CN106890672A - A kind of methyl alcohol converts light olefin catalyst processed and its preparation method and application - Google Patents

A kind of methyl alcohol converts light olefin catalyst processed and its preparation method and application Download PDF

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CN106890672A
CN106890672A CN201510944673.7A CN201510944673A CN106890672A CN 106890672 A CN106890672 A CN 106890672A CN 201510944673 A CN201510944673 A CN 201510944673A CN 106890672 A CN106890672 A CN 106890672A
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catalyst
methyl alcohol
molecular sieve
light olefin
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CN106890672B (en
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付云芝
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Shanghai Runhe Kehua Engineering Design Co.,Ltd.
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A kind of methyl alcohol light olefin catalyst, it is characterized in that with the composition of inorganic matter dry basis be sodium oxide molybdena ＜ 0.1m%, silica 25m%~40m%, aluminum oxide 40m%~60m%, phosphorous oxide 10m%~20m%, boron oxide 0.01m%~1m%；Its 85~95% acid amount is distributed in the range of Hammett acid strength functions Ho+4.8~-3.0；The duct volumetric ratio of ten-ring/twelve-ring is 10~20: 1 in catalyst；It has the abundant mesoporous nanos of aperture ＜ 5 and step Jie's micropore distributed architecture；Catalyst is Chabazite-type (CHA) molecular sieve [mRAl being modified by hydrothermal crystallizing and through secondary synthesis17P12Si7O72], synthesized with its mother liquor and boron compound is modified bi-five-member cycle configuration (MFI) type molecular sieve [R that obtainsnAln-BnSi96-2nO192, n ＜ 27], aluminium sol adhesive and kaolin composition；And after being beaten with remaining mother liquor and condensate liquid mixed grinding, spray shaping is the microspherical catalyst of 55~75 microns of average grain diameter and abrasion index 0.5m%~1.8m%；After scrubbed and oxidizing atmosphere calcination activation, there is preferably activity, selectivity and stability in MTO reactions；Make easy preparation process, environmental protection and low cost due to recycling.

Description

A kind of methyl alcohol converts light olefin catalyst processed and its preparation method and application
Technical field
The present invention is that, on a kind of catalyst of transforming oxygenated organic compound process, more particularly to a kind of methyl alcohol system is light Alkene catalyst and its preparation method and application, belongs to petrochemical industry catalysis technical field.
Background technology
Light olefin (C2 =~C4 =) it is particularly ethene and propylene is that demand is big and the base that has many uses in petro chemical industry This Organic Ingredients, since the seventies, many industrially developed country concentrate strength on exploitation non-petroleum feedstocks and produce the new of light olefin Technology path, in case substitute technology when not being used as petroleum resources supply deficiency.It is relative to the such a petroleum resources of China Few big country has been even more positive effect.Coal or natural gas via process of preparing low carbon olefinic hydrocarbon with methanol (MTO) research and development, It is one and produces the process route that chemical products receive much concern from non-oil resource, wherein, the performance of catalyst is without being suspected to have Important influence.
Mobil companies of the U.S. are most urged using ZSM-5 zeolite molecular sieve earlier than report in 1977 as methanol-to-olefins (MTO) Agent (USP5367100)；U.S. combinating carbide company (UCC) develops novel phosphoric acid sial Series Molecules sieve for 1984 SAPO-n (USP4440871, US4499327), wherein SAPO-34 molecular sieves with suitable acid and pore passage structure due to existing Excellent catalytic performance is showed in MTO reactions.
Catalyst used in the process of current methanol-to-olefins generally uses SAPO molecular sieve and ZSM-5 molecular sieve, and All had been reported that in prior art, such as USP5248647, USP6153552, USP6787501 is reported SAPO-34 molecular sieves, height Ridge soil, binding agent spray drying are made methyl alcohol conversion catalyst；CN102029181B、CN102029182B、 CN102294262A etc. also discloses the preparation method of SAPO silicoaluminophosphamolecular molecular sieves type methanol-to-olefin catalysts.Additionally, CN102380414A also discloses a kind of AlPO-18 and AlPO-34 molecular sieves without element silicon of hydro-thermal method synthesis, for making Standby low in acidity, the preparing olefin by conversion of methanol catalyst method of high stability.
Last century the nineties, German Lurgi companies are based on the methyl alcohol that modified ZSM-5 molecular sieve develops complete set Propylene (MTP) technique processed, the Propylene Selectivity under Product olefins circular response reaches 71.2%, therefore ZSM-5 molecular sieve type The another degree of methyl alcohol light olefin technology causes concern, and has a large amount of reports in prior art, such as US4238631B1, US4328384B1, US4423274B1 and CN104056654A etc., wherein to increase light olefin and reducing C5 +Byproduct is also in boiling Coke is deposited on stone；A kind of C high containing ZSM-5 molecular sieve is disclosed in CN103962170A4Olefine selective microballoon is catalyzed Agent, for the methanol conversion ＞ 99% in fluid bed, C4Selectivity can reach 32%；And CN1352627A is also disclosed The use of the ZSM-5 zeolite catalyst of P Modification is the method for light olefin by methyl alcohol or dimethyl ether conversion.
Being related to MTO catalyst atomizing preparing technique has many reports, such as USP6153552, USP6787501, USP5248647, CN1341584A etc. disclose the spray with SAPO-34, inorganic oxide adhesive and clay class matrix fill Mist preparation method.Because the content of molecular sieve often produces considerable influence to the catalytic performance of MTO catalyst, and macromolecule sieve contains Microspherical catalyst abrasion strength resistance problem is always again difficult point during amount, therefore the prior art of this respect receives much concern, such as Prepared by the wear-resistant methanol conversion catalyst of CN01132533A, really played by reducing molecular sieve content in catalyst and carried The effect of high catalyst abrasion index；It is also conventional method that slurry before spraying is levigate and improves binding agent, such as CN102284302A carries out particle refinement after the slurry of methanol-to-olefin catalyst is mixed, so as to be lived with excellent catalysis Property, selectivity, particularly excellent attrition resistance energy；And CN104162448A is then in the light alkene of the methyl alcohol system of molecular sieve containing SAPO-34 Hydrocarbon catalyst prepare when boehmite in strengthen acid and phosphoric acid method come solve molecular sieve content it is low, not wear-resisting, catalysis The defects such as unstable properties.
In addition to above-mentioned conventional method, the mother liquor of synthesis of molecular sieve is used for catalyst preparation attention, such as CN103170361A prepares methanol-to-olefin catalyst with the liquid produced in SAPO-34 Zeolite synthesis as raw material, reduces Raw material addition reduction production cost simultaneously realizes recycling；CN103706393A is then to add to close after the stirring of material homogeneous It is mother liquid obtained into molecular sieve, wear-resisting methanol-to-olefin catalyst microballoon is produced, reduce cost and refer to attrition of catalyst Number drops to 0.5m%/h-1Below.
Because SAPO type molecular sieve coke selectivities are higher and it is very fast to cause catalyst to inactivate, and ZSM-5 molecular sieve C4With The selectivity of upper alkene and aromatic hydrocarbons is higher, in order to further improve the catalytic performance of MTO catalyst, it is therefore desirable to carry out further Study on the modification.Molecular sieve active component is modified using metal or nonmetalloid be conventional method, such as USP4752651, CN1128676C, CN101555022A etc. are modified to SAPO molecular sieve.There is series report to draw transition metal Enter in SAPO molecular sieve skeleton the MeAPSO molecular sieves for being formed has light olefin selectivity higher to MTO reactions, such as J.Mol.Catal.A 160(2000)437、CN1108867、CN1108868、CN1108869、CN1108870、CN1111091、 CN1132698 etc. discloses related content；In CN101121145B in addition to using transition metal, alkaline-earth metal is also used It is modified；The SAPO-34 system with molecular sieve for preparing being modified using Zn also has more report for MTO catalyst, such as USP7119242, USP6759360, CN1704390A, CN1683079A, to solve catalyst activity, selectivity and the low problem of yield； With rare earth modified SAPO-34 molecular sieve catalysts in CN104096591A, methanol conversion 100%, ethene+propylene total recovery ＞ 80%, triolefin total recovery ＞ 90% and propylene/ethylene ＞ 0.9.
Equally, the modification technology to ZSM-5 molecular sieve also has been reported that, USP4480145 using the zeolite of large crystal ZSM-5-5 and The diffusivity that the silica filling of zeolite pores reduces zeolite improves the ethylene yield that methyl alcohol is converted；USP3911041 uses P Modification ZSM-5 zeolite methyl alcohol is converted into alkene, USP4049573 and USP4088706 by boron or the oxide of magnesium, or further Phosphorous oxides modified ZSM-5 zeolite is added, methyl alcohol is converted into alkene；CN102259013A then adds boron source to obtain in synthesis The ZSM-5 zeolite catalyst of skeleton boracic, effectively to control the medium acid strength and strong acidic site ratio of molecular sieve surface, improves The catalysis activity and stability of MTO reactions.But the acid regulation and control of this unimolecule sieve can influence catalyst conversion activity.
Be solve unimolecule sieve improve MTO catalyst performance on limitation, US2007/0100188A1, AEI the and CHA skeleton classes such as CN101214089A, CN101450806A, CN97180440, CN02805772, CN1525940A The silicoaluminophosphamolecular molecular sieves of the intergrowth phase of type molecular sieve, for MTO catalytic reactions；The CN102430424A ZSM- for first preparing 5 and the complex type molecular sieve of aluminium phosphate molecular sieve, then the catalyst of phosphorus modification preparation is carried out, during methyl alcohol conversion 100% C2 =~C4 =Total low-carbon alkene and Propylene Selectivity are better than individually with the catalyst of ZSM-5 up to 82% and more than 50%； CN104107720A also with the complex type molecular sieve catalysis containing metallic element, improves MTO catalyst stability, selectivity and receipts Rate.Though complex type molecular sieve performance is good, control is neither easy when preparing, it is also inconvenient stably to produce and apply.
Also had been reported that with the catalyst of silicon phosphorus aluminium profiles and Si-Al molecular sieve simultaneously, such as CN102389833A uses SAPO- NaY type molecular sieves after 34 molecular sieves and nitric acid or rare earth nitrades treatment, while being catalyzed lighter hydrocarbons steam cracking alkene and first Alcohol converts alkene processed, solves steam cracking heat supply and methanol-to-olefins heat dissipation problem；CN101676028B, CN102814194B etc. The MTO catalyst simultaneously containing Y classes, ZSM-5 classes and SAPO-34 molecular sieves is prepared for, but the Y molecular sieve analogs of highly acid can influence The selectivity of MTO reactions.
Multistage pore canal in MTO catalyst also has an impact to catalytic performance, and such as CN104525250A is to using triethylamine mould The SAPO-34 molecular sieves that plate agent and same type molecular sieve seed synthesize be calcined after alkali process, obtain very regular many The catalyst of level pore structure type methanol-to-olefins, its activity and selectivity of light olefin are high, reproducible；CN101157057B is then The catalyst that in-situ crystallization SAPO-34 molecular sieves are prepared on microsphere particle also has multistage pore canal.But not modulated is more Level duct, aperture and pore capacities distribution are uncontrolled, and the diffusion and reactivity worth to improving MTO catalyst are also extremely limited, special It is not intensity that catalyst had both been damaged in excessive aperture (5 nanometers of ＞), to improving catalytic performance and obtaining preferable product distribution Also effect is had no, introduces mesoporous on unimolecule sieve catalyst in addition, its practical application effect is not also notable.
Although be related in the prior art MTO catalyst patented technology report it is more, according to MTO response characteristics, for The requirement of active component, so that suitable condition is separately synthesized and modified SAPO-34 and ZSM-5 molecular sieve, composition is conducive to reactant Acid strength-acid amount distribution after the step Jie's microcellular structure system and modulation that are spread with product, to improve the reaction during MTO The technology of thing-product diffusion, catalytic reaction activity, selectivity and stability, there is not been reported；In preparation process, for MTO Reacting middle catalyst carrier diffusion is needed, and organic mould is pulled into the preparation method that agent and mother liquor, condensate circulation are utilized, and makes system Report is also had no in the prior art of the standby easier reasonable, environmental protection of process and low cost.
The content of the invention
The invention aims in the presence of overcoming the shortcomings of prior art, there is provided a kind of oxygen-containing organic compound turns The catalyst of change process, being especially to provide a kind of improves catalyst of methyl alcohol light olefin of catalytic performance and preparation method thereof And application, belong to petrochemical catalyst technology and petrochemical industry course of reaction field.
Usual faujasite (such as Y zeolites, X zeolites), Beta zeolites and modenite large pore zeolite, being capable of catalysis methanol It is converted into hydrocarbon, but often C5 +The selectivity of product of hydro carbons is high, and the selectivity of low-carbon alkene is low；And erionite, T zeolites, chabasie Deng pore zeolite, though the selectivity of alkene can be improved, coking and deactivation is very fast.Therefore many researchs concentrate on ZSM-5 zeolite The zeolite in aperture in, its excellent shape selective catalysis performance can no doubt obtain yield of light olefin higher, but due to acidity too By force, the selectivity of ethene has much room for improvement, C5 +The product distribution of hydro carbons is also unsatisfactory.And SAPO molecular sieve is a class crystalline silico-alumino Phosphate, three dimensional skeletal structure is made up of phosphorus oxygen, alumina and silicon-oxy tetrahedron, and this aperture is about the aperture of 0.43nm and acid The moderate molecular sieve of property is the preferable shape-selective catalyst of a class.Particularly SAPO-34 molecular sieve catalysts, the conversion life of its methyl alcohol Selectivity into ethene will be substantially better than ZSM-5 zeolite, and P/E is than low, catalyst aperture little Yi cokings so that again in product component Raw process becomes frequent.
SAPO and Si-Al molecular sieve are modified in prior art, have only focused on the selectivity of light olefin in MTO, compared with Complex relationship between few diffusion of concern on the whole, activity of conversion, selectivity, accessory substance alkane and coke etc., uses Method it is also more single and linear, it is difficult to obtain ideal effect.And by adding CMC, starch, surface-active in prior art Agent, sesbania powder etc., make the MTO catalyst of preparation obtain multipole hole and abundant mesoporous method, often there is aperture excessive to expanding Dissipate and catalytic performance improvement result be relatively low, and infringement catalyst abrasion strength resistance and relatively costly etc. defect.
Inventor tests the limitation it was unexpectedly observed that to overcome in the presence of numerous prior arts by substantial amounts of, When preparing MTO catalyst, to silicoaluminophosphamolecular molecular sieves and Si-Al molecular sieve in catalyst, using specific separately synthesized and change Property, and the general requirement from MTO reactions to catalyst performance, by nonlinear complicated modulation and both given activities of arranging in pairs or groups The micropore collocation of constituent element and acid distribution, constitute the step Jie's microcellular structure system beneficial to reactant and product Reaction-diffusion terms, adjust Become and suitable catalyst Hammett acid strength function Ho distributions, catalyst can be suppressed and cross strong acid center to light olefin Aromatization activity, makes catalyst in the course of reaction that methanol oxidation converts light olefin processed, obtains yield of light olefin high, especially It is ethene, propene yield, reduces accessory substance and C5 +With the yield of coke, and the activity cycle internal stability having had.
Inventor also found by the preparation method of mother liquid recycling, both solve a large amount of mother liquor emission aftertreatments difficult Problem, makes overall preparation process easier rationally, environmental protection and reduces cost, and organic formwork contained therein is make use of again Agent makes molecular sieve modified and shaping of catalyst form the mesoporous of abundant smaller aperture due (5 nanometers of ＜) in preparing, so that further The truly advantageous reactant in MTO courses of reaction, Jie's micropore distributed architecture system of product diffusion are formed, the anti-of catalyst is improved Activity, selectivity and stability are answered, these inventions and discovery can not in the prior art obtain direct and clear and definite technology Enlightenment.
Therefore specifically, the invention provides a kind of catalyst of methyl alcohol light olefin, it is characterized in that dry with inorganic matter The composition of base weight meter is sodium oxide molybdena ＜ 0.1m%, silica 25m%~40m%, aluminum oxide 40m%~60m%, phosphorous oxide 10m%~20m%, boron oxide 0.1m%~1m%；Its 85~95% acid amount is distributed in acid strength Hammett functions Ho+4.8 In the range of~-3.0；The duct volumetric ratio of ten-ring/twelve-ring is 10~20: 1 in catalyst；With abundant aperture ＜ 5 The mesoporous system and step Jie's micropore distributed architecture of nanometer；The microspherical catalyst is highly suitable to be applied for methyl alcohol conversion and produces light alkene In the course of reaction of hydrocarbon.
Acid strength Hammett functions Ho comparable intuitively reflection molecular sieve and catalyst are in the range of different acid strengths Acid amount distribution situation, refers to understanding of the professional book acquisition in terms of any catalysis in this area to this respect.Ho is by just It is worth negative value and shows acid strength from low to high, molecular sieve and catalyst is catalyzed in the acid amount distribution of different acid strength scopes to it Performance often produces most direct influence, but for current technology development level, often have to its modulation it is non-linear and Unpredictable the characteristics of, be one of major technique knowhow (tricks of the trade) of composition molecular sieve and catalyst performance.It is of the invention MTO catalyst except composition constitute upper and prior art exist it is dramatically different and in addition to causing performance difference, also with prior art Very different catalyst acid intensity distribution feature, and profound influence its catalysis activity, selectivity and stability, which constitute this The core technology content of invention, and direct technical inspiration can not be obtained from prior art and experience.
A kind of methyl alcohol light olefin catalyst provided by the present invention, it is characterised in that described step Jie micropore distribution knot Structure is：0.43 nanometer of aperture pore volume of ten-ring accounts for 0.5 nanometer of mesopore volume of the 40v%~60v% of total pore volume, twelve-ring Account for 30v%~50v% that the 1v%~10v% of total pore volume, the mesoporous pore volume of 2~5 nanometers of smaller aperture due account for total pore volume.＞ 5 receives The mesoporous pore volume of larger aperture of rice accounts for total pore volume 2v%~8v%.
Those skilled in the art know, pore distribution be influence molecular sieve and catalyst performance another it is important because Element, and also there is complicated non-linear correlation relation between catalytic performance, for current catalytic theory and technical merit, also Can not accomplish that accurate theory deduction or experience speculate, can not be tested by simple condition and be distributed and catalytic performance in pore canal system Between set up and clearly associate.One of technology knowhow (tricks of the trade) of catalyst, institute of the present invention are equally constituted to its modulation and composition The mesoporous distribution of abundant smaller aperture due (5 nanometers of ＜) in the MTO catalyst of offer and different from step Jie's micropore of prior art Distribution characteristics constitutes one of core content of catalyst of the present invention, and can not obtain bright from prior art and experience inference True technical inspiration.
A kind of catalyst of methyl alcohol light olefin provided by the present invention, its feature also have the catalyst be by 30m%~ The hydrothermal crystallizing of 40m% and the Chabazite-type (the CHA topological structures, chemical formula [mRAl that are modified through secondary synthesis17P12Si7O72]) Molecular sieve, the hydrothermal crystallizing of 5m%~10m% and through boron compound be modified acquisition bi-five-member cycle configuration type (MFI topological structures, Chemical formula [RnAln-BnSi96-2nO192, n ＜ 27]) molecular sieve, the Alumina gel knot agent of 5m%~20m% and balance kaolin composition, Wherein R is organic formwork agent；The average grain diameter of catalyst microspheres is 55~75 microns and abrasion index 0.5m%~1.8m%.
Preparing olefin by conversion of methanol reaction generally containing SAPO molecular sieve is the demand of reply frequent regeneration, to use recycle stream Change bed operator scheme, catalyst must be the microspheroidal with appropriate particle size distribution.Although therefore above-mentioned mentioned molecular sieve With preferable MTO catalytic performances, but can not be applied directly in industrial production, it is necessary to keep catalytic high as far as possible Under the premise of energy, with preferable abrasion strength resistance, more complete miniature spheroidal looks and suitable size distribution.Usual fluid bed Constituted by active component such as molecular sieve, binding agent and filler matrix with microspherical catalyst, the latter plays dispersion and dilution activity Component, improve catalyst abrasion strength resistance, reduce reaction heat effect, but this also bring catalysis composition, constitute, catalytic performance and Obtaining excellent wear-resistant physical property during complexity when physical property is adjusted and changed, particularly macromolecule sieve content becomes It is abnormal difficult.Though the various reports of intensity are improved in the prior art, when the catalyst being related to is constituted, constitutes different, often It is difficult to obtain directly reference.Therefore, the catalyst in the case of the heterogeneity molecular sieve high level that the present invention is provided, is had Composition, the feature in composition and chemical and physical features, also constitute catalyst of the present invention technology contents and feature it One, and directly reference can not be directly obtained from prior art and experience inference, it is less likely to be people in the art Member institute is apparent.
Present invention also offers a kind of preparation method of methyl alcohol light olefin catalyst, it is characterized by the catalyst preparation bag Include following steps：
(1) by mol ratio SiO2/Al2O3=0.7~1.1, P2O5/SiO2=0.7~1.1, H2O/SiO2=65~80, Organic formwork agent R/Al2O3=0.5~2.2, first by boehmite and organic formwork agent R hybrid reactions at 90~190 DEG C 0.5~5 hour, then the slurry for being made pH value 6.4~7.5 is mixed with phosphoric acid, silica gel and/or Ludox, through 20 DEG C~50 After DEG C ageing 15~30 hours, unmodified chabasie is prepared in then hydrothermal crystallizing 20~100 hours at 170 DEG C~210 DEG C Type molecular screen primary powder.
(2) after above-mentioned unmodified Chabazite-type molecular sieve original powder is calcined 0.5~6 hour through 400 DEG C~650 DEG C, with Crystallization mother liquor, organic formwork agent and deionized water obtained by above-mentioned steps (1), by molecular screen primary powder：Organic formwork agent R: water=1 : 0.01~1: 5~20 weight proportion mixing, hydro-thermal process 15~30 hours, obtains through secondary conjunction at 170 DEG C~210 DEG C Into modified Chabazite-type molecular sieve.
(3) by SiO2/Al2O3=30~90, organic formwork agent R/Al2O3=0.5~40, H2O/SiO2=5~15 rub You proportioning, by above-mentioned steps (1) and (2) are mother liquid obtained mix with boehmite after at 90 DEG C~190 DEG C reaction 0.5~5 Hour, then obtain unmodified through at 130 DEG C~200 DEG C times hydrothermal crystallizings 10~40 hours after mix with silica gel and/or Ludox Bi-five-member cycle configuration type molecular screen primary powder.
(4) by molecular screen primary powder: boride: water=1: 0.01~0.5: 0.1~2 weight proportion, by step (3) gained Unmodified bi-five-member cycle configuration type molecular screen primary powder at 350 DEG C~600 DEG C hydro-thermal process 0.5~4 hour, obtain through boron The modified bi-five-member cycle configuration type molecular sieve of compound.
(5) by step (2) and the modified molecular sieve of step (4) gained, with aluminium sol adhesive, kaolin and deionization Water, by the mother liquor after the concentration of slurry of butt weight content 25m%~40m%, with the crystallization and secondary synthesis of above-mentioned molecular sieve And the condensate liquid in crystallization, modified, roasting and spray process is sufficiently mixed, grinding mashing consolidating to 90v%~95v% Behind body thing particle diameter≤2 micron, in 350 DEG C~650 DEG C of intake air temperature, the spray drying tower of 150 DEG C~350 DEG C of exhaust temperature into Type is microballoon.
(6) catalyst microspheres after spray shaping are washed to the Na of microspheres with solid with 30 DEG C~90 DEG C of deionized water2O After ＜ 0.1m%, the calcination activation 0.5~4 hour under 400 DEG C~650 DEG C of oxidizing atmosphere.
Wherein, described template is nitrogen-containing organic compound：Diethylamine, triethylamine, n-propylamine, isopropylamine, three positive third Amine, tri-isopropyl amine, di-n-propylamine, diisopropylamine, TMAH, tetraethyl ammonium hydroxide, TPAOH, 1, 6- hexamethylene diamines, cyclohexylamine, beautiful jade, monoethanolamine, diethanol amine, triethanolamine, N ', N ', N, N- tetramethyl -1, in 6- hexamethylene diamines A kind of or any several mixture；Preferred organic amine R is in diethylamine, triethylamine, di-n-propylamine, tetraethyl ammonium hydroxide One or more.These have the nitrogen-containing compound can be conveniently by commercially available.
In a kind of preparation method of methyl alcohol light olefin catalyst provided by the present invention, it is characterized by preparation process (4) used boron compound is one or more in boron oxide, boric acid, ammonium borate, boron phosphate in, preferably boric acid, Can easily be obtained by commercially available.
It is used in each preparation process in a kind of preparation method of methyl alcohol light olefin catalyst provided by the present invention The raw materials such as phosphoric acid, boehmite, silica gel, Ludox, can easily be obtained by commercially available.
In a kind of preparation method of methyl alcohol light olefin catalyst provided by the present invention, step (1) and step (3) may be used also To add with synthesized product thing phase identical molecular sieve as crystal seed, to improve the crystallinity of synthetic product, addition is general Less than the 20m% of product, more preferably less than preferably less than 10m%, 5m%, with sharp reduces cost, this method is ability Field technique personnel are known and apply.
In a kind of preparation process of methyl alcohol light olefin catalyst provided by the present invention, material slurry and through spray shaping When the aqueous degree of catalyst microspheres and contained moisture, most water includes that the water of addition can be vapored away in drying process, The final catalytic performance of catalyst is not interfered with.
In a kind of preparation method of methyl alcohol light olefin catalyst provided by the present invention, about Hydrothermal Synthesiss crystallization, change Property treatment and ratio calculating during catalyst preparation, the mixing that feeds intake, the operation of hydro-thermal process be well known to those skilled in the art Routine operation.Involved noun " butt " is technical term well-known to those skilled in the art, refers to absolute dry condition When quality of material.The selection of the scope that feeds intake and the selection of calcination activation condition, those skilled in the art are according to known special Industry knowledge combination prior art, can't be particularly restricted.But the receipts high from required for improving catalyst activity constituent element It is difficult to carry out using for the purposes such as rate, selectivity of product, activity of conversion and stability, and can not be obtained from prior art Obtain and clearly enlighten.
In a kind of preparation method of methyl alcohol light olefin catalyst provided by the present invention, due to raw material type and use Amount, ingredient proportion and hydrothermal crystallizing and the temperature for the treatment of, time, the scope selection of pH value, formation and product thing to material Mutually there is significant impact, can also change and influence product physico-chemical property and catalytic performance.Influence factor it is numerous and uncertain, make Must be adapted to the acquisition of methanol conversion catalyst molecular sieve active component, including catalyst preparation, can only be touched by experimental study Rope, can not from the prior art obtain clear and definite technical inspiration, can not lead in experience and in prior art basis Cross result needed for simple condition test arrangement is obtained.These correlations prepare content, condition and step, and they are to prepared Molecular sieve, the physico-chemical property of finished catalyst and the catalytic performance influence for going out, all constitute one of core substance of the present invention.
Present invention also offers a kind of method of methyl alcohol light olefin, light olefin (being defined as ethene, propylene and butylene) can As the raw material of many chemicals.It is a feature of the present invention that in a fluidized bed reactor, methyl alcohol 350 DEG C of reaction temperature~ 650 DEG C, 0.01~10MPa of reaction pressure, weight space velocity 0.1~50 hour-1Under conditions of urged with one of claims 1 to 3 Agent contact is converted into light olefin, enters after catalyst microspheres inactivation in 550 DEG C~850 DEG C of regenerator and is returned after coke-burning regeneration Reaction is continued to participate in fluidized reactor；Preferred reaction condition is：Reaction temperature is 400 DEG C~550 DEG C, reaction pressure is 0.1~2.5MPa, weight space velocity are 1~10 hour-1, 580 DEG C~780 DEG C of regeneration temperature.
A kind of method of methyl alcohol light olefin provided by the present invention, is further characterized in that addition water vapour or inert gas To adjust methyl alcohol charging partial pressure, and influence can be produced on reaction；Material benzenemethanol used can be free from the methyl alcohol of water, it is also possible to It is aqueous methyl alcohol, can be easily obtained by commercially available, converted with purity 100m% during metering, conversion method is with general Known to the personnel that Tonghua is gained knowledge.
In a kind of method of methyl alcohol light olefin provided by the present invention, involved specific course of reaction and reaction is filled The situation of putting is：After methyl alcohol from head tank is preheated, flash tank is fed into methyl alcohol, steamed from charging flash tank methyl alcohol out Vapour is further heated with middle pressure steam first, is allowed to be changed into overheat methanol steam, after feeding pre-reactor conversion, reacting gas and In lighter hydrocarbons, the steam that methanol stripper tower is come, the methyl alcohol merging feeding MTO main reactors of recovery that follow up device is reclaimed.
Methyl alcohol light olefin MTO main reactors use fluidized-bed catalytic reactor design and use microspherical catalyst, and MTO is anti- Should be an exothermic reaction, when material benzenemethanol enters reactor bottom, reaction begins to be occurred.In reactor methyl alcohol with come from The high-temperature regenerated catalyst directly contact of regenerator, carries out exothermic reaction.
MTO temperature of reactor is controlled with reactor catalyst cooler, and the heat of reaction that catalyst cooler is removed is used To produce high steam, coke is the accessory substance of MTO reactions, and it is attached to catalyst particle surface causes the catalyst activity to reduce Or inactivation, therefore, catalyst must be by coke burning regeneration with activity recovery.Catalyst is regenerated as a continuous process.Separate Decaying catalyst catalyst regenerator is entered by decaying catalyst induction system, the reclaimable catalyst of carbon deposit is again after reaction Rear Returning reactor is burnt in raw device.Catalyst regeneration is exothermic reaction, and the combustion heat is moved by regenerator catalyst cooler Go out, be used to produce steam.
Reaction gas is drawn after the microspherical catalyst that cyclone separator removes entrained with, after lowering the temperature through heat exchanger, delivers to urgency Cold tower.Enter product separator from chilling top of tower admixture of gas out, the most of product water quilt in admixture of gas Condense out into product separator bottom.From product separator top, olefin product out is sent to separation of olefins unit, It is compressed, is fractionated and purifies, product is separated in recovery unit, de- minor amount of water, methyl alcohol and DME.Propylene, ethene are main product Product, byproduct is liquid fuel and gasoline.
Methyl alcohol light olefin catalyst provided by the present invention by the separately synthesized and modified phosphorus sial of specified conditions with Borosilicate aluminum molecular screen, makes catalyst have the medium acid strength for being suitable for MTO reactions and the acid amount distribution concentrated, and possesses well MTO catalyzed conversions activity and light olefins product selectivity, overcome catalyst conversion activity in the prior art and selectivity of product Not enough inherent shortcoming；Ten-ring aperture and twelve-ring mesopore needed for the suitable reaction that catalyst has are arranged in pairs or groups, enriched Smaller aperture due (5 nanometers of ＜) is mesoporous and Jie's micropore distributed architecture system of step configuration, be conducive in MTO courses of reaction In reactant, product and other accessory substances, the circulation and diffusion of organic attachment, obtain catalyst activity, selectivity Stabilization is played.
Mother liquor iterative cycles in methyl alcohol light olefin catalyst preparation process provided by the present invention are utilized, and with crystalline substance The method for changing atomized microball shaping after mother liquor, each operation work condensate liquid mixing are beaten, had both been the small-bore (5 nanometers of ＜) of matrix Mesoporous system provides contribution, necessary mechanical strength when in turn ensure that catalyst is used, due to recycling, mother liquor and Organic amine, the molecular sieve of precipitation and sial raw material in various condensate liquids, recovered liquid etc. are obtained for and effectively collect and sharp again With so as to save these raw material needed for catalyst manufacturing procedures；In combination with eliminating, ion exchange, drying etc. are numerous General labourer's sequence and step, significantly reduce Catalyst Production cost, and make whole catalyst preparation process easier to be rationally and green Colour circle is protected.
Specific embodiment
The present invention is further illustrated for the following examples, but not thereby limiting the invention.
In embodiments, the acid strength using indicator and the method determination sample of n-butylamine titration and acid amount distribution； Using X-ray diffractometer determination sample thing phase and crystallinity；The chemical composition of x-ray fluorescence method determination sample；BET cryogenic nitrogens are inhaled The specific surface area of attached method determination sample, pore volume and mesoporous distribution；The suction of surface weight adsorption balance determination sample different pore size Attached capacity and kinetic diameter (adsorbing medium ammonia, n-hexane, iso-butane etc.)；Catalyst grain size is determined using laser particle analyzer； Microspherical catalyst abrasion strength resistance is determined with gooseneck friabilator；Reaction evaluating is divided product gas with gas chromatograph Analysis.
Other detection referring to (《Oil and oil product test method national standard》Published by China Standards Press 1989 Year).
Embodiment 1
In the autoclave of band stirring, (1) adds 1 liter of deionized water, by 183 grams of boehmites (industrial goods, Al2O3 70m%, Shandong Aluminum Plant) it is (chemical with 225 grams of diethylamine (chemically pure reagent, Beijing chemical reagent company) and 12 grams of di-n-propylamines Pure reagent, Beijing chemical reagent company) hybrid reaction 2 hours at 95 DEG C, then with 300 grams of phosphoric acid (industrial goods, 85m%, Sichuan Profit and catalyst plant), 180 grams of Ludox (industrial goods, 25m% SiO2, Haiyang Chemical Plant, Qingdao), mixing is made pH value 6.7 slurry, after being aged 24 hours through 30 DEG C, then hydrothermal crystallizing 80 hours at 185 DEG C, filtering acquisition SAPO-34 molecular sieves Former powder A, crystallization mother liquor is used for the preparation of step (2) and (3).
(2) by above-mentioned SAPO-34 molecular screen primary powders A through 550 DEG C roasting 1 hour after, with above-mentioned steps (1) filtering obtained by In crystallization mother liquor, 20 grams of diethylamine and 700 grams of deionized water mixing are added, hydro-thermal process 24 hours, filter at 190 DEG C It is mother liquid obtained for preparation process (3) after filtering to the modified SAPO-34 molecular sieve B of secondary synthesis.
(3) in above-mentioned steps (1) and (2) are mother liquid obtained, 3 grams of boehmites (ibid) are added, at 150 DEG C after mixing It is lower reaction 3 hours, then with 50 grams of silica gel (industrial goods, 99m% SiO2, Haiyang Chemical Plant, Qingdao) after mixing through lower water at 160 DEG C Thermal crystallisation 30 hours, is filtrated to get ZSM-5 molecular sieve original powder C, and the mother liquor after filtering is used for preparation process (5).
(4) by the ZSM-5 molecular sieve original powder C obtained by above-mentioned steps (3) and 10 grams of boric acid (chemically pure reagent, 95m%, north Capital chemical reagent company) after ground and mixed is uniform, in 450 DEG C of tube furnace, the Grams Per Hour of water vapour weight flow rate 60, hydro-thermal Treatment 2 hours, obtains the modified B-ZSM-5 molecular sieve D powder of boron compound, and tail gas condensing liquid is used for preparation process (5).
(5) by step (2) and step (4) gained modified SAPO-34 molecular sieve B powder and B-ZSM-5 molecular sieve D powder, With 600 grams of aluminium sol adhesives (industrial goods, Al2O320m%, Sichuan profit and catalyst plant), 400 grams of kaolin (industrial goods, Gu Content 88m%, Kaolin of Suzhou company) with the crystallization and secondary synthesis of above-mentioned molecular sieve after remaining mother liquor and crystallization, change Property, the condensate liquid containing organic formwork agent in roasting and spray process be sufficiently mixed, add 700 grams of deionized waters, grinding Behind mashing to solids particle diameter≤2 micron of 93v%, dried in the small spraying of 600 DEG C of intake air temperature, 280 DEG C of exhaust temperature Microballoon is shaped in device, tail gas condensing liquid is used for next group of sample mashing and prepares use.
(6) catalyst microspheres after above-mentioned spray shaping are respectively washed 10 points in three times with 15 liters 70 DEG C of deionized water After clock, 110 DEG C of dryings 2 hours under 550 DEG C of oxidizing atmosphere (oxygen volumetric concentration 5v%) calcination activation 2 hours, obtain The catalyst of embodiment 1.
Comparative example 1
Using commercially available commodity SAPO-34 molecular sieves (industrial goods, relative crystallinity 90%, phosphorus aluminum ratio 0.5, silica alumina ratio 0.7) with ZSM-5 molecular sieve (industrial goods, crystallinity 90%.Silica alumina ratio 50), also can by USP USP4440871 and USP3702886 prepares SAPO-34 and ZSM-5 molecular sieve respectively, by the molecular sieve ratio of the embodiment 11 of CN101676028B Example, method and condition, under molecular sieve total content same as Example 1, spray shaping prepares microspherical catalyst, and it is right to obtain The catalyst of ratio 1.
Comparative example 2
The step of according to comparative example 1, by identical molecular sieve content, the CMC (works of material butt 1m% are added in mashing Industry product, Na2O ＜ 0.1m%, her Lipha of Suzhou produces), other conditions are prepared with mesoporous contrast with comparative example 1 The catalyst of example 2.
Comparative example 3
According to the method and steps in the embodiment of CN104525250A, the SAPO- of the multi-stage porous after alkali modification is prepared 34 molecular sieves, after also can preparing SAPO-34 according to the method for USP4440871, the method for referring again to step (2) in embodiment 1 It is modified, obtain the modified SAPO-34 molecular sieves of secondary synthesis；According still further to the method and step of the comparative example 3 of CN101676028B Suddenly, a kind of molecular sieves of SAPO-34 containing multi-stage porous after only adding alkali modification in mashing by identical molecular sieve content, prepare The catalyst of comparative example 3.
Comparative example 4
According to the method and steps in the embodiment of CN102259013A, the B-ZSM-5 molecular sieves of boracic are prepared, also may be used After method according to USP3702886 prepares ZSM-5 molecular sieve, then carry out boron compound be modified, obtain B-ZSM-5；And reference The method and steps of the comparative example 6 of CN101676028B, only adds B-ZSM-5 a kind of by identical molecular sieve content in mashing Molecular sieve, prepares the catalyst of comparative example 4.
Embodiment 2
The step of according to embodiment 1, replaced using 240 grams of triethylamines (chemically pure reagent, Beijing chemical reagent company) real The diethylamine and di-n-propylamine in example 1 are applied as organic template agent, to investigate the catalyst performance in the case of single organic formwork agent With the situation of preparation, other preparation condition embodiments 1 are identical, obtain the catalyst of embodiment 2.
Embodiment 3
The step of according to embodiment 1, but 16 grams of SAPO-34 molecular sieves of the gained of embodiments 1 are added in preparation process (1) Former powder is used as crystal seed；The ZSM-5 molecular sieve original powder of the gained of 1 gram of embodiment of addition 1 is prepared and adopted as crystal seed in step (3) The SAPO-34 molecular sieves and ZSM-5 molecular sieve synthesized with crystal seed method, other preparation conditions are same as Example 1, obtain embodiment 3 catalyst.
Embodiment 4
In the autoclave of band stirring, (1) adds 1 liter of deionized water, by 200 grams of boehmites (ibid) and 250 grams Diethylamine (ibid) hybrid reaction 2 hours at 140 DEG C, then with 300 grams of phosphoric acid (ibid), 50 grams of silica gel (ibid), mixing is stirred Mixing into pH value 6.9 slurry, through 40 DEG C of ageings 20 hours after, then hydrothermal crystallizing 60 hours at 190 DEG C, filtering is obtained SAPO-34 molecular screen primary powder A, crystallization mother liquor is used for the preparation of step (2) and (3).
(2) by above-mentioned SAPO-34 molecular screen primary powders A through 500 DEG C roasting 2 hours after, with above-mentioned steps (1) filtering obtained by In crystallization mother liquor, 20 grams of tetraethyl ammonium hydroxides (chemically pure reagent, Beijing chemical reagent company) and 1 liter of deionized water are added Mixing, hydro-thermal process 30 hours at 175 DEG C are filtrated to get the modified SAPO-34 molecular sieve B of secondary synthesis, institute after filtering Obtaining mother liquor is used for preparation process (3).
(3) in above-mentioned steps (1) and (2) are mother liquid obtained, 2 grams of boehmites (ibid) are added, at 140 DEG C after mixing Lower reaction 4 hours, then ZSM- is filtrated to get through at 180 DEG C times hydrothermal crystallizings 20 hours after mix with 200 grams of Ludox (ibid) 5 molecular screen primary powder C, the mother liquor after filtering is used for preparation process (5).
(4) by the ZSM-5 molecular sieve original powder C and 5 grams of boron oxides (chemically pure reagents, Beijing chemical industry obtained by above-mentioned steps (3) Reagent Company) after ground and mixed is uniform, in 450 DEG C of tube furnace, the Grams Per Hour of water vapour weight flow rate 50, hydro-thermal process 3 is small When, the modified B-ZSM-5 molecular sieve D powder of boron compound is obtained, tail gas condensing liquid is used for preparation process (5).
(5) by step (2) and step (4) gained modified SAPO-34 molecular sieve B powder and B-ZSM-5 molecular sieve D powder, With remaining after 500 grams of aluminium sol adhesives (ibid), the 450 grams of crystallization and secondary synthesis of kaolin (ibid) with above-mentioned molecular sieve The condensate liquid containing organic formwork agent in remaining mother liquor and crystallization, modified, roasting and spray process is sufficiently mixed, and is added 500 grams of deionized waters, after grinding mashing to solids particle diameter≤2 micron of 92v%, in 620 DEG C of intake air temperature, exhaust temperature Microballoon is shaped in 285 DEG C of disk-type spray dryer, tail gas condensing liquid is used for next group of sample mashing and prepares use.
(6) catalyst microspheres after above-mentioned spray shaping are respectively washed 15 points at twice with 20 liters 85 DEG C of deionized water Clock, (oxygen volumetric concentration 15v%) calcination activation 1 hour under 600 DEG C of oxidizing atmosphere obtains the catalyst of embodiment 4.
Embodiment 5
The present embodiment is contrasted the catalyst preparation overall process emission behaviour in embodiment 1~4 and comparative example 1~4, Synthesis, crystallization, filtering, the ion exchange of described catalyst preparation overall process including molecular sieve, and catalyst mashing, drying Shaping and washing, dry, calcination activation, are shown in Table 1.
The preparation overall process unit product discharge contrast of table 1, embodiment 1~4 and the catalyst of comparative example 1~4：
From in table 1, in the catalyst preparation overall process of embodiment 1~4, except containing micro Na2O and Trace Silicon aluminum precipitation Thing can not discharge reluctant containing organic matter and salt, the sewage of ammonia nitrogen outside reuse saliferous washings substantially, and this is for follow-up dirty Water process brings conveniently, also makes that whole preparation process is more green, environmental protection.
Embodiment 6
The present embodiment utilizes the instrumental analysis characterizing method described in specific embodiment, to above-described embodiment and contrast The catalyst sample of example is analyzed detection, with the difference of comparative example 1~4 and the catalyst of comparative example 1~4 on physico-chemical property It is different, it is shown in Table the data in 2.
The physico-chemical property contrast situation of table 2, embodiment 1~4 and the catalyst of comparative example 1~4：
Embodiment 7
The catalyst sample obtained in embodiment 1~4 and comparative example 1~4 is carried out into the micro- of preparing olefin by conversion of methanol reaction It is anti-to evaluate, through 600 DEG C before evaluating catalyst, after 100% steam aging is processed 4 hours, respectively by 5 gram of 20~40 particle of mesh Catalyst sample, is fitted into micro- anti-fixed-bed micro-reactor, and nitrogen activation is led to 1 hour at 600 DEG C, is then cooled to 460 DEG C are reacted.Fed using micro pump, 40% methanol aqueous solution, methanol weight air speed 2.0 hours-1, react 4 hours Sampling analysis afterwards, as a result as shown in table 3.
The MTO reaction micro anti-evaluation situations of table 3, embodiment 1~4 and the catalyst of comparative example 1~4：
Can be contrasted from table 3 and found out, the catalyst sample of embodiment 1~4, in an activity cycle, with more preferable Activity stability and selectivity of product, this during using recirculating fluidized bed reaction-regeneration system, is conducive in commercial Application The intensity of circulation of catalyst is reduced, the abrasion of catalyst is reduced.
Embodiment 8
This example demonstrates that catalyst of the present invention and comparative catalyst are used for the effect of MTO reactions.In small-sized fixed fluidisation In bed reactor, catalysis methanol is carried out to the catalyst sample obtained in above-described embodiment and comparative example and converts light olefin processed Experiment.Measure cracked gas in reaction evaluating to accumulate and use gas chromatographic analysis its composition, the water sample after gas-liquid separation uses gas phase Chromatograph determines methyl alcohol and water soluble products content, and evaluation result is shown in Table 4.
The fixed fluidized bed reaction evaluating situations of MTO of table 4, embodiment 1~4 and the catalyst of comparative example 1~4：
Through 600 DEG C before evaluating catalyst, 100% steam aging is processed 4 hours, 200 grams of catalyst sample-loading amount.Reaction bar Part is normal pressure, 460 DEG C of reaction temperature, 680 DEG C of regeneration temperature.Material benzenemethanol is pure for analysis, and water vapour strips charging, water and methyl alcohol Mass ratio is 0.2, and charging methyl alcohol weight (hourly) space velocity (WHSV) is 2.0 hours-1。
The moles of methanol of the moles of methanol/input reaction of the conversion ratio %=reaction consumption of methyl alcohol
As can be seen from Table 4, compared with the catalyst of prior art, can be more effectively using catalyst of the invention Catalysis methanol is converted into light olefin, and with ethene+productivity of propylene higher.
It is last it should be noted that above example is merely to illustrate technical scheme and unrestricted, although ginseng The present invention has been described in detail according to preferred embodiment, it will be understood by those within the art that, can be to the present invention Technical scheme modify or equivalent, and without departing from the spirit and scope of technical solution of the present invention.

Claims (10)

1. a kind of methyl alcohol light olefin catalyst, it is characterized in that with the composition of inorganic matter dry basis be sodium oxide molybdena ＜ 0.1m%, silica 25m%~40m%, aluminum oxide 40m%~60m%, phosphorous oxide 10m%~20m%, boron oxide 0.01m% ~1m%；Its 85~95% acid amount is distributed in the range of Hammett acid strength functions Ho+4.8~-3.0；Ten yuan in catalyst The duct volumetric ratio of ring/twelve-ring is 10~20: 1；Mesoporous system and step Jie's micropore with 5 nanometers abundant of aperture ＜ Distributed architecture；The catalyst is applied in the reaction of methyl alcohol light olefin.
2. a kind of methyl alcohol light olefin catalyst, its feature also has the catalyst to be the hydrothermal crystallizing by 30m%~40m% and pass through Secondary synthesis modified Chabazite-type (CHA topological structures, chemical formula [mRAl17P12Si7O72]) molecular sieve, 5m%~10m% Hydrothermal crystallizing and bi-five-member cycle configuration type (the MFI topological structures, chemical formula [R of the acquisition that is modified through boron compoundnAln-BnSi96- 2nO192, n ＜ 27]) molecular sieve, the aluminium sol adhesive of 5m%~20m% and balance kaolin composition, wherein R is organic formwork Agent；The average grain diameter of catalyst microspheres is 55~75 microns and abrasion index is 0.5m%~1.8m%.
3. a kind of preparation method of methyl alcohol light olefin catalyst, it is characterized by the catalyst preparation comprises the following steps：
(1) by mol ratio SiO2/Al2O3=0.7~1.1, P2O5/SiO2=0.7~1.1, H2O/SiO2=65~80, it is organic Template R/Al2O3=0.5~2.2, first by boehmite and organic formwork agent R hybrid reactions 0.5~5 at 90~190 DEG C Hour, then the slurry for being made pH value 6.4~7.5 is mixed with phosphoric acid, silica gel and/or Ludox, through 20 DEG C~50 DEG C ageings After 15~30 hours, then hydrothermal crystallizing 20~100 hours at 170 DEG C~210 DEG C, prepare unmodified Chabazite-type molecule The former powder of sieve；
(2) by above-mentioned unmodified Chabazite-type molecular sieve original powder through 400 DEG C~650 DEG C roastings 0.5~6 hour after, it is and above-mentioned Crystallization mother liquor, organic formwork agent and deionized water obtained by step (1), by molecular screen primary powder：Organic formwork agent R: water=1: 0.01~1: 5~20 weight proportion mixing, hydro-thermal process 15~30 hours, obtains through secondary synthesis at 170 DEG C~210 DEG C Modified Chabazite-type molecular sieve；
(3) by SiO2/Al2O3=30~90, organic formwork agent R/Al2O3=0.5~40, H2O/SiO2=5~15 mole match somebody with somebody Than, by above-mentioned steps (1) and (2) are mother liquid obtained mix with boehmite after at 90 DEG C~190 DEG C react 0.5~5 hour, Through hydrothermal crystallizing at 130 DEG C~200 DEG C 10~40 hours after mixing with silica gel and/or Ludox again, unmodified double five are obtained Ring structure type molecular screen primary powder；
(4) by molecular screen primary powder: boride: water=1: 0.01~0.5: 0.1~2 weight proportion, by obtained by step (3) not Modified bi-five-member cycle configuration type molecular screen primary powder hydro-thermal process 0.5~4 hour at 350 DEG C~600 DEG C, obtains through boride Modified bi-five-member cycle configuration type molecular sieve；
(5) by step (2) and step (4) the modified molecular sieve of gained, and aluminium sol adhesive, kaolin and deionized water, By the mother liquor after the concentration of slurry of butt weight content 25m%~40m%, with the crystallization and secondary synthesis of above-mentioned molecular sieve and Condensate liquid in crystallization, modified, roasting and spray process is sufficiently mixed, the solids of grinding mashing to 90v%~95v% Behind particle diameter≤2 micron, it is shaped in 350 DEG C~650 DEG C of intake air temperature, the spray drying tower of 150 DEG C~350 DEG C of exhaust temperature Microballoon；
(6) catalyst microspheres after spray shaping are washed to the Na of microspheres with solid with 30 DEG C~90 DEG C of deionized water2O ＜ After 0.1m%, the calcination activation 0.5~4 hour under 400 DEG C~650 DEG C of oxidizing atmosphere.
4. a kind of preparation method of methyl alcohol light olefin catalyst according to claim 3, it is characterised in that described mould Plate agent is nitrogen-containing organic compound：Diethylamine, triethylamine, n-propylamine, isopropylamine, Tri-n-Propylamine, tri-isopropyl amine, di-n-propylamine, Diisopropylamine, TMAH, tetraethyl ammonium hydroxide, TPAOH, 1,6- hexamethylene diamines, cyclohexylamine, beautiful jade, Monoethanolamine, diethanol amine, triethanolamine, N ', N ', N, N- tetramethyl -1, one kind or any several mixing in 6- hexamethylene diamines Thing.
5. the preparation method of a kind of methyl alcohol light olefin catalyst according to claim 4, it is characterised in that described has Machine amine R is one or more in diethylamine, triethylamine, di-n-propylamine, tetraethyl ammonium hydroxide.
6. a kind of methyl alcohol light olefin catalyst according to claim 1, it is characterised in that described step Jie micropore point Cloth structure is：0.43 nanometer of aperture pore volume of ten-ring accounts for 0.5 nanometer of mesopore of the 40v%~60v% of total pore volume, twelve-ring Pore volume accounts for the 1v%~10v% of total pore volume, the mesoporous pore volume of 2~5 nanometers of smaller aperture due and accounts for the 30v%~50v% of total pore volume.＞ 5 nanometers of the mesoporous pore volume of larger aperture accounts for the 2v%~8v% of total pore volume.
7. a kind of preparation method of methyl alcohol light olefin catalyst according to claim 3, it is characterised in that described boron Compound is one or more in boron oxide, boric acid, ammonium borate, boron phosphate.
8. a kind of method of methyl alcohol light olefin, it is characterised in that in a fluidized bed reactor, methyl alcohol 350 DEG C of reaction temperature~ 650 DEG C, 0.01~10MPa of reaction pressure, weight space velocity 0.1~50 hour-1Under conditions of urged with one of claims 1 to 3 Agent contact is converted into light olefin, enters after catalyst microspheres inactivation in 550 DEG C~850 DEG C of regenerator and is returned after coke-burning regeneration Reaction is continued to participate in fluidized-bed reactor.
9. the method for a kind of methyl alcohol light olefin according to claim 8, it is characterised in that described reaction temperature is 400 DEG C~550 DEG C, reaction pressure be 0.1~2.5MPa, weight space velocity be 1~10 hour-1, 580 DEG C~780 DEG C of regenerator temperature.
10. the method for a kind of methyl alcohol light olefin according to claim 8, it is characterised in that addition water vapour or indifferent gas Body come adjust methyl alcohol charging partial pressure.
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