CN104086380B - The preparation method of polymethoxy dimethyl ether - Google Patents
The preparation method of polymethoxy dimethyl ether Download PDFInfo
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- CN104086380B CN104086380B CN201410317689.0A CN201410317689A CN104086380B CN 104086380 B CN104086380 B CN 104086380B CN 201410317689 A CN201410317689 A CN 201410317689A CN 104086380 B CN104086380 B CN 104086380B
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- graphene oxide
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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Abstract
The preparation method of polymethoxy dimethyl ether adopts methyl alcohol and trioxymethylene to be a reactant, and graphene oxide is catalyzer, and at normal pressure, temperature of reaction is under 75-150 DEG C of condition, prepares polymethoxy dimethyl ether.The present invention has temperature of reaction gentleness, and transformation efficiency is high, and catalytic activity is high, the advantage of good stability.
Description
Technical field
The invention belongs to a kind of preparation method of polymethoxy dimethyl ether.
Technical background
Diesel oil is widely used because having higher thermo-efficiency, but due to the discharge severe contamination air of oxynitride and soot, the development of diesel engine is subject to the restriction of emission problem all the time.The effective ways addressed this problem add oxygenated fuel exactly in diesel oil, such as methyl alcohol, dme, methylal, methylcarbonate etc.Wherein polymethoxy dimethyl ether (DMMn) has higher oxygen level (42%-51%) and cetane value (>60), diesel oil combustion position within the engine can be improved, improve thermo-efficiency, reduce pollutant emission, be therefore considered to the diesel-dope having application prospect.
Polyoxymethylene dimethyl ether (DMM
n ) be the general designation of a class polyether material, its chemical formula can be expressed as CH
3(CH
2o)
n oCH
3, wherein n be more than or equal to 1 integer.The DMM of 20% is added in diesel oil
3-8, the highest 80%-90% that reduces of particulate emission, therefore, it is possible to add in diesel oil as the effective diesel-dope of one thus effectively reduce pollution, improves diesel oil rate of utilization.Therefore DMM is developed
nproduct is to extension methyl alcohol downstream industry chain, and exploitation high value added product is significant.
Tradition DMM
npreparation usually adopt methyl alcohol, formaldehyde, paraformaldehyde to be raw material, the catalyzer of employing generally includes liquid acid, solid acid, ionic liquid, Zeo-karb, ionic liquid etc.Wherein BASF AG adopts sulfuric acid or trifluoromethanesulfonic acid to be catalyzer, and dme and trioxymethylene are raw material, and reaction 8h obtains the DMM of massfraction 92%
2-4, liquid acid cost is lower, but liquid acid has severe corrosive to conversion unit, and catalyzer and product are not easily separated.Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences adopts ionic liquid to be catalyzer, uses methyl alcohol and methylal and trioxymethylene to react respectively, obtains the DMM of 43.7% and 53.4% at 60-120 DEG C
3-8, it is high that ionic liquid has catalytic activity, the feature little to equipment corrosion, but ionic liquid cost is higher, and catalyzer and product are difficult to be separated.Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences adopts molecular sieve HMCM-22 to be catalyzer, and with methyl alcohol and trioxymethylene for raw material, molecular sieve is heterogeneous catalytic system, catalyzer easily and product separation, reusable, be the catalyzer of a kind of good synthesis DMMn, but diesel-dope component DMM
3-8productive rate is only 29.39% at 120 DEG C, and result does not make people satisfied.
In recent years, the research of Graphene develops rapidly.Graphene is with SP by carbon atom
2the two-dimension nano materials with hexagonal honeycomb crystalline network of hybridized orbital composition, the advantage such as have that specific surface area is large, intensity is high and conductive capability is strong.Graphene-based carbon material is widely used in chemically modified electrode, chemical power source, catalyzer and pharmaceutical carrier and gas sensor etc.
Graphene oxide is usually used as the presoma preparing Graphene, but graphene oxide has application prospect well as a kind of novel C catalyst, professor DanielR.Dreyer finds to show catalytic activity well in the oxidation of graphene oxide catalysis aromatic alcohol and the hydration reaction of alkynes.Graphene oxide is applied to cellulosic hydrolysis by the Zhang Tao that Chinese science grinds Dalian Chemical Physics Research Institute, obtains the transformation efficiency of 58.6% and the productive rate of 49.9% at 150 DEG C.But, at present using graphene oxide as the research of the synthesis of catalyst polymethoxy dimethyl ether without pertinent literature and patent report.
Summary of the invention
The object of this invention is to provide a kind of temperature of reaction gentle, transformation efficiency is high, and catalytic activity is high, the method for synthesizing polymethoxy dimethyl ether for methyl alcohol and trioxymethylene of good stability.
Synthetic method of the present invention comprises the steps:
Adopt methyl alcohol and trioxymethylene to be reactant, graphene oxide is catalyzer, and at normal pressure, temperature of reaction is under 75-150 DEG C of condition, prepares polymethoxy dimethyl ether.
Methyl alcohol as above and trioxymethylene mol ratio are 0.1-10:1, and graphene oxide consumption is the 1.0-5.0wt% of total reactant.
Reaction times as above is 1-15h.
After reaction as above, liquid product and solid catalyst adopt supercentrifuge to be separated, the product liquid obtained after centrifugal.
Before reaction, graphene oxide is preserved in vacuum drying oven, prevents water that graphene oxide adsorbs and DMM
2occur miscible, be not easy to be separated.
Graphene oxide as above comprises following feature:
Specific surface area should be greater than 65m
2/ g, C/O molar ratio should between 0.8-1.5, and thickness in monolayer is between 0.6-0.8nm, and lateral dimension is at 200nm-10
between.
Graphene oxide of the present invention, first by Hummers legal system for graphite oxide.Its primary process is that the first-selected strong protonic acid and the vitriol oil and concentrated nitric acid of using processes crystalline flake graphite, obtain compound between graphite layers, then add strong oxidizer potassium permanganate to be oxidized it, obtain the graphite oxide being rich in hydroxyl and carboxyl, after obtaining graphite oxide, ultrasonic stripping graphite oxide again, lyophilize obtains graphene oxide.Hummers is shown in concrete preparation, W.S., Jr.; Offeman, R.E.J.Am.Chem.Soc.1958,80,1339(Hummers, W.S., Jr.; Offeman, R.E. JACS 1958,80,1339).
Compared with the prior art the present invention has following substantive distinguishing features:
1, using graphene oxide as catalyzer for being applied to methyl alcohol and trioxymethylene polymethoxy dimethyl ether, still belong to the first time.
2, reaction conditions is gentle, and range of reaction temperature is 75-150 DEG C, reaction easy handling.
3, reaction product is easily separated with graphite oxide catalyst.
4, graphite oxide catalyst of the present invention has very high activity, selectivity and life-span long, obtains the trioxymethylene transformation efficiency of 68-85% and the methanol conversion of 88-96% and the DMM of 40-69% under can realizing 75-150 DEG C of condition
2-8yield.
Embodiment
Below in conjunction with some embodiments, the present invention is further elaborated.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.
The product liquid obtained after centrifugal adopts Shimadzu GC2014C type gas chromatograph (DB – 1 quartz capillary column, hydrogen flame ionization detector) to analyze, and decane is interior mark, programmed temperature method analyzing and testing; Formaldehyde adopts Shimadzu GC14B type gas chromatograph (PorapakT packed column, TCD detector) to analyze.
Embodiment 1
10g crystalline flake graphite and 5.6g SODIUMNITRATE use the sulfuric acid mixing of 120ml98wt%, are placed in ice bath and stir 0.5h.30g potassium permanganate slowly joins in solution, is heated to 20 DEG C and keeps 0.5h, stir.200ml deionized water is slowly added the solution prepared, after solution is heated to 50 DEG C, keep 30min.By solution dilution, add the H of 5ml30wt%
2o
2, then centrifugally wash unnecessary metal ion off, vacuum-drying obtains graphite oxide powder.Graphite oxide powder is placed in deionized water, supersound process 1h, lyophilize obtains graphene oxide.The product specific surface area obtained equals 67m
2/ g, C/O molar ratio is 0.85, and thickness in monolayer is 0.65nm, lateral dimension 250nm.
Add that graphene oxide catalyzer accounts for total reactant quality in a kettle. 5%, the methyl alcohol added and the mol ratio of trioxymethylene are 2:1, under stirring, are heated to 120 DEG C, and reaction 10h, reaction product product liquid gas-chromatography after centrifugal is analyzed.Result shows, methanol conversion 86.82%, and trioxymethylene transformation efficiency 77.87%, catalyzer is to DMM
2-8selectivity reach 68.93wt%.
Embodiment 2
8g crystalline flake graphite and 5g SODIUMNITRATE use the sulfuric acid mixing of 150ml98wt%, are placed in ice bath and stir 1.5h.30g potassium permanganate slowly joins in solution, is heated to 30 DEG C and keeps 0.5h, stir.250ml deionized water is slowly added the solution prepared, after solution is heated to 98 DEG C, keep 50min.By solution dilution, add the H of 20ml30wt%
2o
2, then centrifugally wash unnecessary metal ion off, vacuum-drying obtains graphite oxide powder.Graphite oxide powder is placed in deionized water, supersound process 1h, lyophilize obtains graphene oxide.The product specific surface area obtained equals 65.6m
2/ g, C/O molar ratio is 0.88, and thickness in monolayer is 0.69nm, lateral dimension 230nm.
Add that graphene oxide catalyzer accounts for total reactant quality in a kettle. 1%, the methyl alcohol added and the mol ratio of trioxymethylene are 0.1:1, under stirring, are heated to 75 DEG C, and reaction 1h, reaction product product liquid gas-chromatography after centrifugal is analyzed.Result shows, methanol conversion 89.6%, and trioxymethylene transformation efficiency 70.21%, catalyzer is to DMM
2-8selectivity reach 41.32wt%.
Embodiment 3
10g crystalline flake graphite and 6g SODIUMNITRATE use the sulfuric acid mixing of 150ml98wt%, are placed in ice bath and stir 2h.30g potassium permanganate slowly joins in solution, is heated to 45 DEG C and keeps 1h, stir.500ml deionized water is slowly added the solution prepared, after solution is heated to 98 DEG C, keep 50min.By solution dilution, add the H of 30ml30%
2o
2, then centrifugally wash unnecessary metal ion off, vacuum-drying obtains graphite oxide powder.Graphite oxide powder is placed in deionized water, supersound process 1h, lyophilize obtains graphene oxide.The product specific surface area obtained equals 66m
2/ g, C/O molar ratio is 0.9, and thickness in monolayer is 0.7nm, lateral dimension 350nm.
Add that graphene oxide catalyzer accounts for total reactant quality in a kettle. 3%, the methyl alcohol added and the mol ratio of trioxymethylene are 4:1, under stirring, are heated to 100 DEG C, and reaction 8h, reaction product product liquid gas-chromatography after centrifugal is analyzed.Result shows, methanol conversion 91.73%, and trioxymethylene transformation efficiency 84.63%, catalyzer is to DMM
2-8selectivity reach 45.81wt%.
Embodiment 4
10g crystalline flake graphite and 6g SODIUMNITRATE use the sulfuric acid mixing of 380ml98wt%, are placed in ice bath and stir 2h.20g potassium permanganate slowly joins in solution, is heated to 45 DEG C and keeps 0.7h, stir.400ml deionized water is slowly added the solution prepared, after solution is heated to 98 DEG C, keep 30min.By solution dilution, add the H of 250ml30%
2o
2, then centrifugally wash unnecessary metal ion off, vacuum-drying obtains graphite oxide powder.Graphite oxide powder is placed in deionized water, supersound process 1h, lyophilize obtains graphene oxide.The product specific surface area obtained equals 67m
2/ g, C/O molar ratio is 0.85, and thickness in monolayer is 0.65nm, lateral dimension 360nm.
Add that graphene oxide catalyzer accounts for total reactant quality in a kettle. 2.5%, the methyl alcohol added and the mol ratio of trioxymethylene are 7:1, under stirring, are heated to 110 DEG C, and reaction 5h, reaction product product liquid gas-chromatography after centrifugal is analyzed.Result shows, methanol conversion 92.69%, and trioxymethylene transformation efficiency 80.92%, catalyzer is to DMM
2-8selectivity reach 68.00wt%.
Embodiment 5
10g crystalline flake graphite and 5.6g SODIUMNITRATE use the sulfuric acid mixing of 400ml98wt%, are placed in ice bath and stir 2h.30g potassium permanganate slowly joins in solution, is heated to 45 DEG C and keeps 0.5h, stir.500ml deionized water is slowly added the solution prepared, after solution is heated to 98 DEG C, keep 30min.By solution dilution, add the H of 30ml30%
2o
2, then centrifugally wash unnecessary metal ion off, vacuum-drying obtains graphite oxide powder.Graphite oxide powder is placed in deionized water, supersound process 2h, lyophilize obtains graphene oxide.The product specific surface area obtained equals 69m
2/ g, C/O molar ratio is 0.98, and thickness in monolayer is 0.76nm, lateral dimension 325nm.
Add that graphene oxide catalyzer accounts for total reactant quality in a kettle. 4%, the methyl alcohol added and the mol ratio of trioxymethylene are 4.5:1, under stirring, are heated to 150 DEG C, and reaction 10h, reaction product product liquid gas-chromatography after centrifugal is analyzed.Result shows, methanol conversion 88.98%, and trioxymethylene transformation efficiency 87.59%, catalyzer is to DMM
2-8selectivity reach 54.53wt%.
Embodiment 6
200g crystalline flake graphite and 10g SODIUMNITRATE use the sulfuric acid mixing of 2400ml98wt%, are placed in ice bath and stir 2h.90g potassium permanganate slowly joins in solution, is heated to 45 DEG C and keeps 1h, stir.1500ml deionized water is slowly added the solution prepared, after solution is heated to 98 DEG C, keep 50min.By solution dilution, add the H of 400ml30%
2o
2, then centrifugally wash unnecessary metal ion off, vacuum-drying obtains graphite oxide powder.Graphite oxide powder is placed in deionized water, supersound process 2h, lyophilize obtains graphene oxide.The product specific surface area obtained equals 69m
2/ g, C/O molar ratio is 0.96, and thickness in monolayer is 0.95nm, lateral dimension 560nm.
Add that graphene oxide catalyzer accounts for total reactant quality in a kettle. 5%, the methyl alcohol added and the mol ratio of trioxymethylene are 10:1, under stirring, are heated to 120 DEG C, and reaction 15h, reaction product product liquid gas-chromatography after centrifugal is analyzed.Result shows, methanol conversion 99.86%, and trioxymethylene transformation efficiency 76.61%, catalyzer is to DMM
2-8selectivity reach 60.79wt%.
Claims (3)
1. a preparation method for polymethoxy dimethyl ether, it is characterized in that adopting methyl alcohol and trioxymethylene to be reactant, graphene oxide is catalyzer, and at normal pressure, temperature of reaction is under 75-150 DEG C of condition, reaction 1-15h,
Prepare polymethoxy dimethyl ether;
Described methyl alcohol and trioxymethylene mol ratio are 0.1-10:1, and graphene oxide consumption is the 1.0-5.0wt% of total reactant;
Described graphene oxide comprises following feature:
Specific surface area should be greater than 65m
2/ g, C/O molar ratio should between 0.8-1.5, and thickness in monolayer is between 0.6-0.8nm, and lateral dimension is at 200nm-10
between, graphene oxide by Hummers legal system for graphite oxide;
Described Hummers legal system is that the first-selected strong protonic acid and the vitriol oil and concentrated nitric acid of using processes crystalline flake graphite for graphite oxide process, obtain compound between graphite layers, then add strong oxidizer potassium permanganate to be oxidized it, obtain the graphite oxide being rich in hydroxyl and carboxyl, after obtaining graphite oxide, ultrasonic stripping graphite oxide again, lyophilize obtains graphene oxide.
2. the preparation method of a kind of polymethoxy dimethyl ether as claimed in claim 1, is characterized in that reacting rear liquid product adopts supercentrifuge to be separated with solid catalyst, the product liquid obtained after centrifugal.
3. the preparation method of a kind of polymethoxy dimethyl ether as claimed in claim 1, is characterized in that react front graphene oxide preserves in vacuum drying oven.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962318A (en) * | 2009-07-24 | 2011-02-02 | 中国科学院兰州化学物理研究所 | Method for synthesizing polymethoxy dimethyl ether under catalysis of geminal dicationic ionic liquid |
| CN103288607A (en) * | 2013-06-26 | 2013-09-11 | 苏州奥索特新材料有限公司 | Synthetic method of polymethoxy dimethylether |
| CN103420812A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Polymethoxy dimethyl ether preparation method |
| CN103739458A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Preparation method of polyoxymethylene dimethyl ethers |
| CN103880614A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Synthetic method for polyoxymethylene dimethyl ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AU6032499A (en) * | 1998-11-12 | 2000-06-05 | Bp Amoco Corporation | Preparation of polyoxymethylene dimethyl ethers by acid-activated catalytic conversion of methanol with formaldehyde |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962318A (en) * | 2009-07-24 | 2011-02-02 | 中国科学院兰州化学物理研究所 | Method for synthesizing polymethoxy dimethyl ether under catalysis of geminal dicationic ionic liquid |
| CN103420812A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Polymethoxy dimethyl ether preparation method |
| CN103739458A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Preparation method of polyoxymethylene dimethyl ethers |
| CN103880614A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Synthetic method for polyoxymethylene dimethyl ether |
| CN103288607A (en) * | 2013-06-26 | 2013-09-11 | 苏州奥索特新材料有限公司 | Synthetic method of polymethoxy dimethylether |
Non-Patent Citations (1)
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| 改进Ｈｕｍｍｅｒｓ法化学合成石墨烯及其表征;洪菲等;《化学与生物工程》;20121231;第29卷(第5期);第31-33页 * |
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