal sol of weight portion joins and in the boehmite slurries of acidifying, mixes making beating 20 minutes, then will be in butt 35 weightsREY molecular sieve (the RE of amount part2O3Content is 18.8 % by weight, silica alumina ratio (SiO2With Al2O3Mol ratio) 5.1, China Petrochemical Industry's catalystAsphalt in Shenli Refinery's product) add, pull an oar 1 hour, obtain the first slurries.
By mixing containing potassium material K-1 and the mesoporous silica-alumina materials SA-3 in butt 10 weight portions in butt 10 weight portionsClose, add deionized water, mix making beating and stir 30 minutes, obtain the second slurries. Two kinds of slurries are mixed, and stir at least 30 pointsClock, obtains the slurries that solid content is 30 % by weight. Spraying is dry makes microballoon catalyst composition, then 550 DEG C of roastings 2 hours.Prepared contact agent is numbered C1.
Catalyst composition adopts the wastage of potassium in hydrothermal experiment test composition, and the condition of hydrothermal experiment is: 100%500 DEG C of processing 72h of steam, measure K in the sample composition of hydro-thermal front and back2The weight content of O, with retention rate definition catalyst compositionThe stability of middle potassium. The hot water potassium retention rate of catalyst composition C1 ~ C9 is in table 2.
Preparation Example 14 ~ 21
Method according to embodiment 13 is prepared catalyst composition, adjusts ingredient proportion, makes catalyst composition C2 ~ C9, toolBody charge ratio is in table 2. Inventory is wherein parts by weight.
Table 2
From table 2, adopt the XRD shown in Fig. 1 that has prepared by method provided by the present invention
Principal phase peak containing potassium material as the gasification reactivity component in catalyst composition, the guarantor of potassium after hydrothermal treatment consistsStay rate apparently higher than adopting other reservations as potassium in the catalyst composition of gasification reactivity component containing potassium material and alkaline-earth metalRate.
Preparation comparative example 1
According to the method for preparing catalyst of the embodiment 1 announcing in patent CN200910143623.3 and ingredient proportion preparationComparative catalyst D1. Adopt hydrothermal experiment to test the wastage of catalyst D1 potassium, potassium retention rate and catalyst preparation are thrownMaterial ratio is in table 3.
Preparation comparative example 2
Method for preparing catalyst according to the embodiment 1 announcing in patent CN200910143623.3 has been prepared contrast catalysisAgent D2. Adopt hydrothermal experiment to test the wastage of catalyst D2 potassium, potassium retention rate and catalyst are prepared ingredient proportion in Table3。
Preparation comparative example 3 ~ 5
According to the catalyst composition preparation method of embodiment 13, be only to replace mesoporous silica-alumina materials with kaolin, it is right to prepareThan catalyst composition D3 ~ D6, concrete inventory is in table 3, and inventory is wherein parts by weight.
Can find out from the data of table 2 and table 3, carbon monoxide-olefin polymeric is processed after 72h through 500 DEG C of 100% steam, whenUse method provided by the present invention preparation have the principal phase of XRD shown in Fig. 1 peak containing potassium material urging as gasification reactivity componentThe potassium retention rate of agent composition is high, the potassium apparently higher than other potassium-containing compounds as the catalyst composition of gasification reactivity componentRetention rate. Visible, to adopt method provided by the invention the to prepare stability containing potassium material with the principal phase of XRD shown in Fig. 1 peakDue to other potassium-containing compounds.
Table 3
Test case 1
This test case is used for illustrating that mesoporous material that embodiment 1 ~ 6 provides is through 800 DEG C, 17 hours, 100% steamThe light oil microactivity that processing has. Evaluating feedstock oil used is that boiling range is the huge port straight distillation light diesel oil of 221 ~ 335 DEG C. Evaluate barPart is: oil ratio 1.28, mass space velocity is 40h-1, reaction temperature is 460 DEG C. Evaluation result is in table 4.
Table 4
Mesoporous material Micro-activity (% by weight) Mesoporous material Micro-activity (% by weight) 13 -->
SA-2 24 SSA-2 27
SAS-3 26 SSA-3 28
SA-4 27 SSA-4 30
As can be seen from Table 4, adopt mesoporous silica-alumina materials processing method provided by the invention to obtain mesoporous silica-alumina materials(SSA-2 ~ SSA-4), through 800 DEG C, 100% steam, processes after 17 hours, and its light oil microactivity is than traditional ammonium exchangeThe activity of the mesoporous silica-alumina materials (SA-2 ~ SA-4) obtaining is high 2 ~ 3 percentage points, illustrates and adopts method processing provided by the inventionObtain silica-alumina material cracking activity good.
Test case 2
This test is used for illustrating gasification performance and the cracking of the catalyst composition that embodiment 13 ~ 21 and comparative example 1 ~ 6 providePerformance. Respectively the catalyst composition of above-mentioned preparation aging 8h under 790 DEG C, the condition of 100% steam, then by its fillingIn being 210 grams fixed fluidized bed, reserve carries out cracking and gasification experiment. Cracking experiment condition is: reaction temperature be 520 DEG C,Weight (hourly) space velocity (WHSV) is 20h-1, oil ratio is 8, water-oil factor is 0.35; Gasification experiment condition: gasification temperature is 700 DEG C, and gasifying agent is100% steam, the time of staying of gasifying agent is 50 seconds. The catalyst composition that comparative example 1 ~ 2 provides in addition after cracking experiment,The gasification experiment condition of also announcing according to test case in CN200910143623.3 is carried out gasification experiment, and gasification condition is gasification temperatureDegree is 860 DEG C, and gasifying agent is the oxygen of 80% steam and 20%. Catalyst composition after all gasifications keeps certain coke to protectStay on composition, conventionally > 0.3 % by weight, for example, be 0.4 ~ 0.6 % by weight.
Raw materials used oil properties is in table 5, appreciation condition and the results are shown in Table 6 and table 7.
Table 5
Table 6
In table 6,7, m represents that quality v represents volume
Table 7
In table 6 and table 7:
The intensity of making charcoal: the carbon monoxide-olefin polymeric reserve per ton coke quality of burning per hour, unit is kg/ (th)
Typically, catalyst composition gasification reactivity and after cracking on composition the intensity of making charcoal of coke along with temperatureIncrease and increase, the intensity of making charcoal that contains oxygen in gasifying agent can be better than using 100% steam as gasifying agent making charcoal strongDegree. Can find out from table 6 and table 7, cracking gasification catalyst composition provided by the invention can obtain under lower gasification temperatureTo good gasification result, obtain the higher intensity of making charcoal, gasification product has higher density of hydrogen. Employing the invention providesThe catalyst composition prepared of the mesoporous silica-alumina materials that obtains of preferred mesoporous silica-alumina materials processing method there is better crackingPerformance, coke selectivity is good, light oil yield (total recovery of gasoline and liquefied gas) height. With prepared by existing gasification reactivity component urgingChange composition (referring to C9) and compare, adopt prepared by method provided by the invention have the XRD principal phase peak shown in Fig. 1 containing potassium thingThe gasification reactivity of the catalyst composition that matter is prepared as gasification reactivity component is higher, and the intensity of making charcoal is higher; At same gasification barUnder part, the intensity of making charcoal of gasification reactivity and coke is obviously higher. For example composition C1 ~ C8 provided by the invention is at 700 DEG C, and 100%Gasification reactivity under water vapor conditions and the intensity of making charcoal just can reach 860 DEG C, and the gasification result of 80% steam, when invention providesCatalyst composition in contain simultaneously the XRD principal phase peak shown in mesoporous silica-alumina materials and Fig. 1 when the potassium material, gasification reactivity is moreHeight, this may be because mesoporous silica-alumina materials has improved the distribution of coke, has improved the utilization rate of gasification reactivity component, Jin ErtiHigh gasification performance. Visible, adopt visible use catalyst composition provided by the invention for gasification-cracking PROCESS FOR TREATMENT heavy crudeHydrocarbon is conducive to realize the efficient utilization of petroleum resources, and energy-conservation.
Test case 3
Get that catalyst composition C3 that embodiment 3 provides, catalyst composition C6 that embodiment 6 provides and comparative example 1 provideThe catalyst composition D2 that catalyst composition D1, comparative example 2 provide is the circulation cracking-gasification-regenerating unit of 50 grams at dress dosageOn test. The condition of cracking is: 550 DEG C, and oil ratio 5, cracked stock oil nature is in table 5; In order to reach close making charcoalIntensity, C3, C6, at 700 DEG C, gasify under 100% steam, and D1, D2 are at 860 DEG C, under the condition of 80% steam+20% oxygenGasification, the time of staying of gasifying agent is 50 seconds. The condition of holomorphosis is 680 DEG C, air regenesis, catalysis after holomorphosisCoke content < 0.1% on composition. Repeatedly carry out 40 cycles of cracking-gasification-regeneration, unload catalyst composition, then by catalysisComposition carries out cracking activity (MA) test on light oil micro-reactor. The micro-anti-test evaluation of light oil feedstock oil used is flow processIt is the huge port straight distillation light diesel oil of 221 ~ 335 DEG C. Appreciation condition is: oil ratio 1.28, mass space velocity is 40h-1, reaction temperature is460 DEG C. Evaluating all feedstock oil is that flow process is the huge port straight distillation light diesel oil of 221 ~ 335 DEG C. Appreciation condition is: oil ratio 3.2,Mass space velocity is 16h-1, reaction temperature is 460 DEG C. Micro-activity evaluation result is in table 8.
Table 8
Catalyst composition C3 C6 D1 D2
MA 87 78 21 24
From table 8, under the identical intensity of making charcoal, carry out after the cracking-gasification-regeneration cycle of same number D1, D2Activity far below C3 and C6, this may be because the gasification reactivity of D1 and D2 do not have C3 and C6 high, be to burn in order to reach identicalCharcoal intensity must improve gasification temperature, but in catalyst composition, cracking activity component can occur under high temperature, water vapor conditionsFramework of molecular sieve avalanche, causes expendable loss of activity.

Claims (22)

1. a cracking gasification catalyst composition, by weight percentage, described catalyst composition comprises: 2 % by weight～50 weightsAmount % mesoporous silica-alumina materials, the gasification reactivity component of 5 % by weight～40 % by weight, the cracking activity of 5 % by weight～50 % by weightComponent, the heat-resistant inorganic oxide matrix of the clay of 0～60 % by weight and 10 % by weight～70 % by weight, wherein, described JieHole silica-alumina material has the phase structure of boehmite, taking the anhydrous chemical expression of oxide weight as (0-0.3)Na2O·(40-90)Al2O3·(10-60)SiO2, specific area is 200-400m2/ g, pore volume is 0.5～2.0mL/g, average holeFootpath is 8～20nm, and most probable aperture is 5～15nm.
2. according to catalyst composition claimed in claim 1, it is characterized in that, described mesoporous silica-alumina materials is through peracid treatment,Described acid treatment is to be that 1:5-30:0.03-0.3 contacts at least 0.2 by mesoporous silica-alumina materials, water and inorganic acid according to weight ratioHour.
3. according to catalyst composition claimed in claim 1, it is characterized in that, described mesoporous silica-alumina materials is through acid-treatedMesoporous silica-alumina materials, is made by the method comprising the following steps: the mesoporous silica-alumina materials without ion-exchange is mixed with water and beatSlurry, obtain slurries, then gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, make described mesoporous siliconSodium oxide content in aluminum is higher than 0.2 % by weight, wherein, the described mesoporous silica-alumina materials without ion-exchange, water andThe weight ratio of inorganic acid is 1:5-30:0.03-0.3.
4. according to catalyst composition claimed in claim 1, it is characterized in that, described gasification reactivity component comprises alkali metalAnd/or alkaline-earth metal.
5. according to catalyst composition claimed in claim 1, it is characterized in that, described gasification reactivity component comprises potassium, containing orAlkali-free earth metal, taking the weight of described gasification reactivity component as benchmark, in oxide weight, in described gasification reactivity componentThe content of potassium is 2～100%, and the content of alkaline-earth metal is 0-98 % by weight.
6. according to catalyst composition claimed in claim 1, it is characterized in that, described gasification reactivity component comprises having Fig. 1Shown in XRD principal phase peak containing potassium material.
7. according to catalyst composition claimed in claim 6, it is characterized in that, described have containing of the principal phase of XRD shown in Fig. 1 peakIn potassium material, taking the potassium content of potassium oxide as 8 % by weight～40 % by weight, alkaline earth oxide and potassium oxide mol ratio 1:9～1:0.2, all the other are sial component, SiO2/Al2O3Mol ratio be 1:10～10:1.
8. according to catalyst composition claimed in claim 6, it is characterized in that, described have containing of the principal phase of XRD shown in Fig. 1 peakPotassium oxide content 10 % by weight～30 % by weight in potassium material, alkaline earth oxide and potassium oxide mol ratio 1:5～1:0.5,SiO2/Al2O3Mol ratio be 1:3～3:1.
9. according to the catalyst composition described in claim 6,7 or 8, it is characterized in that, described in there is the principal phase of XRD shown in Fig. 1 peakObtained by following methods containing potassium material: potassium-containing compound, alkaline earth metal compound and sial component are beaten into wet feed, then dryDry become siccative, then obtain after roasting, sintering temperature is 800 DEG C～1150 DEG C, roasting time 1～10h.
10. according to catalyst composition claimed in claim 1, it is characterized in that, described cracking activity component is selected from Y type and boilsStone, there are one or more in MIF structural zeolite and β zeolite.
The preparation method of catalyst composition described in 11. 1 kinds of claims 1, comprise by mesoporous silica-alumina materials, gasification reactivity component,Cracking activity component, clay, heat-resistant inorganic oxide matrix mix making beating, and spraying is dried the step with roasting.
12. according to the preparation method of catalyst composition described in claim 11, it is characterized in that, also comprises the described mesoporous silicon of preparationThe step of aluminum; The preparation method of described mesoporous silica-alumina materials, comprises the following steps: by aluminium source and aqueous slkali in room temperature extremelyIn at 85 DEG C and plastic, the pH value of plastic terminal is 7-11; Then according to SiO2:Al2O3The weight ratio of=1:0.6-9 adds siliconSource, aging 1-10 hour at room temperature to 90 DEG C, carries out ion-exchange by gained solid sediment with ammonium, makes mesoporous containing sodiumIn material, the content of sodium oxide molybdena is higher than 0.2% weight, wherein mesoporous silica-alumina materials (butt): ammonium salt: H2O＝1：(0.1-1)：(10-30)。
13. according to the preparation method of catalyst composition described in claim 11, it is characterized in that, described mesoporous silica-alumina materialsPreparation method comprises acid-treated step; Described acid treatment step be by the mesoporous silica-alumina materials obtaining by ammonium ion exchange byThe ratio that is 1:5-30:0.03-0.3 according to the weight ratio of mesoporous silica-alumina materials, water and inorganic acid contacts at least 0.2 hour.
14. according to the preparation method of catalyst composition described in claim 11, it is characterized in that, described mesoporous silica-alumina materials byThe method comprising the following steps makes: the mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtains slurries, then willGained slurries and inorganic acid contact at least 0.2 hour at room temperature to 100 DEG C, make the sodium oxide molybdena in described mesoporous silica-alumina materialsContent is not higher than 0.2 % by weight, and wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is1:5-30:0.03-0.3。
15. according to the preparation method of catalyst composition described in claim 14, it is characterized in that, described is mesoporous without what exchangeSilica-alumina material is made by the method comprising the following steps: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, plastic eventuallyThe pH value of point is 7-11; Then according to SiO2:Al2O3The weight ratio of=1:0.6-9 adds silicon source, aging at room temperature to 90 DEG CWithin 1-10 hour, obtain colloid admixture, the sediment that described colloid admixture obtains is after filtering described without ionThe silica-alumina material of exchange or by described colloid admixture or after filtering the sediment that obtains be dried and/or roasting afterObtain the described mesoporous silica-alumina materials without ion-exchange.
16. according to the preparation method of catalyst composition described in claim 14, it is characterized in that, the temperature of described contact is 30-80 DEG C, the time of contact is 0.2-2 hour; The weight ratio of the described mesoporous silica-alumina materials without ion-exchange and water and inorganic acidFor 1:6-20:0.05-0.2.
17. according to the preparation method of catalyst composition described in claim 11, it is characterized in that, described gasification reactivity component choosingFrom potassium hydroxide, potash, potassium oxide, potassium nitrate, potassium sulfate, potassium dihydrogen phosphate, potassic feldspar, green bean rock, alunite, asperitiesRock, potassium-bearing shale, phosphorus potassium ore, containing potassium siltstone, there is the chlorination containing potassium material, alkaline-earth metal at the principal phase of XRD shown in Fig. 1 peakOne or more in the phosphate of the nitrate of thing, alkaline-earth metal, the sulfate of alkaline-earth metal, alkaline-earth metal, described alkaliEarth metal is one or more in beryllium, magnesium, calcium, strontium, barium.
18. according to the preparation method of catalyst composition described in claim 17, it is characterized in that, described in there is XRD master shown in Fig. 1Comprising containing potassium substances preparation method of phase peak: potassium-containing compound, alkaline earth metal compound and sial component are beaten into wet feed, thenBe dried into siccative, then described in obtaining after roasting, have the principal phase of XRD shown in Fig. 1 peak containing potassium material, sintering temperature be 800 DEG C～1150 DEG C, roasting time 1～10h.
19. according to the preparation method of catalyst composition described in claim 18, it is characterized in that, described in there is XRD master shown in Fig. 1Phase peak containing potassium material, sintering temperature is 900 DEG C～1100 DEG C, roasting time is 2～8h.
20. according to the preparation method of the catalyst composition described in claim 18, it is characterized in that, described sial component is selected from heightOne or more in ridge soil, imvite, rectorite, attapulgite, illite, sepiolite, diatomite, or be kaolin,Mixing of one or more in imvite, rectorite, attapulgite, illite, sepiolite, diatomite, aluminium colloidal sol and LudoxCompound; Or be the one in kaolin, imvite, rectorite, attapulgite, illite, sepiolite, diatomite, LudoxOr mixture several and aluminium colloidal sol.
21. according to the preparation method of the catalyst composition described in claim 11, it is characterized in that, described gasification reactivity componentFor have the principal phase of XRD shown in Fig. 1 peak containing potassium material.
22. a cracking gasification process for petroleum hydrocarbon, is included in cracker arbitrary to petroleum hydrocarbon and claim 1～9Cracking gasification catalyst composition haptoreaction described in, divides reacted described cracking gasification carbon monoxide-olefin polymeric and oil gasFrom, the deposition that separation is obtained the step that contacts with gasifying agent of the cracking gasification catalyst composition of coke.
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