CN102909075B - Catalyst and method for preparing methyl sec-butyl ether - Google Patents
Catalyst and method for preparing methyl sec-butyl ether Download PDFInfo
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- CN102909075B CN102909075B CN201110217519.1A CN201110217519A CN102909075B CN 102909075 B CN102909075 B CN 102909075B CN 201110217519 A CN201110217519 A CN 201110217519A CN 102909075 B CN102909075 B CN 102909075B
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Abstract
The present invention provides a catalyst and a method for preparing methyl sec-butyl ether. A composite oxide(s) is used as a carrier, and a heteropoly acid(s) is used as the active component for the catalyst for preparing methyl sec-butyl ether. The composite oxide(s) is one or more aluminum composite oxide(s) of MgO-Al2O3, TiO2-Al2O3 and ZrO2-Al2O3, and the heteropoly acid(s) is one or more of phosphotungstic acid, silicotungstic acid, arsenowolframic acid, germanotungtic acid, phospho-molybdic acid, silicomolybdic acid, arsenomolybdic acid and germanomolybdic acid. According to the catalyst and the method of the invention, heteropoly acid-supported aluminum composite oxide catalyst is adopted, so the disadvantages that heteropoly acid Keggin structure of a supported heteropoly acid catalyst is sensitive, the acid amount of the catalyst is easy to lose, separation of the catalyst is difficult and catalyst deactivation brought thereby, and the conversion rate is reduced are overcome.
Description
Technical field
The invention provides a kind of catalyst that hydrocarbon and alcohol etherification reaction are prepared the aluminium base composite oxides carried heteropoly acid of methyl sec-butyl ether that is applicable to, this catalyst is particularly useful for the process of n-butene and methanol etherification synthesizing methyl sec-butyl ether (MSBE).
Technical background
Along with the rapid raising of crude oil in China working ability and the continuous increase of ethylene yield, the C of by-product
4resource is also in continuous expansion, and its total amount has surpassed 3.0Mt/.At present, China is at C
4the utilization rate of hydrocarbon only 10%, all the other are mainly used in civilian liquefied petroleum gas.And developed country's utilization rates such as the U.S., Japan and West Europe have reached 60% ~ 90%, the C of China
4the utilization rate of hydrocarbon lags far behind level of developed countries.Meanwhile, along with developing rapidly of China's natural gas industry, the C still using as fuel now
4hydrocarbon will be faced with stern challenge.
Refinery and cracking of ethylene C
4alkene in hydrocarbon (butadiene, isobutene, n-butene) is important Organic Chemicals, and as domestic fuel, using is the significant wastage to resource, in time rational exploitation and utilization C
4resource, accelerates C
4the utilization rate of hydrocarbon, the chemical products of preparation high added value are particularly important.
At present, methyl tertiary butyl ether(MTBE) (MTBE), as a kind of high-octane addition for leadless gasoline, is mainly for reducing the pollution of vehicle exhaust to environment.Since entering 21 century, the U.S. finds after deliberation, uses the gasoline that adds MTBE, in vehicle exhaust, can detect formaldehyde, and meanwhile, the strong and stimulating smell of MTBE and possible carcinogenesis directly affect air quality.In addition, due to the water-soluble of MTBE, in automobile oil, 3%～10% MTBE finally can move in water environment, and meeting polluted underground water source, therefore, has forbidden MTBE at California, USA.At present, the domestic laws and rules of still not forbidding MTBE in gasoline, therefore, over a period to come, MTBE will continue to become the main component of clean gasoline.But because California, USA has been forbidden MTBE the application of MTBE has been brought to negative effect.Meanwhile, because methyl tertiary butyl ether(MTBE) (MTBE) toxicity is 4.75 times of MSBE, (methyl sec-butyl ether (MSBE) toxic concentration is 141g/m
3, in 15 minutes, small white mouse is lethal; And half lethal concentration (LC to small white mouse
50) be 7.6mmol/L, be equivalent to 669.94g/m
3).Therefore, methyl sec-butyl ether (MSBE) is that methyl tertiary butyl ether(MTBE) (MTBE) is as the fine substitute products of gasoline mediation component.
Methyl sec-butyl ether (MSBE) and methyl tertiary butyl ether(MTBE) (MTBE) be isomer each other, can adopt similar synthetic method.If methyl tertiary butyl ether(MTBE) (MTBE) is to mix isobutene in C-4-fraction and methyl alcohol to carry out selective addition reaction and make.Its course of reaction is: the tertiary carbon atom in isobutene is combined with alcohol after first forming carbonium ion under acidic catalyst effect again and is formed ether.This course of reaction belongs to reversible balance exothermic reaction, and thermal discharge is 37KJ/mol.Under different temperatures, the equilibrium conversion of methyl tertiary butyl ether(MTBE) (MTBE) is as shown in table 1.
under table 1 different temperatures, the equilibrium conversion of methyl tertiary butyl ether(MTBE) (MTBE).
| Temperature, ℃ | 50 | 60 | 70 | 80 | 90 |
| Conversion ratio, % | 96.8 | 95.8 | 94.6 | 93.1 | 91.4 |
Rising reaction temperature energy fast reaction speed, but unfavorable to conversion ratio, in order to obtain higher product yield, etherification reaction is carried out in requirement under suitable temperature conditions, when in raw material, the concentration of isobutene is reduced to finite concentration, the n-butene being adsorbed onto on catalyst surface reacts generation methyl sec-butyl ether (MSBE) with methyl alcohol.Reduce reaction temperature and be conducive to reduce the growing amount that reaction generates methyl sec-butyl ether (MSBE), but in order not reduce the etherification reaction speed of isobutene, need to select the catalyst that low temperature active is high.
Correspondingly, methyl sec-butyl ether (MSBE) can adopt n-butene and methyl alcohol to make through etherificate, but while adopting similar catalyst, the conversion per pass of n-butene is lower (during methyl tertiary butyl ether(MTBE) building-up process used as adopted resin catalyst, the conversion per pass of n-butene is lower than 5%), a large amount of n-butenes need to be carried out to separation and circulation, energy consumption is larger, production cost is high, and complex technical process.
At present, prepare methyl tertiary butyl ether(MTBE) (MTBE) and mostly adopt strongly acidic ion-exchange resin catalyst, molecular sieve catalyst, heteropolyacid catalyst and modified catalyst thereof etc., and there is no the relevant bibliographical information of preparing methyl sec-butyl ether (MSBE) aspect both at home and abroad.
For the preparation of the strongly acidic ion-exchange resin catalyst of methyl tertiary butyl ether(MTBE) (MTBE), be to take the sulfonated polystyrene ion exchange resin that divinylbenzene is crosslinking agent, as Amberlyst-15, D-72 etc.
the main physical parameter of the common resin catalyst of table 2.
| Physical property | Amberlyst-15 | D-72 |
| Exchange capacity, meq/g | 4.8 | 4.39 |
| Specific surface, m 2/g | 40～50 | 14.8 |
| Porosity, % | 30～45 | ? |
| Average pore size, 10 -10m | （20-60NM） | ? |
| The swollen rate that rises, % | 20～30 | ? |
Above-mentioned catalyst has good catalytic activity, but responsive to variations in temperature, when reaction temperature surpasses 90 ℃, active component sulfonic acid group loss speed increases, cause on the one hand the activity of catalyst to decline, cause on the other hand the pollution to the corrosion of equipment and environment, catalyst is easy swelling in course of reaction, can not regenerate, and has affected its service life.
CN1304798A provides a kind of molecular sieve catalyst for the synthesis of methyl tertiary butyl ether(MTBE) and preparation method thereof.This catalyst is comprised of molecular sieve and heteropoly acid, and its weight ratio is molecular sieve: heteropoly acid=(1～100): (1～70), the SiO of molecular sieve
2/ Al
2o
3=3～100.By above-mentioned heteropoly acid (as phosphotungstic acid, silico-tungstic acid): solvent=(1～70): (20～350) weight ratio is dissolved in heteropoly acid in water, ethanol, glacial acetic acid or the third copper solvent, then forms molecular sieve that weight ratio is poured dipping in above-mentioned solution into, standing, suction filtration is dried and obtained product by catalyst.This catalyst activity is high, and the life-span is long, selectively good.
CN1140629A provides a kind of modification Hydrogen beta-zeolite catalyst for methyl tertiary butyl ether(MTBE) (MTBE) and isopropyl ether (IPE) and preparation method thereof.This catalyst is by Hydrogen β zeolite (H β), gama-alumina (γ-Al
2o
3) and boron oxide (B
2o
3) the composite modified Hydrogen beta-zeolite catalyst that forms.This catalyst has reaction temperature strong adaptability, the advantages such as environmentally safe.
CN1152476A provides a kind of super acidic catalyst of preparing methyl tertiary butyl ether(MTBE) (MTBE), and this catalyst be take Hydrogen beta-zeolite as parent, with γ-Al
2o
3for binding agent, after moulding, use again TiCl
4, Fe(NO
3)
3, Zr (NO
3)
4(NH
4)
2sO
4a kind of super acidic catalyst for the synthesis of methyl tertiary butyl ether(MTBE) (MTBE) is made in modification.This catalyst activity and stability, all higher than ion exchange resin, can be recycled after regeneration.
CN1765865A has proposed a kind of methyl alcohol and isobutene etherification method, this patent contacts with isobutene methyl alcohol with a kind of composite catalyst of sulfonation, be 0.2～4.0,35 ℃～160 ℃ of reaction temperatures, reaction pressure be 0.5～2.0 MPa, feed weight air speed 1.0 h at alcohol/alkene ratio
-1～6.0 h
-1reaction condition under react.Wherein, composite catalyst is comprised of inorganic oxide and organic resin, inorganic oxide is selected from one or more in the oxide of periodic table of elements ZhongⅢ B family, IV B family, V B family, VI B family, VII B family, VIII B family, I B family, II B family, III A family, IV A family, V A family element, and organic resin is polymerized by monomer styrene and divinylbenzene.The cross-linked polymer of inorganic oxide and styrene and divinylbenzene is combined with each other at molecular level, this composite catalyst, and range of reaction temperature is wide, and catalyst stability is good, and its steady running cycle is long simultaneously.
Above-mentioned strongly acidic ion-exchange resin catalyst, molecular sieve catalyst, heteropolyacid catalyst and modified catalyst thereof all carry out selective addition for isobutene and methyl alcohol to be prepared methyl tertiary butyl ether(MTBE) (MTBE) and develops.Although methyl tertiary butyl ether(MTBE) (MTBE) and methyl sec-butyl ether (MSBE) is isomer each other, but reactivity worth is also incomplete same, by above-mentioned, for the synthetic catalyst of MTBE, be directly used in MSBE when synthetic, the serviceability of catalyst needs further to improve.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method and corresponding catalyst by n-butene and methyl alcohol etherificate synthesizing methyl sec-butyl ether (MSBE) under the catalyst of aluminium base composite oxides carried heteropoly acid exists, catalyst of the present invention has good reactivity worth.
The present invention prepares the catalyst of methyl sec-butyl ether, take composite oxides as carrier, take heteropoly acid as active component, and described composite oxides are MgO-Al
2o
3, TiO
2-Al
2o
3and ZrO
2-Al
2o
3one or more of middle aluminium base composite oxides, described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, arsenowolframic acid, germanotungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid etc.
The present invention is prepared in the catalyst of methyl sec-butyl ether, Al in aluminium base composite oxides
2o
3weight content be 10%～90%, be preferably 25%～85%, most preferably be 40%～75%.
The present invention is prepared in the catalyst of methyl sec-butyl ether, and the weight ratio of heteropoly acid and aluminium base composite oxides is 0.01:1～2:1, is preferably 0.05:1～1:1, most preferably is 0.2:1～0.5:1.
The present invention prepares the process of methyl sec-butyl ether, comprises following content: the rare and methyl alcohol of the positive fourth of take is raw material, uses the above-mentioned heteropoly acid/aluminium base composite oxides of the present invention catalyst, and the volume space velocity of n-butene is 0.5h
-1～10h
-1, the mol ratio of methyl alcohol and n-butene is 0.9:1～5:1,80 ℃～200 ℃ of reaction temperatures, and reaction pressure is 4.0 MPa～8.0MPa.
Described n-butene is 1-butylene and/or 2-butylene, can use the raw material that the rare weight content of positive fourth is 70%～100%, and in n-butene raw material, the positive rare weight content of fourth is preferably 80%～100%, most preferably is 90%～100%.
The volume space velocity of described n-butene is preferably 0.5h
-1～5.0h
-1, the mol ratio of methyl alcohol and n-butene is preferentially selected 1:1～3:1, and reaction temperature is preferably 80 ℃～160 ℃, and reaction pressure is preferably 5.0 MPa～7.0MPa.
The volume space velocity of described n-butene most preferably is 0.5h
-1～2.0h
-1, the mol ratio of methyl alcohol and n-butene most preferably is 1:1～2:1, and reaction temperature most preferably is 100 ℃～140 ℃, and reaction pressure most preferably is 5.0 MPa～6.0MPa.
The present invention adopts the catalyst of the carrier loaded heteropoly acid of a kind of aluminium base composite oxides, making catalyst carrier obtain suitable specific surface, aperture structure and acidity distributes, can effectively regulate the acid and active of catalyst, overcome the carrier loaded heteropolyacid catalyst of one pack system porous media due to the Keggin structure of the heteropoly acid shortcoming that the easy loss of acid amount, separation difficulty and the catalysqt deactivation bringing, conversion ratio reduce that is easily damaged.Catalyst of the present invention can be realized serialization and produce, and course of reaction is easy and simple to handle, for n-butene and methyl alcohol synthesizing methyl sec-butyl ether, has the advantages such as conversion ratio is high, good stability, is an environmental protection new technology.
The specific embodiment
The present invention generates reaction mechanism and the reaction characteristics of methyl sec-butyl ether (MSBE) according to n-butene and alcohol etherificate, adopt a kind of aluminium base composite oxides carried heteropoly acid as catalyst, under suitable reaction condition, react, overcome the shortcoming that Several Typical Load type heteropolyacid catalyst heteropoly acid Keggin structure is easily damaged, easy loss, separation difficulty and the catalysqt deactivation bringing are measured in acid, conversion ratio reduces.
Catalyst 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 alkaline solution b(potassium hydroxide is joined solution or ammoniacal liquor), under the state of normal gentle agitation, solution b is added drop-wise in a, reaction is precipitated, through washing, filtration, dry, then after method extruded moulding routinely, roasting makes aluminium base composite oxides carrier.
In the preparation process of above-mentioned aluminium base composite oxides, the described reaction time is 4h～24h, is preferably 6h～20h, most preferably is 6h～12h.Described baking temperature is 100 ℃～160 ℃, is preferably 100 ℃～140 ℃, most preferably is 100 ℃～110 ℃.Be 6h～24h described drying time, is preferably 6h～12h, most preferably is 8h～10h.Described sintering temperature is 400 ℃～900 ℃, is preferably 400 ℃～700 ℃, most preferably is 400 ℃～600 ℃.Described roasting time is 6h～24h, is preferably 6h～12h, most preferably is 6h～8h.
By aluminium base composite oxides carrier after moulding, according to the method for routine dipping, in heteropoly acid solution, flood.Dip time is 4h～24h, is preferably 4h～12h, most preferably is 6h～12h.Macerate is dry 4h～12h at 100 ℃～180 ℃, is preferably dry 6h～12h at 100 ℃～160 ℃, most preferably is dry 6 h～8h at 100 ℃～120 ℃.Macerate is roasting 6h～24h at 250 ℃～550 ℃, is preferably roasting 6h～12h at 300 ℃～500 ℃, most preferably is roasting 8h～12h at 350 ℃～450 ℃ and makes heteropoly acid/aluminium base composite oxides catalyst.
Below by specific embodiment, further illustrate method of the present invention and effect.
Embodiment 1
A certain amount of aluminum nitrate and a certain amount of magnesium nitrate are mixed with to aqueous solution a, with deionized water and a certain amount of potassium hydroxide, be configured to aqueous solution b, under the state of normal gentle agitation, solution b is added drop-wise in a, reaction 6h obtains white pasty state precipitation, through washing, filter, at 120 ℃ of dry 8h, method extruded moulding routinely again, then at 500 ℃, roasting 6h makes magnesium-aluminium composite oxide carrier.
A certain amount of phosphomolybdic acid is dissolved in deionized water, the catalyst carrier after above-mentioned shaping and roasting is dipped in assorted many solution, dip time is 10h, and macerate is dry 10h at 110 ℃, and at 400 ℃, roasting 8h, makes catalyst, and catalyst forms in Table 3.
N-butene and methanol etherification are to carry out in the stainless steel fixed bed reactors of Φ 18mm * 1200mm, in reactor, pack above-mentioned catalyst 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 air seal test is qualified, n-butene, methyl alcohol are pumped into preheater with metering, and the volume space velocity of n-butene charging is 0.5h
-1～10h
-1, the mol ratio of methyl alcohol and n-butene is 0.9:1～5:1, and material is preheating to 80 ℃～210 ℃.Material after preheating enters fixed bed reactors and carries out etherification reaction, and controlling reaction temperature is 80 ℃～200 ℃, and reaction pressure is 4.0 MPa～8.0MPa.Unreacted n-butene recycles.Reaction result is in Table 4.
Embodiment 2
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phosphomolybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 3
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phosphomolybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 4
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phosphomolybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 5
Other condition, with embodiment 1, just changes the consumption of magnesium nitrate and phosphomolybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 6
Other condition, with embodiment 1, just changes magnesium nitrate into titanium tetrachloride, and phosphomolybdic acid changes silicomolybdic acid into, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 7
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 8
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 9
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 10
Other condition, with embodiment 1, just changes the consumption of titanium tetrachloride and silicomolybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 11
Other condition is with embodiment 1, and just magnesium nitrate changes zirconium chloride into, and phosphomolybdic acid changes silicomolybdic acid into, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 12
Other condition, with embodiment 1, just changes zirconium chloride and silicomolybdic acid consumption, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 13
Other condition, with embodiment 1, just changes zirconium chloride silicomolybdic acid consumption, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 14
Other condition, with embodiment 1, just changes zirconium chloride silicomolybdic acid consumption, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 15
Other condition, with embodiment 1, just changes zirconium chloride silicomolybdic acid consumption, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 16
Other condition, with embodiment 1, just changes phosphomolybdic acid into phosphotungstic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 17
Other condition, with embodiment 1, just changes phosphomolybdic acid into silico-tungstic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 18
Other condition, with embodiment 1, just changes phosphomolybdic acid into arsenowolframic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 19
Other condition, with embodiment 1, just changes phosphomolybdic acid into germanotungstic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 20
Other condition, with embodiment 1, just changes phosphomolybdic acid into arsenic molybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 21
Other condition, with embodiment 1, just changes phosphomolybdic acid into germanium molybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Embodiment 22
By the catalyst of embodiment 9, according to the evaluation method of embodiment 1, at the volume space velocity of n-butene charging, be 0.5h
-1, the mol ratio of methyl alcohol and n-butene is 2:1, and reaction temperature is 85 ℃, and reaction pressure is under the condition of 5.0 MPa, has carried out stability test, and result of the test table 5 can be found out having good stability of catalyst of the present invention.
Table 5 stability test result.
| Running time/h | N-butene conversion per pass/% |
| 50 | 22.4 |
| 100 | 22.3 |
| 300 | 22.6 |
| 500 | 23.0 |
| 700 | 22.6 |
| 900 | 22.0 |
| 1200 | 22.1 |
Table 3 embodiment and comparative example catalyst form.
| Sequence number | Aluminium oxide in composite oxides, quality % | The mass ratio of heteropoly acid and composite oxides |
| Embodiment 1 | 90 | 0.01:1.0 |
| Embodiment 2 | 70 | 0.05:1.0 |
| Embodiment 3 | 50 | 0.1:1.0 |
| Embodiment 4 | 30 | 0.5:1.0 |
| Embodiment 5 | 10 | 1.0:1.0 |
| Embodiment 6 | 80 | 0.05:1 |
| Embodiment 7 | 60 | 0.06:1 |
| Embodiment 8 | 55 | 0.09:1 |
| Embodiment 9 | 35 | 1.0:1.0 |
| Embodiment 10 | 25 | 1.5:1.0 |
| Embodiment 11 | 40 | 0.01:1.0 |
| Embodiment 12 | 55 | 0.04:1.0 |
| Embodiment 13 | 60 | 0.1:1.0 |
| Embodiment 14 | 70 | 0.5:1.0 |
| Embodiment 15 | 75 | 0.8:1.0 |
| Embodiment 16 | 90 | 0.2:1.0 |
| Embodiment 17 | 70 | 0.15:1.0 |
| Embodiment 18 | 50 | 0.35:1.0 |
| Embodiment 19 | 30 | 0.65:1.0 |
| Embodiment 20 | 10 | 0.7:1.0 |
| Embodiment 21 | 25 | 0.02:1.0 |
| Comparative example 1 | 100 | 0.5:1.0 |
| Comparative example 2 | 100 | 0.45:1.0 |
| Comparative example 3 | 100 | 0.65:1.0 |
| Comparative example 4 | 100 | 0.8:1.0 |
| Comparative example 5 | 100 | 1.0：1.0 |
The reaction condition of table 4 embodiment and comparative example and reaction result.
| Sequence number | Reaction pressure/MPa | Reaction temperature/℃ | N-butene volume space velocity/h -1 | Methyl alcohol/n-butene (mol ratio) | N-butene conversion per pass/% |
| Embodiment 1 | 4.0 | 80 | 0.5 | 0.9 | 16.0 |
| Embodiment 2 | 5.0 | 100 | 1.5 | 2.5 | 17.5 |
| Embodiment 3 | 6.0 | 120 | 3.5 | 5.5 | 20.0 |
| Embodiment 4 | 7.0 | 140 | 5.0 | 7.5 | 17.8 |
| Embodiment 5 | 8.0 | 180 | 10.0 | 9.0 | 15.7 |
| Embodiment 6 | 6.0 | 120 | 2.0 | 1.0 | 14.5 |
| Embodiment 7 | 5.0 | 130 | 2.5 | 1.5 | 18.6 |
| Embodiment 8 | 6.0 | 120 | 1.0 | 2.0 | 18.8 |
| Embodiment 9 | 6.0 | 120 | 1.5 | 3.0 | 22.4 |
| Embodiment 10 | 6.0 | 130 | 1.0 | 1.5 | 24.0 |
| Embodiment 11 | 4.0 | 80 | 0.5 | 0.9 | 20.0 |
| Embodiment 12 | 5.0 | 100 | 1.5 | 2.5 | 17.8 |
| Embodiment 13 | 6.0 | 120 | 3.5 | 5.5 | 15.7 |
| Embodiment 14 | 7.0 | 140 | 5.0 | 7.5 | 14.5 |
| Embodiment 15 | 8.0 | 180 | 10.0 | 9.0 | 14.5 |
| Embodiment 16 | 6.0 | 120 | 2.0 | 1.0 | 18.6 |
| Embodiment 17 | 6.0 | 130 | 2.5 | 1.5 | 18.8 |
| Embodiment 18 | 5.0 | 120 | 1.0 | 2.0 | 22.4 |
| Embodiment 19 | 6.0 | 120 | 1.5 | 3.0 | 24.0 |
| Embodiment 20 | 6.0 | 130 | 1.0 | 1.5 | 15.7 |
| Embodiment 21 | 5.0 | 135 | 1.5 | 2.0 | 14.5 |
| Comparative example 1 | 6.0 | 130 | 1.5 | 1.0 | 12.4 |
| Comparative example 2 | 6.0 | 130 | 1.5 | 1.0 | 10.8 |
| Comparative example 3 | 6.0 | 130 | 1.5 | 1.0 | 9.6 |
| Comparative example 4 | 5.0 | 120 | 1.0 | 1.5 | 11.6 |
| Comparative example 5 | 5.0 | 120 | 1.0 | 1.5 | 10.7 |
Comparative example 1
With a certain amount of phosphomolybdic acid aqueous solution, flood a certain amount of Al
2o
324h, dry 12h at 110 ℃, then roasting 12h is prepared into catalyst at 500 ℃.Evaluating catalyst method is with embodiment 1, and catalyst forms in Table 3, and reaction result is in Table 4.
Comparative example 2
Other condition, with comparative example 1, just changes phosphomolybdic acid into phosphotungstic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Comparative example 3
Other condition, with comparative example 1, just changes phosphomolybdic acid into silico-tungstic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Comparative example 4
Other condition, with comparative example 1, just changes phosphomolybdic acid into arsenic molybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Comparative example 5
Other condition, with comparative example 1, just changes phosphomolybdic acid into germanium molybdic acid, and catalyst forms in Table 3, and reaction result is in Table 4.
Claims (9)
1. a process of preparing methyl sec-butyl ether, take n-butene and methyl alcohol as raw material, it is characterized in that: the catalyst of preparing methyl sec-butyl ether be take composite oxides as carrier, take heteropoly acid as active component, and described composite oxides are MgO-Al
2o
3, TiO
2-Al
2o
3and ZrO
2-Al
2o
3one or more of middle aluminium base composite oxides, described heteropoly acid is one or more in phosphotungstic acid, silico-tungstic acid, arsenowolframic acid, germanotungstic acid, phosphomolybdic acid, silicomolybdic acid, arsenic molybdic acid and germanium molybdic acid; The volume space velocity of n-butene is 0.5h
-1～10h
-1, the mol ratio of methyl alcohol and n-butene is 0.9:1～5:1,80 ℃～200 ℃ of reaction temperatures, and reaction pressure is 4.0 MPa～8.0MPa.
2. according to process claimed in claim 1, it is characterized in that: prepare in the catalyst of methyl sec-butyl ether Al in aluminium base composite oxides
2o
3weight content be 10%～90%.
3. according to process claimed in claim 1, it is characterized in that: prepare in the catalyst of methyl sec-butyl ether Al in aluminium base composite oxides
2o
3weight content be 25%～85%.
4. according to process claimed in claim 1, it is characterized in that: prepare in the catalyst of methyl sec-butyl ether Al in aluminium base composite oxides
2o
3weight content be 40%～75%.
5. according to the process described in claim 1,2,3 or 4, it is characterized in that: prepare in the catalyst of methyl sec-butyl ether, the weight ratio of heteropoly acid and aluminium base composite oxides is 0.01:1～2:1.
6. according to process claimed in claim 5, it is characterized in that: prepare in the catalyst of methyl sec-butyl ether, the weight ratio of heteropoly acid and aluminium base composite oxides is 0.05:1～1:1.
7. according to process claimed in claim 5, it is characterized in that: prepare in the catalyst of methyl sec-butyl ether, the weight ratio of heteropoly acid and aluminium base composite oxides is 0.2:1～0.5:1.
8. according to process claimed in claim 1, it is characterized in that: described n-butene is 1-butylene and/or 2-butylene, and the volume space velocity of n-butene is 0.5h
-1～5.0h
-1, the mol ratio of methyl alcohol and n-butene is 1:1～3:1, and reaction temperature is 80 ℃～160 ℃, and reaction pressure is 5.0 MPa～7.0MPa.
9. according to process claimed in claim 1, it is characterized in that: the volume space velocity of described n-butene is 0.5h
-1～2.0h
-1, the mol ratio of methyl alcohol and n-butene is 1:1～2:1, and reaction temperature is 100 ℃～140 ℃, and reaction pressure is 5.0 MPa～6.0MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4827048A (en) * | 1988-03-14 | 1989-05-02 | Texaco Chemical Company | Method for one-step synthesis of methyl t-butyl ether |
| CN1304798A (en) * | 2000-06-01 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Molecular sieve catalyst for synthesizing methyl tert-butyl ether and its preparing process |
| CN102909081A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Catalyst and method for preparing methyl sec-butyl ether |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4827048A (en) * | 1988-03-14 | 1989-05-02 | Texaco Chemical Company | Method for one-step synthesis of methyl t-butyl ether |
| CN1304798A (en) * | 2000-06-01 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Molecular sieve catalyst for synthesizing methyl tert-butyl ether and its preparing process |
| CN102909081A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Catalyst and method for preparing methyl sec-butyl ether |
Non-Patent Citations (2)
| Title |
|---|
| Al2O3-TiO2复合载体的制备与表征;韦以等;《石油化工》;20061231;第35卷(第2期);第176页第1栏第1段、表2 * |
| 韦以等.Al2O3-TiO2复合载体的制备与表征.《石油化工》.2006,第35卷(第2期),第173-177页. |
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