CN105618128A - Method for preparing efficient etherification catalysts - Google Patents

Method for preparing efficient etherification catalysts Download PDF

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Publication number
CN105618128A
CN105618128A CN201610069240.6A CN201610069240A CN105618128A CN 105618128 A CN105618128 A CN 105618128A CN 201610069240 A CN201610069240 A CN 201610069240A CN 105618128 A CN105618128 A CN 105618128A
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etherification
catalyst
accordance
steam treatment
catalysts
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柯明
颜曦明
宋昭峥
蒋庆哲
周耀文
于沛
刘强
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/7057—Zeolite Beta
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/06—Metal salts, or metal salts deposited on a carrier
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
    • 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
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • B01J2229/36—Steaming
    • 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
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/04—Catalyst added to fuel stream to improve a reaction

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for preparing efficient etherification catalysts. The efficient etherification catalysts can be used for producing ethers gasoline additives with high octane values. The method includes sufficiently mixing beta molecular sieves, gamma-Al2O3, sesbania cannabina powder and dilute nitric acid with one another to obtain mixtures, extruding the mixtures to obtain strips, drying and calcining the strips to obtain base catalysts; modifying the base catalysts in selected rare-earth metal ion exchange process and water vapor treatment process combined modes to ultimately obtain the high-activity etherification catalysts. The beta molecular sieves are used as active components, the gamma-Al2O3 is used as a binder, the sesbania cannabina powder is used as an extrusion aid, and the dilute nitric acid is used as an adhesive solvent. The etherification activity of the efficient etherification catalysts is evaluated under the conditions of the alcohol-to-alkene molar ratio of 0.8-1.2, the reaction temperatures of 60-120 DEG C, the pressures of 1 MPa-5 MPa and the volume space velocities of 0.5 h<-1>-3h<-1>. The method has the advantages that the efficient etherification catalysts are high in etherification activity and excellent in selectivity and stability and are easy to regenerate after being deactivated.

Description

A kind of preparation method of efficient catalyst for etherification
Technical field
The invention belongs to petrochemical industry, the preparation method relating generally to a kind of efficient catalyst for etherification, this catalyst can make active olefin and methanol in the light fraction such as light FCC gasoline, C4 or C5 raffinate react generation high-octane rating alkyl ether react.
Background technology
Gasoline standard forward low-sulfur, low alkene, low aromatic hydrocarbons, low-steam pressure and high-octane rating direction are developed. China's catalytic cracking (FCC) gasoline accounts for about the 70% of product oil, and alkene almost all comes in this in gasoline, state's V gasoline standard has limited olefin(e) centent �� 24%, following state VI standard will propose more harsh restriction, therefore, how effectively to drop alkene and retain octane number and become the study hotspot of oil product processing industry.
Etherification technology can reach Olefin decrease and put forward high-octane dual purpose in single step reaction simultaneously, is improve one of high-level most desirable route of gasoline quality, reply country gasoline, has development and application prospect widely. This technology is that FCC gasoline cuts into weight two component, with light component for raw material, after the pre-treatment step such as chosen property hydrogenation and washing, react with low-carbon (LC) alcohols (methanol, ethanol etc.) under acidic catalyst effect, generate corresponding alkyl ether, it is subsequently isolated out product to be in harmonious proportion with heavy constituent, finally gives etherified gasoline. Olefin(e) centent not only can be reduced by 10%��15% by this technology, octane number also can be made to improve 1-3 unit, and the physico-chemical property of product ether is close with gasoline, has good compatibility, than method more advantages such as directly interpolation ethanol.
External etherificate research starting early, common are the CDTACOL technique of the TAME technique of BP company of Britain, the CDTECH technique of CR&L company of the U.S., the Ethermax technique of American UOP company, Italy's DET technique of Snamprogetti company, the NEXTAME technique of Nexte company of Finland and IFP. The classical technique of the most foreign of domestic technique, is then improved, and wherein studying more has Fusun PetroleumCollege, Qilu Petrochemical academy, Lanzhou Petrochemical academy, Luoyang Petrochemical company etc.
Etherificate is typical acid catalyzed reaction, it then follows electrophilic addition mechanism. The early stage catalyst of application mostly is homogeneous catalyst, such as sulphuric acid, phosphoric acid, benzenesulfonic acid etc., after there is the shortcomings such as etching apparatus, product separation difficulty, waste liquor contamination environment in view of it, people develop again a series of heterogeneous catalysis, such as acid large hole cation exchanger resin, solid super-strong acid, solid-carrying heteropolyacid, molecular sieve etc.
Current industrial commonly used be macropore strong acid cation exchanger resin, the advantage that it has acid height strong, active, preparation cost is low, but under poor heat stability, high temperature, acid site is easy to run off, catalyst life is short, regeneration is difficult, and product colour is relatively deep, and side reaction is more. Patent CN1348941A discloses a kind of with acidic resins for carrier, load active component Pt, Pd, Ni, Co and promoter prepare the preparation method with etherificate, selective hydrogenation and isomerized three function catalyst, but resin heat stability is limited compared with official post reaction temperature. The preparation method of a kind of resin catalyst for light gasoline etherification disclosed in patent CN103586075A, it is, after comonomer generates polymerization Archon, obtain then through conventional sulphonation by 100 parts of styrene, 5-20 part divinylbenzene, 0.1-5 part '-biphenyl diphenol and 0.1-2 part 3-(1-pyrrolidinyl) ethyl acrylate. But catalyst life and reproducibility are not illustrated by patent. Patent CN102557887A discloses a kind of catalyst preparing tert amyl methyl ether(TAME), carrier is macroporous network type polystyrene acid cation exchange resin, major catalyst is one or more in Ru, Rh, Co, Mo, Ni metal or corresponding soluble salt, and auxiliary agent is one or more in ii I or iv main group.
The metal-oxide catalyst that solid super strong acids catalyst for etherification usually promotes with sulfate radical, the acid strength concentrated sulphuric acid higher than 100%, the active height of this kind of catalyst, the advantage such as corrosion-free, pollution-free, but hydrothermal stability is relatively poor. Catalyst disclosed in patent CN102553616A is with amorphous silicon aluminium for carrier, impregnates carrier with sulphuric acid, ammonium sulfate, ammonium hydrogen sulfate or mixed solution, and the load capacity of oxysulfide is 2%-20%, and then stage drying and roasting prepare. Use it for Etherification of Light FCC Gasoline reaction, the octane number of gasoline after ether can be improved 2.1 constituent parts. The catalyst mentioned in patent CN102335599 is to adopt coprecipitation method to prepare, with the big ball of silicon for carrier, with ZrO2For active component, wherein the content of zirconium accounts for the 0.3%-0.7% of vehicle weight, uses it for etherification reaction and can be shown that good activity.
Solid-carrying heteropolyacid is the catalyst that a class is relatively new, loaded by heteropoly acid to suitable porous material will be prepared, considerably increase specific surface area and catalysis activity, but under water environment, still suffer from the problem run off in acid site, and complicated process of preparation, high expensive, currently mainly also rests on lab scale and pilot scale research stage, and commercial Application is promoted slowly. The method that it is catalyst preparing TAME with 1-methyl-3-1-Butyl-1H-imidazole borofluoride ion liquid that patent CN102408316A discloses, temperature 70 C-100 DEG C, alfin ratio 1.1-1.5, ionic liquid addition 0.2%-0.5%, pressure 0.5MPa-0.8MPa, under the reaction condition of air speed 0.9-1.3ml/ml, iso-amylene conversion per pass is more than 70%, but catalyst preparation process and catalyst life and reproducibility is not investigated. Patent CN103787842A mentions with aluminum-base composite metal-oxide MgO-Al2O3��TiO2-Al2O3And ZrO2-Al2O3Deng in one or more be carrier, with one or more in heteropoly acid phosphotungstic acid, silico-tungstic acid, germanotungstic acid, phosphomolybdic acid, aluminosilicate for active component, its catalyst prepared than compound by different quality is used for synthesizing TAME, this catalyst has length service cycle, good stability, advantage that selectivity is high, but catalyst preparation process is complicated.
Molecular sieve catalyst for etherification activity itself is not as good as resin catalyst, especially during low temperature, activity is poor, but because it has adjustable pore structure and acidity, therefore etherification activity can be improved further by successive modified approach, in addition the distinctive type effect of selecting of molecular sieve pore passage can suppress the generation of side reaction, selectivity is excellent, Heat stability is good, and inactivation is regeneration easily. Patent CN1311182A discloses a kind of Etherification of Light FCC Gasoline catalyst, its composition comprises the fluorine of the beta zeolite of 60%-80%, the inorganic oxide of 10%-30% and 1%-10%, this catalyst can improve octane number and oxygen content, but the stability of catalyst is not done detailed examination. Patent CN101138739A relates to a kind of with molecular sieve for carrier, load 1-5% boron trioxide or SO4 2-/Fe2O3Solid super-strong acid is the catalyst for etherification of active component, and this catalyst reacts the advantages such as active height, selectivity are good, renewable for low carbon olefin hydrocarbon etherification. Patent CN1289751A discloses a kind of method that olefin catalytic becomes ether and alcohol ether, with the composite zeolites as catalysts of acid mesopore and large pore zeolite, makes low-carbon alkene carry out hydration and etherification reaction with water and/alcohol, and product mixes gasoline can improve octane number.
In sum, under improving catalyst activity and selective premise, ensure that it has good stability and recyclability as far as possible, be the Main way of catalyst for etherification developmental research. Molecular sieve catalyst for etherification generally reach optimum activity needed for temperature all higher (about 90 DEG C), etherificate is exothermic reaction, temperature is high unfavorable to positive reaction, also easily increase catalyst deactivation rate, affect catalyst life and stability, therefore, the research improving beta-molecular sieve low temperature etherification activity aspect is necessary.
Summary of the invention
In view of prior art situation and Problems existing, the preparation of catalyst for etherification is conducted in-depth research by the present invention, purpose is in that to prepare high activity catalyst for etherification, and the etherificate Olefin decrease using it for low-carbon alkene raffinate or light FCC gasoline improves in octane number reaction.
The preparation method that the present invention provides a kind of efficient catalyst for etherification, it is characterised in that first prepare substrate catalyst, then adopts the mode of rare earth ion exchanged method and steam treatment method compound to be modified processing to it, finally gives catalyst for etherification.
Substrate catalyst of the present invention is with ��-Al2O3For binding agent, beta-molecular sieve is active component, and sesbania powder is extrusion aid, adds dust technology after three's mix homogeneously, through kneading, extrusion, dries and prepares after roasting. Described ��-Al2O3It is obtained after 300 DEG C of-700 DEG C of temperature-programmed calcinations by commercially available macropore, mesopore or aperture boehmite powder; Beta-molecular sieve can be obtained by commercially available or homemade mode, is Hydrogen or sodium form molecular sieve, and silica alumina ratio is 10-80. Substrate catalyst Middle molecule sieve content accounts for 20wt%-70wt%, ��-Al2O3Content accounts for 30wt%-80wt%, and sesbania powder content accounts for 1.0wt%-10.0wt%, and dust technology concentration is 0.2mol/L-0.8mol/L.
Catalyst for etherification of the present invention is to be prepared by rare earth ion exchanged method and steam treatment method composite modifying method, can be after first substrate catalyst being carried out rare earth ion exchanged, carry out steam treatment again, or carry out rare earth ion exchanged again after first it being carried out steam treatment.
Rare earth ion exchanged method of the present invention is that substrate catalyst is carried out ion exchange by the nitrate solution selecting lanthanide rare metal La, Ce, Pr, Nd or Sm, exchange liquid concentration is 0.1mol/L-1.5mol/L, treatment temperature is 10 DEG C-80 DEG C, and the process time is 2h-8h.
Steam treatment method of the present invention is to adopt the steam of 50%-100%, is 0.1mL/min-1.0mL/min at vapor flow, and steam treatment temperature is 200 DEG C-600 DEG C, and the process time completes when being 1h-6h.
The etherification activity evaluation procedure that the present invention relates to is to carry out in homemade micro fixed-bed reactor, is contacted with above-mentioned catalyst under certain condition with absolute methanol mixture by raw material of etherification oil and reacts. Raw material of etherification oil is to be formed by normal hexane, hexene and iso-amylene 5: 3: 2 configurations in mass ratio. In reaction, methanol is 0.8-1.2 with the mol ratio of active olefin, and reaction temperature is 60 DEG C-120 DEG C, and reaction pressure is 1.0MPa-5.0MPa, and air speed is 0.5h-1-3h-1��
Catalyst for etherification prepared by the present invention cannot be only used for producing high-knock rating gasoline additive, can also be used for light FCC gasoline etherificate Olefin decrease and improve octane number reaction, active height, selectivity are good, the feature of excellent in stability, and can be regenerated by the mode of high-temperature roasting after inactivating, catalyst preparing cost is low, and operation is simple.
Detailed description of the invention
In substrate catalyst of the present invention, active component beta-molecular sieve silica alumina ratio is 10-80, and specific surface area is 300m2/g-600m2/ g; Binding agent ��-Al2O3Can being prepared through 300 DEG C of-700 DEG C of temperature-programmed calcinations by boehmite powder, specific surface area is 100m2/g-400m2/ g, pore volume >=0.3cm3/ g. Support preparation method of the present invention is specific as follows: weigh ��-Al in proportion2O3, beta-molecular sieve and sesbania powder, wherein beta-molecular sieve content is the 20wt%-70wt% of substrate catalyst quality, it is preferred to 20wt%-60wt%, it is most preferred that for 30wt%-60wt%; ��-Al2O3Content is the 30wt%-80wt% of substrate catalyst quality, it is preferred to 40wt%-80wt%, it is most preferred that for 40wt%-70wt%; Sesbania powder content is the 1.0wt%-10.0wt% of substrate catalyst quality, it is preferred to 2wt%-8wt%, it is most preferred that for 2wt%-6wt%. Then configuring dilute nitric acid solution, concentration is 0.2mol/L-0.8mol/L, it is preferred to 0.2mol/L-0.7mol/L, it is most preferred that for 0.3mol/L-0.6mol/L. In above-mentioned mixed-powder, add dilute nitric acid solution, after being sufficiently stirred for, be extruded into bar shaped, dry 8h-12h at 60 DEG C-110 DEG C in baking oven, then through in Muffle furnace 300 DEG C of-600 DEG C of roasting 3h-8h, broken and to be sieved into 20-40 order standby after cooling.
Rare earth ion exchanged method concrete operations of the present invention are as follows: first configure the nitrate solution 200ml of lanthanide rare metal La, Ce, Pr, Nd or Sm, concentration is 0.1mol/L-1.5mol/L, it is preferably 0.1mol/L-1.2mol/L, it is most preferred that for 0.1mol/L-1.0mol/L. It is subsequently adding 10g substrate catalyst, heated and stirred 2h-8h in the water bath with thermostatic control of temperature 10 DEG C-80 DEG C, sucking filtration, washing in neutrality, dry 8h-12h to filtrate in the baking oven of 60 DEG C-120 DEG C, then roasting 3h-8h under 300 DEG C of-600 DEG C of Muffle furnaces, standby after cooling.
Steam treatment method concrete operations of the present invention are as follows: steam treatment is to carry out in homemade tubular heater. Quartz curette adds 10g substrate catalyst, is placed on the constant temperature zone of tube furnace, first at N2Under condition, by room temperature temperature programming to predetermined temperature, then passing to the steam treatment scheduled time of the 50%-100% of certain flow, after being disposed, reconvert is to N2It is standby that environment drops to room temperature. Described hydrothermal treatment consists temperature is 200 DEG C-600 DEG C, it is preferred to 200 DEG C-500 DEG C, it is most preferred that be 300 DEG C-500 DEG C; Hydrothermal conditions is 1h-6h, it is preferred to 1h-5h, it is most preferred that for 1h-4h; Vapor flow is 0.1mL/min-1.0mL/min, it is preferred to 0.2mL/min-1.0mL/min, it is most preferred that for 0.2mL/min-0.8mL/min.
Etherificate evaluation procedure of the present invention is to complete in homemade micro fixed-bed reactor, and reaction tube is of a size of 10mm �� 600mm, loads 5mL catalyst at reaction tube constant temperature zone, and remainder fills the little porcelain ball of inertia. Being contacted with catalyst under certain condition with absolute methanol mixture by raw material of etherification oil and react, raw material of etherification oil is to be formed by normal hexane, hexene and iso-amylene 5: 3: 2 configurations in mass ratio.
Etherificate appreciation condition of the present invention is as follows: methanol and iso-amylene mol ratio are 0.8-1.2, it is preferred to 0.9-1.2, it is most preferred that for 0.9-1.1; Reaction temperature is 60 DEG C-120 DEG C, it is preferred to 60 DEG C-110 DEG C, it is most preferred that be 70 DEG C-100 DEG C; Reaction pressure is 1.0MPa-5.0MPa, it is preferred to 1.0MPa-4.0MPa, it is most preferred that for 1.0MPa-3.0MPa; Volume space velocity is 0.5h-1-3.0h-1, it is preferred to 0.5h-1-2.0h-1, it is most preferred that for 0.6h-1-1.5h-1��
Further illustrate below by specific embodiment:
Embodiment 1
Beta-molecular sieve content is the 55% of substrate catalyst quality, ��-Al2O3Content is the 40% of substrate catalyst quality, sesbania powder content is the 5% of substrate catalyst quality, above-mentioned powder adds the dilute nitric acid solution that concentration is 0.6mol/L after sufficiently mixing, bar shaped it is extruded into after kneading, dry 10h in 120 DEG C of baking ovens, roasting 4h in 600 DEG C of Muffle furnaces again, cooling, broken after sieve into the granule of 20-40 order, be substrate catalyst.
With the lanthanum nitrate hexahydrate 200ml of 0.4mol/L, carrier carrying out at 90 DEG C ion exchange, the process time is 6h, and this step need to come again, then after sucking filtration, washing in 120 DEG C of baking ovens dry 12h, then at 500 DEG C roasting 6h, standby after cooling.
Etherificate evaluation response condition: methanol/iso-amylene mol ratio is 1.0, reaction temperature is 80 DEG C, and reaction pressure is 1MPa, and volume space velocity is 1h-1��
Embodiment 2
Substrate catalyst preparation method is identical with embodiment 1, and the difference is that it is carried out ion exchange by the cerous nitrate solution using 0.4mol/L instead, exchange step as described in Example 1, finally carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 3
Substrate catalyst preparation method is identical with embodiment 1, and the difference is that it is carried out ion exchange by the praseodymium nitrate solution using 0.4mol/L instead, exchange step as described in Example 1, finally carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 4
Substrate catalyst preparation method is identical with embodiment 1, and the difference is that it is carried out ion exchange by the neodymium nitrate solution using 0.4mol/L instead, exchange step as described in Example 1, finally carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 5
Substrate catalyst preparation method is identical with embodiment 1, and the difference is that it is carried out ion exchange by the samarium nitrate solution using 0.4mol/L instead, exchange step as described in Example 1, finally carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 6
Substrate catalyst preparation method is identical with embodiment 1, is 0.05mol/L the difference is that Lanthanum (III) nitrate processes the concentration of solution, and the step of ion exchange as described in Example 1, finally carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 7
Substrate catalyst preparation method is identical with embodiment 1, is 0.1mol/L the difference is that Lanthanum (III) nitrate processes the concentration of solution, and the step of ion exchange as described in Example 1, finally carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 8
Substrate catalyst preparation method is identical with embodiment 1, is 0.15mol/L the difference is that Lanthanum (III) nitrate processes the concentration of solution, and the step of ion exchange as described in Example 1, finally carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 9
Substrate catalyst preparation method is identical with embodiment 1, the difference is that using the cerous nitrate solution that concentration is 0.8mol/L instead, it is carried out ion exchange, and exchange step as described in Example 1, finally carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 10
Substrate catalyst preparation method is identical with embodiment 1, the difference is that using the cerous nitrate solution that concentration is 1.0mol/L instead, it is carried out ion exchange, and exchange step as described in Example 1, finally carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 11
Substrate catalyst preparation method is identical with embodiment 1, the difference is that using the cerous nitrate solution that concentration is 1.2mol/L instead, it is carried out ion exchange, and exchange step as described in Example 1, finally carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 12
Substrate catalyst preparation method is identical with embodiment 1, the difference is that it is modified by the mode adopting steam treatment, with the 100% steam treatment substrate catalyst 1h that flow is 0.4mL/min at 300 DEG C, standby after cooling. Finally under above-mentioned same reaction conditions, carry out etherification activity evaluation.
Embodiment 13
Having same steps with embodiment 12, substrate catalyst preparation method as described in Example 1, the difference is that steam treatment temperature changes 400 DEG C into, finally carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 14
Having identical step with embodiment 12, substrate catalyst preparation method is identical with embodiment 1, the difference is that steam treatment temperature changes 500 DEG C into, then carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 15
Having identical step with embodiment 12, substrate catalyst preparation method is identical with embodiment 1, the difference is that the steam treatment time changes 2h into, then carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 16
Having identical step with embodiment 12, substrate catalyst preparation method is identical with embodiment 1, the difference is that the steam treatment time changes 3h into, then carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 17
Having identical step with embodiment 12, support preparation method is identical with embodiment 1, the difference is that the steam treatment time changes 4h into, then carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 18
Having identical step with embodiment 12, substrate catalyst preparation method is identical with embodiment 1, the difference is that the flow of steam is 0.6mL/min, then carries out etherification activity evaluation under above-mentioned same reaction conditions.
Embodiment 19
Substrate catalyst preparation method is identical with embodiment 1, then the step that embodiment 7 is similar is adopted, first with the lanthanum nitrate hexahydrate of 0.1mol/L, substrate catalyst is carried out ion exchange, until sucking filtration, washing, dry and after roasting, again with 100% steam that flow is 0.4mL/min, to its steam treatment 3h at temperature 400 DEG C, obtain simultaneously through the catalyst for etherification of rare earth exchanged and steam treatment.
Embodiment 20
There is with embodiment 19 similar step, but have adjusted the sequencing of two kinds of method of modifying. The substrate catalyst prepared first is processed 3h with 100% steam that flow is 0.4mL/min at temperature 400 DEG C, take out after being cooled to room temperature, with the lanthanum nitrate hexahydrate of 0.1mol/L, it is carried out ion exchange again, until sucking filtration, washing, dry and after roasting, obtain simultaneously through the catalyst for etherification of steam and rare earth exchanged coprocessing.
In embodiment, each catalyst preparation conditions and etherification activity evaluation result are as shown in table 1 below.
Catalyst preparation conditions and etherification activity evaluation result in table 1 embodiment

Claims (10)

1. a preparation method for efficient catalyst for etherification, its feature includes herein below: first with beta-molecular sieve for active component, ��-Al2O3For binding agent, sesbania powder is extrusion aid, and dust technology is peptizer, is adequately mixed, extrusion, prepares substrate catalyst after dry and roasting; Then select rare earth ion exchanged method and steam treatment method complex method that substrate catalyst is modified, final prepared high activity catalyst for etherification.
2. in accordance with the method for claim 1, it is characterised in that described beta-molecular sieve is commercially available or homemade Hydrogen or sodium form molecular sieve, and silica alumina ratio is 10-80.
3. in accordance with the method for claim 1, it is characterised in that described ��-Al2O3It is prepared by commercially available macropore, mesopore or aperture boehmite temperature-programmed calcination under 300 DEG C of-700 DEG C of conditions.
4. in accordance with the method for claim 1, it is characterised in that described 20wt%-70wt%, the ��-Al that beta-molecular sieve content is substrate catalyst quality2O3Content is the 30wt%-80wt% of substrate catalyst quality, and sesbania powder content is the 1.0wt%-10.0wt% of substrate catalyst quality.
5. in accordance with the method for claim 1, it is characterized in that described rare earth ion exchange process is that substrate catalyst is carried out ion exchange by the nitrate solution selecting lanthanide rare metal La, Ce, Pr, Nd or Sm, rare earth nitrate solution concentration is 0.1mol/L-1.5mol/L, treatment temperature is 10 DEG C-80 DEG C, and the process time is 2h-8h.
6. in accordance with the method for claim 1, it is characterised in that in described method for steam treatment, vapor flow is 0.1mL/min-1.0mL/min, steam treatment temperature is 200 DEG C-600 DEG C, and the process time is 1h-6h.
7. in accordance with the method for claim 1, it is characterized in that described rare earth ion exchanged method and the composite modified approach of steam treatment method, can be substrate catalyst first carries out rare earth ion exchanged carry out steam treatment again, or carry out rare earth ion exchanged again after first it being carried out steam treatment.
8. etherification activity evaluation procedure mainly carries out in the micro fixed-bed reactor of self assembly, is contacted with above-mentioned catalyst under certain condition with absolute methanol by raw material of etherification oil and reacts.
9. in accordance with the method for claim 8, it is characterised in that described raw material of etherification oil is to be formed by normal hexane, hexene and iso-amylene 5: 3: 2 configurations in mass ratio.
10. in accordance with the method for claim 8, it is characterised in that etherification activity appreciation condition is: methanol and active olefin mol ratio are 0.8-1.2, and reaction temperature is 60 DEG C-120 DEG C, and reaction pressure is 1MPa-5MPa, and air speed is 0.5h-1-3h-1��
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113617385A (en) * 2021-08-18 2021-11-09 天津长芦海晶集团有限公司 Preparation method of catalyst for olefin hydration reaction

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113617385A (en) * 2021-08-18 2021-11-09 天津长芦海晶集团有限公司 Preparation method of catalyst for olefin hydration reaction

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