CN101048357A - Method for producing polyoxymethylene dimethyl ethers - Google Patents
Method for producing polyoxymethylene dimethyl ethers Download PDFInfo
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- CN101048357A CN101048357A CN 200580036662 CN200580036662A CN101048357A CN 101048357 A CN101048357 A CN 101048357A CN 200580036662 CN200580036662 CN 200580036662 CN 200580036662 A CN200580036662 A CN 200580036662A CN 101048357 A CN101048357 A CN 101048357A
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- dimethyl ether
- cut
- polyoxymethylene dimethyl
- methylal
- alkane
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- -1 polyoxymethylene dimethyl ethers Polymers 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000004821 distillation Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000011541 reaction mixture Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 14
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 abstract 3
- 235000019256 formaldehyde Nutrition 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 229920002866 paraformaldehyde Polymers 0.000 description 10
- 229930040373 Paraformaldehyde Natural products 0.000 description 9
- 239000000539 dimer Substances 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 6
- 150000002373 hemiacetals Chemical class 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000006280 diesel fuel additive Substances 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Images
Abstract
The invention relates to a method for producing a polyoxymethylene dimethyl ether of formula H3CO(CH2O)nCH3, in which n = 2 - 10. According to said method, methylal and trioxane are fed to a reactor and are reacted in the presence of an acidic catalyst. The invention is characterised in that the quantity of water that is introduced into the reaction mixture by means of the methylal, trioxane and/or the catalyst is less than 1 wt. %, in relation to the reaction mixture. Preferably, a fraction containing polyoxymethylene dimethyl ether, where n = 3 and 4, is obtained by distillation and methylal, trioxane and polyoxymethylene dimethyl ether, where n < 3 and optionally n > 4 are fed back to the reaction.
Description
The present invention relates to a kind of method for preparing polyoxymethylene dimethyl ether.Polyoxymethylene dimethyl ether constitutes the series of following general formula:
CH
3O(CH
2O)
nCH
3
Wherein n is 〉=1 numeral.With this serial parent molecule---methylal CH
3O (CH
2O) CH
3Identical, polyoxymethylene dimethyl ether is an acetal.Identical with methylal, they are prepared in reaction in the presence of an acidic catalyst by methyl alcohol and formalin.Identical with other acetal, they are stable under neutrality or alkaline condition, but they in addition be subjected to the erosion of dilute acid.In the first step, hydrolysis is converted into hemiacetal and methyl alcohol with them earlier.In second step, formaldehyde and methyl alcohol in the hemiacetal hydrolysis.
On laboratory scale, polyoxymethylene dimethyl ether prepares by heat low polymerization degree Paraformaldehyde 96 (polyoxymethylene glycol) or paraformaldehyde and methyl alcohol down in 150-180 ℃ in the presence of trace sulfuric acid or hydrochloric acid, and the reaction times is 12-15 hour.The decomposition reaction that causes forming carbonic acid gas like this and form dme.At paraformaldehyde or low polymerization degree Paraformaldehyde 96: the ratio of methyl alcohol is 6: 1 o'clock, obtains wherein n＞100, usually the polymkeric substance of n=300-500.Product washs with sodium sulfite solution, separates by fractional crystallization then.
US2,449,469 have described the method that a kind of wherein methylal and paraformaldehyde or concentrated methylal solution heat in the presence of sulfuric acid.This method provides per molecule to have the polyoxymethylene dimethyl ether of 2-4 formaldehyde unit.
In the recent period, polyoxymethylene dimethyl ether is obvious day by day as the importance of diesel-fuel additive.In order in the conventional diesel engine process combustion, to reduce the formation of flue dust and cigarette ash, add the oxygen compound that only comprises seldom (if any) C-C key, for example methyl alcohol.But such compound usually is insoluble to diesel-fuel and reduces the flash-point of cetane value and/or diesel-fuel mixture.
US5,746,785 to have described molar mass be 80-350 and the preparation method who is equivalent to the polyoxymethylene dimethyl ether of n=1-10, this method is reacted down at 150-240 ℃ in the presence of 0.1 weight % formic acid by 1 part of methylal and 5 parts of paraformaldehydes, perhaps by 1 part of methyl alcohol and 3 parts of paraformaldehydes reactions under 150-240 ℃.The polyoxymethylene dimethyl ether that is obtained adds in the diesel-fuel with the amount of 5-30 weight %.
US6,392,102 have described by the initial logistics that comprises methyl alcohol and formaldehyde being reacted in the presence of an acidic catalyst and simultaneously removing reaction product in catalytic distillation column and have prepared polyoxymethylene dimethyl ether, and wherein said initiator stream is by obtaining the dme oxidation.This method provides methylal, methyl alcohol, water and polyoxymethylene dimethyl ether.
EP-A 1 070 755 has described a kind of polyoxymethylene dimethyl ether that has 2-6 formaldehyde unit by methylal and paraformaldehyde in the presence of three fluosulfonic acid in the prepared in reaction per molecule.Form the wherein polyoxymethylene dimethyl ether of n=2-5 with 94.8% selection rate like this, the pick-up rate of dimer (n=2) is 49.6%.The polyoxymethylene dimethyl ether of gained adds in the diesel-fuel with the amount of 4-11 weight %.
The shortcoming of these known preparation low polymerization degree polyoxymethylene dimethyl ether (wherein n=1-10) methods is to obtain dimer with quite significant degree.The shortcoming of the method that begins with formaldehyde and methyl alcohol is that also water is as reaction product forms and hydrolysis has formed in the presence of an acidic catalyst polyoxymethylene dimethyl ether.Form unsettled hemiacetal like this.Unsettled hemiacetal has reduced the flash-point of diesel-fuel mixture and has therefore damaged its quality.But, the low excessively standard that causes no longer can satisfying by relevant DIN standard code of the flash-point of diesel-fuel mixture.Because boiling point is close, hemiacetal is difficult to remove from polyoxymethylene dimethyl ether.The dimer that forms as primary product has lower boiling and the therefore same flash-point that reduces, and the result not too is suitable as diesel-fuel additive.
The purpose of this invention is to provide improving one's methods of a kind of preparation polyoxymethylene dimethyl ether that no longer has a prior art shortcoming.Specific purposes of the present invention provide the method that a kind of preparation is particularly suitable as the polyoxymethylene dimethyl ether of diesel-fuel additive.Specially suitable is the polyoxymethylene dimethyl ether of n=3 and 4 (tripolymer, the tetramer) wherein.Further purpose of the present invention provides a kind of method for preparing tripolymer and the extra high polyoxymethylene dimethyl ether of tetramer ratio.
Described purpose realizes by a kind of method of the polyoxymethylene dimethyl ether for preparing following formula,
H
3CO(CH
2O)
nCH
3
N=2-10 wherein,
In the method, with methylal (n=1) with three alkane are sent in the reactor and reaction in the presence of an acidic catalyst, wherein introduce the water yield in the reaction mixture and be lower than 1 weight % based on the reaction mixture meter by methylal, three alkane and/or catalyzer.
Generate in the reaction of polyoxymethylene dimethyl ether at methylal and the reaction of three alkane, do not have water to form as by product.This reaction is generally carried out under 50-200 ℃, preferred 90-150 ℃ and 1-20 crust, preferred 2-10 bar pressure.Methylal: the mol ratio of three alkane is generally 0.1-10, preferred 0.5-5.
Described an acidic catalyst can be homogeneous phase or heterogeneous catalyst.Suitable an acidic catalyst is mineral acid such as substantially anhydrous sulfuric acid, sulfonic acid such as trifluoromethayl sulfonic acid and tosic acid, heteropolyacid, acidic ion exchange resin, zeolite, silico-aluminate, silicon-dioxide, aluminum oxide, titanium dioxide and zirconium dioxide.In order to improve their acid concentration, oxide catalyst can mix with sulfate radical or phosphate radical, and doping is generally 0.05-10 weight %.This reaction can be carried out in stirred-tank reactor (CSTR) or tubular reactor.When using heterogeneous catalyst, preferred fixed-bed reactor.When using fixed bed catalyst, product mixtures can contact with anionite-exchange resin so that obtain the product mixtures of basic anacidity subsequently.
By methylal and three alkane with introduce the total amount＜1 weight % of the water in the reaction mixture by catalyzer, preferred＜0.5 weight %, more preferably＜0.2 weight %, weight % especially＜0.1, described per-cent is based on the reaction mixture meter of being made up of methylal, three alkane and catalyzer.For this reason, use three substantially anhydrous alkane and methylals, and if suitable, the water yield by the corresponding introducing of catalyzer is restricted.Boiling point and polyoxymethylene dimethyl ether that hemiacetal (monoether) that forms by hydrolysis in the presence of the water that is derived from the polyoxymethylene dimethyl ether that has formed and low polymerization degree Paraformaldehyde 96 have are suitable, and to remove polyoxymethylene dimethyl ether from these by products more complicated with regard to feasible like this.
In order optionally to obtain the wherein polyoxymethylene dimethyl ether (tripolymer of n=3 and n=4, the tetramer), to comprise tripolymer and tetrameric cut and from the product mixtures of methylal and three alkane reaction, remove, and with unconverted methylal, three alkane and wherein the polyoxymethylene dimethyl ether recirculation of n＜3 enter in the described acid catalyzed reaction.In the another kind of embodiment of the inventive method, wherein the also other recirculation of the polyoxymethylene dimethyl ether of n＞4 enters described reaction.As the result of recirculation, obtain a large amount of especially tripolymer and tetramers.
In a kind of particularly preferred embodiment, by the reaction mixture of the acid catalyzed reaction of methylal and three alkane obtain to comprise methylal first cut, comprise dimer (n=2) second cut, comprise the 3rd cut of the tripolymer and the tetramer (n=3,4) and comprise pentamer and the 4th cut of higher homologue (n＞4) more.Within the scope of the present invention, especially preferably methylal is implemented to separate with the reaction mixture of the acid catalyzed reaction of three alkane with three distillation towers that are connected in series, first cut separates from the product mixtures of this reaction in first distillation tower, second cut separates from remaining mixture in second column, and remaining mixture is separated into third and fourth cut in the 3rd distillation tower.In this case, first distillation tower can be operated under the pressure of for example 0.5-1.5 crust, and second column can for example operated under the 0.05-1 bar pressure, and the 3rd distillation tower can be operated under the pressure of for example 0.001-0.5 crust.Preferred cycle first and second cuts more preferably also enter described reaction with the circulation of the 4th cut in addition.
Using homogeneous catalyst for example when mineral acid or sulfonic acid, described catalyzer is retained in the 4th cut and recirculation enters in the described acid catalyzed reaction.
The present invention further describes with reference to the accompanying drawings.
Fig. 1 has reproduced the process flow sheet according to a kind of embodiment of the inventive method.
The initial logistics 1 that to be made up of methylal and send into reactor 3 with recycle stream 8,11 and 15 by the initial logistics 2 that three alkane are formed, here reaction generates and comprises methylal, three alkane and the product mixtures 4 of the polyoxymethylene dimethyl ether of n=2-10 wherein in the presence of heterogeneous an acidic catalyst.Product logistics 4 is passed through from the bed of being made up of anionite-exchange resin 5, obtains the product mixtures 6 of basic anacidity.This product mixtures is sent into first distillation tower 7, and wherein methylal is removed as recirculation stream 8 from cat head.Ejecta at the bottom of the tower of first distillation tower 79 is introduced second column 10, and wherein dimer (n=2) and three alkane are discharged as recirculation stream 11 from cat head.Ejecta 12 at the bottom of the tower of second column 10 is sent into the 3rd distillation tower 13, discharge trimerization and four polymeric polyoxymethylene dimethyl ethers (n=3,4) mixture from cat head.At the bottom of tower, obtain the recirculation stream of forming by five polymerizations and more senior polymeric polyoxymethylene dimethyl ether (n＞4) 15.
Fig. 2 has reproduced the process flow sheet according to the another kind of embodiment of the inventive method.
Different with method according to Fig. 1, use homogeneous catalyst and send into reactor 3 as other physical supply 16.Be positioned at reactor 3 downstreams by anionite-exchange resin form the bed save, and the reaction product logistics 4 directly send into first distillation tower 7.The bottom product 15 of the 3rd distillation tower comprises homogeneous catalyst in addition.Can remove a small amount of logistics 17 and from the discharging of this flow process, wherein catalyst attrition can compensate by initial logistics 16 from recirculation stream 15.
Embodiment
Embodiment 1
30g three alkane and 103g methylal heated 16 hours down at 100 ℃ with 0.2g sulfuric acid.After 1,2,3,4,5,6,7,8 and 16 hour, extract sample respectively and by gas chromatographic analysis.After 8 hours, obtain the balanced combination thing.It is characterized by: methylal, 48.7%; N=2,24.5%; N=3,11.7%; N=4,5.2%; N＞4, surplus.
17g three alkane, 30g methylal and 15g Amberlite IR 120 ion exchange resin heated 24 hours down at 100 ℃ together.After 24 hours, extract sample and by gas chromatographic analysis.The mixture that obtains comprises methylal and polyoxymethylene dimethyl ether, and it forms distribution following (% represents with weight): methylal, 70%; N=2,18%; N=3,4%; N=4,0.9%; N=5-11,4.5%; N＞11, surplus.
85.6g paraformaldehyde, 452g methylal heated 8 hours down at 100 ℃ with 58g Amberlite IR 120 ion exchange resin.After 8 hours, extract sample and by gas chromatographic analysis.The product mixtures that obtains comprises methylal and polyoxymethylene dimethyl ether, and it forms distribution following (% represents with weight): methylal, 60.6%; N=2,21.9%; N=3,6.8%; N=4,1.9%; And n=5-11,0.07%.
303g three alkane, 1032g methylal and 0.2g trifluoromethanesulfonic acid heated 40 hours down at 100 ℃ together.After 40 hours, extract sample and by gas chromatographic analysis.The mixture that obtains comprises methylal and polyoxymethylene dimethyl ether, and it forms distribution following (% represents with weight): methylal, 45.9%; N=2,25.7%; N=3,14%; N=4,7.1%; N=5-11,1.4%; N＞11, surplus.
30g three alkane, 68.8g methylal, 34.4g dimer (n=2) and 0.2g sulfuric acid heated 12 hours down at 100 ℃ together.After 12 hours, extract sample and by gas chromatographic analysis.The mixture that obtains comprises methylal and polyoxymethylene dimethyl ether, and it forms distribution following (% represents with weight): methylal, 33.5%; N=2,23.6%; N=3,15.8%; N=4,9.9%; N=5-11,2.6%; N＞11, surplus.
30g three alkane, 103.2g dimer (n=2) and 0.2g sulfuric acid heated 12 hours down at 100 ℃ together.After 12 hours, extract sample and by gas chromatographic analysis.The mixture that obtains comprises methylal and polyoxymethylene dimethyl ether, and it forms distribution following (% represents with weight): methylal, 19.5%; N=2,16.7%; N=3,13.2%; N=4,9.8%; N=5-11,4.4%; N＞11, surplus.
30g three alkane, 103g methylal and 0.2g sulfuric acid heated 12 hours down at 100 ℃ together.After 12 hours, extract sample and by gas chromatographic analysis.The mixture that obtains comprises methylal and polyoxymethylene dimethyl ether, and it forms distribution following (% represents with weight): methylal, 47.8%; N=2,24%; N=3,12.8%; N=4,6.0%; N=5-11,0.9%; N＞11, surplus.
Claims (10)
1. method for preparing the polyoxymethylene dimethyl ether of following formula,
H
3CO(CH
2O)
nCH
3
N=2-10 wherein,
In the method, methylal and three alkane are sent in the reactor and in the presence of an acidic catalyst react, wherein the water yield of introducing reaction mixture by methylal, three alkane and/or catalyzer is lower than 1 weight % based on the reaction mixture meter.
2. the method for claim 1, wherein obtain to comprise the cut of the polyoxymethylene dimethyl ether of n=3 wherein and 4 by described reaction mixture by distillation, and methylal, three alkane and wherein the polyoxymethylene dimethyl ether recirculation of n＜3 and optional n＞4 enter described reaction.
3. method as claimed in claim 2, wherein by described reaction mixture obtain to comprise first cut of methylal, the polyoxymethylene dimethyl ether that comprises n=2 wherein and three alkane second cut, comprise n=3 wherein and 4 polyoxymethylene dimethyl ether the 3rd cut and comprise wherein the 4th cut of the polyoxymethylene dimethyl ether of n＞4.
4. method as claimed in claim 3, wherein first cut separates from the product mixtures of this reaction in first distillation tower, second cut separates from remaining mixture in second column, and remaining mixture is separated into third and fourth cut in the 3rd distillation tower.
5. as claim 3 or 4 described methods, wherein the first and second cut recirculation enter described reaction.
6. method as claimed in claim 5, wherein the 4th cut recirculation enters described reaction.
7. as each described method among the claim 1-6, wherein first distillation tower is operated under the pressure of 0.5-1.5 crust, and second column is operated under the 0.05-1 bar pressure, and the 3rd distillation tower is operated under the pressure of 0.001-0.5 crust.
8. as each described method among the claim 1-7, wherein introduce the water yield＜0.2 weight % in the reaction mixture.
9. as each described method among the claim 1-8, wherein an acidic catalyst is to be selected from following homogeneous phase or heterogeneous catalyst: mineral acid, sulfonic acid, heteropolyacid, acidic ion exchange resin, zeolite, silico-aluminate, silicon-dioxide, aluminum oxide, titanium dioxide and zirconium dioxide.
10. as each described method among the claim 1-9, carry out under the wherein said 1-20 of being reflected at bar pressure and 50-200 ℃.
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| DE102004051814 | 2004-10-25 | ||
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Cited By (36)
| 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 |
| CN101972644A (en) * | 2010-11-09 | 2011-02-16 | 中国海洋石油总公司 | Method for preparing polyformaldehyde dimethyl ether by using loaded niobium oxide catalyst |
| CN102040491A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Catalytic synthesis method for polyoxymethylene dimethyl ethers (PODE) by molecular sieves |
| CN102040488A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for synthesizing PODE (polyformaldehyde dimethyl ether) |
| CN102249869A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Technical process for catalytically synthesizing polymethoxy dimethyl ether by ionic liquid |
| CN102295734A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Method for synthesizing polyoxymethylene dimethyl ether |
| CN102372613A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for producing polyformaldehyde dimethyl ether |
| CN102372612A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Preparation method for polyoxymethylene dimethyl ether |
| CN102372615A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing polyformaldehyde dimethyl ether by catalytic distillation |
| CN102372614A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Production method of polyoxymethylene dimethylether |
| CN102372611A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ether |
| CN102432441A (en) * | 2011-09-30 | 2012-05-02 | 天津大学 | Synthesis method of polymethoxy methylal |
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-
2005
- 2005-10-19 CN CN 200580036662 patent/CN101048357A/en active Pending
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