CN104056652B - A kind of hud typed ZSM-5 molecular sieve pellet catalyst - Google Patents
A kind of hud typed ZSM-5 molecular sieve pellet catalyst Download PDFInfo
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Abstract
A kind of hud typed ZSM-5 molecular sieve pellet catalyst, it is characterized in that being formed by kernel component and shell component, said kernel component is made up of ZSM-5 molecular sieve composition and inorganic oxide, the diameter of kernel component accounts at least 50% of the small ball's diameter, said shell component is made up of ZSM-5 molecular sieve composition and inorganic oxide, taking catalyst weight as benchmark, said ZSM-5 molecular sieve composition accounts for 30-95%, inorganic oxide accounts for 5-70%, said ZSM-5 molecular sieve composition, contains with P2O5The phosphorus of the 0.1-10 % by weight of meter and in the rare earth of the 0-10 % by weight of oxide, in said ZSM-5 molecular sieve, alkali metal is less than 0.2 % by weight, SiO in the content of oxide2With A12O3Molar ratio be 100-1000, nitrogen adsorption method measure under BET method specific area be 300-600m2/ g, total pore volume is 0.2-0.6mL/g, the mesoporous pore volume of bore dia >2nm accounts for the 30-70% of total pore volume. Catalyst of the present invention, for Catalytic dehydration of methanol light olefin reaction processed, has the advantages that activity is high, Propylene Selectivity good and the reaction life-span is long.
Description
Technical field
The present invention relates to a kind of pellet catalyst, relate to furtherly a kind of hud typed ZSM-5 molecular sieve littleSphere catalyst.
Background technology
Propylene is important Organic Chemicals, along with increasing rapidly of the derivative demands such as polypropylene, to propyleneDemand also year by year rise. In the tradition source of production of propylene, approximately 70% from cracking petroleum hydrocarbon vapor technique,Separately have 28% from heavy oil catalytic cracking process, all rely on petroleum resources. The decline of oil production capacity and whole world oilThe significantly rising of valency forces researcher to develop new alternative energy source and new process is produced largeChemicals. Large to ripe also realization of methanol conversion technology through synthesis gas by coal, natural gas, living beings etc.Technical scaleization is produced, and is catalytic material dehydration preparing low-carbon olefins (MTO) and preparing propylene from methanol by methyl alcohol(MTP) technology is the novel alkene production technology that is hopeful to replace petroleum path most. Methanol-to-olefins technologyResearch, exploitation, industrialization become the focus of international each major oil companies technological development in recent years.
From Mobil company of the U.S. in 1984 report by after preparing gasoline by methanol process modification for Methanol low-carbon (LC)After alkene (MTO) (Chang, CD etc., J.Catal., SB, 289 (1984)), many zeolites orMolecular sieve is used as the catalyst of MTO reaction, through screening study for many years, mainly concentrates at present two classesMolecular sieve catalyst. Wherein a class concentrates on as the mesopore zeolite of ZSM-5 zeolite etc. USP3911041 is openAdopt at least about the ZSM-5 zeolite of 0.78 % by weight phosphorus modification, methyl alcohol is turned at 300-700 DEG C of temperatureTurn to alkene. USP4049573 and 4088706 discloses by the oxide of boron or magnesium, or further addsEnter phosphorous oxides modified ZSM-5 zeolite, under 250-700 DEG C and 0.2-30 atmospheric pressure, making methanol conversion is alkeneHydrocarbon. The silica filling that USP4480145 discloses use large crystal ZSM-5-5 zeolite and zeolite pores reduces zeoliteDiffusivity, can improve the ethylene yield of methanol conversion. This patent also discloses by 180-820 DEG CHydrothermal treatment consists reduces zeolite alpha active to 6-10, can improve cycle life and the methanol conversion activity of zeolite.USP4549573 discloses while methanol conversion being hydro carbons under 350-700 DEG C and 1-100 atmospheric pressure, usesConstraint factor is the zeolite that 1-12 and silica/alumina mole ratio are 298-2000, can improve lightweightThe productive rate of alkene.
The another kind of important catalyst that is alkene for methanol conversion is SAPO (SAPO) family molecular sieves.This family molecular sieves is invented in the early 1980s by associating carbon compound company of the U.S. (UCC)(USP4440871), wherein SAPO-34 molecular sieve has represented preferably catalytic performance of methanol-to-olefins, butThe rich ethene that produces in this product, yield of ethene reaches 53.8%, and propylene is that 29.1%, P/E is than very low (USP5817906). Recently be reported in Propylene Selectivity in methanol to olefins reaction and reach 45.4%, ethylene contentsStill very high, P/E (propylene/ethylene) weight ratio is less than 1.45 (USP6710218). SAPO Series Molecules sieveCatalyst aperture is little, easily coking, and in product component, P/E, than low, is not suitable for MTP technique.
Last century the nineties, the ZSM-5 molecular sieve of German Lurgi company based on modification developed a set of completeWhole MTP technique, adopts portion of product alkene circular response mode, and Propylene Selectivity reaches 71.2% (PEPReview98-13), make preparing propylene from methanol technology on relevant ZSM-5 molecular sieve cause again researcher'sPay close attention to.
CN1431982A discloses the method with preparing propylene from methanol, enters series connection and fix after methyl alcohol partial dehydrationBed bioreactor, utilize the mode of portion of product circulation to make methanol conversion for light olefin, used catalyst isZSM-5 zeolite catalyst, its alkali metal content is less than 380ppm. The ZnO content of described catalyst is less than 0.1% by weight, CdO content is less than 0.1 % by weight, and BET surface area is 300 to 600m2/ g, pore volume is 0.3To 0.5mL/g(mercury injection method mensuration). The more detailed preparation method of this catalyst referring to US05063187 andUS07229941 is 0.1-0.9 μ m(US05063187 by the elementary crystallite dimension of Hydrothermal Synthesis) or0.01-0.1 μ m(US07229941) ZSM-5 zeolite be dispersed in that to account for the aluminium oxide of catalyst 10-40% stickyIn knot agent, prepare.
CN1084431A disclose a kind of for methyl alcohol or dimethyl ether produce light olefin process phosphorous, rare earth is firstThe ZSM-5 type zeolite catalyst of element and pore structure conditioning agent and employing dehydration reactor and 2～n reaction are again and againThe course of reaction of the multistage insulation fixed bed cracking reactor of raw handover operation, at high temperature (> 400 DEG C) non-Cycling, is on day device of processing methyl alcohol 0.7-1 ton in scale, methanol conversion 100%, C2～C4Olefine selective can be greater than 85%, and can be greater than 600 hours the online duration of runs, and the one-pass operation cycle can be largeIn 24 hours. Wherein ZSM-5 zeolite silica alumina ratio is 40-80, and catalyst phosphorus content is 0.7-5%, lanthanum orLanthanum rich mischmetal content is 0.9-6.5%.
CN1352627A discloses the catalyst that methyl alcohol or dimethyl ether is selectively converted to light olefin, adopts toolThere is the zeolite of 10 ring cross aisles as ZSM-5 zeolite and ZSM-11 zeolite, by adding phosphorus-containing compoundAnd hydrothermal treatment consists makes and the diffusion of zeolite to 2,2-dimethylbutane in the time measuring under 120 DEG C and 8kPaParameter is less than 100s-1, use catalyst prepared by this zeolite for the reaction of methanol conversion, 370-480 DEG C,When methyl alcohol dividing potential drop is 30-150PSia, the conversion per pass of methyl alcohol is less than 95%, because diffusion-restricted is to etheneSelective raising.
The disclosed use moving bed technique of CN1803738A and independently heavy alkene shift step will be organic containing oxygenCompound is converted into the method for propylene, preferably uses ZSM-5 molecular sieve catalyst, transforms at oxygenatedchemicalsIn reactions steps, use moving-burden bed reactor technology, replace the bed technology of prior art; Adopt independentlyHeavy alkene shift step, makes the reaction temperature in oxygenate conversion reaction step reduce by 15 DEG C; Restriction is urgedAgent circulation timei < 700 hour; Product ethene returns to oxygenate conversion reactor, has reduced catalystOn green coke, make the conversion ratio of activity, oxygenatedchemicals of catalyst and Propylene Selectivity substantially close toOr remain on catalyst initial cycle level, be converted into the average of propylene thereby significantly improved oxygenatedchemicalsPropylene circulation productive rate.
CN101172246A discloses the preparation method of propylene catalyst from methanol conversion. By by sial moleThan being roasting after the ZSM-5 molecular sieve of 20-1000 and adhesive mixed-forming, be selected from hydrochloric acid, nitric acid,In sulfuric acid, phosphoric acid or tartaric acid, the acid solution of at least one or ammonium salt solution exchange rear roasting, then experience temperatureThe steam treatment that degree is 400-700 DEG C, and then with being selected from oxalic acid, citric acid, phosphoric acid or tartaric acidAfter at least one acid solution dipping, roasting makes modified molecular sieve catalyst. This catalyst is for methanol conversion systemWhen propylene is evaluated, methanol conversion can reach 100%, and propene yield reaches 47.1%, P/E ratio higher than 6.
CN101172918A discloses after methyl alcohol first contacts with aluminium oxide catalyst and has contacted with above-mentioned catalystRealize two sections of method for transformation of preparing propylene from methanol.
CN101429085A discloses the method for preparing propylene, ethylene light olefin hydrocarbon from methanol/dimethyl ether, usedCatalyst is silica alumina ratio > 50, the binderless ZSM-5 of 0.01-10% rare earth and the modification of 0.01-10% phosphorous oxidesMolecular sieve, comprises ZSM-5, ZSM-11, ZSM-23, ZSM-48 or its mixture.
CN101239326A discloses the preparation method of propylene catalyst from methanol conversion. By silica alumina ratio beThe former powder of ZSM-5 molecular sieve roasting in air atmosphere of 20～1000, the ZSM-5 that removes segment template agent dividesRoasting after at least one the acid solution exchange being selected from hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid for the former powder of son sieve, thenContact rear roasting with at least one aqueous slkali being selected from alkali metal hydroxide or alkali carbonate, thenBe selected from nitric acid, hydrochloric acid, phosphoric acid or sulfuric acid at least one exchange after roasting make required catalyst.Gained catalyst is at 470 DEG C, and methyl alcohol weight space velocity is 1h-1, the methanol conversion that methyl alcohol dividing potential drop is greater than 70 kPasUnder condition, Propylene Selectivity is greater than 40%, and ethylene selectivity is less than 5%, P/E (propylene/ethylene weight) than largeIn 9.
CN101279282A discloses ZSM-5 molecular sieve catalyst and the preparation side thereof for preparing propylene from methanolMethod. By the ZSM-5 mesopore molecular sieve of silica alumina ratio 20-1000 by mass fraction 20-100% be selected from oxidationAfter the binding agent of silicon, clay or aluminium oxide mixes, extrusion, compressing tablet or spray ball forming; Then through be selected from hydrochloric acid,At least one acid solution in nitric acid, sulfuric acid or acetic acid regulates the ammonium salt solution contact of pH value, and product is in temperatureAfter 400-700 DEG C of Water Under steam treatment with being selected from least one solution in oxalic acid, citric acid or maleic acidDipping. Gained modified molecular sieve catalyst is 500 DEG C of reaction temperatures, methyl alcohol air speed 4h-1Under condition, methyl alcoholConversion ratio 100%, propene yield can reach 47%, P/E ratio and exceed 6. The disclosed catalyst of CN101279280ASimilarly.
The high stability molecular sieve catalyst of the disclosed preparing propylene by methanol transformation of CN101279281A and preparation thereofMethod is 20-1000 by silica alumina ratio, and it is former that percentage by weight is counted the ZSM-5 molecular sieve of 25-99.9%Powder be selected from SiO2, clay, A12O3In at least one binding agent through extrusion, compressing tablet or spray ball forming; Warp againCross be selected from ammonium nitrate, ammonium chloride, ammonium sulfate the ammonium salt solution of at least one or be selected from hydrochloric acid, nitric acid, sulfuric acid,In phosphoric acid, acetic acid, the acid solution of at least one is processed at temperature 20-90 DEG C; Then use weight percent meterAt least one solution being selected from lanthanum, cerium nitrate or chloride for 0.1-5% is 20-90 DEG C of bar in temperatureUnder part, process; At temperature 400-700 DEG C of Water Under steam treatment 2-15 hour; Again with being selected from oxalic acid, lemonIn lemon acid, phosphoric acid, maleic acid, at least one floods to obtain required modified molecular sieve catalyst. This catalyst is used forPreparing propylene by methanol transformation reaction, 470 DEG C of reaction temperatures, methyl alcohol air speed 1 hour-1Under condition, methyl alcohol turnsRate can reach 100%, and propene yield exceedes 45%, and the life-span reaches as high as 850 hours.
CN101306381A discloses a kind of ZSM-5 molecular sieve catalyst and system thereof of preparing propylene by methanol transformationPreparation Method. By the ZSM-5 molecular sieve of silica alumina ratio 20-1000 according to the mass fraction 20-99.8% that accounts for catalystAfter the binding agent that meter is selected from silica, clay or aluminium oxide with at least one mixes, extrusion, compressing tablet or spray ballMoulding; Then at least one acid solution in being selected from hydrochloric acid, nitric acid, sulfuric acid or acetic acid regulates pH valueAmmonium salt solution contact, is then selected from least one nitric acid in barium, magnesium or calcium with weight percent meter 0.01-5%The contact of salt or chloride solution, is then selected from phosphoric acid, metavanadic acid by, molybdenum with weight percent meter 0.01-5%At least one salting liquid contact in acid ammonium or ammonium tungstate; Product is at temperature 400-700 DEG C of Water Under steam placeReason is rear with being selected from least one solution impregnation in oxalic acid, citric acid or maleic acid. The catalysis of gained modified molecular screenAgent is 470 DEG C of reaction temperatures, methyl alcohol air speed 1h-1Under condition, methanol conversion 100%, propene yield can reach45%, the life-span reaches 800 hours, has improved that Propylene Selectivity is low, molecular sieve heat endurance and hydrothermally stableProperty, be difficult for coking and deactivation. The disclosed preparing propylene from methanol ZSM-5 of CN101279283A catalyst furtherThe grain size limits of ZSM-5 molecular sieve is in 0.2-1 micrometer range.
CN101347743A discloses high propylene/ethylene than the preparation method of propylene catalyst from methanol conversion.Adopt first with being selected from NaOH, magnesium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or sodium acid carbonateIn at least one aqueous slkali process the former powder of ZSM-5 molecular sieve, be then selected from hydrochloric acid, nitric acid, sulfuric acid or secondAt least one acid solution processing in acid, more mixed with binding agent after temperature is 400-700 DEG C of steam treatmentAfter synthesis type, roasting, then with being selected from least one solution impregnation in oxalic acid, citric acid, phosphoric acid or tartaric acid,After roasting, obtain ZSM-5 Type Zeolites agent. This catalyst can reach material benzenemethanol conversion ratio100%, propene yield can reach 48.2%, P/E weight ratio can reach 10.
CN101234353A discloses a kind of preparing propylene from methanol catalyst, taking account for molecular sieve mass ratio asThe cerium modified H-ZSM-5 molecular sieve of 0.005-0.15, for preparing propylene from methanol reaction, reaction condition is temperature300-500 DEG C, pressure is 0-1Mpa, liquid hourly space velocity (LHSV) is 0.1-10h-1。
CN101176849A disclose a kind of by methyl alcohol or dimethyl ether in high selectivity prepare propylene catalyst andPreparation method. Adopt rare earth element stable molecule sieve structure, alkaline matter to change surface acidity and online siliconAlkanisation carries out modification to active constituent ZSM-5 molecular sieve catalyst, warp to the duct mode such as modifyThe dry catalyst for fluidized-bed reaction of preparing high selectivity production propylene of spraying; The group of this catalystBecome by following percentage by weight: rare earth 0.1-8%, alkaline modifier 0.5-30%, binding agent 20-80%, siliconAlkanisation silicone content 0.05-10%, all the other are ZSM-5 molecular sieve.
CN101433858A discloses a kind of HZSM-5 molecular sieve catalyst of producing propylene from methanol/dimethyl ether, adoptsWith accounting for the W elements modification HZSM-5 molecular sieve catalyst that molecular sieve mass fraction is 0.005-10%, for firstAlcohol propylene reaction processed, reaction condition is temperature 300-500 DEG C, and pressure is 0-1Mpa, and liquid hourly space velocity (LHSV) is0.1-10h-1。
CN101624192A discloses the HZSM-5 molecular sieve catalytic for a kind of producing propylene from methanol/dimethyl etherAgent, the silica alumina ratio of this ZSM-5 molecular sieve is 250-1150, particle diameter is 65-250nm. The system of this molecular sievePreparation Method comprises aluminium source is mixed with organic directed agents, adds silicon source to become gel with organic additive, then existsHydrothermal crystallizing 24-240h at 60-200 DEG C. Wherein organic additive and SiO2Mol ratio be 0.5-8, plantClass is one or more in methyl alcohol, ethanol, acetone and polyvinylpyrrolidone.
CN102050691A discloses the method for preparing low-carbon alkene with coupling between methanol carbon 4 hydrocarbon, adopts silica alumina ratioFor the phosphorous modified ZSM-5 molecular sieve of 15-80 is catalyst.
CN101780417A discloses the catalyst of a kind of methanol conversion paraxylene processed and low-carbon alkene, by mistakeCross metal and rare-earth metal modified after ZSM-5 molecular sieve again through the compound-modified surface acidity of siloxy group andPore structure preparation, the 0.1-10% that wherein levels of transition metals is catalyst is heavy, and rare earth metal content is catalysisThe 0.1-5% of agent is heavy, and the 0.1-8% that siloxy group compound accounts for catalyst in Si is heavy.
CN102125866A discloses a kind of H-ZSM-5 molecular sieve catalyst for preparing propylene from methanol, forAfter evaporating part moisture formation gel during by Hydrothermal Synthesis molecular sieve initiation material, carry out crystallization orientationThe crystallite dimension preparing is less than 300nm, specific area 380-420m2/ g, silica alumina ratio 80-100'sH-ZSM-5 molecular sieve.
Summary of the invention
Although adopted very complicated preparation were established, such as in the initial reactant of synthesis of molecular sieveAdd organically or inorganic assistant, adopt the methods such as the siloxy group of high price is compound modified synthesize and changeProperty ZSM-5 molecular sieve, but it still has much room for improvement for process for preparing propylene from methanol gained olefine selective. Send outA person of good sense is surprised to find that on the basis of a large amount of ZSM-5 molecular sieve developments, when adopting the processing of fluosilicic acid hydro-thermal methodAfter the ZSM-5 molecular sieve of low sodium content, then with phosphorous and carry out the molecular sieve after activation processing containing earth solutionComposition, have special pore structure and distribute, more unexpectedly, and when using it as catalyst with core-casing structureWhen active component, be used for MTP process, can be in keeping methyl alcohol high conversion, propylene/ethylene mass ratioBe significantly improved, based on this, form the present invention.
The object of this invention is to provide a kind of hud typed ZSM-5 molecular sieve bead catalysis of special physico-chemical propertyAgent.
Hud typed ZSM-5 molecular sieve pellet catalyst provided by the invention, it is characterized in that by kernel component andShell component forms, and said kernel component is made up of ZSM-5 molecular sieve composition and inorganic oxide, inThe diameter of nuclear consitution accounts at least 50% of the small ball's diameter, and said shell component is by ZSM-5 molecular sieve compositionWith inorganic oxide composition, taking catalyst weight as benchmark, said ZSM-5 molecular sieve composition accounts for30-95%, inorganic oxide account for 5-70%, and said ZSM-5 molecular sieve composition, contains with P2O5MeterThe phosphorus of 0.1-10 % by weight and in the rare earth of the 0-10 % by weight of oxide, in said ZSM-5 molecular sieve,Alkali metal is less than 0.2 % by weight, SiO in the content of oxide2With A12O3Molar ratio be 100-1000,BET method specific area under nitrogen adsorption method is measured is 300-600m2/ g, total pore volume is 0.2-0.6mL/g,Bore dia > the mesoporous pore volume of 2nm accounts for the 30-70% of total pore volume.
Hud typed ZSM-5 molecular sieve catalyst of the present invention, for Catalytic dehydration of methanol light olefin processed, specialBe that object product is propylene reaction, have the advantages that activity is high, Propylene Selectivity good and the reaction life-span is long.
Brief description of the drawings
Fig. 1 is the XRD diffraction pattern of the ZSM-5 molecular sieve composition of embodiment 1.
Fig. 2 is the MTP reaction life assessment result of embodiment 8 and comparative example 2 catalyst.
Detailed description of the invention
Hud typed ZSM-5 molecular sieve pellet catalyst provided by the invention, it is characterized in that by kernel component andShell component forms, and said kernel component is made up of ZSM-5 molecular sieve composition and inorganic oxide, inThe diameter of nuclear consitution accounts at least 50% of the small ball's diameter, and said shell component is by ZSM-5 molecular sieve compositionWith inorganic oxide composition, taking catalyst weight as benchmark, said ZSM-5 molecular sieve composition accounts for30-95%, inorganic oxide account for 5-70%, and said ZSM-5 molecular sieve composition, contains with P2O5MeterThe phosphorus of 0.1-10 % by weight and in the rare earth of the 0-10 % by weight of oxide, in said ZSM-5 molecular sieve,Alkali metal is less than 0.2 % by weight, SiO in the content of oxide2With A12O3Molar ratio be 100-1000,BET method specific area under nitrogen adsorption method is measured is 300-600m2/ g, total pore volume is 0.2-0.6mL/g,Bore dia > the mesoporous pore volume of 2nm accounts for the 30-70% of total pore volume.
Taking catalyst weight as benchmark, ZSM-5 molecular sieve composition preferably accounts for 50-90%, inorganic oxidePreferably account for 10-50%. Said inorganic oxide is selected from silica and/or aluminium oxide, kernel component and shellInorganic oxide in component can be identical, also can be not identical.
Said kernel component is made up of ZSM-5 molecular sieve composition and inorganic oxide, and inorganic oxide canTo be silica and/or aluminium oxide, be wherein preferably silica; The diameter of said kernel component accounts for beadAt least 50%, preferably at least 60% of diameter can be for example a value in 50-90%.
Said shell component, is made up of ZSM-5 molecular sieve composition and inorganic oxide, and what contain is inorganicOxide can be silica and/or aluminium oxide. Preferably, said inorganic oxide is aluminium oxide.
Of the present invention preferred embodiment in, in kernel component, inorganic oxide is silica, shell groupIn point, inorganic oxide is aluminium oxide.
Said inorganic oxide is conventionally by precursor separately. Said aluminium oxide, its precursor bagDraw together aluminium colloidal sol, polymeric aluminum chloride, boehmite, boehmite and phosphorous modified aluminas etc.; SaidSilica, its precursor comprises silester, Ludox etc.
In said ZSM-5 molecular sieve composition, said phosphorus is with P2O5The preferred content of meter is that 0.2-5 is heavyAmount %, said rare earth is taking the preferred content of oxide as 0-5 % by weight. Said ZSM-5 molecular sieve,Alkali metal in the preferred content of oxide for being less than 0.1 % by weight, SiO2With A12O3Molar ratio preferredFor 150-500, the BET method specific area under nitrogen adsorption method is measured is preferably 350-500m2/ g, totalPore volume is preferably 0.3-0.5mL/g, its median pore diameter > the mesoporous pore volume of 2nm preferably accounts for total pore volume40-60%. Said rare earth is one or more in yttrium, lanthanum, cerium and praseodymium preferably, preferred rare earth unitElement is lanthanum and/or cerium.
Said ZSM-5 molecular sieve composition, its preparation method, comprises alkali metal-free or low alkali is containedThe former powder of ZSM-5 molecular sieve of amount (alkali metal mainly refers to sodium or potassium, is less than 0.2 % by weight in oxide)Remove organic formwork agent through roasting and obtain roasting powder; Roasting powder carries out liquid phase acid treatment and obtains pickling filter cake; WithAnd said pickling filter cake carries out reclaiming and obtaining after the activation processing of phosphorus-containing compound and compounds containing rare earthThe step of ZSM-5 molecular sieve composition, wherein, said roasting powder carries out liquid phase acid treatment and obtains pickling filterThe step of cake is that roasting powder is evenly become to molecular sieve pulp with the acidic aqueous solution making beating that contains fluosilicic acid, and inHydrothermal treatment consists under temperature 100-200 DEG C, pressure 0.1-2Mpa in airtight still, said fluosilicic acid and saidThe mass ratio of the butt of roasting powder is 0.0001-0.1:1, and in said molecular sieve pulp, water and roasting powder is dryThe mass ratio of base is 3-20:1.
In said method, the former powder of the ZSM-5 molecular sieve of said alkali metal-free or low alkali can be originatedIn multiple channel, such as being commercially available, such as alkali metal obtains through ammonium exchange, preferably at alkali metal-freeOr under the sial system of low alkali, Hydrothermal Synthesis obtains. The sial of said alkali metal-free or low alkaliUnder system, to obtain the process of the former powder of ZSM-5 molecular sieve be by aluminium source, silicon source, water and organic formwork to Hydrothermal SynthesisAgent is thoroughly mixed to form reactant mixture, by reactant mixture under agitation, the temperature of 70～200 DEG C,Hydrothermal crystallizing 20～200 hours under self-generated pressure, crystallization product after filtration, washing, dry, said anti-Mole compositing range of answering mixture is organic formwork agent/SiO2=0.03-0.3，SiO2/Al2O3=100-1000，H2O/SiO2=5-30, wherein, said aluminium source is selected from hydrated alumina, aluminum sulfate, aluminum nitrate, hydroxideAluminium, aluminium isopropoxide; Said silicon source is selected from the solid silicon source such as solid silicone, white carbon; Said organic mouldPlate agent is tetraethyl ammonium hydroxide or TPAOH.
Said roasting removes the organic formwork agent in the former powder of ZSM-5 molecular sieve, obtains ZSM-5 molecular sieve roastingThe step of burning powder, roasting condition is preferably ingress of air roasting 0.5-50h at 300-800 DEG C.
Said roasting powder carries out liquid phase acid treatment and obtains pickling filter cake, says more specifically roasting powder and containsHave the acidic aqueous solution making beating of fluosilicic acid evenly to become molecular sieve pulp, and in airtight still temperature 100-200 DEG C,Under pressure 0.1-2Mpa, process, conventionally process 0.5-30h; In a preferred embodiment, said will roastingBurn powder and evenly become molecular sieve pulp with the acidic aqueous solution making beating that contains fluosilicic acid, and process in airtight stillTemperature is that 105-180 DEG C, pressure are 0.11-1Mpa, more preferably temperature 105-150 DEG C, pressure0.12-0.7Mpa. The mass ratio of the butt of said fluosilicic acid and said roasting powder be 0.0001-0.1,Preferably 0.001-0.05, more preferably 0.002-0.01, in said molecular sieve pulp, water and roasting powder doesThe mass ratio of base is 3-20, preferably 4-15, more preferably 5-10. After said processing, through be cooled to lower than80 DEG C, pressure release, to normal pressure, by products therefrom after filtration, obtain alkali metal content in oxide, for example Na2OThe pickling filter cake of content < 0.2 % by weight. The said acidic aqueous solution that contains fluosilicic acid also can further containBe selected from one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and oxalic acid etc.
Said ZSM-5 molecular sieve pickling filter cake is carried out to activation place of phosphorus-containing compound and compounds containing rare earthReason, is by water-soluble the soluble inorganic phosphor-contained compound of required amount of calculation, is selected from containing of required amount of calculationThe aqueous solution of the soluble salt of one or more rare earth elements in yttrium, lanthanum, cerium and praseodymium becomes activator, willActivator mixes with the making beating of ZSM-5 molecular sieve pickling filter cake, then at 80-800 DEG C of temperature, be dried,Roasting. Said soluble inorganic phosphor-contained compound is selected from phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, di(2-ethylhexyl)phosphateOne or more mixtures in hydrogen ammonium; The aqueous solution of the soluble salt of said rare earth element be selected from yttrium, lanthanum,The soluble salt of cerium or praseodymium element, for example, comprise chloride, nitrate etc.
Said catalyst, taking catalyst weight as benchmark, ZSM-5 molecular sieve composition preferably accounts for 50-90%,Inorganic oxide preferably accounts for 10-50%.
Catalyst of the present invention, the granularity of hud typed bead is that diameter is 0.5-5.0mm, employing rotates intoType legal system is standby. Wherein, adopt inorganic oxide, as with silica-based binding agent (precursor of silica) and instituteThe ZSM-5 molecular sieve composition of saying rotates into ball and forms said kernel bead; Then taking kernel bead as kindSon material, adopts inorganic oxide, as with aluminium oxide precursor binding agent and ZSM-5 molecular sieve composition powderBe rotated further moulding, after shaping of catalyst, at 300-800 DEG C, under ingress of air condition, roasting obtains of the present inventionCatalyst.
Pellet catalyst of the present invention, has special pore structure and physical property, can be for methanol dehydrationLight olefin processed, as propylene course of reaction, has best catalytic performance. For example, suppress in propylene, butylene etc.Between product light olefin further there is the side reactions such as hydrogen migration, superimposed, condensation green coke, improve object product thirdAlkene selective; And combination of molecular sieve has high mesoporous volume, be conducive to improve reactant methanol and productThe diffusion rate of light olefin, and can improve the appearance charcoal amount of catalyst, improve the anti-coking deactivation of catalystAbility, the single pass life of extending catalyst. Said methanol dewatered propylene course of reaction, material benzenemethanol canThink refining and moisture refining methyl alcohol, in course of reaction, can add steam or inert gas regulates firstAlcohol charging dividing potential drop. Reaction temperature used is 250 DEG C-600 DEG C, is preferably 350 DEG C-500 DEG C; Reaction usedPressure is 0.1-50 atmospheric pressure, preferred 0.5-5 atmospheric pressure; Weight space velocity used (WHSV) is 0.01-50h-1、Be preferably 0.1-10h-1。
Below by embodiment, the invention will be further described, but in not thereby limiting the inventionHold.
In each embodiment and comparative example, the X-ray powder diffraction of molecular sieve mensuration instrument is GermanyBrukerD5005 diffractometer, adopts CuK alpha ray; Molecular sieve chemical composition x ray fluorescence spectrometryMeasure. N2Adsorption analysis adopts U.S. MicromeriticsASAP2400 adsorption instrument to measure, wherein> mesoporous pore volume=total pore volume-Micropore volume of 2nm.
Raw materials used except special instruction in embodiment, be chemically pure reagent.
The preparation process of example 1-4 explanation ZSM-5 molecular sieve composition.
Embodiment 1
7.8 kilograms of dry glue powders (are weighed to Al containing 74%2O3, Sinopec catalyst Chang Ling branch company produces, underWith) to join 1694 kilograms of TPAOH aqueous solution (containing 20% heavy TPAOH) moltenSeparate, then add 577 kilograms of solid silicones (Qingdao Marine Chemical Co., Ltd. produces, lower same), stir mixedClose 2 hours. Mole consisting of of gained reactant mixture: TPAOH/SiO2=0.2，SiO2/Al2O3=140，H2O/SiO2=9.5. Pack reactant mixture into stainless steel crystallizing kettle, in 130 DEG C, continuous stirring and spontaneous pressureCrystallization 90 hours under power. Then crystallization product filtered, washed and dry 16h, i.e. scores at 120 DEG CThe former powder product A 1 of son sieve.
Above-mentioned dry former powder A1, as in Muffle furnace, in 550 DEG C of roasting 6h, is obtained to roasting molecular sieve powder A2.
Getting the 400 kilograms of above-mentioned roasting molecular sieve of butt powder A2 joins 2800 kilograms of deionized water for stirring and beatsSlurry, then adds 8.84 kilograms of fluorine silicic acid aqueous solutions (containing 30% fluosilicic acid, lower same), is placed in exchange stillSealing, continuing to be warming up to 130 DEG C under stirring, presses as under 0.28Mpa and keeps 1h at still, is then cooled to70 DEG C of filtrations, washing, obtain filter cake product A 3.
14.17 kilograms of ammonium dihydrogen phosphate (ADP)s are dissolved in 300 kilograms of deionized waters, add 350 kilograms of buttsAbove-mentioned molecular sieve filter cake A3 stirring to pulp is even, then slurries is dried to 16h at 140 DEG C, obtains the present inventionCombination of molecular sieve product A 4.
Get the above-mentioned zeolite product A4 of part, measure through X-ray powder diffraction, its result is as Fig. 1Shown in middle diffraction pattern, illustrate that it is ZSM-5. Through XRF analysis, Na in A4 molecular sieve2O content is 0.04%,P2O5Content is 2.69%, and silica alumina ratio is 158. Through low temperature N2-adsorption analysis, the BET method of A4 molecular sieveSpecific area is 469m2/ g, total pore volume is 0.393mL/g, its mesoporous is > the mesoporous pore volume of 2nm is0.203mL/g, accounting for total pore volume ratio is 51.4%.
Embodiment 2
4.5 kilograms of dry glue powders and 1271 kilograms of TPAOH aqueous solution (are contained to 20% heavy tetrapropylAmmonium hydroxide, Sinopec catalyst Jian Chang branch company produces) pack the dissolving of stainless steel crystallizing kettle into, then add260 kilograms of deionized waters and 577 kilograms of solid silicones, be uniformly mixed 2 hours. Gained reactant mixtureMole consist of: TPAOH/SiO2=0.15，SiO2/Al2O3=180，H2O/SiO2=9. Reactant mixture is existedCrystallization 75 hours under 140 DEG C, continuous stirring and self-generated pressure. Then by crystallization product filter, washing, alsoDry 16h at 120 DEG C, obtain molecular screen primary powder product B 1.
Above-mentioned dry former powder B1, as in Muffle furnace, in 550 DEG C of roasting 4h, is obtained to roasting molecular sieve powder B2.
Getting the 200 kilograms of above-mentioned roasting molecular sieve of butt powder B2 joins 1800 kilograms of deionized water for stirring and beatsSlurry, then adds 2.97 kilograms of fluorine silicic acid aqueous solutions, is placed in exchange still and seals, and is continuing liter under stirringTemperature, to 105 DEG C, keeps 1h under still is pressed as 0.13Mpa, is then cooled to 60 DEG C of filtrations, washing, obtains filterCake product B 3.
4.37 kilograms of ammonium dihydrogen phosphate (ADP)s are dissolved in double centner deionized water, then by 6.1 kilogram of six waterClose yttrium nitrate salt and be dissolved in 80 kilograms of deionized waters, and join and in ammonium dihydrogen phosphate, form colloid,In this colloid, add the 180 kilograms of above-mentioned molecular sieve filter cake of butt B3 stirring to pulps even, then by slurriesDry 24h at 120 DEG C, obtain combination of molecular sieve product B 4 of the present invention.
Get the above-mentioned zeolite product B4 of part, measure through X-ray powder diffraction, its diffraction pattern is with figure1 feature, illustrates that it is ZSM-5. Through XRF analysis, Na in B4 molecular sieve2O content is 0.02%, P2O5Content is 1.49%, Y2O3Content is 1.16%, and silica alumina ratio is 188. Through low temperature N2-adsorption analysis, B4The BET method specific area of molecular sieve is 418m2/ g, total pore volume is 0.31mL/g, its mesoporous is > 2nmMesoporous pore volume is 0.14mL/g, and accounting for total pore volume ratio is 45.2%.
Embodiment 3
0.8 kg of hydrogen aluminium oxide is joined to 330 kilograms of TPAOH aqueous solution and dissolve, then add150 grams of deionized waters and 150 kilograms of white carbons (production of Guangdong Hai Hua Chemical Co., Ltd.), be uniformly mixed 2Hour. Mole consisting of of gained reactant mixture: TPAOH/SiO2=0.17，SiO2/Al2O3=300，H2O/SiO2=12. Pack reactant mixture into stainless steel crystallizing kettle, in 120 DEG C, continuous stirring and spontaneous pressureCrystallization 100 hours under power. Then crystallization product filtered, washed and dry 16h at 120 DEG C, to obtain final productMolecular screen primary powder products C 1.
Above-mentioned dry former powder C1, as in Muffle furnace, in 600 DEG C of roasting 2h, is obtained to roasting molecular sieve powder C2.
Getting the above-mentioned roasting molecular sieve of double centner butt powder C2 joins 1000 kilograms of deionized water for stirring and beatsSlurry, then adds 1.11 kilograms of fluorine silicic acid aqueous solutions, is placed in exchange still and seals, and is continuing liter under stirringTemperature, to 150 DEG C, keeps 4h under still is pressed as 0.48Mpa, is then cooled to 40 DEG C of filtrations, washing, obtains filterCake products C 3.
0.68 kilogram of ammonium dihydrogen phosphate (ADP) is dissolved in 40 kilograms of deionized waters, then adds with RE2O3Meter(Sinopec catalyst asphalt in Shenli Refinery product, ree distribution pattern is for containing for the mixed chlorinated rare earth solution of 100g/L60%La2O3，40%CeO2) 4.4L, add the 70 kilograms of above-mentioned molecular sieve filter cake of butt C3 stirring to pulps even,Then slurries are dried to 16h at 120 DEG C, obtain combination of molecular sieve products C 4 of the present invention.
Get the above-mentioned zeolite product C4 of part, measure through X-ray powder diffraction, its diffraction pattern is with figure1 feature, illustrates that it is ZSM-5. Through XRF analysis, Na in C4 molecular sieve2O content is 0.04%, P2O5Content is 0.69%, La2O3Content is 0.42%, CeO2Content is 0.26%, and silica alumina ratio is 374. Through too lowTemperature N2-adsorption analysis, the BET method specific area of C4 molecular sieve is 440m2/ g, total pore volume is 0.323mL/g,Its mesoporous is > the mesoporous pore volume of 2nm is 0.171mL/g, accounting for total pore volume ratio is 52.9%.
Embodiment 4
The roasting molecular sieve powder B2 that gets preparation in double centner butt embodiment 2 joins 800 grams of deionizationsStirring to pulp in water, then adds 7.48 kilograms of fluorine silicic acid aqueous solutions and 1 kilogram of aqueous hydrochloric acid solution (containing 10%Geavy salt acid), be placed in exchange still and seal, continuing to be warming up to 120 DEG C under stirring, press as 0.21Mpa at stillLower maintenance 2h, is then cooled to 50 DEG C of filtrations, washing, obtains filter cake product D3.
1.46 kilograms of ammonium dihydrogen phosphate (ADP)s are dissolved in 50 kilograms of deionized waters, then by 2.39 kilogram of six waterClose lanthanum nitrate salt and be dissolved in 40 kilograms of deionized waters, and join and in ammonium dihydrogen phosphate, form colloid,In this colloid, add the 90 kilograms of above-mentioned molecular sieve filter cake of butt D3 stirring to pulps even, then slurries are existedDry 24h, obtain combination of molecular sieve product D4 of the present invention for 120 DEG C.
Get the above-mentioned zeolite product D4 of part, measure through X-ray powder diffraction, its diffraction pattern is with figure1 feature, illustrates that it is ZSM-5. Through XRF analysis, Na in D4 molecular sieve2O content is 0.02%, P2O5Content is 0.99%, La2O3Content is 1.17%, and silica alumina ratio is 274. Through low temperature N2-adsorption analysis, D4The BET method specific area of molecular sieve is 432m2/ g, total pore volume is 0.32mL/g, its mesoporous is > 2nmMesoporous pore volume is 0.15mL/g, and accounting for total pore volume ratio is 46.9%.
Example 5-8 explanation is with the pellet catalyst of molecular sieve of the present invention.
Embodiment 5
4 and 400 grams of Ludox of 400 grams of butt molecular sieve-4 As in embodiment 1 (are weighed to SiO containing 25%2) fillDivide and mix, then in bowling machine, rotate into pellet catalyst, screening obtains diameter 1.0-1.2mm'sBead; By 4 and 349 grams of aluminium colloidal sol (Sinopec catalyst asphalt in Shenli Refineries of 300 grams of butt molecular sieve-4 AsProduct, containing 21.5% heavy Al2O3, lower with) be fully mixed into alumina base bonding molecular sieve powder.
In bowling machine, continue to add above-mentioned oxidation taking the bead of above-mentioned diameter 1.0-1.2mm as seed materialAluminium base bonding molecular sieve powder rotates into pellet catalyst, and screening obtains the bead of diameter 1.6-2.0mm, gainedBead, through 120 DEG C of oven dry 16h, then obtains pellet catalyst MA4 for 4 hours in 550 DEG C of temperature, roasting.
The 80% weight molecule sieve A4 and 20% that consists of of gained MA4 catalyst weighs binding agent.
Embodiment 6
By 300 grams of butt molecular sieve B4 in embodiment 2 with 211.6 grams of Ludox (containing 25% heavy SiO2）Fully mix, then in bowling machine, rotate into pellet catalyst, screening obtains the little of diameter 1.2-1.4mmBall; 300 grams of butt molecular sieve B4 and 246.2 grams of aluminium colloidal sols are fully mixed into alumina base bondingMolecular sieve powder.
In bowling machine, continue to add alumina base bonding molecule taking the bead of diameter 1.2-1.4mm as seed materialSieve powder rotates into pellet catalyst, and screening obtains the bead of diameter 1.6-2.0mm, and gained bead is through 120 DEG CDry 16h, after in Muffle furnace through 600 DEG C of temperature, roasting 8 hours pellet catalyst MB4.
The 85% weight molecule sieve B4 and 15% that consists of of gained MB4 catalyst weighs binding agent.
Embodiment 7
400 grams of butt molecular sieve C4 and 176 grams of Ludox in embodiment 3 (are weighed to SiO containing 25%2) fillDivide and mix, then in bowling machine, rotate into pellet catalyst, screening obtains diameter 1.4～1.6mm'sBead; 300 grams of butt molecular sieve C4 are fully mixed with 22.6 grams of dry glue powders, 77.6 grams of aluminium colloidal solsBecome alumina base bonding molecular sieve powder.
In bowling machine, continue to add alumina base bonding molecule taking the bead of diameter 1.4-1.6mm as seed materialSieve powder rotates into pellet catalyst, and screening obtains the bead of diameter 1.8-2.2mm, and gained bead is through 120 DEG CDry 16h, then within 2 hours, obtain bar shaped catalyst MC4 in 550 DEG C of temperature, roasting.
The 90% weight molecule sieve C4 and 10% that consists of of gained MC4 catalyst weighs binding agent.
Embodiment 8
By 200 grams of butt molecular sieve D4 in embodiment 4 with 141 grams of Ludox (containing 25% heavy SiO2）Fully mix, then in bowling machine, rotate into pellet catalyst, screening obtains the little of diameter 1.2-1.4mmBall; 150 grams of butt molecular sieve D4 and 23.8 grams of dry glue powders, 41 grams of aluminium colloidal sols are fully mixed into oxygenChange aluminium base bonding molecular sieve powder.
In bowling machine, continue to add alumina base bonding molecule taking the bead of diameter 1.2-1.4mm as seed materialSieve powder rotates into pellet catalyst, and screening obtains the bead of diameter 1.6-2.0mm, and gained bead is through 120 DEG CDry 16h, after in Muffle furnace through 600 DEG C of temperature, roasting 4 hours pellet catalyst MD4.
The 85% weight molecule sieve D4 and 15% that consists of of gained MD4 catalyst weighs binding agent.
Comparative example 1
This comparative example illustrates the preparation process of conventional ZSM-5 molecular sieve.
(Sinopec catalyst Jian Chang branch company produces, the trade mark to get 500 grams of butt ZSM-5 molecular sievesZRP-5B, silica alumina ratio 120～150) after the de-amine of 550 DEG C of roasting 4h is processed, add 3000mL deionizationWater making beating, then add 100 grams of ammonium chlorides and 10 grams of aqueous hydrochloric acid solutions (containing 10% geavy salt acid), and stirringUnder be warming up to 70 DEG C of exchange 1h, filter, washing, filter cake adds 3000mL deionized water making beating again, thenAdd after 100 grams of ammonium chlorides and 10 grams of aqueous hydrochloric acid solutions (containing 10% geavy salt acid), be under agitation warming up to 70 DEG CExchange 1h, through 120 DEG C of oven dry 16h, must contrast sieve sample DBA after filtering, washing.
Get the above-mentioned molecular screen primary powder DBA of part, measure through X-ray powder diffraction, its diffraction pattern is sameFig. 1 feature, illustrates that it is ZSM-5. Through XRF analysis, Na in DBA molecular sieve2O content is 0.01%,Silica alumina ratio is 145. Through low temperature N2-adsorption analysis, the BET method specific area of DBA molecular sieve is 355m2/g，Total pore volume is 0.21mL/g, and its mesoporous is > the mesoporous pore volume of 2nm is 0.03mL/g, accounts for total pore volume ratioBe 14.3%.
Above-mentioned 80 grams of butt molecular sieve DBA are mixed with 20 grams of butt boehmites, continue to add 1.5%Heavy aqueous acetic acid is fully mediated, and then extrudes the bar shaped catalyst of diameter 1.5mm through banded extruder,By 120 DEG C of oven dry 16h, then within 8 hours, obtain bar shaped catalyst CDBA in 600 DEG C of temperature, roasting.
CDBA catalyst consists of 80% weight molecule sieve DBA and 20% heavy Al2O3。
Comparative example 2
The same ZSM-5 molecular sieve that uses fluosilicic acid, obtains under non-hydrothermal treatment consists condition of this comparative example explanationComposition is the catalyst that active component obtains.
(Sinopec catalyst Jian Chang branch company produces, the trade mark to get 1000 grams of butt ZSM-5 molecular sievesZRP-5, silica alumina ratio 80～100) join 8000 grams of deionized water for stirring making beating, then add 460.8Gram fluorine silicic acid aqueous solution, is placed in exchange still, under continuing to stir, is warming up to 70 DEG C, keeps 2h, thenBe cooled to 60 DEG C of filtrations, washing, obtain filter cake. 15.0 grams of ammonium dihydrogen phosphate (ADP)s are dissolved into 500 grams of deionizationsIn water, then 30.0 grams of lanthanum nitrate hexahydrate salt are dissolved in 400 grams of deionized waters, and join phosphoric acidIn ammonium dihydrogen solution, form colloid, in this colloid, add the 900 grams of above-mentioned molecular sieve filter cake of butt stirring to pulpsEvenly, then slurries are dried to 24h at 120 DEG C, must contrast sieve sample DBB.
Get the above-mentioned zeolite product DBB of part, measure through X-ray powder diffraction, its diffraction pattern is sameFig. 1 feature, illustrates that it is ZSM-5. Through XRF analysis, Na in DBB molecular sieve2O content is 0.01%,P2O5Content is 1.02%, La2O3Content is 1.47%, and silica alumina ratio is 285. Through low temperature N2-adsorption analysis,The BET method specific area of DBB molecular sieve is 384m2/ g, total pore volume is 0.20mL/g, its mesoporous is > 2nmMesoporous pore volume be 0.03mL/g, accounting for total pore volume ratio is 15.0%.
(weigh SiO containing 25% by above-mentioned 600 grams of butt molecular sieve DBB and with 423.2 grams of Ludox2) fullyMix, then in bowling machine, rotate into pellet catalyst, screening obtains the bead of diameter 1.4-2.0mm,Gained bead is dried 16h through 120 DEG C, after in Muffle furnace through 600 DEG C of temperature, roasting 4 hours bead is urgedAgent CDBB.
CDBB catalyst consists of 85% weight molecule sieve DBB and 15% heavy SiO2。
Embodiment 9
The present embodiment explanation contains hud typed ZSM-5 molecular sieve pellet catalyst provided by the invention and is applied toThe evaluation result of MTP course of reaction.
MTP reaction evaluating carries out on atmospheric fixed bed micro anti-evaluation device, and this device is by sampling system, anti-Answer device, product-collecting system, regenerative system and temperature control system five part compositions. The catalyst of filling is in reactionWhile evaluating pre-heating temperature elevation, purge to reaction temperature with High Purity Nitrogen, methanol aqueous solution raw material injects with micro-injection pumpIn reactor, the cooling laggard promoting the circulation of qi liquid product of product separates, and gaseous products is collected and gone forward side by side through draining water gathering of gas lawCircumstances in which people get things ready for a trip analysis of spectrum, liquid-phase product is collected laggard circumstances in which people get things ready for a trip analysis of spectrum; After having reacted, temperature of reactor is risen to600 DEG C, pass into oxygen simultaneously and regenerate, regeneration gas is fully oxidized by oxidation furnace, the CO of generation2Gas is by the infrared CO of QGS-08D2Gas analyzer is measured, and obtains post catalyst reaction after integral operationCarbon deposit content.
Become 20-40 order particle for subsequent use through crushing and screening the catalyst sample of embodiment 5-8. MTP reaction is commentedWhen valency, catalyst in reactor loadings is 2 grams. Adopt 50% heavy methanol aqueous solution charging, specifying insteadAnswer charging at temperature to stablize to start to measure after 1h the MTP reaction mass balance in 10min subsequently. Gained firstAlcohol conversion and product are distributed as the mean value in 10min feed time section. The carbon back productive rate (%) of propyleneFor the carbon in product propylene accounts for the mass percent of carbon in charging methyl alcohol. Evaluation response temperature is 470 DEG C, firstAlcohol charging WHSV is 11h-1, reaction pressure is a little more than normal pressure. Gained reaction evaluating the results are shown in table 1.
Comparative example 3
The catalyst that the explanation of this comparative example is contained conventional ZSM-5 molecular sieve is applied to commenting of MTP course of reactionValency result.
Process is with embodiment 9, and difference is that catalyst used is the catalyst of comparative example 1, comparative example 2.
Gained reaction evaluating the results are shown in table 1.
Table 1
| Sample | Methanol conversion, % | Propylene carbon back productive rate, % | Propylene/ethylene mass ratio |
| Catalyst MA4 | 100.0 | 46.3 | 4.5 |
| Catalyst MB4 | 100.0 | 45.1 | 6.0 |
| Catalyst MC4 | 95.5 | 39.8 | 10.9 |
| Catalyst MD4 | 100.0 | 42.3 | 7.8 |
| Contrast medium CDBA | 100.0 | 36.9 | 3.3 |
| Contrast medium CDBB | 94.5 | 37.8 | 5.9 |
Obviously can find out from the evaluation result of table 1, compared with the catalyst of prior art, adopt the present inventionThe catalyst of molecular sieve effectively catalysis methanol conversion obtains propylene, through the modulation of peracidity and pore structure,In keeping methyl alcohol high conversion, propylene/ethylene mass ratio is significantly improved, and this is conducive to reduce anti-Answer the separating energy consumption of ethene in product subsequent separation system, improve the benefit of MTP reaction unit.
Embodiment 10
The present invention illustrates that the catalyst that contains ZSM-5 molecular sieve composition provided by the invention is for MTP processTime life assessment result.
Become 20-40 order particle for subsequent use through crushing and screening the catalyst sample of embodiment 8.
MTP reaction life assessment still adopts the MAT device in embodiment 9 descriptions, catalyst in reactor dressThe amount of filling out is 8 grams. Adopt 50% heavy methanol aqueous solution charging, under 460 DEG C of reaction temperatures, methanol feedingWHSV is 1.5h-1, reaction pressure is carried out life assessment a little more than normal pressure. With methanol conversion lower than 96% workFor the standard of catalysqt deactivation. Gained methanol conversion is listed in Fig. 2 with the result of variations in reaction time.
Comparative example 4
The catalyst of the ZSM-5 molecular sieve that the explanation of this comparative example is contained comparative example 2 is applied to MTP course of reactionLife assessment result.
Process is with embodiment 10, and difference is that catalyst used is the ZSM-5 molecular sieve catalysis of comparative example 2Agent.
Gained methanol conversion is listed in Fig. 2 with the result of variations in reaction time.
Obviously can find out from the evaluation result of Fig. 2, compared with comparative catalyst, adopt molecular sieve of the present inventionCatalyst for MTP when reaction, its one way active lifetime obviously extends, and is conducive to reduce catalyst againRaw number of times and life cycle.
Claims (24)
1. a hud typed ZSM-5 molecular sieve pellet catalyst, is characterized in that by kernel component and shell componentForm, said kernel component is made up of ZSM-5 molecular sieve composition and inorganic oxide, core groupPoint diameter account at least 50% of the small ball's diameter, said shell component by ZSM-5 molecular sieve composition andInorganic oxide composition, taking catalyst weight as benchmark, said ZSM-5 molecular sieve composition accounts for30-95%, inorganic oxide account for 5-70%, and said ZSM-5 molecular sieve composition, contains with P2O5The phosphorus of the 0.1-10 % by weight of meter and in the rare earth of the 0-10 % by weight of oxide, said ZSM-5In molecular sieve, alkali metal is less than 0.2 % by weight, SiO in the content of oxide2With A12O3Mol ratioValue is 100-1000, and the BET method specific area under nitrogen adsorption method is measured is 300-600m2/ g, totalPore volume is 0.2-0.6mL/g, bore dia > the mesoporous pore volume of 2nm accounts for the 30-70% of total pore volume.
2. according to the catalyst of claim 1, wherein, the inorganic oxide of said kernel component is silica.
3. according to the catalyst of claim 1, wherein, the diameter of said kernel component accounts for the small ball's diameter extremelyFew 60%.
4. according to the catalyst of claim 1, wherein, the inorganic oxide of said shell component is aluminium oxide.
5. according to the catalyst of claim 1, wherein, in said kernel component, inorganic oxide is silica,In shell component, inorganic oxide is aluminium oxide.
6. according to the catalyst of claim 1, wherein, in said ZSM-5 molecular sieve composition, phosphorus is with P2O5Meter, content is 0.2-5 % by weight, and said rare earth is taking oxide, content as 0-5 % by weight, instituteThe alkali metal of saying is less than 0.1 % by weight in oxide, content in ZSM-5 molecular sieve.
7. according to the catalyst of claim 1, wherein, said SiO2With A12O3Molar ratio be 150-500.
8. according to the catalyst of claim 1, wherein, said BET method ratio under nitrogen adsorption method is measuredSurface area is 350-500m2/ g, total pore volume is 0.3-0.5mL/g, its median pore diameter > the mesoporous hole of 2nmHold the 40-60% that accounts for total pore volume.
9. according to the catalyst of claim 1, wherein, said rare earth is selected from one in yttrium, lanthanum, cerium and praseodymiumKind or multiple.
10. according to the catalyst of claim 1, taking catalyst weight as benchmark, ZSM-5 molecular sieve composition accounts for50-90 % by weight, inorganic oxide accounts for 10-50 % by weight.
The preparation method of the hud typed ZSM-5 molecular sieve pellet catalyst of one of 11. claim 1-10, its featureSo rotate into ball formation at the precursor and a kind of ZSM-5 molecular sieve composition that adopt inorganic oxideSaid kernel bead; Then taking kernel bead as seed material, adopt inorganic oxide precursor bondingAgent and said ZSM-5 molecular sieve composition powder are rotated further moulding, warp after shaping of catalystAt 300-800 DEG C, under ingress of air condition, roasting obtains, wherein said ZSM-5 molecular sieve composition,Its preparation method, comprises former the ZSM-5 molecular sieve of alkali metal-free or low alkali powder is removed through roastingOrganic formwork agent obtains roasting powder; Roasting powder carries out liquid phase acid treatment and obtains pickling filter cake; And, instituteThe pickling filter cake of saying carries out reclaiming and obtaining after the activation processing of phosphorus-containing compound and compounds containing rare earthThe step of ZSM-5 molecular sieve composition, wherein, said roasting powder carries out liquid phase acid treatment and obtains picklingThe step of filter cake is that roasting powder is evenly become to molecule screening the pulp with the acidic aqueous solution making beating that contains fluosilicic acidLiquid, and in airtight still hydrothermal treatment consists under temperature 100-200 DEG C, pressure 0.1-2Mpa, said fluorineThe mass ratio of the butt of silicic acid and said roasting powder is 0.0001-0.1:1, in said molecular sieve pulpThe mass ratio of the butt of water and roasting powder is 3-20:1.
12. according to the method for claim 11, and wherein, the former powder of said ZSM-5 molecular sieve is to obtain through following processTo: aluminium source, silicon source, water and organic formwork agent are thoroughly mixed to form to reactant mixture, mole compositionScope is organic formwork agent/SiO2＝0.03-0.3，SiO2/Al2O3＝100-1000，H2O/SiO2＝5-30，Wherein organic formwork agent is tetraethyl ammonium hydroxide or TPAOH, and reactant mixture is being stirredMix down, under the temperature of 70～200 DEG C, self-generated pressure hydrothermal crystallizing 20～200 hours, crystallization productAfter filtration, dry at 80-200 DEG C of temperature after washing, obtain the former powder of ZSM-5 molecular sieve.
13. according to the method for claim 12, and wherein, said aluminium source is selected from hydrated alumina, aluminum sulfate, nitreAcid aluminium, aluminium hydroxide or aluminium isopropoxide; Said silicon source is selected from solid silicone or white carbon.
14. according to the method for claim 11, and wherein, said roasting removes organic formwork agent, its condition beIngress of air roasting 0.5-50h at 300-800 DEG C.
15. according to the method for claim 11, wherein, said hydrothermal treatment consists, its condition is in airtight still,Temperature 105-180 DEG C, pressure 0.11-1Mpa.
16. according to the method for claim 11, wherein, said hydrothermal treatment consists, its condition is in airtight still,Temperature 105-150 DEG C, pressure 0.12-0.7Mpa.
17. according to the method for claim 11, wherein, and the matter of the butt of said fluosilicic acid and said roasting powderAmount is than being 0.001-0.05.
18. according to the method for claim 17, wherein, and the matter of the butt of said fluosilicic acid and said roasting powderAmount is than being 0.002-0.01.
19. according to the method for claim 11, wherein, and the butt of water and roasting powder in said molecular sieve pulpMass ratio is 4-15.
20. according to the method for claim 19, wherein, and the butt of water and roasting powder in said molecular sieve pulpMass ratio is 5-10.
The method of 21. 1 kinds of Methanol light olefins, is characterized in that the nucleocapsid of the method with one of claim 1-10Type ZSM-5 molecular sieve pellet catalyst carries out under existing.
22. according to the method for claim 21, and wherein, said light olefin is propylene.
23. according to the method for claim 21, adds steam or inert gas and regulates methanol feeding dividing potential drop, instituteWith reaction temperature be 250 DEG C-600 DEG C; Reaction pressure used is 0.1-50 atmospheric pressure, weight sky usedSpeed is 0.01-50h-1。
24. according to the method for claim 23, and wherein, reaction temperature used is 350 DEG C-500 DEG C; Reaction usedPressure is 0.5-5 atmospheric pressure, and weight space velocity used is 0.1-10h-1。
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| CN116062769A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogen ZSM-5 molecular sieve and preparation method thereof, and xylene isomerization catalyst and preparation method thereof |
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| CN101429085A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Method for producing propylene, ethylene light olefin hydrocarbon |
| CN102040448A (en) * | 2010-12-01 | 2011-05-04 | 复旦大学 | Method for preparing propylene by catalyzing methanol/dimethyl ether with composite molecular sieve with core-shell structure |
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