CN106179455B

CN106179455B - A kind of cracking gasification process of cracking gasification catalyst composition, preparation method and petroleum hydrocarbon

Info

Publication number: CN106179455B
Application number: CN201510212954.3A
Authority: CN
Inventors: 杨雪; 刘倩倩; 朱玉霞; 任飞; 张书红; 郑金玉; 罗一斌
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-04-29
Filing date: 2015-04-29
Publication date: 2019-05-21
Anticipated expiration: 2035-04-29
Also published as: CN106179455A

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% mesopore activity silicon phosphor-aluminum material, wherein, the mesopore activity silicon phosphor-aluminum material has the phase structure of boehmite, and the anhydrous chemical expression in terms of oxide weight is (0-0.2) Na₂O·(50‑86)Al₂O₃·(12‑50)SiO₂·(0.5‑10)P₂O₅, specific surface area is 200~600m²0.5~1.8mL/g of/g, Kong Rongwei, 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 catalyst composition is applied has preferable cracking activity and gasification conversion performance in heavy oil catalytic cracking-gasification group technology, especially while higher yield of gasoline can be obtained.

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 improve the prior art catalyst composition problem that gasification temperature is high in use or cracking performance is not high.

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% mesopore activity silicon phosphor-aluminum material, 1%~40% gasification Active component, 1%~60% cracking active component, 0%~70% clay and 2%~97% heat-resistant inorganic oxide base Matter, the mesopore activity silicon phosphor-aluminum material have the phase structure of boehmite, the anhydrous chemical in terms of oxide weight Expression formula is (0-0.2) Na₂O·(50-86)Al₂O₃·(12-50)SiO₂·(0.5-10)P₂O₅, specific surface area be 200~ 600m²0.5~1.8mL/g of/g, Kong Rongwei, 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 mesoporous silicon phosphor-aluminum material, gasification reactivity component, cracking active component, clay, heat-resistant inorganic oxide matrix are mixed and beaten The step of slurry, spray drying 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 mesopore activity silicon phosphor-aluminum material；It can be obtained under lower gasification temperature Higher intensity of making charcoal, obtains higher density of hydrogen.Mesopore activity silicon phosphor-aluminum material and gasification reactivity component are carried out effective Combination can greatly improve the coke gasification efficiency of catalyst；Catalyst composition of the invention is split for heavy petroleum hydrocarbon When change-gasification integral process, gasification result is good, and gasification temperature is low, and there is stronger petroleum hydrocarbon such as heavy oil conversion performance (to split Change performance), and increase yield of light oil, especially yield of gasoline using the synergistic effect of several molecular sieves and significantly improve.Especially Be with containing in XRD diffracting spectrum 2 angles θ be 21 °, 29 ° and 35 ° at there are the gasification reactivity components of the substance containing potassium at main phase peak It is used cooperatively, not only gasification result is good, and gasification temperature is low, and has stronger hydrocarbon oil conversion ability (cracking performance), and gasifies Loss of active component is few.

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

Detailed description of the invention

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

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

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

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

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% mesopore activity silicon phosphor-aluminum material, 1%~40% gasification reactivity component, 1%~60% cracking activity group Divide, 0%~70% clay and 2%~97% heat-resistant inorganic oxide matrix, the mesopore activity silicon phosphor-aluminum material have There are the phase structure (its X-ray diffracting spectrum is as shown in Figure 2) of boehmite, the anhydrous chemical table in terms of oxide weight It is (0-0.2) Na up to formula₂O·(50-86)Al₂O₃·(12-50)SiO₂·(0.5-10)P₂O₅, specific surface area be 200~ 600m²0.5~1.8mL/g of/g, Kong Rongwei, average pore size are 8~18nm,

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) 4-20, washed after processing 10-300 minutes, Filtering adds rare-earth salt solution and carries 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 mesopore activity silicon phosphor-aluminum material；It can be obtained under lower gasification temperature Higher intensity of making charcoal, obtains higher density of hydrogen.Mesopore activity silicon phosphor-aluminum material and gasification reactivity component are carried out effective Combination can greatly improve the coke gasification efficiency of catalyst；Catalyst composition of the invention is split for heavy petroleum hydrocarbon When change-gasification integral process, gasification result is good, and gasification temperature is low, has stronger petroleum hydrocarbon such as heavy oil conversion performance, and Increase yield of light oil, especially yield of gasoline using the synergistic effect of several molecular sieves to significantly improve.Especially with contain XRD There are the gasification reactivity components of the substance containing potassium at main phase peak to be used cooperatively at 2 angles θ is 21 °, 29 ° and 35 ° in diffracting spectrum, no Only gasification result is good, and 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 % mesopore activity silicon phosphor-aluminum materials of weight %~40, and the gasification of 5 weight of weight %~40 % is living Property component, the cracking active component of 5~50 weight %, the clay of 0 weight of weight %~60 % and 10 weight of weight %~70 % Heat-resistant inorganic oxide matrix.It is further preferred that the catalyst composition includes: the 5 weight % mesopore activity silicon phosphorus of weight %~30 Aluminum material, the gasification reactivity component of 10 weight of weight %~35 %, the cracking active component of 10~35 weight %, 5 weight %~ The heat-resistant inorganic oxide matrix of the clay of 45 weight % and 10 weight of weight %~40 %.

The above-mentioned cracking gasification catalyst composition provided according to the present invention, it is preferable that the mesopore activity silicon phosphor-aluminum material, (0-0.2) Na in terms of oxide weight ratio₂O·(50-86)Al₂O₃·(12-50)SiO₂·(0.5-10)P₂O_5。It is highly preferred that With the anhydrous chemical expression of the weight ratio meter of oxide in the mesopore activity silicon phosphor-aluminum material are as follows: (0.08-0.14) Na₂O·(50-84)Al₂O₃·(12.8-48)SiO₂·(0.8-4.9)P₂O₅。

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

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 second solid sediment and phosphorus source according to P₂O₅: the sediment butt of second solid sediment= (0.005-0.1): 1 weight ratio contact treatment, and by product of contact drying (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, It can be conventional use of various silicon sources in the preparation process of mesopore activity silicon phosphor-aluminum material, for example, aluminum nitrate, sulphur can be selected from One of sour aluminium and aluminium chloride are 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 mesopore activity silicon phosphor-aluminum material, for example, can selected from waterglass, sodium metasilicate, One of tetramethoxy-silicane, 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 mesopore activity silicon phosphor-aluminum material, although Source of aluminium, silicon source and aqueous slkali can respectively be properly selected from the above-mentioned material enumerated, however, the usually aluminium It is at least a kind of for the raw material containing sodium in source, aqueous slkali and silicon source, so that guarantee so to prepare is described without ion exchange Mesopore activity silicon phosphor-aluminum material has the active central hole structure of appropriate size.

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

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

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

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

The step of in above-mentioned steps (4) by second solid sediment and phosphorus source contact treatment, process can have It is a variety of, including obtained solid sediment is pressed into sediment (butt): H₂O=1:(5~20) weight ratio be mixed with beating with water, then Phosphorus source is added in above-mentioned slurries, in room temperature to contact treatment 0.2~5 hour, preferably 0.5~3 hour at 90 DEG C, filtering washing It is 10~20 hours dry at 100 DEG C~150 DEG C afterwards；Or the second solid sediment of gained is directly mixed with phosphorus source in proportion It closes, it is 10~20 hours dry at 100 DEG C~150 DEG C after grinding uniformly.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.

In the preparation method of above-mentioned mesoporous activated silica phosphor-aluminum material, step (4) it is optional can also include that will dry production The step of object is roasted, the condition of the roasting, which generally includes maturing temperature, to be 500-700 DEG C, and preferably calcining time is 1-4 hours.

The type of phosphorus source can be this field conventional selection, for example, can selected from ammonium phosphate, diammonium hydrogen phosphate, One of ammonium dihydrogen phosphate and phosphoric acid are a variety of.

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 One of alkali metal compound, alkaline earth metal compound, group VIII metal compound are a variety of.Wherein, the alkali metal Close object for example potassium hydroxide, potassium carbonate, potassium oxide, potassium nitrate, potassium sulfate, potassium chloride, potassium dihydrogen phosphate, potassium feldspar, green bean rock, Alunite, trachyte, potassium-bearing shale, phosphorus potassium ore, siltstone containing potassium at 2 angles θ are 21 °, 29 ° and 35 ° in XRD diffracting spectrum There are the substances containing potassium at main phase peak (substance has XRD main phase peak shown in Fig. 1), dolomite, olivine at place.When the gasification is lived When property component contains alkaline-earth metal, the compound of alkaline-earth metal, such as chloride, the nitric acid of alkaline-earth metal can be added One of inorganic alkali-earth metals salt such as salt, sulfate, phosphate is a variety of, and the alkaline-earth metal is beryllium, magnesium, calcium, strontium, barium One of or a variety of, preferably calcium and/or magnesium.It, can when the gasification reactivity component contains group VIII metal compound To be added the compound of group VIII metal, such as sulfate, nitrate, chloride, the oxide etc. of group VIII metal are inorganic One of group VIII 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, in the gasification reactivity component content of potassium be 2~ 100 weight %, the content of alkaline-earth metal are 0~98 weight %, and group VIII metal compounds content is 0~98%.Wherein, in order to Solve the problems, such as that potassium lost is serious, the active component containing potassium is preferably that the gasification reactivity component includes XRD diffracting spectrum In 2 angles θ be 21 °, 29 ° and 35 ° at there are the substance containing potassium at main phase peak (have Fig. 1 shown in XRD main phase peak substance containing potassium). Use in XRD diffracting spectrum at 2 angles θ is 21 °, 29 ° and 35 ° there are the substances containing potassium at main phase peak as gasification reactivity component, The gasification efficiency that can be further improved catalyst composition, reduces the loss of potassium, and the cracking that catalyst composition can be improved is living Property.

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

The above-mentioned catalyst composition provided according to the present invention is wherein 21 °, 29 ° and 35 ° at 2 angles θ in XRD diffracting spectrum There are the substance containing potassium at main phase peak (substances containing potassium with XRD main phase peak shown in Fig. 1) to be referred to existing common process at place It is prepared, it is preferable that be in the present invention that there are main phase peaks at 21 °, 29 ° and 35 ° at 2 angles θ in the XRD diffracting spectrum Substance containing potassium is to be prepared by the method comprising the following steps: potassium-containing compound and sial component and optional alkaline-earth metal Compound 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 mesopore activity silicon phosphor-aluminum material, cracking activity Other than component, gasification reactivity component, clay, also contain heat-resistant inorganic oxide matrix, the kind of the heat-resistant inorganic oxide Class can be heat-resistant inorganic oxide matrix commonly used in the art without particular/special requirement, preferably aluminium oxide, silica, titanium oxide, One of magnesia, zirconium oxide, thorium oxide and beryllium oxide and their predecessor are a variety of.The heat resistant inorganic oxidation One of object predecessor 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 mesopore activity silicon phosphor-aluminum material.Invention to the types of the metal traps without particular/special requirement, It can be the common metal traps of the component of the trapping pollution metal such as V, Ni, Fe, Ca, under preferable case, the metal is caught Integrate agent as the precursor of rare earth oxide and/or rare earth oxide.In more preferable situation, the precursor metal of the rare earth oxide is trapped Agent is one of rare earth chloride, carbonated rare earth and rare earth hydrate or a variety of.Wherein, rare earth element can for lanthanum, cerium, praseodymium, One of neodymium, promethium, samarium and europium are a variety of.The mode of entrance of metal agent for capturing can be in mesopore activity silicon phosphorus aluminium in the present invention When material, gasification reactivity component, clay are mixed with beating in the form of an ion or complex form introduce.If in carbon monoxide-olefin polymeric Metal traps can also be deposited on the inorganic oxide in advance by coprecipitation by middle introducing heat-resistant inorganic oxide In.The metal traps can be in same particle with mesopore activity silicon phosphor-aluminum material, 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 Mesoporous silicon phosphor-aluminum material, gasification reactivity component, cracking active component, clay, heat-resistant inorganic oxide matrix are mixed with beating, spraying The step of dry and 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 according to P₂O₅: the sediment butt of second solid sediment=(0.005-0.1): 1 weight ratio contact treatment, and contact is produced Object is dry, or roasts 1~4 hour 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) gasification reactivity containing potassium for obtaining the mesopore activity silicon phosphor-aluminum material obtained in step (1) and step (2) Component and clay, cracking active component, heat-resistant inorganic oxide matrix are mixed with beating, be then spray-dried, 400~ 2~10h is roasted at 800 DEG C；Wherein press dry basis, the mesopore activity silicon phosphor-aluminum material, gasification reactivity component, cracking The dosage of active component, clay and heat-resistant inorganic oxide matrix makes in obtained catalyst composition including 1%~50% The mesopore activity silicon phosphor-aluminum material, 1%~40% gasification reactivity component, 1%~60% cracking activity group Point, 0%~70% clay and 2%~97% heat-resistant inorganic oxide matrix.Wherein, the cracking activity group Y type molecular sieve containing rare earth of the member containing 90-100 weight %, the Y type molecular sieve containing rare earth are selected from the first Y containing rare earth At least one of the Y type molecular sieve of Y type molecular sieve and third containing rare earth of type molecular sieve, second 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；

Preferably, mesopore activity silicon phosphor-aluminum material obtained in above-mentioned steps (1), gasification reactivity component are mixed and is beaten Slurry obtains the first slurries, and by cracking active component, clay, binder is mixed with beating, and the second slurries is obtained, then by the first slurries It is mixed with beating with the second slurries, then is spray-dried, roasts 2~10h at 500~800 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 mesopore activity silicon phosphorus aluminium obtained in step (1) Material, gasification reactivity component are mixed with beating to obtain the first slurries, and by cracking active component, clay, binder is mixed with beating, and obtain the Then first slurries and the second slurries are mixed with beating by two slurries, then be spray-dried, 400~800 DEG C preferably 450~ 2~10h is roasted at 750 DEG C.

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 gasification catalyst composition preparation method provided by the invention, mesopore activity silicon phosphor-aluminum material, gasification are lived The sequence that property component, clay, heat-resistant inorganic oxide matrix are mixed with beating does not have particular/special requirement, for example, can be by the original Material prepares slurries respectively, then mixes prepared slurries；First mesopore activity silicon phosphor-aluminum material can be mixed with clay, so It is mixed with beating again with other components afterwards；Or be mixed with beating gasification reactivity component with clay, it then mixes and beats with other components again Slurry.

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 network when mesopore activity silicon phosphor-aluminum material, gasification reactivity component, cracking active component, clay are mixed with beating Solvate form introduces, and can also be introduced in the form of precipitating after by above-mentioned several component spray drying formings.If being catalyzed Heat-resistant inorganic oxide matrix is introduced in agent composition, in advance can also be deposited on metal traps by coprecipitation described In inorganic oxide.Under preferable case, based on butt, the content of the metal traps is no more than 20 weights of catalyst composition Measure %.The present invention, without particular/special requirement, can be the pollution metal such as trapping V, Ni, Fe, Ca to the type of the metal traps The common metal trapping agent of component, under preferable case, the metal traps are the predecessor of rare earth oxide and/or rare earth oxide Object.In more preferable situation, the precursor of the rare earth oxide be one of rare earth chloride, carbonated rare earth and rare earth hydrate or It is a variety of.Wherein, 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 mesopore activity silicon phosphor-aluminum material₂O、Al₂O₃、SiO₂、P₂O₅Content with x-ray fluorescence method measure (referring to " stone Oily chemical analysis method (RIPP experimental method) ", Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes).

Examples 1 to 6 is used to illustrate the preparation method of mesopore activity silicon phosphor-aluminum material used in the present invention.

Embodiment 1

It is 90gAl with concentration₂O₃The Al of/L₂(SO₄)₃Solution and concentration 102gAl₂O₃The NaAlO of/L, Crater corrosion 1.7₂Solution For reaction raw materials, cocurrent plastic simultaneously adjusts plastic pH=9.0, the quantitative plastic slurries of collection, according to SiO under stirring condition₂: Al₂O₃ It is 60gSiO that concentration is added into plastic slurries for the weight ratio of=1:1.5₂The waterglass of/L is warming up to 80 DEG C and is aged 1.5 hours, Obtain the first solid sediment；Use NH₄Cl solution presses the first solid sediment (butt): ammonium salt: H₂The weight ratio of O=1:1:12, Ion exchange is carried out to sial sediment at 60 DEG C and removes sodium ion, and is eluted with a large amount of deionized waters low to sodium oxide content In 0.3%, the second solid sediment is obtained；Then sodium oxide content is directly lower than to 0.3% the second solid sediment and phosphorus Acid presses P₂O₅: the mixing of the second solid sediment (butt)=0.008:1 weight ratio, it is 10 hours dry in 120 DEG C after grinding uniformly Up to mesoporous active materials provided by the invention.It is denoted as PAM-1.

PAM-1 has typical boehmite crystal phase structure, and X-ray diffraction spectrogram is as shown in Figure 2；Its elemental analysis Chemical composition is 0.14Na₂O·59.3Al₂O₃·39.1SiO₂·0.8P₂O₅；Specific surface area 320m²/ g, Kong Rong 0.78cm³/ g, Average pore size 9.7nm.

Embodiment 2

Preparation process is referring to embodiment 1.Difference is that the second solid sediment and phosphoric acid press P₂O₅: the second solid sediment The weight ratio of (butt)=0.02:1 mixes, 10 hours dry in 120 DEG C after grinding uniformly, and 2 hours are roasted at 550 DEG C i.e. Obtain mesoporous active materials provided by the invention.It is denoted as PAM-2.

PAM-2 has typical boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as Fig. 2 feature；Its elemental analysis Chemical composition is 0.13Na₂O·53.6Al₂O₃·43.7SiO₂·2.0P₂O₅；Specific surface area 307m²/ g, Kong Rong 0.91cm³/ g, Average pore size 11.8nm.

Embodiment 3

First by quantitative concentrations 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in a beaker, with vigorous stirring dropwise by ammonium hydroxide It is added, until system pH=10.5, gelling temperature is 40 DEG C；Under agitation according to SiO₂: Al₂O₃The weight ratio of=1:1.1 Concentration 60gSiO is added into plastic slurries₂The waterglass of/L is warming up to 70 DEG C and is aged 3 hours, obtains the first solid sediment； The first solid sediment of gained is pressed into its sediment (butt): HCl:H₂The weight ratio of O=1:0.08:10 exchanges 30 at 60 DEG C Minute, filtering washing makes sodium oxide content lower than 0.3%, obtains the second solid sediment；Then the second solid of gained is precipitated Object presses its sediment (butt): H₂The weight ratio of O=1:8 is mixed with beating with water, and presses P₂O₅: material butt=0.016:1 weight Amount is reacted 2 hours at 60 DEG C, is provided up to the present invention within dry 10 hours at 120 DEG C after filtering washing than phosphoric acid is added Mesoporous active materials.It is denoted as PAM-3.

PAM-3 has typical boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as Fig. 2 feature；Its elemental analysis Chemical composition is 0.12Na₂O·50.2Al₂O₃·48.0SiO₂·1.5P₂O₅；Specific surface area 289m²/ g, Kong Rong 0.64cm³/ g, Average pore size 8.8nm.

Embodiment 4

Preparation process is referring to embodiment 3.Difference is, wherein the second solid sediment and phosphoric acid press P₂O₅: the second solid is heavy Sediment (butt)=0.05:1 weight ratio of starch mixes, and reacts 1 hour at 80 DEG C, and filtering washes and in 120 DEG C of dryings 10 hours, 2 hours are roasted at 600 DEG C up to mesoporous active materials provided by the invention.It is denoted as PAM-4.

PAM-4 has typical boehmite crystal phase structure, and X-ray diffraction spectrogram is as shown in Figure 2；Its elemental analysis Chemical composition is 0.11Na₂O·51.3Al₂O₃·43.2SiO₂·4.9P₂O₅；Specific surface area 364m²/ g, Kong Rong 1.03cm³/ g, Average pore size 11.3nm.

Embodiment 5

With concentration 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration 102gAl₂O₃The NaAlO of/L, Crater corrosion 2.5₂Solution is Reaction raw materials, cocurrent plastic simultaneously adjust plastic pH=9.5, collect a certain amount of plastic slurries, according to SiO under stirring condition₂: Al₂O₃ It is 60gSiO that concentration is added into plastic slurries for the weight ratio of=1:5.7₂The waterglass of/L is warming up to 70 DEG C and is aged 2 hours；With NH₄Cl solution presses sediment (butt): ammonium salt: H₂The weight ratio of O=1:0.8:15, at 60 DEG C to sial sediment carry out from Son exchange removes sodium ion, and exchange repeats twice, carries out 0.5 hour every time, until sodium oxide content is lower than 0.3%；Then Obtained solid sediment is pressed into sediment (butt): H₂The weight ratio of O=1:8 is mixed with beating with water, and presses P₂O₅: material butt Diammonium hydrogen phosphate is added in the weight ratio of=0.022:1, reacts 1 hour at 70 DEG C, after filtering washing dry 10 at 120 DEG C Hour is up to active mesopore material provided by the invention.It is denoted as PAM-5.

PAM-5 has boehmite phase structure, and X-ray diffraction spectrogram is as shown in Figure 2；Its elementary analytical chemistry group As 0.11Na₂O·84.0Al₂O₃·12.8SiO₂·2.1P₂O₅；Specific surface area 501m²/ g, Kong Rong 1.51cm³/ g, average hole Diameter 12.1nm.

Embodiment 6

First by quantitative concentrations 90gAl₂O₃The Al of/L₂(SO₄)₃Solution is placed in a beaker, with vigorous stirring dropwise by ammonium hydroxide It is added, until system pH=9.5, gelling temperature is 40 DEG C；According to SiO under stirring condition₂: Al₂O₃The weight ratio of=1:1.9 to The waterglass that concentration is 60gSiO2/L is added in plastic slurries, is warming up to 60 DEG C and is aged 3 hours；Obtained solid sediment is pressed Sediment (butt): the weight ratio of HCl:H2O=1:0.06:10 exchanges 30 minutes at 60 DEG C, and filtering washing contains sodium oxide molybdena Amount is lower than 0.3%；Then obtained solid sediment is pressed into sediment (butt): H₂The weight ratio of O=1:8 is mixed with beating with water, And press P₂O₅: diammonium hydrogen phosphate is added in material butt=0.046:1 weight ratio, reacts 1 hour at 60 DEG C, filtering washing It is 10 hours dry at 120 DEG C afterwards, 2 hours are roasted at 550 DEG C up to mesopore activity silicon phosphor-aluminum material provided by the invention. It is denoted as PAM-6.

PAM-6 has boehmite crystal phase structure, and X-ray diffraction spectrogram is the same as feature shown in Fig. 2；Its elemental analysis Group becomes 0.08Na₂O·64.8Al₂O₃·30.5SiO₂·4.5P₂O₅；Specific surface area 392m²/ g, Kong Rong 1.25cm³/ g is put down Equal aperture 12.8nm.

Embodiment 7,8 is used to illustrate the preparation side of the present invention gasification reactivity component used with XRD main phase peak shown in Fig. 1 Method.

Embodiment 7

Weigh 1490 grams in terms of butt kaolin, 450 grams of K₂O, 46 grams of CaO and 14 gram of Na₂O is mixed and added into four suitable Deionized water is measured, makes slurry solid content 15%~50%, stirs at least 30 minutes, it is dry, then roasting 4 is small at 1050 DEG C When, the component of gasification reactivity containing potassium G-1 is made, wherein K₂O content is 22.5%, SiO₂/Al₂O₃Molar ratio be 2, G-1 have figure XRD main phase peak shown in 1 (2 θ of main phase peak is 21 °, 29 °, 35 ° respectively).

Embodiment 8

According to the method preparation substance containing potassium of embodiment 5 as gasification reactivity component, ingredient proportion is adjusted, in terms of butt The component of gasification reactivity containing potassium G-2 is made in 1470 grams of kaolin, 450 grams of KOH and 80 gram of MgO.G-2 has XRD shown in FIG. 1 special It levies main phase peak (2 θ of main phase peak is 21 °, 29 °, 35 ° respectively).

Embodiment 9~15 is used to illustrate the preparation method of catalyst composition used in the present invention.

Embodiment 9

The boehmite of 2 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 0.35, is warming up to 65 DEG C and is acidified 1 hour, obtain slurries.By 19 parts in terms of butt of kaolin (Suzhou carclazyte), in terms of butt The Aluminum sol of 13 parts by weight, which is added in acidified pseudoboehmite slurry, to be mixed with beating 30 minutes, then will in terms of butt 15 Mashing 1 hour is added in the Y type molecular sieve of Y type molecular sieve and 20 parts by weight thirds of the first of parts by weight containing rare earth containing rare earth, obtains To the first slurries.

By the mesopore activity silicon phosphor-aluminum material of the G-1 of substance containing potassium of in terms of butt 23 parts by weight and in terms of butt 8 parts by weight PAM-1 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 C1.

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 68h 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~C9 is shown in Table 2.

Embodiment 10~15

Catalyst composition is prepared according to the method for embodiment 9, ingredient proportion is adjusted, catalyst composition C2~C7 is made, is had Body, which feeds intake, is shown in Table 1.

Table 1

Comparative example 1

This comparative example illustrates the silica-alumina material that structure of similar to thin diaspore is prepared according to process described in CN1565733A.

With concentration 90gAl₂O₃The Al of/L₂(SO₄)₃Solution and concentration 102gAl₂O₃The NaAlO of/L, Crater corrosion 1.7₂Solution is Reaction raw materials, cocurrent plastic simultaneously adjust plastic pH=9.0, plastic slurries are collected, according to SiO under the conditions of stirring is lower₂: Al₂O₃=1: It is 60gSiO that concentration is added into plastic slurries for 1.3 weight ratio₂The waterglass of/L is warming up to 70 DEG C and is aged 2 hours, obtains the One solid sediment；Use NH₄Cl solution presses the first solid sediment (butt): ammonium salt: H₂The weight ratio of O=1:0.8:15,60 Ion exchange is carried out to sial sediment at DEG C and removes sodium ion, exchange repeats twice, carries out 0.5 hour every time, until oxygen Change sodium content and be lower than 0.3%, dries 10 hours at 120 DEG C up to mesoporous silica-alumina material described in CN1565733A.Note For DB-1.

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

Comparative example 2

This comparative example illustrates the mistake of the contrast sample obtained with conventional boehmite and silicon source and phosphorus source reaction modifying Journey.

By a certain amount of industrial boehmite (Shandong Aluminum Plant, Al₂O₃Content 65wt%) it is mixed by the weight ratio and water of 1:15 Close mashing, the dilute hydrochloric acid (concentration 30wt.%) of metering is added in stirring after 30 minutes, continue stirring be added after ten minutes it is quantitative Tetraethoxy-silicane is warming up to 80 DEG C and reacts 4 hours, and the phosphoric acid for adding metering continues stirring 1 hour, then does at 120 DEG C Dry 10 hours, 4 hours contrast samples for obtaining that there is structure of similar to thin diaspore are roasted at 550 DEG C.It is denoted as DB-2.

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

Comparative example 3

Referring to the preparation method of comparative example 1, ammonium exchange process therein is only substituted using sour exchange process.I.e. by DB-1 Intermediate sedimentation object, i.e. the filtered sial sediment of aging is mixed with beating with water by the weight ratio of 1:10, then by HCl solution (concentration is 10 weight %) is by sediment (butt): the weight ratio of HCl=1:0.12 is added in above-mentioned slurries, is connect at 55 DEG C Touching 40 minutes, mesoporous silica-alumina material is obtained after filtering, drying and roasting, is denoted as DB-3.

The feature of the X-ray diffraction spectral line with Fig. 2 of DB-3；Its elemental analysis weight chemical composition is 0.14Na₂O·54.7Al₂O₃·44.5SiO₂。

Comparative example 4~8

According to the catalyst composition preparation method of embodiment 7, preparation comparison catalyst composition D3~D7, specific inventory is shown in Table 2.

Table 2

From table 2 it can be seen that carbon monoxide-olefin polymeric is after 100% vapor, 550 DEG C of processing 68h, it is of the invention when using Provided method preparation has carbon monoxide-olefin polymeric of the substance containing potassium at XRD main phase peak shown in Fig. 1 as gasification reactivity component Potassium retention rate it is high, hence it is evident that the potassium retention rate higher than other potassium-containing compounds as the catalyst composition of gasification reactivity component.It can See, the stability of the substance containing potassium with XRD main phase peak shown in Fig. 1 prepared using method provided by the invention is since other contain Potassium compound.

Test case 1

The gasification performance of catalyst composition of this test for illustrating embodiment 9~15 and the offer of comparative example 4~8 and cracking Performance.Respectively the catalyst composition of above-mentioned preparation under conditions of 800 DEG C, 100% vapor aging 17h, then filled Fill out the fixed fluidized bed middle progress cracking in reserve for 9 grams and gasification experiment.Cracking experiments condition are as follows: reaction temperature be 520 DEG C, Weight (hourly) space velocity (WHSV) is 16h^-1, oil ratio 8, fluidized gas and stripping gas are nitrogen；Gasification experiment condition: gasification temperature is 710 DEG C, Gasifying 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 3, evaluation condition and the results are shown in Table 4 and table 5.

Table 3

Table 4

Table 5

In table 4 and table 5:

Make charcoal intensity: the coke quality that carbon monoxide-olefin polymeric reserve per ton is burnt 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 4 and table 5 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, gasification product density of hydrogen with higher.

Compared to the catalyst using comparative example 1-3 preparation, using mesopore activity silicon phosphor-aluminum material system provided by the invention Standby catalyst composition has better heavy oil conversion performance (cracking performance), light oil yield (total recovery of gasoline and liquefied gas) Height, yield of gasoline are high.It in comparative example 4-8, is compared by catalyst composition prepared by gasification reactivity component, is provided using the present invention Method preparation the catalyst composition that is prepared as gasification reactivity component of the substance containing potassium with XRD main phase shown in FIG. 1 peak Gasification reactivity it is higher, intensity of making charcoal is higher；Under same gasification condition, gasification reactivity and coke make charcoal intensity obviously more It is high.Such as it gasification reactivity of the composition C1~C7 provided by the invention under 710 DEG C, 100% water vapor conditions and makes charcoal intensity 860 DEG C can be reached, the gasification result of 80% vapor contains mesopore activity silicon when inventing simultaneously in the catalyst composition provided When the substance containing potassium at phosphor-aluminum material and XRD main phase shown in FIG. 1 peak, gasification reactivity is higher, this may be because of mesopore activity silicon Phosphor-aluminum material improves the distribution of coke, improves the utilization rate of gasification reactivity component, and then improves gasification performance.

As it can be seen that using catalyst composition provided by the invention for gasify-process processing heavy petroleum hydrocarbon be conducive to Realize the efficient utilization of petroleum resources, yield of light oil is high, and yield of gasoline is high, 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

The catalyst composition 1. a kind of cracking is gasified, by weight percentage, the catalyst composition includes: in 1%~50% Hole activated silica phosphor-aluminum material, 1%~40% gasification reactivity component, 1%~60% cracking active component, 0%~70% Clay and 2%~97% heat-resistant inorganic oxide matrix, the mesopore activity silicon phosphor-aluminum material has boehmite Phase structure, the anhydrous chemical expression in terms of oxide weight are (0-0.2) Na₂O·(50-86)Al₂O₃·(12-50) SiO₂·(0.5-10)P₂O₅, specific surface area is 200~600m²0.5~1.8mL/g of/g, Kong Rongwei, average pore size be 8~ 18nm；The gasification reactivity component includes the compound of potassium, with or without alkaline earth metal compound, with or without group VIII metal Compound；The gasification reactivity component further includes that there are main phase peaks at 2 angles θ is 21 °, 29 ° and 35 ° in XRD diffracting spectrum Substance containing potassium at 2 angles θ is that there are the substances containing potassium at main phase peak by with lower section at 21 °, 29 ° and 35 ° 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；

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.
2. catalyst composition according to claim 1, wherein the specific surface area of the mesopore activity silicon phosphor-aluminum material is 250-550m²/ g, Kong Rongwei 0.6-1.6cm³/ g, average pore size 9-15nm.
3. catalyst composition according to claim 1 or 2, wherein the mesopore activity silicon phosphor-aluminum material is according to lower section Method is prepared:

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

(2) according to SiO₂: Al₂O₃=1:(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 second solid sediment and phosphorus source according to P₂O₅: the sediment butt of second solid sediment= (0.005-0.1): 1 weight ratio contact treatment, and product of contact is dry.
4. catalyst composition according to claim 3, 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.
5. catalyst composition according to claim 3, 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.
6. catalyst composition according to claim 3, 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.
7. catalyst composition according to claim 3, wherein phosphorus source described in step (4) is selected from ammonium phosphate, phosphoric acid hydrogen two One of ammonium, ammonium dihydrogen phosphate and phosphoric acid are a variety of.
8. catalyst composition according to claim 3, wherein further include by gained after drying steps described in step (4) Desciccate roasts 1-4 hours at 500 DEG C -700 DEG C.
9. catalyst composition according to claim 1, wherein the cracking activity constituent element also contains MFI structure molecular sieve, 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 hexamethylene Absorption weight ratio is 4-5；On the basis of the total weight of the cracking activity constituent element, the cracking activity constituent element contains 90-99.9 The MFI structure molecular sieve of the Y type molecular sieve and 0.1-10 weight % containing rare earth of weight %.
10. catalyst composition according to claim 1, wherein the alkaline-earth metal is beryllium, magnesium, calcium, strontium, one in barium Kind is a variety of, and the group VIII metal is Fe and/or Ni.
11. catalyst composition according to claim 1, wherein on the basis of the weight of the gasification reactivity component, with oxygen Compound poidometer, the content of potassium is 2~100% in the gasification reactivity component, and the content of alkaline-earth metal is 0-98 weight %, The content of group VIII metal is 0-98 weight %.
12. 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.
13. catalyst composition according to claim 12, 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.
14. catalyst composition according to claim 1, wherein the maturing temperature is 900 DEG C~1100 DEG C, when roasting Between be 2~8h.
15. 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.
16. the preparation method of catalyst composition described in a kind of any one of claim 1 to 15, including by mesopore activity silicon phosphorus Aluminum material, gasification reactivity component, cracking active component, clay, heat-resistant inorganic oxide matrix are mixed with beating, and are spray-dried and are roasted The step of burning.
17. a kind of cracking gasification process of petroleum hydrocarbon, being included in cracker will appoint in petroleum hydrocarbon and claim 1 to 15 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.