CN103787842B - A kind of preparation method of tert amyl methyl ether(TAME) - Google Patents

A kind of preparation method of tert amyl methyl ether(TAME) Download PDF

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CN103787842B
CN103787842B CN201210427725.XA CN201210427725A CN103787842B CN 103787842 B CN103787842 B CN 103787842B CN 201210427725 A CN201210427725 A CN 201210427725A CN 103787842 B CN103787842 B CN 103787842B
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methyl
reaction
acid
butene
aluminum
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CN103787842A (en
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霍稳周
魏晓霞
刘野
李花伊
田丹
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment

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Abstract

The present invention discloses a kind of preparation method of tert amyl methyl ether(TAME), comprises following content: with 2-methyl butene and methyl alcohol for raw material, and adopt heteropolyacid/aluminum-base composite metal oxide to be catalyzer, the volume space velocity of 2-methyl butene is 1.0h -1~ 5.0h -1, the mol ratio of methyl alcohol and 2-methyl butene is 1.0:1.0 ~ 3.0:1.0, and temperature of reaction is 60 DEG C ~ 120 DEG C, and reaction pressure is 0.05MPa ~ 3.0MPa.The method compared with prior art has the selectivity advantages of higher of length running period, good stability, tert amyl methyl ether(TAME).

Description

A kind of preparation method of tert amyl methyl ether(TAME)
Technical field
The present invention relates to the preparation method of a kind of tert amyl methyl ether(TAME) (TAME).
Background technology
Along with the development of human society; countries in the world are to environment protection pay attention to day by day; in order to reduce the pollution of vehicle exhaust; to unleaded, surge containing the demand of oxygen, stop bracket gasoline; particularly nineteen ninety; since the U.S. promulgates Clean Air Act Amendment (CAA), various countries' refinery, in order to adapt to the requirement of environmental protection, greatly develops reformulated gasoline.
(oxidation style octane value RON is 105 to tert amyl methyl ether(TAME) (TAME), engine octane number MON is 100) be continue another production after methyl tertiary butyl ether (MTBE) (RON is 117, MON is 102) unleaded, containing the desirable oxygenatedchemicals of oxygen and high-octane rating reformulated gasoline.Though the octane value of TAME is a little less than MTBE, in vapour pressure, water, the index such as solubleness is better than MTBE, and produces TAME and also can to reduce in gasoline the active high C_5 olefins with eatmospheric photochemistry.Therefore, along with market is to the continuous increase of ethers oxygenated compounds demand, the research and development of TAME production technology are at home and abroad more and more subject to people's attention.
TAME, by 2-methyl butene and methanol production, has all advantages of MTBE, is even more similar to gasoline.In all ether, TAME effect in environmental protection is maximum, and it can reduce pollution emission, and by the ether of the low-down burning cleaning of C5 conversion of olefines Cheng Leiman vapour pressure (RVP) high for some the most volatile reactive behavior in gasoline.Can reduce the RVP of gasoline owing to adding TAME, this just makes refinery have greater flexibility meeting from now in the control regulation of RVP, and the amount in gasoline of calling in can be more more and do not affect specification gasoline.
Main containing monoolefine and diene hydrocarbons in C5, by tripping device, separable go out the high C5 diolefin of added value, take out remaining after C5 contain the raw material that 2-methyl-1-butene alkene in monoolefine and 2-methyl-2-butene can be used as TAME.So both can solve a large amount of components needed for gasoline blending, also can improve utilization ratio and the value added of C5 comprehensively.
TAME production process and technique and MTBE basic simlarity, usually with 2-methyl butene and methyl alcohol for raw material, liquid phase synthesis under strong acidic ion resin exists, General reactions temperature 60 C ~ 70 DEG C, pressure 0.2 MPa, air speed 1.0h -1~ 2.0h -1, alcohol/alkene mol ratio 1.0 ~ 1.5.
Zeo-karb is the catalyst for etherification industrially extensively adopted at present, and principal item is macropore sulfonic acid ion exchange resin.Mostly adopt Amberlyst-15 (A-15), Amberlyst-35 (A-35), Lewatit K2631, Bayer K2631 type etc. abroad.Domestic, mainly adopt D-72, S-54, D005, QRE type resin catalyst etc. that China researches and develops voluntarily, these resins are all the poly styrene polymers of divinylbenzene crosslink.
US Patent No. 4808270A discloses a kind of preparation method of tert amyl methyl ether(TAME), with methyl alcohol, C5 alkene is raw material, polystyrene resin, sulfonated phenol formaldehyde resin etc. is adopted to be catalyzer, temperature of reaction 40 DEG C ~ 120 DEG C, reaction pressure 0.12 ~ 2.0 MPa, the transformation efficiency of 2-methyl butene is 65%, the selectivity 93.6% of tert amyl methyl ether(TAME).
US Patent No. 5453550A discloses a kind of preparation method of tert amyl methyl ether(TAME), and with methyl alcohol and iso-butylene and 2-methyl butene hydrocarbon mixture for raw material, ion exchange resin is catalyzer, at alkene air speed 0.6h -1, temperature of reaction 62 DEG C, reaction pressure 2.2 MPa, under the condition of methyl alcohol/2-methyl butene mol ratio 1.0 ~ 2.0, the yield 54% ~ 60% of tert amyl methyl ether(TAME).
US Patent No. 4988366A discloses a kind of preparation method of tert amyl methyl ether(TAME), with methyl alcohol, iso-butylene, 2-methyl butene are raw material, acid zeolite, acidic resins (as Amberlyst 15), ZSM-5, β zeolite etc. are catalyzer, under the condition of temperature of reaction 50 DEG C ~ 70 DEG C, synthesized tert amyl methyl ether(TAME).
European patent EP 0026041A1 discloses a kind of preparation method of tert amyl methyl ether(TAME), with methyl alcohol 2-methyl butene for raw material, and zeolite catalyst.Temperature 232 DEG C ~ 288 DEG C, reaction pressure 0.1 MPa, olefin partial pressures <0.05 MPa, alkene air speed 0.2 h -1~ 5 h -1synthesize tert amyl methyl ether(TAME).
" petrochemical complex " the 32nd volume first phase in 2003, the mixing carbon Wuyuan material adopted is cut by FCC gasoline and DCC gasoline and is obtained, and removing the carbon after diolefine five and methyl alcohol is raw material through selec-tive hydrogenation, the QRE type macropore sulfonic acid ion exchange resin catalyzer developed voluntarily with Qilu Petroleum Chemistry Co. Inst. is catalyzer.Adopt the combination etherification technology of pre-reactor and catalytic distillation tower, carried out synthesis TAME process condition experiment, achieve suitable etherification technology parameter, tertiary amylene transformation efficiency can reach 95 more than %, and TAME purity is not less than 97 %.
" fine-chemical intermediate " the 34th volume the 4th phase in 2004, to take out remaining carbon 5 (2-methyl butene content is greater than 20%) and methyl alcohol for raw material, Phenylsulfonic acid type resin is catalyzer, temperature of reaction be 62 DEG C ~ 67 DEG C, the molar ratio of methyl alcohol and 2-methyl butene is 1.4 ~ 1.6, liquid hourly space velocity is 1.3h -1~ 1.5h -1reaction conditions under, the transformation efficiency of 2-methyl butene is greater than 70%.
Volume the 24th phase " Jilin Institute of Chemical Technology journal " calendar year 2001 the 18th, boiling range≤60 DEG C cut is cut containing the 2-methyl butene of 2-methyl butene more than 20% and methyl alcohol for raw material through distillation with light FCC gasoline, wide aperture storng-acid cation exchange resin is produced for catalyzer with Nankai university student, adopt catalytic reaction distillation technology temperature of reaction 70 DEG C ~ 76 DEG C, pressure 0.08 MPa ~ 1.0MPa, air speed is 2h -1condition under, the transformation efficiency of 2-methyl butene reaches as high as 39.15%, TAME purity and can reach 83.44%, then rectifying purity can bring up to more than 95%.
" Journal of Liaoning Institute of Technology " the 20th volume the 6th phase in 2000, with refinery gas's fractionation plant isolated C 5 fraction from liquefied petroleum gas (LPG), wherein containing 2-methyl-1-butene alkene (1.5%, mole fraction, lower same) and 2-methyl-2-butene (23%), the two is collectively referred to as 2-methyl butene, with industrial methanol etherificate under the catalysis of D005 type acidic cation-exchange resin, be prepared into tert amyl methyl ether(TAME), be 0. 6 ~ 0. 7 at methyl alcohol and 2-methyl butene mol ratio, temperature of reaction is 70 DEG C ~ 80 DEG C, and Feed space velocities is 3.0 h -1~ 4.0 h -1, working pressure is under 0.8M Pa condition, and the total conversion rate of 2-methyl butene is 50% ~ 60%.
" Liaoning chemical industry " the 26th volume the 5th phase in 1997, C5 raw material is catalytic cracking stable gasoline < 50 DEG C of cuts, and wherein 2-methyl butene-1 and 2-methyl butene-2 content are respectively 8.7 % and 14.0 %.Methyl alcohol is industrial methanol, content >=99 %, moisture ≯ 0. 7 %, and catalyzer is acidic cation-exchange resin, employing be cartridge type expanded bed reactor.This reactor adopts the mode of circulation heat-obtaining, extracts out by reactor head material, after exterior cooling again bottom Returning reactor, reaches the object taking heat away.The operation of logistics upflowing can prevent granules of catalyst from lump, simultaneously can reduce bed resistance, easy to operate and flexible, can reach higher transformation efficiency.
" refining of petroleum and chemical industry " the 28th volume the 10th phase in 1997, to take out remaining C5 for raw material is through the process with methanol etherification TAME, under adopting domestic catalyst D54 type large hole cation exchanger resin to exist, at temperature of reaction 60 DEG C, LHSV 2.4h -1, methyl alcohol/2-methyl butene amount of substance than 1.00, under the condition of reaction pressure 0.2MPa, the 2-methyl butene taken out in remaining C5 can react with methyl alcohol and generate ether, and the selectivity that the transformation efficiency of 2-methyl butene reaches 63.26%, TAME can reach 99.61%.
" chemical research and application " the 11st volume the 1st phase in 1999, with 2-methyl butene and methyl alcohol for raw material in reactive distillation column with Phenylsulfonic acid Zeo-karb for catalyzer, investigated transformation efficiency 40 DEG C ~ 80 DEG C of etherificates with the change of reaction conditions.69 DEG C, n (2-methyl butene)/n (methyl alcohol)=1/1.2 time, the transformation efficiency of 2-methyl butene etherification reaction reaches as high as 80%, and reaction pressure is little on the impact of the transformation efficiency of 2-methyl butene etherification reaction.
In sum, the advantage of strong acid cation exchange resin catalyst is active high, and easy and product separation, less to equipment corrosion, selectivity is more high.Weak point is then mainly reflected in: 1. resin catalyst less stable, and during raised temperature (being greater than 373.15K), sulfonic acid group easily comes off, and causes catalyst deactivation, etching apparatus polluted product; 2. along with the rising of temperature, resin catalyst selectivity is deteriorated, and oligomerisation side reaction increases, and by product increases; 3. industrial in order to improve olefin conversion, suppress side reaction, often adopt higher alfin ratio, thus cause needing higher energy consumption to realize recycling of alcohol.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of the etherificate synthesizing methyl tert-amyl ether (TAME) under the catalyzer of the metal oxide supported heteropolyacid of aluminum-base composite exists by 2-methyl butene and methyl alcohol, the inventive method has good reactivity worth, has satisfactory stability simultaneously.
A kind of preparation method of tert amyl methyl ether(TAME), comprise following content: with 2-methyl butene (2-methyl-1-butene alkene and/or 2-methyl-2-butene) and methyl alcohol for raw material, adopt heteropolyacid/aluminum-base composite metal oxide to be catalyzer, the volume space velocity of 2-methyl butene is 1.0h -1~ 5.0h -1, the mol ratio of methyl alcohol and 2-methyl butene is 1.0:1.0 ~ 3.0:1.0, and temperature of reaction is 60 DEG C ~ 120 DEG C, and reaction pressure is 0.05 MPa ~ 3.0MPa.
In the inventive method, described heteropolyacid/aluminum-base composite metal oxide catalyst, with aluminum-base composite metal oxide for carrier, take heteropolyacid as active ingredient.Described aluminum-base composite metal oxide is MgO-Al 2o 3, TiO 2-Al 2o 3and ZrO 2-Al 2o 3deng in one or more, described heteropolyacid is one or more in phospho-wolframic acid, silicotungstic acid, arsenowolframic acid, germanotungstic acid, phospho-molybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid etc.
In the inventive method, Al in aluminum-base composite metal oxide 2o 3weight content be 20% ~ 95%, be preferably 30% ~ 90%, most preferably be 40% ~ 70%; The weight ratio of heteropolyacid and aluminium base composite oxides is 0.01:1 ~ 1:1, is preferably 0.2:1 ~ 0.8:1, most preferably is 0.3:1 ~ 0.5:1.
In the inventive method, described 2-methyl butene can use the mixing monoolefine raw material containing 2-methyl butene, also can use pure 2-methyl butene.When using mixing monoolefine raw material, in mixing monoolefine raw material, 2-methyl butene weight content is greater than 15%, is preferably at least 20%, is most preferably at least 25%.
In the inventive method, the volume space velocity of described 2-methyl butene is preferably 1.0h -1~ 3.0h -1, the mol ratio of methyl alcohol and 2-methyl butene is preferably 1.0:1.0 ~ 2.0:1.0, and temperature of reaction is preferably 60 DEG C ~ 100 DEG C, and reaction pressure is preferably 1.0 MPa ~ 2.5MPa.
In the inventive method, the volume space velocity of described 2-methyl butene most preferably is 1.0h -1~ 2.0h -1, the mol ratio of methyl alcohol and 2-methyl butene most preferably is 1.0:1.0 ~ 1.5:1.0, and temperature of reaction most preferably is 70 DEG C ~ 90 DEG C, and reaction pressure most preferably is 1.0 MPa ~ 2.0MPa.
The inventive method adopts a kind of catalyzer of aluminum-base composite metal oxide carrier carried heteropoly acid, this catalyzer has suitable specific surface area, aperture structure and acidity distribution, effectively can regulate acidity and the activity of catalyzer, overcome resin catalyst less stable, sulfonic acid group easily comes off, cause catalyst deactivation, etching apparatus polluted product and the rising along with temperature, resin catalyst selectivity is deteriorated, oligomerisation side reaction increases, by product increases and in order to improve olefin conversion, suppress side reaction, need to adopt shortcoming and the deficiencies such as higher alfin ratio.The inventive method regulates and controls for catalyzer the continuous prodution that processing condition that catalyzer therewith coordinates mutually can realize tert amyl methyl ether(TAME) with aluminum-base composite metal oxide carrier carried heteropoly acid, this reaction process is easy and simple to handle, having the advantages such as transformation efficiency is high, good stability for 2-methyl butene and methanol-fueled CLC tert amyl methyl ether(TAME), is an environmental protection novel process.
Embodiment
The present invention generates reaction mechanism and the reaction characteristics of tert amyl methyl ether(TAME) (TAME) according to 2-methyl butene and methanol etherification, adopt the metal oxide supported heteropolyacid of a kind of aluminum-base composite as catalyzer, react under suitable reaction conditions, overcome resin catalyst less stable, sulfonic acid group easily comes off, cause catalyst deactivation, selectivity is deteriorated, and needs higher energy consumption to realize the shortcoming recycled of alcohol.
Catalyzer of the present invention can be prepared by following method: the aqueous solution a of the preparation corresponding salt of aluminium base composite oxides and aluminum nitrate, preparation basic solution b(potassium hydroxide aqueous solution or ammoniacal liquor), under the state of normal mild stirring, solution b is added drop-wise in a, be obtained by reacting precipitation, through washing, filter, dry, then after method extruded moulding routinely, roasting obtains aluminium base composite oxides carrier.
In the preparation process of above-mentioned aluminium base composite oxides, the described reaction times is 2h ~ 20h, is preferably 4h ~ 16h, most preferably is 6h ~ 12h.Described drying temperature is 90 DEG C ~ 150 DEG C, is preferably 100 DEG C ~ 140 DEG C, most preferably is 110 DEG C ~ 130 DEG C.Described time of drying is 4h ~ 24h, is preferably 6h ~ 16h, most preferably is 10h ~ 12h.Described maturing temperature is 400 DEG C ~ 800 DEG C, is preferably 450 DEG C ~ 700 DEG C, most preferably is 500 DEG C ~ 600 DEG C.Described roasting time is 8h ~ 24h, is preferably 8h ~ 14h, most preferably is 8h ~ 12h.
By shaping rear aluminium base composite oxides carrier, the method for conveniently flooding, floods in heteropolyacid solution.Dipping time is 4h ~ 24h, is preferably 4h ~ 12h, most preferably is 6h ~ 12h.Macerate is dry 4h ~ 12h at 100 DEG C ~ 180 DEG C, is preferably dry 6h ~ 12h at 100 DEG C ~ 160 DEG C, most preferably is dry 6 h ~ 8h at 100 DEG C ~ 120 DEG C.Macerate is roasting 6h ~ 24h at 250 DEG C ~ 550 DEG C, is preferably roasting 6h ~ 12h at 300 DEG C ~ 500 DEG C, most preferably is roasting 8h ~ 12h at 350 DEG C ~ 450 DEG C and obtains heteropolyacid/aluminium base composite oxides catalyzer.
Method of the present invention and effect is further illustrated below by specific embodiment.
Embodiment 1
A certain amount of aluminum nitrate and a certain amount of magnesium nitrate are mixed with aqueous solution a, aqueous solution b is configured to deionized water and a certain amount of potassium hydroxide, under the state of normal mild stirring, solution b is added drop-wise in a, reaction 6h obtains white paste precipitation, through washing, filter, at 120 DEG C of dry 10h, method extruded moulding routinely again, then at 500 DEG C, roasting 8h obtains magnesium-aluminum complex oxide carrier.
Be dissolved in by phospho-molybdic acid in deionized water, the support of the catalyst after above-mentioned shaping and roasting is dipped in assorted many solution, and dipping time is 12h, and macerate is dry 12h at 110 DEG C, roasting 8h at 350 DEG C, obtained catalyzer, and catalyzer composition is in table 1.
2-methyl butene and methanol etherification carry out in the stainless steel fixed-bed reactor of Φ 18mm × 1200mm, above-mentioned catalyzer 30ml is loaded in reactor, reactor head and bottom, be respectively charged into the quartz sand that diameter is Φ 0.5mm ~ 1.2mm, after reactor installs, with nitrogen replacement three times, and tightness test is qualified, 2-methyl butene, methyl alcohol metering are pumped into preheater, and reaction conditions and reaction result are in table 2.
Embodiment 2
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phospho-molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 3
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phospho-molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 4
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phospho-molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 5
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phospho-molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 6
Other condition is with embodiment 1, and just change magnesium nitrate into titanium tetrachloride, phospho-molybdic acid changes silicomolybdic acid into, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 7
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 8
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 9
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 10
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 11
Other condition is with embodiment 1, and just magnesium nitrate changes zirconium tetrachloride into, and phospho-molybdic acid changes silicomolybdic acid into, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 12
Other condition, with embodiment 1, just changes zirconium tetrachloride and silicomolybdic acid consumption, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 13
Other condition, with embodiment 1, just changes zirconium tetrachloride silicomolybdic acid consumption, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 14
Other condition, with embodiment 1, just changes zirconium tetrachloride silicomolybdic acid consumption, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 15
Other condition, with embodiment 1, just changes zirconium tetrachloride silicomolybdic acid consumption, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 16
Other condition, with embodiment 1, just changes phospho-molybdic acid into phospho-wolframic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 17
Other condition, with embodiment 1, just changes phospho-molybdic acid into silicotungstic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 18
Other condition, with embodiment 1, just changes phospho-molybdic acid into arsenowolframic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 19
Other condition, with embodiment 1, just changes phospho-molybdic acid into germanotungstic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 20
Other condition, with embodiment 1, just changes phospho-molybdic acid into arsenic molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 21
Other condition, with embodiment 1, just changes phospho-molybdic acid into germanium molybdic acid, and catalyzer composition is in table 1, and reaction result is in table 2.
Embodiment 22
By the catalyzer of embodiment 12, according to the evaluation method of embodiment 1, be 1.0h at the volume space velocity of 2-methyl butene charging -1, the mol ratio of methyl alcohol and 2-methyl butene is 1.5:1, and temperature of reaction is 70 DEG C, and reaction pressure is under the condition of 1.0MPa, has carried out stability test, test-results table 3.
Comparative example 1
Take aluminum oxide as carrier, according to the dipping method of embodiment 1, by phospho-molybdic acid dipping on alumina, obtained catalyzer, evaluation method is with embodiment 1, and reaction result is in table 2.
Comparative example 2
Using D72 type acidic cation-exchange resin as catalyzer, evaluation method is with embodiment 1, and reaction result is in table 2.
Comparative example 3
Take ZSM-5 as catalyzer, evaluation method is with embodiment 1, and reaction result is in table 2.
Comparative example 4
Comparative example 2 catalyzer, carries out estimation of stability by the evaluation method of embodiment 22, the results are shown in Table 3.
Table 1 embodiment catalyzer forms
Sequence number Aluminum oxide in composite oxides, quality % The mass ratio of heteropolyacid and composite oxides
Embodiment 1 90 0.01:1.0
Embodiment 2 80 0.20:1.0
Embodiment 3 60 0.50:1.0
Embodiment 4 40 0.50:1.0
Embodiment 5 20 0.80:1.0
Embodiment 6 65 0.01:1.0
Embodiment 7 55 0.20:1.0
Embodiment 8 45 0.40:1.0
Embodiment 9 65 0.45:1.0
Embodiment 10 50 0.50:1.0
Embodiment 11 30 0.55:1.0
Embodiment 12 40 0.45:1.0
Embodiment 13 50 0.50:1.0
Embodiment 14 60 0.45:1.0
Embodiment 15 70 0.80:1.0
Embodiment 16 50 0.40:1.0
Embodiment 17 70 0.40:1.0
Embodiment 18 65 0.40:1.0
Embodiment 19 55 0.40:1.0
Embodiment 20 45 0.40:1.0
Embodiment 21 40 0.40:1.0
The reaction conditions of table 2 embodiment and comparative example and reaction result
Sequence number Reaction pressure/MPa Temperature of reaction/DEG C 2-methyl butene volume space velocity/h -1 Methyl alcohol/2-methyl butene (mol ratio) 2-methyl butene per pass conversion/% by mole
Embodiment 1 0.1 65 1.0 1.0 94.6
Embodiment 2 0.5 75 2.0 2.0 95.7
Embodiment 3 1.0 85 3.0 3.0 97.9
Embodiment 4 1.5 95 4.0 1.5 98.1
Embodiment 5 2.0 105 5.0 2.5 94.5
Embodiment 6 2.5 115 1.5 3.0 93.1
Embodiment 7 3.0 60 2.5 1.0 95.7
Embodiment 8 3.0 70 3.5 2.0 97.8
Embodiment 9 2.5 80 1.0 3.0 98.4
Embodiment 10 2.0 90 1.5 1.5 97.9
Embodiment 11 1.5 100 2.0 2.5 98.3
Embodiment 12 1.0 110 2.5 3.0 98.8
Embodiment 13 0.5 120 3.0 1.0 98.2
Embodiment 14 0.05 65 3.5 2.0 98.0
Embodiment 15 3.0 75 4.0 3.0 95.6
Embodiment 16 2.5 85 4.5 1.5 97.8
Embodiment 17 2.0 95 1.0 2.0 98.3
Embodiment 18 1.5 105 1.5 1.1 98.1
Embodiment 19 1.0 115 2.0 1.2 97.7
Embodiment 20 0.5 75 2.5 1.3 98.8
Embodiment 21 0.05 80 3.0 2.0 97.9
Comparative example 1 1.5 65 1.0 1.5 75.6
Comparative example 2 1.5 70 1.5 1.5 85.3
Comparative example 3 1.5 65 2.0 2.0 85.5
Table 3 stability test result
Sequence number Working time/h Embodiment 22 2-methyl butene per pass conversion/% by mole Comparative example 4 2-methyl butene per pass conversion/% by mole
1 50 98.6 86.8
2 100 97.7 86.6
3 150 97.9 85.9
4 200 97.7 85.4
5 250 97.5 85.1
6 300 98.1 85.3
7 350 97.7 84.9
8 400 97.8 84.8
9 450 98.4 84.9
10 500 98.6 84.6
11 550 98.3 84.3
12 600 97.8 84.2
13 650 98.2 83.9
14 700 98.0 83.5
15 750 97.6 83.4
16 800 97.8 83.0
17 850 98.3 82.5
18 900 98.1 81.9
19 950 98.0 81.5
20 1000 98.1 81.4

Claims (5)

1. a preparation method for tert amyl methyl ether(TAME), comprises following content: with 2-methyl butene and methyl alcohol for raw material, and adopt heteropolyacid/aluminum-base composite metal oxide to be catalyzer, the volume space velocity of 2-methyl butene is 1.0h -1~ 5.0h -1the mol ratio of methyl alcohol and 2-methyl butene is 1.0:1.0 ~ 3.0:1.0, temperature of reaction is 60 DEG C ~ 120 DEG C, reaction pressure is 0.05 MPa ~ 3.0Mpa, described heteropolyacid/aluminum-base composite metal oxide catalyst, with aluminum-base composite metal oxide for carrier, take heteropolyacid as active ingredient, described aluminum-base composite metal oxide is MgO-Al 2o 3, TiO 2-Al 2o 3and ZrO 2-Al 2o 3in one or more, described heteropolyacid is one or more in phospho-wolframic acid, silicotungstic acid, arsenowolframic acid, germanotungstic acid, phospho-molybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid, Al in described aluminum-base composite metal oxide 2o 3weight content be 20% ~ 95%, the weight ratio of described heteropolyacid and aluminum-base composite metal oxide is 0.01:1 ~ 1:1.
2. in accordance with the method for claim 1, it is characterized in that: Al in described aluminum-base composite metal oxide 2o 3weight content be 40% ~ 70%.
3. in accordance with the method for claim 1, it is characterized in that: the weight ratio of described heteropolyacid and aluminum-base composite metal oxide is 0.3:1 ~ 0.5:1.
4. in accordance with the method for claim 1, it is characterized in that: the volume space velocity of described 2-methyl butene is 1.0h -1~ 3.0h -1, the mol ratio of methyl alcohol and 2-methyl butene is 1.0:1.0 ~ 2.0:1.0, and temperature of reaction is 60 DEG C ~ 100 DEG C, and reaction pressure is 1.0 MPa ~ 2.5MPa.
5. in accordance with the method for claim 4, it is characterized in that: the volume space velocity of described 2-methyl butene is 1.0h -1~ 2.0h -1, the mol ratio of methyl alcohol and 2-methyl butene is 1.0:1.0 ~ 1.5:1.0, and temperature of reaction is 70 DEG C ~ 90 DEG C, and reaction pressure is 1.0 MPa ~ 2.0MPa.
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冯世宏.甲基叔戊基醚的制备.《辽宁工学院学报(自然科学版)》.2000,第20卷(第6期),第60-62页. *
叔戊烯与甲醇在Cs2.5H0.5PW12040/ SiO2催化剂上的醚化;魏民等;《化学与粘合》;20041231;第343页-第345页 *

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