CN102909041B - Method for synthesizing methyl sec-butyl ether - Google Patents
Method for synthesizing methyl sec-butyl ether Download PDFInfo
- Publication number
- CN102909041B CN102909041B CN201110217560.9A CN201110217560A CN102909041B CN 102909041 B CN102909041 B CN 102909041B CN 201110217560 A CN201110217560 A CN 201110217560A CN 102909041 B CN102909041 B CN 102909041B
- Authority
- CN
- China
- Prior art keywords
- sec
- catalyst
- methyl
- alcohol
- butyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a catalyst for synthesizing methyl sec-butyl ether, a preparation method and an application thereof. The catalyst employs silica gel as a carrier and an acidic salt of cesium phosphotungstate as an active component, and adopts a two-step isovolumetric impregnation method to prepare the supported catalyst of the acidic salt (CS2.5H0.5PW12O40) of the cesium phosphotungstate. The methyl sec-butyl ether (MSBE) is prepared by continuously passing reaction materials composed of sec-butyl alcohol and methyl alcohol through a fixed bed reactor filled with the catalyst and via an intermolecular dehydration substitution reaction. Continuous production of the supported catalyst of the acidic salt (CS2.5H0.5PW12O40) of the cesium phosphotungstate on the fixed bed reactor is realized; the reaction process is simple in operation; and the catalyst has high activity, is easy to recycle and can be used repeatedly.
Description
Technical field
The invention provides Catalysts and its preparation method and the application of a kind of synthesizing methyl sec-butyl ether (MSBE).
Technical background
Methyl sec-butyl ether (MSBE) has identical chemical formula and chemical bond with methyl tertiary butyl ether(MTBE) (MTBE), and atomic arrangement is different, and both are isomer each other.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, can polluted underground water source, so MTBE has been prepared to forbid in the ground such as California, USA.Although up to now, the domestic purpose of still not forbidding MTBE in gasoline, over a period to come, MTBE will continue to become the main component of clean gasoline, but in the long run, China is in line with international standards, and the trend that California, USA forbidding and the whole America may be forbidden MTBE in real time will be brought negative influence to MTBE, especially to exporting the gasoline of the U.S., will be limited.And both toxicity is compared, methyl sec-butyl ether (MSBE) toxic concentration is 141g/m
3, in 15 minutes, small white mouse is lethal; And the half lethal concentration (LC of methyl tertiary butyl ether(MTBE) (MTBE) to small white mouse
50) be 7.6mmol/L, be equivalent to 669.94g/m
3, be 4.75 times of MSBE.Therefore, methyl sec-butyl ether (MSBE) can be used as the substitute products of methyl tertiary butyl ether(MTBE) (MTBE), as 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.
table 1: under 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 the conversion per pass of course of reaction n-butene lower (generally lower than 5%), a large amount of n-butenes need to be carried out to separation and circulation, energy consumption is larger, and 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.
table 2: the main physical parameter of common resin catalyst.
| 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 the present invention adopts the substitution reaction mechanism of sec-butyl alcohol and the intermolecular dehydration of methyl alcohol process to make methyl sec-butyl ether (MSBE), the reaction mechanism that both prepare object product is different, show after deliberation, the above-mentioned catalyst for the preparation of methyl tertiary butyl ether(MTBE) (MTBE) is very unsuitable to the course of reaction of synthesizing methyl sec-butyl ether (MSBE).
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of synthesizing methyl sec-butyl ether catalyst and its preparation method and application, when catalyst of the present invention is used for preparing methyl sec-butyl ether with dehydration between sec-butyl alcohol and methanol molecules, there is sec-butyl alcohol conversion per pass height and the selective advantages of higher of MSBE.
Synthesizing methyl sec-butyl ether catalyst of the present invention, take silica gel as carrier, and active component is Tricesium dodecatungstophosphate acid salt, and the molecular formula of Tricesium dodecatungstophosphate acid salt is C
s2.5h
0.5pW
12o
40, the load capacity of Tricesium dodecatungstophosphate acid salt is catalyst weight 20%～50%, is preferably 30%～40%.
The preparation method of synthesizing methyl sec-butyl ether catalyst of the present invention, comprises following content:
(1) get silica-gel carrier, preparation cesium carbonate solution and Salkowski's solution;
(2) with cesium carbonate solution impregnation silica-gel carrier, then dry, roasting;
(3) the material dipping Salkowski's solution that step (2) obtains, then drying and roasting, obtain final catalyst.
In the above-mentioned method for preparing catalyst of the present invention, silica-gel carrier can be used common commercially available prod, also can prepare by this area conventional method.In cesium carbonate (caesium 133) solution and Salkowski's solution, the consumption of solute is by the required active component Determination of quantity of final catalyst.
In the above-mentioned method for preparing catalyst of the present invention, two impregnation steps can adopt conventional impregnation method, as incipient impregnation, spray, supersaturation impregnating.
In the above-mentioned method for preparing catalyst of the present invention, being dried as normal condition of step (2) and step (3), as being dried 5～20 hours at 80～200 ℃, the roasting condition of step (2) is roasting 3 ~ 10 hours at 300 ~ 400 ℃, and the roasting condition of step (3) is roasting 2 ~ 14 hours at 400 ~ 550 ℃.
Methyl sec-butyl ether catalyst of the present invention is prepared the application in methyl sec-butyl ether at methyl alcohol and sec-butyl alcohol through intermolecular dehydration, and during the liquid of sec-butyl alcohol, volume space velocity is 1.0h
-1～18.0h
-1; The mol ratio of methyl alcohol and sec-butyl alcohol is 0.5:1～15.0:1; Reaction temperature is 100 ℃～200 ℃; Reaction pressure is 1.0MPa～5.0MPa.
Methyl alcohol of the present invention and sec-butyl alcohol are prepared in the method for methyl sec-butyl ether (MSBE) through intermolecular dehydration, and during the liquid of sec-butyl alcohol, volume space velocity is preferably 2.0h
-1～10.0h
-1; The mol ratio of methyl alcohol and sec-butyl alcohol is preferably 2.0:1～6.0:1; Reaction temperature is preferably 120 ℃～180 ℃; Reaction pressure is preferably 2.0 MPa～4.0MPa.
Methyl alcohol of the present invention and sec-butyl alcohol are prepared in the method for methyl sec-butyl ether (MSBE) through intermolecular dehydration, and during the liquid of sec-butyl alcohol, volume space velocity is preferably 2.0h
-1～6.0h
-1; The mol ratio of methyl alcohol and sec-butyl alcohol is preferably 2.0:1～4.0:1; Reaction temperature is preferably 120 ℃～160 ℃; Reaction pressure is preferably 2.0 MPa～3.0MPa.
Acid salt (the C of typical heteropoly acid phosphotungstic acid and its esters acid Tricesium dodecatungstophosphate catalyst and carried phospho-tungstic acid caesium of the present invention
s2.5h
0.5pW
12o
40) catalyst compares, this has larger solubility phosphotungstic acid in water and polar solvent, and heteropoly acid separately or load on suitable carrier and all can be dissolved in reactant or solvent, very easily runs off, and causes active decline, and polluted product; And acid Tricesium dodecatungstophosphate particle is too little, cause separation difficulty, be difficult to be used on fixed bed reactors.Acid salt (the C of carried phospho-tungstic acid caesium prepared by the present invention
s2.5h
0.5pW
12o
40) catalyst, overcome the shortcoming of typical heteropoly acid phosphotungstic acid and its esters acid Tricesium dodecatungstophosphate, on fixed bed reactors, realized serialization production, course of reaction is easy and simple to handle, catalyst reaction activity is high, can reuse, and is eco-friendly new technology.
Synthesizing methyl sec-butyl ether catalyst of the present invention passes through in intermolecular dehydration at methyl alcohol and sec-butyl alcohol with the acid salt catalyst of carried phospho-tungstic acid caesium, there is the selective of very high feed stock conversion and object product, catalyst stability is good, has outstanding serviceability.
The specific embodiment
Below by embodiment, further illustrate method of the present invention and effect.In embodiment, the conversion per pass calculating formula of sec-butyl alcohol is as follows.
Sec-butyl alcohol weight * 100% of the conversion per pass of sec-butyl alcohol=(the sec-butyl alcohol weight adding-unreacted sec-butyl alcohol weight)/add;
MSBE selective=be converted into sec-butyl alcohol weight * 100% of sec-butyl alcohol weight/conversion of object product MSBE.
The present invention obtains the substitution reaction mechanism of ether compound according to alcohol and the intermolecular Dehydration of alcohol, for methyl alcohol and sec-butyl alcohol, pass through intermolecular Dehydration for the reaction characteristics of methyl sec-butyl ether (MSBE), adopts the acid salt (C of carried phospho-tungstic acid caesium
s2.5h
0.5pW
12o
40) as catalyst, under suitable reaction condition, react, overcome typical heteropoly acid and its esters phosphotungstic acid, acid Tricesium dodecatungstophosphate, in use easily loss and particle are too little, cause separation difficulty, be difficult to be used in the shortcoming on fixed bed reactors, on fixed bed reactors, realized serialization production, course of reaction is easy and simple to handle, and the reactivity of catalyst is high, easily reclaim, and reusable.
[embodiment 1]
Acid salt (the C of carried phospho-tungstic acid caesium
s2.5h
0.5pW
12o
40) method for preparing catalyst:
Adopt two step equi-volume impregnatings, get appropriate cesium carbonate (C
s2cO
3) be dissolved in deionized water, carrier silica gel is dipped in above-mentioned solution, sample is dried at 120 ℃, and at 350 ℃, roasting is 5 hours.
By quantitative phosphotungstic acid (H
3pW
12o
40) be dissolved in deionized water, the sample after above-mentioned roasting is dipped in Salkowski's solution, after drying at 120 ℃, at 450 ℃, roasting is 4 hours, obtains catalyst A.
Through XRD analysis, the acid salt (C that the active component of catalyst A is Tricesium dodecatungstophosphate
s2.5h
0.5pW
12o
40), in catalyst, active component content is by weight 38%.
The consumption that changes cesium carbonate and phosphotungstic acid, other condition is constant, obtains catalyst B, and the mass content of the acid salt of active component Tricesium dodecatungstophosphate in catalyst is 20%.
[embodiment 2~
10]
By the acid salt (C of the carried phospho-tungstic acid caesium of embodiment 1 preparation
s2.5h
0.5pW
12o
40) catalyst A is applied to methyl alcohol and sec-butyl alcohol passes through in the course of reaction of intermolecular Dehydration for methyl sec-butyl ether (MSBE).
Course of reaction adopts the fixed bed reactors (material is stainless steel) of Φ 20mm * 1000mm.Reactor is divided into three sections of fillings, and a certain amount of quartz sand is loaded in bottom, and the acid salt (C of 30ml carried phospho-tungstic acid caesium is loaded at position, stage casing
s2.5h
0.5pW
12o
40) catalyst, top loading quartz sand is until fill up.
With the air in nitrogen replacement fixed bed reactors, until airtight qualified after, methyl alcohol and sec-butyl alcohol are sent into preheater by measuring pump ratio as requested, by entering above-mentioned fixed bed reactors after reaction mass preheating, carry out dehydration.Reaction temperature is controlled at 105 ℃, recycles unreacted material.
table 3 embodiment 2 ~ 10 reaction conditions and reaction result.
| Sequence number | Reaction pressure/MPa | Volume space velocity/the h of sec-butyl alcohol -1 | Methyl alcohol/sec-butyl alcohol (mol ratio) | Sec-butyl alcohol conversion per pass/% | MSBE is selective/% |
| Embodiment 2 | 1.0 | 1.0 | 0.5 | 17.9 | 98.6 |
| Embodiment 3 | 2.0 | 2.5 | 3.0 | 32.0 | 98.2 |
| Embodiment 4 | 2.5 | 4.0 | 6.0 | 31.9 | 96.5 |
| Embodiment 5 | 5.0 | 10.0 | 10.0 | 24.8 | 98.1 |
| Embodiment 6 | 1.5 | 15.0 | 15.0 | 14.5 | 96.8 |
| Embodiment 7 | 4.0 | 5.0 | 13.0 | 18.7 | 96.5 |
| Embodiment 8 | 5.0 | 2.0 | 12.0 | 21.6 | 96.3 |
| Embodiment 9 | 1.5 | 10.0 | 1.0 | 23.9 | 95.6 |
| Embodiment 10 | 3.5 | 18.0 | 14.0 | 17.3 | 96.9 |
[embodiment 11 ~ 19]
By the acid salt (C of the carried phospho-tungstic acid caesium of embodiment 1 preparation
s2.5h
0.5pW
12o
40) catalyst B is applied to methyl alcohol and sec-butyl alcohol passes through in the course of reaction of intermolecular Dehydration for methyl sec-butyl ether (MSBE), reaction pressure is controlled at 2.0MPa, recycles unreacted material.
table 4 embodiment 11 ~ 19 reaction conditions and reaction result.
| Sequence number | Reaction temperature/℃ | Volume space velocity/the h of sec-butyl alcohol -1 | Methyl alcohol/sec-butyl alcohol (mol ratio) | Sec-butyl alcohol conversion per pass/% | MSBE is selective/% |
| Embodiment 11 | 100 | 2.0 | 1.5 | 14.6 | 93.8 |
| Embodiment 12 | 120 | 2.5 | 2.0 | 27.1 | 97.9 |
| Embodiment 13 | 150 | 4.0 | 3.5 | 28.3 | 96.6 |
| Embodiment 14 | 130 | 5.5 | 4.0 | 25.6 | 98.4 |
| Embodiment 15 | 160 | 6.0 | 10.0 | 23.5 | 94.8 |
| Embodiment 16 | 200 | 14.0 | 9.0 | 17.1 | 95.6 |
| Embodiment 17 | 180 | 15.0 | 3.0 | 21.3 | 97.1 |
| Embodiment 18 | 170 | 17.0 | 7.5 | 17.3 | 94.6 |
| Embodiment 19 | 110 | 18.0 | 1.0 | 14.1 | 95.8 |
[embodiment 20]
Acid salt (the C of working load type Tricesium dodecatungstophosphate
s2.5h
0.5pW
12o
40) catalyst A, according to the operating condition of embodiment 3, carry out 1500 hours stability experiments.Within the scope of 1500 hours, sec-butyl alcohol conversion per pass remains on 32.0% left and right, and MSBE selectively remains on 98.0% left and right, with initial conversion per pass with selectively compare, substantially remain unchanged.
Use phosphotungstic acid to load on silica-gel carrier, phosphotungstic acid load capacity is identical with the molal quantity of the acid salt of Tricesium dodecatungstophosphate, and by the operating condition of embodiment 3, when reaction starts, sec-butyl alcohol conversion per pass is 33.4%, MSBE is selectively 95.8%, turn round after 500 hours, it is selectively 93.5% that sec-butyl alcohol conversion per pass drops to 25.7%, MSBE, turn round after 1500 hours, reaction temperature improves 50 ℃, and it is selectively 78.6% that sec-butyl alcohol conversion per pass still only has 13.5%, MSBE.
Claims (9)
1. a method for synthesizing methyl sec-butyl ether, is characterized in that: under the effect of catalyst, methyl alcohol and sec-butyl alcohol are prepared methyl sec-butyl ether through intermolecular dehydration, and during the liquid of sec-butyl alcohol, volume space velocity is 1.0h
-1～18.0h
-1; The mol ratio of methyl alcohol and sec-butyl alcohol is 0.5:1～15.0:1; Reaction temperature is 100 ℃～200 ℃; Reaction pressure is 1.0MPa～5.0MPa, and described catalyst be take silica gel as carrier, and active component is Tricesium dodecatungstophosphate acid salt, and the molecular formula of Tricesium dodecatungstophosphate acid salt is C
s2.5h
0.5pW
12o
40, the load capacity of Tricesium dodecatungstophosphate acid salt is catalyst weight 20%～50%.
2. method according to claim 1, is characterized in that the preparation process of catalyst comprises following content:
(1) get silica-gel carrier, preparation cesium carbonate solution and Salkowski's solution;
(2) with cesium carbonate solution impregnation silica-gel carrier, then dry, roasting;
(3) the material dipping Salkowski's solution that step (2) obtains, then drying and roasting, obtain final catalyst.
3. it is characterized in that in accordance with the method for claim 2: in cesium carbonate solution and Salkowski's solution, the consumption of solute is by the required active component Determination of quantity of final catalyst.
4. it is characterized in that in accordance with the method for claim 2: the described impregnation steps of step (2) and step (3) adopts incipient impregnation, sprays or supersaturation dipping.
5. it is characterized in that in accordance with the method for claim 2: being dried at 80～200 ℃ of step (2) and step (3) is dried 5～20 hours.
6. it is characterized in that in accordance with the method for claim 2: the roasting condition of step (2) is roasting at 300～400 ℃ 3～10 hours.
7. it is characterized in that in accordance with the method for claim 2: the roasting condition of step (3) is roasting at 400～550 ℃ 2～14 hours.
8. it is characterized in that in accordance with the method for claim 1: during the liquid of sec-butyl alcohol, volume space velocity is 2.0h
-1～10.0h
-1; The mol ratio of sec-butyl alcohol and methyl alcohol is 2.0:1～6.0:1; Reaction temperature is 120 ℃～180 ℃; Reaction pressure is 2.0MPa～4.0MPa.
9. it is characterized in that in accordance with the method for claim 1: during the liquid of sec-butyl alcohol, volume space velocity is 2.0h
-1～6.0h
-1; The mol ratio of sec-butyl alcohol and methyl alcohol is 2.0:1～4.0:1; Reaction temperature is 120 ℃～160 ℃; Reaction pressure is 2.0MPa～3.0MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110217560.9A CN102909041B (en) | 2011-08-01 | 2011-08-01 | Method for synthesizing methyl sec-butyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110217560.9A CN102909041B (en) | 2011-08-01 | 2011-08-01 | Method for synthesizing methyl sec-butyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102909041A CN102909041A (en) | 2013-02-06 |
| CN102909041B true CN102909041B (en) | 2014-10-15 |
Family
ID=47607756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110217560.9A Active CN102909041B (en) | 2011-08-01 | 2011-08-01 | Method for synthesizing methyl sec-butyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102909041B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103934027B (en) * | 2014-04-24 | 2015-12-30 | 南京德灿化学有限公司 | A kind of solid acid catalyst and its preparation method and application |
| CN108435195B (en) * | 2018-04-25 | 2020-08-07 | 辽宁科技学院 | Preparation method and application of nano cobalt cesium tungstate |
| CN117524570A (en) * | 2023-11-29 | 2024-02-06 | 温州网牌电线电缆有限公司 | High-temperature-resistant double-layer ceramic mica fireproof wire |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4524427B2 (en) * | 2004-09-24 | 2010-08-18 | 国立大学法人北海道大学 | Composition comprising heteropolyacid salt and inorganic oxide and method for producing the same |
| CN100402518C (en) * | 2004-12-30 | 2008-07-16 | 浙江工业大学 | Application of cesium phosphotungstic acid as catalyst for synthesizing acetyl thiophene |
| CN100430319C (en) * | 2005-10-20 | 2008-11-05 | 复旦大学 | Synthesis method of solid ultrastrong acid cesium phospho-welframate |
| CN102127466A (en) * | 2011-01-30 | 2011-07-20 | 山东大学 | Fuel oil oxidative desulfurization method based on silica gel loaded with cesium salt catalyst of heteropoly acid |
-
2011
- 2011-08-01 CN CN201110217560.9A patent/CN102909041B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102909041A (en) | 2013-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109225337B (en) | MOFs (metal-organic frameworks) -encapsulated ionic liquid catalyst and preparation and application thereof | |
| CN101961660B (en) | Porous hybrid-resin solid acid catalyst and preparation method thereof | |
| CN102909077B (en) | Metal-modified cation exchange resin catalyst, preparation method and application thereof | |
| CN102527411B (en) | Catalyst for preparing isoolefin by cracking tertiary alkyl ether, preparation method for catalyst and application of catalyst | |
| JPS587614B2 (en) | Continuous production of lower alcohols, especially isopropanol | |
| CN102909041B (en) | Method for synthesizing methyl sec-butyl ether | |
| CN105618137A (en) | Porous acidic resin catalyst, preparation method and applications thereof | |
| CN113198535B (en) | Preparation method of ceramic surface supported catalytic filler | |
| CN102909081B (en) | Catalyst and method for preparing methyl sec-butyl ether | |
| CN102911019B (en) | Preparation method and application of methyl sec-butyl ether | |
| CN102909075B (en) | Catalyst and method for preparing methyl sec-butyl ether | |
| CN105585456B (en) | The method for preparing polyoxymethylene dimethyl ethers | |
| CN103044214B (en) | Preparation method of ethyl tert butyl ether | |
| CN108057458A (en) | It is a kind of for catalyst of synthesizing methyl tertbutyl ether and its preparation method and application | |
| CN109590029B (en) | Ion exchange resins and uses thereof | |
| CN105583008B (en) | Polyoxymethylene dimethyl ethers catalyst and preparation method thereof | |
| CN101823005B (en) | Catalyst for preparing dimethyl ether from low-temperature methanol by gas phase de-hydration, preparation method and application | |
| CN105585461B (en) | The synthetic method of polyoxymethylene dimethyl ethers | |
| CN103787843B (en) | A kind of method preparing tert amyl methyl ether(TAME) | |
| CN105585460B (en) | The method of synthesizing polyoxymethylene dimethyl ethers | |
| CN101357881B (en) | Method for method for synthesizing dihydromyrcenol from dihydro laurene using niobic acid catalyst | |
| CN109575292B (en) | Ion exchange resin and use thereof | |
| Zhong et al. | Postsynthetic acid modification of amino-tagged metal-organic frameworks: Structure-function relationship for catalytic 5-hydroxymethylfurfural synthesis | |
| CN105566076B (en) | The preparation method of polyoxymethylene dimethyl ethers | |
| CN101497041B (en) | Method for preparing palladium-carrying catalyst with nano Pd by suspension polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |