CN103848729B - A kind of method being prepared polymethoxy methylal by methyl alcohol and formaldehyde - Google Patents
A kind of method being prepared polymethoxy methylal by methyl alcohol and formaldehyde Download PDFInfo
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- CN103848729B CN103848729B CN201210520979.6A CN201210520979A CN103848729B CN 103848729 B CN103848729 B CN 103848729B CN 201210520979 A CN201210520979 A CN 201210520979A CN 103848729 B CN103848729 B CN 103848729B
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- reaction
- formaldehyde
- methyl alcohol
- exchange resin
- 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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Abstract
The present invention relates to a kind of method being prepared polymethoxy methylal by methyl alcohol and formaldehyde, its key step is: at 0.1MPa ~ 6.0MPa, and 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 (CH
3o (CH
2o)
xcH
3, 3≤X≤8); It is characterized in that, wherein said catalyzer is: the loaded catalyst obtained by styrene type acidic cation-exchange resin load tosic acid.The loaded catalyst that the present invention obtains with styrene type acidic cation-exchange resin load tosic acid replaces 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.
Description
Technical field
The present invention relates to a kind of production method of polymethoxy methylal, specifically, relate to a kind of method 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
xthe calorific value of diesel oil can be improved and reduce the discharge of tail gas.Therefore, DMM
xpreparation enjoy the concern of scientists.
So far, many sections of bibliographical informations DMM is had
xpreparation method.As EP1505049A1 discloses: having under sulfonic acid or halogenosulfonic acid (catalyzer) existence condition, prepared the method for DMMx by methyl alcohol and formaldehyde reaction.Have in prior art 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 the preparation DMM selected 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: carry out suitable modification to existing styrene type acidic cation-exchange resin, and the styrene type acidic cation-exchange resin through modification is applicable to prepare DMM by methyl alcohol and formaldehyde reaction
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 existed 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), and the air speed of reaction is 0.1h
-1~ 5000h
-1(preferred reaction velocity is: 1h
-1~ 1000h
-1) and catalyzer existence condition under, by methyl alcohol and formaldehyde 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
3o (CH
2o)
xcH
3, 3≤X≤8); It is characterized in that, wherein said catalyzer is: the loaded catalyst obtained by styrene type acidic cation-exchange resin load tosic acid;
In the gross weight of described styrene type acidic cation-exchange resin and tosic acid (loaded article) for 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, and 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 replaces 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 the present invention's preferred technical scheme, the mol ratio of methyl alcohol and formaldehyde is 1: (1 ~ 20), and the mol ratio of preferred methyl alcohol and formaldehyde is 1: (2 ~ 8).
The present invention's catalyzer (loaded catalyst obtained by styrene type acidic cation-exchange resin load tosic acid) used can be obtained by the preparation method comprised the steps:
(1) vinylbenzene and divinylbenzene monomer are removed stopper with the NaOH solution washing of 5% respectively, then clean with distilled water; The vinylbenzene 80g cleaned 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 is 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, after to be dissolved, add above-mentioned solution A.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, with hot water, ball is washed several times, then with cold water, ball is washed several times, 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 porcelain dish naturally dry, sieves making large-pore white balls used.
(4) put into making large-pore white balls used for 20g the 250ml three-necked bottle that stirring and reflux condensing tube are housed, add 20ml ethylene dichloride and add the 100ml vitriol oil (93%) after swelling 10 minutes, start stirring slow rotation.
(5) be warming up to 70 DEG C, be incubated 1 hour; Be warming up to 80 ~ 85 DEG C in 30 minutes, be incubated 3 hours; Be warming up to 110 DEG C in 30 minutes, 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 and 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.Obtained large hole cation exchanger resin after transition.
(7) take above-mentioned large hole cation exchanger resin 5g, clean with deionized water that to be placed in 250ml beaker stand-by; Then the tosic acid solution of 5wt% is prepared, treat that it dissolves completely to 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 water-bath 50 DEG C, after dipping 4h, filter, and with after deionized water wash several, be placed in loft drier 70 DEG C of dry 12h, the styrene type acidic cation-exchange resin (charge capacity can be surveyed according to weight difference) of modification can be obtained.
Successive reaction mode is adopted 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.) of applicable successive reaction, heating, (preferred temperature of reaction is 60 DEG C ~ 90 DEG C to treat temperature to reach desired reaction temperature 40 DEG C ~ 150 DEG C, 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 with methyl alcohol and formaldehyde for raw material, then 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, its object is to better 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 stopper with the NaOH solution washing of 5% 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, after to be dissolved, add above-mentioned solution A.Finally adding electrolyte sodium chloride 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, with hot water, ball is washed several times, then with cold water, ball is washed several times, 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 porcelain dish naturally dry, sieves 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, add 20ml ethylene dichloride and add the 100ml vitriol oil (93%) after swelling 10 minutes, start stirring slow rotation.
(5) be warming up to 70 DEG C, be incubated 1 hour; Be warming up to 80 ~ 85 DEG C in 30 minutes, be incubated 3 hours; Be warming up to 110 DEG C in 30 minutes, 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 and 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.Obtained macropore strong acid cation exchange resin after transition.
(7) take large hole cation exchanger resin 5g, clean with deionized water that to be placed in 250ml beaker stand-by; Then the tosic acid solution of 5% is prepared, treat that it dissolves completely to 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 water-bath 50 DEG C, after dipping 4h, filter, and with after deionized water wash several, be placed in loft drier 70 DEG C of dry 12h, the styrene type acidic cation-exchange resin (charge capacity recording tosic acid according to weight difference is 2wt%) of modification can be obtained.
Embodiment 2
The reaction of formaldehyde and methyl alcohol is carried out in fixed bed reaction, adopt stainless steel tubular fixed-bed reactor (being of a size of φ 24 × 6 × 600mm), the flat-temperature zone of 45mm is had in reaction tubes under the effect of process furnace, catalyst loading is in flat-temperature zone, and all the other fillings quartz sand (40-60 order) are with stagnant catalyst.The temperature of beds is controlled by AI-708 type Intelligence Regulator, and during constant temperature, the undulated control of bed temperature is within ± 1 ° of C.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 AgilentHP-5 capillary column (0.32mm × 30m), fid detector, area normalization standard measure.
Form ion exchange resin (granularity the is 0.4mm ~ 1.25mm) 1.2g of the modification obtained by embodiment 1 is filled in the flat-temperature zone of above-mentioned fixed-bed reactor, formaldehyde and methanol flow are 30ml/min, the mol ratio of formaldehyde and methyl alcohol is 3: 1, temperature of reaction 70 DEG C, and reaction velocity is 1h
-1~ 1000h
-1, reaction pressure is 0.8MPa ~ 3.0MPa, and reacted product is after gas-liquid separator, liquid product is preserved in receiving flask, in separator or receiving flask, add sodium hydroxide, ensures that reaction product is alkalescence, product good seal for analysis, detect, the product of gas is emptying afterwards by analysis.Reaction result is in table 1.
Comparative example 1
Divided by 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, and 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 obtained by styrene type acidic cation-exchange resin load tosic acid;
In the gross weight of described styrene type acidic cation-exchange resin and tosic acid for 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, and average pore volume is 0.30cm
3/ g ~ 0.9cm
3/ g; 3≤X≤8.
2. the method for claim 1, is characterized in that, wherein in the gross weight of described styrene type acidic cation-exchange resin and tosic acid for 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, it is characterized in that, wherein temperature of reaction is 70 DEG C ~ 80 DEG C.
7. as the method in claim 1 ~ 6 as described in any one, it is characterized in that, wherein, the mol ratio of methyl alcohol and formaldehyde is 1: (1 ~ 20).
8. method as claimed in claim 7, it 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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|---|---|---|---|
| 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 CN103848729A (en) | 2014-06-11 |
| CN103848729B true CN103848729B (en) | 2016-02-17 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104725225B (en) * | 2013-12-23 | 2017-01-18 | 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 |
| CN104447239B (en) * | 2014-10-16 | 2017-05-31 | 白教法 | Methyl alcohol is the method that primitive reaction material continuously produces polymethoxy 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898943A (en) * | 2010-06-04 | 2010-12-01 | 洪正鹏 | Method for synthesizing polyoxymethylene dimethyl ethers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101898943A (en) * | 2010-06-04 | 2010-12-01 | 洪正鹏 | Method for synthesizing polyoxymethylene dimethyl ethers |
Non-Patent Citations (1)
| Title |
|---|
| 甲缩醛合成的本征动力学研究;秦学洵 等;《华东理工大学学报》;19950228;第21卷(第1期);第23-29页 * |
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