CN106179456B - A kind of cracking gasification process of cracking gasification catalyst composition, preparation method and petroleum hydrocarbon - Google Patents

Abstract

The invention discloses the cracking gasification process of a kind of cracking gasification catalyst composition, preparation method and petroleum hydrocarbon, by weight percentage, the catalyst composition includes: 1%~50% mesoporous active materials, and anhydrous chemical expression of the mesoporous active materials in terms of oxide weight is (0-0.2) Na₂O·(40‑85)Al₂O₃·(10‑55)SiO₂·(0.5‑10)P₂O₅·(0.5‑10)M_xO_y, wherein metal M is selected from Mg, one of periodic table of elements IIB, IIIB, IVB, VIIB race's element and lanthanide series rare-earth elements or a variety of, and y is highest valent state when metal M forms oxide, and the numerical value of x and y balances the chemical valence of M and O.It is applied has preferable cracking activity and gasification conversion performance in heavy oil catalytic cracking-gasification group technology, while can obtain higher yield of gasoline.

Description

A kind of cracking gasification of cracking gasification catalyst composition, preparation method and petroleum hydrocarbon Method

Technical field

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

Background technique

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

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

, feedstock oil that colloid/asphalt content less higher containing saturated hydrocarbons is the good raw material of catalytic cracking, using tradition Catalyzed cracking processing mode also produce a certain amount of coke while producing liquefied gas, gasoline, diesel oil, this part of coke exists Burning provides the heat for being used to maintain the certain reaction temperature of system in regenerative system.A certain amount of water is passed through in regenerative system to steam Gas as gasifying agent can while burning by-product part CO, H₂, this partially synthetic gas, which passes through processing, can be used to do Fischer-Tropsch The unstripped gas of synthesis.

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

The gasification temperature of above-mentioned existing catalyst is relatively high, in 860 DEG C of progress gasification reactions, for urging for alkali metal containing Change material, under high temperature hydrothermal condition, the loss of alkali metal carrys out the catalyst containing molecular sieve than more serious in catalyst It says, the rapid avalanche of framework of molecular sieve can occur in 800 DEG C or more of high temperature thermal and hydric environment, and activity reduces rapidly.

The relatively high problem of gasification temperature in order to improve existing catalyst.One kind is disclosed in CN201210262817.7 Cracking gasify catalyst composition, by weight percentage, the catalyst composition include: 1%~50% mesoporous silica-alumina materials, 1%~40% gasification reactivity component, 1%~60% cracking active component, 0%~70% clay and 5%~97% Heat-resistant inorganic oxide matrix, wherein the mesoporous silica-alumina materials have the phase structure of boehmite, with oxide weight The anhydrous chemical expression of meter is (0-0.3) Na₂O·(40-90)Al₂O₃·(10-60)SiO₂, specific surface area 200- 400m²0.5~2.0mL/g of/g, Kong Rongwei, average pore size are 8~20nm, and most probable pore size is 5~15nm.The catalyst composition The gasification temperature of cracking hydrocarbon oil gasification conversion can be reduced.

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

Summary of the invention

The object of the present invention is to provide the cracking gasifications of a kind of cracking gasification catalyst composition, preparation method and petroleum hydrocarbon Method, to overcome the prior art catalyst composition gasification temperature height or the not high problem of cracking performance in use.

To achieve the goals above, the catalyst composition according to an aspect of the invention, there is provided a kind of cracking is gasified, with Weight percent meter, the catalyst composition include: 1%~50% mesoporous active materials, 1%~40% gasification reactivity group Point, 1%~60% cracking active component, 0%~70% clay and 2%~97% heat-resistant inorganic oxide matrix, institute The mesoporous active materials stated have the phase structure of boehmite, and the anhydrous chemical expression in terms of oxide weight is (0- 0.2)Na₂O·(40-85)Al₂O₃·(10-55)SiO₂·(0.5-10)P₂O₅·(0.5-10)M_xO_y, wherein metal M is selected from Mg, One of periodic table of elements IIB, IIIB, IVB, VIIB race's element and lanthanide series rare-earth elements are a variety of, and y is that metal M is formed Highest valent state when oxide, and the numerical value of x and y balances the chemical valence of M and O, specific surface area is 200~500m²/ 0.5~1.5cm of g, Kong Rongwei³/ g, average pore size are 8~18nm,

The cracking activity constituent element contains the Y type molecular sieve containing rare earth of 90-100 weight %, the Y type containing rare earth point Son is screened from the first Y type molecular sieve containing rare earth, the second Y type molecular sieve of Y type molecular sieve and third containing rare earth containing rare earth At least one, wherein the preparation method of the described first Y type molecular sieve containing rare earth includes: under stiring, by the Y containing rare earth Type molecular sieve is contacted with silicon tetrachloride, and the temperature of contact is 100-500 DEG C, and the time of stirring is 1-10 hours, described to contain rare earth Y type molecular sieve and silicon tetrachloride weight ratio be 1:0.05-0.5；

The silica alumina ratio of described second Y type molecular sieve containing rare earth is 5-30, and initial lattice constant is 2.430-2.460nm, Content of rare earth on the basis of the total amount of the described second Y type molecular sieve containing rare earth and in terms of oxide is 10-20 weight %, is put down Weighing apparatus lattice constant and the ratio of initial lattice constant are at least 0.985, wherein the X-ray diffraction analysis molecular sieve is in 2 θ 12.43 ± 0.06 ° and 11.87 ± 0.06 ° of two diffraction peak intensity ratio I₁/I₂Greater than 1；

It is 0.01- that the preparation method of Y type molecular sieve of the third containing rare earth, which includes: by super-stable Y molecular sieves and concentration, The acid solution of 2N is sufficiently mixed at 20-100 DEG C with the ratio of liquid-solid ratio 4-20, washing, filtering after processing 10-300 minutes, then Rare-earth salt solution is added and carries out rare earth ion exchanged, successively washed, filtered and is dried after exchange.

Meanwhile according to another aspect of the present invention, a kind of preparation method of above-mentioned catalyst composition is additionally provided, including Active mesopore material, gasification reactivity component, cracking active component, clay, heat-resistant inorganic oxide matrix are mixed with beating, it is spraying The step of dry and roasting.

In addition, according to a further aspect of the invention, additionally providing a kind of cracking gasification process of petroleum hydrocarbon, being included in and split Change by petroleum hydrocarbon and above-mentioned cracking gasification catalyst composition haptoreaction in reactor, by the cracking gasification catalysis after reaction Agent composition and Oil-gas Separation, the step that the isolated cracking gasification catalyst composition that deposited coke is contacted with gasifying agent Suddenly.

The cracking gasification side of the gasification of cracking provided by the present invention is above-mentioned catalyst composition, preparation method and petroleum hydrocarbon Method can reduce gasification temperature by introducing specific mesoporous active materials；It can be obtained under lower gasification temperature higher It makes charcoal intensity, obtains higher density of hydrogen.Mesoporous active materials are carried out effective combine with gasification reactivity component can be big The big coke gasification efficiency for improving catalyst；Cracking-gasification the integration of catalyst composition of the invention for heavy petroleum hydrocarbon When technique, gasification result is good, and gasification temperature is low, has stronger petroleum hydrocarbon such as heavy oil conversion performance, and utilize several molecules The synergistic effect of sieve increases yield of light oil, especially yield of gasoline and significantly improves.Especially with containing in XRD diffracting spectrum 2 angles θ are that there are the gasification reactivity components of the substance containing potassium at main phase peak to be used cooperatively at 21 °, 29 ° and 35 °, not only gasification result Good, gasification temperature is low, and has stronger hydrocarbon oil conversion ability, and gasification reactivity component is lost less.

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

Detailed description of the invention

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

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

Fig. 2 is the X-ray diffraction spectrogram according to the mesoporous active materials in the specific embodiment of the invention.

Specific embodiment

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

The present invention provides a kind of cracking gasification catalyst compositions, and by weight percentage, the catalyst composition includes: 1%~50% mesoporous active materials, 1%~40% gasification reactivity component, 1%~60% cracking active component, 0%~ 70% clay and 2%~97% heat-resistant inorganic oxide matrix, the mesoporous active materials have boehmite Phase structure (its X-ray diffracting spectrum is as shown in Figure 2), the anhydrous chemical expression in terms of oxide weight are (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, element One of periodic table IIB, IIIB, IVB, VIIB race's element and lanthanide series rare-earth elements are a variety of, and y is that metal M forms oxidation Highest valent state when object, and the numerical value of x and y balances the chemical valence of M and O, specific surface area is 200~500m²/ g, hole Holding is 0.5~1.5cm³/ g, average pore size are 8~18nm,

The cracking activity constituent element contains the Y type molecular sieve containing rare earth of 90-100 weight %, the Y type containing rare earth point Son is screened from the first Y type molecular sieve containing rare earth, the second Y type molecular sieve of Y type molecular sieve and third containing rare earth containing rare earth At least one, wherein the preparation method of the described first Y type molecular sieve containing rare earth includes: under stiring, by the Y containing rare earth Type molecular sieve is contacted with silicon tetrachloride, and the temperature of contact is 100-500 DEG C, and the time of stirring is 1-10 hours, described to contain rare earth Y type molecular sieve and silicon tetrachloride weight ratio be 1:0.05-0.5；

Silica alumina ratio (the i.e. SiO of described second Y type molecular sieve containing rare earth₂/Al₂O₃Molar ratio) be 5-30:1, it is initial brilliant Born of the same parents' 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 dilute in terms of oxide Native content is 10-20 weight %, and balance lattice constant and the ratio of initial lattice constant are at least 0.985, wherein X-ray is spread out It penetrates and analyzes two diffraction peak intensity ratio I that the molecular sieve is 12.43 ± 0.06 ° and 11.87 ± 0.06 ° in 2 θ₁/I₂Greater than 1；

It is 0.01- that the preparation method of Y type molecular sieve of the third containing rare earth, which includes: by super-stable Y molecular sieves and concentration, The acid solution of 2N is sufficiently mixed at 20-100 DEG C with the ratio of liquid-solid ratio (weight ratio) 4-20, and processing is washed after 10-300 minutes It washs, filter, add rare-earth salt solution and carry out rare earth ion exchanged, successively washed, filtered and dried after exchange.

The above-mentioned cracking gasification catalyst composition that is used for of the present invention is that one kind is generated for petroleum hydrocarbon cracking process and cracking Coke gasification anabolic process catalyst composition, more specifically, be related to it is a kind of utilize thermal cracking or/and catalytic cracking process Working process heavy crude hydrocarbon raw material produces light Fuel, while the coke gasification for generating process in gasifying agent presence For the multi-functional catalyst composition of the process of hydrogen or synthesis gas.

The cracking gasification side of the gasification of cracking provided by the present invention is above-mentioned catalyst composition, preparation method and petroleum hydrocarbon Method can reduce gasification temperature by introducing specific mesoporous active materials；It can be obtained under lower gasification temperature higher It makes charcoal intensity, obtains higher density of hydrogen.Mesoporous active materials are carried out effective combine with gasification reactivity component can be big The big coke gasification efficiency for improving catalyst；Cracking-gasification the integration of catalyst composition of the invention for heavy petroleum hydrocarbon When technique, gasification result is good, and gasification temperature is low, has stronger petroleum hydrocarbon such as heavy oil conversion performance, and utilize several molecules The synergistic effect of sieve increases yield of light oil, especially yield of gasoline and significantly improves.Especially with containing in XRD diffracting spectrum 2 angles θ are that there are the gasification reactivity components of the substance containing potassium at main phase peak to be used cooperatively at 21 °, 29 ° and 35 °, not only gasification result Good, gasification temperature is low, and has stronger hydrocarbon oil conversion ability, and gasification reactivity component is lost less.

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

The above-mentioned cracking gasification catalyst composition provided according to the present invention, it is preferable that described with dry weight percentages Catalyst composition includes: the 2 weight % mesoporous active materials of weight %~40, the gasification reactivity component of 5 weight of weight %~40 %, The cracking active component of 5~50 weight %, the heat-resisting nothing of the clay of 0 weight of weight %~60 % and 10 weight of weight %~70 % Machine matrix of oxide.It is further preferred that the catalyst composition includes: the 5 weight % mesoporous active materials of weight %~30,10 weight % The gasification reactivity component of~35 weight %, the cracking active component of 10~35 weight %, the clay of 5 weight of weight %~45 % and The heat-resistant inorganic oxide matrix of 10 weight of weight %~40 %.

The above-mentioned cracking gasification catalyst composition provided according to the present invention, it is preferable that the mesoporous active materials, with oxidation Object weight ratio meter (0-0.2) Na₂O·(40-85)Al₂O₃·(10-55)SiO₂·(0.5-10)P₂O₅·(0.5-10)M_xO_y。More Preferably, with the anhydrous chemical expression of the weight ratio meter of oxide in the mesoporous active materials are as follows: (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 be selected from Mg and/or periodic table of elements IIB, One of IIIB, IVB, VIIB race and/or group of the lanthanides are a variety of.Wherein, IIB, IIIB, IVB, VIIB race metal is selected from The mixing of one of Zn, Y, Ti and Mn or various metals.Preferably, IIB, IIIB, IVB, VIIB race metal be Ti and Mn, Mn and Zn, Ti and Zn, Ti and Y, Mn, Ti and Zn or Y, Mn and Zn.Preferably, IIB, IIIB, IVB, VIIB race gold Belong to is Y or Y, Mn and Zn.

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

The above-mentioned cracking gasification catalyst composition provided according to the present invention, it is preferable that the ratio table of the mesoporous active materials Area is 300~450m²0.7~1.2cm of/g, Kong Rongwei³/ g, average pore size are 10~15nm.

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

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

(2) according to SiO₂: Al₂O₃=1:(1.0-7.5) weight ratio silicon source is added into the plastic slurries, in room temperature It is aged 1-5 hours to 90 DEG C, obtains the first solid sediment；

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

(4) by the compound of second solid sediment and phosphorus source and metal M, according to P₂O₅: M_xO_y: described second is solid The sediment butt of body sediment=(0.005-0.1): (0.005-0.1): 1 weight ratio contact treatment, and by product of contact Dry (drying temperature is preferably 100 DEG C -150 DEG C).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the preparation method of above-mentioned mesoporous active materials, room temperature is usually 5~40 DEG C, for example, can be 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C or 35 DEG C.

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

In the preparation method of above-mentioned mesoporous active materials, the type of phosphorus source described in step (4) can be this field Conventional selection, for example, one of ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid or a variety of can be selected from.

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

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

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

The above-mentioned cracking gasification catalyst composition provided according to the present invention, under preferable case, with the cracking activity constituent element Total weight on the basis of, the cracking activity constituent element contains the Y type molecular sieve containing rare earth of 94-100 weight %.Wherein, The Y type molecular sieve containing rare earth is selected from the first Y type molecular sieve, the second Y type molecular sieve and third containing rare earth containing rare earth and contains At least one of Y type molecular sieve of rare earth, under preferable case, selected from the described first Y type molecular sieve containing rare earth, described second At least two in Y type molecular sieve and the Y type molecular sieve of the third containing rare earth containing rare earth.

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

In the present invention, the specific descriptions of the described second Y type molecular sieve containing rare earth are referred to patent application CN101081369A.What the described second Y type molecular sieve containing rare earth can be prepared according to the conventional method obtains, specific to prepare Method is also referred to patent application CN101081369A, embodiment 1-5 especially therein.

In the present invention, the specific preparation method of Y type molecular sieve of the third containing rare earth is referred to patent application CN1958452A, embodiment 1-6 especially therein.

The above-mentioned cracking gasification catalyst composition provided according to the present invention, the cracking activity constituent element can also contain MFI Structure molecular screen, with the anhydrous chemical composition expression formula of the molar ratio computing of oxide in the MFI structure molecular sieve are as follows: (0.01- 0.25)RE₂O₃·(0.005-0.02)Na₂O·Al₂O₃·(0.2-1.0)P₂O₅·(35-120)SiO₂, the molecular sieve to just oneself The absorption weight ratio of alkane and hexamethylene is 4-5.It is described on the basis of the total weight of the cracking activity constituent element under preferable case Cracking activity constituent element contains the MFI structure molecule of the Y type molecular sieve and 0.1-10 weight % containing rare earth of 90-99.9 weight % Sieve；In preferred situation, the cracking activity constituent element contains the Y type molecular sieve and 1-6 weight containing rare earth of 94-99 weight % Measure the MFI structure molecular sieve of %.

In the present invention, the specific descriptions of the MFI structure molecular sieve are referred to patent application CN1147420A.It is described What MFI structure molecular sieve can be prepared according to the conventional method obtains, and specific preparation method is also referred to patent application CN1147420A, embodiment 1-6 especially therein.

In the above-mentioned cracking gasification catalyst composition provided according to the present invention, it is preferable that the gasification reactivity component includes Alkali metal compound, alkaline earth metal compound and group VIII metal Compound Compound.Wherein, the 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, alum Stone, trachyte, potassium-bearing shale, phosphorus potassium ore, siltstone containing potassium at 2 angles θ are to deposit at 21 °, 29 ° and 35 ° in XRD diffracting spectrum Substance containing potassium (substance has XRD main phase peak shown in Fig. 1), dolomite, olivine at main phase peak.When the gasification reactivity group When dividing containing alkaline-earth metal, the compound of alkaline-earth metal, such as chloride, nitrate, the sulphur of alkaline-earth metal can be added One of inorganic alkali-earth metals salt such as hydrochlorate, phosphate is a variety of, and the alkaline-earth metal is beryllium, in magnesium, calcium, strontium, barium It is one or more, preferably calcium and/or magnesium.When the gasification reactivity component contains group VIII metal compound, Ke Yijia Enter the compound of group VIII metal, such as the inorganic VIII group such as sulfate, nitrate, chloride, oxide of group VIII metal One of metal salt is a variety of.The group VIII metal is preferably Fe and/or Ni.

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

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

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

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

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

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

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

The above-mentioned catalyst composition provided according to the present invention, the clay can be for clays commonly used in the art for example, institute The clay stated can be selected from kaolin, sepiolite, attapulgite, montmorillonite, tired de- stone, diatomite, galapectite, saponite, boron profit One of soil, hydrotalcite are a variety of；It is more preferably selected from kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tires out One of de- stone is a variety of.

The above-mentioned catalyst composition provided according to the present invention, in addition to the mesoporous active materials, cracking active component, gas Change other than active component, clay, also contains heat-resistant inorganic oxide matrix, the type of the heat-resistant inorganic oxide is without special It is required that can be heat-resistant inorganic oxide matrix commonly used in the art, preferably aluminium oxide, silica, titanium oxide, magnesia, One of zirconium oxide, thorium oxide and beryllium oxide and their predecessor are a variety of.The heat-resistant inorganic oxide forerunner One of object such as Aluminum sol, silica solution, phosphorus aluminium glue, boehmite, silicon-aluminum sol is a variety of.

The above-mentioned catalyst composition provided according to the present invention can also contain when being used for residual oil cracking-gasification group technology There are metal traps, based on butt, the content of the metal traps is no more than 20 weight % of catalyst composition, it is preferable that should Metal traps are free on except mesoporous active materials.Invention is to the type of the metal traps without particular/special requirement, Ke Yiwei Trap the common metal traps of the component of the pollution metal such as V, Ni, Fe, Ca, under preferable case, the metal traps are The precursor of rare earth oxide and/or rare earth oxide.In more preferable situation, the precursor metal traps of the rare earth oxide are chlorine Change one of rare earth, carbonated rare earth and rare earth hydrate or a variety of.Wherein, rare earth element can for lanthanum, cerium, praseodymium, neodymium, promethium, One of samarium and europium are a variety of.The mode of entrance of metal agent for capturing can be in mesoporous active materials, gasification reactivity in the present invention When component, clay are mixed with beating in the form of an ion or complex form introduce.If introduced in carbon monoxide-olefin polymeric heat-resisting Metal traps can also be deposited in the inorganic oxide by inorganic oxide in advance by coprecipitation.The metal is caught Collection agent can be in same particle with mesoporous active materials, also may be in different particles.

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

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

(1) silicon source and aqueous slkali are obtained into rubber cement room temperature is at 85 DEG C and plastic, control plastic pH value are 7-11 Liquid；According to SiO₂: Al₂O₃=1:(1.0-7.5) weight ratio silicon source is added into the plastic slurries, in room temperature at 90 DEG C Ageing 1-5 hours, obtains the first solid sediment；By first solid sediment and ammonium salt or acid solution contact treatment, mistake Filter obtains the second solid sediment that sodium oxide content is lower than 0.3 weight %；By second solid sediment and phosphorus source and gold The compound for belonging to M, according to P₂O₅: M_xO_y: the sediment butt of second solid sediment=(0.005-0.1): (0.005- 0.1): 1 weight ratio contact treatment, and roasted 1~4 hour by product of contact drying or at 500 DEG C~700 DEG C；

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

(3) component of gasification reactivity containing potassium for obtaining the mesoporous active materials obtained in step (1) and step (2) with Clay, cracking active component, heat-resistant inorganic oxide matrix are mixed with beating, and are then spray-dried, at 400~800 DEG C Roast 2~10h；Wherein press dry basis, the mesoporous active materials, gasification reactivity component, cracking active component, clay Make the mesopore activity material in obtained catalyst composition including 1%~50% with the dosage of heat-resistant inorganic oxide matrix Material, 1%~40% gasification reactivity component, 1%~60% cracking active component, 0%~70% it is described viscous The native heat-resistant inorganic oxide matrix with 2%~97%.Wherein, the cracking activity constituent element contains 90-100 weight %'s Y type molecular sieve containing rare earth, the Y type molecular sieve containing rare earth are selected from the first Y type molecular sieve containing rare earth, second containing rare earth At least one of the Y type molecular sieve of Y type molecular sieve and third containing rare earth,

Wherein, the preparation method of the described first Y type molecular sieve containing rare earth includes: under stiring, by the Y type containing rare earth point Son sieve is contacted with silicon tetrachloride, and the temperature of contact is 100-500 DEG C, and the time of stirring is 1-10 hours, the Y type containing rare earth The weight ratio of molecular sieve and silicon tetrachloride is 1:0.05-0.5；

The silica alumina ratio of described second Y type molecular sieve containing rare earth is 5-30, and initial lattice constant is 2.430-2.460nm, Content of rare earth on the basis of the total amount of the described second Y type molecular sieve containing rare earth and in terms of oxide is 10-20 weight %, is put down Weighing apparatus lattice constant and the ratio of initial lattice constant are at least 0.985, wherein the X-ray diffraction analysis molecular sieve is in 2 θ 12.43 ± 0.06 ° and 11.87 ± 0.06 ° of two diffraction peak intensity ratio I₁/I₂Greater than 1；

It is 0.01- that the preparation method of Y type molecular sieve of the third containing rare earth, which includes: by super-stable Y molecular sieves and concentration, The acid solution of 2N is sufficiently mixed at 20-100 DEG C with the ratio of liquid-solid ratio 4-20, washing, filtering after processing 10-300 minutes, then Rare-earth salt solution is added and carries out rare earth ion exchanged, successively washed, filtered and is dried after exchange.

Preferably, the mesoporous active materials obtained in above-mentioned steps (1), gasification reactivity component are mixed with beating to obtain First slurries, by cracking active component, clay, binder is mixed with beating, and obtains the second slurries, then by the first slurries and second Slurries are mixed with beating, then are spray-dried, roast 2~10h at 400~800 DEG C, preferably 450-750 DEG C.

The preparation method of above-mentioned catalyst composition provided by according to the present invention, the clay can be commonly used in the art Clay, under preferable case, can selected from kaolin, sepiolite, attapulgite, montmorillonite, tired de- stone, diatomite, galapectite, One of saponite, boron-moisten soil, hydrotalcite are a variety of；More preferably it is selected from kaolin, diatomite, sepiolite, attapulgite, illiteracy One of de- stone and tired de- stone are a variety of；As binder when heat-resistant inorganic oxide matrix has adhesive property, The binder can be binder commonly used in the art, in preferred situation, can choose Aluminum sol, silica solution, intend thin water One of aluminium stone, phosphorus aluminium glue are a variety of.Acid can also be added under preferable case, in the slurries to be acidified, the sour example Such as one of hydrochloric acid, nitric acid, sulfuric acid or a variety of.Preferably, by the mesoporous active materials, gasification obtained in step (1) Active component is mixed with beating to obtain the first slurries, and by cracking active component, clay, binder is mixed with beating, and obtains the second slurries, Then the first slurries and the second slurries are mixed with beating, then are spray-dried, at 400~800 DEG C preferably 450~750 DEG C Roast 2~10h.

Preferably, the inorganic oxide matrix is to exist in the form of an oxide and/or available described inorganic The precursors of inorganic oxides of oxide.The heat-resistant inorganic oxide matrix can be in catalyst composition in the preparation with heat-resisting nothing Machine oxide precursor is added, and then by roasting, heat-resistant inorganic oxide precursor is converted into heat-resistant inorganic oxide, can also be with It first is prepared into heat-resistant inorganic oxide with heat-resistant inorganic oxide precursor, then with heat-resisting in the preparation process of catalyst composition The form of inorganic oxide is added.The temperature wherein roasted is usually less than 800 DEG C, generally 400~750 DEG C.Described is heat-resisting Inorganic oxide matrix have attachment function when, generally also become binder, for example, binder can be Aluminum sol, silica solution, One or more of boehmite, phosphorus aluminium glue.

In cracking provided by the invention gasification catalyst composition preparation method, by mesoporous active materials, gasification reactivity component, The sequence that clay, heat-resistant inorganic oxide matrix are mixed with beating does not have particular/special requirement, for example, the raw material can be made respectively Standby slurries, then mix prepared slurries；First mesoporous active materials can be mixed with clay, then again with other components It is mixed with beating；Or be mixed with beating gasification reactivity component with clay, then it is mixed with beating again with other components.

When catalyst composition of the invention contains metal traps, the incorporation way of metal agent for capturing can be in the present invention In the form of an ion or complex compound shape when mesoporous active materials, gasification reactivity component, cracking active component, clay are mixed with beating Formula introduces, and can also be introduced in the form of precipitating after by above-mentioned several component spray drying formings.If in catalyst combination Heat-resistant inorganic oxide matrix is introduced in object, metal traps can also be deposited on the inorganic oxygen in advance by coprecipitation In compound.Under preferable case, based on butt, the content of the metal traps is no more than 20 weight % of catalyst composition.This Invention, without particular/special requirement, can be the normal of the component of the pollution metal such as trapping V, Ni, Fe, Ca to the type of the metal traps With metal traps, under preferable case, the metal traps are the precursor of rare earth oxide and/or rare earth oxide.More preferably In the case of, the precursor of the rare earth oxide is one of rare earth chloride, carbonated rare earth and rare earth hydrate or a variety of.Its In, rare earth element can be one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium or a variety of.

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

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

(1) petroleum hydrocarbon contacts with catalyst composition provided by the invention in Cracking Unit and carries out cracking reaction, reaction outflow Gas, gasoline fraction, diesel oil distillate, wax oil fraction and the catalyst composition that deposited coke are obtained after object separation；The stone One of petroleum hydrocarbon such as AGO (atmospheric gas oil), vacuum gas oil (VGO), decompression residuum, reduced crude, Propane Deasphalting Oil, wax tailings Or it is a variety of.The reaction condition such as reaction temperature is 450~700 temperature, and reaction weight (hourly) space velocity (WHSV) is 0.1~500h^-1, agent oil It is 0.1~100. than (weight ratio of catalyst composition and petroleum hydrocarbon)

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

(3) the resulting complete regeneration catalyzing composition of step (2) carries heat back to Cracking Unit described in step (1) It is recycled.

Preferably by control regeneration condition, coke on catalyst composition is gasificated into rich in CO and H for above-mentioned steps (2)₂Gas Obtain semi regeneration catalyst composition while body, on composition remaining coke layer can protect catalyst not by gasifying agent into One step is destroyed, and the loss of gasification reactivity component and the inactivation at cracking activity center are reduced.Coke contains in the semi regeneration composition Amount is 0.3~1%.

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

In embodiment and in comparative example:

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

Sodium silicate be it is commercially available, contain SiO₂Concentration is 26.0 weight %, modulus 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 %；

Aluminum sol is middle petrochemical industry joint-stock company Shandong catalyst branch product, Al₂O₃Content is 21.5 weight %；

First Y type molecular sieve containing rare earth is made according to the method for embodiment 5 in CN1683244A；

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

Y type molecular sieve of the third containing rare earth is made according to the method for CN1958452A embodiment 1；

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

Rare earth chloride is purchased from Baogang's Xitu Hi-Tech skill limited liability company.

Na in mesoporous active materials₂O、Al₂O₃、SiO₂、P₂O₅Content with x-ray fluorescence method measure (referring to " petrochemical industry Analysis method (RIPP experimental method) ", Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes).

Examples 1 to 9 is used to illustrate the preparation method of mesoporous active materials used in the present invention.

Embodiment 1

It (1) is 90gAl with concentration₂O₃The Al of/L₂(SO₄)₃Solution and concentration are 102gAl₂O₃/ L, Crater corrosion are 2.5 NaAlO₂Solution is reaction raw materials, using cocurrent plastic mode, mixing plastic is carried out under being vigorously stirred, control system temperature is 40 DEG C, metering plastic slurries are collected in system pH=9.0；(2) under stiring according to SiO₂: Al₂O₃The weight ratio of=1:2 is to plastic It is 60gSiO that concentration is added in slurries₂The waterglass of/L is warming up to 60 DEG C and is aged 3 hours, obtains the first solid sediment；(3) First solid sediment is pressed into its sediment butt: ammonium salt: H₂NH is added in the weight ratio of O=1:0.5:12₄Cl and deionization Water carries out ion exchange to sediment at 60 DEG C and removes sodium ion, and exchange repeats once, and 0.5 hour every time, until oxidation Sodium content is lower than 0.3%, obtains the second solid sediment；(4) the second solid sediment of gained is then pressed into sediment butt: H₂The weight ratio of O=1:8 is mixed with beating with water, and presses P₂O₅: MgO: material butt=0.033:0.022:1 weight ratio is added Phosphoric acid and magnesium nitrate react 1 hour at 80 DEG C, provide up to the present invention within dry 10 hours at 120 DEG C after filtering washing High cracking activity mesopore material.It is denoted as PM-1.

PM-1 has structure of similar to thin diaspore, and X-ray diffraction spectrogram is the same as Fig. 2 feature；Its elementary analytical chemistry group becomes 0.12Na₂O·65.1Al₂O₃·28.2SiO₂·3.2P₂O₅·2.1MgO；Specific surface area 391m²/ g, Kong Rong 0.97cm³/ g is put down Equal aperture 9.9nm.

Embodiment 2

(1) first by concentration be 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in a beaker, and is warming up to 50 DEG C, is added with stirring Concentration is the ammonium hydroxide of 25wt.%, until system pH=10.5, keeping gelling temperature is 40 DEG C, collects metering plastic slurries； (2) and under agitation according to SiO₂: Al₂O₃It is 60gSiO that concentration is added into plastic slurries for the weight ratio of=1:1₂/ L's Waterglass is warming up to 70 DEG C and is aged 1.5 hours, obtains the first solid sediment；(3) first solid sediment is sunk by it Starch butt: NH₄Cl:H₂The weight ratio of O=1:0.08:12 exchanges 30 minutes at 60 DEG C, is repeated once exchange process, filtering Washing obtains the second solid sediment that sodium oxide content is lower than 0.3%；(4) then by the second solid sediment of gained by precipitating Object butt: H₂The weight ratio of O=1:8 is mixed with beating with water, and presses P₂O₅: the sediment butt of the MgO: the second solid sediment= Diammonium hydrogen phosphate and magnesium nitrate is added in the weight ratio of 0.075:0.015:1, reacts 1 hour at 60 DEG C, after filtering washing To third solid sediment, then press MnO₂: manganese chloride mixing is added in the sediment butt of third solid sediment=0.035:1, It is 10 hours dry in 120 DEG C after grinding uniformly, 3 hours are roasted then at 550 DEG C up to high cracking activity mesoporous provided by the invention Material.It is denoted as PM-2.

PM-2 has structure of similar to thin diaspore, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its elementary analytical chemistry group As 0.10Na₂O·47.2Al₂O₃·44.1SiO₂·2.7P₂O₅·1.3MgO·3.5MnO₂；Specific surface area 302m²/ g, Kong Rong 0.7cm³/ g, average pore size 9.3nm.

Embodiment 3

With 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and ammonium hydroxide are that reaction raw materials are vigorously stirred down using cocurrent plastic mode By Al₂(SO₄)₃The ammonium hydroxide that solution and concentration are 25wt.% carries out mixing plastic, and control system pH=9.5 collects metering plastic Slurries simultaneously, under agitation according to SiO₂: Al₂O₃It is 60gSiO that concentration is added into plastic slurries for the weight ratio of=1:2.6₂/ The waterglass of L is warming up to 60 DEG C and is aged 3 hours；Obtained solid sediment is pressed into sediment butt: ammonium salt: H₂O=1:1:12's Weight ratio exchanges 1 hour at 60 DEG C, after filtering washing, by sediment butt: H₂The weight ratio of O=1:10 sinks obtained solid Starch is mixed with beating with water, and presses P₂O₅: ZnO: phosphoric acid and zinc nitrate is added in material butt=0.065:0.025:1 weight ratio, Reacted 1 hour at 60 DEG C, after filtering washing at 120 DEG C dry 15 hours up to phosphorus provided by the invention, metal-modified Mesoporous silica-alumina materials.It is denoted as PM-1.

PM-3 has boehmite crystal phase structure, and X-ray diffraction spectrum is illustrated in Fig. 2；Its elementary analytical chemistry group As 0.10Na₂O·71.7Al₂O₃·19.4SiO₂·6.3P₂O₅·2.3ZnO；Specific surface area 433m²/ g, Kong Rong 1.39cm³/ G, average pore size 12.8nm.

Embodiment 4

By 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in a beaker, and is added with stirring the ammonium hydroxide that concentration is 25wt.%, directly To system pH=9.5, a certain amount of slurries are collected, under agitation according to SiO₂: Al₂O₃The weight ratio of=1:1.6 is to plastic It is 60gSiO that concentration is added in slurries₂The waterglass of/L is warming up to 60 DEG C and is aged 3 hours；By obtained solid sediment by precipitating Object butt: NH₄Cl:H₂The weight ratio of O=1:0.8:12 exchanges 1 hour at 50 DEG C, and filtering washing is lower than sodium oxide content 0.3%；Then filter cake is beaten and is pressed with phosphoric acid, P₂O₅: the mixing of material butt=0.033:1 weight ratio, at 60 DEG C Stirring 1 hour, again by filter cake and zinc nitrate and manganese chloride according to ZnO:MnO after filtering₂: material butt=0.040:0.015:1 Weight ratio mixed grinding it is uniform after it is 10 hours dry in 120 DEG C, 4 hours are roasted then at 550 DEG C up to provided by the invention Phosphorus, metal-modified mesoporous silica-alumina materials.It is denoted as PM-4.

PM-4 has structure of similar to thin diaspore, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its elementary analytical chemistry group As 0.12Na₂O·61.2Al₂O₃·29.9SiO₂·3.0P₂O₅·1.5MnO₂·4.0ZnO；Specific surface area 355m²/ g, Kong Rong 0.80cm³/ g, average pore size 9.0nm.

Embodiment 5

(1) first by concentration be 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in a beaker, under stirring by concentration be 24wt.% Ammonium hydroxide is added, until system pH=9.5, keeping gelling temperature is 35 DEG C, collects metering plastic slurries；(2) and in stirring bar According to SiO under part₂: Al₂O₃It is 60gSiO that concentration is added into plastic slurries for the weight ratio of=1:2.7₂The waterglass of/L, heating It is aged 3 hours to 60 DEG C, obtains the first solid sediment；(3) first solid sediment is pressed into its sediment butt: NH₄Cl:H₂The weight ratio of O=1:0.8:12 exchanges 1 hour at 50 DEG C, and filtering washing obtains sodium oxide content and is lower than 0.3% Second solid sediment；(4) by the second solid sediment (filter cake) reslurry, and P is pressed₂O₅: MnO₂: TiO₂: the second solid is heavy Phosphoric acid, manganese chloride and titanium sulfate is added in sediment butt=0.022:0.023:0.017:1 weight ratio of starch, at 70 DEG C Stirring 2 hours, is obtained by filtration third solid sediment；Third solid sediment is pressed into its sediment butt: ZnO=1:0.05's Weight ratio is directly mixed with zinc nitrate, 10 hours dry in 120 DEG C after grinding uniformly, roasts 4 hours then at 600 DEG C up to this hair The phosphorus of bright offer, metal-modified active mesoporous silica-alumina material.It is denoted as PM-5.

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

Embodiment 6

It (1) is 90gAl with concentration₂O₃The Al of/L₂(SO₄)₃The ammonium hydroxide that solution and concentration are 25wt.% is reaction raw materials, is adopted With intermittent cocurrent plastic, it is vigorously stirred lower by Al₂(SO₄)₃Solution and ammonium hydroxide carry out mixing plastic, control 45 DEG C of gelling temperature, Metering plastic slurries are collected in plastic pH value=10.5；(2) under agitation according to SiO₂: Al₂O₃The weight ratio of=1:2.3 to It is 60gSiO that concentration is added in plastic slurries₂The waterglass of/L is warming up to 60 DEG C and is aged 3 hours, obtains the first solid sediment； (3) first solid sediment is pressed into its sediment butt: ammonium salt: H₂NH is added in the weight ratio of O=1:1:10₄Cl and go from Sub- water exchanges 1 hour at 65 DEG C, and filtering washing obtains the second solid sediment that sodium oxide content is lower than 0.3%；(4) it presses The sediment butt of second solid sediment:: H₂The weight ratio of O=1:8 is mixed with beating with water, and presses P₂O₅: the MgO: the second solid Phosphoric acid and magnesium chloride is added in sediment butt=0.016:0.021:1 weight ratio of sediment, and it is small that 2 are reacted at 60 DEG C When, obtain third solid sediment；Third solid sediment is pressed into its sediment butt: RE₂O₃=1:0.008 with it is mixed chlorinated Earth solution (the La in rare earth in terms of oxide₂O₃And CeO₂Weight ratio be 45:55) mix, grinding uniformly after in 120 DEG C Lower drying 15 hours roasts 4 hours then at 550 DEG C up to active mesoporous catalytic material provided by the invention.It is denoted as PM-6.

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

Embodiment 7

(1) first by concentration be 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in a beaker, and is warming up to 40 DEG C, is added with stirring Concentration is the ammonium hydroxide of 25wt.%, until system pH=9.5, collect metering plastic slurries；(2) and under agitation according to SiO₂: Al₂O₃It is 100gSiO that concentration is added into plastic slurries for the weight ratio of=1:1.7₂The waterglass of/L, be warming up to 60 DEG C it is old Change 2 hours, obtains the first solid sediment；(3) first solid sediment is pressed into its sediment butt: HCl:H₂O=1: The weight ratio of 0.08:12 exchanges 30 minutes at 55 DEG C, and it is heavy that filtering washing obtains second solid of the sodium oxide content lower than 0.3% Starch；(4) by the second solid sediment (filter cake) reslurry, and P is pressed₂O₅: the sediment butt of the second solid sediment= Phosphoric acid is added in the weight ratio of 0.045:1, react 1 hour at 60 DEG C, filters and simultaneously dries 15 hours at 120 DEG C, obtains the Three solid sediments；Third solid sediment is pressed into its sediment butt: MgO:RE₂O₃The weight ratio of=1:0.007:0.021 will Drying sample and magnesium chloride and the mixed chlorinated rare earth solution (La in rare earth in terms of oxide₂O₃And CeO₂Weight ratio be 45: 55) it mixes, it is 10 hours dry in 120 DEG C after grinding uniformly, 4 hours are roasted then at 600 DEG C up in activity provided by the invention Hole catalysis material.It is denoted as PM-7.

PM-7 has boehmite phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its elemental analysis Group becomes 0.11Na₂O·62.8Al₂O₃·29.6SiO₂·4.5P₂O₅·0.7MgO·2.1RE₂O₃；Specific surface area 418m²/ G, Kong Rong 1.06cm³/ g, average pore size 10.1nm.

Embodiment 8

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

PM-8 has typical boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its element Analytical chemistry group becomes 0.10Na₂O·70.2Al₂O₃·24.8SiO₂·1.5P₂O₅·3.1RE₂O₃；Specific surface area 435m²/ g, Hole holds 1.14cm³/ g, average pore size 10.5nm.

Embodiment 9

It (1) is 90gAl with concentration₂O₃The Al of/L₂(SO₄)₃Solution and concentration are 102gAl₂O₃/ L, Crater corrosion are 2.5 NaAlO₂Solution is reaction raw materials, first by Al₂(SO₄)₃Solution is placed in a beaker, and is warming up to 45 DEG C, is added with vigorous stirring NaAlO₂Solution, until system pH=10.0, collect plastic slurries；(2) under stiring according to SiO₂: Al₂O₃=1:2.3's It is 100gSiO that concentration is added into plastic slurries for weight ratio₂The waterglass of/L, and be aged 3 hours in 60 DEG C；Obtain the first solid Sediment；(3) first solid sediment is pressed into its sediment butt: NH₄Cl:H₂The weight ratio of O=1:0.5:10 is at 50 DEG C Lower exchange 30 minutes, repeated exchanged is primary, and filtering washing obtains the second solid sediment that sodium oxide content is lower than 0.3%, will Second solid sediment presses La₂O₃: the sediment butt of the second solid sediment: H₂The weight ratio and nitric acid of O=0.018:1:8 Lanthanum and water mix, and stir 1 hour at 70 DEG C, third solid sediment is obtained by filtration；Third solid sediment is pressed into its sediment Butt: P₂O₅The weight ratio of=1:0.060 is directly mixed with ammonium dihydrogen phosphate, 15 hours dry at 120 DEG C after grinding uniformly, 3 hours are roasted then at 550 DEG C up to provided by the invention phosphorous and rare earth active mesoporous catalytic material.It is denoted as PM-9.

PM-9 has typical boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its element Analytical chemistry group becomes 0.12Na₂O·68.5Al₂O₃·23.4SiO₂·6.0P₂O₅·1.7La₂O₃；Specific surface area 408m²/ g, Hole holds 1.10cm³/ g, average pore size 10.8nm.

Embodiment 10~12 is used to illustrate the system of the present invention gasification reactivity component used with XRD main phase peak shown in Fig. 1 Preparation Method.

Embodiment 10

Weigh 1500 grams in terms of butt kaolin, 400 grams of K₂CO₃With 100 grams of CaO, by three be mixed and added into right amount go from Sub- water makes slurry solid content 15%~50%, stirs at least 20 minutes, dry, then roasts 4 hours at 1000 DEG C, is made The component K-1 of gasification reactivity containing potassium, wherein K₂O content is 20%, CaO/K₂The molar ratio of O is 1/2.4, SiO₂/Al₂O₃Molar ratio There is XRD main phase shown in FIG. 1 peak for 2, K-1 (2 θ of main phase peak is 21 °, 29 °, 35 ° respectively).

Embodiment 11 and 12

The substance containing potassium as gasification reactivity component is prepared according to the method for embodiment 10, adjusts ingredient proportion, preparation contains Potassium gasification reactivity component K-2 and K-3, which specifically feed intake, is shown in Table 1.K-2 and K-3 has XRD feature main phase peak shown in FIG. 1 (main phase peak 2 θ are 21 °, 29 °, 35 ° respectively).

Table 1.

Embodiment 13~19 is used to illustrate the preparation method of catalyst composition used in the present invention.

Embodiment 13

By the high cracking activity mesopore material of the K-1 of substance containing potassium of in terms of butt 20 parts by weight and in terms of butt 5 parts by weight PAM-1 mixing, is added deionized water, is mixed with beating stirring 30 minutes, obtains the first slurries.By the kaolinite of 30 parts by weight of butt meter Soil is added deionized water and is beaten 30 minutes, then sequentially adds Aluminum sol, 10 weight of butt meter of 15 parts by weight of butt meter into slurries First Y-shaped molecular sieve containing rare earth of part and the third Y-shaped molecular sieve containing rare earth of 20 parts by weight are measured, mashing obtains the second slurry in 60 minutes Liquid mixes two kinds of slurries, and stirs at least 30 minutes, obtains the slurries that solid content is 30 weight %.Spray drying is made micro- Then ball catalyst composition roasts 2 hours at 550 DEG C.Obtained contact agent number is C1.

Embodiment 14

The boehmite of 30 parts by weight in terms of butt is mixed with beating with deionized water, and is added into obtained slurries Enter concentration be 36 weight % hydrochloric acid, acid-aluminum ratio (the 36 weight % hydrochloric acid with Al₂O₃The weight ratio of the boehmite of meter) It is 0.3, is warming up to 65 DEG C and is acidified 1 hour, obtain slurries.The Aluminum sol of in terms of butt 10 parts by weight is added to acidified It is mixed with beating in pseudoboehmite slurry 20 minutes, then by the second Y-shaped molecular sieve containing rare earth and 20 of in terms of butt 15 parts by weight The third Y-shaped molecular sieve containing rare earth of parts by weight is added, and is beaten 1 hour, obtains the first slurries.

By the high cracking activity mesopore material of the K-2 of substance containing potassium of in terms of butt 15 parts by weight and in terms of butt 10 parts by weight PAM-2 mixing, is added deionized water, is mixed with beating stirring 30 minutes, obtains the second slurries.Two kinds of slurries are mixed, and are stirred At least 30 minutes, obtain the slurries that solid content is 30 weight %.Microballoon catalyst composition is made in spray drying, then at 550 DEG C Roasting 2 hours.Obtained contact agent number is C2.

Embodiment 15~19

Catalyst composition is prepared according to the method for embodiment 13 and embodiment 14, ingredient proportion is adjusted, catalyzed combination is made Object C3~C7, specifically feeds intake and is shown in Table 2.

Wastage of the catalyst composition using potassium in hydrothermal experiment test composition, the condition of hydrothermal experiment are as follows: 100% 550 DEG C of processing 65h of vapor measure K in the sample composition of hydro-thermal front and back₂The weight content of O defines catalyst composition with retention rate The stability of middle potassium.The hot water potassium retention rate of catalyst composition C1~C7 is shown in Table 2.

Table 2.

As can be seen from Table 2, using the substance containing potassium with XRD main phase peak shown in Fig. 1 of method provided by the present invention preparation As the gasification reactivity component in catalyst composition, after hydro-thermal process the retention rate of potassium be apparently higher than using other containing potassium The retention rate of substance and alkaline-earth metal as potassium in the catalyst composition of gasification reactivity component.

Comparative example 1~3 is used to illustrate the preparation method of comparative catalyst.

Comparative example 1

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

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

Comparative example 2

Mesoporous silica-alumina material is prepared according to the embodiment 1 that patent CN1565733 is announced, is denoted as DB-2.

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

Comparative example 3

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

DB-3 has structure of similar to thin diaspore, the same Fig. 2 of X-ray diffraction spectrogram；Its elementary analytical chemistry group becomes 0.08Na₂O·77.2Al₂O₃·15.9SiO₂·1.5MgO·1.0TiO₂；Specific surface area 496m²/ g, Kong Rong 1.38cm³/ g is put down Equal aperture 11.2nm.

Comparative example 4

Referring to the preparation method of the mesoporous silica-alumina materials DB-2 of comparative example 2, difference is, substitutes it using sour exchange process In ammonium exchange process.I.e. by the intermediate sedimentation object of DB-2, the i.e. filtered sial sediment of aging, the weight of 1:10 is pressed with water Press sediment (butt) than being mixed with beating, then by HCl solution (concentration is 10 weight %): the weight ratio of HCl=1:0.12 is added Into above-mentioned slurries, is contacted 40 minutes at 55 DEG C, obtain mesoporous silica-alumina materials after filtering, drying and roasting, be denoted as DB-4.

Same Fig. 2 of X-ray diffraction spectrogram of DB-4；Its elemental analysis weight chemical composition is 0.11Na₂O·73.7Al₂O₃· 26.2SiO₂。

Comparative example 5~10

Catalyst composition is prepared according to the method for embodiment 13, ingredient proportion is adjusted, catalyst composition D1~D6 is made,

Specific inventory is shown in Table 3.

Table 3.

It can be seen that carbon monoxide-olefin polymeric after 100% vapor, 550 DEG C of processing 65h from the data of table 2 and table 3, when Use method preparation provided by the present invention that there is the urging as gasification reactivity component of substance containing potassium at XRD main phase peak shown in Fig. 1 The potassium retention rate of agent composition is high, hence it is evident that the potassium higher than other potassium-containing compounds as the catalyst composition of gasification reactivity component Retention rate.As it can be seen that the stability of the substance containing potassium with XRD main phase peak shown in Fig. 1 using method provided by the invention preparation Due to other potassium-containing compounds.

Test case 1

This test is for illustrating embodiment 13~19 and preparing the gasification performance for the catalyst composition that comparative example 5~10 provides And cracking performance.Respectively the catalyst composition of above-mentioned preparation under conditions of 790 DEG C, 100% vapor aging 8h, then will It is seated in fixed fluidized bed middle progress cracking and the gasification experiment that reserve is 210 grams.Cracking experiments condition are as follows: reaction temperature is 520 DEG C, weight (hourly) space velocity (WHSV) 20h-1, oil ratio 8, water-oil factor 0.35；Gasification experiment condition: gasification temperature is 720 DEG C, gas Agent is 100% vapor.The coke that catalyst composition after all gasifications keeps certain is retained on composition, usually > 0.3 Weight %, for example, 0.4~0.6 weight %.

The property of raw materials used oil is shown in Table 4, evaluation 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 up per hour, unit are kg/ (th)

Typically, catalyst composition gasification reactivity and after cracking on composition the intensity of making charcoal of coke with temperature Increase and increase, contain in gasifying agent oxygen intensity of making charcoal can be better than using 100% vapor as gasifying agent making charcoal it is strong Degree.From table 5 and table 6 as can be seen that cracking provided by the invention gasification catalyst composition (C1-C7) is relative to aforementioned background art In mentioned documents CN200910143623.3 (gasification temperature needs to be higher than 860 DEG C), can be in lower gasification At a temperature of obtain good gasification result, obtain higher intensity of making charcoal, density of hydrogen is higher.

Moreover, with compared to the catalyst prepared using comparative example 1~4, using active mesopore material provided by the invention The catalyst composition of preparation has better cracking performance, and coke selectivity is good, light oil yield (total receipts of gasoline and liquefied gas Rate) it is high.Compared with the catalyst composition (referring to D4) of existing gasification reactivity component preparation, prepared using method provided by the invention The gasification reactivity of catalyst composition that is prepared as gasification reactivity component of the substance containing potassium with XRD main phase shown in FIG. 1 peak Higher, intensity of making charcoal is higher；Under same gasification condition, the intensity of making charcoal of gasification reactivity and coke is considerably higher.

It can be seen that when containing active mesopore material and XRD master shown in FIG. 1 in the catalyst composition that invention provides simultaneously When the substance containing potassium at phase peak, gasification reactivity is higher, this may be to improve because the activity mesopore material improves the distribution of coke The utilization rate of gasification reactivity component, and then improve gasification performance.As it can be seen that adopting visible catalyst composition provided by the invention For gasify-process processing heavy petroleum hydrocarbon is advantageously implemented the efficient utilizations of petroleum resources, and energy conservation.

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

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

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

Claims (22)

1. The catalyst composition 1. a kind of cracking is gasified, by weight percentage, the catalyst composition includes: in 1%~50% Hole active material, 1%~40% gasification reactivity component, 1%~60% cracking activity constituent element, 0%~70% clay and 2%~97% heat-resistant inorganic oxide matrix, the mesoporous active materials have the phase structure of boehmite, with oxidation The anhydrous chemical expression of object poidometer is (0-0.2) Na₂O·(40-85)Al₂O₃·(10-55)SiO₂·(0.5-10) P₂O₅·(0.5-10)M_xO_y, wherein metal M is selected from Mg, periodic table of elements IIB, IIIB, IVB, VIIB race's element and group of the lanthanides One of rare earth element is a variety of, y be metal M formed oxide when highest valent state, and the numerical value of x and y make M and The chemical valence of O balances, and specific surface area is 200~500m²0.5~1.5cm of/g, Kong Rongwei³/ g, average pore size are 8~18nm,

   The cracking activity constituent element contains the Y type molecular sieve containing rare earth of 90-100 weight %, the Y type molecular sieve containing rare earth In the first Y type molecular sieve containing rare earth, the second Y type molecular sieve of Y type molecular sieve and third containing rare earth containing rare earth extremely Few one kind, wherein the preparation method of the described first Y type molecular sieve containing rare earth includes: under stiring, by the Y type containing rare earth point Son sieve is contacted with silicon tetrachloride, and the temperature of contact is 100-500 DEG C, and the time of stirring is 1-10 hours, the Y type containing rare earth The weight ratio of molecular sieve and silicon tetrachloride is 1:0.05-0.5；

   The silica alumina ratio of described second Y type molecular sieve containing rare earth is 5-30, and initial lattice constant is 2.430-2.460nm, with institute Stating the content of rare earth on the basis of the total amount of the second Y type molecular sieve containing rare earth and in terms of oxide is 10-20 weight %, and balance is brilliant The ratio of born of the same parents' constant and initial lattice constant is at least 0.985, wherein the X-ray diffraction analysis molecular sieve 2 θ be 12.43 ± 0.06 ° and 11.87 ± 0.06 ° of two diffraction peak intensity ratio I₁/I₂Greater than 1；

   It is 0.01-2N that the preparation method of Y type molecular sieve of the third containing rare earth, which includes: by super-stable Y molecular sieves and concentration, Acid solution is sufficiently mixed at 20-100 DEG C with the ratio of liquid-solid ratio 4-20, and washing, filtering, add after processing 10-300 minutes Rare-earth salt solution carries out rare earth ion exchanged, is successively washed, filtered and is dried after exchange；

   The gasification reactivity component includes that there are the objects containing potassium at main phase peak at 2 angles θ is 21 °, 29 ° and 35 ° in XRD diffracting spectrum Matter；

   It wherein, is that there are the substances containing potassium at main phase peak by with lower section at 21 °, 29 ° and 35 ° at 2 angles θ in the XRD diffracting spectrum Method obtains: potassium-containing compound, sial component and optional alkaline earth metal compound is beaten into wet feed, are then dried into siccative, It is obtained after roasting again, maturing temperature is 800 DEG C~1150 DEG C, 1~10h of calcining time.
2. 2. catalyst composition according to claim 1, wherein with the weight ratio meter of oxide in the mesoporous active materials Anhydrous chemical expression are as follows: (0.07-0.12) Na₂O·(47-72)Al₂O₃·(16.3-44)SiO₂·(1.5-6.3) P₂O₅·(1.7-8.6)M_xO_y。
3. 3. catalyst composition according to claim 1, wherein the specific surface area of the mesoporous active materials be 300~ 450m²0.7~1.2cm of/g, Kong Rongwei³/ g, average pore size are 10~15nm.
4. 4. catalyst composition according to claim 1, wherein IIB, IIIB, IVB, VIIB race metal be selected from Zn, Y, One of Ti and Mn or a variety of.
5. 5. catalyst composition according to claim 1, wherein IIB, IIIB, IVB, VIIB race metal is Ti and Mn, Mn and Zn, Ti and Zn, Ti and Y, Mn, Ti and Zn or Y, Mn and Zn.
6. 6. catalyst composition according to claim 1, wherein IIB, IIIB, IVB, VIIB race metal be Y or Y, Mn and Zn.
7. 7. catalyst composition described in any one of -6 according to claim 1, wherein the mesoporous active materials are according to following Method is prepared:

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

   (2) according to SiO₂: Al₂O₃=1:(1.0-7.5) weight ratio silicon source is added into the plastic slurries, in room temperature to 90 It is aged 1-5 hours at DEG C, obtains the first solid sediment；

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

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

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

   It is by step (2) resulting first by the process of first solid sediment and acid solution contact treatment in step (3) Solid sediment presses its sediment butt: acid: H₂O=1:(0.03-0.30): the weight ratio of (5-30) is in room temperature at 100 DEG C At least exchange 0.2 hour.
10. 10. catalyst composition according to claim 7, wherein ammonium salt described in step (3) be selected from ammonium chloride, ammonium sulfate, One of ammonium nitrate, ammonium carbonate and ammonium hydrogen carbonate are a variety of；Acid in the acid solution is in sulfuric acid, hydrochloric acid and nitric acid It is one or more.
11. 11. catalyst composition according to claim 7, wherein phosphorus source described in step (4) is selected from ammonium phosphate, phosphoric acid hydrogen One of diammonium, ammonium dihydrogen phosphate and phosphoric acid are a variety of.
12. 12. catalyst composition according to claim 7, wherein by second solid sediment and phosphorus in step (4) Source, metal M compound contact treatment process, selected from it is following a), b), c), d) one of process:

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

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

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

    D) second solid sediment is directly mixed with the compound of phosphorus source, metal M in proportion, 100 after grinding uniformly It is 10-20 hours dry at DEG C -150 DEG C.
13. 13. catalyst composition according to claim 7, wherein further include by institute after drying steps described in step (4) Desciccate is obtained to roast 1-4 hours at 500 DEG C -700 DEG C.
14. 14. catalyst composition according to claim 7, wherein the compound of metal M described in step (4) is water-soluble Compound.
15. 15. catalyst composition according to claim 7, wherein the compound of metal M described in step (4) is metal M's Nitrate, sulfate or chloride.
16. 16. catalyst composition according to claim 1, wherein the cracking activity constituent element also contains MFI structure molecule It sieves, with the anhydrous chemical composition expression formula of the molar ratio computing of oxide in the MFI structure molecular sieve are as follows: (0.01-0.25) RE₂O₃·(0.005-0.02)Na₂O·Al₂O₃·(0.2-1.0)P₂O₅·(35-120)SiO₂, the molecular sieve is to n-hexane and ring The absorption weight ratio of hexane is 4-5；On the basis of the total weight of the cracking activity constituent element, the cracking activity constituent element contains The MFI structure molecular sieve of the Y type molecular sieve and 0.1-10 weight % containing rare earth of 90-99.9 weight %.
17. 17. catalyst composition according to claim 1, wherein in the XRD diffracting spectrum 2 angles θ be 21 °, 29 ° and There are in the substance containing potassium at main phase peak at 35 °, the potassium content in terms of potassium oxide is the 8 weight % of weight %~40, with or without alkali Earth metal, remaining is sial component, alkaline earth oxide and potassium oxide molar ratio (0~1): 0.2, SiO₂/Al₂O₃Mole Than for 1:10~10:1.
18. 18. catalyst composition according to claim 17, wherein in the XRD diffracting spectrum 2 angles θ be 21 °, 29 ° and There are the 10 weight % of weight %~30 of potassium oxide content in the substance containing potassium at main phase peak, alkaline earth oxide and oxidations at 35 ° Potassium molar ratio 1:5~1:0.5, SiO₂/Al₂O₃Molar ratio be 1:3~3:1.
19. 19. catalyst composition according to claim 1, wherein the maturing temperature is 900 DEG C~1100 DEG C, when roasting Between be 2~8h.
20. 20. catalyst composition according to claim 1, wherein the sial group is selected from kaolin, montmorillonite, tired support One of stone, attapulgite, illite, sepiolite, diatomite are a variety of, or are kaolin, montmorillonite, rectorite, recessed One of convex stick stone, illite, sepiolite, diatomite, Aluminum sol, boehmite or a variety of and silica solution mixture； It or is one of kaolin, montmorillonite, rectorite, attapulgite, illite, sepiolite, diatomite, silica solution or a variety of With the mixture of Aluminum sol or boehmite.
21. 21. the preparation method of catalyst composition described in a kind of any one of claim 1 to 20, including by mesopore activity material Material, gasification reactivity component, cracking activity constituent element, clay, heat-resistant inorganic oxide matrix are mixed with beating, and are spray-dried and are roasted Step.
22. 22. a kind of cracking gasification process of petroleum hydrocarbon, being included in cracker will appoint in petroleum hydrocarbon and claim 1 to 20 The gasification catalyst composition haptoreaction of cracking described in meaning one, by the cracking gasification carbon monoxide-olefin polymeric and oil after reaction Gas separation, the step of the isolated cracking gasification catalyst composition that deposited coke and gasifying agent are contacted.