CN103787843A - Method for preparing tert-amyl methyl ether - Google Patents
Method for preparing tert-amyl methyl ether Download PDFInfo
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- CN103787843A CN103787843A CN201210427854.9A CN201210427854A CN103787843A CN 103787843 A CN103787843 A CN 103787843A CN 201210427854 A CN201210427854 A CN 201210427854A CN 103787843 A CN103787843 A CN 103787843A
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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
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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
- 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
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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
- 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
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Abstract
The invention discloses a method for preparing tert-amyl methyl ether. The method is as follows: raw materials of 2-methylbutene and methanol, a catalyst of a heteropolyacid / titanium based composite oxide as, volume space velocity of 2-methylbutene of 0.5-5.0 / h, molar ratio of methanol and 2-methylbutene of 1.0:1.0-5.0:1.0, reaction temperature of 80-200 DEG C, and reaction pressure of 0.5-5.0 MPa. Compared with the prior art, the method has the advantages of long running period, good stability and high selectivity of tert-amyl methyl ether.
Description
Technical field
The invention discloses one and prepare the method for tert amyl methyl ether(TAME) (TAME).
Technical background
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; demand unleaded, that contain oxygen, stop bracket gasoline is surged; 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, is greatly developed reformulated gasoline.
(oxidation style octane value RON is 105 to tert amyl methyl ether(TAME) (TAME), engine octane number MON is 100) be the desirable oxygenatedchemicals that methyl tertiary butyl ether (MTBE) (RON is that 117, MON is 102) another production is afterwards unleaded, contain oxygen and high-octane rating reformulated gasoline that continues.Though the octane value of TAME is a little less than MTBE, in vapour pressure, water, in the index such as solubleness, is better than MTBE, and produces TAME and also can reduce in gasoline and the active high carbon pentaene hydrocarbon of eatmospheric photochemistry.Therefore,, along with the continuous increase of market to 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 is effect maximum aspect environmental protection, 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) that in gasoline, some the most volatile reactive behavior is high.Can reduce the RVP of gasoline owing to adding TAME, this just makes refinery have greater flexibility meeting from now on aspect 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 the raw material that C5 after remaining contains 2-methyl-1-butene alkene in monoolefine and 2-methyl-2-butene and can be used as TAME.So both can solve gasoline and be in harmonious proportion required a large amount of components, also can improve utilization ratio and the value added of C5 comprehensively.
TAME production process is substantially similar with MTBE to technique, and conventionally take 2-methyl butene and methyl alcohol as raw material, under strong acidic ion resin exists, liquid phase is synthetic, 60 ℃～70 ℃ of general temperature of reaction, pressure 0.2 MPa, air speed 1.0h
-1～2.0h
-1, alcohol/alkene mol ratio 1.0～1.5.
Zeo-karb is the current catalyst for etherification in industrial extensive employing, and principal item is macropore sulfonic acid ion exchange resin.External Amberlyst-15 (A-15), Amberlyst-35 (A-35), Lewatit K2631, the Bayer K2631 type etc. of mostly adopting.Domestic D-72, S-54 that China researches and develops voluntarily, D005, QRE type resin catalyst etc. of mainly adopting, these resins are all the poly styrene polymers of divinylbenzene crosslink.
U.S. Pat 4808270A discloses a kind of preparation method of tert amyl methyl ether(TAME), with methyl alcohol, C5 alkene is raw material, adopting polystyrene resin, sulfonated phenol formaldehyde resin etc. is catalyzer, 40 ℃ ~ 120 ℃ of temperature of reaction, 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).
U.S. Pat 5453550A discloses a kind of preparation method of tert amyl methyl ether(TAME), and take methyl alcohol and iso-butylene and 2-methyl butene hydrocarbon mixture as raw material, ion exchange resin is catalyzer, at alkene air speed 0.6h
-1, 62 ℃ of temperature of reaction, 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).
U.S. Pat 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 50 ℃～70 ℃ of temperature of reaction, have synthesized tert amyl methyl ether(TAME).
European patent EP 0026041A1 discloses a kind of preparation method of tert amyl methyl ether(TAME), take methyl alcohol 2-methyl butene as raw material, and zeolite catalyst.At 232 ℃～288 ℃ of temperature, 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 adopting is cut and is obtained by FCC gasoline and DCC gasoline, and be raw material through selecting carbon five and methyl alcohol after hydrogenation and removing diolefine, the QRE type macropore sulfonic acid ion exchange resin catalyzer of developing voluntarily take Qilu Petroleum Chemistry Co. Inst. is catalyzer.The combination etherification technology that adopts pre-reactor and catalytic distillation tower, has carried out synthetic TAME process condition experiment, has obtained suitable etherification technology parameter, and more than tertiary amylene transformation efficiency can reach 95 %, TAME purity is not less than 97 %.
" fine-chemical intermediate " the 34th the 4th phase of volume in 2004, to take out remaining carbon 5 (2-methyl butene content is greater than 20%) and methyl alcohol as raw material, Phenylsulfonic acid type resin is catalyzer, and the molar ratio that is 62 ℃～67 ℃, methyl alcohol and 2-methyl butene in temperature of reaction 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%.
The 18th the 24th phase of volume of " Jilin Institute of Chemical Technology journal " calendar year 2001, take light FCC gasoline through distillation cut boiling range≤60 ℃ cut containing the more than 20% 2-methyl butene of 2-methyl butene and methyl alcohol as raw material, produce wide aperture storng-acid cation exchange resin as catalyzer take the university student of Nankai, adopt catalytic reaction distillation technology 70 ℃～76 ℃ of temperature of reaction, 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 83.44%, then rectifying purity can be brought up to more than 95%.
" Journal of Liaoning Institute of Technology " the 20th the 6th phase of volume in 2000, with refinery gas's fractionation plant isolated C 5 fraction from liquefied petroleum gas (LPG), wherein contain 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 ℃～80 ℃, and charging air speed is 3.0 h
-1～4.0 h
-1, working pressure is under 0.8M Pa condition, the total conversion rate of 2-methyl butene is 50%～60%.
" Liaoning chemical industry " the 26th the 5th phase of volume in 1997, C5 raw material is 50 ℃ of cuts of catalytic cracking stable gasoline <, 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 %, 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, and Returning reactor bottom again after exterior cooling, reaches the object of taking heat away.The operation of logistics upflowing can prevent granules of catalyst caking, can reduce bed resistance simultaneously, easy to operate and flexible, can reach higher transformation efficiency.
" petrochemical complex " the 27th the 2nd phase of volume in 1998, to take out the process of remaining C5 as raw material warp and methanol etherification TAME processed, adopt under the existence of domestic catalyst D54 type large hole cation exchanger resin, at 60 ℃ of temperature of reaction, LHSV 2.4h
-1, methyl alcohol/2-methyl butene amount of substance is than 1.00, under the condition of reaction pressure 0.2MPa, the 2-methyl butene of taking out in remaining C5 can react with methyl alcohol generation ether, the selectivity that the transformation efficiency of 2-methyl butene reaches 63.26%, TAME can reach 99.61%.
" chemical research and application " the 11st the 1st phase of volume in 1999, take 2-methyl butene and methyl alcohol as raw material in reactive distillation column take Phenylsulfonic acid Zeo-karb as catalyzer, investigated the variation with reaction conditions at the transformation efficiency of 40 ℃～80 ℃ of etherificates.At 69 ℃, n (2-methyl butene)/n (methyl alcohol)=1/1.2 o'clock, the transformation efficiency of 2-methyl butene etherification reaction reaches as high as 80%, and reaction pressure is little on the transformation efficiency impact of 2-methyl butene etherification reaction.
In sum, the advantage of strong acid cation exchange resin catalyst is active high, easy and product separation, and less to equipment corrosion, selectivity is more high.Weak point is mainly reflected in: 1. resin catalyst less stable, and when rising 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 variation, oligomerisation side reaction increases, and by product increases; 3. industrial in order to improve olefin conversion, suppress side reaction, often adopt higher alfin ratio, thereby cause higher energy consumption realizing recycling of alcohol.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method by 2-methyl butene and methyl alcohol etherificate synthesizing methyl tert-amyl ether (TAME) under the catalyzer of Ti-base composite oxide carried heteropoly acid exists, the inventive method has good reactivity worth, has satisfactory stability simultaneously.
Prepare a method for tert amyl methyl ether(TAME), comprise following content: take 2-methyl butene (2-methyl-1-butene alkene and/or 2-methyl-2-butene) and methyl alcohol as raw material, take heteropolyacid/Ti-base composite oxide as catalyzer, the volume space velocity of 2-methyl butene is 0.5h
-1～5.0h
-1, the mol ratio of methyl alcohol and 2-methyl butene is 1.0:1.0～5.0:1.0, and temperature of reaction is 80 ℃～200 ℃, and reaction pressure is 0.5 MPa～5.0Mpa.
In the inventive method, described heteropolyacid/Ti-base composite oxide catalyzer, take Ti-base composite oxide as carrier, take heteropolyacid as active ingredient.Described Ti-base composite oxide is TiO
2-SiO
2and TiO
2-ZrO
2, TiO
2one or more in-MgO are mixed, and described heteropolyacid is one or more mixing 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, Ti-base composite oxide TiO
2weight content be 30%～75%, be preferably 35%～75%, most preferably be 45%～70%.The weight ratio of heteropolyacid and Ti-base composite oxide is 0.05:1～1:1, is preferably 0.3:1～0.8:1, most preferably is 0.3:1～0.5:1.
In the inventive method, described 2-methyl butene can use the mixing monoolefine raw material that contains 2-methyl butene, also can use pure 2-methyl butene.In the time using mixing monoolefine raw material, mix 2-methyl butene weight content in monoolefine raw material and be greater than 10%, be preferably at least 15%, be most preferably at least 20%.
In the inventive method, the volume space velocity of described 2-methyl butene is preferably 1.0h
-1～4.0h
-1, the mol ratio of methyl alcohol and 2-methyl butene is preferably 1.0:1～4.0:1, and temperature of reaction is preferably 90 ℃～160 ℃, and reaction pressure is preferably 1.0 MPa～4.0MPa.
In the inventive method, the volume space velocity of described 2-methyl butene most preferably is 1.5h
-1～3.0h
-1, the mol ratio of methyl alcohol and 2-methyl butene most preferably is 1.5:1.0～3.0:1.0, and temperature of reaction most preferably is 100 ℃～140 ℃, and reaction pressure most preferably is 1.0 MPa～2.0MPa.
The inventive method adopts the catalyzer of the carrier loaded heteropolyacid of a kind of Ti-base composite oxide, make support of the catalyst obtain suitable specific surface, aperture structure and acidity distribution, can effectively regulate the acid and active of catalyzer, overcome the carrier loaded heteropolyacid catalyst of single component porous medium due to the easy decomposes of Keggin structure, the easy loss of acid amount, separation difficulty and the catalyst deactivation bringing of heteropolyacid, the shortcoming that transformation efficiency reduces.The inventive method is take the carrier loaded heteropolyacid of Ti-base composite oxide as catalyzer and regulate and control the serialization that catalyzer is coordinated mutually therewith processing condition can realize tert amyl methyl ether(TAME) and produce, 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 methyl alcohol synthesizing methyl tert-amyl ether, is an environmental protection novel process.
Embodiment
Catalyzer of the present invention can be prepared by following method: the aqueous solution a of the preparation corresponding salt of Ti-base composite oxide and titanium salt, preparation basic solution b(potassium hydroxide is joined solution or ammoniacal liquor), under the state of normal mild stirring, solution b is added drop-wise in a, reaction is precipitated, through washing, filter, dry, then after method extruded moulding routinely, roasting makes Ti-base composite oxide carrier.
In the preparation process of above-mentioned Ti-base composite oxide, the described reaction times is 3h～24h, is preferably 5h～20h, most preferably is 6h～12h.Described drying temperature is 100 ℃～180 ℃, is preferably 100 ℃～160 ℃, most preferably is 100 ℃～120 ℃.Be 8h～24h described time of drying, is preferably 6h～16h, most preferably is 8h～12h.Described maturing temperature is 400 ℃～600 ℃, is preferably 400 ℃～550 ℃, most preferably is 400 ℃～500 ℃.Described roasting time is 8h～24h, is preferably 8h～20h, most preferably is 8h～16h.
By Ti-base composite oxide carrier after moulding, according to the method for routine dipping, in heteropolyacid solution, flood.Dipping time is 6h～24h, is preferably 6h～16h, most preferably is 8h～12h.Macerate is dry 6h～12h at 100 ℃～160 ℃, is preferably dry 6h～10h at 100 ℃～140 ℃, most preferably is dry 8h～10h at 100 ℃～120 ℃.Macerate is roasting 8h～24h at 350 ℃～650 ℃, is preferably roasting 8h～16h at 400 ℃～550 ℃, most preferably is roasting 10h～12h at 450 ℃～550 ℃ and makes heteropolyacid/Ti-base composite oxide catalyzer.
Further illustrate method of the present invention and effect below by specific embodiment.
Embodiment 1
A certain amount of magnesium nitrate and a certain amount of titanium tetrachloride are mixed with to aqueous solution a, preparation potassium hydroxide alkalescence solution b, under the state of normal mild stirring, solution b is added drop-wise in a, reaction 10h obtains white pasty state precipitation, through washing, filter, at 120 ℃ of dry 10h, method extruded moulding routinely again, then at 500 ℃, roasting 8h makes Ti-base composite oxide carrier.
A certain amount of phospho-molybdic acid is dissolved in deionized water, the support of the catalyst after above-mentioned shaping and roasting is dipped in assorted many solution, dipping time is 8h, and macerate is dry 10h at 120 ℃, and at 450 ℃, roasting 10h, makes catalyzer, and catalyzer physical property is in table 1.
2-methyl butene and methanol etherification are to carry out in the stainless steel fixed-bed reactor of Φ 18mm × 1200mm, in reactor, pack above-mentioned catalyzer 30ml into, reactor head and bottom, be respectively charged into the quartz sand that diameter is Φ 0.5mm～1.2mm, after reactor installs, use nitrogen replacement three times, and tightness test is qualified, 2-methyl butene, methyl alcohol are pumped into preheater with metering, 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 forms 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 forms 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 forms 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 forms in table 1, and reaction result is in table 2.
Embodiment 6
Other condition, with embodiment 1, just changes magnesium nitrate into zirconium tetrachloride, and phospho-molybdic acid changes silicomolybdic acid into, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 7
Other condition, with embodiment 6, just changes the consumption of zirconium tetrachloride and silicomolybdic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 8
Other condition, with embodiment 6, just changes the consumption of zirconium tetrachloride and silicomolybdic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 9
Other condition, with embodiment 6, just changes the consumption of zirconium tetrachloride and silicomolybdic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 10
Other condition, with embodiment 6, just changes the consumption of zirconium tetrachloride and silicomolybdic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 11
Other condition, with embodiment 1, just changes magnesium nitrate into silicon tetrachloride, and phospho-molybdic acid changes phospho-wolframic acid into, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 12
Other condition, with embodiment 11, just changes the consumption of silicon tetrachloride and phospho-wolframic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 13
Other condition, with embodiment 11, just changes the consumption of silicon tetrachloride and phospho-wolframic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 14
Other condition, with embodiment 11, just changes the consumption of silicon tetrachloride and phospho-wolframic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 15
Other condition, with embodiment 11, just changes the consumption of silicon tetrachloride and phospho-wolframic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 16
Other condition, with embodiment 1, just changes phospho-molybdic acid into silicotungstic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 17
Other condition, with embodiment 1, just changes phospho-molybdic acid into arsenowolframic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 18
Other condition, with embodiment 1, just changes phospho-molybdic acid into germanotungstic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 19
Other condition, with embodiment 1, just changes phospho-molybdic acid into arsenic molybdic acid, and catalyzer forms in table 1, and reaction result is in table 2.
Embodiment 20
Other condition, with embodiment 1, just changes phospho-molybdic acid into germanium molybdic acid, and catalyzer forms 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 forms in table 1, and reaction result is in table 2.
Embodiment 22
By the catalyzer of embodiment 21, according to the evaluation method of embodiment 1, be 1.5h at the volume space velocity of 2-methyl butene charging
-1, the mol ratio of methyl alcohol and 2-methyl butene is 2:1, and temperature of reaction is 100 ℃, and reaction pressure is under the condition of 2.0 MPa, has carried out stability test, test-results table 3.
Comparative example 1
Flood a certain amount of TiO with a certain amount of phospho-molybdic acid aqueous solution
224h, dry 12h at 110 ℃, then roasting 12h is prepared into catalyzer at 500 ℃.Evaluating catalyst method is with embodiment 1, and catalyzer forms in table 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
Take β zeolite as catalyzer, evaluation method is with embodiment 1, and reaction result is in table 2.
Comparative example 5
Take ZSM-5 as carrier, according to the dipping method of embodiment 1, phospho-molybdic acid is immersed on ZSM-5 molecular sieve, make catalyzer, evaluation method is with embodiment 1, and reaction result is in table 2.
Comparative example 6
Comparative example 5 catalyzer, carry out estimation of stability by the evaluation method of embodiment 22, the results are shown in Table 3.
Table 1 embodiment and comparative example catalyzer composition
| Sequence number | Titanium oxide in composite oxides, quality % | The mass ratio of heteropolyacid and composite oxides |
| Embodiment 1 | 10 | 0.05:1.0 |
| Embodiment 2 | 30 | 0.10:1.0 |
| Embodiment 3 | 50 | 0.30:1.0 |
| Embodiment 4 | 70 | 0.40:1.0 |
| Embodiment 5 | 45 | 0.50:1.0 |
| Embodiment 6 | 15 | 0.20:1.0 |
| Embodiment 7 | 65 | 0.40:1.0 |
| Embodiment 8 | 55 | 0.50:1.0 |
| Embodiment 9 | 75 | 0.60:1.0 |
| Embodiment 10 | 70 | 0.65:1.0 |
| Embodiment 11 | 20 | 0.20:1.0 |
| Embodiment 12 | 50 | 0.30:1.0 |
| Embodiment 13 | 60 | 0.40:1.0 |
| Embodiment 14 | 70 | 0.50:1.0 |
| Embodiment 15 | 75 | 0.55:1.0 |
| Embodiment 16 | 35 | 0.20:1.0 |
| Embodiment 17 | 45 | 0.30:1.0 |
| Embodiment 18 | 55 | 0.40:1.0 |
| Embodiment 19 | 65 | 0.50:1.0 |
| Embodiment 20 | 75 | 0.60:1.0 |
| Embodiment 21 | 50 | 0.40:1.0 |
The reaction conditions of table 2 embodiment and comparative example 1 and reaction result
| Sequence number | Reaction pressure/MPa | Temperature of reaction/℃ | 2-methyl butene volume space velocity/h -1 | Methyl alcohol/2-methyl butene (mol ratio) | 2-methyl butene transformation efficiency/% |
| Embodiment 1 | 1.0 | 80 | 0.5 | 5.0 | 93.6 |
| Embodiment 2 | 2.0 | 100 | 1.5 | 4.0 | 94.7 |
| Embodiment 3 | 3.0 | 120 | 2.5 | 3.0 | 97.1 |
| Embodiment 4 | 4.0 | 140 | 3.5 | 2.0 | 97.8 |
| Embodiment 5 | 5.0 | 160 | 5.0 | 1.0 | 97.3 |
| Embodiment 6 | 2.0 | 90 | 2.0 | 4.0 | 93.1 |
| Embodiment 7 | 2.5 | 130 | 2.5 | 3.0 | 97.7 |
| Embodiment 8 | 3.5 | 150 | 3.0 | 2.0 | 97.8 |
| Embodiment 9 | 4.0 | 170 | 3.5 | 1.5 | 92.4 |
| Embodiment 10 | 4.5 | 190 | 4.5 | 1.0 | 93.2 |
| Embodiment 11 | 3.0 | 100 | 1.5 | 3.0 | 92.1 |
| Embodiment 12 | 3.5 | 110 | 1.5 | 2.0 | 98.1 |
| Embodiment 13 | 4.0 | 120 | 2.0 | 1.0 | 97.3 |
| Embodiment 14 | 3.0 | 130 | 2.0 | 3.0 | 97.9 |
| Embodiment 15 | 4.0 | 140 | 2.0 | 2.0 | 93.5 |
| Embodiment 16 | 3.0 | 95 | 1.5 | 3.0 | 91.8 |
| Embodiment 17 | 3.5 | 105 | 1.5 | 2.0 | 97.4 |
| Embodiment 18 | 4.0 | 115 | 2.0 | 1.0 | 97.1 |
| Embodiment 19 | 4.0 | 125 | 2.0 | 2.0 | 98.7 |
| Embodiment 20 | 3.5 | 135 | 2.0 | 3.0 | 94.8 |
| Embodiment 21 | 3.0 | 125 | 1.5 | 2.5 | 98.1 |
| Comparative example 1 | 3.0 | 120 | 1.5 | 2.0 | 84.6 |
| Comparative example 2 | 3.0 | 120 | 1.5 | 2.0 | 86.5 |
| Comparative example 3 | 3.0 | 125 | 1.5 | 3.0 | 89.3 |
| Comparative example 4 | 4.0 | 125 | 2.0 | 3.0 | 89.2 |
| Comparative example 5 | 4.0 | 130 | 2.0 | 3.0 | 88.9 |
Table 3 stability test result
| Sequence number | Working time/h | Embodiment 222-methyl butene transformation efficiency/% by mole | Comparative example 62-methyl butene transformation efficiency/% by mole |
| 1 | 50 | 97.4 | 87.8 |
| 2 | 100 | 97.2 | 87.6 |
| 3 | 150 | 97.8 | 86.9 |
| 4 | 200 | 97.3 | 87.0 |
| 5 | 250 | 97.2 | 86.6 |
| 6 | 300 | 97.9 | 88.3 |
| 7 | 350 | 97.8 | 86.9 |
| 8 | 400 | 97.4 | 85.8 |
| 9 | 450 | 97.6 | 86.9 |
| 10 | 500 | 97.3 | 85.6 |
| 11 | 550 | 97.1 | 85.5 |
| 12 | 600 | 97.2 | 83.8 |
| 13 | 650 | 97.9 | 84.1 |
| 14 | 700 | 97.4 | 84.5 |
| 15 | 750 | 97.3 | 83.5 |
| 16 | 800 | 97.8 | 82.9 |
| 17 | 850 | 97.6 | 82.7 |
| 18 | 900 | 97.7 | 82.0 |
| 19 | 950 | 97.8 | 81.8 |
| 20 | 1000 | 97.1 | 81.5 |
Claims (10)
1. a method of preparing tert amyl methyl ether(TAME), is characterized in that: comprise following content: take 2-methyl butene and methyl alcohol as raw material, take heteropolyacid/Ti-base composite oxide as catalyzer, the volume space velocity of 2-methyl butene is 0.5h
-1～5.0h
-1, the mol ratio of methyl alcohol and 2-methyl butene is 1.0:1.0～5.0:1.0, and temperature of reaction is 80 ℃～200 ℃, and reaction pressure is 0.5 MPa～5.0Mpa.
2. method according to claim 1, is characterized in that: described heteropolyacid/Ti-base composite oxide catalyzer, and take Ti-base composite oxide as carrier, take heteropolyacid as active ingredient.
3. method according to claim 1 and 2, is characterized in that: described Ti-base composite oxide is TiO
2-SiO
2and TiO
2-ZrO
2, TiO
2one or more mixing in-MgO.
4. method according to claim 1 and 2, is characterized in that: described heteropolyacid is one or more mixing in phospho-wolframic acid, silicotungstic acid, arsenowolframic acid, germanotungstic acid, phospho-molybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid.
5. method according to claim 1 and 2, is characterized in that: described Ti-base composite oxide TiO
2weight content be 30%～75%.
6. method according to claim 5, is characterized in that: described Ti-base composite oxide TiO
2weight content be 45%～70%.
7. method according to claim 1 and 2, is characterized in that: the weight ratio of heteropolyacid and Ti-base composite oxide is 0.05:1～1:1.
8. method according to claim 7, is characterized in that: the weight ratio of heteropolyacid and Ti-base composite oxide is 0.3:1～0.5:1.
9. method according to claim 1, is characterized in that: the volume space velocity of described 2-methyl butene is preferably 1.0h
-1～4.0h
-1, the mol ratio of methyl alcohol and 2-methyl butene is preferably 1.0:1～4.0:1, and temperature of reaction is preferably 90 ℃～160 ℃, and reaction pressure is preferably 1.0 MPa～4.0 MPa.
10. method according to claim 9, is characterized in that: the volume space velocity of described 2-methyl butene is 1.5h
-1～3.0h
-1, the mol ratio of methyl alcohol and 2-methyl butene is 1.5:1.0～3.0:1.0, and temperature of reaction is 100 ℃～140 ℃, and reaction pressure is 1.0 MPa～2.0 MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622385A (en) * | 2016-12-19 | 2017-05-10 | 聊城大学 | Double-core magnesium-germanium tungsten oxide cluster catalyst and preparing method and application thereof |
| CN107537568A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of method of modifying of cationic ion-exchange resin and the method for preparing tert amyl methyl ether(TAME) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04224539A (en) * | 1990-04-16 | 1992-08-13 | Texaco Chem Co | Process for producing tert-amyl methyl ether from c5 olefin fraction |
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2012
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04224539A (en) * | 1990-04-16 | 1992-08-13 | Texaco Chem Co | Process for producing tert-amyl methyl ether from c5 olefin fraction |
Non-Patent Citations (2)
| Title |
|---|
| 冯世宏: "甲基叔戊基醚的制备", 《辽宁工学院学报（自然科学版）》, vol. 20, no. 6, 31 December 2000 (2000-12-31), pages 60 - 62 * |
| 魏民等: "叔戊烯与甲醇在Cs2.5H0.5PW12040/ SiO2催化剂上的醚化", 《化学与粘合》, 31 December 2004 (2004-12-31), pages 343 - 345 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107537568A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of method of modifying of cationic ion-exchange resin and the method for preparing tert amyl methyl ether(TAME) |
| CN107537568B (en) * | 2016-06-23 | 2020-03-17 | 中国石油化工股份有限公司 | Modification method of cation exchange resin and method for preparing tert-amyl methyl ether |
| CN106622385A (en) * | 2016-12-19 | 2017-05-10 | 聊城大学 | Double-core magnesium-germanium tungsten oxide cluster catalyst and preparing method and application thereof |
| CN106622385B (en) * | 2016-12-19 | 2019-01-29 | 聊城大学 | A kind of double-core magnesium-germanium tungsten oxygen cluster catalyst, preparation method and its usage |
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