CN1341584A - Abrasion-resisting catalyst for producing light olefin - Google Patents

Abrasion-resisting catalyst for producing light olefin Download PDF

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CN1341584A
CN1341584A CN01132533A CN01132533A CN1341584A CN 1341584 A CN1341584 A CN 1341584A CN 01132533 A CN01132533 A CN 01132533A CN 01132533 A CN01132533 A CN 01132533A CN 1341584 A CN1341584 A CN 1341584A
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catalyzer
weight
molecular sieve
catalyst
silicon
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P·T·巴格
T·L·马克
J·A·卡奇
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Honeywell UOP LLC
Universal Oil Products Co
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Universal Oil Products Co
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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
    • B01J29/82—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
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/12—Silica and alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C07C2527/16—Phosphorus; Compounds thereof containing oxygen
    • C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Catalyst compositions that are effective for the conversion of methanol to light olefins (e.g. ethylene) are disclosed. The catalysts comprise a crystalline metalloaluminophosphate molecular sieve (e.g. SAPO-34) and a matrix material comprising an inorganic oxide binder and a filler, preferably a clay (e.g. kaolin). It has been discovered that by maintaining the content of the molecular sieve at 40 % or less by weight, the overall catalyst attrition resistance is markedly improved.

Description

The abrasion-resisting catalyst that is used for light-olefin production
Background of invention
The increase of the supply finite sum cost of crude oil impels people to research and produce the alternative method of hydrocarbon product.A kind of such method is to be methanol conversion that (described light olefin refers to C for hydrocarbon, especially light olefin 2-C 4Alkene).Why people become interested to the method for methanol conversion alkene (MTO) and are based on such fact, produce synthetic gas, process synthetic gas then to produce methyl alcohol, obtain methyl alcohol with coal or Sweet natural gas thus.
The method that with methanol conversion is light olefin is known in this field.Initial silico-aluminate or zeolite are used as and carry out the required catalyzer of this conversion.For example, referring to US-A-4238631B1, US-A-4328384B1 and US-A-4423274B1.These patents also disclose for increase to the selectivity of light olefin and make the formation of C5+ byproduct reduce to minimum and sedimentation of coke on zeolite.
These prior aries also disclose aluminosilicophosphate (SAPO) can be used for the method that catalysis methanol is converted into alkene.Thereby US-A-4499327B1 discloses many SAPO family molecular sieves, and can be used for methanol conversion be alkene.Preferred SAPO is that its hole is even as big as adsorbs xenon (dynamically diameter is 4.0 dusts) and be small enough to repel those of Trimethylmethane (dynamically diameter is 5.0 dusts).A kind of particularly preferred SAPO is SAPO-34.US-A-4752651B1 discloses use non-zeolite molecular sieve (NZMS) (comprising ELAPO and MeAPO molecular sieve) catalysis methanol and has been converted into the reaction of alkene.
The particle diameter of molecular sieve is put down in writing in US5126308B1 to active influence.In described 308 patents, disclose 50% molecular sieve diameter of particle and had activity and the weather resistance that has increased greater than 2.0 microns molecular sieve less than 1.0 microns and no more than 10% diameter of particle.Described 308 patents also disclose the restriction silicone content also can improve catalytic performance between the 0.005-0.05 molfraction.In addition about particle size, the crystalline size that US-A-5912393 discloses average minimum is at least 0.1 micron molecular sieve and helps the selectivity of ethene to propylene.
Carbonaceous byproduct (known to coke) can deposit and be accumulated on the solid catalyst under the normal operating condition of MTO reaction.At last, a large amount of catalyst pores is blocked, needs to pass through regeneration or coke combustion step to recover activity of such catalysts.By temporarily stopping normal methanol conversion is the conversion of olefines process, and catalyst bed is under the oxygen containing atmospheric condition to be enough to the combustioncatalysts coke, can carry out catalyst regeneration off and on thus.Yet more advantageously be, can avoid the loss that produces because of shut-down being transported to the small part catalyzer keeps producing alkene in the independent regenerator vessel in reactor vessel reaction, described reactor vessel closely links to each other with revivifier.Use fluidized-bed to finish moving of catalyzer, fluid catalytic cracking (FCC) operation that this and refinery extensively adopt is closely similar.
Thereby with regard to being used for catalyzer that methanol conversion is a light olefin, the performance that described catalyzer physically stands to react with regenerative environ-ment obviously is a main problem of considering.The abrasion performance of the most suitable sign catalyzer of physical strength or anti-breaking property in this case, this abrasion and fracture be since between the catalyzer or the interaction between catalyzer and the equipment cause.These interactions comprise the direct impact and because the abrasion that catalyzer is produced in the solid surface motion of inner particles.Attrition of catalyst can influence the recharge rate of raw catalyst conversely again and and then influence mean life of catalyzer.The particulate that is produced by wear attrition of catalyst generally uses cyclonic separator to separate from the effluent liquid of reactor and revivifier, and described cyclonic separator can be caught the little particle to 10 microns of particle diameter.The removal of littler dust granule is finished by rod-curtain precipitator and so-called the 3rd section separator.Thereby the speed of wear attrition of catalyst directly influences these cyclonic separators and settling vessel dimensional requirement and service efficiency.In addition, the removal of catalyst fines not exclusively can be polluted light olefin product stream (entrained solids) dust granule of discharging is entered in the environment.
Thereby to be used for methanol conversion be that the wear resistant of the catalyzer of alkene is a crucial character, and the mechanical property that improves the anti-abrasion performance of catalyzer is a field of constantly advancing and making great efforts and studying.For example, WO99/21653 discloses the preparation method of the molecular sieve catalyst that is used for hydrocarbon and oxidation conversion, and wherein this method attempts to improve the wear resistant of catalyzer.Its disclosure points out that also the catalyzer of the SAPO-34 molecular sieve (as 50 weight %) of adding maximum amount in assigned formula has persistent abrasion performance index or generation particulate still less with respect to the catalyzer with lower aq SAPO-34 molecular sieve (as 25 weight %).
By contrast, the applicant finds in fact to have improved with respect to the usage quantity that substrate material or tackiness agent have reduced crystalline metal aluminophosphate molecular sieve (as SAPO-34) wear resistant of catalyzer.
Brief summary of the invention
The present invention relates to a kind of catalyzer and use this catalyzer the method for methanol conversion as light olefin.Described method is included in the catalyzer that methyl alcohol and wear resistant have been improved and contacts to make light olefin.Described catalyzer comprises the crystalline metal aluminophosphate molecular sieve, and described molecular screen base can be used empirical formula (EL in anhydrous chemical constitution xAl yP z) O 2Expression, wherein EL is selected from silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and composition thereof; " x " is the molfraction of EL, and its value is at least 0.005; " y " is the molfraction of Al, and its value is at least 0.01; " z " is the molfraction of P, and its value is at least 0.01; And x+y+z=1.The weight of molecular sieve with respect to the weight of catalyzer less than 40 weight %.Catalyzer also comprises the substrate material that contains inorganic oxide adhesive and filler.
Detailed Description Of The Invention
A principal character of catalyzer of the present invention is the ELAPO molecular sieve.ELAPO has AlO 2, PO 2And ELO 2The molecular sieve of the three-dimensional microporous framework structure of tetrahedron element.General ELAPO has following empirical formula
(EL xAl yP z)O 2
Wherein EL is selected from: silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and composition thereof; " x " is the molfraction of EL, and its value is at least 0.005; " y " is the molfraction of Al, and its value is at least 0.01; " z " is the molfraction of P, and its value is at least 0.01; And x+y+z=1.When EL is the mixture of described element, the total amount of the element mixture that " x " representative exists.Preferred element (EL) is silicon, magnesium and cobalt, particularly preferably is silicon.
The preparation of different ELAPO is known in the prior art, can be at US-A-4554143 B1 (FeAPO); US-A-4440871 B1 (SAPO); US-A-4853197 B1 (MAPO, MnAPO, ZnAPO, CoAPO); US-A-4793984 B1 (CAPO) finds among US-A-4752651 B1 and the US-A-4310440 B1.Usually, the ELAPO molecular sieve is synthesized by hydrothermal crystallization by the reaction mixture that contains reaction raw materials EL, aluminium, phosphorus and template.Reaction raw materials EL is salt such as the muriate and the nitrate of EL element.When EL was silicon, preferred raw material was fuming, colloidal or sedimentary silicon-dioxide.Preferred reaction raw materials aluminium and phosphorus are pseudobochmite aluminium and phosphoric acid.Preferred template is amine and quaternary ammonium compound.Particularly preferred template is tetraethylammonium hydroxide (TEAOH).
A preferred method for preparing the ELAPO molecular sieve with crystal habit is described among the US-A-5912393, and wherein average minimum crystalline size is at least 0.1 micron, preferably is at least 0.2 micron.Resemble in described 393 patents illustratedly,, can obtain the ethene (with respect to propylene) of higher output yield when average minimum size is at least 0.1 micron crystallite when being used as methanol conversion and being the catalyzer of light olefin.
After preliminary synthesizing, in the hole of ELAPO, contain some organic formwork agents usually.In order to keep the catalyst activity of ELAPO, the template in the hole must be removed, by in the oxygen containing atmosphere under 200-700 ℃ temperature heating ELAPO powder be removed up to template, this process needs several hrs usually.
The content that an embodiment preferred of the present invention is an element in the ELAPO molecular sieve (EL) changes between the 0.005-0.05 molfraction.If EL is more than one element, the total concn of all elements is between the 0.005-0.05 molfraction so.A particularly preferred embodiment is that wherein EL is silicon (being often referred to SAPO).Can be described in US-A-4440871 B1 by SAPO used in this invention; Any among US-A-5126308B1 and the US-A-5191141 B1.Be applicable to that SAPO catalyzer of the present invention comprises SAPO-11, SAPO-17 and SAPO-34, wherein SAPO-34 and SAPO-17 are preferred.
Crystalline metal aluminate or phosphate or ELAPO molecular sieve are incorporated in the solid particulate, and wherein ELAPO is that the amount of light olefin exists to impel desired methanol conversion effectively.In one aspect, solid particulate comprises the ELAPO molecular sieve of catalytically effective amount and comprises inorganic oxide adhesive and the substrate material of filler, and described substrate material provides the desired physical strength or the wear resistant of adherent catalyzer.Determined that when crystalline metal aluminate or phosphate during less than 40% (preferred 20%) of total catalyst weight, the wear resistant of catalyzer significantly improves.Thereby total substrate material is at least 60 weight % with respect to total catalyst weight, is preferably 80 weight %.In a preferred embodiment, less than 1%, described data are to measure by the standard wear test that is used for fluid catalyst to the per hour weight reduction that this content of substrate material will make the adherent catalyzer with respect to catalyst weight.Have effective catalytic amount in order to ensure the ELAPO molecular sieve, substrate material with respect to the weight of catalyst composition preferably less than 95 weight %.Yet in some cases, the catalyzer that uses the content of substrate material to surpass 95 weight % also is fine, and this depends on the chemistry and the physical restriction of the specific reaction that reactor size applies.
Except improving the intensive property of catalyzer, substrate material makes the bigger particle size of the bonding formation of molecular sieve microcrystal powder to be applicable to industrial catalytic process.Described ELAPO/ substrate material mixture can form multiple shape, comprises extrusion molding thing, spherical, sheet etc.In fact substrate material usually is porous to a certain extent, and can or cannot promote the conversion of desired methyl alcohol to light olefin effectively.Substrate material can also promote the conversion of incoming flow, and usually can reduce selectivity to target product or goods with respect to catalyzer.
Substrate material comprises inorganic oxide adhesive and filler.The example of preferred adhesive material comprises (but being not limited thereto) aluminum oxide, silicon-dioxide, aluminum phosphate, silica-alumina, zirconium white, titanium oxide and composition thereof.Filler material for example can comprise: the material of synthetic or natural generation such as clay, metal oxide, silicon-dioxide, aluminum oxide, silica-alumina and composition thereof.When relating to the type of operable tackiness agent and filler, should be noted that used term silica-alumina is not meant the physical mixture of silicon-dioxide and aluminum oxide, and be meant the acidity and the amorphous material of cogelled or co-precipitation.This term is known in the field, for example is described in US-A-3909450 B1; Among US-A-3274124 B1 and the US-A-4988659 B1.In this respect, may form other amorphous material cogelled or co-precipitation, these materials also are effective as tackiness agent or filler material.These materials comprise silica-magnesia, silicon-dioxide-zirconium white, silica-thorium oxide, silica-beryllia, silicon-dioxide-titanium oxide, silica-alumina-Thorotrast, silica-alumina-zirconium white, aluminate or phosphate, their mixture etc.Preferred filler is a clay, and this is because known clay all is inert basically under multiple reaction conditions.The clay that is fit to comprises the commercial product of buying such as kaolin, kaolinite, montmorillonite, talcum and wilkinite.Can with exploitation come out natural form use these clays, or use them with the high reactivity form, make their activation by the acid treatment process typically.The market supply merchant of these clays comprises ThieleKaolin Company (Sandersville, GA), American Colloidal Co. (ArilngtonHeights, IL), GSA Resources, Inc. (Tucson, AZ), Albion KaolinCo. (Hephzibah, Ga), and other company.
In Preparation of catalysts of the present invention, the slurries of ELAPO crystalline metal aluminate or phosphate powder, filler and inorganic oxide adhesive have been formed.Resemble already mentionedly, described slurries will contain suitable colloidal sol or solid support material, and wherein inorganic oxide adhesive is used for the suspending molecule sieve.In the adherent catalyst composition, add under the situation of aluminum oxide, silicon-dioxide, magnesium oxide, zirconium white or titania binder the suitable water-sol that adopts in the present invention.For example, any unsettled aluminum oxide can mix formation aluminium colloidal sol with water and acid.Employed acid can comprise mineral acid such as nitric acid, hydrochloric acid and sulfuric acid, or organic acid, especially carboxylic acid such as formic acid, acetate, propionic acid etc.On the other hand, aluminium colloidal sol can prepare like this, for example metallic aluminium is dissolved in the hydrochloric acid, then aluminium colloidal sol and alumina powder is mixed.When wanting to obtain alumina adhesive, also can use the solution of boehmite or aluminum nitrate to replace aluminium colloidal sol.
The silicon sol that is used to form some types of the adherent catalyzer that is used in the MTO method be can obtain from the market contain the dispersive silica colloidal particulate water-sol or organosol.For example, water glass can and can combine with acidic aluminum sol with the final formation usefulness silica-alumina tackiness agent in the catalyzer in the end as silicon sol.In addition, silicon sol also can be used to form the silica binder of molecular sieve catalyst.Silicic acid is another possible silica source.If want magnesium oxide adhesive, initial slurries should contain the magnesium alkoxide of hydrolysis.When zirconia binder was used to Preparation of catalysts, preferred initial acidic sol was an aqueous zirconium acetate solution, and described solution preferably combines with the urea gelifying agent.When using titania binder, the preferred titanium oxychloride solution of acidic sol, described solution also are preferably to combine with the urea gelifying agent.The acid colloidal suspensions of various inorganic oxides can suppliers from the market be buied, as Nano Tehcnologies, Inc. (Ashland, MA).The quantity that adds the colloidal sol in the slurries accounts for the 5-50% of adherent molecular sieve catalyst weight based on typical binder constituents.Preferably, the content of tackiness agent is 10-30 weight %.Resemble above-mentionedly, in the end whole compositions of the substrate material in the catalyzer (being inorganic oxide adhesive and filler) are at least 60%, are limited in below the 40 weight % with the content with the crystal aluminophosphate molecular sieve.Preferably, total substrate material accounts for 80% of catalyst weight at least, more preferably accounts for 80-95%.The person skilled in the art of those this areas will understand the relation between the ratio of the weight ratio of molecular sieve and colloidal sol in the slurries and molecular sieve in the resultant catalyzer and tackiness agent easily.
Resemble and discussed, slurries also should contain filler except the colloidal sol that contains inorganic oxide adhesive.Filler itself can be with Powdered rather than join inorganic oxide (as aluminum oxide) in the slurries with the colloidal sol shape.Preferably, filler is the clay that is fit to that is provided above a kind of being selected from.Determined that clay has improved the bulk strength of bonding catalyst, this improvement can be by test (being abrasion loss) last measuring of catalyzer in the standard wear test.Owing to the catalyzer that loses of friction can measured by fluidized catalyst in the given time in the air, the fines of collecting and weighing and produced calculates abrasive amount then, in the average percent of primary catalyst weight per hour.Have been found that by using weight to be less than 40% molecular sieve preferably be less than 20%, abrasive amount preferably less than 0.8%, is more preferably less than 0.5% per hour can be controlled at less than 1 weight % with respect to whole catalyzer.
Comprise that in slurries other performance to final catalyzer may drop within protection scope of the present invention by influential composition too.For example, WO99/21653 discloses and has used outside phosphorus source, comprises potential phosphorus source and desired relative quantity in catalyst component.
According to the average particle size particle size of the molecular sieve crystal that lumps in the slurries, can grind described slurries dividing these cakings, thereby reduce caking particulate size and/or the distribution of narrower particle size is provided.Grinding can be adopted method well known in the art such as ball milling, and the time is from 30 minutes to 5 hours, preferably from 1.5 hours to 3 hours.Can think that the slurries that the distribution of use particle size obtains adjusting have in this way improved the structure properties of adherent molecular sieve catalyst.Must note the inundue crystalline structure of described slurries that grind to avoid the saboteur to sieve.
Should be noted that slurries usually also contain water except containing molecular sieve powder, inorganic oxide adhesive colloidal sol and filler.The amount of water often is adjusted behind any grinding operation, and this is in order to make the viscosity of grinding rear slurry between the 30-600 centipoise.Before drying, the general preferred slurry content thorough mixing that makes is formed to guarantee uniform slurries.For example in most of the cases 15 minutes high shear mixing can obtain the uniformity coefficient that suits effectively.Make slurries begin gelling before afterwards drying step of beginning be very important, after mixing, carry out 1 hour the time usually.
Well-mixed slurries (through formerly grinding or without formerly grinding) then under 50-300 ℃ temperature dry 1-24 hour to form the particle of exsiccant, shaping.These particles both can also can be without the grinding of back or otherwise reduced in size so that the physicals of catalyzer to be provided through the grinding of back, and these performances have produced again finally wants drooping characteristic, fluidization rate, diffusion resistance and other performance.The diameter of the particulate average effective of dry forming is the 10-300 micron, preferred 20-150 micron.For aspherical particle, described effective diameter is meant to have this numeral equally if shaped particles is molded as spherical its diameter.In a preferred embodiment, the particle of dry forming is essentially spherical.Resulting in this case catalyst shape usually refers to microballoon.
A kind of method of preferred dry slurries is spraying dryings known in the field.When adopting this technology, slurries are sent to and make slurries be dispersed into the nozzle of many droplets.Particle is dried in the air by spray-dryer and stream or adverse current then.The person skilled in the art of this area knows, the dry forming particulate size of spray-dryer ejection determine by many factors, comprises the kind of the diameter of equipment and height, nozzle, and if wheel per minute rotating speed (RPM) during use disc spray device.The big inadequately particle of spray-dryer ejection can be separated and be sent the inlet slurries back to, thereby has improved the overall yield of catalyzer.Yet, often wish that the particle that circulates was crushed to less than 5 microns before mixing with the slurries of sending into spray-dryer.Using an advantage of spray drying technology is the particle (if desired) that it can prepare dry forming, and it is spherical that described particle is essentially, and therefore is applicable to dynamic moving-bed catalysis process.Yet, if do not consider drying means, the preferred 10-300 micron of particulate effective size of grain.
The granules of catalyst of dry forming can contact with the moisture exchange solution of ionic compound alternatively and put processing in order.Aqueous exchange solution is characterised in that it can remove the undesired metallic cation that may occupy the ion exchange site of molecular sieve effectively.For example, crystal aluminate or phosphate switch is usually occupied by sodium, potassium, magnesium or other positively charged ion to a certain extent.These materials may be from the inorganic mould material that is present in molecular sieve, or more generally from the starting material (as aluminium colloidal sol) of inorganic oxide adhesive.In the designed use of catalyzer (is alkene as methanol conversion), these metallic cations can promote side reaction, reduce the speed of goal response, perhaps make the katalysis of goal response complicated.The metallic cation that some raw materials (as silicic acid) of inorganic oxide adhesive are not expected basically, thereby adopt the dry granules of this raw material production not need to contact with exchange solution.Before the arrangement step and need water to rinse out undesired solid on the catalyzer and/or remaining exchange solution afterwards.
Preferably, exchange solution comprises a kind of ammonium compound, and especially ammonium sulfate, volatile salt, bicarbonate of ammonia, ammonium nitrate, ammonium hydroxide and various ammonium halide have been found effective to the arrangement step.This effectiveness can be removed the metallic cation pollutent that is contained in the above-mentioned substance from exchange solution, thereby the crystal aluminophosphate molecular sieve composition of catalyzer is converted into its hydrogen form basically.Thereby the arrangement step can be converted into the metallic cation-switch of molecular sieve hydrogen-switch of wanting.The condition of arrangement step comprises that the temperature that exchanges solution is 5-95 ℃, and be 0.5-10 hour duration of contact, depends on temperature and other factors duration of contact.Arrangement step or carry out in batches or carry out continuously.
At last, the particle of dry forming (through or without arrangement) in air atmosphere 400-900 ℃ temperature lower calcination 1-10 hour to solidify inorganic oxide adhesive effectively.Calcining step can also be removed any residual mould material that may be present in the crystalline metal aluminophosphate molecular sieve.In some cases, catalyzer activates under an improved calcining step, and wherein organic formwork agent at first decomposes in the purity nitrogen air-flow.Increase oxygen concn then with any residual hydrocarbon in the burning molecular sieve.It also is possible that drying step and calcination operation are combined into a step.
Methyl alcohol is contacted with the catalyzer that contains the ELAPO molecular sieve to finish the conversion of methyl alcohol to light olefin, formed the light olefin of wanting thus.Methyl alcohol can be liquid phase or vapour phase, preferably vapour phase.Contacting of methyl alcohol and ELAPO catalyzer can be carried out or carry out in the batch-wise mode in mode continuously, preferred successive mode.Must be enough to make methanol conversion the duration of contact of methyl alcohol and EIAPO catalyzer is the light olefins product of wanting.When described method was carried out in the batch-wise mode, be 0.001-1 hour duration of contact, preferred 0.01-1.0 hour.Adopt long duration of contact at a lower temperature, and under comparatively high temps, adopt short duration of contact.In addition, when described method is carried out in a continuous manner, be 1-1000hr based on the weight hourly space velocity (WHSV) of methyl alcohol -1, preferred 1-100hr -1As known in the art, weight hourly space velocity is the ratio of the weight flow velocity of methyl alcohol divided by catalyst weight.This term has per hour shown how many normal catalyzer of the present invention are arranged in action with respect to methyl alcohol.
Usually, in order to form light olefin with enough fast speed, this method must at high temperature be carried out.Thereby this method is carried out under 300-600 ℃, preferably at 400-550 ℃, most preferably at 450-525 ℃.Described method can be carried out under the pressure that comprises autogenous pressure of a wide region.Thereby pressure can change in the scope of 0kPa (0psig)-1724kPa (250psig), preferred 34kPa (5psig)-345kPa (50psig).
Alternatively, in order more effectively to be that alkene can dilute methanol feeding with inert diluent with methanol conversion.The example that can use thinner is helium, argon, nitrogen, carbon monoxide, carbonic acid gas, hydrogen, water vapour, paraffinic hydrocarbons (as methane), aromatic hydrocarbon (as benzene, toluene) and composition thereof.The consumption of thinner can change in wide region, normally the 5-90 mole % of charging, preferably 25-75 mole %.
The practical structures of conversion zone can adopt catalytic reaction device known in the field.Thereby, the zone that can adopt one conversion zone or a large amount of serial or parallel connections.In this conversion zone methyl alcohol by one contain the ELAPO catalyzer the bed charging.When using the multi-reaction-area territory, can connect and use one or more ELAPO catalyzer to want the product mixture that obtains with preparation.Available dynamic bed system (as fluidized-bed or moving-bed) replaces fixed bed.This dynamic system will help the regeneration (may need) of any ELAPO catalyzer.The regeneration of catalyzer if desired, the ELAPO catalyzer can be imported regeneration zone continuously as moving-bed.Here catalyzer is for example removed carbonaceous material by the oxygenizement of oxygen-containing atmosphere and is regenerated.
Resemble top saidly, abrasion-resisting catalyst of the present invention is particularly useful for the operating environment of the strictness of dynamic fluidized bed apparatus.This operating method makes catalyzer of the present invention use cyclic regeneration whole or in part afterwards in conversion process.The regenerative power of regenerated catalyzer for example especially seems valuable to the MTO method by this way, if not regeneration here, the quick coking meeting activity of spent catalyst soon, thereby need shutoff operation equipment with off line regeneration or reload catalyzer.These processes have caused a large amount of wastes of operating time and cost usually.
The following examples are used to explain the present invention and should not be construed as restriction to the protection domain of claim of the present invention.
Embodiment 1-6
In order to study the abrasion performance effect of crystal aluminophosphate molecular sieve catalyst composition, prepare six catalyst samples according to aforementioned preparation method.In the slurries of this embodiment, contain molecular sieve SAPO-34, kaolin and silicon sol and aluminium colloidal sol.Specifically, the silica-alumina adhesive composition comprises that volume ratio is 2: 1 the acidifying Tai-Ace S 150 (claiming acid alum usually) and the mixture of water glass.Described alum contains the have an appointment free sulfuric acid of 12.8 weight % and the aluminium sesquioxide of 2.5 weight %, and sodium silicate solution is 16%SiO 2, Na 2O: SiO 2Ratio be 3.2.
The solution that is used for the salic source of tackiness agent and silica source is mixed under the condition of controlled temperature and pH with an injector.After the mixing, adhesive composition is added in the container and uses high-shear mixer constantly to stir.Import kaolin (R-87 is purchased from Thiele Kaolin Company) then at leisure.In order to finish the preparation of slurries, in mixture, add ground SAPO-34 molecular sieve.
Through after 10-15 minute the stirring, slurries are pumped to and sparge the also dry formation mean diameter of dry device is the spheroidal particle (being microballoon) of 70-100 micron.The condition of spray-drying process comprises that temperature in and temperature out are respectively 340 ℃ and 135 ℃.Then with alum liquor ion-exchange resulting granules to obtain being essentially the molecular sieve of hydrogen form.After the arrangement step, according to aforesaid method particle be dried and calcine with to the end catalyzer.
Six catalyst samples have been represented two kinds of different compositions, and every kind of composition has three samples.First kind of composition is 40%SAPO-34 by weight, 40% kaolin and 20% inorganic oxide adhesive.Resemble top saidly, inorganic oxide adhesive is that the weight ratio of silica/alumina is 90/10 mixture.Second kind of composition is 20%SAPO-34 by weight, 60% kaolin and 20% inorganic oxide adhesive.Inorganic oxide adhesive also is that the weight ratio of silica/alumina is 90/10 mixture.
The calcining back is tested down at 650 ℃ for the wear resistant of different catalyst samples.The standardized test that use is used for fluid catalyst is measured the wear resistant of described catalyzer.This method comprises that the sample with each catalyzer is placed in the pipe, wet air with predetermined flow velocity by this pipe so that a fluidizing environment to be provided.The catalyzer fines that comes out from catalyst separating is collected, and per hour weighs once to draw the speed of catalyst breakage.By with respect to the catalyst weight of the initial loading weight percent catalyst weight of counting loss recently of damaged catalyzer per hour.Stop test after 5 hours.
Different catalyst compositions, arrangement (i.e. exchange) condition and to wear away concise and to the point result as shown in table 1.
The abrasion resistance of table 1 differing molecular sieve catalyst
Embodiment Catalyst composition, weight % Finishing condition Abrasion (weight %/hour)
?SAPO-34 Kaolin Inorganic oxide adhesive Solution Temperature
?1 ?40％ 40％ 20％ Ammonium sulfate 7.2℃ 0.9
?2 ?20％ 60％ 20％ Ammonium sulfate 7.2℃ 0.2
?3 ?40％ 40％ 20％ Ammonium sulfate 35℃ 0.7
?4 ?40％ 40％ 20％ Volatile salt 7.2℃ 0.7
?5 ?20％ 60％ 20％ Volatile salt 7.2℃ 0.2
?6 ?40％ 40％ 20％ Volatile salt 35℃ 0.7
Because the MTO reactor design on the market is generally loaded employed total catalyst and made tangible restriction, the SAP0-34 of 20 weight % forms can easily be had the more existing catalyzer replacement of polymer sieve content.Thereby it is the feasible way of abrasive reality that reduces catalyzer owing to form fines that the SAPO-34 content of spray-dried catalyst is reduced to less than 40%.The content of SAPO-34 is preferably less than 20% in the catalyzer, even low to 5% or still less, remaining is substrate material (being clay or inorganic oxide adhesive) sometimes, this catalyzer is the better surrogate of existing prescription catalyzer.

Claims (10)

1, a kind of being used for methanol conversion is the catalyzer of alkene, comprises crystalline metal aluminophosphate molecular sieve and substrate material, and described catalyzer is characterised in that described crystalline metal aluminate or phosphate can represent with following formula based on the chemical constitution of moisture-free basis
(EL xAl yP z) O 2Wherein EL is selected from following element: silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and composition thereof; " x " is the molfraction of EL, and its value is at least 0.005; " y " is the molfraction of Al, and its value is at least 0.01; " z " is the molfraction of P, and its value is at least 0.01; And x+y+z=1, described substrate material comprises inorganic oxide adhesive and filler, the weight of molecular sieve with respect to the weight of catalyzer less than 40%.
2, according to the catalyzer of claim 1, wherein the EL element is selected from silicon, magnesium, cobalt, nickel and composition thereof.
3, according to the catalyzer of claim 1 or 2, wherein the EL element is a silicon.
4, according to any one described catalyzer among the claim 1-3, wherein tackiness agent is selected from aluminum oxide, silicon-dioxide, aluminum phosphate, silica-alumina, zirconium white, titanium oxide and composition thereof.
5, according to any one described catalyzer among the claim 1-4, wherein filler is selected from the clay of kaolin, kaolinite, montmorillonite, talcum and wilkinite and composition thereof.
6, according to any one described catalyzer among the claim 1-5, wherein the content of molecular sieve is 5-20% with respect to the weight of catalyzer.
7, according to any one described catalyzer among the claim 1-6, wherein the content of inorganic oxide adhesive is 10-30% with respect to the weight of catalyzer.
8, according to any one described catalyzer among the claim 1-7, wherein abrasive catalyzer per hour is less than 1% by weight.
9, any one catalyzer is application in the method for light olefin in methanol conversion among the claim 1-8, and described method is included under the conversion condition catalyzer is contacted with methyl alcohol to produce alkene.
10, according to the method for claim 9, wherein said conversion condition is meant temperature from 300 ℃ to 600 ℃, pressure from 0kPa to 17224kPa (250psig) and weight hourly space velocity from 1hr -1To 100hr -1
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