CN106179456A

CN106179456A - A kind of cracking gasification catalyst composition, its preparation method and the cracking gasification process of petroleum hydrocarbon

Info

Publication number: CN106179456A
Application number: CN201510213608.7A
Authority: CN
Inventors: 刘倩倩; 杨雪; 朱玉霞; 任飞; 张书红; 郑金玉; 罗斌; 罗一斌
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: CN106179456B

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 mesoporous active materials of 1%～50%, and the anhydrous chemical expression that this mesoporous active materials is counted with oxide weight is for (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 element, and one or more in lanthanide series rare-earth elements, and y is that metal M maximum when forming oxide closes valence state, and the numerical value of x and y makes the quantivalence of M and O balance.It is applied has preferable cracking activity and gasification conversion performance in RFCC-gasification group technology, can obtain higher yield of gasoline simultaneously.

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.The gasification that alkali and alkaline earth metal ions is conventional is urged Agent, adds a certain amount of alkali and alkaline earth metal ions in Cracking catalyst and can promote to sink on catalyst The gasification of long-pending coke.CN200810246526.2 discloses and a kind of has containing of cracking and gasification function concurrently The catalyst of alkali and alkaline earth metal ions, this catalyst contains the boehmite of 35%～60%, 2%～10% Alumina gel, the Kaolin of 20%～49.5%, the alkali metal in terms of oxide of 5%～30% and alkaline earth gold Belonging to, this catalyst has cracking hydrocarbon oil products distribution and the optimization function of gasification reaction available gas productivity. CN200910078392.2 discloses a kind of coke transfer agent, Kaolin including 50%～80%, The binding agent of 10%～39.5% and 10%～30% alkali and alkaline earth metal ions in terms of oxide, wherein glue In knot agent, the mass ratio of boehmite and Alumina gel is (1.2～6): 1, alkali and alkaline earth metal ions former Son ratio is (0.05～0.8): 1, and this catalyst is at the catalytic cracking catalytic coke simultaneously of catalysis heavy crude Gasification.CN200910143623.3 discloses a kind of inferior heavy oil cracking and gasifying catalyst, including carrying Body, binding agent, gasification reactivity component and cracking active component, wherein gasification reactivity component be alkali metal and Alkaline-earth metal, on the basis of catalyst total amount, to count content be 2%～30% to oxide, alkali metal and alkaline earth The atomic ratio of metal is (0.05～1.1): 1, and cracking active component is silica alumina ratio selecting between 20～200 Shaped molecular sieve.

The gasification temperature of above-mentioned existing catalyst is higher, all carries out gasification reaction at 860 DEG C, for containing Alkali-metal catalysis material, under high-temperature water heat condition, in catalyst, alkali-metal loss ratio is more serious, For the catalyst containing molecular sieve, the high-temperature water thermal environment more than 800 DEG C can occur molecular sieve The rapid avalanche of skeleton, activity reduces rapidly.

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

Although above-mentioned existing catalyst can reduce cracking hydrocarbon oil gasification convert gasification temperature, but in order to Optimizing the product slates that cracking hydrocarbon oil gasification converts, the cracking performance of existing catalyst also needs to carry further High.

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, to overcome prior art catalyst composition in use gasification temperature high, Or the highest problem of cracking performance.

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 material of 1%～50% The clay of the cracking active component of gasification reactivity component, 1%～60%, 0%～70% of material, 1%～40% With the heat-resistant inorganic oxide matrix of 2%～97%, described mesoporous active materials has boehmite Phase structure, the anhydrous chemical expression counted with oxide weight is for (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 element, and in lanthanide series rare-earth elements Planting or multiple, y is that maximum during metal M formation oxide closes valence state, and the numerical value of x and y makes The quantivalence balance of M and O, specific surface area is 200～500m²/ g, pore volume is 0.5～1.5cm³/ g is flat All apertures are 8～18nm,

Described cracking activity constituent element contains the Y type molecular sieve containing rare earth of 90-100 weight %, described contains The Y type molecular sieve of rare earth contains the Y type molecular sieve of rare earth, the second Y type molecule containing rare earth selected from first At least one in sieve and the 3rd Y type molecular sieve containing rare earth, wherein, the described first Y containing rare earth The preparation method of type molecular sieve includes: under agitation, by the Y type molecular sieve containing rare earth and Silicon chloride. Contact, the temperature of contact is 100-500 DEG C, and the time of stirring is 1-10 hour, the described Y containing rare earth Type molecular sieve is 1:0.05-0.5 with the weight ratio of Silicon chloride.；

The silica alumina ratio of the described second Y type molecular sieve containing rare earth is 5-30, and initial lattice constant is 2.430-2.460nm, on the basis of the total amount of the described second Y type molecular sieve containing rare earth and with oxide The content of rare earth of meter is 10-20 weight %, and balance lattice constant is at least with the ratio of initial lattice constant 0.985, wherein, this molecular sieve of X-ray diffraction analysis is 12.43 ± 0.06 ° and 11.87 ± 0.06 ° at 2 θ Two diffraction peak intensities compare I₁/I₂More than 1；

Described 3rd preparation method of Y type molecular sieve containing rare earth includes: by super-stable Y molecular sieves and Concentration is that the acid solution of 0.01-2N is sufficiently mixed at 20-100 DEG C with the ratio of liquid-solid ratio 4-20, processes Wash after 10-300 minute, filter, add rare earths salt and carry out rare earth ion exchanged, after exchange Carry out successively washing, filter and being dried.

Meanwhile, according to another aspect of the present invention, the system of a kind of above-mentioned catalyst composition is additionally provided Preparation Method, including by activity mesopore material, gasification reactivity component, cracking active component, clay, resistance to The mixing making beating of hot inorganic oxide matrix, is spray-dried and the step of roasting.

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 mesoporous active materials, gasification temperature can be reduced；Can be relatively Higher intensity of making charcoal is obtained, it is thus achieved that higher density of hydrogen under low gasification temperature.By mesopore activity Material and gasification reactivity component effectively combine the coke gasification efficiency that can be greatly improved catalyst； When the catalyst composition of the present invention is used for the cracking-gasification integral process of heavy petroleum hydrocarbon, gasification result Good, gasification temperature is low, has stronger petroleum hydrocarbon such as heavy oil conversion performance, and utilizes several molecule The synergism of sieve increases yield of light oil, especially yield of gasoline and significantly improves.Especially with contain It XRD diffracting spectrum is the gasification containing potassium material that there is principal phase peak at 21 °, 29 ° and 35 ° at 2 θ angles Active component with the use of, not only gasification result is good, and gasification temperature is low, and has stronger hydrocarbon ils and turn Change ability, and the loss of gasification reactivity component is 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 spectrogram according to the mesoporous active materials in the specific embodiment of the invention.

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: gasification reactivity component, 1%～60% of mesoporous active materials, 1%～40% of 1%～50% The clay of cracking active component, 0%～70% and the heat-resistant inorganic oxide matrix of 2%～97%, described Mesoporous active materials there is phase structure (its X-ray diffracting spectrum such as Fig. 2 institute of boehmite Show), the anhydrous chemical expression counted with oxide weight is for (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, unit Element periodic chart IIB, IIIB, IVB, VIIB race element, and the one or many in lanthanide series rare-earth elements Kind, y be metal M formed oxide time maximum close valence state, and the numerical value of x and y make M and The quantivalence balance of O, specific surface area is 200～500m²/ g, pore volume is 0.5～1.5cm³/ g, average hole Footpath is 8～18nm,

Silica alumina ratio (the i.e. SiO of the described second Y type molecular sieve containing rare earth₂/Al₂O₃Mol ratio) be 5-30:1, initial lattice constant is 2.430-2.460nm, with the described second Y type molecular sieve containing rare earth Total amount on the basis of and the content of rare earth counted with oxide for 10-20 weight %, balance lattice constant is with just The ratio of beginning lattice constant is at least 0.985, and wherein, this molecular sieve of X-ray diffraction analysis at 2 θ is Two diffraction peak intensities of 12.43 ± 0.06 ° and 11.87 ± 0.06 ° compare I₁/I₂More than 1；

Described 3rd preparation method of Y type molecular sieve containing rare earth includes: by super-stable Y molecular sieves and Concentration be 0.01-2N acid solution with the ratio of liquid-solid ratio (weight ratio) 4-20 at 20-100 DEG C fully Mixing, washs after processing 10-300 minute, filters, add rare earths salt and carry out rare earth ion friendship Change, carry out successively after exchange washing, filter and being dried.

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.

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 % mesoporous active materials, 5 weights Amount %～the gasification reactivity component of 40 weight %, the cracking active component of 5～50 weight %, 0 weight %～60 The clay of weight % and 10 weight %～the heat-resistant inorganic oxide matrix of 70 weight %.It is further preferred that it is described Catalyst composition includes: 5 weight %～30 weight % mesoporous active materials, 10 weight %～35 weight % Gasification reactivity component, the cracking active component of 10～35 weight %, the clay of 5 weight %～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 Material, (0-0.2) Na in terms of oxide weight ratio₂O·(40-85)Al₂O₃·(10-55)SiO₂·(0.5-10) P₂O₅·(0.5-10)M_xO_y。It is highly preferred that with the mass ratio range of oxide in described mesoporous active materials Anhydrous chemical expression be: (0.07-0.12) Na₂O·(47-72)Al₂O₃·(16.3-44)SiO₂· (1.5-6.3)P₂O₅·(1.7-8.6)M_xO_y。

The above-mentioned catalyst composition provided according to the present invention, it is preferable that metal M is selected from Mg and/or unit One or more in element periodic chart IIB, IIIB, IVB, VIIB race and/or group of the lanthanides.Wherein, described IIB, IIIB, IVB, VIIB race metal one or more metals in Zn, Y, Ti and Mn Mixing.Preferably, described 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.Preferably, described IIB, IIIB, IVB, VIIB race metal is Y or Y, Mn and Zn.

It is dilute that described lanthanide series rare-earth elements (RE) is preferably lanthanum, cerium mischmetal, pure lanthanum rare earth or pure cerium Soil.Wherein in mischmetal, lanthanum cerium be varied from market situation than meeting, but performance is the most by mixed The impact of composition and division in a proportion example, it is special therefore not do for the proportioning of lanthanum and cerium in this lanthanum, cerium mischmetal Regulation, it can be arbitrarily than mixing.

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 material is 300～450m²/ g, pore volume is 0.7～1.2cm³/ g, average pore size is 10～15nm.

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 and the compound of metal M, according to P₂O₅: M_xO_y: the precipitate butt of described second solid sediment=(0.005-0.1): (0.005-0.1): 1 Weight ratio contact processes, and product of contact is dried (baking 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 sources, example in the preparation technology of mesoporous active materials As, one or more in aluminum nitrate, aluminum sulfate and aluminum chloride can be selected from.

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 mesoporous active materials, for example, it is possible to Selected from waterglass, sodium silicate, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy One or more in silicon and silicon oxide.

The above-mentioned catalyst composition provided according to the present invention, in the preparation process of mesoporous active materials, Although source of aluminium, silicon source and aqueous slkali each suitably can select from the above-mentioned material enumerated Select, but, a kind of in usual source of aluminium, aqueous slkali and silicon source is the raw material containing sodium, from And ensure that the thus prepared described mesoporous active materials without ion exchange has the activity of appropriate size Central hole structure.

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.

Contacting the compound of the second solid sediment and phosphorus source and metal M in above-mentioned steps (4) Processing procedure can have a various ways, such as following a), b), c), d) during any one:

A) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight Than mixing making beating with water, then the compound of phosphorus source, metal M is added sequentially in above-mentioned serosity, Room temperature to contact at 90 DEG C processes at least 0.2 hour, and preferably contact processes 0.2-5 hour, more preferably connects Synapsis is managed 0.5-3 hour, is dried 10-20 hour after filtering washing at 100 DEG C-150 DEG C；

B) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight Than mixing making beating with water, then phosphorus source or metal M are joined in above-mentioned serosity, in room temperature to 90 DEG C Lower contact processes at least 0.2 hour, and preferably contact processes 0.2-5 hour, and more preferably contact processes 0.5-3 Hour, the metal M directly not added with early stage after filtration or the compound of phosphorus source are mixed in proportion, It is dried 10-20 hour at 100 DEG C-150 DEG C after grinding uniformly；

C) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight Than mixing making beating with water, then the compound of phosphorus source He the first metal M is joined in above-mentioned serosity, At room temperature to 90 DEG C, contact processes at least 0.2 hour, preferably contact process 0.2-5 hour, more preferably Contact processes 0.5-3 hour, obtains the 3rd solid sediment after filtration, then by straight for the 3rd solid sediment Connect the compound with the second metal M to mix, at 100 DEG C-150 DEG C, after grinding uniformly, be dried 10-20 Hour, wherein, the compound of described the first metal M identical with the compound of the second metal M or Different；

D) by direct for described second solid sediment and phosphorus source, optional magnesium source and metal M compound It is mixed in proportion, is dried 10-20 hour at 100 DEG C-150 DEG C after grinding uniformly.

In aforesaid way c), for compound and the change of the second metal M of the first metal M Particular compound and the consumption of compound included in compound do not have particular/special requirement, as long as can Make described second solid sediment and phosphorus source and the compound of metal M, be finally according to P₂O₅: M_xO_y: the precipitate butt of described second solid sediment=(0.005-0.1): (0.005-0.1): 1 Weight ratio mix.

In the preparation method of above-mentioned mesoporous active materials, 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.

Further, optionally, the preparation method at above-mentioned activity mesopore material can also include dry product Thing carries out the step of roasting, and the condition of described roasting generally includes sintering temperature can be 500-700 DEG C, Roasting time can be 1-4 hour.

In the preparation method of above-mentioned mesoporous active materials, described in step (4), the kind of phosphorus source is permissible Conventional for this area selects, for example, it is possible to selected from ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate With one or more in phosphoric acid.

Described in above-mentioned steps (4) in the compound of metal M, metal M is selected from Mg, element Periodic chart IIB, IIIB, IVB, VIIB race element, and one or more in lanthanide series rare-earth elements, Wherein described IIB, IIIB, IVB, VIIB race metal be preferably in Zn, Y, Ti and Mn one Kind or the mixing of various metals, the mixing of the mixing of described various metals such as Ti and Mn, Mn and The mixing of Zn, the mixing of Ti and Zn, the mixing of Ti and Y, the mixing of Mn, Ti and Zn and Y, The mixing of Mn and Zn.Wherein modified for Y material and the mixed and modified material tool of Y, Mn and Zn There is optimal cracking reaction performance.

In the preparation method of above-mentioned mesoporous active materials, the compound of metal M described in step (4) It can be any one water miscible compound.

In the present invention, in the weight ratio of the solid sediment exchanged without ion, water and mineral acid, The described solid sediment weight without ion exchange is the weight in terms of butt.In the present invention, with The weight of butt meter refers to the weight after under conditions of about 800 DEG C roasting 1 hour.

The above-mentioned cracking gasification catalyst composition provided according to the present invention, under preferable case, splits with described On the basis of changing the gross weight of active component, described cracking activity constituent element contains the described of 94-100 weight % Y type molecular sieve containing rare earth.Wherein, the described Y type molecular sieve containing rare earth is selected from the first Y containing rare earth Type molecular sieve, second containing in the Y type molecular sieve of rare earth and the 3rd Y type molecular sieve containing rare earth at least One, under preferable case, selected from described first containing the Y type molecular sieve of rare earth, described second containing rare earth Y type molecular sieve and the described 3rd containing rare earth Y type molecular sieve at least two.

In the present invention, the concrete preparation method of the described first Y type molecular sieve containing rare earth is referred to specially Profit application CN1683244A, embodiment 5,6 and 8 the most therein.

In the present invention, the specific descriptions of the described second Y type molecular sieve containing rare earth are referred to patent Shen Please CN101081369A.Described second Y type molecular sieve containing rare earth can be prepared according to the conventional method Obtain, concrete preparation method can also be with reference to patent application CN101081369A, wherein Embodiment 1-5.

In the present invention, the concrete preparation method of the described 3rd Y type molecular sieve containing rare earth is referred to specially Profit application CN1958452A, embodiment 1-6 the most therein.

The above-mentioned cracking gasification catalyst composition provided according to the present invention, described cracking activity constituent element is all right Containing MFI structure molecular sieve, anhydrous with the molar ratio computing of oxide in described MFI structure molecular sieve Chemical 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.Excellent In the case of choosing, on the basis of the gross weight of described cracking activity constituent element, described cracking activity constituent element contains The Y type molecular sieve containing rare earth of 90-99.9 weight % and the MFI structure molecular sieve of 0.1-10 weight %； In the case of preferred, described cracking activity constituent element contains the Y type molecule containing rare earth of 94-99 weight % Sieve and the MFI structure molecular sieve of 1-6 weight %.

In the present invention, the specific descriptions of described MFI structure molecular sieve are referred to patent application CN1147420A.What described MFI structure molecular sieve can be prepared according to the conventional method obtains, specifically Preparation method can also be with reference to patent application CN1147420A, embodiment 1-6 the most therein.

According in the above-mentioned cracking gasification catalyst composition that the present invention provides, it is preferable that described gasification reactivity Component includes alkali metal compound, alkaline earth metal compound, and group VIII metal Compound Compound. 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, potassium-bearing shale, phosphorus potassium Ore, containing potassium siltstone, XRD diffracting spectrum is at 21 °, 29 ° and 35 °, there is principal phase at 2 θ angles Peak containing potassium material (this material has the peak of XRD principal phase shown in Fig. 1), dolomite, olivine.Work as institute State gasification reactivity component when contain alkaline-earth metal, the compound of alkaline-earth metal, such as alkali can be added One or many in the inorganic alkali-earth metal salt such as the chloride of earth metal, nitrate, sulfate, phosphate Kind, 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, group VIII metal can be added Compound, the inorganic VIII such as the sulfate of such as group VIII metal, nitrate, chloride, oxide One or more in race's slaine.Described group VIII metal is preferably Fe and/or Ni.

In the above-mentioned cracking gasification catalyst composition for processing heavy petroleum hydrocarbon that the present invention provides, preferably Ground, described gasification reactivity component includes the compound of potassium, with or without alkaline earth metal compound, containing or not Containing 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 oxide is 2～100 weight %, and the content of alkaline-earth metal is 0～98 Weight %, group VIII metal compounds content is 0～98%.Wherein, in order to solve serious the asking of potassium lost Topic, the described active component containing potassium be preferably described gasification reactivity component include in XRD diffracting spectrum 2 θ angles be there is principal phase peak at 21 °, 29 ° and 35 ° (there is XRD principal phase shown in Fig. 1 containing potassium material Peak containing potassium material).Using in XRD diffracting spectrum at 2 θ angles is to there is principal phase at 21 °, 29 ° and 35 ° Peak containing potassium material as gasification reactivity component, the gasification efficiency of catalyst composition can be improved further, Reduce the loss of potassium, 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.

The above-mentioned catalyst composition provided according to the present invention, except described mesoporous active materials, cracking are lived Beyond property component, gasification reactivity component, clay, possibly together with heat-resistant inorganic oxide matrix, described is resistance to The kind of hot inorganic oxide, without particular/special requirement, can be heat-resistant inorganic oxide matrix commonly used in the art, Be preferably aluminium oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide and beryllium oxide and it Predecessor in one or more.Described heat-resistant inorganic oxide predecessor such as Alumina gel, silicon One or more in colloidal sol, 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 is free on outside mesoporous active materials.Invent institute State the kind of metal traps without particular/special requirement, can be that trapping V, Ni, Fe, Ca etc. pollute metal The conventional metal traps of component, under preferable case, described metal traps be rare earth oxide and/ Or the precursor of rare earth oxide.In the case of more preferably, the precursor metal traps of described rare earth oxide is One or more in rare earth chloride, carbonated rare earth and rare earth hydrate.Wherein, rare earth element can be One or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium.The entrance of metal agent for capturing in the present invention Mode can mesoporous active materials, gasification reactivity component, clay mixing making beating time in the form of an ion or Complex form introduces.If introducing heat-resistant inorganic oxide in carbon monoxide-olefin polymeric, it is also possible to pass through Metal traps is deposited in described inorganic oxide by coprecipitation in advance.This metal traps can be with Mesoporous active materials is in same granule, it is also possible to be in different granules.

Meanwhile, the preparation method of a kind of above-mentioned catalyst composition, the method bag are additionally provided in the present invention Include activity mesopore material, gasification reactivity component, cracking active component, clay, heat resistant inorganic oxidation The mixing making beating of thing substrate, 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 and phosphorus source and the compound of metal M, According to P₂O₅: M_xO_y: the precipitate butt of described second solid sediment=(0.005-0.1): (0.005-0.1): the weight ratio contact of 1 processes, and product of contact is dried or then at 500 DEG C～700 DEG C Lower roasting 1～4 hours；

(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 mesoporous active materials 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 in Hole active material, gasification reactivity component, cracking active component, clay and heat-resistant inorganic oxide matrix Consumption makes described mesoporous active materials, 1%～40% that obtained catalyst composition includes 1%～50% The described clay of described cracking active component, 0%～70% of described gasification reactivity component, 1%～60% With 2%～97% described heat-resistant inorganic oxide matrix.Wherein, described cracking activity constituent element contains 90-100 The Y type molecular sieve containing rare earth of weight %, the described Y type molecular sieve containing rare earth contains rare earth selected from first Y type molecular sieve, second containing in the Y type molecular sieve of rare earth and the 3rd Y type molecular sieve containing rare earth extremely Few one,

Wherein, the preparation method of the described first Y type molecular sieve containing rare earth includes: under agitation, will contain The Y type molecular sieve of rare earth contacts with Silicon chloride., and the temperature of contact is 100-500 DEG C, the time of stirring For 1-10 hour, the described Y type molecular sieve containing rare earth was 1:0.05-0.5 with the weight ratio of Silicon chloride.；

Described 3rd preparation method of Y type molecular sieve containing rare earth includes: by super-stable Y molecular sieves and Concentration is that the acid solution of 0.01-2N is sufficiently mixed at 20-100 DEG C with the ratio of liquid-solid ratio 4-20, processes Wash after 10-300 minute, filter, add rare earths salt and carry out rare earth ion exchanged, depend on after exchange Secondary carrying out washs, filters and is dried.

Preferably, by the described mesoporous active materials obtained in above-mentioned steps (1), gasification reactivity component Mixing making beating obtains the first serosity, by cracking active component, and clay, binding agent mixing making beating, obtain the Two serosity, then mix making beating by the first serosity and the second serosity, then carry out being spray-dried, 400～800 DEG C, roasting 2～10h at preferably 450-750 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 described mesoporous active materials, the mixing making beating of gasification reactivity component that obtain in (1) obtain the first serosity, By cracking active component, clay, binding agent mixing making beating, obtain the second serosity, then by the first serosity Pull an oar with the second serosity mixing, then carry out being spray-dried, roasting at 400～800 DEG C preferably 450～750 DEG C Burn 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.

In the cracking gasification catalyst composition preparation method that the present invention provides, by mesoporous active materials, gasification The order of active component, clay, heat-resistant inorganic oxide matrix mixing making beating does not has particular/special requirement, such as, Described raw material can be prepared serosity respectively, then by prepared serosity mixing；Can be first by mesopore Active material mixes with clay, mixes making beating with other component the most again；Or by gasification reactivity component with viscous Soil mixing making beating, 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 when mesoporous active materials, gasification reactivity component, cracking active component, clay mixing making beating In the form of an ion or complex form introduce, it is also possible to after by above-mentioned several component spray drying formings Introduce with the form of precipitation.If introducing heat-resistant inorganic oxide matrix in carbon monoxide-olefin polymeric, also may be used In advance metal traps is deposited in described inorganic oxide by coprecipitation.Under preferable case, Based on butt, the content of described metal traps is less than 20 weight % of catalyst composition.The present invention To the kind of described metal traps without particular/special requirement, can be that trapping V, Ni, Fe, Ca etc. pollute The common metal trapping agent of the component of metal, under preferable case, described metal traps be rare earth oxide and / or the precursor of rare earth oxide.In the case of more preferably, the precursor of described rare earth oxide be rare earth chloride, One or more in carbonated rare earth and rare earth hydrate.Wherein, rare earth element can be lanthanum, cerium, praseodymium, One or more in 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 containing rare earth prepares according to the method for embodiment in CN1683244A 5；

Second Y type molecular sieve containing rare earth prepares according to the method for embodiment in CN101081369A 1；

3rd Y type molecular sieve containing rare earth prepares according to the method for CN1958452A embodiment 1；

MFI structure molecular sieve prepares according to the method for embodiment 1 in patent application CN1147420A；

Rare earth chloride is purchased from Xitu Hi-Tech skill limited company of Baogang.

Na in mesoporous active materials₂O、Al₂O₃、SiO₂、P₂O₅Content x-ray fluorescence method measure (seeing " Petrochemical Engineering Analysis method (RIPP experimental technique) ", Yang Cui surely waits and compiles, Science Press, and 1990 Year publishes).

Embodiment 1～9 is for illustrating the preparation method of mesoporous active materials used by the present invention.

Embodiment 1

(1) with concentration as 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration are 102gAl₂O₃/ L, severe Property than be 2.5 NaAlO₂Solution is reaction raw materials, uses and flows plastic mode, being stirred vigorously down Row mixing plastic, controlling system temperature is 40 DEG C, system pH=9.0, collects metering plastic serosity； (2) under agitation according to SiO₂: Al₂O₃The weight ratio of=1:2 adds concentration in plastic serosity 60gSiO₂The waterglass of/L, is warming up to 60 DEG C and is aged 3 hours, obtain the first solid sediment；(3) By described first solid sediment by its precipitate butt: ammonium salt: H₂The weight ratio of O=1:0.5:12 Add NH₄Cl and deionized water, carry out ion exchange at 60 DEG C and remove sodium ion, hand over precipitate Change and repeat once, each 0.5 hour, to sodium oxide content less than 0.3%, obtain the second solid and sink Shallow lake thing；(4) then gained the second solid sediment is pressed precipitate butt: H₂The weight ratio of O=1:8 Mix making beating with water, and press P₂O₅: the weight ratio of MgO: material butt=0.033:0.022:1 adds Enter phosphoric acid and magnesium nitrate, react 1 hour at 80 DEG C, at 120 DEG C, after filtering washing, be dried 10 Hour i.e. obtain the high cracking activity mesopore material that the present invention provides.It is designated as PM-1.

PM-1 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is with Fig. 2 feature；Its element divides Analysis chemical composition is 0.12Na₂O·65.1Al₂O₃·28.2SiO₂·3.2P₂O₅·2.1MgO；Specific surface area 391 m²/ g, pore volume 0.97cm³/ g, average pore size 9.9nm.

Embodiment 2

(1) it is first 90gAl by concentration₂O₃The Al of/L₂(SO₄)₃Solution is placed in beaker, is warming up to 50 DEG C, The lower concentration that adds of stirring is the ammonia of 25wt.%, until system pH=10.5, holding gelling temperature is 40 DEG C, collect metering plastic serosity；(2) and under agitation according to SiO₂: Al₂O₃=1:1's It is 60gSiO that weight ratio adds concentration in plastic serosity₂The waterglass of/L, is warming up to 70 DEG C of ageings 1.5 Hour, obtain the first solid sediment；(3) by described first solid sediment by its precipitate butt: NH₄Cl:H₂The weight ratio of O=1:0.08:12 exchanges 30 minutes at 60 DEG C, is repeated once exchange Process, filters washing and obtains the sodium oxide content the second solid sediment less than 0.3%；(4) then will Gained the second solid sediment presses precipitate butt: H₂The weight ratio of O=1:8 mixes making beating with water, and By P₂O₅: the weight ratio of the precipitate butt=0.075:0.015:1 of the MgO: the second solid sediment Add diammonium phosphate and magnesium nitrate, react 1 hour at 60 DEG C, obtain the 3rd after filtering washing solid Body precipitate, then press MnO₂: the precipitate butt=0.035:1 of the 3rd solid sediment adds chlorination Manganese mixes, and is dried 10 hours in 120 DEG C after grinding uniformly, then at 3 hours i.e. get Ben Fa of 550 DEG C of roastings The high cracking activity mesopore material of bright offer.It is designated as PM-2.

PM-2 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is with feature shown in Fig. 2；Its yuan Element analytical chemistry consists of 0.10Na₂O·47.2Al₂O₃·44.1SiO₂·2.7P₂O₅·1.3MgO·3.5MnO₂； Specific surface area 302m²/ g, pore volume 0.7cm³/ g, average pore size 9.3nm.

Embodiment 3

With 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and ammonia are reaction raw materials, use and flow plastic mode, It is stirred vigorously lower by Al₂(SO₄)₃Solution and the ammonia that concentration is 25wt.% carry out mixing plastic, control volume It is pH=9.5, collects metering plastic serosity also, under agitation according to SiO₂: Al₂O₃=1:2.6 Weight ratio to add concentration in plastic serosity be 60gSiO₂The waterglass of/L, is warming up to 60 DEG C of ageings 3 Hour；Gained solid sediment is pressed precipitate butt: ammonium salt: H₂The weight ratio of O=1:1:12 exists Exchange 1 hour at 60 DEG C, after filtering washing, by precipitate butt: H₂The weight ratio of O=1:10 will Gained solid sediment mixes making beating with water, and presses P₂O₅: ZnO: material butt=0.065:0.025: The weight ratio of 1 adds phosphoric acid and zinc nitrate, reacts 1 hour at 60 DEG C, filters after washing in 120 DEG C The phosphorus i.e. obtaining the present invention and providing, metal-modified mesoporous silica-alumina materials are provided down 15 hours.It is designated as PM-1.

PM-3 has boehmite crystal phase structure, and its X-ray diffraction spectrum is illustrated in Fig. 2；Its yuan Element analytical chemistry consists of 0.10Na₂O·71.7Al₂O₃·19.4SiO₂·6.3P₂O₅·2.3ZnO；Specific surface Long-pending 433m²/ g, pore volume 1.39cm³/ g, average pore size 12.8nm.

Embodiment 4

By 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in beaker, and stirring lower addition concentration is 25wt.% Ammonia, until system pH=9.5, collect a certain amount of serosity, under agitation according to SiO₂: Al₂O₃It is 60gSiO that the weight ratio of=1:1.6 adds concentration in plastic serosity₂The waterglass of/L, heats up It is aged 3 hours to 60 DEG C；Gained solid sediment is pressed precipitate butt: NH₄Cl:H₂O=1:0.8: The weight ratio of 12 exchanges 1 hour at 50 DEG C, filters washing and makes sodium oxide content be less than 0.3%；Then Filter cake is pulled an oar and presses with phosphoric acid, P₂O₅: the part by weight mixing of material butt=0.033:1, then at Stir 1 hour at 60 DEG C, after filtration again by filter cake and zinc nitrate and manganese chloride according to ZnO:MnO₂: It is dried 10 in 120 DEG C little after the part by weight mixed grinding of material butt=0.040:0.015:1 is uniform Time, within 4 hours, i.e. obtain, then at 550 DEG C of roastings, phosphorus, the metal-modified mesoporous silica-alumina materials that the present invention provides. It is designated as PM-4.

PM-4 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is with feature shown in Fig. 2；Its yuan Element analytical chemistry consists of 0.12Na₂O·61.2Al₂O₃·29.9SiO₂·3.0P₂O₅·1.5MnO₂·4.0ZnO； Specific surface area 355m²/ g, pore volume 0.80cm³/ g, average pore size 9.0nm.

Embodiment 5

(1) it is first 90gAl by concentration₂O₃The Al of/L₂(SO₄)₃Solution is placed in beaker, by dense under stirring Spending and add for 24wt.% ammonia, until system pH=9.5, keeping gelling temperature is 35 DEG C, collects Metering plastic serosity；(2) and under agitation according to SiO₂: Al₂O₃The weight ratio of=1:2.7 to Adding concentration in plastic serosity is 60gSiO₂The waterglass of/L, is warming up to 60 DEG C and is aged 3 hours, obtain First solid sediment；(3) by described first solid sediment by its precipitate butt: NH₄Cl:H₂O The weight ratio of=1:0.8:12 exchanges 1 hour at 50 DEG C, and filtration washing obtains sodium oxide content and is less than Second solid sediment of 0.3%；(4) by the second solid sediment (filter cake) reslurry, and press P₂O₅: MnO₂: TiO₂: the precipitate butt=0.022:0.023:0.017 of the second solid sediment: The weight ratio of 1 adds phosphoric acid, manganese chloride and titanium sulfate, stirs 2 hours at 70 DEG C, is filtrated to get the Three solid sediments；By the 3rd solid sediment by the weight of its precipitate butt: ZnO=1:0.05 Than directly mix with zinc nitrate, be dried 10 hours in 120 DEG C after grinding uniformly, then at 600 DEG C of roastings 4 Hour i.e. obtain phosphorus, metal-modified activity mesoporous silicon aluminum that the present invention provides.It is designated as PM-5.

PM-5 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is with feature shown in Fig. 2；Its yuan Element analytical chemistry consists of 0.10Na₂O·72.5Al₂O₃·16.3SiO₂·2.2P₂O₅·2.1MnO₂·1.5TiO₂ ·5.0ZnO；Specific surface area 439m²/ g, pore volume 1.28cm³/ g, average pore size 11.7nm.

Embodiment 6

(1) with concentration as 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and the ammonia that concentration is 25wt.% are Reaction raw materials, uses batch (-type) and flows plastic, being stirred vigorously lower by Al₂(SO₄)₃Solution and ammonia are carried out Mixing plastic, controls gelling temperature 45 DEG C, plastic pH value=10.5, collects metering plastic serosity；(2) Under agitation according to SiO₂: Al₂O₃The weight ratio of=1:2.3 adds concentration in plastic serosity 60gSiO₂The waterglass of/L, is warming up to 60 DEG C and is aged 3 hours, obtain the first solid sediment；(3) By described first solid sediment by its precipitate butt: ammonium salt: H₂The weight ratio of O=1:1:10 adds NH₄Cl and deionized water, exchange 1 hour at 65 DEG C, and filtration washing obtains sodium oxide content and is less than Second solid sediment of 0.3%；(4) by the precipitate butt of the second solid sediment:: H₂O=1: The weight ratio of 8 mixes making beating with water, and presses P₂O₅: the precipitate butt of the MgO: the second solid sediment The weight ratio of=0.016:0.021:1 adds phosphoric acid and magnesium chloride, reacts 2 hours at 60 DEG C, Obtain the 3rd solid sediment；By the 3rd solid sediment by its precipitate butt: RE₂O₃=1:0.008 With mixed chlorinated rare earth solution (La in terms of oxide in rare earth₂O₃And CeO₂Weight ratio be 45: 55) mix mutually, be dried 15 hours at 120 DEG C after grinding uniformly, then at 550 DEG C of roastings within 4 hours, be Obtain the active mesoporous catalytic material that the present invention provides.It is designated as PM-6.

PM-6 has boehmite phase structure, and its X-ray diffraction spectrogram is as shown in Figure 2；Its yuan Element analytical chemistry consists of 0.07Na₂O·69.7Al₂O₃·25.3SiO₂·1.5P₂O₅·2.0MgO ·0.8RE₂O₃；Specific surface area 409m²/ g, pore volume 1.13cm³/ g, average pore size 11.0nm.

Embodiment 7

(1) it is first 90gAl by concentration₂O₃The Al of/L₂(SO₄)₃Solution is placed in beaker, is warming up to 40 DEG C, The lower concentration that adds of stirring is the ammonia of 25wt.%, until system pH=9.5, rubber cement is measured in collection Liquid；(2) and under agitation according to SiO₂: Al₂O₃The weight ratio of=1:1.7 is in plastic serosity Addition concentration is 100gSiO₂The waterglass of/L, is warming up to 60 DEG C and is aged 2 hours, obtain the first solid Precipitate；(3) by described first solid sediment by its precipitate butt: HCl:H₂O=1:0.08: The weight ratio of 12 exchanges 30 minutes at 55 DEG C, and filtration washing obtains sodium oxide content and is less than 0.3% Second solid sediment；(4) by the second solid sediment (filter cake) reslurry, and P is pressed₂O₅: the The weight ratio of the precipitate butt=0.045:1 of two solid sediments adds phosphoric acid, reacts at 60 DEG C 1 hour, filter and be dried 15 hours at 120 DEG C, obtain the 3rd solid sediment；By the 3rd solid Precipitate presses its precipitate butt: MgO:RE₂O₃The weight ratio of=1:0.007:0.021 is by dry sample Product and magnesium chloride and mixed chlorinated rare earth solution (La in terms of oxide in rare earth₂O₃And CeO₂Weight Amount ratio is 45:55) mixing, it is dried 10 hours in 120 DEG C after grinding uniformly, then at 600 DEG C of roastings 4 Hour i.e. obtain the active mesoporous catalytic material that the present invention provides.It is designated as PM-7.

PM-7 has boehmite phase structure, and its X-ray diffraction spectrogram is with feature shown in Fig. 2； Its elementary analytical chemistry consists of 0.11Na₂O·62.8Al₂O₃·29.6SiO₂·4.5P₂O₅·0.7MgO·2.1 RE₂O₃；Specific surface area 418m²/ g, pore volume 1.06cm³/ g, average pore size 10.1nm.

Embodiment 8

(1) with concentration as 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and the ammonia that concentration is 25wt.% are Reaction raw materials, uses batch (-type) and flows plastic, being stirred vigorously lower by Al₂(SO₄)₃Solution and ammonia are carried out Mixing plastic, controls gelling temperature 50 DEG C, plastic pH value=9.0, collects metering plastic serosity；(2) Under agitation according to SiO₂: Al₂O₃The weight ratio of=1:2.3 adds concentration in plastic serosity 100gSiO₂The waterglass of/L, is warming up to 70 DEG C and is aged 2 hours, obtain the first solid sediment；(3) By described first solid sediment by its precipitate butt: ammonium salt: H₂The weight ratio of O=1:0.8:12 Exchange 1 hour at 60 DEG C, after filtering washing, obtain the second solid sediment；First press P₂O₅: second The precipitate butt of solid sediment: H₂The weight ratio of O=0.016:1:8 is by phosphoric acid and Na₂O content The second solid sediment less than 0.3% and water mixing making beating, and react 1 hour at 70 DEG C, obtain 3rd solid sediment；By the 3rd solid sediment by its precipitate butt: RE₂O₃=1:0.031's Weight ratio is directly by mixed chlorinated rare earth (La in terms of oxide in rare earth₂O₃And CeO₂Weight ratio For 60:40) and precipitate mixing, it is dried 15 hours at 120 DEG C after grinding uniformly, then at 550 DEG C Roasting i.e. obtains the active mesoporous catalytic material of the phosphorous and rare earth that the present invention provides for 4 hours.It is designated as PM-8.

PM-8 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with shown in Fig. 2 Feature；Its elementary analytical chemistry consists of 0.10Na₂O·70.2Al₂O₃·24.8SiO₂·1.5P₂O₅ ·3.1RE₂O₃；Specific surface area 435m²/ g, pore volume 1.14cm³/ g, average pore size 10.5nm.

Embodiment 9

(1) with concentration as 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration are 102gAl₂O₃/ L, severe Property than be 2.5 NaAlO₂Solution is reaction raw materials, first by Al₂(SO₄)₃Solution is placed in beaker, rises Temperature, to 45 DEG C, adds NaAlO with vigorous stirring₂Solution, until system pH=10.0, receives Integrated rubber cement liquid；(2) under agitation according to SiO₂: Al₂O₃The weight ratio of=1:2.3 is to plastic serosity Middle addition concentration is 100gSiO₂The waterglass of/L, and be aged 3 hours in 60 DEG C；Obtain the first solid Precipitate；(3) by described first solid sediment by its precipitate butt: NH₄Cl:H₂O=1:0.5: The weight ratio of 10 exchanges 30 minutes at 50 DEG C, and once, filtration washing obtains sodium oxide and contains repeated exchanged The amount the second solid sediment less than 0.3%, presses La by the second solid sediment₂O₃: the second solid precipitation The precipitate butt of thing: H₂The weight ratio of O=0.018:1:8 mixes with Lanthanum (III) nitrate and water, stirs at 70 DEG C Mix 1 hour, be filtrated to get the 3rd solid sediment；By the 3rd solid sediment by its precipitate butt: P₂O₅The weight ratio of=1:0.060 directly mixes with ammonium dihydrogen phosphate, dry at 120 DEG C after grinding uniformly Dry 15 hours, within 3 hours, i.e. obtain the active mesopore of the phosphorous and rare earth that the present invention provides then at 550 DEG C of roastings Catalysis material.It is designated as PM-9.

PM-9 has typical boehmite crystal phase structure, and its X-ray diffraction spectrogram is with shown in Fig. 2 Feature；Its elementary analytical chemistry consists of 0.12Na₂O·68.5Al₂O₃·23.4SiO₂·6.0P₂O₅ ·1.7La₂O₃；Specific surface area 408m²/ g, pore volume 1.10cm³/ g, average pore size 10.8nm.

Embodiment 10～12 is for illustrating that the gasification used by the present invention with the peak of XRD principal phase shown in Fig. 1 is lived The preparation method of property component.

Embodiment 10

Weigh in terms of butt 1500 grams of Kaolin, 400 grams of K₂CO₃With 100 grams of CaO, three is mixed Merge and add appropriate amount of deionized water, make slurry solid content 15%～50%, stir at least 20 minutes, dry Dry, then roasting 4 hours at 1000 DEG C, prepare gasification reactivity component K-1 in potassium, wherein K₂O content It is 20%, CaO/K₂The mol ratio of O is 1/2.4, SiO₂/Al₂O₃Mol ratio be 2, K-1 has XRD principal phase peak (principal phase peak 2 θ is 21 °, 29 °, 35 ° respectively) shown in Fig. 1.

Embodiment 11 and 12

According to the method for embodiment 10 prepare as gasification reactivity component containing potassium material, adjust rate of charge Example, preparation specifically feeds intake be shown in Table 1 containing potassium gasification reactivity component K-2 and K-3.K-2 and K-3 has figure XRD feature principal phase peak (principal phase peak 2 θ is 21 °, 29 °, 35 ° respectively) shown in 1.

Table 1.

Embodiment 13～19 is for illustrating the preparation method of catalyst composition used by the present invention.

Embodiment 13

The high cracking containing potassium material K-1 with in terms of butt 5 weight portions of in terms of butt 20 weight portions is lived Property mesopore material PAM-1 mixing, add deionized water, mixing making beating stirring 30 minutes, obtain first Serosity.By the Kaolin of butt meter 30 weight portion, add deionized water and pull an oar 30 minutes, then to serosity In be sequentially added into the Alumina gel of butt meter 15 weight portion, butt meter 10 weight portion first containing Y-type rare earth Molecular sieve and the 3rd Y-shaped molecular sieve containing rare earth of 20 weight portions, pull an oar and obtain the second serosity in 60 minutes, By two kinds of serosity mixing, and stir at least 30 minutes, obtain the serosity that solid content is 30 weight %.Spray Mist is dried makes microsphere catalyst composition, then 550 DEG C of roastings 2 hours.Obtained contact agent is compiled Number it is C1.

Embodiment 14

The boehmite of 30 weight portions in terms of butt is mixed with deionized water making beating, and to obtaining Serosity in add concentration be the hydrochloric acid of 36 weight %, acid aluminum ratio (described 36 weight % hydrochloric acid with Al₂O₃The weight ratio of the boehmite of meter) it is 0.3, it is warmed up to 65 DEG C and is acidified 1 hour, obtain serosity. Join the Alumina gel of in terms of butt 10 weight portions in the most acidified boehmite serosity to mix and beat Starch 20 minutes, then by the second Y-shaped molecular sieve containing rare earth of in terms of butt 15 weight portions and 20 weight portions The 3rd Y-shaped molecular sieve containing rare earth add, pull an oar 1 hour, obtain the first serosity.

The high cracking containing potassium material K-2 with in terms of butt 10 weight portions of in terms of butt 15 weight portions is lived Property mesopore material PAM-2 mixing, add deionized water, mixing making beating stirring 30 minutes, obtain second Serosity.By two kinds of serosity mixing, and stir at least 30 minutes, obtain the slurry that solid content is 30 weight % Liquid.Spray drying makes microsphere catalyst composition, then 550 DEG C of roastings 2 hours.Obtained connects Touch the numbered C2 of agent.

Embodiment 15～19

Prepare catalyst composition according to the method for embodiment 13 and embodiment 14, adjust ingredient proportion, system Become catalyst composition C3～C7, specifically feed intake and be shown in Table 2.

Catalyst composition uses the wastage of potassium, the bar of hydrothermal experiment in hydrothermal experiment test compositions Part is: 100% steam 550 DEG C processes 65h, K in sample composition before and after mensuration hydro-thermal₂The weight of O contains Amount, with the stability of potassium in retention rate definition catalyst composition.The hot water potassium of catalyst composition C1～C7 Retention rate is shown in Table 2.

Table 2.

From table 2, 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, at potassium after hydrothermal treatment consists Apparently higher than employing, other contain potassium material and the alkaline-earth metal catalysis group as gasification reactivity component to retention rate The retention rate of potassium in compound.

Comparative example 1～3 is for illustrating the preparation method of comparative catalyst.

Comparative example 1

(1) with concentration as 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and the ammonia that concentration is 25wt.% are Reaction raw materials, uses and flows plastic mode, is stirred vigorously lower by Al₂(SO₄)₃Solution and ammonia mix Rubber polymer, controlling system temperature is 40 DEG C, system pH=9.5, collects metering plastic serosity；(2) And under agitation according to SiO₂: Al₂O₃The weight ratio of=1:2.6 adds concentration in plastic serosity For 102gSiO₂The waterglass of/L, is warming up to 70 DEG C and is aged 2 hours, obtain the first solid sediment；(3) By described first solid sediment by its precipitate butt: ammonium salt: H₂The weight ratio of O=1:0.8:15, At 60 DEG C, solid sediment is carried out ion exchange and removes sodium ion, sodium oxide is washed till 0.3%, To the second solid sediment；(4) again add water making beating by the precipitate (filter cake) of the second solid sediment, Press again and press P₂O₅: the weight ratio of the precipitate butt=0.05:1 of the second solid sediment is mixed with phosphoric acid Close, be warming up to 60 DEG C and stir 1 hour, be dried at 120 DEG C after filtration and i.e. obtain contrast material in 10 hours. It is designated as DB-1.

DB-1 has structure of similar to thin diaspore, and its X-ray diffraction spectrogram is with shown in Fig. 2；Its element divides Analysis chemical composition is 0.12Na₂O·62.5Al₂O₃·31.7SiO₂·5.0P₂O₅；Specific surface area 413m²/ g, hole Hold 0.97cm³/ g, average pore size 9.4nm.

Comparative example 2

The embodiment 1 announced according to patent CN1565733 prepares mesoporous silicon aluminum, is designated as DB-2.

DB-2 has structure of similar to thin diaspore；Its elementary analytical chemistry consists of 0.12Na₂O·73.7Al₂O₃·26.2SiO₂；Specific surface area 362m²/ g, pore volume 1.19cm³/ g, average hole Footpath 12.8nm.

Comparative example 3

(1) it is first 90gAl by concentration₂O₃The Al of/L₂(SO₄)₃Solution is placed in beaker, by dense under stirring Spending and add for 25wt.% ammonia, until system pH=10.0, keeping gelling temperature is 40 DEG C, collects meter Amount plastic serosity；(2) under agitation according to SiO₂: Al₂O₃The weight ratio of=1:3 is to becoming rubber cement Adding concentration in liquid is 60gSiO₂The waterglass of/L, is warming up to 80 DEG C and is aged 1 hour, obtain first solid Body precipitate；(3) by described first solid sediment by its precipitate butt: HCl:H₂O=1:0.08: The weight ratio of 12 exchanges 30 minutes at 50 DEG C, and filtration washing obtains sodium oxide content and is less than 0.3% Second solid sediment；(4) by gained the second solid sediment by its precipitate butt: H₂O=1:10 Weight ratio mix making beating with water, and press MgO:TiO₂: the precipitate butt of the second solid sediment= The weight ratio of 0.017:0.012:1 adds magnesium nitrate and titanium sulfate, reacts 2 hours at 60 DEG C, Be dried at 120 DEG C after filtering washing the product that obtains after 10 hours as reference metal-modified in Hole silica-alumina material, is designated as DB-3.

DB-3 has structure of similar to thin diaspore, the same Fig. 2 of its X-ray diffraction spectrogram；Its elementary analysis Consist of 0.08Na₂O·77.2Al₂O₃·15.9SiO₂·1.5MgO·1.0TiO₂；Specific surface area 496m²/ g, Pore volume 1.38cm³/ g, average pore size 11.2nm.

Comparative example 4

With reference to the preparation method of the mesoporous silica-alumina materials DB-2 of comparative example 2, difference is, uses acid to hand over Process of changing substitutes ammonium exchange process therein.Will the intermediate sedimentation thing of DB-2, after the most aging filtration Sial precipitate, mixes making beating with water by the weight ratio of 1:10, then (concentration is 10 weights by HCl solution Amount %) by precipitate (butt): the weight ratio of HCl=1:0.12 joins in above-mentioned serosity, at 55 DEG C Lower contact 40 minutes, through filtering, be dried and obtaining mesoporous silica-alumina materials after roasting, is designated as DB-4.

Same Fig. 2 of X-ray diffraction spectrogram of DB-4；Its elementary analysis weight chemistry consists of 0.11Na₂O·73.7Al₂O₃·26.2SiO₂。

Comparative example 5～10

Prepare catalyst composition according to the method for embodiment 13, adjust ingredient proportion, make catalyzed combination Thing D1～D6,

Concrete inventory is shown in Table 3.

Table 3.

From the data of table 2 and table 3 it can be seen that carbon monoxide-olefin polymeric is through 100% steam 550 DEG C After processing 65h, when the method provided by the present invention preparation of use has the peak of XRD principal phase shown in Fig. 1 High as the potassium retention rate of the carbon monoxide-olefin polymeric of gasification reactivity component containing potassium material, hence it is evident that higher than other Potassium-containing compound is as the potassium retention rate of the catalyst composition of gasification reactivity component.Visible, use this Prepared by the method for bright offer has the stability containing potassium material at the peak of XRD principal phase shown in Fig. 1 due to it His potassium-containing compound.

Test case 1

The catalyst composition that this test provides for embodiment 13～19 and preparation comparative example 5～10 are described Gasification performance and cracking performance.Respectively the catalyst composition of above-mentioned preparation 790 DEG C, 100% water steaming Aging 8h under conditions of gas, being then seated in reserve is to split in 210 grams fixed fluidized bed Change and gasification experiment.Cracking experiments condition is: reaction temperature is 520 DEG C, weight (hourly) space velocity (WHSV) is 20h-1, Oil ratio is 8, and water-oil factor is 0.35；Gasification experiment condition: gasification temperature is 720 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 4, appreciation condition and the results are shown in Table 5 and table 6.

Table 4.

Table 5.

Table 6

In table 5 and table 6:

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 in compositions coke make charcoal strong Degree increases along with the increase of temperature, and in gasifying agent, the intensity of making charcoal containing oxygen can be better than with 100% water Steam is as the intensity of making charcoal of gasifying agent.From table 5 and table 6 it can be seen that the present invention provide cracked gas Change catalyst composition (C1-C7) relative to the documents mentioned by aforementioned background art CN200910143623.3 (gasification temperature needs higher than 860 DEG C), can be under lower gasification temperature Obtaining good gasification result, obtain higher intensity of making charcoal, density of hydrogen is higher.

And, with compared to the catalyst using comparative example 1～4 to prepare, use the activity that the present invention provides Catalyst composition prepared by mesopore material has more preferable cracking performance, and coke selectivity is good, and light oil is received Rate (gasoline and the total recovery of liquefied gas) is high.Catalyst composition (the ginseng prepared with existing gasification reactivity component See D4) compare, prepared by the method using the present invention to provide has the XRD principal phase peak shown in Fig. 1 The gasification reactivity of the catalyst composition prepared as gasification reactivity component containing potassium material is higher, intensity of making charcoal Higher；Under same gasification condition, the intensity of making charcoal of gasification reactivity and coke is considerably higher.

As can be seen here, when the catalyst composition that invention provides contains active mesopore material and Fig. 1 institute simultaneously The XRD principal phase peak shown containing potassium material time, gasification reactivity is higher, and this is possibly due to this activity mesopore Material improves the distribution of coke, improves the utilization rate of gasification reactivity component, and then improves gasification Performance.Visible, adopt the catalyst composition of visible present invention offer for the-process process weight that gasifies Matter petroleum hydrocarbon 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 cracking activity group of gasification reactivity component, 1%～60% of mesoporous active materials, 1%～40% of 1%～50% Point, 0%～the clay of 70% and the heat-resistant inorganic oxide matrix of 2%～97%, described mesoporous active materials Having the phase structure of boehmite, the anhydrous chemical expression counted with oxide weight is for (0-0.2) Na₂O·(40-85)Al₂O₃·(10-55)SiO₂·(0.5-10)P₂O₅·(0.5-10)M_xO_y, its Middle metal M is selected from Mg, periodic table of elements IIB, IIIB, IVB, VIIB race element, and group of the lanthanides One or more in rare earth element, y is that maximum during metal M formation oxide closes valence state, and x The quantivalence making M and O with the numerical value of y balances, and specific surface area is 200～500m²/ g, pore volume is 0.5～1.5cm³/ g, average pore size is 8～18nm,

Catalyst composition the most according to claim 1, wherein, described mesoporous active materials is with oxygen Compound mass ratio range (0-0.2) Na₂O·(40-85)Al₂O₃·(10-55)SiO₂·(0.5-10)P₂O₅· (0.5-10)M_xO_y。

Catalyst composition the most according to claim 1, wherein, the ratio of described mesoporous active materials Surface area is 300～450m²/ g, pore volume is 0.7～1.2cm³/ g, average pore size is 10～15nm.

Catalyst composition the most according to claim 1, wherein, described IIB, IIIB, IVB, One or more in Zn, Y, Ti and Mn of VIIB race metal, preferably Ti and Mn, Mn And Zn, Ti and Zn, Ti and Y, Mn, Ti Yu Zn or Y, Mn and Zn, the most described IIB, IIIB, IVB, VIIB race metal is Y or Y, Mn and Zn.

5. according to the catalyst composition described in any one in claim 1-4, wherein, described mesopore Active material prepares in accordance with the following methods:

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

Catalyst composition the most according to claim 5, wherein, aluminum source described in step (1) is selected One or more in aluminum nitrate, aluminum sulfate and aluminum chloride；Described alkaline solution is selected from ammonia, hydrogen One or more in sodium hydroxide solution, potassium hydroxide solution and sodium aluminate solution；In step (2) Described silicon source selected from waterglass, sodium silicate, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, In one or more in four butoxy silicon and silicon oxide, and source of aluminium, alkaline solution, silicon source extremely Few one is containing sodium raw materials.

Catalyst composition the most according to claim 5, wherein,

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

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

Catalyst composition the most according to claim 5, wherein, ammonium salt described in step (3) selects One or more in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate；Described acid One or more in sulphuric acid, hydrochloric acid and nitric acid of acid in solution.

Catalyst composition the most according to claim 5, wherein, phosphorus source described in step (4) is selected One or more in ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate and phosphoric acid.

Catalyst composition the most according to claim 5, wherein, by described the in step (4) Two solid sediments contact processing procedure with the compound of phosphorus source, metal M, selected from following a), b), C), d) during one:

A) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight Than mixing making beating with water, then the compound of phosphorus source, metal M is added sequentially in above-mentioned serosity, Room temperature processes at least 0.2 hour to contact at 90 DEG C, is dried after filtering washing at 100 DEG C-150 DEG C 10-20 hour；

B) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight Than mixing making beating with water, then phosphorus source or metal M are joined in above-mentioned serosity, in room temperature to 90 DEG C Lower contact processes at least 0.2 hour, after filtration directly and early stage does not adds the chemical combination of metal M or phosphorus source Thing is mixed in proportion, and is dried 10-20 hour after grinding uniformly at 100 DEG C-150 DEG C；

C) by described second solid sediment by its precipitate butt: H₂O=1:(5-20) weight Than mixing making beating with water, then the compound of phosphorus source He the first metal M is joined in above-mentioned serosity, At room temperature to 90 DEG C, contact processes at least 0.2 hour, obtains the 3rd solid sediment after filtration, then will 3rd solid sediment directly mixes with the compound of the second metal M, at 100 DEG C after grinding uniformly 10-20 hour, wherein, the compound of described the first metal M and the second metal it is dried at-150 DEG C The compound of M is identical or different；

D) direct for the described second solid sediment compound with phosphorus source, metal M is mixed in proportion, It is dried 10-20 hour at 100 DEG C-150 DEG C after grinding uniformly.

11. catalyst compositions according to claim 5, wherein, are dried described in step (4) After step, also include gained desciccate roasting 1-4 hour at 500 DEG C-700 DEG C.

12. catalyst composition according to claim 5, wherein, metal described in step (4) The compound of M is water miscible compound, the nitric acid that compound is metal M of the most described metal M Salt, sulfate or chloride.

13. catalyst compositions according to claim 1, wherein, described cracking activity constituent element also contains There is MFI structure molecular sieve, anhydrous with the molar ratio computing of oxide in described 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；With On the basis of the gross weight of described cracking activity constituent element, described cracking activity constituent element contains 90-99.9 weight % The Y type molecular sieve containing rare earth and the MFI structure molecular sieve of 0.1-10 weight %.

14. catalyst compositions according to claim 1, wherein, described gasification reactivity component bag Include the one in alkali metal compound, alkaline earth metal compound, and group VIII metal compound or many Kind.

15. according to the catalyst composition described in claim 1 or 14, wherein, and described gasification reactivity Component is selected from potassium hydroxide, potassium carbonate, potassium oxide, potassium nitrate, potassium sulfate, potassium chloride, di(2-ethylhexyl)phosphate Hydrogen potassium, potassium feldspar, green bean rock, alunite, trachyte, potassium-bearing shale, phosphorus potassium ore, containing potassium powder Sandstone, XRD diffracting spectrum at 2 θ angles is exist at 21 °, 29 ° and 35 ° principal phase peak containing potassium material, The chloride of dolomite, olivine and alkaline-earth metal, nitrate, sulfate, phosphate, and One or more in the sulfate of group VIII metal, nitrate, chloride, oxide.

16. catalyst compositions stated according to claim 15, wherein, described alkaline-earth metal be beryllium, magnesium, One or more in calcium, strontium, barium, described group VIII metal is Fe and/or Ni.

17. according to the catalyst composition described in claim 1 or 14, wherein, and described gasification reactivity group Divide the compound including potassium, with or without alkaline earth metal compound, with or without group VIII metal chemical combination Thing, on the basis of the weight of described gasification reactivity component, in terms of oxide weight, described gasification reactivity In component, the content of potassium is 2～100%, and the content of alkaline-earth metal is 0-98 weight %, group VIII metal Content is 0-98 weight %.

18. according to the catalyst composition described in claim 1 or 14, wherein, and described gasification reactivity group Point include XRD diffracting spectrum at 2 θ angles is exist at 21 °, 29 ° and 35 ° principal phase peak containing potassium thing Matter.

19. catalyst compositions according to claim 18, wherein, in described XRD diffracting spectrum At 2 θ angles be exist at 21 °, 29 ° and 35 ° principal phase peak containing the potassium content in potassium material, in terms of potassium oxide Being 8 weight %～40 weight %, with or without alkaline-earth metal, remaining is sial component, alkaline-earth metal oxygen Compound and potassium oxide mol ratio (0～1): 0.2, SiO₂/Al₂O₃Mol ratio be 1:10～10:1.

20. catalyst compositions according to claim 19, 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 Amount %～30 weight %, alkaline earth oxide and potassium oxide mol ratio 1:5～1:0.5, SiO₂/Al₂O₃'s Mol ratio is 1:3～3:1.

21. catalyst compositions according to claim 18, wherein, in described XRD diffracting spectrum It is that 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 will be contained Compound, sial component and optional alkaline earth metal compound are beaten into wet feed, are then dried into siccative, Obtaining after roasting, sintering temperature is 800 DEG C～1150 DEG C, roasting time 1～10h again.

22. catalyst compositions according to claim 21, wherein, described sintering temperature is 900 DEG C ～1100 DEG C, roasting time is 2～8h.

23. catalyst compositions according to claim 21, wherein, described sial component is selected from height One in ridge soil, montmorillonite, rectorite, attapulgite, illite, meerschaum, kieselguhr or Multiple, or be Kaolin, montmorillonite, rectorite, attapulgite, illite, meerschaum, silicon One or more in diatomaceous earth, Alumina gel, boehmite and the mixture of Ludox；Or it is high In ridge soil, montmorillonite, rectorite, attapulgite, illite, meerschaum, kieselguhr, Ludox One or more with Alumina gel or the mixture of boehmite.

24. a preparation method for catalyst composition described in any one in claim 1 to 23, bag Include activity mesopore material, gasification reactivity component, cracking active component, clay, heat resistant inorganic oxidation The mixing making beating of thing substrate, is spray-dried and the step of roasting.

The cracking gasification process of 25. 1 kinds of petroleum hydrocarbons, is included in petroleum hydrocarbon and power in cracker Profit requires the cracking gasification catalyst composition haptoreaction in 1 to 23 described in any one, after reacting Described cracking gasification carbon monoxide-olefin polymeric and Oil-gas Separation, isolated be deposited splitting of coke The step that activating QI catalyst composition contacts with gasifying agent.