CN102875338B - Method for preparing glycerol ether by catalytic glycerol ether reaction - Google Patents
Method for preparing glycerol ether by catalytic glycerol ether reaction Download PDFInfo
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- CN102875338B CN102875338B CN201210405813.XA CN201210405813A CN102875338B CN 102875338 B CN102875338 B CN 102875338B CN 201210405813 A CN201210405813 A CN 201210405813A CN 102875338 B CN102875338 B CN 102875338B
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Abstract
The invention provides a method for preparing glycerol ether by catalytic glycerol ether reaction, particularly a method for generating glycerol ether by reacting glycerol or glycerite with olefin or alcohol under the action of a catalyst. The invention is characterized in that the catalyst is a functionalized graphene catalyst which is formed by connecting acidic organic functional group with catalytic activity onto graphene used as the support. The invention has the characteristics of high reaction activity, high polyether selectivity, mild reaction conditions and the like.
Description
Technical field
The present invention relates to a kind of method that catalyzing glycerol etherification reaction prepares glyceryl ether.
Background technology
Glycerine is a kind of reproducible industrial raw material, can produce in a large number in the hydrolytic process of animal-plant oil.Be that the glycerine polyether (glycerine diether, glycerine three ether) of Material synthesis has the physico-chemical property being suitable as fuel oil additive with glycerine.As glycerine tertiary butyl diether and the glycerine tertiary butyl three ether add in diesel oil and biofuel the quantity discharged that can reduce Tail Gas (solid particulate, hydrocarbon polymer and carbon monoxide etc.) to, low-temperature fluidity (cloud point and toughness) (the US 6015440A) of fuel oil can also be improved simultaneously.And the key that promotion take glycerine as Material synthesis glycerine polyether reaction industrialization develops effective catalyst.
According to the difference of adopted catalyst type, the method that the catalyzing glycerol etherification reaction worked out at present prepares glyceryl ether can be divided into: adopt the method for liquid acid homogeneous catalytic reaction and adopt the method for solid catalyst heterogeneous catalytic reaction.
The good homogeneous catalyst of effect has p-methyl benzenesulfonic acid (US 5476971A; A.Behr, L.Obendorf, Chem.Ing.Tech, 2001,73:1463-1467; A.Behr, L.Obendorf, Eng.Life Sci, 2002,2:185-189].Acid strong and fully can contact with reactant due to it, therefore its reactive behavior is higher, and not easily cause isobutene polymerisation when being raw material with iso-butylene.But because itself and product dissolve each other, be not easily separated from product after reaction, product postprocessing bothers and easily produces contaminative waste liquid, so its application is restricted.
The solid catalyst that can carry out inhomogeneous reaction has clear superiority in product separation.Good reaction effect has been obtained by reacting by the mesoporous silicon catalyst glycerine etherificate of sulfonic acid modified, but the easy inactivation of catalyzer, when reusing, the selectivity of reactive behavior and product all there occurs reduction (J.A.Melero, G.Vicente, G.Morales, et al.Appl.Catal.A, 2008,346:44-51).With the restriction of HBeta and HY acidic zeolite catalyzing glycerol etherification reaction by molecular sieve pore passage steric effect, the not high (K. of selectivity of polyether
d.Mravec, A.Kaszonyi, et al.Appl.Catal.A, 2007,328:1-13; L.Xiao, J.Mao, J.Zhou, et al.Appl.Catal.A:Gen, 2011,393:88-95).
As the c-based nanomaterial of a new generation, Graphene has attracted the interest of large quantities of researcher once coming out.Pure Graphene (Pristine graphene) is sp
2the two dimensional crystal that hydbridized carbon atoms forms with six-ring, and its surface of the Graphene adopting natural flake graphite chemical separation to make is containing a large amount of oxygen-containing functional group, be called as graphene oxide or graphene oxide (Graphene oxide), graphene oxide generates reduced graphene (Reduced graphene oxide) after reduction.The C-C bond of Graphene is very firm, has 2630m
2the bigger serface of/g, physical strength is high, stable chemical performance.At the reduced graphene produced after graphene oxide reduction, its basal plane and edge section carbon atom are sp
3hydridization and store and have active H, is therefore had the ability of carrying out chemical reaction with other organic molecules, can be synthesized the graphen catalyst of functionalization by surface chemical modification.But the relevant report of catalyzing glycerol etherification reaction up to the present, is not also carried out about the graphen catalyst utilizing grafting to have the acid organo-functional group of catalytic activity.
Summary of the invention
The object of this invention is to provide a kind of adopt heterogeneous catalytic reaction have that reactive behavior is high, polyether selectivity is good, reaction conditions is gentle, the method preparing glyceryl ether of good stability.
The object of the invention is to be achieved by the following technical programs.
The method that catalyzing glycerol etherification reaction of the present invention prepares glyceryl ether a kind of glycerine or glycerine solution and alkene or alcohol is reacted the method generating glyceryl ether under the effect of catalyzer, it is characterized in that, the catalyzer adopted is functionalization graphene catalyzer, it has following composition: be carrier with Graphene, and Graphene is connected with the acid organo-functional group with catalytic activity.
The reaction conditions of described glycerine etherification reaction is preferably: reaction pressure is normal pressure ~ 2MPa, and temperature of reaction is 60 ~ 90 DEG C, in glycerine solution the mass percentage of glycerine be 1% ~ be less than 100%, alkene is iso-butylene, and alcohol is the trimethyl carbinol or isopropylcarbinol.
After preferably adopting oxidation graft process, in conjunction with ultrasonic separation or dilatometry, crystalline flake graphite is prepared into graphene oxide as the Graphene of carrier, then the reduced graphene (namely utilizing the Graphene that chemical method prepares) that graphene oxide is prepared through reduction reaction.The Graphene that method obtains thus contains many active H on its basal plane and edge, can introduce other organo-functional groups (what introduce in the present invention is the acid organo-functional group with catalytic activity) by chemically modified substitute activity H on the C atom be connected with active H.This Graphene can synthesize voluntarily (such as can adopt the method synthesis recorded in CN 101549864A), also can adopt business-like product.
The modified catalyst prepared with the following method preferably adopted by described catalyzer: Graphene and the diazonium compound containing the acid organo-functional group with catalytic activity are disperseed in ethanol, in the ice-water bath of 0 ~ 5 DEG C and under Keep agitation, add Hypophosporous Acid, 50 solution to react, reaction product after filtration, salt pickling and washing after, lyophilize, obtains a modified catalyst (chemical grafting).The CH functional group (being expressed as H-C-Graphene) Graphene connecting active H (is expressed as [X-N with diazonium compound by the method
+≡ N] A
-or X-N=N-B, X are the acid organo-functional group with catalytic activity, A is the acid group example hydrochloric acid root, sulfate radical etc. that form diazonium salt; B is be the organic group of non-carbon with N coupling end) react, acid organo-functional group substitute activity H and being grafted on the C atom of Graphene.Reaction equation can be expressed as (situation when taking diazonium compound as diazonium salt is example):
In order to obtain better glycerol conversion yield and higher glycerine diether, glycerine three ether selectivity, more preferably carry out twice modified catalyst that modification again obtains using an above-mentioned modified catalyst as Graphene raw material, particularly preferably carry out three modified catalysts that modification again obtains using twice modified catalyst as Graphene raw material.
Specifically, the preparation method of described twice modified catalyst is as follows: Graphene and the diazonium compound containing the acid organo-functional group with catalytic activity are disperseed in ethanol, in the ice-water bath of 0 ~ 5 DEG C and under Keep agitation, add Hypophosporous Acid, 50 solution to react, reaction product after filtration, salt pickling and washing after, lyophilize, obtains a modified catalyst; Using a modified catalyst obtaining as Graphene raw material, repeat aforesaid operations, obtain twice modified catalyst.
The preparation method of three modified catalysts is as follows: Graphene and the diazonium compound containing the acid organo-functional group with catalytic activity are disperseed in ethanol, in the ice-water bath of 0 ~ 5 DEG C and under Keep agitation, add Hypophosporous Acid, 50 solution to react, reaction product after filtration, salt pickling and washing after, lyophilize, obtains a modified catalyst; Using a modified catalyst obtaining as Graphene raw material, repeat aforesaid operations, obtain twice modified catalyst; Using twice modified catalyst obtaining as Graphene raw material, repeat aforesaid operations, obtain three modified catalysts.
In above-mentioned reaction, each amounts of components is preferably: use 10 ~ 90 grammes per square metre nitrogen compounds relative to 1 gram of Graphene, uses 10 ~ 15 milliliters of ethanol and 20 ~ 30 milliliters of 50%(w/w relative to 1 grammes per square metre nitrogen compound) Hypophosporous Acid, 50 of concentration.Described diazonium compound is preferably diazobenzene sulfonic acid or diazobenzene sulfonic acid sodium.These diazonium compounds can be obtained through diazotization reaction by aminocompound, also can use business-like product.
Because Graphene is two-dimension plane structure, sterically hindered little, therefore use graphen catalyst catalyzing glycerol etherification reaction can provide open space for glycerine diether, the macromolecular synthesis of glycerine three ether, thus obtain higher glycerine diether, glycerine three ether selectivity.In addition, because graphen catalyst had both played acid organo-functional group (the preferred Phenylsulfonic acid functional group of the present invention) catalytic activity in glycerine etherification reaction, play again the advantage (namely formed solid catalyst and carry out heterogeneous catalytic reaction) of Graphene, while maintenance high reaction activity, therefore to turn avoid in homogeneous catalytic reaction system catalyzer and the unfavorable factor such as product difficulty is separated.And the present invention also has the advantages such as reaction conditions gentleness, catalyst stability be good.
Accompanying drawing explanation
Fig. 1 is the thermogravimetric characterization result of the sulfonated graphene catalyzer of preparation in embodiment 3.
Embodiment
The beneficial effect further illustrating embodiments of the present invention below in conjunction with embodiment and comparative example and produce; but the following examples are only the present invention's preferably embodiment; protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Embodiment 1
1. catalyst preparing:
(1) ultrasonic disperse of Graphene and diazonium salt: get 0.3g Graphene (adopting the method synthesis recorded in CN 101549864A), 9g (obtains through diazotization reaction by Sulphanilic Acid diazo Phenylsulfonic acid, detailed preparation process is see " Experiment of Organic Chemistry " (second edition), Lanzhou University, Fudan University, Wang Qinglian writes, P203) and 100ml dehydrated alcohol (analytical pure) put into the Erlenmeyer flask of 500ml, at room temperature 50Hz ultrasonic disperse 0.5 hour.
(2) grafting reaction: the Erlenmeyer flask crossed by ultrasonic disperse is inserted in ice-water bath, under in control bottle, fluid temperature stirs at 2 ~ 5 DEG C and at the continuing magnetic force of 300rpm, add 100ml 50%(w/w) Hypophosporous Acid, 50 react 30 minutes after, then add 100ml 50%(w/w) Hypophosporous Acid, 50 to continue under ice bath stirring reaction 1.5 hours.
(3) catalyzer aftertreatment: by the product filtering separation of (2), obtain the Graphene filter cake that grafting is modified, use 200ml hydrochloric acid soln (1mol/L) washing leaching cake afterwards, extremely neutral with deionized water wash again, vacuum freeze drier is put into dry 24 hours after filter cake is freezing, obtain fluffy functionalization graphene catalyzer (modified catalyst), called after " sulfonated graphene catalyzer ".
2. reaction test:
Get the beaker that 100mg sulfonated graphene catalyzer and 120ml dioxane (solvent) put into 200ml, under room temperature, 50Hz is after ultrasonic 20 minutes, transfers in reactor by the dispersion liquid obtained; In reactor, add 4g glycerine, reactor is loaded reaction unit and checks resistance to air loss; Then in reactor, pour 10g iso-butylene, reacting by heating still, start timing, carry out etherification reaction when temperature-stable is at 70 DEG C, reaction carries out 7 hours; After reaction terminates, collect gas-phase product and liquid product, catalyzer is reclaimed by filtration.
3. reaction result:
Collect gas-phase product and liquid product with gas-chromatography (adopt hydrogen flame detector (FID), hydrogen as carrier gas, marker method) analyze its composition.Result shows: glycerol conversion yield (transform the glycerine molar weight fallen calculate divided by the glycerine molar weight dropped in reaction raw materials to react) for 89%, the selectivity of the glycerine tertiary butyl one ether, glycerine tertiary butyl diether and the glycerine tertiary butyl three ether (with generate target product consume glycerine molar weight and calculate divided by the glycerine molar weight reacted away) be respectively 44%, 50% and 6%.
Embodiment 2
1. catalyst preparing: with the catalyst preparation process in embodiment 1, carries out twice modification.Be about to the modified catalyzer obtained for the first time and repeat the operation of catalyst preparation process (1) to (3) again, finally obtain the catalyzer of twice modification.
2. reaction test: with reaction test process in embodiment 1.
3. reaction result: glycerol conversion yield is 94%, the selectivity of the glycerine tertiary butyl one ether, glycerine tertiary butyl diether and the glycerine tertiary butyl three ether is respectively 40%, 52% and 8%.
Embodiment 3
1. catalyst preparing: with the catalyst preparation process in embodiment 1, carries out three modifications.Be about to the modified catalyzer obtained for the first time and repeat the operation of catalyst preparation process (1) to (3) again, obtain the catalyzer of twice modification, twice modified catalyzer obtained is repeated the operation of catalyst preparation process (1) to (3) again, finally obtains the catalyzer of three modifications.
2. reaction test: with reaction test process in embodiment 1.
3. reaction result: glycerol conversion yield is 96%, the selectivity of the glycerine tertiary butyl one ether, glycerine tertiary butyl diether and the glycerine tertiary butyl three ether is respectively 25%, 60% and 15%.
Embodiment 4
1. catalyst preparing: with the catalyst preparation process in embodiment 2.
2. reaction test: the consumption except sulfonated graphene catalyzer is except 50mg, other are with reaction test process in embodiment 1.
3. reaction result: glycerol conversion yield is 85%, the selectivity of the glycerine tertiary butyl one ether, glycerine tertiary butyl diether and the glycerine tertiary butyl three ether is respectively 60%, 37% and 3%.
Embodiment 5
1. catalyst preparing: with the catalyst preparation process in embodiment 2.
2. reaction test: except temperature of reaction is 90 DEG C, other are with reaction test process in embodiment 1.
3. reaction result: glycerol conversion yield is 83%, the selectivity of the glycerine tertiary butyl one ether, glycerine tertiary butyl diether and the glycerine tertiary butyl three ether is respectively 58%, 38% and 4%.
Embodiment 6
1. catalyst preparing: with the catalyst preparation process in embodiment 2.
2. reaction test: except pouring except 20g iso-butylene in reactor, other are with reaction test process in embodiment 1.
3. reaction result: glycerol conversion yield is 90%, the selectivity of the glycerine tertiary butyl one ether, glycerine tertiary butyl diether and the glycerine tertiary butyl three ether is respectively 25%, 60% and 15%.
Embodiment 7
1. catalyst preparing: with the catalyst preparation process in embodiment 3.
2. reaction test: with reaction test process in embodiment 6.
3. reaction result: glycerol conversion yield is 95%, the selectivity of the glycerine tertiary butyl one ether, glycerine tertiary butyl diether and the glycerine tertiary butyl three ether is respectively 16%, 59% and 25%.
Comparative example 1
1. catalyzer: p-methyl benzenesulfonic acid (analytical pure).
2. reaction test: get the beaker that 100mg p-methyl benzenesulfonic acid and 120ml dioxane put into 200ml, 50Hz is after ultrasonic 20 minutes under room temperature, transfers in reactor by the dispersion liquid obtained; In reactor, add 4g glycerine, reactor is loaded reaction unit and checks resistance to air loss; Then in reactor, pour 10g iso-butylene, reacting by heating still, start timing, carry out etherification reaction when temperature-stable is at 70 DEG C, reaction carries out 7 hours; After reaction terminates, collect gas-phase product and liquid product, catalyzer is reclaimed by filtration.
3. reaction result: glycerol conversion yield is 47%, the selectivity of the glycerine tertiary butyl one ether, glycerine tertiary butyl diether and the glycerine tertiary butyl three ether is respectively 74%, 22% and 4%.As can be seen here, under the same reaction conditions, the present invention is all better than the transformation efficiency of glycerine etherificate and selectivity taking p-methyl benzenesulfonic acid as the reaction result of catalyzer.
Comparative example 2
1. catalyzer: with the vitriol oil of 98% purity (Ke Miou reagent) for catalyzer, without any process.
2. reaction test: get the beaker that the 100mg vitriol oil and 120ml dioxane put into 200ml, 50Hz is after ultrasonic 20 minutes under room temperature, transfers in reactor by the dispersion liquid obtained; In reactor, add 4g glycerine, reactor is loaded reaction unit and checks resistance to air loss; Then in reactor, pour 10g iso-butylene, reacting by heating still, start timing, carry out etherification reaction when temperature-stable is at 70 DEG C, reaction carries out 7 hours; After reaction terminates, collect gas-phase product and liquid product, catalyzer is reclaimed by filtration.
3. reaction result: glycerol conversion yield is 30%, the selectivity of the glycerine tertiary butyl one ether, glycerine tertiary butyl diether and the glycerine tertiary butyl three ether is respectively 70%, 25% and 5%.As can be seen here, under the same reaction conditions, the present invention is all better than the reaction result of traditional sulfuric acid homogeneous catalyst to the transformation efficiency of glycerine etherificate and selectivity.
Comparative example 3
1. catalyzer: with not sulphur-modified Graphene for catalyzer.
2. reaction test: get the beaker that the not sulphur-modified Graphene of 100mg and 120ml dioxane put into 200ml, 50Hz is after ultrasonic 20 minutes under room temperature, transfers in reactor by the dispersion liquid obtained; In reactor, add 4g glycerine, reactor is loaded reaction unit and checks resistance to air loss; Then in reactor, pour 10g iso-butylene, reacting by heating still, start timing, carry out etherification reaction when temperature-stable is at 70 DEG C, reaction carries out 7 hours; After reaction terminates, collect gas-phase product and liquid product, catalyzer is reclaimed by filtration.
3. reaction result: substantially can't detect product.As can be seen here, in sulfonated graphene catalyzer used in the present invention, the sulfonic acid functional group of institute's grafting has played good catalytic activity effect.
In addition, the present invention, in order to investigate the thermostability of sulfonated graphene catalyzer, carries out thermogravimetric analysis (as shown in Figure 1) for the sulfonated graphene catalyzer of preparation in embodiment 3 to it.As can be seen from Figure 1, near 300 ~ 400 DEG C, there is the peak that dissociates in the Phenylsulfonic acid functional group of sulfonated graphene catalyst surface grafting, more stable within 200 DEG C.
Claims (6)
1. a catalyzing glycerol etherification reaction prepares the method for glyceryl ether, a kind of glycerine or glycerine solution and alkene are reacted the method generating glyceryl ether under the effect of catalyzer, it is characterized in that, the catalyzer adopted is functionalization graphene catalyzer, it has following composition: be carrier with Graphene, and Graphene is connected with the acid organo-functional group with catalytic activity; As the Graphene of carrier be adopt oxidation graft process, in conjunction with ultrasonic separation or dilatometry, crystalline flake graphite is prepared into graphene oxide after, then by reduced graphene that graphene oxide prepares through reduction reaction; The modified catalyst prepared with the following method adopted by described catalyzer: Graphene and the diazonium compound containing the acid organo-functional group with catalytic activity are disperseed in ethanol, in the ice-water bath of 0 ~ 5 DEG C and under Keep agitation, add Hypophosporous Acid, 50 solution to react, reaction product after filtration, salt pickling and washing after, lyophilize, obtains a modified catalyst.
2. method according to claim 1, is characterized in that, the reaction pressure of described glycerine etherification reaction is normal pressure ~ 2MPa, and temperature of reaction is 60 ~ 90 DEG C, in glycerine solution the mass percentage of glycerine be 1% ~ be less than 100%, alkene is iso-butylene.
3. method according to claim 1, it is characterized in that, described catalyzer replaces with twice modified catalyst adopted and prepare with the following method: Graphene and the diazonium compound containing the acid organo-functional group with catalytic activity are disperseed in ethanol, in the ice-water bath of 0 ~ 5 DEG C and under Keep agitation, add Hypophosporous Acid, 50 solution to react, reaction product after filtration, salt pickling and washing after, lyophilize, obtains a modified catalyst; Using a modified catalyst obtaining as Graphene raw material, repeat aforesaid operations, obtain twice modified catalyst.
4. method according to claim 1, it is characterized in that, described catalyzer replaces with three modified catalysts adopted and prepare with the following method: Graphene and the diazonium compound containing the acid organo-functional group with catalytic activity are disperseed in ethanol, in the ice-water bath of 0 ~ 5 DEG C and under Keep agitation, add Hypophosporous Acid, 50 solution to react, reaction product after filtration, salt pickling and washing after, lyophilize, obtains a modified catalyst; Using a modified catalyst obtaining as Graphene raw material, repeat aforesaid operations, obtain twice modified catalyst; Using twice modified catalyst obtaining as Graphene raw material, repeat aforesaid operations, obtain three modified catalysts.
5. according to the method in claim 1-4 described in any one, it is characterized in that, use 10 ~ 90 grammes per square metre nitrogen compounds relative to 1 gram of Graphene, use the Hypophosporous Acid, 50 of 10 ~ 15 milliliters of ethanol and 20 ~ 30 milliliter of 50% concentration relative to 1 grammes per square metre nitrogen compound.
6. according to the method in claim 1-4 described in any one, it is characterized in that, described diazonium compound is diazobenzene sulfonic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103910612B (en) * | 2014-03-06 | 2015-08-19 | 大连大学 | A kind of method of catalyst etherifying preparing glycerin ether from glycerol |
| CN103896772A (en) * | 2014-03-06 | 2014-07-02 | 大连大学 | Method for preparing glyceride by using catalytic esterification of glycerinum |
| CN104628682B (en) * | 2015-02-16 | 2017-11-10 | 大连大学 | A kind of method for being catalyzed 5 hydroxymethylfurfurals and preparing alkoxymethylfurfural |
| CN104628683B (en) * | 2015-02-16 | 2017-03-08 | 大连大学 | A kind of method that catalysis Fructose prepares 5 Hydroxymethylfurfural and 5 t-butoxymethyl furfurals |
| CN105732332B (en) * | 2016-02-05 | 2017-12-01 | 中北大学 | Glycerine alkyl ether production method and process units based on heterogeneous catalysis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476971A (en) * | 1995-01-13 | 1995-12-19 | Arco Chemical Technology, L.P. | Glycerine ditertiary butyl ether preparation |
| CN101549864A (en) * | 2009-04-30 | 2009-10-07 | 上海大学 | Method for simply and innoxiously preparing single-layer graphene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476971A (en) * | 1995-01-13 | 1995-12-19 | Arco Chemical Technology, L.P. | Glycerine ditertiary butyl ether preparation |
| CN101549864A (en) * | 2009-04-30 | 2009-10-07 | 上海大学 | Method for simply and innoxiously preparing single-layer graphene |
Non-Patent Citations (1)
| Title |
|---|
| Development of a Process for the Acid-Catalyzed Etherification of Glycerine and Isobutene Forming Glycerine Tertiary Butyl Ethers;Arno Behr et al.;《Eng. life Sci.》;20021231;第2卷(第7期);185-189 * |
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