CN103506152A - Catalyst for treating hydrotreated raw oil - Google Patents
Catalyst for treating hydrotreated raw oil Download PDFInfo
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- CN103506152A CN103506152A CN201210213656.2A CN201210213656A CN103506152A CN 103506152 A CN103506152 A CN 103506152A CN 201210213656 A CN201210213656 A CN 201210213656A CN 103506152 A CN103506152 A CN 103506152A
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Abstract
The invention discloses a catalyst for treating hydrotreated raw oil. The catalyst mainly comprises 5-35wt% of heat-resistant inorganic oxides, 0-65wt% of clay, 5-50wt% of modified meso-porous aluminum silicon materials and 15-60wt% of molecular sieve mixtures, wherein the molecular sieve mixtures comprise beta molecular sieves and MFI (Melt Flow Index) molecular sieves; measured by taking the weight of the catalyst as a reference, the content of the beta molecular sieves is 10-55wt%, and the content of the MFI molecular sieves is 5-25wt%; the weight ratio of the beta molecular sieves to the modified meso-porous materials is (1:5)-(5:1); the weight ratio of the beta molecular sieves to the MFI molecular sieves is not lower than 1. The catalyst is used for converting hydrotreated raw oil and has relatively high propylene and isobutene yields.
Description
Technical field
The present invention relates to a kind of catalyst of processing hydrotreated feed oil, relate to furtherly a kind of catalytic cracking catalyst that utilizes hydrotreated feed oil to produce propylene and butylene.
Background technology
Along with oil property variation increasingly, heavy raw oil hydrotreatment is more and more come into one's own, but hydrotreatment is unsuitable for producing the low-carbon alkenes such as propylene, butylene, therefore utilize hydrotreated feed oil to produce propylene for raw material catalytic cracking and gradually come into one's own.Different from conventional fcc raw material, it is H/C ratio that hydrotreated feed oil has higher saturation degree, has more cycloalkane and with the mononuclear aromatics of naphthenic ring.It is often not high that the oil of hydrotreatment at present transforms the productivity of low carbon olefin hydrocarbon such as propylene, butylene, do not have to find for hydrogenating materials oil, to transform the catalyst of producing low-carbon alkene exploitation specially.
CN101134172B discloses a kind of catalytic cracking catalyst, it contains 1%～60% zeolite mixture, 5%～99% heat-resistant inorganic oxide and 0～70% clay, take zeolite mixture gross weight as benchmark, in described zeolite mixture, contain 1%～75% the Β zeolite by phosphorus and transition metal M modification, 25%～99% the zeolite with MFI structure and 0～74% large pore zeolite.This catalyst can be used for hydrocarbons catalytic conversion process and produces low-carbon alkene.But this patent does not relate to hydrotreated feed oil transforms production low-carbon alkene, and it is not high for hydrotreatment oil conversion propylene and isobutene productive rate.
CN200710179420 discloses a kind of Cracking catalyst of being made by the mesopore zeolite that contains dehydrogenation component, its dehydrogenation component is for adopting one or more in palladium, platinum, iron-cobalt-nickel, chromium, molybdenum, tungsten, vanadium, and mesopore zeolite is ZSM-5 or the ZRP Series Molecules sieve with MFI structure.This catalyst is mainly to produce for conventional fcc raw material the catalyst that low-carbon alkene is developed, and does not relate to and improves propylene and the butylene productive rate that hydrotreatment oil transforms, and it is not high for hydrotreatment oil conversion propylene and isobutene productive rate.
Summary of the invention
The present inventor finds under study for action, naphthenic ring for example in hydrotreatment oil by aromatic rings, through the saturated naphthenic ring obtaining of hydrogenation, there is open loop cracking reaction in some in catalytic cracking process, transform and produce low-carbon alkene, some is fragrant fluidized dehydrogenation formation aromatic rings and other product again, this causes mononuclear aromatics virtueization formation dicyclo and above aromatic hydrocarbons or the heavier product of formation again on the one hand, make product complex distribution, institute's hydrogen supply may, with negative hydrogen ion form saturation of olefins, cause productivity of low carbon olefin hydrocarbon and optionally reduce on the other hand.Prior art is normally oily for non-hydrogenating materials for the production of the catalyst of low-carbon alkene, does not consider that the transformation characteristics of hydrotreated feed oil is developed or optimizes, and when transforming for hydrogenating materials, productivity of low carbon olefin hydrocarbon is not high.Therefore, the present inventor, on the basis of lot of experiments research, has proposed exploitation and for hydrogenating materials oil, has transformed the technical thought of the catalyst of producing low-carbon alkene.
The technical problem to be solved in the present invention is to provide a kind of catalyst that transforms production propylene and butylene for hydrotreatment oil, this catalyst, for transforming containing cycloalkane and/or with the more hydrotreatment oil of the mononuclear aromatics of naphthenic ring, has higher propylene and isobutene yield.The other technical problem that the present invention will solve is to provide the preparation method of described catalyst.
The invention provides a kind of catalyst transforming for hydrotreatment oil, take catalyst weight as benchmark, mainly comprise modification mesoporous silica-alumina materials in butt 5-50 % by weight, in the molecular sieve mixture of butt 15-60 % by weight, in the heat-resistant inorganic oxide of oxide 5-35 % by weight with in the clay of butt 0-65%; Wherein said molecular sieve mixture comprises beta molecular sieve and MFI molecular sieve, and described beta molecular sieve is with the ratio of the weight of described MFI molecular sieve for being not less than 1, and the weight ratio of described beta molecular sieve and described modified mesoporous material is 1:5-5:1.
Conventionally, the weight of catalyst of take is benchmark, and in described catalyst, the content of beta molecular sieve is 10-55 % by weight, and the content of described MFI molecular sieve is 2-25 % by weight.
The weight ratio of described beta molecular sieve and MFI molecular sieve is not less than 1, is generally 1:1-12:1.
The present invention also provides a kind of preparation method of the catalyst transforming for hydrotreatment oil provided by the present invention, comprise forming and comprise described molecular sieve mixture, modification mesoporous silica-alumina materials, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide precursor, contain or catalyst slurry not argillaceous spray-dired step.
Catalyst provided by the invention is produced low-carbon alkene for the cracking of hydrotreated feed oil, has higher propylene and butylene productive rate, has higher isobutene productive rate, and in liquefied gas, the concentration of propylene and isobutene is high, and in gasoline fraction aromatic hydrocarbons, BTX ratio is higher; In diesel oil and heavy oil, can also have lower polycyclic aromatic hydrocarbons (PAH) content and paraffinicity, thereby be conducive to obtain the low and higher diesel oil of Cetane number of pour point, total aromatics yield is lower.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the modification mesoporous silica-alumina materials of embodiment 1 preparation.
The specific embodiment
In the present invention, low-carbon alkene refers in particular to C3-C4 alkene; Light gasoline fraction, refers to that initial boiling point is 70-85, and the end point of distillation is the gasoline fraction of 140-150 ℃.Light aromatic hydrocarbons refers to benzene, toluene, ethylbenzene and dimethylbenzene, with BTX, represents benzene, toluene and dimethylbenzene.
Catalyst provided by the invention, take total catalyst weight as benchmark, comprising beta molecular sieve and thering is the Clay composition of the molecular sieve mixture of MFI structure molecular screen, the heat-resistant inorganic oxide of 5-35 % by weight and 0-65 % by weight by the modification mesoporous silica-alumina materials of 5-50 % by weight, 15-60 % by weight; Under optimum condition, the content of described modification mesoporous silica-alumina materials is 5-40 % by weight, the content of molecular sieve mixture is 15-50 % by weight, the content of heat-resistant inorganic oxide is 5-30 % by weight, the content of clay is 0-55 % by weight, the content of described beta molecular sieve is 10-45 % by weight, is preferably 15-40 % by weight, and the content of described MFI molecular sieve is 5-22 % by weight.The weight ratio of described beta molecular sieve and described MFI molecular sieve (also referred to as the molecular sieve with MFI structure) is preferably 2:1-9:1, more preferably 3:1-6:1.The weight ratio of described beta molecular sieve and described modified mesoporous material is 1:5-5:1, is preferably 1:3-2:1.For example, described catalyst can be by the beta molecular sieve of 12-30 % by weight, the clay of the MFI molecular sieve of 3-15 % by weight, 15-45 % by weight, the modification mesoporous silica-alumina materials of the binding agent of 15-35 % by weight and 5-25 % by weight form.
Described modification mesoporous silica-alumina materials is the mesoporous silica-alumina materials through exchange sodium, and it is (0-0.3) Na that described modification mesoporous silica-alumina materials be take the anhydrous expression formula of oxide weight
2o (40-90) Al
2o
3(10-60) SiO
2.Its specific area 200-400m
2/ g, pore volume is that 0.5-2.0ml/g is preferably 1.0-2.0ml/g, and average pore size is that 5-25nm is preferably 8-15nm, and most probable aperture is 5-15nm, preferably 5-10nm.Described modification mesoporous silica-alumina materials preferably has boehmite crystal phase structure.
Modification mesoporous silica-alumina materials of the present invention can obtain according to existing method, for example according to the disclosed method of CN1854258A, obtain, the method is by CN1565733A(mesoporous silica-alumina materials or the prepared mesoporous silica-alumina materials of embodiment described in CN1565733A claim 1-10 for example) said mesoporous silica-alumina materials obtains after acidification.The condition of acidification is, under room temperature to 80 ℃, 0.1～0.3 sour aluminum ratio condition, mesoporous silica-alumina materials is contacted to 0.5～3 hour with inorganic acid.Described inorganic acid is one or more in hydrochloric acid, nitric acid and sulfuric acid for example.
Preferred, described modification mesoporous silica-alumina materials is obtained by the method comprising the following steps:
Mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour common 0.2-10 hour at room temperature to 100 ℃, make sodium oxide content in described mesoporous silica-alumina materials not higher than 0.2 % by weight, wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:5-30:0.03-0.3.The mesoporous silica-alumina materials that the method obtains has higher propylene and butylene yield.The weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is preferably 1:(6-20): (0.05-0.2), 1:(8-15 more preferably): (0.07-0.16).In the present invention, in the weight ratio of the mesoporous silica-alumina materials without ion-exchange, water and inorganic acid, the weight of the described mesoporous silica-alumina materials without ion-exchange is in its butt; The weight of described inorganic acid refers to the weight of inorganic acid composition, and for example, when described inorganic acid adds fashionablely with the form of aqueous hydrochloric acid solution, the weight of described inorganic acid refers to the weight of HCl in aqueous hydrochloric acid solution.In the process of the described mesoporous silica-alumina materials of preparation, the condition that described slurries are contacted with inorganic acid can be conventional ion-exchange condition.Under preferable case, the temperature of described contact is 30-80 ℃, more preferably 40-70 ℃; The time of described contact is 0.2-2 hour, more preferably 0.3-1.5 hour.
In the present invention, in the weight ratio of the mesoporous silica-alumina materials without ion-exchange, water and inorganic acid, the described mesoporous silica-alumina materials weight without ion-exchange is the weight in butt.In the present invention, the weight in butt refers to the weight of roasting after 1 hour under the condition of approximately 800 ℃.
In the present invention, described inorganic acid can be the inorganic acid of various routines, for example can be for being selected from one or more in sulfuric acid, hydrochloric acid and nitric acid.
In the process of the described modification mesoporous silica-alumina materials of preparation, the mode that described slurries are contacted with inorganic acid does not have special requirement, inorganic acid can be joined in described slurries and mix contact, also described slurries can be added and in inorganic acid, mix contact.Under preferable case, inorganic acid is joined and in described slurries, mixes contact.
In the present invention, described mesoporous silica-alumina materials preferably has boehmite crystal phase structure, and its X-ray diffracting spectrum as shown in Figure 1.And, described modification mesoporous silica-alumina materials, the anhydrous chemical expression of oxide weight of take is (0-0.2) Na
2o(40-90) Al
2o
3(10-60) SiO
2.
In the process of the described modification mesoporous silica-alumina materials of preparation, the described mesoporous silica-alumina materials without ion-exchange can be the conventional various mesoporous silica-alumina materials without any ion-exchange in this area.The described mesoporous silica-alumina materials without ion-exchange can prepare according to conventional method, and its preparation method for example can comprise: Jiang Lv source and aqueous slkali at room temperature to 85 ℃ in and plastic, plastic terminal pH is 7-11; Then according to SiO
2: Al
2o
3=1:(0.6-9) weight ratio adds silicon source, and aging 1-10 hour at room temperature to 90 ℃, then filters.In the present invention, the sial sediment obtaining after described filtration can directly be used as the described mesoporous silica-alumina materials without ion-exchange, also can be dried and/or roasting after as the described mesoporous silica-alumina materials without ion-exchange.Described aluminium source can be conventional various aluminium source of using, this area, and described aluminium source for example can be for being selected from one or more in aluminum nitrate, aluminum sulfate or aluminium chloride.Described silicon source can be conventional various silicon source of using, this area, and described silicon source can be for example at least one in silica gel, waterglass, sodium metasilicate, silicon tetraethyl, silica, Ludox and silicon gel.Described aqueous slkali can be the conventional various aqueous slkalis that use in this area, for example, can be one or more in ammoniacal liquor, potassium hydroxide solution, sodium aluminate solution and sodium hydroxide solution.
In the process of the described mesoporous silica-alumina materials without ion-exchange of preparation, although described Lv Yuan,Gui source and aqueous slkali can suitably be selected separately from the above-mentioned material of enumerating, yet, having at least in common described aluminium source, aqueous slkali He Gui source is a kind of for containing the raw material of sodium, thereby guarantees that the described mesoporous silica-alumina materials without ion-exchange of so preparation has the meso-hole structure of appropriate size.
In the present invention, in the described mesoporous silica-alumina materials without ion-exchange, take the sodium content of sodium oxide molybdena is 0.5-15 % by weight.And in described catalytic cracking catalyst of the present invention, the sodium content in sodium oxide molybdena in the described mesoporous silica-alumina materials of preparing without the mesoporous silica-alumina materials of ion-exchange described in adopting is generally below 0.2 % by weight.
In catalyst provided by the present invention, beta molecular sieve and described modified mesoporous material weight ratio be 1:5-5:1, be preferably 1:3-3:1.
In catalyst provided by the invention, the weight ratio of described beta molecular sieve and described MIF molecular sieve (also referred to as the molecular sieve with MFI structure) is preferably 2-9:1, more preferably 3-6:1, and two kinds of 75-100 % by weight that molecular sieve weight sum is described molecular sieve mixture weight.Described beta molecular sieve can be Hydrogen, also can be that phosphorus and/or transition metal modified beta molecular sieve can be for example through one or more the element modified beta zeolites in P, Re, Fe, Co, Ni, Cu, Mn, Zn and Sn, or be their mixture, be preferably the beta molecular sieve of Hydrogen beta molecular sieve, phosphorus modification, through P be selected from one or more in the beta molecular sieve of one or more modifications in Fe, Co, Ni and Cu, the silica alumina ratio (SiO of described Beta molecular sieve
2/ Al
2o
3mol ratio) be generally 8-200, preferably 10-100.Described MFI molecular sieve is the high-silica zeolite with pentasil structure, it can be one or more in the existing molecular sieve with MIF structure, it is for example ZSM-5 zeolite, one or more in ZRP zeolite, can be process P, Re, Fe, Co, Ni, Cu, Mn, Zn, Sn, one or more element modified ZSM-5 such as Mo and Ga and process P, Re, Fe, Co, Ni, Cu, Mn, Zn, Sn, the mixture of one or more in one or more element modified ZRP series zeolite such as Mo and Ga, particularly be selected from the ZRP zeolite (CN1052290A containing rare earth, CN1058382A, US5232675), phosphorous ZRP zeolite (CN1194181A, US5951963), the ZRP zeolite (CN1147420A) of phosphorous and rare earth, ZRP zeolite (the CN1211469A of phosphorous and alkaline-earth metal, CN1211470A, US6080698) and phosphorous and ZRP zeolite (CN1465527A transition metal, CN1611299A) one or more in.Silica alumina ratio (the SiO of described MFI molecular sieve
2/ Al
2o
3mol ratio) be generally 10-300, preferably 15-150.
In catalyst provided by the invention, described molecular sieve mixture comprises beta molecular sieve and MFI molecular sieve, also can comprise other molecular sieve that is no more than 25 % by weight.In described molecular sieve mixture, beta molecular sieve (beta-molecular sieve) is not less than 1:1 with the weight ratio of MFI molecular sieve, be preferably 3:1-6:1, and these two kinds of molecular sieve weight sums account for the 75-100 % by weight of molecular sieve mixture, described other molecular sieve is preferably clinoptilolite and/or modenite, the content 0-25 % by weight of described other molecular sieve.Preferably, described molecular sieve mixture is not containing the molecular sieve of faujasite structure, and described faujasite structure molecular screen is Y zeolite, X-type molecular sieve for example.Described molecular sieve mixture is preferably the mixture of beta molecular sieve and MFI structure molecular screen or is the mixture of clinoptilolite and/or modenite, beta molecular sieve and MFI structure molecular screen, and beta molecular sieve and the weight ratio 3:1-6:1 with the molecular sieve of MFI structure, in these cases, introduce described clinoptilolite, can improve more significantly liquefied gas yield.
In catalyst provided by the invention, one or more in the optional catalytic cracking catalyst of described heat-resistant inorganic oxide in conventional heat-resistant inorganic oxide, for example be commonly used for one or more in the heat-resistant inorganic oxide in binding agent and modified additive material, described binding agent is one or more in silica, aluminium oxide, silica-alumina, phosphorus-aluminium compound for example; Described modified additive material is P for example
2o
5, Al
2o
3.Preferred heat-resistant inorganic oxide is one or more in aluminium oxide, silica, silica-alumina, phosphorous oxides, phosphorous oxide-aluminium oxide.The modified material of introducing when these heat-resistant inorganic oxides can be derived from the binding agent that when preparation introduce and/or be derived from preparation, described binding agent is one or more in aluminium oxide, hydrated alumina, aluminium colloidal sol, Ludox, silicon gel, waterglass, silica-alumina gel, silicon-aluminum sol, acidification pseudo-boehmite, phosphaljel, aluminium phosphate sol and their precursor or various modifier for example.Described binding agent can be by being purchased or preparing according to existing method, for example, the method preparation that acidification pseudo-boehmite can provide according to patent US4010116, US4206085, the method preparation that Ludox can provide according to US Patent No. 3957689, US3867308, the method preparation that aluminium phosphate sol can provide according to patent CN1008974C, CN1083512A.Preferred binding agent is one or more in boehmite, aluminium colloidal sol and phosphorus aluminium colloidal sol and/or silicon phosphorus aluminium colloidal sol.
Clay of the present invention is selected from one or more in the clay that is usually used in Cracking catalyst, for example one or more in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite.These clays are that those of ordinary skills are known, are preferably kaolin or halloysite.The content of catalyst medium clay soil provided by the invention is generally 5-45 % by weight.
The preparation method of provided by the inventionization catalyst, described modification mesoporous silica-alumina materials, clay, binding agent, molecular sieve mixture are mixed to making beating, make catalyst slurry, described catalyst slurry is sprayed dry, can carry out according to the preparation method of existing Cracking catalyst or auxiliary agent, for example the method in patent CN1098130A, CN1362472A, CN1727442A, CN1132898C or CN1727445A.Preferably, the preparation method of described catalyst slurry is: described modified clay, binding agent are mixed to making beating, add or do not add acid, at 60-80 ℃, stir aging 30-120min, make the first slurries, again the first slurries are mixed to making beating with mesoporous silica-alumina materials and mixed molecular sieve, making the second slurries is catalyst slurry, the second slurries are sprayed to be dried obtains described catalyst microspheres, and preferred binding agent is one or more in boehmite, acidification pseudo-boehmite, aluminium colloidal sol, phosphorus aluminium colloidal sol, silicon-aluminum sol, Ludox and silicon phosphorus aluminium colloidal sol.Wherein, in the first slurries, can also introduce acid, the pH value that the consumption of acid makes to state slurries is 1-5, be preferably 1.5-4, described acid is selected from one or more of water-soluble organic acid and inorganic acid, one or more in the carboxylic acid that preferably hydrochloric acid, nitric acid, oxalic acid, phosphoric acid and carbon number are 1-10.Preferably the solid content of prepared catalyst slurry is 5～45 % by weight.
In method for preparing catalyst provided by the invention, by the dry catalyst microspheres that obtains of catalyst slurry spraying, this catalyst microspheres can be directly used in course of reaction, also can comprise the step of the dry catalyst microspheres roasting obtaining of spraying, or comprise steps such as the dry catalyst microspheres washing obtaining of spraying, dry, roasting and ammonium exchanges.Described washing, dry, roasting and ammonium are exchanged for prior art, and the present invention does not have specific (special) requirements.
The more feedstock oil of mononuclear aromatics that catalyst provided by the invention is applicable to contain cycloalkane and contains naphthenic ring, for example hydrotreatment oil contains the more paraffin-base oil material of cycloalkane with some.In described hydrotreatment oil, dicyclo and fragrant number of rings are preferably no more than 15 % by weight more than the polycyclic aromatic hydrocarbon content of two, and described hydrotreatment oil wax content is preferably no more than 20 % by weight, and naphthene content is not less than 30 % by weight.The condition of described catalytic cracking can be with reference to existing RFCC condition, and for example reaction temperature is 450-650 ℃, and agent weight of oil is than being 3-10, and weight (hourly) space velocity (WHSV) is 1-500h
-1, weight (hourly) space velocity (WHSV) 2-20h for example
-1.
The present invention is described further for the following examples, but therefore do not limit the present invention.
In embodiment and comparative example: beta molecular sieve solid content used 95.2 % by weight, silica alumina ratio (SiO
2/ Al
2o
3mol ratio) be 25, sodium oxide content 0.1 % by weight; ZRP-1, silica alumina ratio (SiO
2/ Al
2o
3mol ratio) be 30, Na
2o content is 0.1 % by weight, phosphorus content 1 % by weight, Re
2o
3content 2 % by weight, solid content 95 % by weight; The lattice constant of DASY0.0 molecular sieve is 2.443nm, Na
2o content is 0.85 % by weight, solid content 92.0 % by weight; Above molecular sieve is catalyst asphalt in Shenli Refinery of China Petrochemical Industry product is provided.Aluminium colloidal sol is provided by catalyst asphalt in Shenli Refinery of China Petrochemical Industry, its Al
2o
3content is 21.5 % by weight, and boehmite is Shandong Aluminum Plant's industrial products, and solid content is 62.0 % by weight, and kaolin is that Suzhou China Kaolin Co., Ltd produces, and solid content is 76 % by weight.In comparative example and embodiment, chemical reagent used does not indicate especially, and its specification is chemical pure.
In each embodiment, the Na of mesoporous material used
2o, Al
2o
3, SiO
2with XRF, measure (see " Petrochemical Engineering Analysis method " (RIPP test method) Yang Cuiding Deng Bian， Science Press, nineteen ninety publishes) with the content of modified metal-oxide
Embodiment 1
The preparation of modification mesoporous silica-alumina materials
By concentration, be 90g Al
2o
3the Al of/L
2(SO
4)
3solution and concentration are 102g Al
2o
3/ L, causticity are than the NaAlO that is 1.7
2solution stream add in continuous gel formation still, and colloid generating kettle effective volume is 200ml, Al
2(SO
4)
3the flow of solution is 20ml/min, regulates NaAlO
2it is 9 that flow keeps plastic pH value, and plastic temperature is 55 ℃; Collect the slurries 300ml after plastic, under stirring condition, adding 127ml content is 60g SiO
2the waterglass of/L (modulus 3.1) aqueous solution, be warming up to 80 ℃ aging 4 hours, then filter.
The sial sediment obtaining after filtering be take to weight ratio and mix making beating with water as 1:12, again by hydrochloric acid solution by described sial sediment (butt): the weight ratio of HCl=1:0.14 adds in the slurries that obtain after making beating, at 60 ℃, sial sediment is carried out to acid exchange to remove sodium ion wherein, be 30 minutes swap time, then filter, and the sediment obtaining after filtering is dried and roasting successively, thereby obtain modification mesoporous silica-alumina materials, JK1.This mesoporous silica-alumina materials sample has boehmite crystal phase structure, and its X-ray diffraction spectral line as shown in Figure 1; Its elementary analysis weight chemical composition is 0.06Na
2o73.8Al
2o
326.0SiO
2.Its physical and chemical performance is as shown in table 1.
Embodiment 2
According to the method for implementing 1 in CN 1854258A, make mesoporous silica-alumina materials SH-SA-1, the present invention is designated as JK2.
Embodiment 3
The preparation process of mesoporous material JK3 is basic identical with the mesoporous silica-alumina materials SA-2 of embodiment in CN1565733A 2, just adopts sour exchange process to substitute ammonium exchange process wherein.Be about to the intermediate sedimentation thing of SA-2, it is the sial sediment after aging filtration, by the weight ratio of 1:10, mix making beating with water, again by HCl solution by sediment (butt): the weight ratio of HCl=1:0.12 joins in above-mentioned slurries, at 55 ℃, sial sediment is carried out to acid exchange to remove sodium ion wherein, be 40 minutes swap time, after filtration, to obtain mesoporous material after dry and roasting be modification mesoporous silica-alumina materials of the present invention, is designated as JK3.This sample has the feature of the X-ray diffraction spectral line of curve 2 in accompanying drawing; Its elementary analysis weight chemical composition is 0.10Na
2o58.9Al
2o
340.9SiO
2; The physico-chemical parameters such as its specific surface, pore volume are listed in table 1.
Embodiment 4
The preparation process of mesoporous material JK4 is basic identical with the mesoporous silica-alumina materials SA-5 of embodiment in CN1565733A 5, just adopts sour exchange process to substitute ammonium exchange process wherein.Be about to the intermediate sedimentation thing of SA-5, it is the sial sediment after aging filtration, by the weight ratio of 1:8, mix making beating with water, again by these slurries by sediment (butt): the weight ratio of HCl=1:0.15 joins in rare HCl solution, at 50 ℃, sial sediment is carried out to acid exchange to remove sodium ion wherein, be 20 minutes swap time, after filtration, obtain modification mesoporous silica-alumina materials after dry and roasting, is designated as JK4.This sample has the feature of the X-ray diffraction spectral line of curve 2 in accompanying drawing; Its elementary analysis weight chemical composition is 0.05Na
2o74.2Al
2o
325.7SiO
2; The physico-chemical parameters such as its specific surface, pore volume are listed in table 1.
Comparative example 1
Adopt the mesoporous silica-alumina materials SA-1 in CN1565733A, be designated as JK0, its chemical composition is
0.12Na
2O·73.7Al
2O
3·26.2SiO
2；
Table 1
Embodiment 5
(1), in 15kg decationized Y sieve water, add 7.5kg (in butt, lower same) kaolin making beating, then add 2.4kg(with Al
2o
3meter, lower with) boehmite, stir 10 minutes, with hydrochloric acid, its pH value is adjusted to 2, stir 10 minutes, stop stirring, at 70 ℃ standing aging 1 hour, add 3.6kg aluminium colloidal sol (with Al
2o
3meter, lower same), stir, obtain aluminium oxide-clay slurry;
(2) in 15kg decationized Y sieve water, add 6.0kgbeta molecular sieve (in butt, down together), 1.5kgZRP-1(is in butt, lower same) molecular sieve, 4.0kg(is lower same in butt) prepared modification mesoporous silica-alumina materials JK1, pull an oar 30 minutes, obtain the mixed serum of molecular sieve and modified mesoporous material, these slurries are joined in aluminium oxide-clay slurry prepared by above-mentioned steps (1), stir 0.5h, obtain catalyst slurry, by the catalyst slurry spray drying forming obtaining, 500 ℃ of roastings 1.5 hours, obtain catalytic cracking catalyst C1.Composition and the physical and chemical performance of C1 are listed in table 2.
Embodiment 6-8
According to method Kaolinite Preparation of Catalyst C2, C3 and the C4 of embodiment 5, different is the proportioning of adjusting beta and ZRP-1, and its proportioning is in Table 2.
Embodiment 9
According to the method in embodiment 5, prepare catalytic cracking catalyst, difference is, with described mesoporous silica-alumina materials JK2, replaces described mesoporous silica-alumina materials JK1, and to regulate beta molecular sieve and mesoporous silica-alumina materials ratio be 4:1, thereby make catalytic cracking catalyst C5, its concrete proportioning is in Table 2.
Embodiment 10
According to the method in embodiment 5, prepare catalytic cracking catalyst, difference is, with described mesoporous silica-alumina materials JK3, replaces described mesoporous silica-alumina materials JK1, and to regulate beta molecular sieve and mesoporous silica-alumina materials ratio be 8:5, thereby make catalytic cracking catalyst C5, its concrete proportioning is in Table 2.
Embodiment 11
According to the method in embodiment 5, prepare catalytic cracking catalyst, difference is, with described mesoporous silica-alumina materials JK4, replaces described mesoporous silica-alumina materials JK1, and to regulate beta molecular sieve and mesoporous silica-alumina materials ratio be 1: 1, thereby make catalytic cracking catalyst C5, its concrete proportioning is in Table 2.
Comparative example 2
According to the method Kaolinite Preparation of Catalyst of embodiment 5, different is not add MFI structural zeolite, obtains catalyst D1, and its proportioning is in Table 2.
Comparative example 3
According to the method Kaolinite Preparation of Catalyst of embodiment 5, different, the content of MFI structural zeolite is 3:1 with the ratio of the content of beta zeolite, obtains catalyst D2, and its proportioning is in Table 2.
Comparative example 4
According to the method preparation of embodiment 5, at catalyst, different is to use mesoporous silica-alumina materials JK0 to replace JK2 wherein, obtains catalyst D3, and its proportioning is in Table 2.
Comparative example 5
According to the method preparation of embodiment 4, at catalyst, different is without modification mesoporous silica-alumina materials, obtains catalyst D4, and its proportioning is in Table 2.
Comparative example 6
By 6.8gH
3pO
4(concentration 85 % by weight) and 3.2g nitrate trihydrate copper are dissolved in the aqueous solution and 100g (butt) the beta molecular sieve hybrid infusion obtaining in 90g water, dry, and gained sample is calcination process 2h at 550 ℃, obtains approximately containing 4.0 % by weight P
2o
5, 4.0 % by weight CuO modification beta molecular sieve, be designated as P-Cu-beta molecular sieve.
(1) in 15kg decationized Y sieve water, add 7.5kg kaolin making beating, then add 2.4kg boehmite, with hydrochloric acid, its pH value is adjusted to 2, stir, stop stirring, at 70 ℃ standing aging 1 hour, add 3.6kg (with Al
2o
3meter) aluminium colloidal sol, stirs, and obtains aluminium oxide-clay slurry.
(2) in 15kg decationized Y sieve water, add the prepared P-Cu-beta molecular sieve of 4.5kg, 1.1kgZRP-1 molecular sieve, 1.9Kg DASY0.0 molecular sieve and, 4.0kg(butt) the modification mesoporous Si-Al JK1 that makes, 4.0 making beating 30 minutes, obtain the mixed serum of molecular sieve and modified mesoporous material, these slurries are joined in aluminium oxide-clay slurry prepared by above-mentioned steps (1), stir 0.5h, obtain catalyst slurry, by then by the slurries spray drying forming obtaining, 500 ℃ of roastings 1.5 hours, obtain catalytic cracking catalyst D5.Composition and the physical and chemical performance of D5 are listed in table 2.
Embodiment 12-19
Illustrate that prepared catalyst is for the reactivity worth of hydrogenation VGO.
Catalyst C1-C7 prepared by embodiment 5-11 was at 800 ℃, with 100% steam aging 12 hours, use miniature fixed fluidized bed ACE reaction unit to evaluate the cracking performance of catalyst, the loadings of catalyst reactor is 9 grams, and reaction temperature is 500 ℃, and weight (hourly) space velocity (WHSV) is 16h
-1, pass into HTVGO in the sand shown in hydrogenation VGO(table 3) and the mixture of steam, to evaluate, steam accounts for 25 % by weight of hydrogenation VGO, reaction condition and the results are shown in Table 4.
Table 2
Comparative example 7-11:
The catalyst of preparing in comparative example explanation employing comparative example is for the reactivity worth of hydrogenation VGO.
Catalyst D1-D5 prepared by comparative example was at 800 ℃, with 100% steam aging 12 hours, use respectively miniature fixed fluidized bed ACE reaction unit to evaluate the cracking performance of catalyst, the loadings of catalyst reactor is 9 grams, oil ratio is 4, reaction temperature is 500 ℃, and weight (hourly) space velocity (WHSV) is 16h
-1, pass into hydrogenation VGO(as shown in table 3) to evaluate, steam consumption is 25 % by weight of hydrogenation VGO, reaction condition and the results are shown in Table 4.
Embodiment 20
According to the method Kaolinite Preparation of Catalyst of comparative example 6, different is not add y-type zeolite, and replaces with the JK1 of equivalent, is designated as C8, according to the method for embodiment 12-19, evaluates, and evaluation result is in Table 5.
Embodiment 21:
(1) in 15kg decationized Y sieve water, add 7.5kg kaolin making beating, then add 2.4kg boehmite, with hydrochloric acid, its pH value is adjusted to 2, stir, stop stirring, at 70 ℃ standing aging 1 hour, add 3.6kg (with Al
2o
3meter) aluminium colloidal sol, stirs, and obtains aluminium oxide-clay slurry.
(2) in 15kg decationized Y sieve water, add 6.0kg(butt) beta molecular sieve, 1.5kg(butt) ZRP-1 molecular sieve, 0.5kg(butt) (sodium oxide content is 0.2 % by weight to clinoptilolite, Si/A mol ratio=4.9) and 4.0kg(butt) the modification mesoporous Si-Al JK1 that makes, pull an oar 30 minutes, obtain the mixed serum of molecular sieve and modified mesoporous material, these slurries are joined in aluminium oxide-clay slurry prepared by above-mentioned steps (1), stir 0.5h, obtain catalyst slurry, by then by the slurries spray drying forming obtaining, 500 ℃ of roastings 1.5 hours, obtain catalytic cracking catalyst C9.
(3) reactivity worth for hydrogenation VGO by catalyst C9, reaction condition and method are with embodiment 12-19, and reaction result is in Table 5.
Table 3
Hydrogenation VGO shown in table 3 is obtained through hydrogenation by the VGO that reduces pressure, and the composition of decompression VGO is in Table 3.
Hydroconversion condition: hydrogen dividing potential drop 8.5MPa, 375 ℃ of temperature, NiMoW catalyst, hydrogen and oil volume compare 600:1.
Table 4
Table 5
From table 4 and table 5: catalyst aims hydrotreated feed oil provided by the invention has higher propylene and butylene productive rate, has higher isobutene productive rate, and in liquefied gas, propylene and isobutylene concentration are higher, and in gasoline aromatic hydrocarbons, BTX ratio is higher.In gasoline aromatic hydrocarbons, BTX ratio is high, is conducive to reduce the cost of low-carbon alkene and aromatic hydrocarbons extraction and application.In addition, can reduce the virtue degree of bavin heavy oil (diesel oil and heavy oil), be conducive to improve the Cetane number of diesel oil, can hold concurrently and produce lower pour point diesel oil.And can improve bavin heavy oil quality, increase the ratio that mononuclear aromatics accounts for total aromatic hydrocarbons.From table 5, add a small amount of clinoptilolite and there is obvious effect to improving liquefied gas yield, and can improve propylene and butylene productive rate.
Embodiment 22
According to the method Kaolinite Preparation of Catalyst of embodiment 5, the content of different is JK1 is 35% weight, and the content of beta molecular sieve is 10 % by weight, and the content of ZRP-1 molecular sieve is 5 % by weight, and the content of alumina binder is 30 % by weight, and the content of clay is 15 % by weight.
Embodiment 23
According to the method Kaolinite Preparation of Catalyst of embodiment 5, the content of different is JK1 is 5% weight, and the content of beta molecular sieve is 40 % by weight, and the content of ZRP-1 molecular sieve is 20 % by weight, and the content of alumina binder is 10 % by weight, and the content of clay is 25 % by weight.
Claims (12)
1. for hydrotreatment oil, transform a catalyst of producing propylene and isobutene, described catalyst mainly by the heat-resistant inorganic oxide of 5-35 % by weight, the modification mesoporous silica-alumina materials of the clay of 0-65 % by weight, 5-50 % by weight and the molecular sieve mixture of 15-60 % by weight form; Wherein said molecular sieve mixture comprises beta molecular sieve and MFI molecular sieve, and described beta molecular sieve is not less than 1 with the ratio of the weight of MFI molecular sieve, and the weight ratio of described beta molecular sieve and described modified mesoporous material is 1:5-5:1.
2. according to catalyst claimed in claim 1, it is characterized in that, described modification mesoporous silica-alumina materials has boehmite crystal phase structure, and it is (0-0.2) Na that described modification mesoporous silica-alumina materials be take the anhydrous expression formula of oxide weight
2o (40-90) Al
2o
3(10-60) SiO
2; The specific area of described modification mesoporous silica-alumina materials is 200-400m
2/ g, pore volume are that 0.5-2.0ml/g, average pore size are that 5-25nm, most probable aperture are 5-15nm.
3. according to catalyst claimed in claim 2, it is characterized in that 1, described modification mesoporous silica-alumina materials is made by the method comprising the following steps: the mesoporous silica-alumina materials without ion-exchange mixed to making beating with water, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 ℃, make sodium oxide content in described mesoporous silica-alumina materials not higher than 0.2 % by weight, wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:5-30:0.03-0.3.
4. according to catalyst claimed in claim 3, it is characterized in that, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:6-20:0.05-0.2; Preferably, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:8-15:0.07-0.16.
5. according to the catalyst described in any one in claim 3-4, it is characterized in that, the Contact Temperature of described slurries and inorganic acid is 30-80 ℃, and be 0.2-2 hour time of contact.
6. according to the catalyst described in claim 3-5 any one, wherein, the preparation method of the described mesoporous silica-alumina materials without ion-exchange comprises: Jiang Lv source and aqueous slkali at room temperature to 85 ℃ in and plastic, the pH of plastic terminal is 7-11; Then according to SiO
2: Al
2o
3=1:(0.6-9) weight ratio adds silicon source, and aging 1-10 hour at room temperature to 90 ℃, then filters.
7. according to the catalytic cracking catalyst described in any one in claim 3-6, wherein, the sodium content of sodium oxide molybdena of take in the described mesoporous silica-alumina materials without ion-exchange is 0.5-15 % by weight.
8. according to catalyst claimed in claim 1, it is characterized in that, the weight ratio of described beta molecular sieve and described MIF molecular sieve is 2-9:1, and two kinds of described molecular sieve sums account for the 75-100 % by weight of molecular sieve mixture total amount, described beta molecular sieve and described modified mesoporous material weight ratio be 1:3-3:1.
9. according to catalyst claimed in claim 1, it is characterized in that, described molecular sieve mixture comprises modenite and/or clinoptilolite, and the gross weight of molecular sieve mixture of take is benchmark, in the content of the described clinoptilolite of butt and/or modenite, is no more than 25 % by weight; Described molecular sieve mixture does not comprise faujasite substantially.
10. according to catalyst claimed in claim 1, it is characterized in that, described MFI molecular sieve is ZRP molecular sieve and/or phosphorous and ZSM-5 molecular sieve transition metal, described beta molecular sieve is Hydrogen or for phosphorus and/or transition metal modified beta molecular sieve, described heat-resistant inorganic oxide comprises one or more in aluminium oxide, silica, silica-alumina, phosphorous oxides, phosphorous oxide-aluminium oxide.
The preparation method of the catalyst described in 11. 1 kinds of claim 1-12 any one, comprise clay is mixed, added or do not add to described molecular sieve mixture, modification mesoporous silica-alumina materials, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide precursor, making beating, spray-dired step.
12. according to the preparation method of the catalyst described in claim 13, it is characterized in that, described preparation method is as follows:
1) the described modification mesoporous silica-alumina materials of preparation;
2) form the slurries that comprise modification mesoporous silica-alumina materials, molecular sieve mixture and water;
3) form the slurries that comprise binding agent, clay;
4) 2) add 1 in the slurries that obtain) slurries that obtain form catalyst slurry;
5) by step 3) spraying of the catalyst slurry that obtains is dry;
6) roasting.
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