CN106179477A

CN106179477A - A kind of cracking gasification catalyst composition, its preparation method and the cracking gasification process of petroleum hydrocarbon

Info

Publication number: CN106179477A
Application number: CN201510213622.7A
Authority: CN
Inventors: 杨雪; 朱玉霞; 任飞; 刘倩倩; 郑金玉; 罗斌; 罗一斌; 张书红
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-04-29
Filing date: 2015-04-29
Publication date: 2016-12-07
Anticipated expiration: 2035-04-29
Also published as: CN106179477B

Abstract

The invention discloses a kind of cracking gasification catalyst composition, its preparation method and the cracking gasification process of petroleum hydrocarbon, by weight percentage, described catalyst composition includes: the mesopore activity silicon phosphor-aluminum material of 1%～50%, wherein, the anhydrous chemical expression that described activity mesopore material is counted with oxide weight is for (0-0.2) Na₂O·(50-86)Al₂O₃·(12-50)SiO₂·(0.5-10)P₂O₅, specific surface area is 200～600m²/ g, pore volume is 0.5～1.8mL/g, and average pore size is 8～18nm.Described cracking activity constituent element contains the Y type molecular sieve component of 50-95 weight % and the MFI structure molecular sieve component of 5-50 weight %.This catalyst composition is applied has preferable cracking activity and gasification conversion performance, especially while higher yield of liquefied gas can be obtained in RFCC-gasification group technology.

Description

A kind of cracking gasification catalyst composition, its preparation method and the cracking gasification process of petroleum hydrocarbon

Technical field

The present invention relates to a kind of cracking gasification catalyst composition and preparation method thereof, and apply this cracking The cracking gasification process of the petroleum hydrocarbon of gasification catalysis compositions.

Background technology

At present, when catalyzed cracking processing heavy, inferior feedstock oil, to catalytic cracking process itself and catalysis Agent proposes challenge, and inferior heavy oil on-catalytic is processed, including delayed coking, fluid coking, flexicoking Etc. be increasingly subject to pay attention to.But what coking process existed that coke yield high and low quality coke is difficult by asks Topic, delayed coking can produce the most low value-added petroleum coke, and therefore petroleum resources do not obtain height Effect utilizes.

The coke part combustion that the fluid coking of Exxon Neftegas Limited's exploitation and flexicoking technique produce Burning and provide system thermal, remainder uses air or oxygen, steam etc. at high temperature (about 900 DEG C) Gasification generation has certain low-heat value gas.On the one hand this technique use high-temperature gasification, and energy consumption is higher, separately On the one hand CO and H in institute's producing coal gas₂Comparision contents low, calorific value is relatively low, and its added value is the lowest.

, colloid/asphalt content less raw oil higher containing saturated hydrocarbons is the good raw material of catalytic cracking, Traditional catalyzed cracking processing mode is used also to produce while producing liquefied gas, gasoline, diesel oil certain The coke of amount, this part of coke burns offer for maintaining the certain reaction temperature of system in regenerative system Heat.Regenerative system is passed through a certain amount of steam as gasifying agent can while burning by-product Part CO, H₂, this partial synthesis gas can be used to do the unstripped gas of F-T synthesis through processing.

Add catalyst in gasification and can reduce the activation energy of gasification reaction, reduce gasification temperature, subtract The addition of few gasifying agent, adjusts the composition of synthesis gas.Alkali metal, alkaline-earth metal and group VIII metal are Conventional gasifying catalyst, adds a certain amount of alkali metal, alkaline-earth metal and VIII in Cracking catalyst Race's metal can promote the gasification of deposit coke on catalyst.CN200810246526.2 discloses one Planting and have cracking and the alkali metal containing of gasification function and the catalyst of alkaline-earth metal concurrently, this catalyst contains The boehmite of 35%～60%, the Alumina gel of 2%～10%, the Kaolin of 20%～49.5%, 5%～30% The alkali and alkaline earth metal ions in terms of oxide, this catalyst has cracking hydrocarbon oil products distribution and gasification The optimization function of reaction available gas productivity.CN200910078392.2 discloses a kind of coke transfer Agent, the binding agent of Kaolin, 10%～39.5% including 50%～80% and 10%～30% is in terms of oxide Alkali and alkaline earth metal ions, wherein in binding agent, the mass ratio of boehmite and Alumina gel 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 at catalysis heavy crude The gasification of catalytic cracking simultaneously catalytic coke.CN200910143623.3 discloses a kind of inferior heavy oil Cracking gasifying catalyst, including carrier, binding agent, gasification reactivity component and cracking active component, wherein Gasification reactivity component is alkali and alkaline earth metal ions, and on the basis of catalyst total amount, oxide counts content and be 2%～30%, alkali metal is (0.05～1.1) with the atomic ratio of alkaline-earth metal: 1, and cracking active component is silicon Aluminum ratio shape-selective molecular sieve between 20～200.

The gasification temperature of above-mentioned existing catalyst is higher, all carries out gasification reaction at 860 DEG C, and splits Change activity the highest, for the catalysis material of alkali metal containing, under high-temperature water heat condition, alkali gold in catalyst The loss ratio belonged to is more serious, the high temperature hydro-thermal for the catalyst containing molecular sieve, more than 800 DEG C Environment can occur the rapid avalanche of framework of molecular sieve, activity reduce rapidly.

The problem higher in order to improve the gasification temperature of existing catalyst.Public affairs in CN201210262817.7 Having opened a kind of cracking gasification catalyst composition, by weight percentage, described catalyst composition includes: The cracking activity of gasification reactivity component, 1%～60% of mesoporous silica-alumina materials, 1%～40% of 1%～50% The clay of component, 0%～70% and the heat-resistant inorganic oxide matrix of 5%～97%, wherein, described Jie Hole silica-alumina material has the phase structure of boehmite, and the anhydrous chemical in terms of oxide weight is expressed Formula is (0-0.3) Na₂O·(40-90)Al₂O₃·(10-60)SiO₂, specific surface area is 200-400m²/ g, Pore volume is 0.5～2.0mL/g, and average pore size is 8～20nm, and most probable pore size is 5～15nm.This catalysis Compositions can reduce the gasification temperature that cracking hydrocarbon oil gasification converts.

Although a kind of cracking gasification catalyst composition can drop disclosed in above-mentioned CN201210262817.7 The gasification temperature that the gasification of low cracking hydrocarbon oil converts, but its cracking activity still needs to improve further.

Summary of the invention

It is an object of the invention to provide a kind of cracking gasification catalyst composition, its preparation method and petroleum hydrocarbon Cracking gasification process, with improve prior art catalyst composition in use gasification temperature high, The problem that cracking activity is the highest, potassium lost is serious.

To achieve these goals, according to an aspect of the invention, it is provided a kind of cracking gasification is urged Changing compositions, by weight percentage, described catalyst composition includes: the mesopore activity silicon of 1%～50% The cracking active component of gasification reactivity component, 1%～60%, 0%～70% of phosphor-aluminum material, 1%～40% Clay and the heat-resistant inorganic oxide matrix of 2%～97%, described mesopore activity silicon phosphor-aluminum material tool Having the phase structure of boehmite, the anhydrous chemical expression counted with oxide weight is for (0-0.2) Na₂O·(50-86)Al₂O₃·(12-50)SiO₂·(0.5-10)P₂O₅, specific surface area is 200～600m²/ g, Pore volume is 0.5～1.8mL/g, and average pore size is 8～18nm.

Additionally, according to a further aspect of the invention, the cracking gasification side of a kind of petroleum hydrocarbon is additionally provided Method, is included in cracker the catalyst composition haptoreaction that petroleum hydrocarbon and above-mentioned cracking gasified, By reacted described cracking gasification carbon monoxide-olefin polymeric and Oil-gas Separation, deposited isolated The step that the cracking gasification catalyst composition of coke contacts with gasifying agent.

Splitting of the present invention above-mentioned provided cracking gasification catalyst composition, its preparation method and petroleum hydrocarbon Change gasification process, by introducing specific mesopore activity silicon phosphor-aluminum material, gasification temperature can be reduced；Can To obtain higher intensity of making charcoal under relatively low gasification temperature, it is thus achieved that higher density of hydrogen.In Jiang Hole activated silica phosphor-aluminum material and gasification reactivity component effectively combine and can be greatly improved catalyst Coke gasification efficiency；Simultaneously as the addition of mesopore activity silicon phosphor-aluminum material, add in catalyst The diffusion of the content in hole, beneficially heavy oil macromole and cracking, the therefore described catalyzed combination of the present invention Thing can show higher catalytic cracking activity, more preferable coke during RFCC Selectivity, is particularly obtained in that higher yield of liquefied gas.The catalyst composition of the present invention is for weight During the cracking of matter petroleum hydrocarbon-gasification integral process, gasification result is good, and gasification temperature is low, has stronger Petroleum hydrocarbon such as heavy oil conversion performance, and utilize several molecular sieve synergism increase light oil receive Rate, especially yield of gasoline significantly improve.With containing in XRD diffracting spectrum at 2 θ angles it is especially The gasification reactivity component containing potassium material at principal phase peak is there is with the use of, not only gas at 21 °, 29 ° and 35 ° Changing effective, gasification temperature is low, and has stronger hydrocarbon oil conversion ability, and gasification reactivity component stream Lose few.

Other features and advantages of the present invention will give specifically in detailed description of the invention part subsequently Bright.

Accompanying drawing explanation

Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, It is used for explaining the present invention together with detailed description below, but is not intended that limitation of the present invention. In the accompanying drawings:

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

Fig. 2 is the X-ray diffraction spectrum according to the mesopore activity silicon phosphor-aluminum material in the specific embodiment of the invention Figure.

Fig. 3 is the X-ray diffraction spectrogram of the material of comparative example 2.

Detailed description of the invention

Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place The detailed description of the invention described is merely to illustrate and explains the present invention, is not limited to the present invention.

The invention provides a kind of cracking gasification catalyst composition, by weight percentage, described catalysis Compositions includes: the gasification reactivity component of mesopore activity silicon phosphor-aluminum material, 1%～40% of 1%～50%, The clay of cracking active component, 0%～70% of 1%～60% and the heat-resistant inorganic oxide base of 2%～97% Matter, described mesopore activity silicon phosphor-aluminum material has the phase structure of boehmite, and (its X-ray is spread out Penetrate collection of illustrative plates as shown in Figure 2), the anhydrous chemical expression counted with oxide weight is for (0-0.2) Na₂O· (50-86)Al₂O₃·(12-50)SiO₂·(0.5-10)P₂O₅, specific surface area is 200～600m²/ g, Pore volume is 0.5～1.8mL/g, and average pore size is 8～18nm.

The present invention above-mentioned for cracking gasification catalyst composition be a kind of for petroleum hydrocarbon cracking process and The catalyst composition of the coke gasification anabolic process that cracking produces, in particular, relates to a kind of utilization heat Cracking, or/and catalytic cracking process processed heavy petroleum hydrocarbon raw material production light Fuel, is being gasified simultaneously The multi-functional of the process that coke gasification is hydrogen or synthesis gas that the course of processing produces is urged under participating in by agent Change compositions.

In the present invention, described specific surface area, pore volume and average pore size all use nitrogen absorption under low temperature-desorption Method is measured, and the instrument used is the physical and chemical adsorption instrument of Micro meritics company of the U.S. ASAP2400。

The above-mentioned cracking gasification catalyst composition provided according to the present invention, it is preferable that with butt weight hundred Proportion by subtraction meter, described catalyst composition includes: 2 weight %～40 weight % mesopore activity silicon phosphor-aluminum materials, 5 The gasification reactivity component of weight %～40 weight %, the cracking active component of 5～50 weight %, 0 weight Measure %～the clay of 60 weight % and 10 weight %～the heat-resistant inorganic oxide matrix of 70 weight %.More excellent Choosing, described catalyst composition includes: 5 weight %～30 weight % mesopore activity silicon phosphor-aluminum materials, 10 weights Amount %～the gasification reactivity component of 35 weight %, the cracking active component of 10～35 weight %, 5 weights Measure %～the clay of 45 weight % and 10 weight %～the heat-resistant inorganic oxide matrix of 40 weight %.

The above-mentioned cracking gasification catalyst composition provided according to the present invention, it is preferable that described mesopore activity Silicon phosphor-aluminum material, (0-0.2) Na in terms of oxide weight ratio₂O·(50-86)Al₂O₃·(12-50)SiO₂· (0.5-10)P₂O_5。It is highly preferred that with the mass ratio range of oxide in described mesopore activity silicon phosphor-aluminum material Anhydrous chemical expression be: (0.08-0.15) Na₂O·(50-80.4)Al₂O₃·(13.7-48)SiO₂· (0.8-2.8)P₂O₅。

The above-mentioned cracking gasification catalyst composition provided according to the present invention, it is preferable that described mesopore activity The specific surface area of silicon phosphor-aluminum material is 250-550m²/ g, pore volume is 0.6-1.6cm³/ g, average pore size is 9-15nm。

The above-mentioned catalyst composition provided according to the present invention, wherein activity mesopore material is referred to existing Technique is prepared, it is preferable that the most described activity mesopore material is according to including following step Rapid method prepares:

(1) aluminum source and aqueous slkali being neutralized at room temperature to 85 DEG C plastic, controlling plastic pH value is 7-11, Obtain plastic serosity；

(2) according to SiO₂: Al₂O₃=1:(1.0-7.5) weight ratio add in described plastic serosity Silicon source, is aged 1-5 hour at room temperature to 90 DEG C, obtains the first solid sediment；

(3) described first solid sediment is contacted process with ammonium salt or acid solution, be filtrated to get oxidation Sodium content is less than the second solid sediment of 0.3 weight %；

(4) by described second solid sediment and phosphorus source according to P₂O₅: described second solid sediment The weight ratio contact of precipitate butt=(0.005-0.1): 1 processes, and by product of contact dry (dry Dry temperature is preferably 100 DEG C-150 DEG C).

Specifically, described in above-mentioned steps (1), aluminum source can be existing various can be converted into oxygen Change the material of aluminum, can be conventional use of various aluminum in the preparation technology of mesopore activity silicon phosphor-aluminum material Source, for example, it is possible to one or more in aluminum nitrate, aluminum sulfate and aluminum chloride.

Described in above-mentioned steps (1), alkaline solution can be the existing various material presenting alkalescence, For example, it is possible in ammonia, sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution One or more.Wherein, the concentration of described alkaline solution can be the conventional selection of this area, at this Do not repeat.

Described in above-mentioned steps (2), silicon source can be the existing various thing that can be converted into silicon oxide Matter, can be conventional use of various sial in the preparation technology of mesopore activity silicon phosphor-aluminum material, such as, Waterglass, sodium silicate, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four fourths can be selected from One or more in epoxide silicon and silicon oxide.

The above-mentioned catalyst composition provided according to the present invention, in the preparation of mesopore activity silicon phosphor-aluminum material Cheng Zhong, although source of aluminium, silicon source and aqueous slkali each can be fitted from the above-mentioned material enumerated Local select, but, a kind of in usual source of aluminium, aqueous slkali and silicon source is former containing sodium Material, thus ensure that the thus prepared described mesopore activity silicon phosphor-aluminum material without ion exchange has suitable Active central hole structure when size.

The present invention is to described first solid sediment contacts in above-mentioned steps (3) side processed with ammonium salt Method is not particularly limited, for example, it is possible to include the first solid sediment by its precipitate butt: Ammonium salt: H₂O=1:(0.1-1): the weight ratio of (5-30) swaps at room temperature to 100 DEG C. Wherein, the number of times of described contact can be 1-3 time, and each time of contact can have with 0.5-1 hour Body should make the content of sodium oxide in the solid product obtained be as the criterion less than 0.3 weight %.

Additionally, the kind of ammonium salt can be the conventional selection of this area described in above-mentioned steps (3), For example, it is possible to one in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate or Multiple.

The present invention method to described first solid sediment being contacted with acid solution in above-mentioned steps (3) It is not particularly limited, for example, it is possible to include described first solid sediment by its precipitate butt: Acid: H₂O=1:(0.03-0.3): the weight ratio of (5-30) exchanges at least at room temperature to 100 DEG C 0.2 hour.

Additionally, the kind of acid solution can be the conventional selection of this area described in above-mentioned steps (3), Usually mineral acid, such as, the acid in described acid solution can be selected from sulphuric acid, hydrochloric acid and nitric acid One or more.

In above-mentioned steps (4), described second solid sediment is contacted with phosphorus source the step processed, its Process can have multiple, including by gained solid sediment by precipitate (butt): H₂O=1:(5～ 20) weight ratio mixes making beating with water, then phosphorus source is added in above-mentioned serosity, connects at room temperature to 90 DEG C Synapsis is managed 0.2～5 hour, preferably 0.5～3 hour, is dried after filtering washing at 100 DEG C～150 DEG C 10～20 hours；Or gained the second solid sediment is directly mixed in proportion with phosphorus source, grinds all It is dried 10～20 hours at 100 DEG C～150 DEG C after even.Room temperature is usually 5～40 DEG C, such as, can be 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C or 35 DEG C.

In the preparation method of above-mentioned mesopore activity silicon phosphor-aluminum material, optional can also the wrapping of step (4) Including the step that desciccate carries out roasting, the condition of described roasting generally includes sintering temperature and can be 500-700 DEG C, preferably roasting time is 1-4 hour.

In the preparation method of above-mentioned mesopore activity silicon phosphor-aluminum material, the kind of phosphorus source described in step (4) Class can be the conventional selection of this area, for example, it is possible to selected from ammonium phosphate, diammonium phosphate, di(2-ethylhexyl)phosphate One or more in hydrogen ammonium and phosphoric acid.

The described catalytic cracking catalyst provided according to the present invention, with the gross weight of described cracking activity constituent element Meter, described cracking activity constituent element contains the first molecular sieve component of 50-95 weight % and 5-50 weight % Second molecular sieve component, described first molecular sieve component is the first Y type molecular sieve, the 2nd Y type molecule At least one in sieve and the 3rd Y type molecular sieve, described second molecular sieve component is the first MFI structure Molecular sieve and/or the second MFI structure molecular sieve, wherein,

Described first Y type molecular sieve is the DASY molecular sieve containing rare earth；

Described second Y type molecular sieve is REY molecular sieve；

The content of rare earth counted with rare earth oxide in described 3rd Y type molecular sieve for 12-16 weight %, with P₂O₅The phosphorus content of meter is 0.5-7 weight %, this molecular sieve³¹In P MAS H NMR spectroscopy, chemical shift The percent of total peak area is accounted for more than 85% for the peak area of-14 ± 2ppm He-23 ± 2ppm resonance signal, This molecular sieve²⁷In Al MAS H NMR spectroscopy, chemical shift is that the peak area of 0 ± 2ppm resonance signal accounts for The percent of total peak area is more than 20%；

Described first MFI structure molecular sieve forms with the anhydrous chemical of the molar ratio computing of oxide and expresses Formula is: (0.01-0.25) RE₂O₃·(0.005-0.02)Na₂O·Al₂O₃·(0.2-1.0)P₂O₅·935-120)SiO₂, This molecular sieve is 4-5 to the absorption weight ratio of normal hexane and hexamethylene；

Described second MFI structure molecular sieve anhydrous chemical composition expression formula in terms of oxide weight ratio is: (0-0.3)Na₂O·(0.5-5.5)Al₂O₃·(1.3-10)P₂O₅·(0.7-15)M1_xO_y·(0.01-5) M2_mO_n·(70-97)SiO₂, wherein, M1 is Fe, Co or Ni, and x represents the atomic number of M1, y Representing the number meeting M1 oxidation state requisite oxygen, M2 is selected from Zn, Mn, Ga or Sn, and m represents The atomic number of M2, n represents the number meeting M2 oxidation state requisite oxygen.

Under preferable case, in terms of the gross weight of described cracking activity constituent element, described cracking activity constituent element contains First molecular sieve component of 65-86 weight % and the second molecular sieve component of 14-35 weight %.In the present invention In, the first molecular sieve component in described cracking activity constituent element and the part by weight of the second molecular sieve component are all In terms of butt.

In the case of further preferably, described first molecular sieve component be selected from described first Y type molecular sieve, The mixture of at least two in described second Y type molecular sieve and described 3rd Y type molecular sieve, described Second molecular sieve component is described first MFI structure molecular sieve or described second MFI structure molecular sieve.

In the present invention, described first Y type molecular sieve is the DASY molecular sieve containing rare earth.Described contain The DASY molecular sieve of rare earth is the hydro-thermal super stable molecular sieve containing rare earth, wherein with RE₂O₃(rare earth oxide) The content of rare earth of meter can be 1.5-3.0 weight %.The described DASY molecular sieve containing rare earth can be each Kind of commercially available prod, such as, can be the DASY2.0 molecular sieve purchased from middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery.

In the present invention, described second Y type molecular sieve is REY molecular sieve.Described REY molecular sieve is Rare earth Y type molecular sieve, it can be various commercially available REY zeolite products, such as, can be purchased from middle stone Change catalyst asphalt in Shenli Refinery.

In the present invention, in described 3rd Y type molecular sieve, content of rare earth in terms of rare earth oxide is 12-16 weight %, with P₂O₅The phosphorus content of meter is 0.5-7 weight %, this molecular sieve³¹P MAS NMR In spectrum, chemical shift is-14 ± 2ppm and the peak area of-23 ± 2ppm resonance signal accounts for the hundred of total peak area Mark is more than 85%, molecular sieve²⁷In Al MAS H NMR spectroscopy, chemical shift is 0 ± 2ppm resonance letter Number peak area account for the percent of total peak area more than 20%.

In the preferred case, with P in described 3rd Y type molecular sieve₂O₅The phosphorus content of meter is 1-3 weight %.

In the preferred case, described 3rd Y type molecular sieve³¹In P MAS H NMR spectroscopy, chemical shift Peak area for-14 ± 2ppm He-23 ± 2ppm resonance signal accounts for the percent of total peak area more than 90%.

In the preferred case, the lattice constant of described 3rd Y type molecular sieve is

In the present invention, the specific descriptions of described 3rd Y type molecular sieve are referred to patent application CN101088917A。

In the present invention, what described 3rd Y type molecular sieve can be prepared according to the conventional method obtains, tool The preparation method of body can also be with reference to patent application CN101088917A, embodiment 1-4 the most therein.

In the present invention, anhydrous with the molar ratio computing of oxide of described first MFI structure molecular sieve Learning composition expression formula is: (0.01-0.25) RE₂O₃·(0.005-0.02)Na₂O·Al₂O₃·(0.2-1.0)P₂O₅· (35-120)SiO₂, this molecular sieve is 4-5 to the absorption weight ratio of normal hexane and hexamethylene.

The x-ray diffraction spectra data of described first MFI structure molecular sieve are as shown in table 1 below, each in table Relative intensity value represented by symbol is as shown in the table, in the following table, and VS:80-100%；S:60-80%； M:40-60%；W:20-40%；VW: < 20%.

D value (× 10^-1Nanometer)	I/I₀
		11.2±0.2	VS
10.1±0.2	M
		9.8±0.2	VW
3.85±0.04	VS
		3.81±0.04	S
3.75±0.04	W
		3.72±0.04	M
3.65±0.04	M
		3.60±0.04	W

In described first MFI structure molecular sieve, rare earth is included in molecular sieve intracrystalline.Rare earth is from dividing The faujasite seeds containing rare earth used during son sieve synthesis.

In described first MFI structure molecular sieve, phosphorus aluminum chemistry in framework of molecular sieve is combined, should Molecular sieve exists²⁷Al H NMR spectroscopy has corresponding to Al (4Si) coordination (i.e. Al is derived from by oxygen and four Individual Si atom forms tetrahedral structure), chemical shift is the spectral peak of 55ppm, and has correspondence In Al (4P) coordination (i.e. Al atom forms tetrahedral structure by oxygen and four P atoms), chemical shift Spectral peak for 39ppm；This molecular sieve exists³¹P H NMR spectroscopy then has and is coordinated (i.e. corresponding to P (4Al) There is PO₄Tetrahedron and adjacent AlO₄Tetrahedral interaction), chemical shift be-29ppm Spectral peak.

In the preferred case, the phosphorus in described first MFI structure molecular sieve is uniformly distributed in molecular sieve crystalline substance Xiang Zhong.The analysis result of transmission electron microscope-energy dispersion spectrum (TEM-EDS) shows at any single crystal Phosphorus content in Li and molecular sieve mutually in phosphorus content close.

Described first MFI structure molecular sieve is 4-5 to the absorption weight ratio of normal hexane Yu hexamethylene, is inhaling Enclosure temperature is 40 DEG C, adsorption time is 3 hours, absorption phase pressure P/P₀Under conditions of=0.20-0.25, This molecular sieve is 98-105 milligrams per gram to the adsorbance of normal hexane, and the adsorbance to hexamethylene is 20-25 Milligrams per gram.This absorption weight ratio (4-5) is apparently higher than this ratio (2-25) of ZSM-5 zeolite.

In the present invention, the specific descriptions of described first MFI structure molecular sieve are referred to patent application CN1147420A。

In the present invention, what described first MFI structure molecular sieve can be prepared according to the conventional method obtains Arriving, concrete preparation method can also be with reference to patent application CN1147420A, enforcement the most therein Example 1-6.

In the present invention, described second MFI structure molecular sieve anhydrous chemical in terms of oxide weight ratio Composition expression formula is: (0-0.3) Na₂O·(0.5-5.5)Al₂O₃·(1.3-10)P₂O₅·(0.7-15)M1_xO_y· (0.01-5)M2_mO_n·(70-97)SiO₂, wherein, M1 is Fe, Co or Ni, and x represents M1's Atomic number, y represents the number meeting M1 oxidation state requisite oxygen, and M2 is selected from Zn, Mn, Ga or Sn, M represents the atomic number of M2, and n represents the number meeting M2 oxidation state requisite oxygen.

In the preferred case, described second MFI structure molecular sieve is calculated as (0-0.2) with oxide weight ratio Na₂O·(0.9-5.0)Al₂O₃·(1.5-7)P₂O₅·(0.9-10)M1_xO_y·(0.5-2)M2_mO_n·(82-92)SiO₂。

In the preferred case, M1 be Fe, M2 be Zn.

In the present invention, the specific descriptions of described second MFI structure molecular sieve are referred to patent application CN1611299A。

In the present invention, what described second MFI structure molecular sieve can be prepared according to the conventional method obtains Arriving, concrete preparation method can also be with reference to patent application CN1611299A, enforcement the most therein Example 1-11.

According in the above-mentioned cracking gasification catalyst composition that the present invention provides, it is preferable that described gasification reactivity Component includes the one in alkali metal compound, alkaline earth metal compound, and group VIII metal compound Or it is multiple.Wherein, described alkali metal compound such as potassium hydroxide, potassium carbonate, potassium oxide, potassium nitrate, Potassium sulfate, potassium chloride, potassium dihydrogen phosphate, potassium feldspar, green bean rock, alunite, trachyte, containing potassium page Rock, phosphorus potassium ore, containing potassium siltstone, XRD diffracting spectrum is at 21 °, 29 ° and 35 ° at 2 θ angles Exist principal phase peak containing potassium material (this material has the peak of XRD principal phase shown in Fig. 1), dolomite, Fructus Canarii albi Stone.When described gasification reactivity component contains alkaline-earth metal when, the compound of alkaline-earth metal can be added, Such as in the inorganic alkali-earth metal salt such as the chloride of alkaline-earth metal, nitrate, sulfate, phosphate one Planting or multiple, described alkaline-earth metal is one or more in beryllium, magnesium, calcium, strontium, barium, preferably calcium And/or magnesium.When described gasification reactivity component contains group VIII metal compound when, VIII can be added The nothings such as the sulfate of the compound of race's metal, such as group VIII metal, nitrate, chloride, oxide One or more in machine group VIII metal salt.Described group VIII metal is preferably Fe and/or Ni.

In the above-mentioned cracking gasification catalyst composition that the present invention provides, it is preferable that described gasification reactivity component Including the compound of potassium, with or without the compound of alkaline-earth metal, with or without the chemical combination of group VIII metal Thing, on the basis of the weight of described gasification reactivity component, in terms of oxide weight, described gasification reactivity group In point, the content of potassium is 2～100 weight %, and the content of alkaline-earth metal is 0～98 weight %, group VIII metal Compounds content is 0～98%.Wherein, the problem serious in order to solve potassium lost, described is active containing potassium Component is preferably described gasification reactivity component and includes is 21 ° at 2 θ angles in XRD diffracting spectrum, 29 ° and Exist at 35 ° principal phase peak containing potassium material (have the peak of XRD principal phase shown in Fig. 1 containing potassium material).Adopt With XRD diffracting spectrum at 2 θ angles is exist at 21 °, 29 ° and 35 ° principal phase peak containing potassium material conduct Gasification reactivity component, can improve the gasification efficiency of catalyst composition further, reduces the loss of potassium, and And the cracking activity of catalyst composition can be improved.

Preferably, in above-mentioned gasification reactivity component, be 21 ° at 2 θ angles in described XRD diffracting spectrum, Exist at 29 ° and 35 ° principal phase peak containing potassium material, the potassium content in terms of potassium oxide is 8 weight %～40 weights Amount %, with or without alkaline-earth metal, remaining is sial component, alkaline earth oxide and potassium oxide mole Than (0～1): 0.2, SiO₂/Al₂O₃Mol ratio be 1:10～10:1.It is highly preferred that described XRD spreads out Penetrate in collection of illustrative plates 2 θ angles be exist at 21 °, 29 ° and 35 ° principal phase peak containing potassium material in potassium oxide content 10 weight %～30 weight %, alkaline earth oxide and potassium oxide mol ratio 1:5～1:0.5, SiO₂/Al₂O₃ Mol ratio be 1:3～3:1.

The above-mentioned catalyst composition provided according to the present invention, wherein XRD diffracting spectrum at 2 θ angles is Exist at 21 °, 29 ° and 35 ° principal phase peak containing potassium material (have the peak of XRD principal phase shown in Fig. 1 containing potassium Material) it is referred to existing common process and is prepared, it is preferable that the most described XRD In diffracting spectrum 2 θ angles be exist at 21 °, 29 ° and 35 ° the material containing potassium at principal phase peak be according to including under The method stating step prepares: potassium-containing compound and sial component are beaten with optional alkaline earth metal compound Starching into wet feed, obtain after being then dried into siccative, then roasting, sintering temperature is 800 DEG C～1150 DEG C, roasting The burning time 1～10h.

Preferably, above-mentioned XRD diffracting spectrum is at 21 °, 29 ° and 35 °, there is principal phase peak at 2 θ angles The preparation method containing potassium material in, alkaline earth oxide and potassium oxide mol ratio 0～1:0.2, sial SiO in component₂/Al₂O₃Mol ratio be 1:10～10:1；And sial component in terms of butt and with alkaline earth gold The weight sum of the alkaline earth metal compound of genus oxide meter and the weight of the potassium-containing compound in terms of potassium oxide Amount ratio is (60～92): (8～40).In order to preferably realize the purpose of the present invention, preparation activity is higher Gasification reactivity component, under preferable case, sintering temperature is 900 DEG C～1100 DEG C, and roasting time is 2～8h.

Above-mentioned preparation is contained in the method for potassium material by the present invention, with potassium-containing compound, alkaline earth metal compound With sial component making beating making beating mode without particular/special requirement, can by they with random order mix, such as Three kinds of materials can be pulled an oar respectively, the most again by three kinds of serosity mixing making beating, it is also possible to by three kinds of materials First mechanical mixture, is adding the making beating of a certain amount of deionized water, and the solid content controlling serosity is existing 15%～50%.

The above-mentioned catalyst composition provided according to the present invention, wherein prepares in XRD diffracting spectrum at 2 θ angles Be exist at 21 °, 29 ° and 35 ° principal phase peak containing potassium material during, described potassium-containing compound is selected from One or more in potassium oxide, potassium hydroxide, potassium carbonate, potassium nitrate, potassium sulfate, potassium chloride, institute State alkaline earth metal compound for selected from alkaline earth oxide, alkaline earth metal carbonate, alkaline earth nitrate, One or more in alkali earth metal sulfate, alkaline earth metal chloride.Can be such as calcium oxide, carbon Acid calcium, calcium nitrate, calcium chloride, calcium sulfate, magnesium oxide, magnesium carbonate, magnesium chloride, magnesium nitrate, sulphuric acid One or more in magnesium.

The above-mentioned catalyst composition provided according to the present invention, wherein prepares in XRD diffracting spectrum at 2 θ angles Be exist at 21 °, 29 ° and 35 ° principal phase peak containing potassium material during, described sial component contains Silicon and aluminium element, can be selected from clay, silicon oxide, silica precursors, aluminium oxide, alumina precursor One or more, preferably clay.Can be selected from the crystal aluminosilicate ore deposit of any layer structure Thing, such as Kaolin, montmorillonite, rectorite, attapulgite, illite, meerschaum and kieselguhr, aluminum One or more in colloidal sol, Ludox, boehmite, and at least one material contains element silicon, At least one material contains aluminium element；Or be Kaolin, montmorillonite, rectorite, attapulgite, she One or more in profit stone, meerschaum, kieselguhr, Alumina gel, boehmite are mixed with Ludox Compound；Or it is Kaolin, montmorillonite, rectorite, attapulgite, illite, meerschaum, diatom One or more in soil, Ludox and Alumina gel or the mixture of boehmite.

The above-mentioned catalyst composition provided according to the present invention, described clay can be clay commonly used in the art Such as, described clay can be selected from Kaolin, meerschaum, attapulgite, montmorillonite, tired de-stone, One or more in kieselguhr, galapectite, saponite, boron-moisten soil, brucite；More preferably selected from height One or more in ridge soil, kieselguhr, meerschaum, attapulgite, montmorillonite and tired de-stone.

According to the present invention provide above-mentioned catalyst composition, except described mesopore activity silicon phosphor-aluminum material, Beyond cracking active component, gasification reactivity component, clay, possibly together with heat-resistant inorganic oxide matrix, institute The kind of the heat-resistant inorganic oxide stated, without particular/special requirement, can be heat resistant inorganic oxidation commonly used in the art Thing substrate, preferably aluminium oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide and oxidation One or more in beryllium and their predecessor.Described heat-resistant inorganic oxide predecessor such as aluminum One or more in colloidal sol, Ludox, phosphorus aluminium glue, boehmite, silicon-aluminum sol.

The above-mentioned catalyst composition provided according to the present invention, when for residual oil cracking-gasification group technology Can also contain metal traps, based on butt, the content of described metal traps is less than catalyzed combination 20 weight % of thing, it is preferable that this metal traps be free on described mesopore activity silicon phosphor-aluminum material, it Outward.Invent the kind of described metal traps without particular/special requirement, can be to trap V, Ni, Fe, Ca Deng the conventional metal traps of the component polluting metal, under preferable case, described metal traps is oxygen Change rare earth and/or the precursor of rare earth oxide.In the case of more preferably, the precursor metal of described rare earth oxide Trapping agent is one or more in rare earth chloride, carbonated rare earth and rare earth hydrate.Wherein, rare earth unit Element can be one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium.In the present invention, metal catches The mode of entrance of agent can be when mesopore activity silicon phosphor-aluminum material, gasification reactivity component, clay mixing making beating In the form of an ion or complex form introduce.If introducing heat resistant inorganic oxidation in carbon monoxide-olefin polymeric Thing, it is also possible in advance metal traps is deposited in described inorganic oxide by coprecipitation.This gold Belong to trapping agent to be in same granule with mesopore activity silicon phosphor-aluminum material, it is also possible to be in different In Li.

Meanwhile, the preparation method of a kind of above-mentioned catalyst composition, the method bag are additionally provided in the present invention Include activity mesoporous silicon phosphor-aluminum material, gasification reactivity component, cracking active component, clay, heat-resisting nothing The mixing making beating of machine matrix of oxide, is spray-dried and the step of roasting.

According to the preparation method of above-mentioned catalyst composition provided by the present invention, by activity mesopore material, After the mixing of gasification reactivity component, clay, heat-resistant inorganic oxide matrix, according to the conventional method of this area Pull an oar, be spray-dried and roasting.In one of the present invention preferred embodiment, above-mentioned catalysis The preparation method of compositions, comprises the following steps:

(1) aluminum source and aqueous slkali being neutralized at room temperature to 85 DEG C plastic, controlling plastic pH value is 7-11, Obtain plastic serosity；According to SiO₂: Al₂O₃=1:(1.0-7.5) weight ratio to described plastic serosity Middle addition silicon source, is aged 1-5 hour at room temperature to 90 DEG C, obtains the first solid sediment；By described First solid sediment contacts process with ammonium salt or acid solution, is filtrated to get sodium oxide content less than 0.3 weight Second solid sediment of amount %；By described second solid sediment with phosphorus source according to P₂O₅: described second The weight ratio contact of the precipitate butt of solid sediment=(0.005-0.1): 1 processes, and contact is produced Thing is dried, or roasting 1～4 hours at 500 DEG C～700 DEG C；

(2) potassium-containing compound and sial component are mixed making beating with optional alkaline earth metal compound, so Post-drying becomes siccative, then at 800 DEG C～1150 DEG C, preferably 900 DEG C～1100 DEG C of roastings, roasting time 1～10h, The gasification reactivity component containing potassium is obtained after roasting；The wherein alkaline-earth metal chemical combination in terms of alkaline earth oxide The mol ratio 0～1:0.2 of thing and the potassium-containing compound in terms of potassium oxide, preferably 1:5～1:0.5, SiO₂/Al₂O₃ Mol ratio be 1:10～10:1, preferably 1:3～3:1, with the obtained gasification reactivity component containing potassium On the basis of butt weight, in the obtained gasification reactivity component containing potassium, the potassium content in terms of potassium oxide is 8 Weight %～40 weight %；

(3) the described mesopore activity silicon phosphor-aluminum material obtained in step (1) and step (2) are obtained Containing potassium gasification reactivity component and clay, the mixing making beating of cracking active component, heat-resistant inorganic oxide matrix, Then carry out being spray-dried, roasting 2～10h at 400～800 DEG C；Wherein press dry basis, described Mesopore activity silicon phosphor-aluminum material, gasification reactivity component, cracking active component, clay and heat resistant inorganic oxygen The consumption of compound substrate makes the described mesopore activity silicon that obtained catalyst composition includes 1%～50% The described cracking active component of described gasification reactivity component, 1%～60% of phosphor-aluminum material, 1%～40%, The described clay of 0%～70% and the described heat-resistant inorganic oxide matrix of 2%～97%.

Preferably, the described mesopore activity silicon phosphor-aluminum material obtained in above-mentioned steps (1), gasification are lived Property component mixing making beating obtain the first serosity, by cracking active component, clay, binding agent mixing making beating, Obtain the second serosity, then the first serosity and the second serosity mixed making beating, then carry out being spray-dried, Roasting 2～10h at 400～800 DEG C.

According to the preparation method of above-mentioned catalyst composition provided by the present invention, described clay can be this The clay that field is conventional, under preferable case, can be selected from Kaolin, meerschaum, attapulgite, illiteracy de- One or more in stone, tired de-stone, kieselguhr, galapectite, saponite, boron-moisten soil, brucite；More It is preferably selected from the one in Kaolin, kieselguhr, meerschaum, attapulgite, montmorillonite and tired de-stone Or it is multiple；Binding agent, described bonding it is when heat-resistant inorganic oxide matrix has adhesive property when Agent can be binding agent commonly used in the art, preferably in the case of, can select Alumina gel, Ludox, One or more in boehmite, phosphorus aluminium glue.Under preferable case, described serosity also can add acid It is acidified, one or more in described acid such as hydrochloric acid, nitric acid, sulphuric acid.Preferably, will step Suddenly the mixing making beating of the described mesopore activity silicon phosphor-aluminum material that obtains in (1), gasification reactivity component obtains the One serosity, by cracking active component, clay, binding agent mixing making beating, obtains the second serosity, then will First serosity and the mixing making beating of the second serosity, then carry out being spray-dried, at 400～800 DEG C preferably 450～750 DEG C Lower roasting 2～10h.

Preferably, described inorganic oxide matrix is for existing in the form of an oxide and/or can obtain The precursors of inorganic oxides of described inorganic oxide.Described heat-resistant inorganic oxide matrix can be in catalysis group Compound adds with heat-resistant inorganic oxide precursor in the preparation, is then passed through roasting, heat-resistant inorganic oxide Precursor is converted into heat-resistant inorganic oxide, it is also possible to be first prepared as heat-resisting with heat-resistant inorganic oxide precursor Inorganic oxide, then with the form addition of heat-resistant inorganic oxide in the preparation process of catalyst composition. Wherein the temperature of roasting is usually less than 800 DEG C, generally 400～750 DEG C.Described heat resistant inorganic oxidation When thing substrate has attachment function, generally also become binding agent, such as, binding agent can be Alumina gel, One or more in Ludox, boehmite, phosphorus aluminium glue.

The present invention provide cracking gasification catalyst composition preparation method in, by mesopore activity silicon phosphor-aluminum material, The order of gasification reactivity component, clay, heat-resistant inorganic oxide matrix mixing making beating does not has particular/special requirement, For example, it is possible to described raw material to be prepared respectively serosity, then by prepared serosity mixing；Can be first Mesopore activity silicon phosphor-aluminum material is mixed with clay, mixes making beating with other component the most again；Maybe will gasification Active component mixes making beating with clay, mixes making beating with other component the most again.

When the catalyst composition of the present invention contains metal traps, the introducing of metal agent for capturing in the present invention Mode can be in mesopore activity silicon phosphor-aluminum material, gasification reactivity component, cracking active component, clay mixing During making beating in the form of an ion or complex form introduce, it is also possible to will above-mentioned several components spray drying After molding, the form with precipitation introduces.If introducing heat-resistant inorganic oxide matrix in carbon monoxide-olefin polymeric, In advance metal traps can also be deposited in described inorganic oxide by coprecipitation.Preferable case Under, based on butt, the content of described metal traps is less than 20 weight % of catalyst composition.This Invent the kind of described metal traps without particular/special requirement, can be to trap V, Ni, Fe, Ca etc. Polluting the common metal trapping agent of the component of metal, under preferable case, described metal traps is dilute for oxidation Soil and/or the precursor of rare earth oxide.In the case of more preferably, the precursor of described rare earth oxide is that chlorination is dilute One or more in soil, carbonated rare earth and rare earth hydrate.Wherein, rare earth element can be lanthanum, cerium, One or more in praseodymium, neodymium, promethium, samarium and europium.

The preparation method of above-mentioned catalyst composition that the present invention provides, described preferred embodiment in, only Being described the preparation method of catalyst composition, the technical characteristic identical with product no longer carries out weight Multiple description.

Additionally, also provide for the using method of a kind of described catalyst composition, this using method in the present invention Comprise the steps:

(1) petroleum hydrocarbon contacts at the catalyst composition that Cracking Unit provides with the present invention and carries out cracking reaction, Reaction effluent obtains gas, gasoline fraction, diesel oil distillate, wax oil fraction and deposited coke after separating Catalyst composition；Described petroleum hydrocarbon such as AGO (atmospheric gas oil), vacuum gas oil (VGO), decompression residuum, often One or more in pressure residual oil, Propane Deasphalting Oil, wax tailings.Described reaction condition is the most anti- Answering temperature is 450～700 temperature, and reaction weight (hourly) space velocity (WHSV) is 0.1～500h^-1, oil ratio (catalyst composition Weight ratio with petroleum hydrocarbon) it is 0.1～100.

(2) catalyst composition (band charcoal catalyst composition) that deposited coke of step (1) gained enters Entering gasification unit, by controlling gasification condition, charcoal and gasifying agent reaction on described catalyst composition generate Rich in CO and H₂Gas, the catalyst composition regenerated the most completely or semi regeneration catalysis group Compound, described semi regeneration catalyst composition is at regeneration unit, under conditions of with the presence of oxygen, makes described Remain charcoal on catalyst composition to occur to burn completely, obtain complete regeneration catalyzing compositions；Described gasification Condition refers to existing gasification process, gasification condition such as: gasification temperature is 650～800 DEG C and can be 680～750 DEG C, gasifying agent can be by the steam of 70～100 volume % and the oxygen of 0～30 volume %, example As included more than 0 and being less than or equal to the oxygen of 20 volume % and be more than or equal to 80 and little 100 volume % Steam.

(3) the complete regeneration catalyzing compositions of step (2) gained is carried heat and is returned to step (1) Described Cracking Unit recycles.

Coke on catalyst composition preferably by controlling regeneration condition, is gasificated into richness by above-mentioned steps (2) Containing CO and H₂Obtaining semi regeneration catalyst composition while gas, coke layer remaining in compositions can With guard catalyst not by the further destruction of gasifying agent, the loss and the cracking that reduce gasification reactivity component are lived The inactivation at property center.In described semi regeneration compositions, coke content is 0.3～1%.

The present invention will be further described by the following examples, but not thereby limiting the invention.

In an embodiment with in comparative example:

Hydrochloric acid is produced by Beijing Chemical Plant, chemical pure, concentration 36-38 weight %；

Sodium silicate is commercially available, containing SiO₂Concentration is 26.0 weight %, and modulus is 3.2；

Halloysite is produced by Kaolin of Suzhou company, and solid content is 74.0 weight %；

Boehmite is Shandong Aluminum Plant's industrial products, and solid content is 62.0 weight %；

Alumina gel is Shandong catalyst branch company of middle petrochemical industry joint-stock company product, Al₂O₃Content is 21.5 weights Amount %；

First Y type molecular sieve is DASY2.0 molecular sieve, middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery produce；

Second Y type molecular sieve is REY molecular sieve, middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery produce；

3rd Y type molecular sieve prepares according to the method for embodiment 1 in patent application CN101088917A；

First MFI structure molecular sieve is according to the method system of embodiment 1 in patent application CN1147420A ?；

Second MFI structure molecular sieve is according to the method system of embodiment 1 in patent application CN1611299A ?；

Na in mesopore activity silicon phosphor-aluminum material₂O、Al₂O₃、SiO₂、P₂O₅Content XRF (seeing " Petrochemical Engineering Analysis method (RIPP experimental technique) ", Yang Cui waits and compiles method mensuration surely, scientific publication Society, nineteen ninety publication).

Embodiment 1～6 is for illustrating the preparation method of mesopore activity silicon phosphor-aluminum material used by the present invention.

Embodiment 1

With concentration as 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration 102gAl₂O₃/ L, Crater corrosion 1.7 NaAlO₂Solution is reaction raw materials, and flows plastic and regulate plastic pH=9.0, collects quantitative plastic Serosity, according to SiO under stirring condition₂: Al₂O₃The weight ratio of=1:1.5 adds dense in plastic serosity Degree is 60gSiO₂The waterglass of/L, is warming up to 80 DEG C and is aged 1.5 hours, obtain the first solid sediment； Use NH₄Cl solution is by the first solid sediment (butt): ammonium salt: H₂The weight ratio of O=1:1:12, At 60 DEG C, sial precipitate is carried out ion exchange and removes sodium ion, and with a large amount of deionized water drip washing extremely Sodium oxide content is less than 0.3%, obtains the second solid sediment；Then directly sodium oxide content is less than Second solid sediment of 0.3% and phosphoric acid press P₂O₅: the second solid sediment (butt)=0.008:1 Weight ratio mixing, be dried in 120 DEG C after grinding uniformly and within 10 hours, i.e. obtain the mesopore activities that the present invention provides Material.It is designated as PAM-1.

PAM-1 has typical boehmite crystal phase structure, its X-ray diffraction spectrogram such as Fig. 2 institute Show；Its elementary analytical chemistry consists of 0.14Na₂O·59.3Al₂O₃·39.1SiO₂·0.8P₂O₅；Specific surface Long-pending 320m²/ g, pore volume 0.78cm³/ g, average pore size 9.7nm.

Embodiment 2

Preparation process is with reference to embodiment 1.Difference is, wherein phosphorus source selects ammonium dihydrogen phosphate, and second is solid Body precipitate and phosphoric acid press P₂O₅: the weight ratio mixing of the second solid sediment (butt)=0.04:1, Being dried 10 hours in 120 DEG C after grinding uniformly, at 600 DEG C, roasting i.e. obtains the present invention for 2 hours provides Mesoporous active materials.It is designated as PAM-2.

PAM-2 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is special with Fig. 2 Levy；Its elementary analytical chemistry consists of 0.15Na₂O·56.9Al₂O₃·38.5SiO₂·4.0P₂O₅；Specific surface Long-pending 348m²/ g, pore volume 0.99cm³/ g, average pore size 11.4nm.

Embodiment 3

First by quantitative concentrations 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in beaker, with vigorous stirring Being added dropwise over by ammonia, until system pH=10.5, gelling temperature is 40 DEG C；Press under agitation According to SiO₂: Al₂O₃The weight ratio of=1:1.1 adds concentration 60gSiO in plastic serosity₂The waterglass of/L, It is warming up to 70 DEG C be aged 3 hours, obtains the first solid sediment；By gained the first solid sediment by it Precipitate (butt): HCl:H₂The weight ratio of O=1:0.08:10 exchanges 30 minutes at 60 DEG C, Filtering washing makes sodium oxide content be less than 0.3%, obtains the second solid sediment；Then by gained second Solid sediment presses its precipitate (butt): H₂The weight ratio of O=1:8 mixes making beating with water, and presses P₂O₅: the weight ratio of material butt=0.016:1 adds phosphoric acid, reacts 2 hours, mistake at 60 DEG C Drainage is dried at 120 DEG C after washing and within 10 hours, i.e. obtains the mesoporous active materials that the present invention provides.It is designated as PAM-3。

PAM-3 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is special with Fig. 2 Levy；Its elementary analytical chemistry consists of 0.12Na₂O·50.2Al₂O₃·48.0SiO₂·1.5P₂O₅；Specific surface Long-pending 289m²/ g, pore volume 0.64cm³/ g, average pore size 8.8nm.

Embodiment 4

Preparation process is with reference to embodiment 3.Difference is, wherein the second solid sediment and phosphoric acid press P₂O₅: The weight ratio mixing of precipitate (the butt)=0.03:1 of the second solid sediment, reacts 2 at 60 DEG C Hour, filter washing and be dried 10 hours in 120 DEG C, 2 hours i.e. get Ben Fa of roasting at 600 DEG C The mesoporous active materials of bright offer.It is designated as PAM-4.

PAM-4 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is special with Fig. 2 Levy；Its elementary analytical chemistry consists of 0.11Na₂O·55.4Al₂O₃·41.2SiO₂·2.9P₂O₅；Specific surface Long-pending 331m²/ g, pore volume 0.89cm³/ g, average pore size 10.7nm.

Embodiment 5

With concentration 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration 102gAl₂O₃/ L, Crater corrosion 2.5 NaAlO₂Solution is reaction raw materials, and flows plastic and regulate plastic pH=9.5, collects a certain amount of one-tenth Rubber cement liquid, under agitation according to SiO₂: Al₂O₃The weight ratio of=1:4.2 adds in plastic serosity Enter concentration 60gSiO₂The waterglass of/L, is warming up to 70 DEG C and is aged 2 hours；Use NH₄Cl solution is by precipitation Thing (butt): ammonium salt: H₂The weight ratio of O=1:0.8:15, is carried out sial precipitate at 60 DEG C Ion exchange removes sodium ion, and exchange repeats twice, carries out 0.5 hour every time, contains to sodium oxide Amount is less than 0.3%；Then gained solid sediment is pressed precipitate (butt): H₂The weight of O=1:8 Than mixing making beating with water, and press P₂O₅: the weight ratio of material butt=0.06:1 adds diammonium phosphate, React 2 hours at 60 DEG C, be dried at 120 DEG C after filtering washing and within 10 hours, i.e. obtain the present invention and carry The active mesopore material of confession.It is designated as PAM-5.

PAM-5 has boehmite phase structure, and its X-ray diffraction spectrogram is with Fig. 2 feature；Its Elementary analytical chemistry consists of 0.08Na₂O·80.4Al₂O₃·13.7SiO₂·5.8P₂O₅；Specific surface area 509 m²/ g, pore volume 1.42cm³/ g, average pore size 11.2nm.

Embodiment 6

With concentration 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration 102gAl₂O₃/ L, Crater corrosion 1.7 NaAlO₂Solution is reaction raw materials, and flows plastic and regulate plastic pH=10.5, collects quantitative one-tenth Rubber cement liquid, under agitation according to SiO₂: Al₂O₃The weight ratio of=1:3 adds in plastic serosity Concentration 60gSiO₂The waterglass of/L, is warming up to 60 DEG C and is aged 3 hours；Use NH₄Cl solution presses precipitate (butt): ammonium salt: H₂The weight ratio of O=1:1:10, carries out ion to sial precipitate at 60 DEG C Exchange removes sodium ion, and with a large amount of deionized water drip washing to sodium oxide content less than 0.3 weight %；So After gained solid sediment pressed precipitate (butt): H₂The weight ratio of O=1:10 mixes making beating with water, And press P₂O₅: the weight ratio of material butt=0.031:1 adds diammonium phosphate, anti-at 60 DEG C Answer 2 hours, be dried at 120 DEG C after filtering washing and within 10 hours, i.e. obtain the mesopore activity silicon that the present invention provides Phosphor-aluminum material.It is designated as PAM-6.

PAM-6 has boehmite crystal phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 2； Its elementary analytical chemistry consists of 0.10Na₂O·70.6Al₂O₃·26.1SiO₂·3.0P₂O₅；Specific surface area 409 m²/ g, pore volume 1.06cm³/ g, average pore size 10.3nm.

Embodiment 7,8 is for illustrating the gasification reactivity used by the present invention with the peak of XRD principal phase shown in Fig. 1 The preparation method of component.

Embodiment 7

Weigh in terms of butt 1500 grams of Kaolin, 430 grams of KOH and 70 grams of MgO, three is mixed And add appropriate amount of deionized water, make slurry solid content 10%～50%, stir at least 20 minutes, be dried, Roasting 3 hours at 1050 DEG C again, prepare gasification reactivity component G-1 in potassium, wherein K₂O content is 21.5%, MgO/K₂The mol ratio of O is 1/2.6, SiO₂/Al₂O₃Mol ratio be 2, G-1 has figure XRD principal phase peak (principal phase peak 2 θ is 21 °, 29 °, 35 ° respectively) shown in 1.

Embodiment 8

Prepare containing potassium material as gasification reactivity component, according in terms of butt according to the method for embodiment 7 1350 grams of Kaolin, 350 grams of K₂CO₃, 200 grams of CaO, 100 grams of boehmites feed intake, and prepare Containing potassium gasification reactivity component G-2.Wherein K₂O content is 17.5%, CaO/K₂The mol ratio of O is 1/1, SiO₂/Al₂O₃Mol ratio be 1.7:1.G-2 has the XRD feature principal phase peak (principal phase shown in Fig. 1 Peak 2 θ is 21 °, 29 °, 35 ° respectively).

Embodiment 9～15 is for illustrating the preparation method of catalyst composition used by the present invention.

Embodiment 9

The boehmite of 2 weight portions in terms of butt is mixed with deionized water making beating, and to obtaining Adding concentration in serosity is the hydrochloric acid of 30 weight %, acid aluminum ratio (described 36 weight % hydrochloric acid with Al₂O₃ The weight ratio of the boehmite of meter) it is 0.3, it is warmed up to 60 DEG C and is acidified 1 hour, obtain serosity.Will Kaolin (Suzhou hargil), the Alumina gel of in terms of butt 23 weight portions of in terms of butt 10 parts join Mixing making beating 60 minutes in the most acidified boehmite serosity, then by terms of butt 10 weight portions First Y type molecular sieve (RE₂O₃Content is 2.3 weight %, middle Effect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery product), Second Y type molecular sieve (RE of 10 weight portions₂O₃Content is 18.8 weight %, and middle Effect of Catalysis In Petrochemistry agent is neat Shandong branch company product) and the first MFI structure molecular sieve addition of 10 weight portions, pull an oar 1 hour, To the first serosity.

By the mesopore activity containing potassium material G-1 Yu in terms of butt 10 weight portions of in terms of butt 25 weight portions Silicon phosphor-aluminum material PAM-1 mixes, and adds deionized water, mixing making beating stirring 60 minutes, obtains second Serosity.By two kinds of serosity mixing, and stir at least 30 minutes, obtain the slurry that solid content is 35 weight % Liquid.Spray drying makes microsphere catalyst composition, then 500 DEG C of roastings 2 hours.Obtained connects Touch the numbered C1 of agent.

Catalyst composition uses the wastage of potassium, the condition of hydrothermal experiment in hydrothermal experiment test compositions For: 90% steam 550 DEG C processes 72h, K in sample composition before and after mensuration hydro-thermal₂The 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 is shown in Table 1.

Embodiment 10～15

Prepare catalyst composition according to the method for embodiment 9, adjust ingredient proportion, make catalyst composition C2～C7, specifically feeds intake and is shown in Table 1, and the hot water potassium retention rate of catalyst composition C2～C7 is shown in Table 1.

Table 1

From table 1, use prepared by method provided by the present invention to have XRD principal phase shown in Fig. 1 Peak containing potassium material as the gasification reactivity component in catalyst composition, the guarantor of potassium after hydrothermal treatment consists Stay rate apparently higher than using other containing potassium material as the guarantor of potassium in the catalyst composition of gasification reactivity component Stay rate.

Comparative example 1

The explanation of this comparative example prepares structure of similar to thin diaspore according to the process described in CN1565733A Silica-alumina material.

With concentration 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration 102gAl₂O₃/ L, Crater corrosion 1.7 NaAlO₂Solution is reaction raw materials, and flows plastic and regulate plastic pH=9.0, collects plastic serosity, stirs According to SiO under the conditions of mixing down₂: Al₂O₃The weight ratio of=1:1.3 adds concentration in plastic serosity 60gSiO₂The waterglass of/L, is warming up to 70 DEG C and is aged 2 hours, obtain the first solid sediment；Use NH₄Cl Solution is by the first solid sediment (butt): ammonium salt: H₂The weight ratio of O=1:0.8:15, at 60 DEG C Under sial precipitate carried out ion exchange remove sodium ion, exchange repeats twice, carries out 0.5 every time Hour, to sodium oxide content less than 0.3%, it is dried at 120 DEG C and i.e. obtains CN1565733A in 10 hours Described in mesoporous silicon aluminum.It is designated as DB-1.

The X-ray diffraction spectrogram of DB-1 is with Fig. 2 feature；Its elementary analytical chemistry consists of 0.16Na₂O ·54.7Al₂O₃·44.5SiO₂；Specific surface area 329m²/ g, pore volume 0.82cm³/ g, average pore size 10.0nm.

Comparative example 2

The contrast that the explanation of this comparative example obtains with silicon source and phosphorus source reaction modifying with conventional boehmite The process of sample.

By a certain amount of industry boehmite (Shandong Aluminum Plant, Al₂O₃Content 65wt%) press 1:15 Weight ratio mix making beating with water, add the dilute hydrochloric acid (concentration is 30wt.%) of metering after stirring 30 minutes, Add quantitative tetraethoxy-silicane after continuing stirring 10 minutes, be warming up to 80 DEG C and react 4 hours, then add The phosphoric acid entering metering continues stirring 1 hour, is then dried 10 hours at 120 DEG C, at 550 DEG C The comparative sample that roasting obtains having structure of similar to thin diaspore for 4 hours.It is designated as DB-2.

The X-ray diffraction spectrogram of DB-2 is as shown in Figure 3；Its elementary analytical chemistry consists of 0.08Na₂O ·50.1Al₂O₃·45.2SiO₂·4.2P₂O₅；Specific surface area 247m²/ g, pore volume 0.49cm³/ g, average hole Footpath 7.5nm.

Comparative example 3

With reference to the preparation method of the mesoporous silicon aluminum DB-1 of comparative example 1, simply use acid exchange process Substitute ammonium exchange process therein.Will the intermediate sedimentation thing of DB-1, the sial after the most aging filtration sinks Shallow lake thing, mixes making beating with water by the weight ratio of 1:10, then by HCl solution (concentration is 10 weight %) By precipitate (butt): the weight ratio of HCl=1:0.12 joins in above-mentioned serosity, contact at 55 DEG C 40 minutes, through filtering, be dried and obtaining mesoporous silica-alumina materials after roasting, it is designated as DB-3.

The X-ray diffraction spectrogram of DB-2 is as shown in Figure 2；Its elementary analysis weight chemistry consists of 0.14Na₂O·54.7Al₂O₃·44.5SiO₂。

Comparative example 4～8

According to the catalyst composition preparation method of embodiment 9, feed intake according to table 2 and prepare contrast catalyzed combination Thing D1～D4.

Table 2

From the data of Tables 1 and 2 it can be seen that carbon monoxide-olefin polymeric is at 90% steam 550 DEG C After reason 72h, when the method provided by the present invention preparation of use has containing of the peak of XRD principal phase shown in Fig. 1 Potassium material is high as the potassium retention rate of the carbon monoxide-olefin polymeric of gasification reactivity component, hence it is evident that higher than other containing potassium Compound is as the potassium retention rate of the catalyst composition of gasification reactivity component.Visible, use the present invention to provide The stability containing potassium material with the peak of XRD principal phase shown in Fig. 1 prepared of method owing to other are containing potassium Compound.

Test case 1

This test is for illustrating embodiment 9～15 and the gasification of catalyst composition that provides of comparative example 4～8 Energy and cracking performance.Respectively the catalyst composition of above-mentioned preparation 800 DEG C, the condition of 100% steam Under aging 4h, being then seated in reserve is to carry out cracking in 210 grams fixed fluidized bed and gasification is real Test.Cracking experiments condition is: reaction temperature is 530 DEG C, weight (hourly) space velocity (WHSV) is 20h^-1, oil ratio is 8, Water-oil factor is 0.3；Gasification experiment condition: gasification temperature is 690 DEG C, gasifying agent is 100% steam. Catalyst composition after all gasifications keeps certain coke to be retained in compositions, generally > 0.3 weight %, For example, 0.4～0.6 weight %.

Raw materials used oil properties is shown in Table 3, appreciation condition and the results are shown in Table 4 and table 5.

Table 3

Table 4

Table 5

In table 4 and table 5:

Make charcoal intensity: the coke quality that carbon monoxide-olefin polymeric reserve per ton is burnt per hour, unit is kg/(t·h)

Typically, catalyst composition gasification reactivity and after cracking the intensity of making charcoal of coke in compositions Increasing along with the increase of temperature, in gasifying agent, the intensity of making charcoal containing oxygen can be better than with 100% water steaming Gas is as the intensity of making charcoal of gasifying agent.From table 4 and table 5 it can be seen that the cracking that the present invention provides is gasified Catalyst composition (C1-C7) is relative to the documents mentioned by aforementioned background art CN200910143623.3 (gasification temperature needs higher than 860 DEG C), can be at lower gasification temperature Obtaining good gasification result under (690 DEG C), obtain higher intensity of making charcoal, gasification product has relatively High density of hydrogen.

It is known that the low catalyst composition Middle molecule that can effectively reduce of gasification temperature sieves active center Deactivation rate.When catalyst composition proportioning is identical, compare the mesopore activity using comparative example 1-2 to prepare Catalyst composition prepared by silicon phosphor-aluminum material, prepared by the mesopore activity silicon phosphor-aluminum material using the present invention to provide Catalyst composition there is more preferable cracking performance, yield of light oil (gasoline and the total recovery of liquefied gas) High, liquefied gas yield height.The XRD master having shown in Fig. 1 prepared by the method using the present invention to provide The gasification reactivity of the catalyst composition prepared as gasification reactivity component containing potassium material at phase peak is higher, makes charcoal Intensity is higher；Under same gasification condition, the intensity of making charcoal of gasification reactivity and coke is considerably higher.When The catalyst composition that invention provides contains the XRD shown in mesopore activity silicon phosphor-aluminum material and Fig. 1 simultaneously Principal phase peak containing potassium material time, gasification reactivity is higher, and this is possibly due to mesopore activity silicon phosphor-aluminum material and changes It is apt to the distribution of coke, has improve the utilization rate of gasification reactivity component, and then improve gasification performance.Can See, adopt the catalyst composition of visible present invention offer for the-process process heavy petroleum hydrocarbon that gasifies It is advantageously implemented the efficient utilization of petroleum resources, and energy-conservation.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned Detail in embodiment, in the technology concept of the present invention, can be to the skill of the present invention Art scheme carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.

It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid not Necessary repetition, various possible compound modes are illustrated by the present invention the most separately.

Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as It is without prejudice to the thought of the present invention, and it should be considered as content disclosed in this invention equally.

Claims

1. a cracking gasification catalyst composition, by weight percentage, described catalyst composition includes: the clay of the cracking active component of gasification reactivity component, 1%～60%, 0%～70% of mesopore activity silicon phosphor-aluminum material, 1%～40% of 1%～50% and the heat-resistant inorganic oxide matrix of 2%～97%, described mesopore activity silicon phosphor-aluminum material has the phase structure of boehmite, and the anhydrous chemical expression counted with oxide weight is for (0-0.2) Na₂O·(50-86)Al₂O₃·(12-50)SiO₂·(0.5-10)P₂O₅, specific surface area is 200～600m²/ g, pore volume is 0.5～1.8mL/g, and average pore size is 8～18nm.

Catalyst composition the most according to claim 1, wherein, described mesopore activity silicon phosphor-aluminum material (0-0.2) Na in terms of oxide weight ratio₂O·(50-86)Al₂O₃·(12-50)SiO₂·(0.5-10)P₂O₅。

Catalyst composition the most according to claim 1, wherein, the specific surface area of described mesopore activity silicon phosphor-aluminum material is 250-550m²/ g, pore volume is 0.6-1.6cm³/ g, average pore size is 9-15nm.

4. according to the catalyst composition described in any one in claim 1-3, wherein, described mesopore activity silicon phosphor-aluminum material prepares in accordance with the following methods:

(1) aluminum source and aqueous slkali being neutralized at room temperature to 85 DEG C plastic, controlling plastic pH value is 7-11, obtains plastic serosity；

(2) according to SiO₂: Al₂O₃=1:(1.0-7.5) weight ratio in described plastic serosity, add silicon source, at room temperature to 90 DEG C be aged 1-5 hour, obtain the first solid sediment；

(3) described first solid sediment is contacted process with ammonium salt or acid solution, be filtrated to get the sodium oxide content the second solid sediment less than 0.3 weight %；

(4) by described second solid sediment and phosphorus source according to P₂O₅: the weight ratio contact of the precipitate butt of described second solid sediment=(0.005-0.1): 1 processes, and product of contact is dried.

Catalyst composition the most according to claim 4, wherein, one or more in aluminum nitrate, aluminum sulfate and aluminum chloride of aluminum source described in step (1)；One or more in ammonia, sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution of described alkaline solution；One or more in waterglass, sodium silicate, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon and silicon oxide of silicon source described in step (2), and in source of aluminium, alkaline solution, silicon source, at least one is containing sodium raw materials.

Catalyst composition the most according to claim 4, wherein,

It is by its precipitate butt by the first solid sediment of step (2) gained that described first solid sediment contacts in step (3) process processed with ammonium salt: ammonium salt: H₂O=1:(0.1-1): the weight ratio of (5-30) exchanges at room temperature to 100 DEG C, until sodium oxide content is less than 0.3 weight % in solid sediment,

Described first solid sediment is contacted with acid solution the process processed by step (3), is by its precipitate butt by the first solid sediment of step (2) gained: acid: H₂O=1:(0.03-0.30): the weight ratio of (5-30) at least exchanges 0.2 hour at room temperature to 100 DEG C.

Catalyst composition the most according to claim 4, wherein, one or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate of ammonium salt described in step (3)；One or more in sulphuric acid, hydrochloric acid and nitric acid of acid in described acid solution.

Catalyst composition the most according to claim 4, wherein, one or more in ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate and phosphoric acid of phosphorus source described in step (4).

Catalyst composition the most according to claim 4, wherein, described in step (4) after drying steps, also includes gained desciccate roasting 1-4 hour at 500 DEG C-700 DEG C.

Catalyst composition the most according to claim 1, wherein, in terms of the gross weight of described cracking activity constituent element, described cracking activity constituent element contains the first molecular sieve component of 50-95 weight % and the second molecular sieve component of 5-50 weight %, described first molecular sieve component is at least one in the first Y type molecular sieve, the second Y type molecular sieve and the 3rd Y type molecular sieve, described second molecular sieve component is the first MFI structure molecular sieve and/or the second MFI structure molecular sieve, wherein, described first Y type molecular sieve is the DASY molecular sieve containing rare earth；Described second Y type molecular sieve is REY molecular sieve；The content of rare earth counted with rare earth oxide in described 3rd Y type molecular sieve is for 12-16 weight %, with P₂O₅The phosphorus content of meter is 0.5-7 weight %, this molecular sieve³¹In P MAS H NMR spectroscopy, chemical shift is that the peak area of-14 ± 2ppm and-23 ± 2ppm resonance signal accounts for the percent of total peak area more than 85%, this molecular sieve²⁷In Al MAS H NMR spectroscopy, chemical shift is that the peak area of 0 ± 2ppm resonance signal accounts for the percent of total peak area more than 20%；

Forming expression formula with the anhydrous chemical of the molar ratio computing of oxide in described first MFI structure molecular sieve is: (0.01-0.25) RE₂O₃·(0.005-0.02)Na₂O·Al₂O₃·(0.2-1.0)P₂O₅·(35-120)SiO₂, this molecular sieve is 4-5 to the absorption weight ratio of normal hexane and hexamethylene；Described second MFI structure molecular sieve anhydrous chemical composition expression formula in terms of oxide weight ratio is: (0-0.3) Na2O (0.5-5.5) Al₂O₃·(1.3-10)P₂O₅·(0.7-15)M1_xO_y·(0.01-5)M2_mO_n·(70-97)SiO₂, wherein, M1 is Fe, Co or Ni, and x represents the atomic number of M1, and y represents the number meeting M1 oxidation state requisite oxygen, and M2 is selected from Zn, Mn, Ga or Sn, and m represents the atomic number of M2, and n represents the number meeting M2 oxidation state requisite oxygen.

11. catalyst compositions according to claim 10, wherein, in terms of the gross weight of described cracking activity constituent element, described cracking activity constituent element contains the first molecular sieve component of 65-86 weight % and the second molecular sieve component of 14-35 weight %.

12. catalyst compositions according to claim 1, wherein, described gasification reactivity component includes one or more in alkali metal compound, alkaline earth metal compound, and group VIII metal compound.

13. according to the catalyst composition described in claim 1 or 12, wherein, described gasification reactivity component is selected from potassium hydroxide, potassium carbonate, potassium oxide, potassium nitrate, potassium sulfate, potassium chloride, potassium dihydrogen phosphate, potassium feldspar, green bean rock, alunite, trachyte, potassium-bearing shale, phosphorus potassium ore, containing potassium siltstone, XRD diffracting spectrum it is 21 ° at 2 θ angles, exist at 29 ° and 35 ° principal phase peak containing potassium material, dolomite, olivine, chloride with alkaline-earth metal, nitrate, sulfate, phosphate, and the sulfate of group VIII metal, nitrate, chloride, one or more in oxide.

14. catalyst compositions stated according to claim 13, wherein, described alkaline-earth metal is one or more in beryllium, magnesium, calcium, strontium, barium, and described group VIII metal is Fe and/or Ni.

15. according to the catalyst composition described in claim 1 or 12, wherein, described gasification reactivity component includes the compound of potassium, with or without alkaline earth metal compound, with or without group VIII metal compound, on the basis of the weight of described gasification reactivity component, in terms of oxide weight, in described gasification reactivity component, the content of potassium is 2～100%, and the content of alkaline-earth metal is 0-98 weight %, and the content of group VIII metal is 0-98 weight %.

16. according to the catalyst composition described in claim 1 or 12, wherein, described gasification reactivity component include XRD diffracting spectrum at 2 θ angles is exist at 21 °, 29 ° and 35 ° principal phase peak containing potassium material.

17. catalyst compositions according to claim 16, wherein, described XRD diffracting spectrum at 2 θ angles is exist at 21 °, 29 ° and 35 ° principal phase peak containing in potassium material, potassium content in terms of potassium oxide is 8 weight %～40 weight %, with or without alkaline-earth metal, remaining is sial component, alkaline earth oxide and potassium oxide mol ratio (0～1): 0.2, SiO₂/Al₂O₃Mol ratio be 1:10～10:1.

18. catalyst compositions according to claim 17, wherein, in described XRD diffracting spectrum 2 θ angles be exist at 21 °, 29 ° and 35 ° principal phase peak containing potassium material in potassium oxide content 10 weight %～30 weight %, alkaline earth oxide and potassium oxide mol ratio 1:5～1:0.5, SiO₂/Al₂O₃Mol ratio be 1:3～3:1.

19. catalyst compositions according to claim 16, wherein, described XRD diffracting spectrum is the material containing potassium that there is principal phase peak at 21 °, 29 ° and 35 ° is obtained by following methods at 2 θ angles: potassium-containing compound, sial component are beaten into wet feed with optional alkaline earth metal compound, then siccative it is dried into, obtain after roasting again, sintering temperature is 800 DEG C～1150 DEG C, roasting time 1～10h.

20. catalyst compositions according to claim 19, wherein, described sintering temperature is 900 DEG C～1100 DEG C, and roasting time is 2～8h.

21. catalyst compositions according to claim 19, wherein, one or more in Kaolin, montmorillonite, rectorite, attapulgite, illite, meerschaum, kieselguhr of described sial component, or be the mixture of one or more in Kaolin, montmorillonite, rectorite, attapulgite, illite, meerschaum, kieselguhr, Alumina gel, boehmite and Ludox；Or it is one or more in Kaolin, montmorillonite, rectorite, attapulgite, illite, meerschaum, kieselguhr, Ludox and Alumina gel or the mixture of boehmite.

The preparation method of catalyst composition described in any one in 22. 1 kinds of claim 1 to 21, including by activity mesoporous silicon phosphor-aluminum material, gasification reactivity component, cracking active component, clay, heat-resistant inorganic oxide matrix mixing making beating, it is spray-dried and the step of roasting.

The cracking gasification process of 23. 1 kinds of petroleum hydrocarbons, it is included in petroleum hydrocarbon and the cracking gasification catalyst composition haptoreaction described in any one in claim 1 to 21 in cracker, by reacted described cracking gasification carbon monoxide-olefin polymeric and Oil-gas Separation, the step that the cracking gasification catalyst composition that deposited coke of isolated is contacted with gasifying agent.