CN105583005A - Catalyst for catalytically pyrolyzing naphtha to produce propylene, preparation method thereof, and method of catalytically pyrolyzing the naphtha to produce the propylene - Google Patents
Catalyst for catalytically pyrolyzing naphtha to produce propylene, preparation method thereof, and method of catalytically pyrolyzing the naphtha to produce the propylene Download PDFInfo
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Abstract
The invention provides a catalyst for catalytically pyrolyzing naphtha to produce propylene and a preparation method thereof. On the basis of the total weight of the catalyst, the catalyst includes, by weight, 50-95% of a molecular sieve and 5-50% of a substrate. The molecular sieve includes a first molecular sieve, a second molecular sieve and a third molecular sieve. The first molecular sieve has a structure of ten-membered ring one-dimension elliptical-shaped pore channels, the second molecular sieve has a structure of twelve-membered ring pore channels, and the third molecular sieve is a small-pore molecular sieve with maximum pore channel diameter being lower than 0.45 nm. The invention also provides a method of catalytically pyrolyzing the naphtha to produce the propylene. The catalyst can increase the yield of propylene and is more than 2 in propylene/ethylene ratio.
Description
Technical field
The Catalysts and its preparation method and the naphtha that the present invention relates to naphtha catalytic cracking product propylene are urgedChange cracking and produce the method for propylene, particularly, relate to a kind of catalyst of naphtha catalytic cracking product propylene,Prepare naphtha catalytic cracking and produce the method for catalyst of propylene and the catalyst making thereof, and a kind ofNaphtha catalytic cracking produces the method for propylene.
Background technology
Propylene is one of most widely used basic organic chemical industry raw material, mainly for the production of polypropylene, differentPropyl benzene, acrylonitrile, acrylic acid etc. Propylene is mainly derived from ethylene cracker and the refining of petrochemical plant at presentThe catalytic cracking unit of oil factory. Along with global propylene demand rapid growth, the output difficulty of traditional processing technologyTo satisfy the demands, the technology of therefore developing propylene enhancing has become important in petrochemical iy produced technologyExhibition direction.
Conventional cracking of ethylene is mainly to pass through steam heat producing ethylene by cracking and propylene taking naphtha as raw material,Limited by heat scission reaction mechanism, general ethene is major product, and propylene is byproduct, propylene/ethyleneRatio is for maximum limit is approximately 0.65, and higher than this ratio, total olefin productive rate will decline. This process need disappearsConsuming a large amount of high-quality feed naphthas, is the process of a high energy consumption. The propylene of 66-70% is with steaming at presentVapour pyrolysis technology is produced.
Catalytic pyrolysis is than the low about 50-200 DEG C of the reaction temperature of steam heat cracking, and energy consumption is lower. And urgeThe reaction mechanism of changing cracking is conducive to form propylene molecules, therefore can realize naphtha and produce propene yieldIncrease.
CN101491772A discloses a kind of catalyst for naphtha catalytic cracking, with weight percentComprise following active component than meter: a) 80-99.5% be selected from ZSM-5 and modenite coexisting molecular sieve,At least one in the coexisting molecular sieve of the coexisting molecular sieve of ZSM-5 and β zeolite or ZSM-5 and Y zeoliteKind; With at least one element in periodic table of elements VA family element that is selected from that carries b) surplus thereonOr its oxide. But the diene yield of the ethene that this catalyst can obtain and propylene is also lower.
CN102861604A discloses a kind of producing olefin hydrocarbon by catalytic pyrolysis of naphtha catalyst, wherein, pressesThe weight content meter of whole catalyst, the EU-1/ZSM-5 composite molecular screen that contains 60-90%, 0.5-3%'sHeteropoly acid. When this catalyst is actually used in naphtha catalytic cracking, although can ethene and propylene diene receiptsRate is high, but propylene/ethylene is lower than also, and the propone output of acquisition is little.
As can be seen here, carry out naphtha catalytic cracking and will realize more large-tonnage propylene, also need new useProduce the catalyst of propylene in naphtha catalytic cracking.
Summary of the invention
The object of the invention is to carry out naphtha catalytic cracking and produce when propylene, propylene in order to overcome prior artThe problem that output is little, provides naphtha catalytic cracking to produce Catalysts and its preparation method and the naphtha of propyleneCatalytic pyrolysis produces the method for propylene.
To achieve these goals, the invention provides a kind of catalyst of naphtha catalytic cracking product propylene,Taking the gross weight of this catalyst as benchmark, the molecular sieve that this catalyst contains 50-95 % by weight and 5-50 are heavyThe matrix of amount %; Described molecular sieve contains the first molecular sieve, the second molecular sieve and type three-molecular screen alternating, described inThe first molecular sieve is the molecular sieve with ten-ring one dimension ellipse duct structure, and described the second molecular sieve isHave the molecular sieve of twelve-ring pore passage structure, described type three-molecular screen alternating is that maximum duct opening diameter existsSmall pore molecular sieve below 0.45nm.
The present invention also provides a kind of method of the catalyst of preparing naphtha catalytic cracking product propylene, the partyMethod comprises: (1) mixes substrate source, water and optional acid solution, forms slurries;
(2), by molecular sieve or contain molecular sieve and the suspension of water mixes with described slurries, obtainCatalyst mixture carries out moulding, the dry and roasting of the line option of going forward side by side;
Described molecular sieve contains the first molecular sieve, the second molecular sieve and type three-molecular screen alternating, described the first moleculeSieve is for having the molecular sieve of ten-ring one dimension ellipse duct structure, and described the second molecular sieve is for having 12The molecular sieve of membered ring channel structure, described type three-molecular screen alternating be maximum duct opening diameter 0.45nm withUnder small pore molecular sieve.
The present invention also provides a kind of method of the catalyst of preparing naphtha catalytic cracking product propylene, the partyMethod comprises: (1) mixes substrate source, water, the first molecular sieve and optional acid solution, forms slurries;
(2) by the second molecular sieve and type three-molecular screen alternating or contain the second molecular sieve and type three-molecular screen alternating andThe suspension of water mixes with described slurries, and the catalyst mixture obtaining carries out moulding, the line option of going forward side by sideBe dried and roasting; Described the first molecular sieve is the molecular sieve with ten-ring one dimension ellipse duct structure,Described the second molecular sieve is the molecular sieve with twelve-ring pore passage structure, and described type three-molecular screen alternating is maximumThe small pore molecular sieve of duct opening diameter below 0.45nm.
The present invention also provides the catalyst being made by method provided by the invention.
The present invention also provides a kind of naphtha catalytic cracking to produce the method for propylene, and the method comprises: at stoneUnder cerebrol catalytic cracking reaction condition, naphtha is contacted with catalyst with water, obtain propylene product, itsIn, described catalyst comprises catalyst provided by the invention.
Adopt catalyst provided by the invention, can improve the yield of propylene, and obtain propylene/ethyleneMore than 2.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, retouch in this placeThe detailed description of the invention of stating only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides the catalyst that a kind of naphtha catalytic cracking produces propylene, with the gross weight of this catalystAmount is benchmark, the matrix of the molecular sieve that this catalyst contains 50-95 % by weight and 5-50 % by weight; DescribedMolecular sieve contains the first molecular sieve, the second molecular sieve and type three-molecular screen alternating, and described the first molecular sieve is for havingThe molecular sieve of ten-ring one dimension ellipse duct structure, described the second molecular sieve is for having twelve-ring ductThe molecular sieve of structure, described type three-molecular screen alternating is the aperture of maximum duct opening diameter below 0.45nmMolecular sieve.
In catalyst provided by the invention, adopt the first molecular sieve, the second molecular sieve and type three-molecular screen alternating to doFor catalytic pyrolysis active component, can obtain the yield of higher naphtha catalytic cracking product propylene.
According to the present invention, described the first molecular sieve is the molecule with ten-ring one dimension ellipse duct structureSieve, preferably duct opening diameter is in 0.45-0.56 nanometer.
According to the present invention, the molecular sieve that preferably described the first molecular sieve is TON structure and/or MTT knotThe molecular sieve of structure, wherein structure type TON, MTT refer to dividing of international zeolite federation (IZA) nameSub-sieve structure, for describing the space topological structure in molecular sieve duct. The molecule of described TON structureSieve, comprises Theta-1 zeolite, ISI-1 zeolite, KZ-2 zeolite, NU-10 zeolite, ZSM-22 zeoliteWith SSZ-32 zeolite etc., the molecular sieve of MTT structure comprises ZSM-23 zeolite, EU-13 zeolite, ISI-4Zeolite and KZ-1 zeolite etc.
For the present invention, preferably described the first molecular sieve is Theta-1 zeolite, ISI-1 zeolite, KZ-2Zeolite, NU-10 zeolite, ZSM-22 zeolite, SSZ-32 zeolite, ZSM-23 zeolite, EU-13 boilAt least one in stone, ISI-4 zeolite and KZ-1 zeolite.
According to the present invention, the molecular sieve that preferably described the first molecular sieve is TON structure and MTT structureThe mixture of molecular sieve. More preferably, the molecular sieve of the molecular sieve of described TON structure and MTT structureWeight ratio is 0.1-10:1, more preferably 1-5:1.
According to the preferred embodiment of the present invention, the molecular sieve of described TON structure, preferably includes Theta-1In zeolite, ISI-1 zeolite, KZ-2 zeolite, NU-10 zeolite, ZSM-22 zeolite and SSZ-32 zeoliteOne or more.
According to the preferred embodiment of the present invention, the molecular sieve of described MTT structure, preferably includesOne or more in ZSM-23 zeolite, EU-13 zeolite, ISI-4 zeolite and KZ-1 zeolite.
A preferred embodiment of the invention, the molecular sieve of described TON structure is ZSM-22The mixture of zeolite and NU-10 zeolite, the weight ratio of the two is 2-5:1; The molecule of described MTT structureSieve is the mixture of ISI-4 zeolite and ZSM-23 zeolite, and the weight ratio of the two is 2-5:1.
In the present invention, the sial atomic molar of described the first molecular sieve can be 0.1-100 than (Si/Al):1; Be preferably 30-80:1.
According to the present invention, preferably, the duct opening diameter of described the second molecular sieve is 0.6-0.75 nanometer.More preferably, described the second molecular sieve there is AET for being selected from, AFR, AFS, AFI, BEA, BOG,Dividing of CFI, CON, GME, IFR, ISV, LTL, MEI, MOR, OFF and SAO structureAt least one in son sieve. Particularly preferably, described the second molecular sieve be Beta, SAPO-5, SAPO-40,At least one in SSZ-13, CIT-1, ITQ-7, ZSM-18, modenite and sodium chabazite.
In the present invention, in described the second molecular sieve, sial atomic molar can be 0.1-100 than (Si/Al):1; Be preferably 30-80:1.
According to the present invention, preferably, described type three-molecular screen alternating has ATT for being selected from, ATN, CHA,At least one in the molecular sieve of ITE, STI, WEN structure. More preferably, described type three-molecular screen alternatingFor at least one in ITQ-3, SAPO-34 and cancrinite.
According to the present invention, under preferable case, described the first molecular sieve, described the second molecular sieve and describedThe weight ratio of type three-molecular screen alternating is 0.1-15:0.1-5:1, is preferably 1-10:1-2:1.
According to the present invention, preferably, taking the gross weight of this catalyst as benchmark, this catalyst contains 60-95The matrix of the molecular sieve of % by weight and 5-40 % by weight.
According to the present invention, under preferable case, described matrix can be selected from aluminium oxide, silica, amorphousAt least one in sial, zirconia, titanium oxide, boron oxide and alkaline earth oxide.
The catalyst that meets the aforementioned requirement of the present invention all can be realized object of the present invention, and the present invention is prepared itMethod is without particular/special requirement, and according to one of the present invention preferred embodiment, described catalyst is by following stepRapid preparation: (1) mixes substrate source, water and optional acid solution, forms slurries;
(2), by molecular sieve or contain molecular sieve and the suspension of water mixes with described slurries, obtainCatalyst mixture carries out moulding, the dry and roasting of the line option of going forward side by side;
Described molecular sieve contains the first molecular sieve, the second molecular sieve and type three-molecular screen alternating, described the first moleculeSieve is for having the molecular sieve of ten-ring one dimension ellipse duct structure, and described the second molecular sieve is for having 12The molecular sieve of membered ring channel structure, described type three-molecular screen alternating be maximum duct opening diameter 0.45nm withUnder small pore molecular sieve.
The preferred embodiment of one according to the present invention, preferred catalyst of the present invention as followsPreparation: (1) mixes substrate source, water, the first molecular sieve and optional acid solution, forms slurries;
(2) by the second molecular sieve and type three-molecular screen alternating or contain the second molecular sieve and type three-molecular screen alternating andThe suspension of water mixes with described slurries, and the catalyst mixture obtaining carries out moulding, the line option of going forward side by sideBe dried and roasting; Described the first molecular sieve is the molecular sieve with ten-ring one dimension ellipse duct structure,Described the second molecular sieve is the molecular sieve with twelve-ring pore passage structure, and described type three-molecular screen alternating is maximumThe small pore molecular sieve of duct opening diameter below 0.45nm.
The method according to this invention, the kind of described the first molecular sieve, the second molecular sieve, type three-molecular screen alternatingIn the process of aforementioned products Presentation, describe in detail, do not repeat to repeat at this.
According to the present invention, under preferable case, described the first molecular sieve, described the second molecular sieve and describedThe weight ratio of type three-molecular screen alternating is 0.1-15:0.1-5:1, is preferably 1-10:1-2:1.
According to the present invention, under preferable case, described substrate source can be the described roasting in step (2)Condition under can change the material of matrix into, described matrix be aluminium oxide, silica, amorphous aluminum silicide,At least one in zirconia, titanium oxide, boron oxide and alkaline earth oxide; Described substrate source and instituteIn the catalyst that the addition of stating molecular sieve makes to obtain, taking the gross weight of this catalyst as benchmark, matrixContent be 5-50 % by weight, the content of molecular sieve is 50-95 % by weight, preferably total with this catalystWeight is benchmark, the matrix of the molecular sieve that this catalyst contains 60-95 % by weight and 5-40 % by weight.
In one embodiment of the present invention, can adopt silica source and alumina source preparation the invention providesCatalyst in matrix.
In one embodiment of the invention, described silica source can be silica or silica contentBe greater than the natural crystal of 45 % by weight. Preferably, described silica source can be laminated clay column, diatomAt least one in soil, expanded perlite, silicalite, Ludox, macropore silicon oxide and silica gel.
In one embodiment of the invention, described alumina source can be described in step (2)Under the condition of roasting, can change the material of aluminium oxide into. Preferably, described alumina source is aqua oxidationOne or more in aluminium, aluminium colloidal sol and boehmite; Described hydrated alumina be boehmite,At least one in false boehmite, hibbsite and amorphous hydroted alumina.
In one embodiment of the invention, the silica in the catalyst obtaining and the amount of aluminium oxideSummation is designated as the amount of matrix. In addition, although contain aluminium oxide and silica, institute in described molecular sieveThe amount that the amount of the silica that contains in molecular sieve and aluminium oxide stated still be can be regarded as described molecular sieve, is not counted in oxygenSiClx and aluminium oxide. In the catalyst being made by method provided by the invention, the content of each component is according to throwingMaterial amount calculates.
In the present invention, described in step (1), optional acid solution can be according to substrate source choice for useAcid solution acidifying or do not use acid solution acidifying. In one embodiment, when using aluminium colloidal sol and/or siliconColloidal sol during as alumina source or silica source, can not use acid solution acidifying; Intend thin water aluminium when usingWhen stone and/or kaolin, can use acid solution acidifying. The consumption of described acid solution can make described slurryThe pH value of liquid is 1-5, is preferably 1.5-4. Described acid solution can be selected from water-soluble inorganic acid and/Or organic acid, can be for example at least one in hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
In the present invention, in step (1), add the amount of water not limit especially, as long as can obtainSlurries described in step (1). For example add the amount of water to make the solid content of the described slurries that obtainFor 5-60 % by weight, be preferably 10-30 % by weight.
In the present invention, the addition that forms the water of described suspension in step (2) can be not specialLimit, as long as can obtain the suspension described in step (2). For example add the amount of water to makeTo the solid content of described suspension be 15-60 % by weight, be preferably 20-35 % by weight.
In step of the present invention (2), described catalyst mixture can be wet mixture, paste mixture,The form such as dough or slurries. By described moulding, described catalyst mixture can be shaped to and extrudeThing, sheet, pill, ball or micro-spherical particle. For example, described catalyst mixture is dough or pasteWhen mixture, can make described catalyst mixture moulding (preferably extrusion molding) form particle, preferably straightFootpath is at 1.0-8.0mm, and length, at the cylindrical extrudate of 2.0-5.0mm, then makes the extrudate of gainedBe dried, roasting. If described catalyst mixture is wet mixture form, can make this mixture thickChange, through super-dry aftershaping. Can also described catalyst mixture be slurries form, dry by sprayingForming granularity is the microballoon of 20-200 micron, reaches the object of moulding. Dry for the ease of spraying, dryThe solid content of dry procatalyst mixture can be 10-50 % by weight, is preferably 20-50 % by weight.
In the present invention, public affairs that the drying means of described catalyst mixture and condition are those skilled in the artKnow, for example, dry method can be dry, oven dry, forced air drying. Under preferable case, step (2)In, dry temperature can be room temperature to 400 DEG C, is preferably 100-350 DEG C; The described dry timeBe at least 0.5 hour, be preferably 0.5-60 hour.
In the present invention, the roasting condition of described catalyst mixture also can by those skilled in the art public affairsKnow, in general, the temperature of described roasting is 400-700 DEG C, is preferably 450-650 DEG C; Described roastingTime be at least 0.5 hour, be preferably 0.5-100 hour, more preferably 0.5-10 hour.
The present invention also provides the catalyst being made by method provided by the invention.
According to the present invention, taking the gross weight of this catalyst as benchmark, this catalyst contains 50-95 % by weightMolecular sieve and the matrix of 5-50 % by weight; Described molecular sieve contain the first molecular sieve, the second molecular sieve andType three-molecular screen alternating, described the first molecular sieve is the molecular sieve with ten-ring one dimension ellipse duct structure,Described the second molecular sieve is the molecular sieve with twelve-ring pore passage structure, and described type three-molecular screen alternating is maximumThe small pore molecular sieve of duct opening diameter below 0.45nm.
The present invention also provides a kind of naphtha catalytic cracking to produce the method for propylene, and the method comprises: at stoneUnder cerebrol catalytic cracking reaction condition, naphtha is contacted with catalyst with water, obtain propylene product, itsIn, described catalyst comprises catalyst provided by the invention.
According to the present invention, under preferable case, described naphtha catalytic cracking reaction condition comprises: temperature is520-590 DEG C, pressure is 0.1-0.2MPa, water/oily feed weight is than being 0.3-2, when naphtha feed weighsAir speed is 2-40h-1。
According to the present invention, under preferable case, alkene, 40-60 that described naphtha contains 0.5-1.5 % by weightThe alkane of % by weight, the cycloalkane of 20-40 % by weight and 10-20 % by weight aromatic hydrocarbons.
Below will describe the present invention by embodiment.
In following examples, gas-phase product character, by gas chromatography, adopts Agilent companyThe Instrument measuring of HP6890 model. Yield and selectively calculating by following formula:
Yield=(object product (C2 ＝+C3 ＝) growing amount/reaction-ure feeding amount) × 100%
Selectively=(object product (C2 ＝～C4 ＝) growing amount/reactant inversion quantity) × 100%
Embodiment 1
The present embodiment is for illustrating preparation method and the naphtha catalytic cracking of catalyst provided by the inventionProduce the method for propylene.
(1) Kaolinite Preparation of Catalyst. By 28 grams of boehmites (Shandong Aluminum Plant, containing butt 20 grams) and50 grams of deionized waters are under agitation mixed, and add the concentrated hydrochloric acid (chemistry that 3.6 grams of concentration are 36 % by weightPure, Beijing Chemical Plant produce) stir acidifying after 1 hour, be warming up to 60 DEG C of acidifyings 1 hour, pH value is3.0. In the time that temperature is reduced to below 40 DEG C, add that (Nanjing Ji Cang receives containing 50 grams, ZSM-22 molecular sieveRice Science and Technology Ltd., Si/Al mol ratio=60:1), (self-control, Si/Al rubs for 20 grams, Beta molecular sieveYour ratio=50:1) and 10 grams, SAPO-34 molecular sieve (Tianjin Chemist Technology Development Co., Ltd,Si/Al mol ratio=0.25:1) suspension (solid content is 20 % by weight), mix after stir 1 hourObtain catalyst mixture.
Described catalyst mixture adopts the pelletizing of single-screw extruder extruded moulding, dries 120 under room temperatureDry after 5 hours at DEG C, at 480 DEG C, roasting obtains catalyst for 1 hour.
Catalyst composition is respectively by feed intake calculating: ZSM-22, Beta and SAPO-34 molecular sieve content50 % by weight, 20 % by weight, 10 % by weight, alumina content is 20 % by weight.
(2) produce propylene. The Catalyst packing that (1) is made is in fixed bed reactors, by naphtha(containing alkene 1 % by weight, containing alkane 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 weight%, basic nitrogen 0.5 μ g/g) and water after 250 DEG C of preheatings, inject fixed bed reactors. Wherein naphthaThe weight (hourly) space velocity (WHSV) of injecting is 2.3hr-1, water/oily feed weight ratio is 0.46. Reaction temperature is 520 DEG C, pressesPower is 0.2MPa. Reaction result is in table 1.
Embodiment 2
The present embodiment is for illustrating preparation method and the naphtha catalytic cracking of catalyst provided by the inventionProduce the method for propylene.
(1) Kaolinite Preparation of Catalyst. Contain ZSM-23 molecular screen (the limited public affairs of Shanghai Zhuo Yue chemical industry by 32 gramsDepartment, Si/Al mol ratio=50:1), (Shen, Shanghai environmental friendly material covered with clouds is limited for 32 grams of mordenite molecular sievesCompany, Si/Al mol ratio=80:1) and 30 grams of ITQ-3 molecular sieves (self-control, Si/Al mol ratio=10:1) mechanical mixture adds the Ludox (solid content is 30 % by weight) containing 6 grams of silica after evenly,Through compression molding, obtain catalyst.
Catalyst composition contains by calculating: the ZSM-23 that feeds intake, mordenite molecular sieve and ITQ-3 molecular sieveAmount is 32 % by weight, 32 % by weight, 30 % by weight, and silicon oxide substrate content is 6 % by weight.
(2) produce propylene. The Catalyst packing that (1) is made is in fixed bed reactors, by naphtha(containing alkene 1 % by weight, containing alkane 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 weight%, basic nitrogen 0.5 μ g/g) and water after 250 DEG C of preheatings, inject fixed bed reactors. Wherein naphthaThe weight (hourly) space velocity (WHSV) of injecting is 36.5hr-1, water/oily feed weight ratio is 0.96. Reaction temperature is 570 DEG C,Pressure is 0.1MPa. Reaction result is in table 1.
Embodiment 3
The present embodiment is for illustrating preparation method and the naphtha catalytic cracking of catalyst provided by the inventionProduce the method for propylene.
(1) Kaolinite Preparation of Catalyst. By 21 grams of boehmites, (catalyst Nanjing branch company, containing butt 15Gram), 32 grams of kaolin (catalyst asphalt in Shenli Refinery, containing 25 grams of butts) and 90 grams of deionized waters existStir lower mixing, add 4.0 grams of red fuming nitric acid (RFNA)s (chemical pure, Beijing Chemical Plant produces) stirring acidifying 1 littleTime after be warming up to 60 DEG C of acidifyings 1 hour, pH value is 2.8. In the time that temperature is reduced to below 40 DEG C, addEnter to contain 50 grams of NU-10 molecular sieves (self-control, Si/Al mol ratio=80:1), 5 grams of SSZ-13 moleculesSieve (self-control, Si/Al mol ratio=40:1) and 5 grams of cancrinites (Kai Long mining industry Co., Ltd, Si/AlMol ratio=3:1) suspension (solid content is 35 % by weight), mix after stir within 1 hour, urgedAgent mixture.
Described catalyst mixture adopts NiroBowenNozzleTowerTMThe spray dryer of modelSpray dry, spraying drying pressure is 8.5MPa to 9.5MPa, and inlet temperature is below 500 DEG C,Outlet temperature is about 150 DEG C. First at 150 DEG C, be dried 1 hour by the dry microballoon obtaining of spraying, soAfter at 480 DEG C roasting within 1 hour, obtain catalyst.
Catalyst composition is 50 weights by calculating: the NU-10 that feeds intake, SSZ-13 molecular sieve and cancrinite contentAmount %, 5 % by weight, 5 % by weight, matrix (aluminium oxide+kaolin) content is 40 % by weight.
(2) produce propylene. Naphtha (containing alkene 1 % by weight, containing alkane 56 % by weight, is contained to cycloalkanesHydrocarbon 32 % by weight, containing aromatic hydrocarbons 11 % by weight, basic nitrogen 0.5 μ g/g) and water after 250 DEG C of preheatings, injectIn fluidized-bed reactor. The catalyst that (1) is made adds in fluidized-bed reactor with fluidisation state, itsThe weight (hourly) space velocity (WHSV) that middle naphtha injects is 4.6hr-1, water/oily feed weight ratio is 1.61. Reaction temperature is590 DEG C, pressure is 0.1MPa. Reaction result is in table 1.
Embodiment 4
According to the method cracking naphtha of embodiment 3, different, in catalyst the first molecular sieve byZSM-22 zeolite (sial atomic molar ratio is 30) and ISI-4 zeolite (sial atomic molar ratio is 30)Replace, and the part by weight of the two is 1:1.
Embodiment 5
According to the method cracking naphtha of embodiment 3, different, in catalyst the first molecular sieve by(sial atomic molar ratio is for NU-10 zeolite (sial atomic molar ratio is 80) and ZSM-23 zeolite50) replace, and the part by weight of the two is 2:1.
Embodiment 6
According to the method cracking naphtha of embodiment 3, different, in catalyst the first molecular sieve bySSZ-32 zeolite (sial atomic molar ratio is 30) and KZ-1 zeolite (sial atomic molar ratio is 50)Replace, and the part by weight of the two is 5:1.
Embodiment 7
According to the method cracking naphtha of embodiment 4, different, the first molecular sieve in catalystZSM-22 zeolite is by ZSM-22 zeolite (sial atomic molar ratio is 30) and NU-10 zeolite (sialAtomic molar ratio is 30), the weight ratio of the two is 3:1; ISI-4 zeolite is by ISI-4 zeolite (sial atomMol ratio is 30) and the mixture of ZSM-23 zeolite (sial atomic molar ratio is 30) replace, twoPerson's weight ratio is 4:1.
Embodiment 8
The present embodiment is for illustrating preparation method and the naphtha catalytic cracking of catalyst provided by the inventionProduce the method for propylene.
Kaolinite Preparation of Catalyst, according to the method Kaolinite Preparation of Catalyst of embodiment 6, different, the first molecular sieveSeparate and feed intake with the second molecular sieve, type three-molecular screen alternating, specific as follows:
(1) Kaolinite Preparation of Catalyst. By 21 grams of boehmites, (catalyst Nanjing branch company, containing butt 15Gram), 50 gram of first molecular sieve (SSZ-32 zeolite (sial atomic molar ratio is 30) and KZ-1 zeolite(sial atomic molar ratio is 50), and the part by weight of the two is 5:1), 32 grams of kaolin (catalysisAgent asphalt in Shenli Refinery, containing 25 grams of butts) and 183 grams of deionized waters under agitation mix, add 8.1Gram red fuming nitric acid (RFNA) (chemical pure, Beijing Chemical Plant produces) stirs acidifying and after 1 hour, is warming up to 60 DEG C of acidifyings 1Hour, pH value is 2.8. In the time that temperature is reduced to below 40 DEG C, adds and contain 5 grams of SSZ-13 moleculesSieve (self-control, Si/Al mol ratio=40:1) and 5 grams of cancrinites (Kai Long mining industry Co., Ltd, Si/AlMol ratio=3:1) suspension (solid content is 35 % by weight), mix after stir within 1 hour, urgedAgent mixture.
Described catalyst mixture adopts NiroBowenNozzleTowerTMThe spray dryer of modelSpray dry, spraying drying pressure is 8.5MPa to 9.5MPa, and inlet temperature is below 500 DEG C,Outlet temperature is about 150 DEG C. First at 150 DEG C, be dried 1 hour by the dry microballoon obtaining of spraying, soAfter at 480 DEG C roasting within 1 hour, obtain catalyst.
Catalyst forms by the calculating that feeds intake: the first molecular sieve, SSZ-13 molecular sieve and cancrinite content are50 % by weight, 5 % by weight, 5 % by weight matrix (aluminium oxide+kaolin) content are 40 % by weight.
(2) produce propylene. Naphtha (containing alkene 1 % by weight, containing alkane 56 % by weight, is contained to cycloalkanesHydrocarbon 32 % by weight, containing aromatic hydrocarbons 11 % by weight, basic nitrogen 0.5 μ g/g) and water after 250 DEG C of preheatings, injectIn fluidized-bed reactor. The catalyst that (1) is made adds in fluidized-bed reactor with fluidisation state, itsThe weight (hourly) space velocity (WHSV) that middle naphtha injects is 4.6hr-1, water/oily feed weight ratio is 1.61. Reaction temperature is590 DEG C, pressure is 0.1MPa. Reaction result is in table 1.
Comparative example 1
According to the method for embodiment 1, different, ZSM-22 zeolite and SAPO-34 molecular sieve are equalBeta zeolite by equivalent replaces, and molecular sieve is all the second molecular sieve.
Comparative example 2
According to the method for embodiment 1, different, Beta zeolite and SAPO-34 molecular sieve by etc.The ZSM-22 zeolite of amount replaces, and molecular sieve is all the first molecular sieve.
Comparative example 3
According to the method for embodiment 1, different, ZSM-22 zeolite, Beta zeolite are by equivalentSAPO-34 molecular sieve replaces, and molecular sieve is all type three-molecular screen alternating.
Table 1
Can find out from the data result of table 1, catalyst provided by the invention contains the first molecular sieve,Two molecular sieves and type three-molecular screen alternating, produce in propylene carrying out naphtha catalytic cracking, can obtain high secondAlkene and propene yield, and wherein propylene/ethylene ratio is greater than 1, can realize producing more propylene.
Claims (13)
1. naphtha catalytic cracking produces the catalyst of propylene, taking the gross weight of this catalyst as benchmark,The matrix of the molecular sieve that this catalyst contains 50-95 % by weight and 5-50 % by weight; Described molecular sieve containsThe first molecular sieve, the second molecular sieve and type three-molecular screen alternating, described the first molecular sieve is for having ten-ring one dimensionThe molecular sieve of ellipse duct structure, described the second molecular sieve is the molecule with twelve-ring pore passage structureSieve, described type three-molecular screen alternating is the small pore molecular sieve of maximum duct opening diameter below 0.45nm.
2. catalyst according to claim 1, wherein,
The molecular sieve that described the first molecular sieve is TON structure and/or the molecular sieve of MTT structure, preferablyThe mixture of the molecular sieve that described the first molecular sieve is TON structure and the molecular sieve of MTT structure; Preferably,The weight ratio of the molecular sieve of the molecular sieve of described TON structure and MTT structure is 0.1-10:1, more preferablyFor 1-5:1; The molecular sieve of described TON structure comprise Theta-1 zeolite, ISI-1 zeolite, KZ-2 zeolite,One or more in NU-10 zeolite, ZSM-22 zeolite and SSZ-32 zeolite; Described MTT structureMolecular sieve comprise the one in ZSM-23 zeolite, EU-13 zeolite, ISI-4 zeolite and KZ-1 zeoliteOr multiple; More preferably the molecular sieve of described TON structure is the mixed of ZSM-22 zeolite and NU-10 zeoliteCompound, the weight ratio of the two is 2-5:1; The molecular sieve of described MTT structure is ISI-4 zeolite and ZSM-23The mixture of zeolite, the weight ratio of the two is 2-5:1;
The duct opening diameter of described the second molecular sieve is 0.6-0.75 nanometer, be preferably be selected from there is AET,AFR、AFS、AFI、BEA、BOG、CFI、CON、GME、IFR、ISV、LTL、MEI、At least one in the molecular sieve of MOR, OFF and SAO structure;
Described type three-molecular screen alternating be selected from there is ATT, ATN, CHA, ITE, STI and WEN structureAt least one in molecular sieve.
3. catalyst according to claim 1, wherein, described the first molecular sieve, described secondThe weight ratio of molecular sieve and described type three-molecular screen alternating is 0.1-15:0.1-5:1.
4. catalyst according to claim 1, wherein, taking the gross weight of this catalyst as benchmark,The matrix of the molecular sieve that this catalyst contains 60-95 % by weight and 5-40 % by weight.
5. catalyst according to claim 1, wherein, described matrix is selected from aluminium oxide, oxidationAt least one in silicon, amorphous aluminum silicide, zirconia, titanium oxide, boron oxide and alkaline earth oxide.
6. prepare the method that naphtha catalytic cracking produces the catalyst of propylene, the method comprises:
(1) substrate source, water and optional acid solution are mixed, form slurries;
(2), by molecular sieve or contain molecular sieve and the suspension of water mixes with described slurries, obtainCatalyst mixture carries out moulding, the dry and roasting of the line option of going forward side by side;
Described molecular sieve contains the first molecular sieve, the second molecular sieve and type three-molecular screen alternating, described the first moleculeSieve is for having the molecular sieve of ten-ring one dimension ellipse duct structure, and described the second molecular sieve is for having 12The molecular sieve of membered ring channel structure, described type three-molecular screen alternating be maximum duct opening diameter 0.45nm withUnder small pore molecular sieve.
7. prepare the method that naphtha catalytic cracking produces the catalyst of propylene, the method comprises:
(1) substrate source, water, the first molecular sieve and optional acid solution are mixed, form slurries;
(2) by the second molecular sieve and type three-molecular screen alternating or contain the second molecular sieve and type three-molecular screen alternating andThe suspension of water mixes with described slurries, and the catalyst mixture obtaining carries out moulding, the line option of going forward side by sideBe dried and roasting;
Described the first molecular sieve is the molecular sieve with ten-ring one dimension ellipse duct structure, described secondMolecular sieve is the molecular sieve with twelve-ring pore passage structure, and described type three-molecular screen alternating is maximum duct openingThe small pore molecular sieve of diameter below 0.45nm.
8. according to the method described in claim 6 or 7, wherein,
The molecular sieve that described the first molecular sieve is TON structure and/or the molecular sieve of MTT structure, preferablyThe mixture of the molecular sieve that described the first molecular sieve is TON structure and the molecular sieve of MTT structure; Preferably,The weight ratio of the molecular sieve of the molecular sieve of described TON structure and MTT structure is 0.1-10:1, more preferablyFor 1-5:1; The molecular sieve of described TON structure comprise Theta-1 zeolite, ISI-1 zeolite, KZ-2 zeolite,One or more in NU-10 zeolite, ZSM-22 zeolite and SSZ-32 zeolite; Described MTT structureMolecular sieve comprise the one in ZSM-23 zeolite, EU-13 zeolite, ISI-4 zeolite and KZ-1 zeoliteOr multiple; More preferably the molecular sieve of described TON structure is the mixed of ZSM-22 zeolite and NU-10 zeoliteCompound, the weight ratio of the two is 2-5:1; The molecular sieve of described MTT structure is ISI-4 zeolite and ZSM-23The mixture of zeolite, the weight ratio of the two is 2-5:1;
The duct opening diameter of described the second molecular sieve is 0.6-0.75 nanometer, be preferably be selected from there is AET,AFR、AFS、AFI、BEA、BOG、CFI、CON、GME、IFR、ISV、LTL、MEI、At least one in the molecular sieve of MOR, OFF and SAO structure;
Described type three-molecular screen alternating has ATT for being selected from, ATN, CHA, ITE, STI and WEN structureMolecular sieve at least one.
9. according to the method described in claim 6 or 7, wherein, described the first molecular sieve, describedThe weight ratio of two molecular sieves and described type three-molecular screen alternating is 0.1-15:0.1-5:1.
10. according to the method described in claim 6 or 7, wherein, described substrate source is in step (2)The condition of described roasting under can change the material of matrix into, described matrix be aluminium oxide, silica,At least one in amorphous aluminum silicide, zirconia, titanium oxide, boron oxide and alkaline earth oxide; InstituteIn the catalyst that the addition of stating substrate source and molecular sieve makes to obtain, taking the gross weight of this catalyst as baseStandard, the content of matrix is 5-50 % by weight, the content of molecular sieve is 50-95 % by weight.
11. catalyst that made by the method described in any one in claim 6-10.
12. 1 kinds of naphtha catalytic crackings produce the method for propylene, and the method comprises: split in naphtha catalysisSeparate under reaction condition, naphtha contacted with catalyst with water, obtain propylene product, it is characterized in that,Described catalyst comprises the catalyst described in any one in claim 1-5 and 11.
13. methods according to claim 12, wherein, described naphtha catalytic cracking reaction barPart comprises: temperature is 520-590 DEG C, and pressure is 0.1-0.2MPa, and water/oily feed weight ratio is 0.3-2,Naphtha feed weight (hourly) space velocity (WHSV) is 2-40h-1。
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