CN105582996A - 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. The catalyst includes: a well-shaped carrier, and an active component coating which is distributed on the inner surface and/or the outer surface of the well-shaped carrier. A molecular sieve includes a first molecular sieve and a second molecular sieve, wherein the first molecular sieve has a structure of ten-membered ring two-dimension elliptical-shaped pore channels and the second molecular sieve has a structure of twelve-membered ring 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 3 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 the work that is distributed in 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 contains the first molecular sieveWith the second molecular sieve; Described the first molecular sieve is the molecule with ten-ring two-dimensional elliptic type pore passage structureSieve, described the second molecular sieve is the molecular sieve with twelve-ring pore passage 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;
(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;
Wherein, described molecular sieve contains the first molecular sieve and the second molecular sieve; Described the first molecular sieve is toolHave the molecular sieve of ten-ring two-dimensional elliptic type pore passage structure, described the second molecular sieve is for having twelve-ring holeThe molecular sieve of road structure.
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 3.
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: ruleWhole structure carrier and the active component coating that is distributed in ordered structure carrier inner surface and/or outer surface; With instituteThe gross weight of stating catalyst is benchmark, and the content of described active component coating is 10-50 % by weight; With instituteThe gross weight of stating active component coating is benchmark, and described active component coating contains dividing of 50-95 % by weightThe matrix of son sieve and 5-50 % by weight; Described molecular sieve contains the first molecular sieve and the second molecular sieve; DescribedThe first molecular sieve is the molecular sieve with ten-ring two-dimensional elliptic type pore passage structure, and described the second molecular sieve isThere is the molecular sieve of twelve-ring pore passage structure.
In the present invention, use the molecular sieve that contains the first molecular sieve and the second molecular sieve as lytic activity groupDivide, can obtain the yield of high naphtha catalytic cracking product propylene.
According to one of the present invention preferred embodiment, described active component coating comprises inside and outside two-layer,Wherein, internal layer contains described the first molecular sieve, and skin contains described the second molecular sieve. Wherein, internal layer refers toBe contact with ordered structure carrier perisporium layer; Skin refers to the layer being arranged on internal layer, near pipeCenter, road.
According to the present invention, preferably in internal layer active component coating gross weight, contain 50-95 % by weightThe matrix of the first molecular sieve and 5-50 % by weight; In outer active component coating gross weight, contain 50-95The second molecular sieve of % by weight and the matrix of 5-50 % by weight.
In the present invention, internal layer coating adopts the first molecular sieve as catalytic pyrolysis active component, outer coatingAdopt the second molecular sieve as catalytic pyrolysis active component, and separately by the first molecular sieve and the second moleculeSieve and matrix are made active component coating and are distributed on ordered structure carrier, form ordered structure catalyst,Can obtain the yield that higher naphtha catalytic cracking produces propylene.
According to the present invention, described the first molecular sieve is the molecule with ten-ring two-dimensional elliptic type pore passage structureSieve, preferably duct opening diameter is in 0.45-0.56 nanometer.
According to the present invention, molecular sieve and/or MFS structure that preferably described the first molecular sieve is FER structureMolecular sieve. Structure type FER and MFS refer to the molecular sieve knot of international zeolite federation (IZA) nameStructure, 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.
Preferably described the first molecular sieve is ZSM-35 zeolite, Ferrierite zeolite, FU-9 zeolite, ISI-6At least one in zeolite, NU-23 zeolite, Sr-D zeolite, ZSM-57 zeolite and COK-5 zeolite.
According to the present invention, the molecular sieve that preferably described the first molecular sieve is FER structure and MFS structureThe mixture of molecular sieve. More preferably, the molecular sieve of the molecular sieve of described FER structure and MFS structureWeight ratio is 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 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 0.65-0.7 nanometer.More preferably, described the second molecular screening from have AET, 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 ratio can be 0.1-100:1.
According to the present invention, under preferable case, the weight ratio of described the first molecular sieve and described the second molecular sieveFor 1-15:1, be preferably 1.5-7:1.
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.
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 molecular sieve and aqueous solvent grind, and obtains molecular sieve pulp;
(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;
Wherein, described molecular sieve contains the first molecular sieve and the second molecular sieve; Described the first molecular sieve is toolHave the molecular sieve of ten-ring two-dimensional elliptic type pore passage structure, described the second molecular sieve is for having twelve-ring holeThe molecular sieve of road structure.
The preferred embodiment of one according to the present invention, method of the present invention is prepared and is urged as followsAgent: (1) mixes the first molecular sieve and the second molecular sieve separately and grinds with aqueous solvent, obtainsA part screening the pulp liquid and the second molecular sieve pulp;
(2) described the first molecular sieve pulp, the second molecular sieve pulp are mixed separately to shape with substrate sourceBecome the first active component coating slurries and the second active component coating slurries;
(3) apply ordered structure carrier with described the first active component coating slurries, dry roasting,Then applying with the second active component coating slurries the ordered structure that is distributed with the first active component coating carriesBody, dry 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 of matrix is 5-50% 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, for example 5-10 micron, the solid content of described molecular sieve pulp is 15-70 % by weight, for example 50-65% by weight, described aqueous solvent is such as deionized water of water.
According to one of the present invention preferred embodiment, the first molecular sieve pulp described in step (1)Sieve particle diameter d with the second molecular sieve pulp90The 1-10 micron of respectively doing for oneself, for example 5-10 micron,The solid content of described the first molecular sieve pulp and the second molecular sieve pulp 15-70 % by weight of respectively doing for oneself, for example50-65 % by weight, described aqueous solvent is such as deionized water of 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, is preferably 10-40 % by weight, instituteState substrate source taking the total content of matrix as 0.3-18 % by weight, be preferably 4-15 % by weight.
According to one of the present invention preferred embodiment, with described the first active component coating slurries andTwo active component coating slurries gross weight is separately benchmark, described the first molecular sieve (or second molecular sieve)The content 3-60 % by weight of respectively doing for oneself, be preferably 10-40 % by weight, described substrate source is total in matrixContent is 0.3-18 % by weight, is preferably 4-15 % by weight.
According to one of the present invention preferred embodiment, form the first active component coating slurries and secondSubstrate source kind and the consumption of active component coating slurries can be identical or different, specifically can be according to realityNeed to select.
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。
A preferred embodiment of the invention, the first active component coating described in step (2)Described in slurries, the weight ratio of dispersant and described the first molecular sieve is 0.0005-0.015:1, and described second livesDescribed in property component coating slurries, the weight ratio of dispersant and described the second molecular sieve is 0.0006-0.002:1.
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 laminated clay column, diatomite, expanded perlite, silicalite, Ludox, macroporeAt least one in silica 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 hydrated alumina, aluminium colloidal sol and boehmite;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 molecular sieve that property component coating contains 50-95 % by weight and the matrix of 5-50 % by weight; Described molecular sieve containsThere are the first molecular sieve and the second molecular sieve; Described the first molecular sieve is for having ten-ring two-dimensional elliptic type ductThe molecular sieve of structure, described the second molecular sieve is the molecular sieve with twelve-ring pore passage structure.
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, and water/oily feed weight is than being 0.3-2, and catalyst is with active groupDivide coating meter, naphtha feed weight (hourly) space velocity (WHSV) 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 56.2 grams of ZSM-35 molecular sieves (Shanghai Zhuo Yue Chemical Co., Ltd.,Si/Al mol ratio=30:1) mix with 56.2 grams of deionized waters, wet ball grinding becomes molecular sieve pulp, pointSon sieve particle diameter d90=10 micron. In slurries, add 28.4 grams of aluminium colloidal sols (salic 22 weightsAmount %, catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces), stir 10 minutes, add polyglycol solution 1.5Gram (polyglycol solution percetage by weight is 2 % by weight), stirs and within 20 minutes, obtains the first active componentCoating slurries 1.
The first active component coating slurries 1 are applied to cordierite honeycomb carrier, and (carrier hole density is 100 holes/ square centimeter, the sectional area in each hole is 7 square millimeters, percent opening is 80%, being just shaped as of holeSquare), roasting 5 hours at dry 5 hours and 500 DEG C, obtains catalyst precarsor 1 at 120 DEG C, itsIn, active component coating content is 15 % by weight.
By mixed with 30 grams of deionized waters 30 grams of Beta molecular sieves (self-control, Si/Al mol ratio=100:1)Close, wet ball grinding becomes molecular sieve pulp, sieve particle diameter d 90=10 micron, and solid content is 50% by weight. In slurries, add 15.0 grams of aluminium colloidal sols (salic 22 % by weight, China Petrochemical Industry's catalystAsphalt in Shenli Refinery produces), stir 10 minutes, add 1.0 grams of (polyglycol solutions of polyglycol solutionPercetage by weight is 2 % by weight), stir and within 20 minutes, obtain the second active component coating slurries 2.
By at 1,120 DEG C of the second active component coating slurries 2 coated catalysts precursor, dry 5 hours alsoRoasting 5 hours at 500 DEG C, wherein, outer active component coating content is 9 % by weight. With active groupPoint coating gross weight meter: molecular sieve content is 90 % by weight, and matrix (aluminium oxide) content is 10 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. The weight (hourly) space velocity (WHSV) that wherein naphtha injects(with respect to the gross weight of active component coating) is 25hr-1, water/oily feed weight ratio is 0.46. ReactionTemperature 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 molecular sieves (ZeolystInternational of molecular sieve international corporation,Si/Al mol ratio=10:1) mix with 20 grams of deionized waters, wet ball grinding becomes slurries, molecule in slurriesSieve particle diameter d90=8 micron; In slurries, add 150 grams of peptization boehmites (salic18 % by weight, pH value is 2.8, catalyst asphalt in Shenli Refinery of China Petrochemical Industry product), stir 15 minutes; AddEnter 3.2 grams of polyacrylic acid solution (polyacrylic acid solution percetage by weight is 1 % by weight), polypropylene is acid-solubleLiquid addition is 10 % by weight of molecular sieve weight, stirs 30 minutes, obtains, and obtains first active groupDivide coating slurries 1.
By the first active component coating slurries 1 apply cordierite honeycomb carrier (carrier hole density be 80 holes/Square centimeter, 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 precarsor 1, wherein, and activityComponent coating levels is 10 % by weight.
By 32 grams of mordenite molecular sieves (Shanghai Shen Tan environmental friendly material Co., Ltd, Si/Al mol ratio=80:1) mix with 30 grams of deionized waters, wet ball grinding becomes molecular sieve pulp, sieve particle diameterD90=10 micron, solid content is 50 % by weight. In slurries, add 122 grams of aluminium colloidal sols (salic22 % by weight, catalyst asphalt in Shenli Refinery of China Petrochemical Industry produces), stir 10 minutes, add polyethylene glycol molten1.0 grams of liquid (polyglycol solution percetage by weight is 2 % by weight), stir and within 20 minutes, obtain the second workProperty component coating slurries 2.
By at 1,120 DEG C of the second active component coating slurries 2 coated catalysts precursor, dry 5 hours alsoRoasting 5 hours at 500 DEG C, its ectomesoderm active component coating content is 10 % by weight. With active componentCoating gross weight meter: molecular sieve 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. The weight (hourly) space velocity (WHSV) that wherein naphtha injects(with respect to the gross weight of active component coating) is 36.5hr-1, water/oily feed weight ratio is 0.96. InsteadAnswering 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. Contain ZSM-57 molecular sieve (Si/Al mol ratio=80:1) by 70 gramsMix with 60 grams of distilled water, wet ball grinding becomes slurries, sieve particle diameter d 90=5 micron in slurries;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 divided into 3 % by weight and 5 % by weight), stir and obtain for 30 minutesThe first active component coating slurries 1.
By the first active component coating slurries 1 apply cordierite honeycomb carrier (carrier hole density be 20 holes/Square centimeter, 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 precarsor 1, wherein active groupDividing coating levels is 20 % by weight.
10 grams of SSZ-13 (Si/Al mol ratio=40:1) are mixed to wet method ball with 10 grams of deionized watersWear into molecular sieve pulp, sieve particle diameter d 90=10 micron, solid content is 50 % by weight. ?(silicon oxide-containing 21 % by weight, catalyst asphalt in Shenli Refinery of China Petrochemical Industry goes out in slurries, to add 20 grams of LudoxProduct), stir 10 minutes, (polyglycol solution percetage by weight is to add 1.0 grams of polyglycol solutions2 % by weight), stir and within 20 minutes, obtain the second active component coating slurries 2.
By at 1,120 DEG C of the second active component coating slurries 2 coated catalysts precursor, dry 5 hours alsoRoasting 5 hours at 500 DEG C, wherein, outer active component coating content is 10 % by weight.
Taking active component coating gross weight: molecular sieve content is as 70 % by weight, matrix (silica)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. Wherein, the heavy space-time that naphtha injectsSpeed (with respect to the gross weight of active component coating) is 4.6hr-1, water/oily feed weight ratio is 1.61. InsteadAnswering temperature is 590 DEG C, and pressure is 0.2Pa. Reaction result is in table 1.
Embodiment 4
According to the method cracking naphtha of embodiment 3, different, in catalyst the first molecular sieve by(sial atomic molar ratio is for ZSM-35 zeolite (sial atomic molar ratio is 30) and COK-5 zeolite50) 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 Ferrierite zeolite (sial atomic molar ratio is 50) and ZSM-57 zeolite80) 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 byFU-9 zeolite (sial atomic molar ratio is 50) and ZSM-57 zeolite (sial atomic molar ratio is 30)Replace, and the part by weight of the two is 5:1.
Embodiment 7
According to the method cracking naphtha of embodiment 4, different, in catalyst in the first molecular sieveZSM-35 zeolite is by ZSM-35 zeolite (sial atomic molar ratio is 30) and Ferrierite zeolite (siliconAluminium atomic molar ratio is 30) mixture replace, the weight ratio of the two is 3:1; COK-5 zeolite by(sial atomic molar ratio is for ZSM-57 zeolite (sial atomic molar ratio is 50) and COK-5 zeolite50) mixture replaces, and the weight ratio of the two is 4:1.
Embodiment 8
Carry out according to the method for embodiment 3, different, by the first active component coating slurries and secondActive component coating slurries apply ordered structure carrier after mixing, and are then dried and roasting, dryDry identical with embodiment 3 with temperature roasting, dry total time and the total time of roasting and embodiment 3Dry identical with the total time of roasting after applying, all the other conditions are all identical.
Embodiment 9
Carry out according to the method for embodiment 3, different, first use described the second active component coating slurriesApply ordered structure carrier, then be dried and roasting, then carry out with the first active component coating slurriesApply, be then dried and roasting, temperature dry and roasting is identical with embodiment 3, all the other conditionsAll identical.
Comparative example 1
According to the method for embodiment 1, different, ZSM-35 molecular sieve is by the Beta zeolite generation of equivalentReplace, molecular sieve is all the second molecular sieve.
Comparative example 2
According to the method for embodiment 1, different, Beta zeolite is by the ZSM-35 molecular sieve generation of equivalentReplace, molecular sieve is all the first molecular sieve.
Comparative example 3
Carry out according to the method for embodiment 3, different, the catalyst of use is prepared as follows:
By 56.2 grams of ZSM-5 molecular sieves (Nankai University produces, Si/Al mol ratio=30:1) and 56.2Gram deionized water is mixed, and wet ball grinding becomes molecular sieve pulp, sieve particle diameter d 90=10 micron,,Solid content is 50 % by weight. In slurries, add 28.4 grams of aluminium colloidal sols (salic 22 % by weight, inEffect of Catalysis In Petrochemistry agent asphalt in Shenli Refinery produces), stir and obtain mix slurry through extruded moulding in 20 minutes.
Catalyst composition: ZSM-5 molecular sieve content is 90 % by weight, and matrix (aluminium oxide) content is10 % by weight.
Table 1
Can find out from the data result of table 1, in the preferred embodiment of the present invention, the invention providesCatalyst adopt ordered structure carrier and be distributed in the two of ordered structure carrier inner surface and/or outer surfaceLayer active component coating; Wherein internal layer molecular sieve has ten-ring two-dimensional elliptic type pore passage structure, is preferablyThe one of FER or MFS structure, outer for thering is the molecular sieve in twelve-ring duct. Carrying out stone brainOil catalytic pyrolysis produces in propylene, can obtain high ethene and propene yield, and wherein, propylene/ethyleneThan being greater than 3, can realize producing more propylene.
Claims (17)
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 contains the first molecular sieve and the second molecular sieve; Described first pointSon sieve is for having the molecular sieve of ten-ring two-dimensional elliptic type pore passage structure, and described the second molecular sieve is for having tenThe molecular sieve of two membered ring channel structures.
2. catalyst according to claim 1, wherein, inside and outside described active component coating comprisesTwo-layer, wherein, internal layer contains described the first molecular sieve, and skin contains described the second molecular sieve; Preferably,In internal layer active component coating gross weight, the first molecular sieve that contains 50-95 % by weight and 5-50 weightThe matrix of %; In outer active component coating gross weight, the second molecular sieve that contains 50-95 % by weightMatrix with 5-50 % by weight.
3. catalyst according to claim 1 and 2, wherein, described the first molecular sieve is FERThe molecular sieve of the molecular sieve of structure and/or MFS structure, preferably described the first molecular sieve is described FER knotThe mixture of the molecular sieve of the molecular sieve of structure and 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; MoreThe molecular sieve of preferred described FER structure is the mixture of ZSM-35 zeolite and Ferrierite zeolite; InstituteThe molecular sieve of stating MFS structure is the mixture of ZSM-57 zeolite and COK-5 zeolite.
4. catalyst according to claim 1 and 2, wherein, the duct of described the second molecular sieveOpening diameter is 0.6-0.75 nanometer, described the second molecular screening from have AET, AFR, AFS, AFI,BEA, BOG, CFI, CON, GME, IFR, ISV, LTL, MEI, MOR, OFF andAt least one in the molecular sieve of SAO structure.
5. catalyst according to claim 1 and 2, wherein, described the first molecular sieve with described inThe weight ratio of the second molecular sieve is 1-15:1.
6. catalyst according to claim 1 and 2, wherein, with described active component coatingGross weight is benchmark, the molecular sieve that described active component coating contains 54-90 % by weight and 10-46 weightThe matrix of %; Taking the gross weight of described catalyst as benchmark, the content of described active component coating is 15-30% by weight.
7. catalyst according to claim 1 and 2, wherein, described ordered structure carrier is selected fromThere is the monolithic substrate of the parallel pore passage structure of both ends open.
8. catalyst according to claim 1 and 2, wherein, described ordered structure carrier cutThe hole density of face is 6-140 hole/square centimeter, and the sectional area in each hole is 0.4-10 square millimeter, perforateRate is 50-80%.
9. catalyst according to claim 1 and 2, wherein, described ordered structure carrier is selected fromIn cordierite honeycomb carrier, mullite honeycomb substrate, cellular alumina carrier and metal alloy honeycomb substrateAt least one.
10. catalyst according to claim 1 and 2, wherein, described matrix be selected from aluminium oxide,In silica, amorphous aluminum silicide, zirconia, titanium oxide, boron oxide and alkaline earth oxide at leastA kind of.
Prepare the method for the catalyst of naphtha catalytic cracking product propylene claimed in claim 1 for 11. 1 kinds,The method comprises:
(1) molecular sieve and aqueous solvent mixed and ground, obtaining molecular sieve pulp;
(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;
Wherein, described molecular sieve contains the first molecular sieve and the second molecular sieve; Described the first molecular sieve is toolHave the molecular sieve of ten-ring two-dimensional elliptic type pore passage structure, described the second molecular sieve is for having twelve-ring holeThe molecular sieve of road structure.
12. methods according to claim 11, wherein, the method comprises:
(1) the first molecular sieve and the second molecular sieve mixed with aqueous solvent separately and ground, obtainingA part screening the pulp liquid and the second molecular sieve pulp;
(2) described the first molecular sieve pulp, the second molecular sieve pulp are mixed separately to shape with substrate sourceBecome the first active component coating slurries and the second active component coating slurries;
(3) apply ordered structure carrier with described the first active component coating slurries, dry roasting,Then applying with the second active component coating slurries the ordered structure that is distributed with the first active component coating carriesBody, dry roasting.
13. methods according to claim 11, wherein, in step (1), described molecule screening the pulpIn liquid, sieve particle diameter d 90 is 1-10 micron, and the solid content of described molecular sieve pulp is that 15-70 is heavyAmount %, described aqueous solvent is deionized water.
14. methods according to claim 11, wherein, active component described in step (2) is coated withLayer slurries also contain dispersant, and the weight ratio of described dispersant and described molecular sieve is below 0.2 and is greater than0。
15. catalyst that made by the method described in any one in claim 11-14.
16. 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 15.
17. methods according to claim 16, 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,Catalyst is in active component coating, and naphtha feed weight (hourly) space velocity (WHSV) is 2-40h-1。
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| CN1152261A (en) * | 1994-07-08 | 1997-06-18 | 埃克森化学专利公司 | Molecular sieves and processes for their manufacture |
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| CN1152261A (en) * | 1994-07-08 | 1997-06-18 | 埃克森化学专利公司 | Molecular sieves and processes for their manufacture |
| CN1223603A (en) * | 1996-05-29 | 1999-07-21 | 埃克森化学专利公司 | Zeolite catalyst and its use in hydrocarbon conversion |
| WO2005035118A1 (en) * | 2003-09-25 | 2005-04-21 | Exxonmobil Chemical Patents Inc. | Multi component catalyst and its use in catalytic cracking |
| CN101102981A (en) * | 2004-12-22 | 2008-01-09 | 埃克森美孚化学专利公司 | Oxygenate to olefin manufacture and recovery process |
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