CN103566962A - Multifunctional catalysis composition - Google Patents

Abstract

A multifunctional catalysis composition comprises 1-50wt% of a mesoporous aluminosilicate material, 1-40wt% of a gasification active component, 1-60wt% of a cracking active component, 0-70wt% of clay and 5-97wt% of a heatproof inorganic oxide matrix, wherein the mesoporous aluminosilicate material has a phase structure of pseudo-boehmite, has an anhydrous chemical expression formula of (0-0.3)Na2O.(40-90)Al2O3.(10-60)SiO2 by weight of oxide, and has a specific surface area of 200-400m<2>/g, a pore volume of 0.5-2.0mL/g, an average aperture of 8-20nm and a most probable aperture of 5-15nm The catalysis composition can reduce the gasification temperature of the cracking gasification conversion of hydrocarbon oil.

Description

A kind of multi-functional catalyst composition

Technical field

The present invention relates to a kind of catalyst composition of the coke gasification anabolic process for petroleum hydrocarbon cracking process and cracking generation, in particular, relate to a kind of thermal cracking and/or catalytic cracking process processing processing petroleum hydrocarbon raw material of utilizing and produce light Fuel, the coke gasification simultaneously under gasifying agent participates in, process being produced is the multi-functional catalyst composition of the process of hydrogen or synthesis gas.

Background technology

At present, when catalyzed cracking processing heavy, inferior feedstock oil, catalytic cracking process itself and catalyst have been proposed to challenge, 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 process exists the high and low quality coke of coke yield to be difficult to the problem of utilizing, delayed coking can produce a large amount of low value-added petroleum cokes, so 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 system thermal, and remainder adopts air or oxygen, steam etc. to produce and have certain low-heat value gas in high temperature (900 ℃ of left and right) gasification.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 gas ₂content lower, calorific value is lower, 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, adopt traditional catalyzed cracking processing mode also to produce a certain amount of coke when producing liquefied gas, gasoline, diesel oil, this part coke burns in regenerative system to be provided for maintaining the heat of the certain reaction temperature of system.In regenerative system, pass into a certain amount of steam as gasifying agent can be when burning by-product part CO, H ₂, this part synthesis gas can be used for doing the synthetic unstripped gas of Fischer-Tropsch through processing.

In gasification, add catalyst can reduce the activation energy of gasification reaction, reduce gasification temperature, reduce the addition of gasifying agent, adjust the composition of synthesis gas.Alkali and alkaline earth metal ions is conventional gasifying catalyst, adds the gasification that a certain amount of alkali and alkaline earth metal ions can promote deposit coke on catalyst in Cracking catalyst.In CN200810246526.2, announced a kind of alkali metal containing of cracking and gasification function and catalyst of alkaline-earth metal of having concurrently, this catalyst contains 35% ~ 60% boehmite, 2% ~ 10% aluminium colloidal sol, 20% ~ 49.5% kaolin, 5% ~ 30% the alkali and alkaline earth metal ions in oxide, this catalyst has the optimization function of the distribution of cracking hydrocarbon oil product and gasification reaction available gas productive rate.In CN200910078392.2, announced a kind of coke transfer agent, comprise 50% ~ 80% kaolin, 10% ~ 39.5% binding agent and 10% ~ 30% alkali and alkaline earth metal ions in oxide, wherein in binding agent, the mass ratio of boehmite and aluminium colloidal sol is (1.2 ~ 6): 1, the atomic ratio of alkali and alkaline earth metal ions is (0.05 ~ 0.8): 1, and this catalyst is in the catalytic cracking gasification of catalytic coke simultaneously of catalysis heavy crude.CN200910143623.3 has announced a kind of inferior heavy oil cracking and gasifying catalyst, comprise carrier, binding agent, gasification reactivity component and cracking activity component, wherein gasification reactivity component is alkali and alkaline earth metal ions, take catalyst total amount as benchmark, oxide content be 2% ~ 30%, the atomic ratio of alkali metal and alkaline-earth metal is (0.05 ~ 1.1): 1, and 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 at 860 ℃, carry out gasification reaction, catalysis material for alkali metal containing, under high-temperature water heat condition, in catalyst, alkali-metal loss is more serious, for the catalyst containing molecular sieve, in more than 800 ℃ high-temperature water thermal environments, can there is the rapid avalanche of framework of molecular sieve, activity reduces rapidly.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of catalyst composition that petroleum hydrocarbon cracking transforms and promotes coke gasification that is applicable to, 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, the butt weight of described cracking gasification catalyst composition of take is benchmark, according to weight percent meter, described catalyst composition comprises the mesoporous silica-alumina materials in butt 1% ~ 50%, cracking activity component in butt 1% ~ 60%, in 1% ~ 40% gasification reactivity component of butt, in 0% ~ 70% clay of butt with in 5% ~ 97% heat-resistant inorganic oxide matrix of butt; Wherein, described mesoporous silica-alumina materials has the phase structure of boehmite, and the anhydrous chemical expression of oxide weight of take is (0-0.3) Na ₂o(40-90) Al ₂o ₃(10-60) SiO ₂, specific area is 200-400m ²/ g, pore volume is 0.5 ~ 2.0mL/g, and average pore size is 8 ~ 20nm, and most probable aperture is 5 ~ 15nm.

The present invention also provides a kind of preparation method of described composition, comprises mesoporous silica-alumina materials, cracking activity component, gasification reactivity component, clay and heat-resistant inorganic oxide matrix are mixed to 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, according to the method preparation of announcing in CN1565733A, comprise the following steps: by during aluminium source and aqueous slkali are at room temperature to 85 ℃ and plastic, the pH value of plastic terminal is 7-11; Then according to SiO ₂: Al ₂o ₃=1:(0.6-9) weight ratio adds silicon source, aging 1-10 hour at room temperature to 90 ℃, gained solid sediment is carried out to ion-exchange with ammonium, make 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: H ₂o=1:(0.1-1): (10-30).

Described mesoporous silica-alumina materials is acid-treated mesoporous silica-alumina materials preferably, can be by according to the method described above for example according to CN1261217C(CN1565733A) mesoporous silica-alumina materials prepared of claim 1 ~ 6 or the disclosed method of embodiment 1-5 obtains with acid treatment, the ratio that its processing method is is 1:5-30:0.03-0.3 by mesoporous silica-alumina materials, water and inorganic acid according to weight ratio is mixed, contact 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 silica-alumina materials is made by the method comprising the following steps: the mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 ℃, make sodium oxide content in described mesoporous silica-alumina materials not higher than 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.The described mesoporous silica-alumina materials without ion-exchange can be prepared by the following method: by during aluminium source and aqueous slkali are at room temperature to 85 ℃ and plastic, the pH value of plastic terminal is 7-11; Then according to SiO ₂: Al ₂o ₃the weight ratio of=1:0.6-9 adds silicon source, aging 1-10 hour at room temperature to 90 ℃, obtain colloid admixture, described colloid admixture is filtered to the sediment (filter cake) obtaining and be the described mesoporous silica-alumina materials without ion-exchange, or after the drying precipitate that above-mentioned filtration is obtained and/or roasting, obtain product and be the described mesoporous silica-alumina materials without ion-exchange, or by described colloid admixture dry/or roasting after the product that obtains be the described mesoporous silica-alumina materials without ion-exchange.Described room temperature can be 5 ~ 40 ℃, for example, can be 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃.

Described gasification reactivity component comprises at least one of alkali metal and/or alkali earth metal.One or more in the optional material that contains alkali metal and/or alkali earth metal certainly of described gasification reactivity component, for example be selected from potassium 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 containing potassium material, the chloride of alkaline-earth metal, the nitrate of alkaline-earth metal, the sulfate of alkaline-earth metal, one or more in the phosphate of alkaline-earth metal, described alkaline-earth metal is beryllium, magnesium, calcium, strontium, one or more in barium.

Preferably, described gasification reactivity component comprises potassium, contains or alkali-free earth metal; In described gasification reactivity component, the content of potassium oxide is 2 % by weight ~ 100 % by weight, the content of alkaline earth oxide is 0-98 % by weight, preferably, the content of described potassium oxide can be 10 % by weight ~ 90 % by weight, and the mol ratio of alkaline earth oxide and potassium oxide is 1:9 ~ 1:0.2.Described gasification reactivity component can be selected from potassium 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 containing one or more in potassium material, or also comprise the chloride of alkaline-earth metal, the sulfate of the nitrate of alkaline-earth metal, alkaline-earth metal, one or more in the phosphate of alkaline-earth metal; In order to solve the serious problem of potassium lost, described containing potassium active component be preferably 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 gasification reactivity component, can further improve the gasification efficiency of catalyst composition, reduce the loss of potassium, and can improve the cracking activity of catalyst composition.

The described potassium material that contains with the principal phase of XRD shown in Fig. 1 peak comprises potassium oxide, alkaline earth oxide and sial component, wherein, comprise 8 % by weight ~ 40 % by weight potassium oxides, alkaline earth oxide and potassium oxide mol ratio 1:9 ~ 1:0.2, all the other are sial component, SiO ₂/ Al ₂o ₃mol ratio be 1:10 ~ 10:1.Preferably, the described content containing potassium oxide in potassium material with the principal phase of XRD shown in Fig. 1 peak is 10 % by weight ~ 30 % by weight, and the content of butt sial component of take is 40 % by weight ~ 89 % by weight, alkaline earth oxide and potassium oxide mol ratio 1:5 ~ 1:0.5, SiO ₂/ Al ₂o ₃mol 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 phase figure 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 earth metal compound and sial component are pulled an oar into wet feed, then be dried into siccative, after roasting, obtain, sintering temperature is 900 ℃ ~ 1150 ℃, roasting time 1 ~ 10h again; Described potassium-containing compound is one or more that are selected from potassium oxide, potassium hydroxide, potash, potassium nitrate, and described alkaline earth metal compound is one or more that are selected from alkaline earth oxide, alkaline earth metal carbonate, alkaline earth nitrate.Described sial component preferably includes the crystal aluminosilicate mineral with layer structure.Described sial component can be selected from one or more in kaolin, imvite, rectorite, attapulgite, sepiolite, illite, diatomite, aluminium colloidal sol, Ludox, and wherein aluminium colloidal sol, Ludox are not used separately.

Described cracking activity constituent element can be selected from Y zeolite, has the molecular sieve of MFI structure, one or more in beta-molecular sieve.Described Y zeolite is for example one or more in REY, REUSY, USY, HY, REHY.Described MFI molecular sieve is for example one or more in ZSM-5, ZRP, ZSP.Described beta-molecular sieve can be phosphorus or metal-modified molecular sieve.

Described clay can for the conventional clay in this area for example, described clay can be selected from one or more in kaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil, hydrotalcite; More preferably be selected from one or more in kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone.

Cracking gasification catalyst composition provided by the invention contains the heat-resistant inorganic oxide matrix except described mesoporous silica-alumina materials, cracking activity component, gasification reactivity component, clay, the kind of described heat-resistant inorganic oxide is without specific (special) requirements, can be the conventional heat-resistant inorganic oxide matrix in this area, be preferably one or more in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and beryllium oxide and their predecessor.Described heat-resistant inorganic oxide predecessor is one or more in aluminium colloidal sol, Ludox, phosphorus aluminium glue, boehmite, silicon-aluminum sol for example.Described heat-resistant inorganic oxide matrix can add with heat-resistant inorganic oxide precursor in the preparation at catalyst composition, then pass through roasting, heat-resistant inorganic oxide precursor conversion generates heat-resistant inorganic oxide, also can first with heat-resistant inorganic oxide precursor, be prepared into heat-resistant inorganic oxide, then in the preparation process of catalyst composition, the form with heat-resistant inorganic oxide adds.Wherein the temperature of roasting is usually less than 800 ℃, is generally 400 ~ 750 ℃.When described heat-resistant inorganic oxide matrix has attachment function, conventionally also become binding 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 metal traps while being used for residual oil cracking-gasification group technology, by butt, the content of described metal traps is no more than 20 % by weight of catalyst composition, and preferably, this metal traps is free on outside described mesoporous silica-alumina materials.Invention without specific (special) requirements, can be polluted the conventional metal traps of the component of metal to the kind of described metal traps for trapping V, Ni, Fe, Ca etc., under preferable case, described metal traps is the precursor of rare earth oxide and/or rare earth oxide.More preferably in situation, the precursor metal traps 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.In the present invention, the mode of entrance of metal agent for capturing can be introduced with ionic species or complex form when mesoporous silica-alumina materials, gasification reactivity component, clay mix making beating.If introduce heat-resistant inorganic oxide in carbon monoxide-olefin polymeric, can also in advance metal traps be deposited in described inorganic oxide by coprecipitation.This metal traps 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 described mesoporous silica-alumina materials of method preparation of the announcement of claim 1 ~ 6 in CN1565733A or CN1261217C or embodiment 1 ~ 5;

B) will be according to A) mesoporous silica-alumina materials prepared of described method mixes according to the weight ratio of mesoporous silica-alumina materials, water and inorganic acid=1:5-30:0.03-0.3, contact at least 0.2 hour mesoporous silica-alumina materials described in preparation;

C) mesoporous silica-alumina materials without ammonium exchange is mixed to making beating, obtains slurries with water, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 ℃, obtain 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; In the preparation process of this preferred mesoporous silica-alumina materials, without carrying out ammonium exchange, can not produce ammonia nitrogen waste water, the preparation process that makes this catalyst composition relatively environmental protection and cost lower.In addition, in the preparation process of described mesoporous silica-alumina materials, only need to use an inorganic acid to carry out ion-exchange and can obtain sodium oxide content lower than the mesoporous silica-alumina materials of 0.2 % by weight, thereby reduced production cost and improved production efficiency;

(2) the described mesoporous silica-alumina materials obtaining in step (1), cracking activity component, gasification reactivity component, clay, heat-resistant inorganic oxide matrix and water are mixed to making beating, then spray be dried, roasting 2 ~ 10h at 400 ~ 799 ℃.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 cracking activity component, clay, binding agent mixes making beating, obtain the second slurries, then the first slurries and the second slurries mixed to making beating, then spray be dried, roasting 2 ~ 10h at 500 ~ 800 ℃.

Gasification reactivity component described in step (2) comprises alkali metal and/or alkaline-earth metal, is preferably the material that comprises potassium, and this material contains or alkali-free earth metal.Described containing potassium material for example potassium 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 containing one or more in potassium material.When described gasification reactivity component contains alkaline-earth metal, the compound that can add alkaline-earth metal, one or more in the chloride of alkaline-earth metal, sulfate, nitrate, carbonate, oxide, hydroxide for example, 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: potassium-containing compound, alkaline earth metal compound and sial component are pulled an oar into wet feed, are then dried into siccative, then obtain after roasting, sintering temperature is 800 ℃ ~ 1150 ℃, roasting time 1 ~ 10h; Described potassium-containing compound is one or more that are selected from potassium oxide, potassium hydroxide, potash, potassium nitrate, described alkaline earth metal compound is one or more that are selected from alkaline earth oxide, alkaline earth metal carbonate, alkaline earth nitrate, for example, can be one or more in calcium oxide, calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, magnesia, magnesium carbonate, magnesium chloride, magnesium nitrate, magnesium sulfate.In described sial component, silica and alumina molar ratio are 1:10 ~ 10:1, are preferably 1:3 ~ 3:1.Described sial component contains silicon and aluminium element, can be selected from one or more in clay, silica, silica precursors, aluminium oxide, alumina precursor, is preferably clay.Described in preparation, there is containing in potassium substance process of the principal phase of XRD shown in Fig. 1 peak, after sial component is mixed with alkaline-earth metal and/or alkaline components, through roasting, obtain described gasification reactivity component, and then mix making beating with mesoporous silica-alumina materials, cracking activity component, clay, heat-resistant inorganic oxide and water.

In cracking gasification catalyst composition preparation method provided by the invention, described clay can be the conventional clay in this area, under preferable case, can be selected from one or more in kaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil, hydrotalcite; More preferably be selected from one or more in kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone.

In cracking gasification catalyst composition preparation process provided by the invention, add heat-resistant inorganic oxide matrix, described heat-resistant inorganic oxide matrix can be heat-resistant inorganic oxide precursor and/or heat-resistant inorganic oxide.The kind of described heat-resistant inorganic oxide, without specific (special) requirements, can be the conventional heat-resistant inorganic oxide in this area, is preferably one or more in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and beryllium oxide.Heat-resistant inorganic oxide or heat-resistant inorganic oxide precursor are commonly referred to binding agent when having adhesive property, described binding agent, for example one or more in aluminium colloidal sol, Ludox, boehmite, phosphorus aluminium glue.In preparation process, can add heat-resistant inorganic oxide precursor, then pass through roasting, heat-resistant inorganic oxide precursor conversion is heat-resistant inorganic oxide, also can first with heat-resistant inorganic oxide precursor, be prepared into heat-resistant inorganic oxide, then in the preparation process of catalyst composition, the form with heat-resistant inorganic oxide adds.

In cracking gasification catalyst composition preparation method provided by the invention, the order of mesoporous silica-alumina materials, gasification reactivity component, clay, heat-resistant inorganic oxide matrix being mixed to making beating does not have specific (special) requirements, for example, can, by described raw material difference prepared slarry, then prepared slurries be mixed; Can first mesoporous silica-alumina materials be mixed with clay, and then mix making beating with other component; Or gasification reactivity component is mixed to making beating with clay, and then mix making beating with other component.

When catalyst composition of the present invention contains metal traps, in the present invention, the introducing mode of metal agent for capturing can be introduced with ionic species or complex form when mesoporous silica-alumina materials, gasification reactivity component, cracking activity component, clay mix making beating, also the form with precipitation after above-mentioned several component spray drying formings can introduced.If introduce heat-resistant inorganic oxide matrix in carbon monoxide-olefin polymeric, can also in advance metal traps be deposited in described inorganic oxide by coprecipitation.Under preferable case, by butt, the content of described metal traps is no more than 20 % by weight of catalyst composition.The present invention without specific (special) requirements, can pollute the common metal trapping agent of the component of metal to the kind of described metal traps for trapping V, Ni, Fe, Ca etc., under preferable case, described metal traps is the precursor of rare earth oxide and/or rare earth oxide.More preferably in situation, 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 under lower gasification temperature, obtain the higher intensity of making charcoal, obtain higher density of hydrogen.Mesoporous silica-alumina materials and gasification reactivity component are carried out to the coke gasification efficiency that effective combination can improve catalyst greatly; The inventor finds unexpectedly simultaneously, with the mesoporous silica-alumina materials without ion-exchange of preparing in CN1565733A, mix making beating with water, obtain slurries, mix with inorganic acid again, the catalyst composition that the mesoporous silica-alumina materials that the method for removing Na that the mesoporous silica-alumina materials making at least 0.2 hour this ad hoc approach of room temperature to 100 ℃ exchange replaces conventional ammonium exchange or ammonium exchange and inorganic acid to combine obtains makes, there is better catalytic coke vaporization ability, reduce gasification temperature, improve yield of light oil.When catalyst composition of the present invention is used for cracking-gasification integral process of heavy petroleum hydrocarbon, gasification result is good, and gasification temperature is low, has for example heavy oil conversion performance of stronger petroleum hydrocarbon.Especially when described gasification reactivity component be have the principal phase of XRD shown in Fig. 1 peak containing potassium material, not only gasification result is good, gasification temperature is low, and has stronger hydrocarbon oil conversion ability, and gasification reactivity component runs off few.

Accompanying drawing explanation

Fig. 1 is the XRD phase figure containing potassium active component of the present invention.

Fig. 2 is the X-ray diffracting spectrum of the mesoporous silica-alumina materials that obtains of mesoporous silica-alumina materials of the present invention and traditional ammonium switching method, wherein, curve 1 is the spectral line that the mesoporous silica-alumina materials obtaining is processed in the exchange through twice ammonium described in CN1565733A, and curve 2 is spectral lines of the mesoporous silica-alumina materials that obtains of Preparation Example 4.

The specific embodiment

Provided by the invention for processing the cracking gasification catalyst composition of heavy petroleum hydrocarbon, this catalytic cracking composition contains mesoporous silica-alumina materials, cracking activity component, gasification reactivity component, clay, heat-resistant inorganic oxide matrix, with butt weight percent meter, described catalyst composition comprises: 1% ~ 50% mesoporous silica-alumina materials in butt, 1% ~ 60% cracking activity component in butt, 1% ~ 40% gasification reactivity component in butt, 0% ~ 70% clay in butt and 5% ~ 97% heat-resistant inorganic oxide matrix in butt; Preferably, by weight percentage, described catalyst composition comprises: 2 % by weight ~ 60 % by weight mesoporous silica-alumina materials, the gasification reactivity component of 5 % by weight ~ 40 % by weight, the cracking activity component of 5 ~ 50 % by weight, the heat-resistant inorganic oxide matrix of the clay of 0 % by weight ~ 60 % by weight and 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, the heat-resistant inorganic oxide matrix of the clay of 5 % 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 the following steps: by during aluminium source and aqueous slkali are at room temperature to 85 ℃ and plastic, the pH value of plastic terminal is 7-11; Then according to SiO ₂: Al ₂o ₃the weight ratio of=1:0.6-9 adds silicon source, aging 1-10 hour at room temperature to 90 ℃, gained solid sediment is carried out to ion-exchange with ammonium, make 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: H ₂o=1:(0.1-1): (10-30).

Mesoporous silica-alumina materials obtained above, preferably through peracid treatment, described acid treatment comprises the mesoporous silica-alumina materials after ammonium exchange and inorganic acid contacted at least 0.2 hour at room temperature to 100 ℃, the temperature of described contact is 30-80 ℃, is preferably 40-70 ℃; 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, described acid-treated mesoporous silica-alumina materials is made by the method comprising the following steps: the mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 ℃, make sodium oxide content in described mesoporous silica-alumina materials not higher than 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.In order better to realize object of the present invention, under preferable case, the weight ratio of the described mesoporous silica-alumina materials without 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 specific (special) requirements, and conventional inorganic acid all can be realized object of the present invention, and under preferable case, the inorganic acid using is selected from one or more in sulfuric acid, hydrochloric acid and nitric acid.The mode that the present invention contacts with inorganic acid described slurries is without specific (special) requirements, they can be mixed with random order, for example inorganic acid can be joined in slurries and mixes, also slurries can be joined in inorganic acid and mix, wherein, preferred hybrid mode is for to join inorganic acid in slurries and to mix.In the present invention, the condition that described slurries contact with inorganic acid can be conventional ion-exchange condition.For the present invention, under preferable case, the temperature of described contact is 30-80 ℃, is preferably 40-70 ℃; The time of contact is 0.2-2 hour, is preferably 0.3-1.5 hour, more preferably 0.5-1 hour.The weight ratio of the described mesoporous silica-alumina materials without 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.

In the present invention, in the weight ratio of the mesoporous silica-alumina materials without ion-exchange, water and inorganic acid, the described mesoporous silica-alumina materials weight without ion-exchange is the weight in butt.In the present invention, the weight in butt refers to the weight of roasting after 1 hour under the condition of 800 ℃.

In the present invention, described mesoporous silica-alumina materials preferably has boehmite crystal phase structure, and its X-ray diffracting spectrum is as shown in the curve 2 of Fig. 2.And in described mesoporous silica-alumina materials, the anhydrous chemical expression of oxide weight of take is (0-0.2) Na ₂o(40-90) Al ₂o ₃(10-60) SiO ₂.

In the present invention, the described silica-alumina material without ion-exchange can be the sediment obtaining after filtering, can be also dried and/or roasting after the mesoporous silica-alumina materials that obtains.

Silica-alumina material preparation method without ion-exchange: by during aluminium source and aqueous slkali are at room temperature to 85 ℃ and a plastic, the pH value of plastic terminal is 7-11; Then according to SiO ₂: Al ₂o ₃the weight ratio of=1:0.6-9 adds silicon source, and then aging 1-10 hour at room temperature to 90 ℃ filters and be precipitated thing (filter cake).The sediment that this filtration obtains can be used as the silica-alumina material without 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 conventional various aluminium source of using in the preparation technology of mesoporous silica-alumina materials, 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 the conventional various sial that use in the preparation technology of mesoporous silica-alumina materials, for example, can be at least one in silica gel, waterglass, sodium metasilicate, silicon tetraethyl, silica, Ludox and silicon gel.

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 example, can be one or more in ammoniacal liquor, potassium hydroxide solution, sodium aluminate solution and sodium hydroxide solution.

According to the present invention, although ,Gui source, described aluminium source and aqueous slkali can suitably be selected separately from the above-mentioned material of enumerating, yet, in common described aluminium source, aqueous slkali and silicon source, having at least a kind of is the raw material containing sodium, thereby guarantees that the described mesoporous silica-alumina materials without ion-exchange of so preparation has the meso-hole structure of appropriate size.According to of the present invention preferred embodiment a kind of, described aluminium source is selected from one or more in aluminum nitrate, aluminum sulfate and aluminium chloride, described alkali is selected from one or more in ammoniacal liquor, potassium hydroxide, NaOH and sodium metaaluminate, described silicon source is selected from one or more in waterglass, sodium metasilicate, silicon tetraethyl and silica, and in aluminium source wherein, alkali and silicon source, has at least a kind of for containing sodium raw materials.

In the present invention, in the described mesoporous silica-alumina materials without ion-exchange, take the sodium content of sodium oxide molybdena is 0.5-15 % by weight.And in described catalyst composition of the present invention, the sodium content in sodium oxide molybdena in the described preferred mesoporous silica-alumina materials of preparing without the mesoporous silica-alumina materials of ion-exchange described in adopting is generally below 0.2 % by weight.

Provided by the invention for processing the cracking gasification catalyst composition of petroleum hydrocarbon, preferably, described gasification reactivity component comprises potassium, contain or alkali-free earth metal, the weight of described gasification reactivity component of take is 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 gasification reactivity component can be any active component containing potassium, contain or alkali-free earth metal, containing potassium active component for example potassium hydroxide, potash, 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 containing one or more in potassium material.Wherein, preferably have 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 earth metal compound and sial component are pulled an oar into wet feed, then be dried into siccative, after roasting, obtain, sintering temperature is 800 ℃ ~ 1150 ℃, roasting time 1 ~ 10h again; In order better to realize object of the present invention, the active higher gasification reactivity component of preparation, under preferable case, sintering temperature is 900 ℃ ~ 1100 ℃, roasting time is 2 ~ 8h.The making beating mode that the present invention pulls an oar containing use potassium-containing compound, alkaline earth metal compound and sial component described in potassium material to described preparation is without specific (special) requirements, they can be mixed with random order, 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 the first mechanical mixture of three kinds of materials, 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 has containing in potassium substance process of the principal phase of XRD shown in Fig. 1 peak, one or more in the optional autoxidation potassium of described potassium-containing compound, potassium hydroxide, potash, potassium nitrate, described alkaline earth metal compound can be selected from one or more in alkaline earth oxide, alkaline earth metal carbonate, alkaline earth nitrate.Described in the present invention have the principal phase of XRD shown in Fig. 1 peak containing in the preparation of potassium gasification substance active component, described sial component can be selected from the crystal aluminosilicate mineral of any layer structure, as one or more in kaolin, imvite, rectorite, attapulgite, illite, sepiolite and diatomite, aluminium colloidal sol, Ludox.

The preparation method of described catalyst composition provided by the invention, preferred embodiment a kind of, comprise the following steps:

(1) mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 ℃, obtain 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;

(2) potassium-containing compound, alkaline earth metal compound and sial component are mixed to making beating, be then dried into siccative, then 800 ℃ ~ 1150 ℃ preferably 900 ℃ ~ 1100 ℃ roastings, roasting time 1 ~ 10h, obtains the gasification reactivity component containing potassium after roasting; Wherein the alkaline earth metal compound of alkaline earth oxide meter is for example 1:5 ~ 1:0.5 with take the mol ratio 1:9 ~ 1:0.2 of potassium-containing compound of potassium oxide, SiO ₂/ Al ₂o ₃mol ratio be 1:10 ~ 10:1 for example for 1:3 ~ 3:1, the butt weight of the resulting gasification reactivity component containing potassium of take is benchmark, resulting is 8 % by weight ~ 40 % by weight containing take the potassium content of potassium oxide in the gasification reactivity component of potassium;

(3) the described mesoporous silica-alumina materials obtaining in step (1) and step (2) are obtained containing potassium gasification reactivity component and clay, cracking activity component, heat-resistant inorganic oxide matrix are mixed making beating, then spray be dried, roasting 2 ~ 10h at 400 ~ 800 ℃; Wherein press butt weighing scale, the consumption of described mesoporous silica-alumina materials, gasification reactivity component, cracking activity component, clay and heat-resistant inorganic oxide matrix makes resulting 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% described heat-resistant inorganic oxide matrix.Wherein, described clay can be the conventional clay in this area, under preferable case, can be selected from one or more in kaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil, hydrotalcite; More preferably be selected from one or more in kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone; When heat-resistant inorganic oxide matrix has adhesive property, be binding agent, described binding agent can be the conventional binding agent in this area, in preferred situation, can select one or more in aluminium colloidal sol, Ludox, boehmite, phosphorus aluminium glue.Under preferable case, also can add acid to carry out acidifying in described slurries, described acid is one or more in hydrochloric acid, nitric acid, sulfuric acid for example.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 cracking activity component, clay, binding agent mixes making beating, obtain the second slurries, then the first slurries and the second slurries mixed to making beating, then spray be dried, at 400 ~ 800 ℃ of preferred roasting 2 ~ 10h at 450 ~ 750 ℃.

The preparation method of described catalyst composition provided by the invention, described preferred embodiment in, only the preparation method of catalyst composition is described, be 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 silica-alumina materials weight without ion-exchange is the weight in butt.In the present invention, the weight in butt refers to the weight of roasting after 1 hour under the condition of 800 ℃.According to method of the present invention, the present invention is to the kind of described inorganic acid without specific (special) requirements, and conventional inorganic acid all can be realized object of the present invention, and under preferable case, the inorganic acid using is selected from one or more in sulfuric acid, hydrochloric acid and nitric acid.In order better to realize object of the present invention, under preferable case, the weight ratio of the described mesoporous silica-alumina materials without 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 mode that gained slurries contact with inorganic acid is without specific (special) requirements, they can be mixed with random order, for example inorganic acid can be joined in slurries and mixes, also slurries can be joined in inorganic acid and mix, wherein, preferred hybrid mode is for to join inorganic acid in slurries and to mix.The condition that described slurries are contacted with inorganic acid can be conventional ion-exchange condition.Under preferable case, the temperature of described contact is 30-80 ℃, is preferably 40-70 ℃; The time of contact is 0.2-2 hour, is preferably 0.3-1.5 hour, more preferably 0.5-1 hour.

According to the preparation method of catalyst composition provided by the invention, described a kind of preferred embodiment in, in step (1), the described mesoporous silica-alumina materials without ion-exchange can be the conventional various mesoporous silica-alumina materials without any ion-exchange in this area.The described mesoporous silica-alumina materials without ion-exchange can prepare according to conventional method, and its preparation method for example can comprise: by during aluminium source and aqueous slkali are at room temperature to 85 ℃ and plastic, plastic endpoint pH is 7-11; Then according to SiO ₂: Al ₂o ₃the weight ratio of=1:0.6-9 adds silicon source, and aging 1-10 hour at room temperature to 90 ℃, then filters.In the present invention, the sial sediment obtaining after described filtration can directly be used as the described mesoporous silica-alumina materials without ion-exchange, also can be dried and/or roasting after as the described mesoporous silica-alumina materials without ion-exchange.,Gui source, described aluminium source and aqueous slkali all with describe above identical.

For there is and/or can obtain the precursors of inorganic oxides of described inorganic oxide with oxide form in described inorganic oxide matrix.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, obtains gas, gasoline fraction, diesel oil distillate, wax oil cut and deposited the catalyst composition of coke after reaction effluent separation; Described petroleum hydrocarbon is one or more in AGO (atmospheric gas oil), vacuum gas oil (VGO), decompression residuum, reduced crude, To Propane Deasphalting Oil, wax tailings for example.Described reaction condition for example reaction temperature 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, by controlling gasification condition, the charcoal on described catalyst composition and gasifying agent reaction generate is rich in CO and H ₂gas, obtain catalyst composition or the half regeneration catalyzing composition of holomorphosis, described half regeneration catalyzing composition is at regeneration unit, under the condition that has oxygen to exist simultaneously, 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 is for example: gasification temperature is 650 ~ 890 ℃, gasification temperature can be 650 ~ 860 ℃ or 680 ~ 750 ℃, gasifying agent can comprise the steam of 70 ~ 100 volume % and the oxygen of 0 ~ 30 volume %, and for example gasifying agent comprises and is 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 steam of little 100 volume %; 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) and recycle.

Above-mentioned steps (2) preferably, by controlling regeneration condition, is gasificated into coke on catalyst composition to be rich in CO and H ₂in the time of gas, obtain half regeneration catalyzing composition, the further destruction that on composition, remaining coke layer can guard catalyst be subject to gasifying agent, reduces the loss of gasification reactivity component and the inactivation at cracking activity center.In described half regenerative compositions, coke content 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 Industry ₂o ₃content is 21.5 % by weight), kaolin provides (solid content is 80 % by weight) by Chinese Suzhou, and boehmite provides (solid content is 65.8 % by weight) by Shandong Aluminum Plant.DASY-2.0 molecular sieve is produced by catalyst asphalt in Shenli Refinery of China Petrochemical Industry, is designated as Y-1; REY molecular sieve has catalyst asphalt in Shenli Refinery of China Petrochemical Industry to produce, 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; Y zeolite phosphorous and rare earth is prepared according to the method for embodiment in CN1353086A 1, is designated as Y-4; The method preparation that a kind of super stable molecular sieve containing rare earth is announced according to embodiment in CN1958452A patent 1, is designated as Y-5; MFI molecular sieve makes according to the method for embodiment in CN1147420 1, is designated as Y-6.In comparative example and embodiment, chemical reagent used does not indicate especially, and its specification is chemical pure.

In each embodiment, K in product ₂o, Na ₂o, Al ₂o ₃, SiO ₂content with x-ray fluorescence method, measure (can be referring to < < Petrochemical Engineering Analysis method (RIPP experimental technique) > >, Yang Cui is the volume such as surely, 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, again by HCl solution (concentration is 10 % by weight) by SA-3(butt): the weight ratio of HCl=1:0.09 is mixed with SA-3, at 50 ℃, contact 40 minutes, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, be 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 preparation process of mesoporous silica-alumina materials SSA-2 is basic identical with the mesoporous silica-alumina materials SA-2 of embodiment in CN1565733A 2, just adopts sour exchange process to substitute ammonium exchange process wherein.Be about to the intermediate sedimentation thing of SA-2, it is the sial sediment after aging filtration, by the weight ratio of 1:10, mix making beating with water, again by HCl solution (concentration is 10 % by weight) by sediment (butt): the weight ratio of HCl=1:0.12 joins in above-mentioned slurries, at 55 ℃, contact 40 minutes, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, be designated as SSA-2.This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 2; Its elementary analysis weight chemical composition is 0.1Na ₂o58.9Al ₂o ₃40.9SiO ₂.

Preparation Example 5

The preparation process of mesoporous silica-alumina materials SSA-3 is basic identical with the mesoporous silica-alumina materials SA-3 of embodiment in CN1565733A 3, just adopts sour exchange process to substitute ammonium exchange process wherein.Be about to the intermediate sedimentation thing of SA-3, it is the sial sediment after aging filtration, by the weight ratio of 1:12, mix making beating with water, again by HCl solution (concentration is 10 % by weight) by sediment (butt): the weight ratio of HCl=1:0.09 joins in above-mentioned slurries, at 50 ℃, contact 40 minutes, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, be designated as SSA-3.This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 2; Its elementary analysis weight chemical composition is 0.09Na ₂o73.9Al ₂o ₃25.9SiO ₂.

Preparation Example 6

The preparation process of mesoporous silica-alumina materials SSA-4 is basic identical with the mesoporous silica-alumina materials SA-4 of embodiment in CN1565733A 4, just adopts sour exchange process to substitute ammonium exchange process wherein.Be about to the intermediate sedimentation thing of SA-4, it is the sial sediment after aging filtration, by the weight ratio of 1:12, mix making beating with water, again by HCl solution (concentration is 10 % by weight) by sediment (butt): the weight ratio of HCl=1:0.14 joins in above-mentioned slurries, at 60 ℃, contact 30 minutes, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, be designated as SSA-4.This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 2; Its elementary analysis weight chemical composition is 0.06Na ₂o73.8Al ₂o ₃26.0SiO ₂.

Preparation Example 7 ~ 11 is for illustrating the preparation method of the gasification reactivity component at XRD principal phase peak shown in the present invention Fig. 1 of having used.

Preparation Example 7

Take in 1776 grams of kaolin of butt, 210 grams of K ₂o and 14 grams of CaO, mix three add appropriate amount of deionized water, makes slurry solid content 15% ~ 50%, stirs at least 20 minutes, dry, then roasting 4 hours at 1000 ℃, makes containing potassium gasification reactivity component K-1, wherein K ₂o content is 10.5%, CaO/K ₂the mol ratio of O is 1/9, SiO ₂/ Al ₂o ₃mol ratio be that 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, containing potassium gasification reactivity component K-2, K-3, K-4, K-5, K-6, specifically feeds intake in Table 1.What embodiment 7 ~ 12 was prepared all has the XRD feature principal phase peak shown in Fig. 1 (principal phase peak 2 θ are respectively 21 °, 29 °, 35 °) containing potassium material

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 is the hydrochloric acid of 36 % by weight to adding concentration in the slurries that obtain, sour aluminum ratio (described 36 % by weight hydrochloric acid with Al ₂o ₃the weight ratio of the boehmite of meter) be 0.2, be warmed up to 65 ℃ of acidifyings 1 hour, obtain slurries.By the kaolin in 20 parts of butts (Suzhou carclazyte), in the aluminium colloidal sol of butt 10 weight portions, join in the boehmite slurries of acidifying and mix making beating 20 minutes, then by the REY molecular sieve (RE in butt 35 weight portions ₂o ₃content is 18.8 % by weight, silica alumina ratio (SiO ₂with Al ₂o ₃mol ratio) catalyst asphalt in Shenli Refinery of 5.1， China Petrochemical Industry product) add, pull an oar 1 hour, obtain the first slurries.

The potassium material K-1 that contains in butt 10 weight portions is mixed with the mesoporous silica-alumina materials SA-3 in butt 10 weight portions, 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 minutes, obtain the slurries that solid content is 30 % by weight.Spraying is dry makes microballoon catalyst composition, then 550 ℃ 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 ℃ of steam are processed 72h, measures K in the sample composition of hydro-thermal front and back ₂the weight content of O, with the stability of potassium in retention rate definition catalyst composition.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, and concrete 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 retention rate of potassium after hydrothermal treatment consists apparently higher than adopt other containing potassium material and alkaline-earth metal as the catalyst composition of gasification reactivity component in the retention rate of potassium.

Preparation comparative example 1

According to the method for preparing catalyst of the embodiment 1 announcing in patent CN200910143623.3 and ingredient proportion, prepared comparative catalyst D1.Adopt hydrothermal experiment to test the wastage of catalyst D1 potassium, potassium retention rate and catalyst are prepared ingredient proportion in Table 3.

Preparation comparative example 2

Method for preparing catalyst according to the embodiment 1 announcing in patent CN200910143623.3 has been prepared comparative catalyst D2.Adopt hydrothermal experiment to test the wastage of catalyst D2 potassium, potassium retention rate and catalyst are prepared ingredient proportion in Table 3.

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, preparation contrast catalyst composition D3 ~ D6, concrete inventory is in Table 3, and inventory is wherein parts by weight.

From the data of table 2 and table 3, can find out, carbon monoxide-olefin polymeric is processed after 72h through 500 ℃ of 100% steam, when using method preparation provided by the present invention to there is the high as the potassium retention rate of the carbon monoxide-olefin polymeric of gasification reactivity component containing potassium material of the principal phase of XRD shown in Fig. 1 peak, the potassium retention rate apparently higher than other potassium-containing compounds as the catalyst composition of gasification reactivity component.Visible, adopt the stability containing potassium material with the principal phase of XRD shown in Fig. 1 peak prepared by method provided by the invention due 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 ℃, 17 hours, the light oil microactivity that 100% steam treatment has.Evaluating feedstock oil used is that boiling range is the huge port straight distillation light diesel oil of 221 ~ 335 ℃.Appreciation condition is: oil ratio 1.28, mass space velocity is 40h ^-1, reaction temperature is 460 ℃.Evaluation result is in Table 4.

Table 4

Mesoporous material	Micro-activity (% by weight)	Mesoporous material	Micro-activity (% by weight)
				SA-2	24	SSA-2	27
SAS-3	26	SSA-3	28
				SA-4	27	SSA-4	30

[0115]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 ℃, 100% steam, process after 17 hours, the activity of the mesoporous silica-alumina materials (SA-2 ~ SA-4) that its light oil microactivity obtains than traditional ammonium exchange is high 2 ~ 3 percentage points, illustrates that employing method processing provided by the invention obtains silica-alumina material cracking activity good.

Test case 2

Gasification performance and the cracking performance of the catalyst composition that this test is used for illustrating that embodiment 13 ~ 21 and comparative example 1 ~ 6 provide.Respectively the catalyst composition of above-mentioned preparation aging 8h under 790 ℃, the condition of 100% steam, be then seated in reserve and be in 210 grams fixed fluidized bed and carried out cracking and gasification experiment.Cracking experiment condition is: reaction temperature is that 520 ℃, weight (hourly) space velocity (WHSV) are 20h ^-1, oil ratio is 8, water-oil factor is 0.35; Gasification experiment condition: gasification temperature is 700 ℃, gasifying agent is 100% steam, the time of staying of gasifying agent is 50 seconds.The catalyst composition that comparative example 1 ~ 2 provides is in addition after cracking experiment, and the gasification experiment condition of also announcing according to test case in CN200910143623.3 is carried out gasification experiment, and gasification condition is that gasification temperature is 860 ℃, and gasifying agent is the oxygen of 80% steam and 20%.Catalyst composition after all gasifications keeps certain coke to be retained on composition, and >0.3 % by weight, for example, be 0.4 ~ 0.6 % by weight conventionally.

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 the increase of temperature, increase, the intensity of making charcoal that contains oxygen in gasifying agent can be better than usings the make charcoal intensity of 100% steam as gasifying agent.From table 6 and table 7, can find out, cracking gasification catalyst composition provided by the invention can obtain good gasification result under lower gasification temperature, obtains the higher intensity of making charcoal, and gasification product has higher density of hydrogen.Catalyst composition prepared by the mesoporous silica-alumina materials that adopts preferred mesoporous silica-alumina materials processing method provided by the invention to obtain has better cracking performance, and coke selectivity is good, light oil yield (total recovery of gasoline and liquefied gas) height.The catalyst composition (referring to C9) of preparing with existing gasification reactivity component is compared, adopt the gasification reactivity of the catalyst composition of preparing as gasification reactivity component containing potassium material with the XRD principal phase peak shown in Fig. 1 prepared by method provided by the invention higher, the intensity of making charcoal is higher; Under same gasification condition, 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 ℃, gasification reactivity under 100% water vapor conditions and the intensity of making charcoal just can reach 860 ℃, the gasification result of 80% steam, in the catalyst composition that invention provides, contain simultaneously the XRD principal phase peak shown in mesoporous silica-alumina materials and Fig. 1 when the potassium material, gasification reactivity is higher, this may be because mesoporous silica-alumina materials has improved the distribution of coke, has improved the utilization rate of gasification reactivity component, and then has improved gasification performance.Visible, adopt visible use catalyst composition provided by the invention and for gasify-cracking PROCESS FOR TREATMENT heavy petroleum hydrocarbon, be conducive to realize the efficient utilization of petroleum resources, and energy-conservation.

Test case 3

Get catalyst composition D1 that catalyst composition C3 that embodiment 3 provides, catalyst composition C6 that embodiment 6 provides and comparative example 1 provide, catalyst composition D2 that comparative example 2 provides and at dress dosage be on the circulation cracking-gasification-regenerating unit of 50 grams and test.The condition of cracking is: 550 ℃, and oil ratio 5, cracked stock oil nature is in Table 5; In order to reach the close intensity of making charcoal, C3, C6, at 700 ℃, gasify under 100% steam, and D1, D2, at 860 ℃, gasify under the condition of 80% steam+20% oxygen, and the time of staying of gasifying agent is 50 seconds.The condition of holomorphosis is 680 ℃, air regenesis, coke content <0.1% on catalyst composition after holomorphosis.Repeatedly carry out cracking-gasify-regenerate 40 cycles, unload catalyst composition, then catalyst composition is carried out on light oil micro-reactor to cracking activity (MA) test.The micro-anti-test evaluation of light oil feedstock oil used is that flow process is the huge port straight distillation light diesel oil of 221 ~ 335 ℃.Appreciation condition is: oil ratio 1.28, mass space velocity is 40h ^-1, reaction temperature is 460 ℃.Evaluating all feedstock oil is that flow process is the huge port straight distillation light diesel oil of 221 ~ 335 ℃.Appreciation condition is: oil ratio 3.2, mass space velocity is 16h ^-1, reaction temperature is 460 ℃.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, the activity of D1, D2 is far below C3 and C6, this may be because the gasification reactivity of D1 and D2 do not have C3 and C6 high, in order to reach identical, be that the intensity of making charcoal must improve gasification temperature, yet in catalyst composition can there is framework of molecular sieve avalanche in cracking activity component under high temperature, water vapor conditions, causes expendable loss of activity.

Claims (21)

1. cracking gasification 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, and the anhydrous chemical expression of oxide weight of take is (0-0.3) Na ₂o(40-90) Al ₂o ₃(10-60) SiO ₂, specific area is 200-400m ²/ g, pore volume is 0.5 ~ 2.0mL/g, and average pore size 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, and described acid treatment is according to weight ratio, to be that 1:5-30:0.03-0.3 contacts at least 0.2 hour by mesoporous silica-alumina materials, water and inorganic acid.

3. according to catalyst composition claimed in claim 1, it is characterized in that, described mesoporous silica-alumina materials is through acid-treated mesoporous silica-alumina materials, by the method comprising the following steps, made: the mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 ℃, make sodium oxide content in described mesoporous silica-alumina materials not higher than 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.

4. according to catalyst composition claimed in claim 1, it is characterized in that, described gasification reactivity component comprises alkali metal and/or alkaline-earth metal.

5. according to catalyst composition claimed in claim 1, it is characterized in that, described gasification reactivity component comprises potassium, contain or alkali-free earth metal, the weight of described gasification reactivity component of take is benchmark, in oxide weight, in described gasification reactivity component, the content of potassium is 2 ~ 100%, and the content of alkaline-earth metal is 0-98 % by weight.

6. according to the catalyst composition described in claim 1 or 5, it is characterized in that, described gasification reactivity component comprise have the principal phase of XRD shown in Fig. 1 peak containing potassium material.

7. according to catalyst composition claimed in claim 6, it is characterized in that, described have the principal phase of XRD shown in Fig. 1 peak containing in potassium material, the potassium content of potassium oxide of take is 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, SiO ₂/ Al ₂o ₃mol ratio be 1:10 ~ 10:1.

8. according to catalyst composition claimed in claim 6, it is characterized in that, described have the principal phase of XRD shown in Fig. 1 peak containing potassium oxide content 10 % by weight ~ 30 % by weight in potassium material, alkaline earth oxide and potassium oxide mol ratio 1:5 ~ 1:0.5, SiO ₂/ Al ₂o ₃mol ratio be 1:3 ~ 3:1.

9. according to the catalyst composition described in claim 6,7 or 8, it is characterized in that, being obtained by following methods containing potassium material of the peak of XRD principal phase shown in the described Fig. 1 of having: potassium-containing compound, alkaline earth metal compound and sial component are pulled an oar into wet feed, then be dried into siccative, after roasting, obtain again, sintering temperature is 800 ℃ ~ 1150 ℃, 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 zeolite, have one or more in MIF structural zeolite and β zeolite.

The preparation method of catalyst composition described in 11. 1 kinds of claims 1, comprises mesoporous silica-alumina materials, gasification reactivity component, cracking activity component, clay, heat-resistant inorganic oxide matrix is mixed to making beating, 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 step of preparing described mesoporous silica-alumina materials; The preparation method of described mesoporous silica-alumina materials, comprises the following steps: by during aluminium source and aqueous slkali are at room temperature to 85 ℃ and plastic, the pH value of plastic terminal is 7-11; Then according to SiO ₂: Al ₂o ₃the weight ratio of=1:0.6-9 adds silicon source, aging 1-10 hour at room temperature to 90 ℃, gained solid sediment is carried out to ion-exchange with ammonium, make the content that contains sodium oxide molybdena in the mesoporous material of sodium not higher than 0.2% weight, wherein mesoporous silica-alumina materials (butt): ammonium salt: H ₂o=1:(0.1-1): (10-30).

13. according to the preparation method of catalyst composition described in claim 11, it is characterized in that, the preparation method of described mesoporous silica-alumina materials comprises acid-treated step; Described acid treatment step is that the ratio that is 1:5-30:0.03-0.3 according to the weight ratio of mesoporous silica-alumina materials, water and inorganic acid by the mesoporous silica-alumina materials obtaining by ammonium ion exchange 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 is made by the method comprising the following steps: the mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 ℃, make sodium oxide content in described mesoporous silica-alumina materials not higher than 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.

15. according to the preparation method of catalyst composition described in claim 14, it is characterized in that, the described mesoporous silica-alumina materials without exchange is made by the method comprising the following steps: by during aluminium source and aqueous slkali are at room temperature to 85 ℃ and plastic, the pH value of plastic terminal is 7-11; Then according to SiO ₂: Al ₂o ₃the weight ratio of=1:0.6-9 adds silicon source, at room temperature to 90 ℃, aging 1-10 hour obtains colloid admixture, the sediment that described colloid admixture obtains be after filtering the described silica-alumina material without ion-exchange or by described colloid admixture or the sediment obtaining after filtering be dried and/or roasting after the mesoporous silica-alumina materials without ion-exchange described in obtaining.

16. according to the preparation method of catalyst composition described in claim 13 or 14, it is characterized in that, the temperature of described contact is 30-80 ℃, and 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 acid is 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 is selected from potassium 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 containing potassium material, the chloride of alkaline-earth metal, the nitrate of alkaline-earth metal, the sulfate of alkaline-earth metal, one or more in the phosphate of alkaline-earth metal, described alkaline-earth metal is beryllium, magnesium, calcium, strontium, one or more in barium.Wherein, described gasification reactivity component be preferably have the principal phase of XRD shown in Fig. 1 peak containing potassium material.

18. according to the preparation method of catalyst composition described in claim 17, it is characterized in that, comprising containing potassium substances preparation method of the peak of XRD principal phase shown in the described Fig. 1 of having: potassium-containing compound, alkaline earth metal compound and sial component are pulled an oar into wet feed, then be dried into siccative, described in obtaining after roasting again, have the principal phase of XRD shown in Fig. 1 peak containing potassium material, sintering temperature is 800 ℃ ~ 1150 ℃, roasting time 1 ~ 10h.

19. according to the preparation method of catalyst composition described in claim 18, it is characterized in that, described in have the principal phase of XRD shown in Fig. 1 peak containing potassium material, sintering temperature is 900 ℃ ~ 1100 ℃, 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 one or more in kaolin, imvite, rectorite, attapulgite, illite, sepiolite, diatomite, or is one or more and the mixture of Ludox in kaolin, imvite, rectorite, attapulgite, illite, sepiolite, diatomite, aluminium colloidal sol; Or be one or more and the mixture of aluminium colloidal sol in kaolin, imvite, rectorite, attapulgite, illite, sepiolite, diatomite, Ludox.

The cracking gasification process of 21. 1 kinds of petroleum hydrocarbons, be included in cracker the cracking gasification catalyst composition haptoreaction described in petroleum hydrocarbon and claim 1 ~ 9 any one, by reacted described cracking gasification carbon monoxide-olefin polymeric and Oil-gas Separation, 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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