CN106179433B - A kind of cracking gasification process of cracking gasification catalyst composition, preparation method and heavy petroleum hydrocarbon for processing heavy petroleum hydrocarbon - Google Patents

Abstract

The cracking gasification process of cracking the gasification catalyst composition, preparation method and heavy petroleum hydrocarbon that the invention discloses a kind of for processing heavy petroleum hydrocarbon.By weight percentage, the catalyst composition includes: 1%~80% active mesopore material, and active mesopore material has the phase structure of boehmite, and the anhydrous chemical expression in terms of oxide weight is (0-0.2) Na₂O·(40‑85)Al₂O₃·(10‑55)SiO₂·(0.5‑10)P₂O₅·(0.5‑10)M_xO_y, metal M is selected from Mg, one of periodic table of elements IIB, IIIB, IVB, VIIB race's element and lanthanide series rare-earth elements or a variety of, highest valent state when y is metal M formation oxide, and the numerical value of x and y balances the chemical valence of M and O.The catalyst composition gasifies for heavy petroleum hydrocarbon cracking, and cracking performance is good, and gasification temperature is low.

Description

A kind of cracking gasification catalyst composition, its preparation side for processing heavy petroleum hydrocarbon The cracking gasification process of method and heavy petroleum hydrocarbon

Technical field

Cracking gasification catalyst composition and preparation method thereof that the present invention relates to a kind of for processing heavy petroleum hydrocarbon, and Using the cracking gasification process of the heavy petroleum hydrocarbon of cracking gasification catalyst composition.

Background technique

Currently, proposing and choosing to catalytic cracking process itself and catalyst when catalyzed cracking processing heavy, inferior feedstock oil War, inferior heavy oil non-catalytic processing, including delayed coking, fluid coking, flexicoking etc. are paid more and more attention.But coking work Skill has that the high and low quality coke of coke yield is difficult to be utilized, and delayed coking can generate a large amount of low value-added stones Oil coke, therefore petroleum resources are not utilized efficiently.

Coke a part burning that the fluid coking of Exxon Neftegas Limited's exploitation and flexicoking technique generate provides system System heat, remainder, which is generated using air or oxygen, vapor etc. in (900 DEG C or so) gasifications of high temperature, has certain low heat value Coal gas.On the one hand the technique uses high-temperature gasification, energy consumption is higher, CO and H in another aspect institute producing coal gas₂Comparision contents it is low, Calorific value is lower, and added value is also very low.

Catalyst, which is added, in gasification can reduce the activation energy of gasification reaction, reduce gasification temperature, reduce gasifying agent Additional amount, adjust the composition of synthesis gas.Alkali and alkaline earth metal ions are common gasifying catalysts, are added in Cracking catalyst Add a certain amount of alkali and alkaline earth metal ions that can promote the gasification of deposit coke on catalyst.It is public in CN200810246526.2 A kind of catalyst of the alkali metal containing for having both cracking and gasification function and alkaline-earth metal of cloth, the catalyst is containing 35%~60% Boehmite, 2%~10% Aluminum sol, 20%~49.5% kaolin, 5%~30% alkali gold in terms of oxide Belong to and alkaline-earth metal, the catalyst have the optimization function of cracking hydrocarbon oil product distribution and gasification reaction available gas yield. Disclose a kind of coke transfer agent in CN200910078392.2, including 50%~80% kaolin, 10%~39.5% Binder and 10%~30% alkali and alkaline earth metal ions in terms of oxide, wherein boehmite and Aluminum sol in binder Mass ratio be (1.2~6): 1, the atomic ratios of alkali and alkaline earth metal ions is (0.05~0.8): 1, the catalyst is in catalysis weight The catalytic cracking of matter crude oil while the gasification of catalytic coke.CN200910143623.3 discloses a kind of inferior heavy oil cracking and gasifying Catalyst, including carrier, binder, gasification reactivity component and cracking active component, wherein gasification reactivity group be divided into alkali metal and Alkaline-earth metal, on the basis of catalyst total amount, oxide count content be 2%~30%, the atomic ratio of alkali metal and alkaline-earth metal For (0.05~1.1): 1, cracking active component is shape-selective molecular sieve of the silica alumina ratio between 20~200.

The gasification temperature of above-mentioned existing catalyst is relatively high, in 860 DEG C of progress gasification reactions, for urging for alkali metal containing Change material, under high temperature hydrothermal condition, the loss of alkali metal is than more serious in catalyst.

The relatively high problem of gasification temperature in order to improve existing catalyst.A kind of use is disclosed in CN201210262943 Gasify catalyst composition in the cracking of processing heavy petroleum hydrocarbon, by weight percentage, the catalyst composition includes: 1%~ 70% mesoporous silica-alumina materials, 1%~60% gasification reactivity component, 0%~70% clay and 5%~98% heat-resisting nothing Machine matrix of oxide, wherein the mesoporous silica-alumina materials have the phase structure of boehmite, in terms of oxide weight Anhydrous chemical expression is (0-0.3) Na₂O·(40-90)Al₂O₃·(10-60)SiO₂, specific surface area 200-400m²/ g, hole Holding is 0.5~2.0mL/g, and average pore size is 8~20nm, and most probable pore size is 5~15nm.The catalyst composition is used for heavy stone Petroleum hydrocarbon cracking gasification, gasification temperature are low.

Although above-mentioned existing catalyst can reduce the gasification temperature of cracking hydrocarbon oil gasification conversion, in order to optimize hydrocarbon ils The product distribution of cracking gasification conversion, the cracking performance of existing catalyst also need to further increase.

Summary of the invention

The catalyst composition of cracking gasification is used in use process for the prior art the object of the present invention is to provide a kind of Middle gasification temperature is high or cracking performance needs the problem of further increasing, and provides a kind of for processing splitting for heavy petroleum hydrocarbon Change the cracking gasification process of gasification catalysis composition, preparation method and heavy petroleum hydrocarbon.

To achieve the goals above, according to an aspect of the present invention, it provides a kind of for processing splitting for heavy petroleum hydrocarbon Change gasification catalysis composition, by weight percentage, the catalyst composition include: 1%~80% active mesopore material, 1%~60% gasification reactivity component, 0%~70% clay and 2%~98% heat-resistant inorganic oxide matrix, wherein The activity mesopore material has the phase structure of boehmite, and the anhydrous chemical expression in terms of oxide weight is (0-0.2)Na₂O·(40-85)Al₂O₃·(10-55)SiO₂·(0.5-10)P₂O₅·(0.5-10)M_xO_y, wherein metal M is selected from One of Mg, periodic table of elements IIB, IIIB, IVB, VIIB race's element and lanthanide series rare-earth elements are a variety of, and y is metal M Form highest valent state when oxide, and the numerical value of x and y balance the chemical valence of M and O, specific surface area for 200~ 500m²0.5~1.5cm of/g, Kong Rongwei³/ g, average pore size are 8~18nm.

According to another aspect of the present invention, a kind of preparation method of above-mentioned catalyst composition is additionally provided, including will be lived The step of property mesopore material, gasification reactivity component, clay, heat-resistant inorganic oxide matrix are mixed with beating, are spray-dried and roast.

In addition, according to a further aspect of the invention, a kind of cracking gasification process of heavy petroleum hydrocarbon is additionally provided, including By heavy petroleum hydrocarbon and above-mentioned cracking gasification catalyst composition haptoreaction in cracker, by the cracking after reaction Gasifying catalyst composition and Oil-gas Separation, by the isolated cracking gasification catalyst composition that deposited coke and gasifying agent The step of contact.

The present invention it is above-mentioned provided by for process heavy petroleum hydrocarbon cracking gasification catalyst composition, preparation method and The cracking gasification process of heavy petroleum hydrocarbon, by introducing specific active mesopore material, using this active mesopore material because of gold Belong to and nonmetallic ingredient introducing and special matching relationship to the distribution situation in material acid site and acid strength effectively adjusts with Improve, improves heavy oil conversion performance, while reducing gasification temperature；Higher burning can be obtained under lower gasification temperature Charcoal intensity obtains higher density of hydrogen.Catalyst composition of the invention is used for cracking-gasification one chemical industry of heavy petroleum hydrocarbon When skill, gasification result is good, and gasification temperature is low, has stronger heavy oil conversion performance (cracking performance is preferable).Especially with contain There are the cooperations of the gasification reactivity component of the substance containing potassium at main phase peak to make at 2 angles θ is 21 °, 29 ° and 35 ° in XRD diffracting spectrum With not only gasification result is good, and gasification temperature is low, and has stronger heavy oil conversion performance (cracking performance is preferable), and gasifies and live Property component be lost it is few.

Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.

Detailed description of the invention

The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:

Fig. 1 is the XRD object phasor of the active component of the present invention containing potassium.

Fig. 2 is the X-ray diffracting spectrum of active mesopore material of the invention.

Specific embodiment

Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

The cracking gasification catalyst composition that the present invention provides a kind of for processing heavy petroleum hydrocarbon, with weight percent Meter, the catalyst composition include: 1%~80% active mesopore material, 1%~60% gasification reactivity component, 0%~ 70% clay and 2%~98% heat-resistant inorganic oxide matrix, wherein it is described activity mesopore material have boehmite Phase structure, and the anhydrous chemical expression in terms of oxide weight be (0-0.2) Na₂O·(40-85)Al₂O₃·(10- 55)SiO₂·(0.5-10)P₂O₅·(0.5-10)M_xO_y, wherein metal M is selected from Mg, the periodic table of elements IIB, IIIB, IVB, VIIB One of race's element and lanthanide series rare-earth elements are a variety of, highest valent state when y is metal M formation oxide, and x With the numerical value of y the chemical valence of M and O is balanced, specific surface area is 200~500m²0.5~1.5cm of/g, Kong Rongwei³/ g, it is average Aperture is 8~18nm.

The above-mentioned cracking gasification catalyst composition for processing heavy petroleum hydrocarbon of the present invention is a kind of for heavy petroleum hydrocarbon The catalyst composition for the coke gasification anabolic process that cracking process and cracking generate, more specifically, being related to a kind of using hot Cracking or/and catalytic cracking process working process heavy crude hydrocarbon raw material produce light Fuel, while will in gasifying agent presence The coke gasification that process generates is the multi-functional catalyst composition of the process of hydrogen or synthesis gas.

The present invention it is above-mentioned provided by for process heavy petroleum hydrocarbon cracking gasification catalyst composition, preparation method and The cracking gasification process of heavy petroleum hydrocarbon, by introducing specific active mesopore material, using this active mesopore material because of gold Belong to and nonmetallic ingredient introducing and special matching relationship to the distribution situation in material acid site and acid strength effectively adjusts with Improve, improves heavy oil conversion performance, while reducing gasification temperature；Higher burning can be obtained under lower gasification temperature Charcoal intensity obtains higher density of hydrogen.Catalyst composition of the invention is used for cracking-gasification one chemical industry of heavy petroleum hydrocarbon When skill, gasification result is good, and gasification temperature is low, has stronger heavy oil conversion performance.

In the present invention, the specific surface area, Kong Rong and average pore size are all made of nitrogen absorption under low temperature-desorption method and are surveyed It is fixed.

The above-mentioned catalyst composition provided according to the present invention, it is preferable that with oxide in the activity mesoporous active materials Weight ratio meter anhydrous chemical expression are as follows: (0.07-0.17) Na₂O·(55-76)Al₂O₃·(16.2-34.5)SiO₂· (0.6-6.0)P₂O₅·(1.7-8.6)M_xO_y。

The above-mentioned catalyst composition provided according to the present invention, it is preferable that by weight percentage, the catalyst composition packet It includes: the 2 weight % activity mesopore materials of weight %~60, the gasification reactivity component of 5 weight of weight %~40 %, 0 weight %~60 The heat-resistant inorganic oxide matrix of the butt meter of the clay of weight % and 10 weight of weight %~70 %.It is further preferred that the catalysis Composition includes: the 5 weight % activity mesopore materials of weight %~50, the gasification reactivity component of 10 weight of weight %~35 %, and 10 The heat-resistant inorganic oxide matrix of the clay of the weight of weight %~55 % and 10 weight of weight %~40 %.

The above-mentioned catalyst composition provided according to the present invention, it is preferable that it is described activity mesopore material specific surface area be 300-450m²/ g, Kong Rongwei 0.7-1.2cm³/ g, average pore size 10-15nm.

The above-mentioned catalyst composition provided according to the present invention, it is preferable that metal M be selected from Mg and/or periodic table of elements IIB, One of IIIB, IVB, VIIB race and/or group of the lanthanides are a variety of.Wherein, IIB, IIIB, IVB, VIIB race metal is selected from One of Zn, Y, Ti and Mn or a variety of.Preferably, IIB, IIIB, IVB, VIIB race metal be Ti and Mn, Mn and Zn, Ti and Zn, Ti and Y, Mn, Ti and Zn or Y, Mn and Zn.Preferably, IIB, IIIB, IVB, VIIB race metal be Y or Y, Mn and Zn.

The lanthanide series rare-earth elements (RE) are preferably lanthanum, cerium mischmetal, pure lanthanum rare earth or pure cerium mischmetal.It wherein mixes dilute Lanthanum cerium ratio can be varied with market situation in soil, but performance is not influenced substantially by mixed proportion, thus for this lanthanum, The proportion of lanthanum and cerium does not do particular provisions in cerium mischmetal, can be any than mixing.

The above-mentioned catalyst composition provided according to the present invention, wherein active mesopore material is referred to prior art system It is standby, it is preferable that the active mesopore material described in the present invention is to be prepared by the method comprising the following steps:

(1) silicon source and aqueous slkali are obtained into rubber cement room temperature is at 85 DEG C and plastic, control plastic pH value are 7-11 Liquid；

(2) according to SiO₂: Al₂O₃=1:(0.6-9) weight ratio silicon source is added into the plastic slurries, room temperature extremely It is aged 1-5 hours at 90 DEG C, obtains the first solid sediment；

(3) by first solid sediment and ammonium salt or acid solution contact treatment, sodium oxide content is obtained by filtration and is lower than The second solid sediment of 0.3 weight %；

(4) compound of second solid sediment and phosphorus source and metal M, according to P₂O₅: M_xO_y: second solid The sediment butt of sediment=(0.005-0.1): (0.005-0.1): 1 weight ratio contact treatment, and product of contact is done It is dry, wherein the metal M is selected from Mg, one of periodic table of elements IIB, IIIB, IVB, VIIB race and group of the lanthanides or a variety of gold Belong to.

Specifically, the silicon source described in above-mentioned steps (1) can be the existing various substances that can be converted into aluminium oxide, Can be conventional use of various silicon sources in the preparation process of active mesopore material, for example, can selected from aluminum nitrate, aluminum sulfate and One of aluminium chloride is a variety of.

The alkaline solution described in above-mentioned steps (1) can be the existing various substances that alkalinity is presented, for example, can select From one of ammonium hydroxide, sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution or a variety of.Wherein, the alkalinity is molten The concentration of liquid can be the conventional selection of this field, and therefore not to repeat here.

The silicon source described in above-mentioned steps (2) can be the existing various substances that can be converted into silica, Ke Yiwei Conventional use of various sial in the preparation process of active mesopore material, for example, waterglass, sodium metasilicate, four methoxies can be selected from One of base silicon, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon and silica are a variety of.

The above-mentioned catalyst composition provided according to the present invention, in the preparation process of active mesopore material, although the aluminium Source, silicon source and aqueous slkali can respectively be properly selected from the above-mentioned material enumerated, however, usually source of aluminium, alkali It is at least a kind of for the raw material containing sodium in solution and silicon source, to guarantee in the activity without ion exchange so prepared Hole silica-alumina material has the active central hole structure of appropriate size.

The present invention is not to special by first solid sediment and the method for ammonium salt contact treatment in above-mentioned steps (3) Ground limits, for example, may include by the first solid sediment by its sediment butt: ammonium salt: H₂O=1:(0.1-1): (5-30) Weight ratio in room temperature to swapping at 100 DEG C.Wherein, the number of the contact can be 1-3 times, each time of contact Can be with 0.5-1 hours, the content of sodium oxide molybdena is lower than subject to 0.3 weight % in the solid product that should specifically make.

In addition, the type of the ammonium salt described in above-mentioned steps (3) can be the conventional selection of this field, for example, can select From one of ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate or a variety of.

The present invention is to the method for contacting first solid sediment with acid solution in above-mentioned steps (3) without particularly It limits, for example, may include by first solid sediment by its sediment butt: acid: H₂O=1:(0.03-0.3): (5- 30) weight ratio is in room temperature to exchanging at least 0.2 hour at 100 DEG C.

In addition, the type of the acid solution described in above-mentioned steps (3) can be the conventional selection of this field, it is usually inorganic Acid, for example, the acid in the acid solution can be selected from one of sulfuric acid, hydrogen chloride and nitric acid or a variety of.

It can by the contact treatment process of the second solid sediment and phosphorus source and the compound of metal M in above-mentioned steps (4) By there are many in a manner of, for example, it is following a), b), c), d) any one of process:

A) second solid sediment is pressed into its sediment butt: H₂O=1:(5-20 weight ratio) is mixed with water beats Slurry, then the compound of phosphorus source, metal M is added sequentially in above-mentioned slurries, it is small to contact treatment at least 0.2 at 90 DEG C in room temperature When, it preferably contact treatment 0.2-5 hours, more preferable contact treatment 0.5-3 hours, is done at 100 DEG C -150 DEG C after filtering washing It is 10-20 hours dry；

B) second solid sediment is pressed into its sediment butt: H₂O=1:(5-20 weight ratio) is mixed with water beats Slurry, then phosphorus source or metal M compound are added in above-mentioned slurries, in room temperature to contact treatment at 90 DEG C at least 0.2 hour, It is preferred that contact treatment 0.2-5 hours, more preferable contact treatment 0.5-3 hours, the metal M not being added with early period directly after filtering or The compound of person's phosphorus source mixes in proportion, 10-20 hours dry at 100 DEG C -150 DEG C after grinding uniformly；

C) second solid sediment is pressed into its sediment butt: H₂O=1:(5-20 weight ratio) is mixed with water beats Slurry, then the compound of phosphorus source and the first metal M is added in above-mentioned slurries, room temperature to contact treatment at 90 DEG C at least 0.2 hour, preferably contact treatment 0.2-5 hours more preferable contact treatment 0.5-3 hours, obtain third solid precipitating after filtering Object, then third solid sediment is directly mixed with the compound of second of metal M, after grinding uniformly at 100 DEG C -150 DEG C It is 10-20 hours dry, wherein the compound of the compound and second of metal M of the first metal M is identical or different；

D) second solid sediment is directly mixed with phosphorus source, optional magnesium source and metal M compound in proportion, It is 10-20 hours dry at 100 DEG C -150 DEG C after grinding uniformly.

In aforesaid way c), compound for the first metal M and included in the compound of second of metal M There is no particular/special requirements for particular compound and the dosage of compound, as long as enabling to second solid sediment and phosphorus source It is finally according to P with the compound of metal M₂O₅: M_xO_y: sediment butt=(0.005- of second solid sediment 0.1): (0.005-0.1): 1 weight ratio mixing.

It further, optionally, can also include roasting desciccate in the preparation method of above-mentioned active mesopore material The step of, the condition of the roasting, which generally includes maturing temperature, to be 500-700 DEG C, and calcining time can be 1-4 hours.

The type of the phosphorus source described in above-mentioned steps (4) can be the conventional selection of this field, for example, phosphoric acid can be selected from One of ammonium, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid are a variety of.

In the compound of the metal M described in above-mentioned steps (4), metal M be selected from Mg, periodic table of elements IIB, IIIB, One of IVB, VIIB race element and lanthanide series rare-earth elements are a variety of, wherein described IIB, IIIB, IVB, VIIB race gold Belong to the mixing of preferably one of Zn, Y, Ti and Mn or various metals, the mixing such as Ti's and Mn of described various metals Mixing, Mn and the mixing of Zn, the mixing of Ti and Zn, mixing, the mixing of Mn, Ti and Zn and the mixing of Y, Mn and Zn of Ti and Y. The mixed and modified material of the material and Y, Mn and Zn that wherein Y is modified has optimal cracking reaction performance.

The compound of the metal M described in above-mentioned steps (4) can be any one water-soluble compound.

The compound of the metal M described in above-mentioned steps (4) is nitrate, sulfate or the chloride of metal.With magnesium source For, one of magnesium nitrate, magnesium chloride and magnesium sulfate or a variety of can be selected from.

In the present invention, in the weight ratio of solid sediment, water and inorganic acid without ion exchange, it is described without from The solid sediment weight of son exchange is the weight in terms of butt.In the present invention, the weight in terms of butt refers at about 800 DEG C Under conditions of roast 1 hour after weight.

In the above-mentioned cracking gasification catalyst composition for processing heavy petroleum hydrocarbon provided by the invention, it is preferable that described Gasification reactivity component includes one of alkali metal compound, alkaline earth metal compound and group VIII metal compound or more Kind.Wherein, the alkali metal compound such as potassium hydroxide, potassium carbonate, potassium oxide, potassium nitrate, potassium sulfate, potassium chloride, phosphoric acid Potassium dihydrogen, potassium feldspar, green bean rock, alunite, trachyte, potassium-bearing shale, phosphorus potassium ore, siltstone containing potassium, in XRD diffracting spectrum It is that there are the substances containing potassium at main phase peak (substance has XRD main phase peak shown in Fig. 1), white clouds at 21 °, 29 ° and 35 ° at 2 angles θ Stone, olivine.When the gasification reactivity component contains alkaline-earth metal, the compound of alkaline-earth metal can be added, such as One of inorganic alkali-earth metals salt such as chloride, nitrate, sulfate, phosphate of alkaline-earth metal or a variety of, described alkali Earth metal is one of beryllium, magnesium, calcium, strontium, barium or a variety of, preferably calcium and/or magnesium.When the gasification reactivity component contains VIII When race's metallic compound, the compound of group VIII metal can be added, for example, the sulfate of group VIII metal, nitrate, One of inorganic group VIII metal salt such as chloride, oxide is a variety of.The group VIII metal is preferably Fe and/or Ni.

In the above-mentioned cracking gasification catalyst composition for processing heavy petroleum hydrocarbon provided by the invention, it is preferable that described Gasification reactivity component includes potassium compound, with or without alkaline earth metal compound, with or without group VIII metal compound, with institute On the basis of the weight for stating gasification reactivity component, in terms of oxide weight, in the gasification reactivity component content of potassium oxide be 2~ 100 weight %, the content of alkaline-earth metal are 0~98 weight %, and group VIII metal compounds content is 0~98%.Wherein, in order to Solve the problems, such as that potassium lost is serious, the active component containing potassium is preferably that the gasification reactivity component includes XRD diffracting spectrum In 2 angles θ be 21 °, 29 ° and 35 ° at there are the substance containing potassium at main phase peak (have Fig. 1 shown in XRD main phase peak substance containing potassium). Use in XRD diffracting spectrum at 2 angles θ is 21 °, 29 ° and 35 ° there are the substances containing potassium at main phase peak as gasification reactivity component, The gasification efficiency that can be further improved catalyst composition, reduces the loss of potassium, and the cracking that catalyst composition can be improved is living Property.

Preferably, it in above-mentioned gasification reactivity component, is deposited at 2 angles θ is 21 °, 29 ° and 35 ° in the XRD diffracting spectrum Substance containing potassium at main phase peak, potassium content in terms of potassium oxide are the 8 weight % of weight %~40, with or without alkaline-earth metal, Remaining is sial component, alkaline earth oxide and potassium oxide molar ratio (0~1): 0.2, SiO₂/Al₂O₃Molar ratio be 1:10~ 10:1.It is highly preferred that there are oxygen in the substance containing potassium at main phase peak at 2 angles θ is 21 °, 29 ° and 35 ° in the XRD diffracting spectrum Change the 10 weight % of weight %~30 of potassium content, alkaline earth oxide and potassium oxide molar ratio 1:5~1:0.5, SiO₂/Al₂O₃'s Molar ratio is 1:3~3:1.

The above-mentioned catalyst composition provided according to the present invention is wherein 21 °, 29 ° and 35 ° at 2 angles θ in XRD diffracting spectrum There are the substance containing potassium at main phase peak (substances containing potassium with XRD main phase peak shown in Fig. 1) to be referred to existing common process at place It is prepared, it is preferable that be in the present invention that there are main phase peaks at 21 °, 29 ° and 35 ° at 2 angles θ in the XRD diffracting spectrum Substance containing potassium is to be prepared by the method comprising the following steps: potassium-containing compound and sial component and optional alkaline-earth metal Compound, optional group VIII metal compound be beaten into wet feed, be then dried into siccative, then obtain after roasting, maturing temperature It is 800 DEG C~1150 DEG C, 1~10h of calcining time.

It preferably, is that there are the substances containing potassium at main phase peak at 21 °, 29 ° and 35 ° at 2 angles θ in above-mentioned XRD diffracting spectrum In preparation method, alkaline earth oxide and 0~1:0.2 of potassium oxide molar ratio, SiO in sial component₂/Al₂O₃Molar ratio be 1:10~10:1；And the sum of the sial component in terms of butt and the weight of alkaline earth metal compound in terms of alkaline earth oxide Weight ratio with the potassium-containing compound in terms of potassium oxide is (60~92): (8~40).In order to preferably realize mesh of the invention , the higher gasification reactivity component of preparation activity, under preferable case, maturing temperature is 900 DEG C~1100 DEG C, calcining time 2 ~8h.

The present invention is in the method for above-mentioned preparation substance containing potassium, with potassium-containing compound, alkaline earth metal compound and sial group Dividing the mashing mode of mashing can be mixed them with random order without particular/special requirement, such as three kinds of substances can be beaten respectively Three kinds of slurries, are then mixed with beating by slurry again, a certain amount of deionized water can also be added in three kinds of substance elder generation mechanical mixtures Mashing, and the solid content of slurries is controlled in 15 weight of weight %~50 %.

The above-mentioned catalyst composition provided according to the present invention, wherein prepare in XRD diffracting spectrum 2 angles θ be 21 °, 29 ° and There are during the substance containing potassium at main phase peak at 35 °, the potassium-containing compound is selected from potassium oxide, potassium hydroxide, potassium carbonate, nitre One or more of sour potassium, potassium sulfate, potassium chloride, the alkaline earth metal compound are selected from alkaline earth oxide, alkaline earth One or more of metal carbonate, alkaline earth nitrate, alkali earth metal sulfate, alkaline earth metal chloride.Such as it can be One of calcium oxide, calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, magnesia, magnesium carbonate, magnesium chloride, magnesium nitrate, magnesium sulfate Or it is several.

The above-mentioned catalyst composition provided according to the present invention, wherein prepare in XRD diffracting spectrum 2 angles θ be 21 °, 29 ° and There are during the substance containing potassium at main phase peak at 35 °, the sial component contains silicon and aluminium element, can selected from clay, One of silica, silica precursors, aluminium oxide, alumina precursor are a variety of, preferably clay.It can be selected from any one The crystal aluminosilicate mineral of layer structure, such as kaolin, montmorillonite, rectorite, attapulgite, illite, sepiolite and silicon One or more of diatomaceous earth, Aluminum sol, silica solution, boehmite, and at least one substance contains element silicon, it is at least one Substance contains aluminium element；Or it is molten for kaolin, montmorillonite, rectorite, attapulgite, illite, sepiolite, diatomite, aluminium One of glue, boehmite or a variety of and silica solution mixture；It or is kaolin, montmorillonite, rectorite, concave convex rod One of stone, illite, sepiolite, diatomite, silica solution or a variety of mixtures with Aluminum sol or boehmite.

Meanwhile a kind of preparation method of above-mentioned catalyst composition is additionally provided in the present invention, this method includes will be active The step of mesopore material, gasification reactivity component, clay, heat-resistant inorganic oxide matrix are mixed with beating, are spray-dried and roast.

The preparation method of above-mentioned catalyst composition provided by according to the present invention, by active mesopore material, gasification reactivity group Divide, after the mixing of clay, heat-resistant inorganic oxide matrix, is beaten according to conventional methods in the art, is spray-dried and roasts ?.In a kind of preferred embodiment of the present invention, the preparation method of above-mentioned catalyst composition, comprising the following steps:

(1) silicon source and aqueous slkali are obtained into rubber cement room temperature is at 85 DEG C and plastic, control plastic pH value are 7-11 Liquid；According to SiO₂: Al₂O₃=1:(0.6-9) weight ratio silicon source is added into the plastic slurries, in room temperature to old at 90 DEG C Change 1-5 hours, obtains the first solid sediment；By first solid sediment and ammonium salt or acid solution contact treatment, filtering Obtain the second solid sediment that sodium oxide content is lower than 0.3 weight %；By second solid sediment and phosphorus source and metal M Compound, according to P₂O₅: M_xO_y: the sediment butt of second solid sediment=(0.005-0.1): (0.005- 0.1): 1 weight ratio contact treatment, and roasted 1~4 hour by product of contact drying or at 500 DEG C~700 DEG C；

(2) potassium-containing compound and sial component are mixed with beating with optional alkaline earth metal compound, are then dried into dry Material, then at 800 DEG C~1150 DEG C, preferably 900 DEG C~1100 DEG C roastings, 1~10h of calcining time obtains the gas containing potassium after roasting Change active component；Wherein the alkaline earth metal compound in terms of alkaline earth oxide and the potassium-containing compound in terms of potassium oxide rub You are 0~1:0.2 of ratio, preferably 1:5~1:0.5, SiO₂/Al₂O₃Molar ratio be 1:10~10:1, preferably 1:3~3:1, with On the basis of the dry weight of the obtained gasification reactivity component containing potassium, with oxidation in the obtained gasification reactivity component containing potassium The potassium content of potassium meter is 8 weight of weight %~40 %；

(3) by the activity mesopore material and the obtained component of gasification reactivity containing potassium of step (2) obtained in step (1) and Clay, heat-resistant inorganic oxide matrix are mixed with beating, and are then spray-dried, at 400~800 DEG C, preferably 400~750 DEG C 2~10h of lower roasting；Dry basis is wherein pressed, activity mesopore material obtained in the step (1), step (2) obtain The component of gasification reactivity containing potassium, clay, heat-resistant inorganic oxide matrix dosage make in obtained catalyst composition include 1%~ The 80% active mesopore material, 1%~60% gasification reactivity component, 0%~70% clay and 2%~ 98% heat-resistant inorganic oxide matrix.

The preparation method of above-mentioned catalyst composition provided by according to the present invention, wherein the clay can be normal for this field Clay can be selected from kaolin, sepiolite, attapulgite, montmorillonite, tired de- stone, diatomite, Ai Luo under preferable case One of stone, saponite, boron-moisten soil, hydrotalcite are a variety of；Be more preferably selected from kaolin, diatomite, sepiolite, attapulgite, One of montmorillonite and tired de- stone are a variety of.

The preparation method of above-mentioned catalyst composition provided by according to the present invention, wherein the heat-resistant inorganic oxide matrix Can be heat-resistant inorganic oxide precursor and/or heat-resistant inorganic oxide, according to the present invention provided by above-mentioned catalyst composition Preparation method, the type of the heat-resistant inorganic oxide can be heat resistant inorganic oxygen commonly used in the art without particular/special requirement One of compound, preferably aluminium oxide, silica, titanium oxide, magnesia, zirconium oxide, thorium oxide and beryllium oxide are a variety of.It is resistance to Commonly referred to as binder when hot inorganic oxide or heat-resistant inorganic oxide precursor have an adhesive property, the bonding One or more of agent, such as Aluminum sol, silica solution, boehmite, phosphorus aluminium glue, Silica hydrogel, alumina gel, silica-alumina gel. Acid can also be added under preferable case, in the slurries to be acidified, described acid such as one of hydrochloric acid, nitric acid, sulfuric acid or more Kind.In the preparation method of the above-mentioned catalyst composition of the present invention, heat-resistant inorganic oxide precursor can be added, it is resistance to then by roasting Hot precursors of inorganic oxides is converted into heat-resistant inorganic oxide, first can also be prepared into heat-resisting nothing with heat-resistant inorganic oxide precursor Then machine oxide is added in the form of heat-resistant inorganic oxide in the preparation process of catalyst composition.

According to the present invention in above-mentioned cracking gasification catalyst composition preparation method, by active mesopore material, gasification reactivity group Point, the sequence that is mixed with beating of clay, heat-resistant inorganic oxide matrix there is no particular/special requirement, for example, can be by the raw material point Slurries are not prepared, are then mixed with beating prepared slurries；First active mesopore material can also be mixed with clay, then again It is mixed with beating with other components；Or gasification reactivity component is mixed with clay, is then mixed again with other components.

When catalyst composition of the invention contains metal traps, the incorporation way of metal agent for capturing can be in the present invention It in the form of an ion or complex form introduces when active mesopore material, gasification reactivity component, clay are mixed with beating, can also be with It is introduced in the form of precipitating after by above-mentioned several component spray drying formings.If introducing heat-resisting nothing in carbon monoxide-olefin polymeric Metal traps can also be deposited in the inorganic oxide by machine matrix of oxide in advance by coprecipitation.It is preferred that feelings Under condition, based on butt, the content of the metal traps is no more than 20 weight % of catalyst composition.The present invention is to the metal The type of trapping agent can be the common metal trapping agent of the component of the pollution metal such as trapping V, Ni, Fe, Ca without particular/special requirement, Under preferable case, the metal traps are the precursor of rare earth oxide and/or rare earth oxide.In more preferable situation, the oxygen The precursor for changing rare earth is one of rare earth chloride, carbonated rare earth and rare earth hydrate or a variety of.Wherein, rare earth element can be with For one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium or a variety of.

The preparation method of above-mentioned catalyst composition provided by the invention, in the preferred embodiment, only to catalysis group The preparation method for closing object is described, and no longer carries out repeated description with the identical technical characteristic in product.

In addition, also providing a kind of application method of catalyst composition in the present invention, which includes as follows Step:

(1) heavy petroleum hydrocarbon contacts with catalyst composition provided by the invention in Cracking Unit and carries out cracking reaction, reaction Gas, gasoline fraction, diesel oil distillate, wax oil fraction and the catalyst composition that deposited coke are obtained after effluent separation；It is described Heavy petroleum hydrocarbon such as decompression residuum, reduced crude, Propane Deasphalting Oil, wax tailings, the reaction condition for example reacts Temperature is 450~700 DEG C, and weight (hourly) space velocity (WHSV) is 0.1~500h^-1, oil ratio (the cracking gasification catalyst composition and heavy crude Hydrocarbon weight ratio) it is 0.1~100.

(2) the resulting catalyst composition (band charcoal catalyst composition) that deposited coke of step (1) enters gasification unit, leads to Control gasification condition is crossed, the charcoal and gasifying agent reaction on the catalyst composition generate and be rich in CO and H₂Gas, obtain simultaneously Complete regenerated catalyst composition or semi regeneration catalyst composition, the semi regeneration catalyst composition are having in regeneration unit Under the conditions of oxygen is existing, makes to remain charcoal generation completely burned on the catalyst composition, obtain complete regeneration catalyzing composition； The gasification condition can refer to existing gasification process, gasification condition for example: gasification temperature is 650~800 DEG C, preferably 680~ 750 DEG C, gasifying agent may include the vapor of 70~100 volume % and the oxygen of 0~30 volume %, for example including be greater than 0 and Oxygen less than or equal to 20 volume % and more than or equal to 80 and the vapor of small 100 volume %.

(3) the resulting complete regeneration catalyzing composition of step (2) carries heat and returns to step (1) described Cracking Unit.

Preferably by control regeneration condition in the step of application method of above-mentioned catalyst composition (2), by catalyst composition Upper coke is gasificated into rich in CO and H₂Obtain semi regeneration catalyst composition while gas, remaining coke layer can be on composition Guard catalyst by the further destruction of gasifying agent, does not reduce the loss of gasification reactivity component and the inactivation at cracking activity center. Coke content is 0.3 weight of weight %~1 % in the semi regeneration composition.

The present invention will will be further described by embodiment below, but not thereby limiting the invention.

In embodiment and in comparative example:

Aluminum sol provides (Al by middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery₂O₃Content is 21.5 weight %), kaolin is by Suzhou China Kaolin Co., Ltd provides (solid content is 80 weight %), and by Shandong Aluminum Plant's offer, (solid content is 65.8 weights to boehmite Measure %).Chemical reagent used is not specifically specified in comparative example and embodiment, and specification is that chemistry is pure.

In embodiments, K in product₂O、Na₂O、Al₂O₃、SiO₂、P₂O₅、M_xO_yContent measured with x-ray fluorescence method (reference can be made to " petrochemical analysis method (RIPP experimental method) ", Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes), Middle metal M is selected from Mg and/or one of periodic table of elements IIB, IIIB, IVB, VIIB race and/or group of the lanthanides or a variety of.Sample object Mutually measured using X-ray diffraction method.Sample specific surface area, pore volume, average pore size are measured by nitrogen absorption under low temperature-desorption method.

Embodiment 1-9 is used to illustrate the preparation method of activity mesopore material used in the present invention.

Embodiment 1

It (1) is 90gAl with concentration₂O₃The Al of/L₂(SO₄)₃The ammonium hydroxide that solution and concentration are 25wt.% is reaction raw materials, is adopted With cocurrent plastic mode, it is vigorously stirred lower by Al₂(SO₄)₃Solution and ammonium hydroxide carry out mixing plastic, and control system temperature is 45 DEG C, Metering plastic slurries are collected in system pH=9.5；(2) and under agitation according to SiO₂: Al₂O₃The weight ratio of=1:1.8 It is 60gSiO that concentration is added into plastic slurries₂The waterglass of/L is warming up to 60 DEG C and is aged 3 hours, obtains the first solid precipitating Object；(3) first solid sediment is pressed into its sediment butt: ammonium salt: H₂The weight ratio of O=1:1:12 is handed at 60 DEG C It changes 1 hour, filtering washing obtains the second solid sediment that sodium oxide content is lower than 0.3%；(4) by the second solid sediment Sediment butt: H₂The second solid sediment of gained is mixed with beating by the weight ratio of O=1:10 with water, and presses P₂O₅: Y₂O₃: second Phosphoric acid is added in sediment butt=0.038:0.032:1 weight ratio of solid sediment and yttrium nitrate solution is mixed, then Reacted 2 hours at 70 DEG C, after filtering washing at 120 DEG C dry 15 hours up to phosphorus provided by the invention, metal-modified Mesoporous silica-alumina material.It is denoted as PM-1.

PM-1 has boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its elemental analysis Group becomes 0.12Na₂O·65.4Al₂O₃·27.2SiO₂·3.7P₂O₅·3.1Y₂O₃；Specific surface area 418m²/ g, Kong Rong 1.09cm³/ g, average pore size 10.4nm.

Embodiment 2

It (1) is 90gAl with concentration₂O₃The Al of/L₂(SO₄)₃Solution and concentration are 102gAl₂O₃/ L, Crater corrosion are 2.5 NaAlO₂Solution is reaction raw materials, using cocurrent plastic mode, mixing plastic is carried out under being vigorously stirred, control system temperature is 40 DEG C, metering plastic slurries are collected in system pH=10.5；(2) under stiring according to SiO₂: Al₂O₃The weight ratio of=1:1.2 to It is 100gSiO that concentration is added in plastic slurries₂The waterglass of/L is warming up to 70 DEG C and is aged 2 hours, obtains the first solid precipitating Object；(3) first solid sediment is pressed into its sediment butt: HCl:H₂The weight ratio of O=1:0.08:15 is handed at 60 DEG C It changes 30 minutes, filtering washing obtains the second solid sediment that sodium oxide content is lower than 0.3%；(4) P is pressed₂O₅: TiO₂: MnO₂: Sediment butt=0.015:0.035:0.049:1 weight ratio of second solid sediment is by the second solid sediment and phosphoric acid Ammonium dihydrogen, titanium sulfate and manganese chloride are mixed, 15 hours dry at 120 DEG C after grinding uniformly, small then at 600 DEG C of roastings 4 When up to phosphorus provided by the invention, metal-modified mesoporous silica-alumina material.It is denoted as PM-2.

PM-2 has boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its elemental analysis Group becomes 0.17Na₂O·55.1Al₂O₃·34.4SiO₂·1.5P₂O₅·3.5TiO₂·4.9MnO₂；Specific surface area 312m²/ G, Kong Rong 0.87cm³/ g, average pore size 11.1nm.

Embodiment 3

(1) first by concentration be 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in a beaker, under stirring by concentration be 24wt.% Ammonium hydroxide is added, until system pH=9.5, keeping gelling temperature is 35 DEG C, collects metering plastic slurries；(2) and in stirring bar According to SiO under part₂: Al₂O₃It is 60gSiO that concentration is added into plastic slurries for the weight ratio of=1:2.7₂The waterglass of/L, heating It is aged 3 hours to 60 DEG C, obtains the first solid sediment；(3) first solid sediment is pressed into its sediment butt: NH₄Cl:H₂The weight ratio of O=1:0.8:12 exchanges 1 hour at 50 DEG C, and filtering washing obtains sodium oxide content and is lower than 0.3% Second solid sediment；(4) by the second solid sediment (filter cake) reslurry, and P is pressed₂O₅: MnO₂: TiO₂: the second solid is heavy Phosphoric acid, manganese chloride and titanium sulfate is added in sediment butt=0.022:0.023:0.017:1 weight ratio of starch, at 70 DEG C Stirring 2 hours, is obtained by filtration third solid sediment；Third solid sediment is pressed into its sediment butt: ZnO=1:0.05's Weight ratio is directly mixed with zinc nitrate, 10 hours dry in 120 DEG C after grinding uniformly, roasts 4 hours then at 600 DEG C up to this hair The phosphorus of bright offer, metal-modified active mesoporous silica-alumina material.It is denoted as PM-3.

PM-3 has structure of similar to thin diaspore, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its elementary analytical chemistry group As 0.10Na₂O·72.5Al₂O₃·16.3SiO₂·2.2P₂O₅·2.1MnO₂·1.5TiO₂·5.0ZnO；Specific surface area 439m²/ g, Kong Rong 1.28cm³/ g, average pore size 11.7nm.

Embodiment 4

It (1) is 90gAl with concentration₂O₃The Al of/L₂(SO₄)₃The ammonium hydroxide that solution and concentration are 25wt.% is reaction raw materials, is adopted With intermittent cocurrent plastic, it is vigorously stirred lower by Al₂(SO₄)₃Solution and ammonium hydroxide carry out mixing plastic, control 45 DEG C of gelling temperature, Metering plastic slurries are collected in plastic pH value=10.5；(2) under agitation according to SiO₂: Al₂O₃The weight ratio of=1:2.3 to It is 60gSiO that concentration is added in plastic slurries₂The waterglass of/L is warming up to 60 DEG C and is aged 3 hours, obtains the first solid sediment； (3) first solid sediment is pressed into its sediment butt: ammonium salt: H₂NH is added in the weight ratio of O=1:1:10₄Cl and go from Sub- water exchanges 1 hour at 65 DEG C, and filtering washing obtains the second solid sediment that sodium oxide content is lower than 0.3%；(4) it presses The sediment butt of second solid sediment:: H₂The weight ratio of O=1:8 is mixed with beating with water, and presses P₂O₅: the MgO: the second solid Phosphoric acid and magnesium chloride is added in sediment butt=0.016:0.021:1 weight ratio of sediment, and it is small that 2 are reacted at 60 DEG C When, obtain third solid sediment；Third solid sediment is pressed into its sediment butt: RE₂O₃=1:0.008 with it is mixed chlorinated Earth solution (the La in rare earth in terms of oxide₂O₃And CeO₂Weight ratio be 45:55) mix, grinding uniformly after in 120 DEG C Lower drying 15 hours roasts 4 hours then at 550 DEG C up to active mesoporous catalytic material provided by the invention.It is denoted as PM-4.

PM-4 has boehmite phase structure, and X-ray diffraction spectrogram is as shown in Figure 2；Its elementary analytical chemistry group As 0.07Na₂O·69.7Al₂O₃·25.3SiO₂·1.5P₂O₅·2.0MgO·0.8RE₂O₃；Specific surface area 409m²/ g, hole Hold 1.13cm³/ g, average pore size 11.0nm.

Embodiment 5

(1) first by concentration be 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in a beaker, and is warming up to 40 DEG C, is added with stirring Concentration is the ammonium hydroxide of 25wt.%, until system pH=9.5, collect metering plastic slurries；(2) and under agitation according to SiO₂: Al₂O₃It is 100gSiO that concentration is added into plastic slurries for the weight ratio of=1:1.7₂The waterglass of/L, be warming up to 60 DEG C it is old Change 2 hours, obtains the first solid sediment；(3) first solid sediment is pressed into its sediment butt: HCl:H₂O=1: The weight ratio of 0.08:12 exchanges 30 minutes at 55 DEG C, and it is heavy that filtering washing obtains second solid of the sodium oxide content lower than 0.3% Starch；(4) by the second solid sediment (filter cake) reslurry, and P is pressed₂O₅: the sediment butt of the second solid sediment= Phosphoric acid is added in the weight ratio of 0.045:1, react 1 hour at 60 DEG C, filters and simultaneously dries 15 hours at 120 DEG C, obtains the Three solid sediments；Third solid sediment is pressed into its sediment butt: MgO:RE₂O₃The weight ratio of=1:0.007:0.021 will Drying sample and magnesium chloride and the mixed chlorinated rare earth solution (La in rare earth in terms of oxide₂O₃And CeO₂Weight ratio be 45: 55) it mixes, it is 10 hours dry in 120 DEG C after grinding uniformly, 4 hours are roasted then at 600 DEG C up in activity provided by the invention Hole catalysis material.It is denoted as PM-5.

PM-5 has boehmite phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its elemental analysis Group becomes 0.11Na₂O·62.8Al₂O₃·29.6SiO₂·4.5P₂O₅·0.7MgO·2.1RE₂O₃；Specific surface area 418m²/ G, Kong Rong 1.06cm³/ g, average pore size 10.1nm.

Embodiment 6

It (1) is 90gAl with concentration₂O₃The Al of/L₂(SO₄)₃The ammonium hydroxide that solution and concentration are 25wt.% is reaction raw materials, is adopted With cocurrent plastic mode, it is vigorously stirred lower by Al₂(SO₄)₃Solution and ammonium hydroxide carry out mixing plastic, and control system temperature is 40 DEG C, Metering plastic slurries are collected in system pH=9.5；(2) and under agitation according to SiO₂: Al₂O₃The weight ratio of=1:3 to It is 100gSiO that concentration is added in plastic slurries₂The waterglass of/L is warming up to 70 DEG C and is aged 1 hour, obtains the first solid precipitating Object；(3) first solid sediment is pressed into its sediment butt: ammonium salt: H₂The weight ratio and NH of O=1:1:10₄Cl and go from Sub- water mixing carries out ion exchange to sodium oxide content at 55 DEG C and is lower than 0.3%, obtains the second solid sediment；(4) by the The sediment butt of two solid sediments: the weight ratio of MgO=1:0.012 is mixed with magnesium nitrate, dry in 120 DEG C after grinding uniformly Dry 10 hours；, third solid sediment is obtained by filtration；Third solid sediment is pressed into its sediment butt: RE₂O₃=1:0.039 With the mixed chlorinated rare earth solution (La in rare earth in terms of oxide₂O₃And CeO₂Weight ratio be 45:55) mix, mix, grind Mill is uniformly rear 10 hours dry；It is finally mixed again with phosphoric acid, up to active mesoporous catalytic material provided by the invention after drying.Note For PM-6.

PM-6 has boehmite phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its elemental analysis Group becomes 0.09Na₂O·76.1Al₂O₃·16.2SiO₂·2.1P₂O₅·1.2MgO·3.9RE₂O₃；Specific surface area 420m²/ G, Kong Rong 1.05cm³/ g, average pore size 10.0nm.

Embodiment 7

It (1) is 90gAl with concentration₂O₃The Al of/L₂(SO₄)₃The ammonium hydroxide that solution and concentration are 25wt.% is reaction raw materials, is adopted With intermittent cocurrent plastic, it is vigorously stirred lower by Al₂(SO₄)₃Solution and ammonium hydroxide carry out mixing plastic, control 50 DEG C of gelling temperature, Metering plastic slurries are collected in plastic pH value=9.0；(2) under agitation according to SiO₂: Al₂O₃The weight ratio of=1:2.3 to It is 100gSiO that concentration is added in plastic slurries₂The waterglass of/L is warming up to 70 DEG C and is aged 2 hours, obtains the first solid precipitating Object；(3) first solid sediment is pressed into its sediment butt: ammonium salt: H₂The weight ratio of O=1:0.8:12 is handed at 60 DEG C It changes 1 hour, obtains the second solid sediment after filtering washing；First press P₂O₅: the sediment butt of the second solid sediment: H₂O= The weight ratio of 0.016:1:8 is by phosphoric acid and Na₂Second solid sediment of the O content lower than 0.3% and water are mixed with beating, and in 70 It is reacted 1 hour at DEG C, obtains third solid sediment；Third solid sediment is pressed into its sediment butt: RE₂O₃=1:0.031 Weight ratio directly by the mixed chlorinated rare earth (La in rare earth in terms of oxide₂O₃And CeO₂Weight ratio be 60:40) and precipitating Object mixing, after grinding uniformly dry 15 hours at 120 DEG C, roasted then at 550 DEG C 4 hours up to provided by the invention phosphorous and The active mesoporous catalytic material of rare earth.It is denoted as PM-7.

PM-7 has typical boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its element Analytical chemistry group becomes 0.10Na₂O·70.2Al₂O₃·24.8SiO₂·1.5P₂O₅·3.1RE₂O₃；Specific surface area 435m²/ g, Hole holds 1.14cm³/ g, average pore size 10.5nm.

Embodiment 8

It (1) is 90gAl with concentration₂O₃The Al of/L₂(SO₄)₃Solution and concentration are 102gAl₂O₃/ L, Crater corrosion are 2.5 NaAlO₂Solution is reaction raw materials, first by Al₂(SO₄)₃Solution is placed in a beaker, and is warming up to 45 DEG C, is added with vigorous stirring NaAlO₂Solution, until system pH=10.0, collect plastic slurries；(2) under stiring according to SiO₂: Al₂O₃=1:2.3's It is 100gSiO that concentration is added into plastic slurries for weight ratio₂The waterglass of/L, and be aged 3 hours in 60 DEG C；Obtain the first solid Sediment；(3) first solid sediment is pressed into its sediment butt: NH₄Cl:H₂The weight ratio of O=1:0.5:10 is at 50 DEG C Lower exchange 30 minutes, repeated exchanged is primary, and filtering washing obtains the second solid sediment that sodium oxide content is lower than 0.3%, will Second solid sediment presses La₂O₃: the sediment butt of the second solid sediment: H₂The weight ratio and nitric acid of O=0.018:1:8 Lanthanum and water mix, and stir 1 hour at 70 DEG C, third solid sediment is obtained by filtration；Third solid sediment is pressed into its sediment Butt: P₂O₅The weight ratio of=1:0.060 is directly mixed with ammonium dihydrogen phosphate, 15 hours dry at 120 DEG C after grinding uniformly, 3 hours are roasted then at 550 DEG C up to provided by the invention phosphorous and rare earth active mesoporous catalytic material.It is denoted as PM-8.

PM-8 has typical boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 1；Its element Analytical chemistry group becomes 0.12Na₂O·68.5Al₂O₃·23.4SiO₂·6.0P₂O₅·1.7La₂O₃；Specific surface area 408m²/ g, Hole holds 1.10cm³/ g, average pore size 10.8nm.

Embodiment 9

(1) first by concentration be 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in a beaker, under stirring by concentration be 25wt.% Ammonium hydroxide is added, until system pH=9.0, collect metering plastic slurries；(2) and under agitation according to SiO₂: Al₂O₃= It is 60gSiO that concentration is added into plastic slurries for the weight ratio of 1:2.6₂The waterglass of/L is warming up to 60 DEG C and is aged 2 hours, obtains First solid sediment；(3) first solid sediment is pressed into its sediment butt: HCl:H₂The weight of O=1:0.08:10 Than exchanging 1 hour at 50 DEG C, filtering washing makes Na₂O content is lower than 0.3% the second solid sediment；(4) the second solid is pressed The sediment butt of sediment: RE₂O₃=the 1:0.055 and mixed chlorinated rare earth solution (La in rare earth in terms of oxide₂O₃With CeO₂Weight ratio be 60:40) mix, it is 10 hours dry in 120 DEG C after grinding uniformly, obtain third solid sediment；It will Its sediment butt: P is pressed after third solid sediment reslurry₂O₅=1:0.008 is mixed with phosphoric acid, and it is small that 1 is stirred at 70 DEG C When, 2 hours are roasted up to provided by the invention phosphorous and rare earth active mesoporous catalytic material in 550 DEG C after filtration drying.Note For PM-9.

PM-9 has typical boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its element Analytical chemistry group becomes 0.11Na₂O·72.4Al₂O₃·21.2SiO₂·0.6P₂O₅·5.3RE₂O₃；Specific surface area 396m²/ g, Hole holds 0.96cm³/ g, average pore size 9.7nm.

Embodiment 10

With 90g Al₂(SO₄)₃Solution and concentration are 102gAl₂O₃The NaAlO2 solution that/L, Crater corrosion are 2.5 is that reaction is former Material, cocurrent plastic simultaneously adjust plastic pH=9.0, collect quantitative plastic slurries, and under agitation according to SiO₂: Al₂O₃= It is 60gSiO that concentration is added into plastic slurries for the weight ratio of 1:2₂The waterglass of/L is warming up to 60 DEG C and is aged 3 hours；Cross drainage After washing, by sediment butt: ammonium salt: H₂NH is added in the weight ratio of O=1:0.5:12₄Cl and deionized water, to precipitating at 60 DEG C Object carries out ion exchange and removes sodium ion, and exchange repeats once, and 0.5 hour every time, until sodium oxide content is lower than 0.3%； Then obtained solid sediment is pressed into sediment butt: H₂The weight ratio of O=1:8 is mixed with beating with water, and presses P₂O₅: MgO: material Expect that phosphoric acid and magnesium nitrate is added in butt=0.033:0.022:1 weight ratio, reacted 1 hour at 80 DEG C, after filtering washing 10 hours are dried at 120 DEG C up to high cracking activity mesopore material provided by the invention.It is denoted as PM-10.

PM-10 has structure of similar to thin diaspore, and X-ray diffraction spectrogram is as shown in Figure 2；Its elementary analytical chemistry group becomes 0.12Na₂O·65.1Al₂O₃·28.2SiO₂·3.2P₂O₅·2.1MgO；Specific surface area 391m²/ g, Kong Rong 0.97cm³/ g is put down Equal aperture 9.9nm.

Embodiment 11~13 is used to illustrate the system of the present invention gasification reactivity component used with XRD main phase peak shown in Fig. 1 Preparation Method.

Embodiment 11

1480 grams in terms of butt kaolin, 420 grams of KOH, 100 grams of CaO are weighed, three is mixed and added into appropriate deionization Water makes slurry solid content 15%~50%, stirs at least 30 minutes, makes slurries by ball milling, controls the flat of slurry mixture Equal partial size is dry less than 10 μm, then roasts 4 hours at 1050 DEG C, the component of gasification reactivity containing potassium G-1 is made, wherein K₂O content For 21%, SiO₂/Al₂O₃Molar ratio be 2, G-1 have XRD main phase shown in FIG. 1 peak.

Embodiment 12~13

According to the method preparation substance containing potassium of embodiment 10 as gasification reactivity component, ingredient proportion is adjusted, preparation contains potassium Gasification reactivity component G-2, G-3, specifically feeds intake and is shown in Table 1.G-2 and G-3 all has XRD feature main phase peak shown in FIG. 1 (main phase peak 2 θ are 21 °, 29 °, 35 ° respectively).

Table 1

Embodiment 14~20 is used to illustrate the preparation method of catalyst composition used in the present invention.

Embodiment 14

By the G-1 of substance containing potassium of in terms of butt 35 parts by weight and in terms of butt 40 parts by weight by butt kaolin and in terms of 15 Parts by weight Aluminum sol is mixed with beating with deionized water, is stirred 20 minutes, is obtained the first slurries.By the work of in terms of butt 10 parts by weight Property mesopore material PM-1 be mixed with beating with deionized water, stir 30 minutes, obtain the second slurries.Two kinds of slurries are mixed, and are stirred It mixes at least 30 minutes, obtains the slurries that solid content is 30 weight %.Microballoon catalyst composition is made in spray drying, then 550 DEG C roasting 2 hours.Obtained contact agent number is C-1.

Embodiment 15

The boehmite of 40 parts by weight in terms of butt is mixed with beating with deionized water, and is added into obtained slurries Enter the hydrochloric acid that concentration is 36 weight %, acid-aluminum ratio (weight ratio of the 36 weight % hydrochloric acid and the boehmite of butt meter) is 0.4, it is warming up to 60 DEG C and is acidified 2 hours, obtain the first slurries.By the G-2 of substance containing potassium of in terms of butt 30 parts by weight and with butt It counts 15 parts by weight Aluminum sols to be mixed with beating with deionized water, stirs 20 minutes, obtain the second slurries.Will in terms of butt 15 parts by weight Active mesopore material PM-3 be mixed with beating with deionized water, stir 30 minutes, obtain third slurries.By three kinds of slurries with any A kind of mode mixes, and stirs at least 30 minutes, obtains the slurries that solid content is 30 weight %.Microballoon catalysis is made in spray drying Then composition roasts 2 hours at 550 DEG C.Obtained contact agent number is C-2.

Wastage of the catalyst composition using potassium in hydrothermal experiment test composition, the condition of hydrothermal experiment are as follows: 100% 550 DEG C of processing 60h of vapor measure K in the sample composition of hydro-thermal front and back₂The content of O defines potassium in catalyst composition with retention rate Stability.The hot water potassium retention rate of catalyst composition C-2 is shown in Table 2.

Embodiment 16~20

Catalyst composition is prepared according to the method for embodiment 14 or 15, ingredient proportion is adjusted, catalyst composition C-3 is made ~C-7 specifically feeds intake and is shown in Table 2, and the hot water potassium retention rate of catalyst composition C-3~C-7 is shown in Table 2.

Table 2

Comparative example 1~4 is used to illustrate the preparation method for mesoporous silica-alumina material.

Comparative example 1

It (1) is 90gAl with concentration₂O₃The Al of/L₂(SO₄)₃The ammonium hydroxide that solution and concentration are 25wt.% is reaction raw materials, is adopted With cocurrent plastic mode, it is vigorously stirred lower by Al₂(SO₄)₃Solution and ammonium hydroxide carry out mixing plastic, and control system temperature is 40 DEG C, Metering plastic slurries are collected in system pH=9.5；(2) and under agitation according to SiO₂: Al₂O₃The weight ratio of=1:2.6 It is 102gSiO that concentration is added into plastic slurries₂The waterglass of/L is warming up to 70 DEG C and is aged 2 hours, obtains the first solid precipitating Object；(3) first solid sediment is pressed into its sediment butt: ammonium salt: H₂The weight ratio of O=1:0.8:15, at 60 DEG C Ion exchange is carried out to solid sediment and removes sodium ion, sodium oxide molybdena is washed till 0.3%, obtains the second solid sediment；(4) it presses The sediment (filter cake) of second solid sediment again plus water mashing, then is pressed and by P₂O₅: the sediment of the second solid sediment is dry Base=0.05:1 weight ratio is mixed with phosphoric acid, is warming up to 60 DEG C and is stirred 1 hour, is within dry 10 hours at 120 DEG C after filtering Obtain contrast material.It is denoted as DB-1.

DB-1 has structure of similar to thin diaspore, and X-ray diffraction spectrogram is the same as shown in Fig. 2；Its elementary analytical chemistry group becomes 0.12Na₂O·62.5Al₂O₃·31.7SiO₂·5.0P₂O₅；Specific surface area 413m²/ g, Kong Rong 0.97cm³/ g, average pore size 9.4nm。

Comparative example 2

Referring to the preparation method of the mesoporous silica-alumina materials SA-1 of embodiment 1 in patent CN1565733A, only handed over using acid It changes process and substitutes ammonium exchange process therein.I.e. by the intermediate sedimentation object of SA-1, the i.e. filtered sial sediment of aging, with water It is mixed with beating by the weight ratio of 1:10, then HCl solution (concentration is 10 weight %) is pressed into sediment (butt): HCl=1:0.12 Weight ratio be added in above-mentioned slurries, contacted 40 minutes at 55 DEG C, mesoporous silicon aluminium obtained after filtering, drying and roasting Material, is denoted as DB-2.

The X-ray diffraction spectrogram of DB-2 is the same as shown in Fig. 2；Its elemental analysis weight chemical composition is 0.1Na₂O· 73.7Al₂O₃·26.2SiO₂。

Comparative example 3

Mesoporous silica-alumina material is prepared according to the embodiment 1 that patent CN1565733 is announced, is denoted as DB-3.

DB-3 has structure of similar to thin diaspore；Its elementary analytical chemistry group becomes 0.12Na₂O·73.7Al₂O₃· 26.2SiO₂；Specific surface area 362m²/ g, Kong Rong 1.19cm³/ g, average pore size 12.8nm.

Comparative example 4

(1) first by concentration be 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in a beaker, under stirring by concentration be 25wt.% Ammonium hydroxide is added, until system pH=10.0, keeping gelling temperature is 40 DEG C, collects metering plastic slurries；(2) under agitation According to SiO₂: Al₂O₃It is 60gSiO that concentration is added into plastic slurries for the weight ratio of=1:3₂The waterglass of/L is warming up to 80 DEG C Ageing 1 hour, obtains the first solid sediment；(3) first solid sediment is pressed into its sediment butt: HCl:H₂O= The weight ratio of 1:0.08:12 exchanges 30 minutes at 50 DEG C, and filtering washing obtains the second solid that sodium oxide content is lower than 0.3% Sediment；(4) the second solid sediment of gained is pressed into its sediment butt: H₂The weight ratio of O=1:10 is mixed with beating with water, and By MgO:TiO₂: magnesium nitrate and sulfuric acid is added in sediment butt=0.017:0.012:1 weight ratio of the second solid sediment Titanium reacts 2 hours at 60 DEG C, gold of the product obtained after 10 hours dry at 120 DEG C after filtering washing as reference Belong to modified mesoporous silica-alumina material, is denoted as DB-4.

DB-4 has structure of similar to thin diaspore, and X-ray diffraction spectrogram is similar to Fig. 2；Its elementary analytical chemistry group becomes 0.08Na₂O·77.2Al₂O₃·15.9SiO₂·1.5MgO·1.0TiO₂；Specific surface area 496m²/ g, Kong Rong 1.38cm³/ g is put down Equal aperture 11.2nm.

Comparative example 5~10 is used to illustrate the preparation method of comparative catalyst.

Comparative example 5~10 prepares catalyst according to the method that preparation example 13 and 14 provides, and specific inventory is shown in Table 3, is made Catalyst composition D-1~D-6.Wherein comparison preparation example 5 is prepared according to the proportion of embodiment 14, except that being replaced with DB-1 PM-3；It prepares comparative example 6 and compares preparation example 7 and prepared according to the proportion of embodiment 16, except that being replaced with DB-2, DB-3 PM-6。

Table 3

Can be seen that from the data of table 2 and table 3 has XRD main phase shown in Fig. 1 using method provided by the present invention preparation The substance containing potassium at peak as gasification reactivity component carbon monoxide-olefin polymeric after 100% vapor, 550 DEG C of processing 60h, potassium protect The potassium retention rate for staying rate to be apparently higher than other potassium-containing compounds as the catalyst composition of gasification reactivity component.As it can be seen that using this The stability of the substance containing potassium with XRD main phase peak shown in Fig. 1 for the method preparation that invention provides is higher.

Test case 1

This test is for illustrating the gasification performance of catalyst composition that embodiment 14~20 and comparative example 5~10 provide and splitting Change performance.Respectively the catalyst composition of above-mentioned preparation under conditions of 780 DEG C, 100% vapor aging 8h, then filled Fill out the fixed fluidized bed middle progress cracking in reserve for 150 grams and gasification experiment.Cracking experiments condition are as follows: reaction temperature 510 DEG C, weight (hourly) space velocity (WHSV) 25h^-1, oil ratio 10, water-oil factor 0.35；Gasification experiment condition: gasification temperature is 720 DEG C, gasifying agent For 100% vapor.Catalyst composition after all gasifications retains certain coke, usual 0.3 weight % of >, and for example, 0.4 ~0.6 weight %, the property of raw materials used oil are shown in Table 4, evaluation condition and the results are shown in Table 5 and table 6.

Table 4

Table 5

Make charcoal intensity: the coke quality that carbon monoxide-olefin polymeric reserve per ton is burnt up per hour, unit are kg/ (th).

Table 6

Typically, catalyst composition gasification reactivity and after cracking on composition the coke burning degree of coke with temperature Increase and increase, when containing oxygen in gasifying agent coke burning degree can be better than using 100% vapor as gasifying agent burning it is strong Degree.

From table 5, table 6 as can be seen that gas of the catalyst composition provided by the invention under 720 DEG C, 100% water vapor conditions Change activity and coke burning degree can reach existing catalyst (documents in technical background) at 860 DEG C, the gas of 80% vapor Change effect, and hydrogen content is high in gas (butt).It can be seen that composition gasification reactivity provided by the invention is higher, lower The coke burning degree of coke significantly improves under gasification temperature, gasification product density of hydrogen with higher.Using provided by the invention Catalyst composition that the substance containing potassium with XRD main phase shown in FIG. 1 peak is prepared as gasification reactivity component and using general The composition of ventilationization active component preparation is compared, and potassium retention rate is high, and coke burning degree is higher, and gasification reactivity is higher.Using this hair Bright offer active mesopore material preparation catalyst composition than use according to comparative example 1~6 preparation active mesopore material for The cracking performance that cracking activity constituent element prepares catalyst composition is good, and light oil yield is high.As it can be seen that the present invention is due to introducing active mesoporous The utilization rate of gasification reactivity component has can be improved in material, improves gasification performance, reduces gasification temperature.Catalysis provided by the invention The gasification temperature of composition is low, and activity is high, using catalyst composition provided by the invention for the-process processing heavy that gasifies Petroleum hydrocarbon is advantageously implemented the efficient utilization of petroleum resources, is beneficial to energy conservation.

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (22)

1. Catalyst composition, by weight percentage, the catalyzed combination 1. a kind of cracking for processing heavy petroleum hydrocarbon is gasified Object include: 1%~80% active mesopore material, 1%~60% gasification reactivity component, 0%~70% clay and 2%~ 98% heat-resistant inorganic oxide matrix, wherein the activity mesopore material has the phase structure of boehmite, and with oxygen The anhydrous chemical expression of compound poidometer is (0-0.2) Na₂O·(40-85)Al₂O₃·(10-55)SiO₂·(0.5-10) P₂O₅·(0.5-10)M_xO_y, wherein metal M is selected from Mg, periodic table of elements IIB, IIIB, IVB, VIIB race's element and group of the lanthanides One of rare earth element is a variety of, y be metal M formed oxide when highest valent state, and the numerical value of x and y make M and The chemical valence of O balances, and specific surface area is 200~500m²0.5~1.5cm of/g, Kong Rongwei³/ g, average pore size are 8~18nm；Institute The compound that gasification reactivity component includes potassium is stated, with or without alkaline earth metal compound, with or without group VIII metal compound； The gasification reactivity component further includes that there are the objects containing potassium at main phase peak at 2 angles θ is 21 °, 29 ° and 35 ° in XRD diffracting spectrum Matter at 2 angles θ is that there are the substances containing potassium at main phase peak to be obtained by following methods at 21 °, 29 ° and 35 ° in the XRD diffracting spectrum: Potassium-containing compound, sial component and optional alkaline earth metal compound are beaten into wet feed, are then dried into siccative, then after roasting It obtains, maturing temperature is 800 DEG C~1150 DEG C, 1~10h of calcining time.
2. 2. catalyst composition according to claim 1, wherein it is described activity mesopore material specific surface area be 300~ 450m²0.7~1.2cm of/g, Kong Rongwei³/ g, average pore size are 10~15nm.
3. 3. catalyst composition according to claim 1, wherein IIB, IIIB, IVB, VIIB race metal be selected from Zn, Y, One of Ti and Mn or a variety of.
4. 4. catalyst composition according to claim 3, wherein IIB, IIIB, IVB, VIIB race metal is Ti and Mn, Mn and Zn, Ti and Zn, Ti and Y, Mn, Ti and Zn or Y, Mn and Zn.
5. 5. catalyst composition according to claim 3, wherein IIB, IIIB, IVB, VIIB race metal be Y or Y, Mn and Zn.
6. 6. catalyst composition as claimed in any of claims 1 to 5, wherein it is described activity mesopore material according to Lower section method is prepared:

   (1) silicon source and aqueous slkali are obtained into plastic slurries room temperature is at 85 DEG C and plastic, control plastic pH value are 7-11；

   (2) according to SiO₂: Al₂O₃=1:(0.6-9) weight ratio silicon source is added into the plastic slurries, in room temperature to 90 DEG C Lower ageing 1-5 hours, obtains the first solid sediment；

   (3) by first solid sediment and ammonium salt or acid solution contact treatment, sodium oxide content is obtained by filtration lower than 0.3 weight Measure the second solid sediment of %；

   (4) by the compound of second solid sediment and phosphorus source and metal M, according to P₂O₅: M_xO_y: the second solid precipitating The sediment butt of object=(0.005-0.1): (0.005-0.1): 1 weight ratio contact treatment, and product of contact is dry.
7. 7. catalyst composition according to claim 6, wherein silicon source described in step (1) be selected from aluminum nitrate, aluminum sulfate and One of aluminium chloride is a variety of；It is molten that the aqueous slkali is selected from ammonium hydroxide, sodium hydroxide solution, potassium hydroxide solution and sodium metaaluminate One of liquid is a variety of；Silicon source described in step (2) is selected from waterglass, sodium metasilicate, tetramethoxy-silicane, tetraethoxy-silicane, four One of propoxyl group silicon, four butoxy silicon and silica are a variety of, and at least one of source of aluminium, aqueous slkali, silicon source are Containing sodium raw materials.
8. 8. catalyst composition according to claim 6, wherein

   It by the process of first solid sediment and ammonium salt contact treatment is that step (2) resulting first is solid in step (3) Body sediment presses its sediment butt: ammonium salt: H₂O=1:(0.1-1): the weight ratio of (5-30) in room temperature to exchanging at 100 DEG C, Until sodium oxide content is lower than 0.3 weight % in solid sediment；

   It by the process of first solid sediment and acid solution contact treatment is by step (2) resulting first in step (3) Solid sediment presses its sediment butt: acid: H₂O=1:(0.03-0.30): the weight ratio of (5-30) is in room temperature at 100 DEG C Exchange at least 0.2 hour.
9. 9. catalyst composition according to claim 6, wherein ammonium salt described in step (3) be selected from ammonium chloride, ammonium sulfate, One of ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate are a variety of；Acid in the acid solution is in sulfuric acid, hydrochloric acid and nitric acid It is one or more.
10. 10. catalyst composition according to claim 6, wherein by second solid sediment and phosphorus in step (4) Source, metal M compound contact treatment process, selected from it is following a), b), c), d) one of process:

    A) second solid sediment is pressed into its sediment butt: H₂O=1:(5-20 weight ratio) is mixed with beating with water, then The compound of phosphorus source, metal M is added sequentially in above-mentioned slurries, in room temperature to contact treatment at 90 DEG C at least 0.2 hour, mistake Drainage is 10-20 hours dry at 100 DEG C -150 DEG C after washing；

    B) second solid sediment is pressed into its sediment butt: H₂O=1:(5-20 weight ratio) is mixed with beating with water, then The compound of phosphorus source or metal M is added in above-mentioned slurries, in room temperature to contact treatment at 90 DEG C at least 0.2 hour, mistake The compound or phosphorus source for the metal M not being added with early period directly after filter mix in proportion, at 100 DEG C -150 DEG C after grinding uniformly Lower dry 10-20 hours；

    C) second solid sediment is pressed into its sediment butt: H₂O=1:(5-20 weight ratio) is mixed with beating with water, then The compound of phosphorus source and the first metal M is added in above-mentioned slurries, it is small to contact treatment at least 0.2 at 90 DEG C in room temperature When, third solid sediment is obtained after filtering, then third solid sediment is directly mixed with the compound of second of metal M, It is 10-20 hours dry at 100 DEG C -150 DEG C after grinding uniformly, wherein the compound and second of gold medal of the first metal M The compound for belonging to M is identical or different；

    D) second solid sediment is directly mixed with the compound of phosphorus source, metal M in proportion, 100 after grinding uniformly It is 10-20 hours dry at DEG C -150 DEG C.
11. 11. catalyst composition according to claim 6, wherein further include by institute after drying steps described in step (4) Desciccate is obtained to roast 1-4 hours at 500 DEG C -700 DEG C.
12. 12. catalyst composition according to claim 6, wherein phosphorus source described in step (4) is selected from ammonium phosphate, phosphoric acid hydrogen One of diammonium, ammonium dihydrogen phosphate and phosphoric acid are a variety of；The compound of the metal M is water-soluble compound.
13. 13. catalyst composition according to claim 6, wherein the compound of metal M described in step (4) is metal M's Nitrate, sulfate or chloride.
14. 14. catalyst composition according to claim 1, wherein the alkaline-earth metal is beryllium, magnesium, calcium, strontium, one in barium Kind is a variety of, and the group VIII metal is Fe and/or Ni.
15. 15. according to claim 1 or catalyst composition described in 14, wherein on the basis of the weight of the gasification reactivity component, In terms of oxide weight, the content of potassium is 2~100% in the gasification reactivity component, and the content of alkaline-earth metal is 0-98 weight % is measured, the content of group VIII metal is 0-98 weight %.
16. 16. catalyst composition according to claim 1, wherein in the XRD diffracting spectrum 2 angles θ be 21 °, 29 ° and There are in the substance containing potassium at main phase peak at 35 °, the potassium content in terms of potassium oxide is the 8 weight % of weight %~40, with or without alkali Earth metal, remaining is sial component, alkaline earth oxide and potassium oxide molar ratio (0~1): 0.2, SiO₂/Al₂O₃Mole Than for 1:10~10:1.
17. 17. catalyst composition according to claim 16, wherein in the XRD diffracting spectrum 2 angles θ be 21 °, 29 ° and There are the 10 weight % of weight %~30 of potassium oxide content in the substance containing potassium at main phase peak, alkaline earth oxide and oxidations at 35 ° Potassium molar ratio 1:5~1:0.5, SiO₂/Al₂O₃Molar ratio be 1:3~3:1.
18. 18. catalyst composition according to claim 1, wherein the maturing temperature is 900 DEG C~1100 DEG C, calcining time For 2~8h.
19. 19. catalyst composition according to claim 1, wherein the sial group is selected from kaolin, montmorillonite, tired support One of stone, attapulgite, illite, sepiolite, diatomite are a variety of, or are kaolin, montmorillonite, rectorite, recessed One of convex stick stone, illite, sepiolite, diatomite, Aluminum sol, boehmite or a variety of and silica solution mixture； It or is one of kaolin, montmorillonite, rectorite, attapulgite, illite, sepiolite, diatomite, silica solution or a variety of With the mixture of Aluminum sol or boehmite.
20. 20. the preparation method of catalyst composition described in a kind of any one of claim 1 to 19, including by active mesoporous material The step of material, gasification reactivity component, clay, heat-resistant inorganic oxide matrix are mixed with beating, are spray-dried and roast.
21. 21. the preparation method of catalyst composition according to claim 20, wherein the clay is selected from kaolin, silicon One of diatomaceous earth, sepiolite, attapulgite, montmorillonite and tired de- stone are a variety of；The heat-resistant inorganic oxide is selected from oxygen Change one of aluminium, silica, titanium oxide, magnesia, zirconium oxide, thorium oxide and beryllium oxide or a variety of.
22. 22. a kind of cracking gasification process of heavy petroleum hydrocarbon, is included in heavy petroleum hydrocarbon and claim 1 in cracker To the gasification catalyst composition haptoreaction of cracking described in any one of 19, by the cracking gasifying catalyst group after reaction The step of closing object and Oil-gas Separation, the isolated cracking gasification catalyst composition that deposited coke and gasifying agent contacted.