CN105582997A - 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, wherein the catalyst includes a structured carrier, and an active component coating which is distributed on inner surfaces and/or outer surfaces of the structured carrier. A molecular sieve has a structure of ten-membered ring two-dimension elliptical-shaped pore channels. 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 1 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,This catalyst comprises ordered structure carrier and is distributed in the work of ordered structure carrier inner surface and/or outer surfaceProperty component coating; Taking the gross weight of described catalyst as benchmark, the content of described active component coating is10-50 % by weight; Taking the gross weight of described active component coating as benchmark, described active component coating containsThere are the molecular sieve of 50-95 % by weight and the matrix of 5-50 % by weight; Described molecular sieve is for having ten-ring twoThe molecular sieve of dimension ellipse duct structure.
The present invention also provides a kind of method of the catalyst of preparing naphtha catalytic cracking product propylene, the partyMethod comprises: (1) mixes molecular sieve and aqueous solvent grind, and obtains molecular sieve pulp, described moleculeSieve is for having the molecular sieve of ten-ring two-dimensional elliptic type pore passage structure; (2) by described molecular sieve pulp and instituteState substrate source and mix, form active component coating slurries; (3) apply with described active component coating slurriesOrdered structure carrier dry and roasting.
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 is catalyst provided by the invention.
Adopt catalyst provided by the invention, can improve the yield of propylene, and obtain propylene/ethyleneMore than 1. For example, in embodiment 1, adopt ordered structure carrier and contain to there is ten-ring two-dimensional ellipticThe catalyst of the active component coating of the molecular sieve of type pore passage structure, the product that naphtha catalytic cracking obtainsIn, C2 ＝-C4 ＝Be selectively 90.8%, C2 ＝+C3 ＝Yield be 68.23%, C3 ＝/C2 ＝Be 1.7, canTo realize producing more propylene.
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.
In the present invention, use term ordered structure catalyst to refer to and comprise that ordered structure carrier carries with being distributed inThe catalyst of the active component coating of body inner surface and/or outer surface; Ordered structure carrier is for having regular knotThe carrier of structure is as honeycomb substrate; Monolithic reactors is for having loaded ordered structure catalyst as catalystThe fixed bed reactors of bed.
The invention provides the catalyst that a kind of naphtha catalytic cracking produces propylene, this catalyst comprises regularStructure carrier and the active component coating that is distributed in ordered structure carrier inner surface and/or outer surface; With describedThe gross weight of catalyst is benchmark, and the content of described active component coating is 10-50 % by weight; With describedThe gross weight of active component coating is benchmark, the molecule that described active component coating contains 50-95 % by weightThe matrix of sieve and 5-50 % by weight; Described molecular sieve is to have dividing of ten-ring two-dimensional elliptic type pore passage structureSon sieve.
The present invention has the molecular sieve of ten-ring two-dimensional elliptic type pore passage structure, is preferably FER or MFSThe one of structure is as catalytic pyrolysis active component, and molecular sieve and matrix are made to active component coatingBe distributed on ordered structure carrier, form ordered structure catalyst, can obtain higher naphtha catalysisThe yield of propylene is produced in cracking.
According to the present invention, described molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure,Preferably duct opening diameter is in 0.45-0.56 nanometer.
According to the present invention, the molecular sieve that preferred described molecular sieve is FER structure and/or MFS structure pointSon sieve. Structure type FER and MFS refer to the molecular sieve structure of international zeolite federation (IZA) name,For describing the space topological structure in molecular sieve duct. The molecular sieve of described FER structure comprisesZSM-35 zeolite, Ferrierite zeolite, FU-9 zeolite, ISI-6 zeolite, NU-23 zeolite and Sr-DZeolites etc., the molecular sieve of MFS structure comprises ZSM-57 zeolite and COK-5 zeolite etc.
Preferred described molecular sieve is that ZSM-35 zeolite, Ferrierite zeolite, FU-9 zeolite, ISI-6 boilAt least one in stone, NU-23 zeolite, Sr-D zeolite, ZSM-57 zeolite and COK-5 zeolite.
According to the present invention, the molecular sieve that preferred described molecular sieve is FER structure and the molecule of MFS structureThe mixture of sieve. More preferably, the weight of the molecular sieve of the molecular sieve of described FER structure and MFS structureThan being 0.1-10:1, more preferably 1-5:1.
More preferably the molecular sieve of described FER structure is ZSM-35 zeolite, Ferrierite zeolite, FU-9At least one in zeolite, ISI-6 zeolite, NU-23 zeolite and Sr-D zeolite, more preferablyAt least one in ZSM-35 zeolite, Ferrierite zeolite and FU-9 zeolite.
More preferably the molecular sieve of MFS structure is at least one in ZSM-57 zeolite and COK-5 zeolite.
According to one of the present invention preferred embodiment, the molecular sieve of preferred described FER structure isThe mixture of ZSM-35 zeolite and Ferrierite zeolite, more preferably the weight ratio of the two is 2-5:1; DescribedThe molecular sieve of MFS structure is the mixture of ZSM-57 zeolite and COK-5 zeolite, more preferably the twoWeight ratio is 2-5:1.
In the present invention, the sial atomic molar of described molecular sieve can be 0.1-100:1 than (Si/Al);Be preferably 30-80:1.
According to the present invention, preferably, taking the gross weight of described active component coating as benchmark, described activityThe matrix of the molecular sieve that component coating contains 54-90 % by weight and 10-46 % by weight.
According to the present invention, preferably, taking the gross weight of described catalyst as benchmark, described active component is coated withThe content of layer is 15-30 % by weight.
According to the present invention, described ordered structure carrier can be for providing catalyst bed in fixed bed reactorsLayer. This ordered structure carrier can be the carrier block of monoblock, and inside forms hollow pore passage structure, ductInwall on the catalyst coat that can distribute, space, duct can be as the flowing space of fluid. Preferably feelingsUnder condition, described ordered structure carrier is selected from the monolithic substrate of the parallel pore passage structure with both ends open.Described ordered structure carrier can be that the regular carrier of honeycomb fashion that cross section has cellular perforate (is called for short honeycombCarrier).
According to the present invention, under preferable case, the hole density in the cross section of described ordered structure carrier is 6-140Hole/square centimeter, is preferably 20-100 hole/square centimeter; The sectional area in each hole is 0.4-10 square of milliRice, is preferably 2-7 square millimeter; Percent opening is 50-80%. The shape in hole can be square (or the wingWing square, in square hole, the centre bit of four edges is equipped with the inside wing of perpendicular edge, and its length isThe 1/5-2/5 of the square length of side), equilateral triangle, regular hexagon, circle and corrugated in one.
According to the present invention, under preferable case, described ordered structure carrier can be selected from cordierite honeycomb carrier,At least one in mullite honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrate.
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.
Catalyst of the present invention can be prepared according to various methods, as long as can prepare, the present invention is aforementioned to be wantedThe catalyst of asking, for the present invention, preferred catalyst of the present invention is prepared as follows: (1)Molecular sieve and aqueous solvent are mixed and ground, obtain molecular sieve pulp, described molecular sieve is for having ten yuanThe molecular sieve of ring two-dimensional elliptic type pore passage structure; (2) described molecular sieve pulp is mixed to shape with substrate sourceBecome active component coating slurries; (3) apply ordered structure carrier dry with described active component coating slurriesDry and roasting.
According to the present invention, under preferable case, the addition of described substrate source and described molecular sieve makes to obtainActive component coating in, taking the gross weight of this active component coating as benchmark, the content total amount of matrix is5-50 % by weight, the content of molecular sieve is 50-95 % by weight.
In method provided by the invention, described substrate source is for providing the base of the active component preparingMatter, the present invention to this without particular/special requirement. It should be noted that working as described matrix is silica and/or oxidationWhen aluminium, although contain aluminium oxide and silica, the oxygen containing in described molecular sieve in described molecular sieveThe amount of SiClx and aluminium oxide still be can be regarded as the amount of described molecular sieve, is not counted in silica and aluminium oxide. ByIn the active component that method provided by the invention makes, the content of each component calculates according to inventory.
According to the present invention, sieve particle diameter d in molecular sieve pulp described in step (1)90For 1-10Micron, is preferably 5-10 micron, and the solid content of described molecular sieve pulp is 15-70 % by weight, described containingAqueous solvent is deionized water.
According to the present invention, preferably, with the described active component coating slurries that obtain in step (2)Gross weight is benchmark, and the content of described molecular sieve is 3-60 % by weight, in the described substrate source of buttTotal content is 0.3-18 % by weight.
According to the present invention, described in step (2), active component coating slurries can also contain dispersant,The weight ratio of described dispersant and described molecular sieve is below 0.2 and is greater than 0; Be preferably 0.0005-0.015:1。
According to the present invention, dispersant described in step (2) is selected from and contains polyhydroxy, polyvinyl and poly-The compound of at least one group in carboxylic acid group, for example polyethylene glycol, glycerine, polyvinyl alcohol or poly-One or more in acrylic acid, are preferably polyethylene glycol and/or polyacrylic acid.
According to the present invention, step (3) can be starched described active component coating by various painting methodsLiquid is distributed on the inner surface and/or outer surface of ordered structure carrier, prepares catalyst provided by the invention.The method of described coating can be that water is coated with method, infusion process or spray process. The concrete operations that apply can referenceMethod described in CN1199733C is carried out. The temperature of described coating is preferably 10-70 DEG C, more preferablyFor 15-35 DEG C, the pressure of coating is preferably-0.04 MPa to 0.4 MPa, and coating time is preferably 0.1-100Second.
According to the present invention, the ordered structure carrier that applies good described active component coating slurries is driedAnd roasting. Described dry method and condition are conventionally known to one of skill in the art, for example, and dry sideMethod can be dry, oven dry, forced air drying. Under preferable case, in step (3), dry temperatureCan be room temperature to 300 DEG C, be preferably 100-200 DEG C; The described dry time is at least 0.5 hour,Be preferably 1-10 hour.
According to the present invention, the condition of roasting described in step (3) can be also those skilled in the art instituteKnown, in general, the temperature of described roasting is 400-800 DEG C, is preferably 500-700 DEG C; Described roastingThe time of burning is at least 0.5 hour, is preferably 1-10 hour.
According to the present invention, the kind of described molecular sieve is described in detail aforementioned, does not repeat them here.
According to the present invention, in the time that described matrix is silica, substrate source can be silica source, preferably instituteStating silica source is the natural crystal that silica or silica content are greater than 45 % by weight. Preferably, instituteStating silica source can be Ludox, laminated clay column, diatomite, expanded perlite, silicalite, hydrolysisAt least one in silica, macropore silicon oxide and silica gel.
According to the present invention, in the time that described matrix is aluminium oxide, substrate source can be alumina source, described oxygenChanging aluminium source can be for changing the material of aluminium oxide under the condition of the described roasting of step (3). ExcellentSelection of land, described alumina source is one or more in boehmite, hydrated alumina and aluminium colloidal sol;Described hydrated alumina is boehmite, false boehmite, hibbsite and amorphous hydrogen-oxygenChange at least one in aluminium.
The present invention also provides the catalyst being made by method provided by the invention.
According to the present invention, this catalyst comprises ordered structure carrier and is distributed in ordered structure carrier inner surfaceAnd/or the active component coating of outer surface; Taking the gross weight of described catalyst as benchmark, described active componentThe content of coating is 10-50 % by weight; Taking the gross weight of described active component coating as benchmark, described workThe total content that property component coating contains silica and aluminium oxide is 5-50 % by weight, and the content of molecular sieve is50-95 % by weight; Described molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure. ExcellentThe total content that selection of land contains silica and aluminium oxide is 5-20 % by weight, and the content of molecular sieve is that 80-95 is heavyAmount %.
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 is 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, than for 0.3-2, is preferably 0.4-1.7;Catalyst is in active component coating, and naphtha feed weight (hourly) space velocity (WHSV) is 2-40h-1, be preferably2.3-36.5h-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 56.2 grams of ZSM-35 molecular sieves, (Nanjing Ji Cang nanosecond science and technology are limitedCompany, Si/Al mol ratio=30:1) mix with 56.2 grams of deionized waters, wet ball grinding becomes molecule screening the pulpLiquid, sieve particle diameter d90=10 microns, solid content is 50 % by weight. In slurries, add 28.4Gram aluminium colloidal sol (salic 22 % by weight, catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces), stirs 10Minute, (in polyglycol solution, the percetage by weight of polyethylene glycol is to add 1.5 grams of polyglycol solutions2 % by weight), stir and within 20 minutes, obtain catalyst coat slurries (coating slurries).
By active component coating slurries, (carrier hole density is 100 holes/flat to apply cordierite honeycomb carrierSquare centimetre, the sectional area in each hole is 7 square millimeters, and percent opening is 80%, hole be shaped as square),At 120 DEG C, roasting 5 hours at dry 5 hours and 500 DEG C, obtains catalyst, and wherein, active component is coated withLayer content is 15 % by weight.
By feeding intake, calculated activity component coating forms: ZSM-35 molecular sieve content is 90 % by weight, matrix(aluminium oxide) content is 10 % by weight.
(2) produce propylene. The catalyst that (1) is made, as beds, forms ordered structure anti-Answer device, wherein, the gross weight of active component coating is 62.5 grams. By naphtha (containing alkene 1 % by weight,Containing alkane 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, basic nitrogen 0.5 μ g/g)After 250 DEG C of preheatings, inject above-mentioned monolithic reactors with water. Wherein, the heavy space-time that naphtha injectsSpeed (weight of naphtha is with respect to the gross weight of active component coating) is 2.3hr-1, water/oily feed weightThan being 0.46. Reaction temperature is 520 DEG C, and pressure is 0.1MPa. 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. By 32 grams of Ferrierite zeolite powders (self-control, Si/Al mol ratio=50:1) mix with 20 grams of deionized waters, wet ball grinding becomes slurries, sieve particle diameter d in slurries90＝8Micron; (salic 18 % by weight, pH value is in slurries, to add 150 grams of peptization boehmites2.8, catalyst asphalt in Shenli Refinery of China Petrochemical Industry product), stir 15 minutes; Add polyacrylic acid solution 3.2Gram (in polyacrylic acid solution, polyacrylic acid percetage by weight is 1 % by weight), stirs 30 minutes, obtainsCatalyst coat slurries.
By active component coating slurries, apply cordierite honeycomb carrier (carrier hole density be 80 holes/squareCentimetre, the sectional area in each hole is 5 square millimeters, percent opening is 60%, hole be shaped as circle),At 120 DEG C, roasting 5 hours at dry 5 hours and 500 DEG C, obtains catalyst, and wherein, active component is coated withLayer content is 20 % by weight.
By feeding intake, calculated activity component coating forms: Ferrierite zeolite content is 54 % by weight, matrix(aluminium oxide) content is 46 % by weight.
(2) produce propylene. The catalyst that (1) is made, as beds, forms ordered structure anti-Answer device, wherein, the gross weight of active component coating is 59 grams. By naphtha (containing alkene 1 % by weight,Containing alkane 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, basic nitrogen 0.4 μ g/g)After 250 DEG C of preheatings, inject above-mentioned monolithic reactors with water. Wherein, the heavy space-time that naphtha injectsSpeed (weight of naphtha is with respect to the gross weight of active component coating) is 36.5hr-1, water/oily charging weightAmount is than being 0.96. Reaction temperature is 570 DEG C, and 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 70 grams of ZSM-57 zeolites (self-control, Si/Al mol ratio=80:1)Mix with 60 grams of distilled water, wet ball grinding becomes slurries, sieve particle diameter d in slurries90=5 microns;In slurries, add 143 grams of acidic silicasols (silicon oxide-containing 21 % by weight, China Petrochemical Industry's catalyst ShandongBranch company's product), stir 60 minutes; Add 12.6 grams of polyethylene glycol and polyacrylic acid mixed solutions (poly-Ethylene glycol and polyacrylic acid percetage by weight are respectively 3 % by weight and 5 % by weight), stir 30 minutesTo catalyst coat slurries.
By active component coating slurries, apply cordierite honeycomb carrier (carrier hole density be 20 holes/squareCentimetre, the sectional area in each hole is 2 square millimeters, percent opening is 75%, hole be shaped as circle),At 120 DEG C, roasting 5 hours at dry 5 hours and 500 DEG C, obtains catalyst, and wherein, active component is coated withLayer content is 30 % by weight.
By feeding intake, calculated activity component coating forms: ZSM-57 zeolite content is 70 % by weight, matrix (oxygenSiClx) content is 30 % by weight.
(2) produce propylene. The catalyst that (1) is made, as beds, forms ordered structure anti-Answer device, wherein, the gross weight of active component coating is 100 grams. By naphtha (containing alkene 1 % by weight,Containing alkane 56 % by weight, containing cycloalkane 32 % by weight, containing aromatic hydrocarbons 11 % by weight, basic nitrogen 0.6 μ g/g)After 250 DEG C of preheatings, inject above-mentioned monolithic reactors with water. The weight (hourly) space velocity (WHSV) that wherein naphtha injects(weight of naphtha is with respect to the gross weight of active component coating) is 4.6hr-1, water/oily feed weight ratioBe 1.61. Reaction temperature is 590 DEG C, and pressure is 0.2MPa. Reaction result is in table 1.
Embodiment 4
According to the method cracking naphtha of embodiment 3, different, in catalyst, molecular sieve is by ZSM-35Zeolite (sial atomic molar ratio is 30) and COK-5 zeolite (sial atomic molar ratio is 50) 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, molecular sieve is by FerrieriteZeolite (sial atomic molar ratio is 50) and ZSM-57 zeolite (sial atomic molar ratio is 80) generationReplace, 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, molecular sieve is by FU-9Zeolite (sial atomic molar ratio is 50) and ZSM-57 zeolite (sial atomic molar ratio is 30) generationReplace, and the part by weight of the two is 5:1.
Embodiment 7
According to the method cracking naphtha of embodiment 4, different, ZSM-35 in molecular sieve in catalystZeolite is by ZSM-35 zeolite (sial atomic molar ratio is 30) and Ferrierite zeolite (sial atomMol ratio is 30) mixture replace, the weight ratio of the two is 3:1; COK-5 zeolite is by ZSM-57Mixing of zeolite (sial atomic molar ratio is 50) and COK-5 zeolite (sial atomic molar ratio is 50)Compound replaces, and the weight ratio of the two is 4:1.
Comparative example 1
(1) Kaolinite Preparation of Catalyst. By 56.2 grams of ZSM-5 zeolites, (Nankai University produces, Si/Al moleRatio=30:1) mix with 56.2 grams of deionized waters, wet ball grinding becomes molecular sieve pulp, sieve particleDiameter d90=10 microns, solid content is 50 % by weight. In slurries, add 28.4 grams of aluminium colloidal sols (containing oxygenChange aluminium 22 % by weight, catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces), stir and within 20 minutes, obtain mixtureSlurries are through extruded moulding.
By feeding intake, calculated activity component coating forms: ZSM-5 zeolite content is 90 % by weight, matrix (oxygenChange aluminium) content is 10 % by weight.
(2) produce propylene. The catalyst that (1) is made, as beds, forms fixed bed reactionDevice. By naphtha (containing alkene 1 % by weight, containing alkane 56 % by weight, containing cycloalkane 32 % by weight,Containing aromatic hydrocarbons 11 % by weight, basic nitrogen 0.5 μ g/g) and water after 250 DEG C of preheatings, to inject above-mentioned fixed bed anti-Answer device. The weight (hourly) space velocity (WHSV) (with respect to the gross weight of beds) that wherein naphtha injects is 4.6hr-1，Water/oily feed weight ratio is 1.61. Reaction temperature is 590 DEG C, and pressure is 0.1MPa. Reaction result is shown inTable 1.
Comparative example 2
According to the method for embodiment 1, different, the catalyst of use is to contain 18 % by weightThe particle of the matrix (aluminium oxide) of ZSM-35 zeolite (sial atomic molar ratio is 30) and 82 % by weightDiameter is the bar shaped catalyst that 2mm, length are 5mm.
Calculate (C2 ＝+C3 ＝) yield and (C2 ＝～C4 ＝) selective, the results are shown in Table 1.
Comparative example 3
According to the method for embodiment 1, different, the work of active component coating in ordered structure catalystProperty component molecular sieve is Beta zeolite (sial atomic molar ratio is 30), and all the other are all identical.
Calculate (C2 ＝+C3 ＝) yield and (C2 ＝～C4 ＝) selective, the results are shown in Table 1.
Table 1
Can find out from the data result of table 1, catalyst provided by the invention adopt ordered structure carrier andContain and there is ten-ring two-dimensional elliptic type pore passage structure, be a kind of active group of FER or MFS structurePoint coating, produces in propylene carrying out naphtha catalytic cracking, can obtain high ethene and propene yield,And wherein propylene/ethylene ratio is greater than 1, can realize producing more propylene.
Claims (16)
1. naphtha catalytic cracking produces a catalyst for propylene, and this catalyst comprises: ordered structure carriesBody and the active component coating that is distributed in ordered structure carrier inner surface and/or outer surface; With described catalystGross weight be benchmark, the content of described active component coating is 10-50 % by weight; With described active groupThe gross weight of point coating is benchmark, the molecular sieve that described active component coating contains 50-95 % by weight andThe matrix of 5-50 % by weight; Described molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure.
2. catalyst according to claim 1, wherein, described molecular sieve is dividing of FER structureThe molecular sieve of son sieve and/or MFS structure.
3. catalyst according to claim 2, wherein, described molecular sieve is described FER structureMolecular sieve and the mixture of the molecular sieve of MFS structure, wherein, the molecular sieve of FER structure and MFSThe weight ratio of the molecular sieve of structure is 0.1-10:1, is preferably 1-5:1; The molecular sieve of described FER structureFor ZSM-35 zeolite, Ferrierite zeolite, FU-9 zeolite, ISI-6 zeolite, NU-23 zeolite and Sr-DAt least one in zeolite, is preferably in ZSM-35 zeolite, Ferrierite zeolite and FU-9 zeoliteA kind of; The molecular sieve of MFS structure is at least one in ZSM-57 zeolite and COK-5 zeolite.
4. catalyst according to claim 3, wherein, the molecular sieve of described FER structure isThe mixture of ZSM-35 zeolite and Ferrierite zeolite; The molecular sieve of described MFS structure is ZSM-57The mixture of zeolite and COK-5 zeolite.
5. according to the catalyst described in any one in claim 1-4, wherein, with described active groupThe gross weight of point coating is benchmark, the molecular sieve that described active component coating contains 54-90 % by weight andThe matrix of 10-46 % by weight.
6. according to the catalyst described in any one in claim 1-4, wherein, with described catalystGross weight be benchmark, the content of described active component coating is 15-30 % by weight.
7. catalyst according to claim 1, wherein, described ordered structure carrier is selected to be hadThe monolithic substrate of the parallel pore passage structure of both ends open.
8. catalyst according to claim 7, wherein, the cross section of described ordered structure carrierHole density is 6-140 hole/square centimeter, and the sectional area in each hole is 0.4-10 square millimeter, and percent opening is50-80％。
9. according to the catalyst described in any one in claim 1,7 and 8, wherein, described regularStructure carrier is selected from cordierite honeycomb carrier, mullite honeycomb substrate, cellular alumina carrier and metal and closesAt least one in gold honeycomb substrate.
10. 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.
Prepare the naphtha catalytic cracking described in any one in claim 1-10 for 11. 1 kinds and produce propyleneThe method of catalyst, the method comprises:
(1) molecular sieve and aqueous solvent mixed and ground, obtaining molecular sieve pulp, described molecular sieveFor thering is the molecular sieve of ten-ring two-dimensional elliptic type pore passage structure;
(2) described molecular sieve pulp is mixed with substrate source, form active component coating slurries;
(3) apply ordered structure carrier dry and roasting with described active component coating slurries.
12. methods according to claim 11, wherein, in step (1), described molecule screening the pulpSieve particle diameter d in liquid90For 1-10 micron, the solid content of described molecular sieve pulp is that 15-70 is heavyAmount %, described aqueous solvent is deionized water.
13. methods according to claim 11, wherein, in step (2), described active componentCoating slurries also contain dispersant, and the weight ratio of described dispersant and described molecular sieve is below 0.2 and largeIn 0.
14. catalyst that made by the method described in any one in claim 11-13.
15. 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 1-10 and 14.
16. methods according to claim 15, 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 is than being 0.3-2;Catalyst is in active component coating, and naphtha feed weight (hourly) space velocity (WHSV) is 2-40h-1。
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