CN103848729A - Method for preparing polyoxymethylenedimethylether by using methanol and formaldehyde - Google Patents
Method for preparing polyoxymethylenedimethylether by using methanol and formaldehyde Download PDFInfo
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- CN103848729A CN103848729A CN201210520979.6A CN201210520979A CN103848729A CN 103848729 A CN103848729 A CN 103848729A CN 201210520979 A CN201210520979 A CN 201210520979A CN 103848729 A CN103848729 A CN 103848729A
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- reaction
- formaldehyde
- exchange resin
- styrene type
- tosic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing polyoxymethylenedimethylether by using methanol and formaldehyde. The method mainly comprises the following step: reacting methanol with formaldehyde under the condition that the pressure is 0.1-6.0MPa and the reaction air speed is 0.1-5,000 h<-1> in the presence of a catalyst to obtain a target object CH3O(CH2O)xCH3, wherein X is more than or equal to 3 and less than or equal to 8. The method is characterized in that the catalyst is a supported catalyst obtained by loading p-toluenesulfonic acid onto styrene type acid cation exchange resin. By replacing styrene type acid cation exchange resin (catalyst) used in the conventional method for preparing CH3O(CH2O)xCH3 (X is more than or equal to 3 and less than or equal to 8) with the supported catalyst obtained by loading p-toluenesulfonic acid onto styrene type acid cation exchange resin, the selectivity of preparation reactions is enhanced.
Description
Technical field
The present invention relates to a kind of production method of polymethoxy methylal, specifically, relate to a kind of method of being prepared polymethoxy methylal by methyl alcohol and formaldehyde.
Background technology
Polymethoxy methylal (is called for short DMM
x) be a kind of oil dope, its average cetane value (CN) value is 76, and oxygen level is high.DMM
xcan improve the calorific value of diesel oil and reduce the discharge of tail gas.Therefore, DMM
xpreparation enjoy the concern of scientists.
So far, existing many sections of bibliographical informations DMM
xpreparation method.As EP 1505049A1 discloses: having under sulfonic acid or halogenosulfonic acid (catalyzer) existence condition, prepared the method for DMMx by methyl alcohol and formaldehyde reaction.In prior art, have that feed stock conversion is low, DMMx(3≤X≤8 in product) problem such as the not high and complex process of selectivity.Tracing it to its cause, may be selected preparation DMM in prior art
3-8catalyzer there is some defect.
Sign in this, provide one to be applicable to prepare DMM by methyl alcohol and formaldehyde reaction
3-8novel catalyzer, become the technical issues that need to address of the present invention.
Summary of the invention
The present inventor finds through extensive and deep research: existing styrene type acidic cation-exchange resin is carried out to suitable modification, be applicable to prepare DMM by methyl alcohol and formaldehyde reaction through the styrene type acidic cation-exchange resin of modification
3-8, and DMM
3-8selectivity increase significantly, DMM
3-8product (its molecular formula: CH
3o (CH
2o)
xcH
3, 3≤X≤8) selectivity can improve 10%～20%.
One object of the present invention is, provides a kind of and prepares polymethoxy methylal (CH by methyl alcohol and formaldehyde
3o (CH
2o)
xcH
3, 3≤X≤8) method, overcome the defect existing in prior art.
Method of the present invention, its key step is: at 0.1MPa～6.0MPa, (preferred reaction pressure is 0.8MPa～3.0MPa), the air speed of reaction is 0.1h
-1～5000h
-1(preferred reaction velocity is: 1h
-1～1000h
-1) and catalyzer existence condition under, in 40 DEG C～150 DEG C (preferred temperature of reaction is 60 DEG C～90 DEG C, and best temperature of reaction is 70 DEG C～80 DEG C) reactions, obtain target compound (CH by methyl alcohol and formaldehyde
3o (CH
2o)
xcH
3, 3≤X≤8); It is characterized in that, wherein said catalyzer is: the loaded catalyst being obtained by styrene type acidic cation-exchange resin load tosic acid;
Taking the gross weight of described styrene type acidic cation-exchange resin and tosic acid (loaded article) as 100%, tosic acid accounts for the preferred 0.2wt%～20wt% of 0.1wt%～30wt%();
The specific surface area (BET) of described loaded catalyst is 70m
2/ g ~ 100m
2/ g, mean pore size is 35nm ~ 60nm, average pore volume is 0.3cm
3/ g ~ 0.9cm
3/ g.
The loaded catalyst that the present invention obtains with styrene type acidic cation-exchange resin load tosic acid is replaced existing preparation CH
3o (CH
2o)
xcH
3styrene type acidic cation-exchange resin (catalyzer) used in (3≤X≤8) method, improves the selectivity of this preparation feedback.
Embodiment
In preferred technical scheme of the present invention, the mol ratio of methyl alcohol and formaldehyde is 1: (1～20), the mol ratio of preferred methyl alcohol and formaldehyde is 1: (2～8).
The present invention's catalyzer (loaded catalyst being obtained by styrene type acidic cation-exchange resin load tosic acid) used can be made by the preparation method who comprises the steps:
(1) vinylbenzene and divinylbenzene monomer are removed to stopper with 5% NaOH solution washing respectively, then clean with distilled water; Clean vinylbenzene 80g and divinylbenzene 20g and benzoyl peroxide (initiator) 1.1g and mixture (pore-creating agent) 65g that is made up of n-hexyl alcohol and Pentyl alcohol are mixedly configured into solution A for subsequent use.
(2) get gelatin (dispersion medium) 2.4g, polyacrylamide (helping dispersion medium) 0.15g puts in 400g water, to be dissolved after, add above-mentioned A solution.Finally adding sodium-chlor 20g and methylene blue (stopper).
(3) start mixing control device, regulate mixing speed to control the granularity of spheroid.Be warming up to 78 DEG C and keep 2h, 85 DEG C keep 2h, and 95 DEG C keep 4h, after completion of the reaction, incline and supernatant liquid, ball is washed several times with hot water, then ball is washed several times with cold water, with steam distillation, steam pore-creating agent (mixture of n-hexyl alcohol and Pentyl alcohol), then bead is poured in nylon cloth bag, after water is dried, resin is placed in to porcelain dish and naturally dries, sieve making large-pore white balls used.
(4) by the making large-pore white balls used 20g 250ml three-necked bottle that stirring and reflux condensing tube are housed of putting into, add 20ml ethylene dichloride after swelling 10 minutes, to add the 100ml vitriol oil (93%), start stirring slow rotation.
(5) be warming up to 70 DEG C, be incubated 1 hour; In 30 minutes, be warming up to 80 ~ 85 DEG C, be incubated 3 hours; In 30 minutes, be warming up to 110 DEG C, be incubated 1 hour, steam ethylene dichloride simultaneously.
(6) be cooled to room temperature, pump the vitriol oil in reaction flask with suction filtration rod, add 50ml74% sulfuric acid to stir 10 minutes, under agitation slowly drip distilled water diluting, temperature is less than 35 DEG C.With distilled water repetitive scrubbing to pH=7.After transition, make large hole cation exchanger resin.
(7) take above-mentioned large hole cation exchanger resin 5g, clean with deionized water that to be placed in 250ml beaker stand-by; Then prepare the tosic acid solution of 5wt%, treat that it dissolves completely and get the 20g tosic acid aqueous solution and pour in clean 250ml beaker, heating in water bath to 50 DEG C, after temperature-stable, add large hole cation exchanger resin, keep 50 DEG C of water-baths, after dipping 4h, filter, and with after deionized water wash several, be placed in 70 DEG C of dry 12h of loft drier, can make the styrene type acidic cation-exchange resin (can survey charge capacity according to weight difference) of modification.
Adopt successive reaction mode to implement the present invention, catalyzer and quartz sand are filled in the reactor (as tower-type fixed bed or moving-burden bed reactor etc.) that is applicable to successive reaction, heating, (preferred temperature of reaction is 60 DEG C～90 DEG C to treat temperature to reach 40 DEG C～150 DEG C of desired reaction temperatures, best temperature of reaction is 70 DEG C～80 DEG C), the pressure of reaction is: 0.1MPa～6.0MPa, (preferred reaction pressure is 0.8MPa～3.0MPa), start charging, as taking methyl alcohol and formaldehyde as raw material, the mol ratio of methyl alcohol and formaldehyde is 1: (1～20), (mol ratio of preferred methyl alcohol and formaldehyde is 1: (2～8)), the air speed of reaction is: 0.1h
-1～5000h
-1(preferred reaction velocity is 1h
-1～1000h
-1), reaction product, through condenser condenses, obtains product in liquid header.After stopped reaction, in reaction product system, add inorganic alkaline compound (as sodium hydroxide or potassium hydroxide etc.).
Below by embodiment, the present invention is further elaborated, and its object is better to understand content of the present invention.Therefore, the cited case does not limit the scope of the invention.
Embodiment 1
(1) vinylbenzene and divinylbenzene monomer are removed to stopper with 5% NaOH solution washing respectively, then clean with distilled water; Clean vinylbenzene 80g and divinylbenzene 20g and initiator benzoyl peroxide 1.1g and pore-creating agent n-hexyl alcohol and Pentyl alcohol mixture 65g are mixedly configured into solution A for subsequent use.
(2) get dispersion medium gelatin 2.4g, help dispersion medium polyacrylamide 0.15g to put in 400g dispersion medium water, to be dissolved after, add above-mentioned A solution.Finally adding ionogen sodium-chlor 20g and stopper methylene blue.
(3) start mixing control device, regulate mixing speed to control the granularity of spheroid.Be warming up to 78 DEG C and keep 2h, 85 DEG C keep 2h, and 95 DEG C keep 4h, after completion of the reaction, incline and supernatant liquid, ball is washed several times with hot water, then ball is washed several times with cold water, with steam distillation, steam pore-creating agent n-hexyl alcohol and Pentyl alcohol, then bead is poured in nylon cloth bag, after water is dried, resin is placed in to porcelain dish and naturally dries, sieve making large-pore white balls used.
(4) 20g Archon is put into the 250ml three-necked bottle that stirring and reflux condensing tube are housed, added 20ml ethylene dichloride after swelling 10 minutes, to add the 100ml vitriol oil (93%), start stirring slow rotation.
(5) be warming up to 70 DEG C, be incubated 1 hour; In 30 minutes, be warming up to 80 ~ 85 DEG C, be incubated 3 hours; In 30 minutes, be warming up to 110 DEG C, be incubated 1 hour, steam ethylene dichloride simultaneously.
(6) be cooled to room temperature, pump the vitriol oil in reaction flask with suction filtration rod, add 50ml 74% sulfuric acid to stir 10 minutes, under agitation slowly drip distilled water diluting, temperature is less than 35 DEG C.With distilled water repetitive scrubbing to pH=7.After transition, make macropore strong acid cation exchange resin.
(7) take large hole cation exchanger resin 5g, clean with deionized water that to be placed in 250ml beaker stand-by; Then prepare 5% tosic acid solution, treat that it dissolves completely and get 20g tosic acid solution and pour in clean 250ml beaker, heating in water bath to 50 DEG C, after temperature-stable, add large hole cation exchanger resin, keep 50 DEG C of water-baths, after dipping 4h, filter, and with after deionized water wash several, be placed in 70 DEG C of dry 12h of loft drier, can make the styrene type acidic cation-exchange resin (charge capacity that records tosic acid according to weight difference is 2wt%) of modification.
Embodiment 2
Formaldehyde carries out with reacting in fixed bed reaction of methyl alcohol, adopt stainless steel tubular type fixed-bed reactor (being of a size of φ 24 × 6 × 600mm), under the effect of process furnace, in reaction tubes, there is the flat-temperature zone of 45mm, catalyst loading is in flat-temperature zone, and all the other filling quartz sands (40-60 order) are with stagnant catalyst.The temperature of beds is by the control of AI-708 type Intelligence Regulator, when constant temperature, in be controlled at ± 1 ° of C of the fluctuation of bed temperature.Stock liquid formaldehyde and methyl alcohol adopt 2PB00C type constant-flux pump metering feeding.Before and after reaction, liquid phase compositional analysis adopts gas chromatograph, and chromatographic column is Agilent HP-5 capillary column (0.32mm × 30m), fid detector, area normalization standard measure.
The Hydrogen ion exchange resin of the modification being obtained by embodiment 1 (granularity is 0.4mm～1.25mm) 1.2g is filled in the flat-temperature zone of above-mentioned fixed-bed reactor, formaldehyde and methyl alcohol flow are 30ml/min, the mol ratio of formaldehyde and methyl alcohol is 3: 1,70 DEG C of temperature of reaction, and reaction velocity is 1h
-1～1000h
-1, reaction pressure is 0.8MPa～3.0MPa, reacted product is after gas-liquid separator, liquid product is preserved in receiving flask, in separator or receiving flask, adds sodium hydroxide, ensures that reaction product is alkalescence, product good seal is for analyzing, detecting, and the product of gas is rear emptying by analysis.Reaction result is in table 1.
Comparative example 1
Outside tosic acid modified phenylethylene type acidic cation-exchange resin in existing styrene type acidic cation-exchange resin alternative embodiment 2, other reaction conditions is identical with enforcement 2, investigates its reaction preference.Concrete outcome is in table 1.
Table 1
Claims (8)
1. prepare CH for one kind
3o (CH
2o)
xcH
3method, its key step is: at 0.1MPa～6.0MPa, the air speed of reaction is 0.1h
-1～5000h
-1and under catalyzer existence condition, reacted in 40 DEG C～150 DEG C by methyl alcohol and formaldehyde, obtain target compound; It is characterized in that, wherein said catalyzer is: the loaded catalyst being obtained by styrene type acidic cation-exchange resin load tosic acid;
Taking the gross weight of described styrene type acidic cation-exchange resin and tosic acid as 100%, tosic acid accounts for 0.1wt%～30wt%;
The specific surface area (BET) of described loaded catalyst is 70m
2/ g～100m
2/ g, mean pore size is 35nm ~ 60nm, average pore volume is 0.30cm3/g ~ 0.9cm3/g; 3≤X≤8.
2. the method for claim 1, is characterized in that, wherein, taking the gross weight of described styrene type acidic cation-exchange resin and tosic acid as 100%, tosic acid accounts for 0.2wt%～20wt%.
3. the method for claim 1, is characterized in that, reaction pressure is 0.8MPa～3.0MPa.
4. the method for claim 1, is characterized in that, wherein reaction velocity is 1h
-1～1000h
-1.
5. the method for claim 1, is characterized in that, wherein temperature of reaction is 60 DEG C～90 DEG C.
6. method as claimed in claim 5, is characterized in that, wherein temperature of reaction is 70 DEG C～80 DEG C.
7. the method as described in any one in claim 1～6, is characterized in that, wherein, the mol ratio of methyl alcohol and formaldehyde is 1: (1～20).
8. method as claimed in claim 7, is characterized in that, wherein, the mol ratio of methyl alcohol and formaldehyde is 1: (2～8).
Priority Applications (1)
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|---|---|---|---|
| CN201210520979.6A CN103848729B (en) | 2012-12-07 | 2012-12-07 | A kind of method being prepared polymethoxy methylal by methyl alcohol and formaldehyde |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210520979.6A CN103848729B (en) | 2012-12-07 | 2012-12-07 | A kind of method being prepared polymethoxy methylal by methyl alcohol and formaldehyde |
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|---|---|
| CN103848729A true CN103848729A (en) | 2014-06-11 |
| CN103848729B CN103848729B (en) | 2016-02-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104447239A (en) * | 2014-10-16 | 2015-03-25 | 白教法 | Method for continuously producing polymethoxy dimethyl ether by using methanol as original reaction material |
| CN104725225A (en) * | 2013-12-23 | 2015-06-24 | 中国科学院大连化学物理研究所 | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate |
| CN105669452A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Method for preparing methyl formate and coproducing dimethyl ether |
| CN106311328A (en) * | 2016-08-12 | 2017-01-11 | 江苏色可赛思树脂有限公司 | Method for preparing catalyst for synthesis of polyoxymethylene dimethyl ether |
Citations (1)
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| CN101898943A (en) * | 2010-06-04 | 2010-12-01 | 洪正鹏 | Method for synthesizing polyoxymethylene dimethyl ethers |
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| CN101898943A (en) * | 2010-06-04 | 2010-12-01 | 洪正鹏 | Method for synthesizing polyoxymethylene dimethyl ethers |
Non-Patent Citations (1)
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| 秦学洵 等: "甲缩醛合成的本征动力学研究", 《华东理工大学学报》, vol. 21, no. 1, 28 February 1995 (1995-02-28), pages 23 - 29 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725225A (en) * | 2013-12-23 | 2015-06-24 | 中国科学院大连化学物理研究所 | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate |
| CN104447239A (en) * | 2014-10-16 | 2015-03-25 | 白教法 | Method for continuously producing polymethoxy dimethyl ether by using methanol as original reaction material |
| CN105669452A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Method for preparing methyl formate and coproducing dimethyl ether |
| CN105669452B (en) * | 2014-11-17 | 2018-08-24 | 中国科学院大连化学物理研究所 | A method of preparing methyl formate combined producing dimethyl ether |
| CN106311328A (en) * | 2016-08-12 | 2017-01-11 | 江苏色可赛思树脂有限公司 | Method for preparing catalyst for synthesis of polyoxymethylene dimethyl ether |
| CN106311328B (en) * | 2016-08-12 | 2019-01-29 | 江苏色可赛思树脂有限公司 | A method of preparing the catalyst for synthesizing polymethoxy dimethyl ether |
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| CN103848729B (en) | 2016-02-17 |
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