CN102786396A - Method for preparation of polyoxymethylene dimethyl ethers by catalysis of cyclic amide ionic liquid - Google Patents
Method for preparation of polyoxymethylene dimethyl ethers by catalysis of cyclic amide ionic liquid Download PDFInfo
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- CN102786396A CN102786396A CN201210248585XA CN201210248585A CN102786396A CN 102786396 A CN102786396 A CN 102786396A CN 201210248585X A CN201210248585X A CN 201210248585XA CN 201210248585 A CN201210248585 A CN 201210248585A CN 102786396 A CN102786396 A CN 102786396A
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Abstract
Belonging to the technical field of ionic liquid catalysis, the invention relates to a method for preparation of polyoxymethylene dimethyl ethers through catalysis of a cyclic amide ionic liquid. The method takes trioxymethylene and methanol or trioxymethylene and methylal as raw materials, and adopts a cyclic amide ionic liquid as a catalyst for catalytic preparation of polyoxymethylene dimethyl ethers. When the reaction finishes, the ionic liquid and the product can undergo automatic phase splitting. The ionic liquid used in the invention has a simple preparation process and a low price. The invention has the advantages that: (1) the catalyst has high catalytic activity and less consumption; (2) the catalyst has low toxicity and is easily biodegradable; (3) the reaction conditions are mild, and the reaction time is short; and (4) the reaction process is simple, the product is well distributed after reaction, and the raw material utilization rate is high.
Description
Technical field
The present invention relates to a kind of is catalyzer with cyclic amide class ionic liquid, and catalytic trimerization formaldehyde and methyl alcohol or trioxymethylene and methylal prepare the method for polyoxymethylene dimethyl ether, belong to ionic liquid-catalyzed technical field.
Background technology
Polyoxymethylene dimethyl ether as diesel-dope is the common name of one type of material, molecular formula CH
3(CH
2O)
nCH
3, wherein n equals 2 ~ 11, and they have high cetane value (on average up to 76) and high oxygen level (45% ~ 49%), and good with the mutual solubility of diesel oil, and suitable oil dope is generally the polyoxymethylene dimethyl ether (DMM of 3≤n≤8
3-8), be higher than ultra-low-sulphur diesel with the mediation quality of diesel oil, in diesel oil, add 10%-30%, can reduce NO significantly
x, CO and flue dust discharging, reduce the tail gas pollution 50% or more, and can increase the oilness of diesel oil significantly, therefore be considered to a kind of have application prospect environmental protection fuel oil interpolation component.
US5746785 has described the preparation method of the polyoxymethylene dimethyl ether of n=1～10; This method through a methylal and five parts of paraformaldehydes in the presence of 0.1% (w) formic acid 150 ~ 240 ℃ of reactions; Perhaps through a methyl alcohol and three parts of paraformaldehydes 150 ~ 240 ℃ of reactions, the amount that the polyoxymethylene dimethyl ether of gained can 5 ~ 30 weight % adds in the diesel-fuel.
EP-A1070755 has described and a kind ofly in the presence of three fluosulfonic acid, has prepared the polyoxymethylene dimethyl ether that has 2-6 formaldehyde unit in the molecule through methylal and paraformaldehyde.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%, and the polyoxymethylene dimethyl ether of gained joins in the diesel oil fuel with the amount of 4 ~ 11 weight %.
BASF AG has reported that liquid acid catalysis synthesizes DMM
3-8Technology (WO2006/045506A1); Use sulfuric acid, trifluoromethanesulfonic acid to be catalyzer; Methyl alcohol, methylal, Paraformaldehyde 96, trioxymethylene etc. are raw material, obtained the series product of n=1～10, but catalyzer have corrodibility to equipment; Products distribution is unreasonable, transformation efficiency and the component DMM that can be used for oil dope
3-8Be lower than 30%, separate also relatively difficulty simultaneously.
Reported that with methyl alcohol and trioxymethylene be reactant among the orchidization place patent CN101182367 of the Chinese Academy of Sciences, the selection ionic liquid is a catalyzer, under comparatively gentle condition, and catalysis synthesizing polyoxymethylene dme; Wherein ion liquid cationic moiety is selected from a kind of in glyoxaline cation, pyridylium, quaternary ammonium salt cationic, the season phosphonium salt positively charged ion, and anionicsite is selected from a kind of in p-methyl benzenesulfonic acid root, trifluoromethane sulfonic acid root, methylsulphonic acid root, bisulfate ion, the trifluoroacetic acid root.
Summary of the invention
The objective of the invention is to overcome and have shortcomings such as catalyst activity is lower, preparation process complicacy in the prior art, and a kind of preparation method of polyoxymethylene dimethyl ether is provided.The thought of invention is that to adopt trioxymethylene and methyl alcohol or trioxymethylene be raw material with methylal, and selection cyclic amide class ionic liquid is a catalyzer, under the condition of gentleness comparatively, and catalysis synthesizing polyoxymethylene dme.
Reaction can be represented through following formula:
Wherein n represents 1 to 8 integer.
Wherein n represents 1 to 7 integer.
A kind of preparation method of polyoxymethylene dimethyl ether; Carry out according to following step: cyclic amide class ionic liquid is a catalyzer; With trioxymethylene and methyl alcohol is raw material, 80 ~ 150 ℃ of temperature of reaction, and catalytic preparation polyoxymethylene dme under reaction original pressure 0.5 ~ 4MPa condition.
Wherein said ionic liquid is a cyclic amide class ionic liquid, and chemical structure of general formula is:
Wherein m represents 0 to 8 integer, preferentially selects m=0,3 or 4;
X
-Be bisulfate ion, dihydrogen phosphate, p-methyl benzenesulfonic acid root, trifluoromethayl sulfonic acid root, a kind of in methylsulphonic acid root, trifluoroacetic acid root, formate, the acetate.
Wherein said catalyst levels is total reactant quality 0.01 ~ 10wt%.
The mass ratio of wherein said trioxymethylene and methyl alcohol is 1:0.1～5.
Be raw material with trioxymethylene and methylal perhaps in the aforesaid method, the mass ratio that rubs of wherein said trioxymethylene and methylal is 1:0.5～10.
Advantage of the present invention is:
1, selected ionic liquid synthesis condition is gentle, the reaction times is short, and the preparation raw materials cost is lower, but mass preparation.
2, selected ionic liquid is stable to water and air, has stronger acidity, and toxicity is low, is prone to by biological degradation.
3, catalyst levels is few, only 0.01 ~ 10wt%; Catalytic activity is high, and transformation efficiency is high, and reaction finishes after product and catalyzer phase-splitting automatically.
4, reaction conditions is gentle, 80 ~ 150 ℃ of temperature, reaction original pressure 0.5 ~ 4MPa; Reaction process is simple, easy and simple to handle, easy to control.
5, the reaction after product distributes, and raw material availability is high.
6, problems such as no equipment corrosion and environmental pollution, the production process environmental friendliness has reduced the corrosion-resistant requirement of equipment simultaneously, the expense of reducing investment outlay.
Embodiment
Catalyzer represent as shown in the formula:
Embodiment 1:
In the 100ml autoclave, add 5.0wt% catalyzer a successively, 29.03g trioxymethylene, 2.97g methyl alcohol.Inflated with nitrogen slowly is heated to 110 ℃ of stirring reaction 6h to pressure 2MPa, and after cooling was left standstill, product was through gas chromatographic analysis, and it forms distribute (% representes with weight) as follows: trioxymethylene, 0.68%; Methyl alcohol, 9.47%; Methylal, 51.67%; N=2,20.20%; N=3 ~ 8,17.98%, n>8, do not detect.
Embodiment 2:
In the 100ml autoclave, add 3.0wt% catalyzer b successively, 9.01g trioxymethylene, 8.04g methyl alcohol.Inflated with nitrogen slowly is heated to 120 ℃ of stirring reaction 5h to pressure 3MPa, and after cooling was left standstill, product was through gas chromatographic analysis, and it forms distribute (% representes with weight) as follows: trioxymethylene, 1.39%; Methyl alcohol, 9.03%; Methylal, 45.34%; N=2,22.94%; N=3 ~ 8,21.3%, n>8, do not detect.
Embodiment 3:
In the 100ml autoclave, add 6.0wt% catalyzer c successively, 9.01g trioxymethylene, 6.75g methyl alcohol.Inflated with nitrogen slowly is heated to 115 ℃ of stirring reaction 7h to pressure 2.5MPa, and after cooling was left standstill, product was through gas chromatographic analysis, and it forms distribute (% representes with weight) as follows: trioxymethylene, 1.94%; Methyl alcohol, 7.31%; Methylal, 40.21%; N=2,24.12%; N=5 ~ 8,26.39%, n>8, surplus.
Embodiment 4:
In the 100ml autoclave, add 2.0wt% catalyzer d successively, 5.01g trioxymethylene, 25.02g methyl alcohol.Inflated with nitrogen slowly is heated to 120 ℃ of stirring reaction 4h to pressure 3MPa, and after cooling was left standstill, product was through gas chromatographic analysis, and it forms distribute (% representes with weight) as follows: trioxymethylene, 0.98%; Methylal, 37.53%; N=2,28.66%; N=3 ~ 8,32.81%, n>8, surplus.
Embodiment 5:
In the 100ml autoclave, add 8.0wt% catalyzer e successively, 13.54g trioxymethylene, 20.31g methyl alcohol.Inflated with nitrogen slowly is heated to 100 ℃ of stirring reaction 5h to pressure 0.5MPa, and after cooling was left standstill, product was through gas chromatographic analysis, and it forms distribute (% representes with weight) as follows: trioxymethylene, 2.12%; Methylal, 36.56%; N=2,26.8%; N=3 ~ 8,34.48%, n>8, surplus.
Embodiment 6:
In the 100ml autoclave, add 1.0wt% catalyzer a successively, 10.57g trioxymethylene, 4.92g methylal.Inflated with nitrogen slowly is heated to 100 ℃ of stirring reaction 1h to pressure 1.5MPa, and after cooling was left standstill, product was through gas chromatographic analysis, and it forms distribute (% representes with weight) as follows: trioxymethylene, 1.86%; Methylal, 32.16%; N=2,26.97%; N=3 ~ 8,38.78%, n>8, surplus.
Embodiment 7:
In the 100ml autoclave, add 0.01wt% catalyzer b successively, 13.52g trioxymethylene, 19.21g methylal.Inflated with nitrogen slowly is heated to 105 ℃ of stirring reaction 5h to pressure 0.9MPa, and after cooling was left standstill, product was through gas chromatographic analysis, and it forms distribute (% representes with weight) as follows: trioxymethylene, 2.12%; Methylal, 36.56%; N=2,26.8%; N=3 ~ 8,34.48%, n>8, surplus.
Embodiment 8:
In the 100ml autoclave, add 10.0wt% catalyzer c successively, 9.00g trioxymethylene, 5.77g methylal.Inflated with nitrogen slowly is heated to 95 ℃ of stirring reaction 7h to pressure 3.5MPa, and after cooling was left standstill, product was through gas chromatographic analysis, and it forms distribute (% representes with weight) as follows: trioxymethylene, 2.31%; Methyl alcohol 5.75%; Methylal, 32.96%; N=2,28.11%; N=3 ~ 8,30.85%, n>8, surplus.
Embodiment 9:
In the 100ml autoclave, add 2.0wt% catalyzer d successively, 15.01g trioxymethylene, 25.02g methylal.Inflated with nitrogen slowly is heated to 120 ℃ of stirring reaction 4h to pressure 3MPa, and after cooling was left standstill, product was through gas chromatographic analysis, and it forms distribute (% representes with weight) as follows: trioxymethylene, 0.98%; Methylal, 37.53%; N=2,28.66%; N=3 ~ 8,32.81%, n>8, surplus.
Embodiment 10:
In the 100ml autoclave, add 8.0wt% catalyzer e successively, 1.54g trioxymethylene, 15.31g methylal.Inflated with nitrogen slowly is heated to 100 ℃ of stirring reaction 5h to pressure 0.5MPa, and after cooling was left standstill, product was through gas chromatographic analysis, and it forms distribute (% representes with weight) as follows: trioxymethylene 0.34%; Methyl alcohol 11.61%; Methylal, 54.12%; N=2,19.73%; N=3 ~ 8,14.20%, n>8, do not detect.
Claims (6)
1. the preparation method of a polyoxymethylene dimethyl ether; It is characterized in that carrying out according to following step: cyclic amide class ionic liquid is a catalyzer; With trioxymethylene and methyl alcohol or trioxymethylene and methylal is raw material; 80 ~ 150 ℃ of temperature of reaction, catalytic preparation polyoxymethylene dme under reaction original pressure 0.5 ~ 4MPa condition.
2. the preparation method of a kind of polyoxymethylene dimethyl ether according to claim 1 is characterized in that wherein said ionic liquid is a cyclic amide class ionic liquid, and chemical structure of general formula is:
Wherein m represents 0 to 8 integer,
X
-Be bisulfate ion, dihydrogen phosphate, p-methyl benzenesulfonic acid root, trifluoromethayl sulfonic acid root, a kind of in methylsulphonic acid root, trifluoroacetic acid root, formate, the acetate.
3. the preparation method of a kind of polyoxymethylene dimethyl ether according to claim 1 is characterized in that wherein said catalyst levels is a total reactant quality 0.01 ~ 10%.
4. the preparation method of a kind of polyoxymethylene dimethyl ether according to claim 1 is characterized in that with trioxymethylene and methyl alcohol be raw material, and wherein the mass ratio of trioxymethylene and methyl alcohol is 1:0.1～5.
5. the preparation method of a kind of polyoxymethylene dimethyl ether according to claim 1 is characterized in that being raw material with trioxymethylene and methylal perhaps, and wherein the mass ratio of trioxymethylene and methylal is 1:0.5～10.
6. the preparation method of a kind of polyoxymethylene dimethyl ether according to claim 2 is characterized in that wherein m=0,3 or 4.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106635249A (en) * | 2016-10-17 | 2017-05-10 | 江苏高科石化股份有限公司 | Method for preparing bio-lubricant base oil through hydrosilylation of biodiesel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665414A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Method for catalytically synthesizing polymethoxy methylal by using ionic liquid |
| CN102120728A (en) * | 2011-01-10 | 2011-07-13 | 常州大学 | Sulfonic- functionalized caprolactam acidic ion liquid and preparation method thereof |
| CN102249868A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Technical process for preparing polymethoxy dimethyl ether by subjecting formaldehyde and methanol to acetalation reaction |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665414A (en) * | 2008-09-04 | 2010-03-10 | 中国科学院兰州化学物理研究所 | Method for catalytically synthesizing polymethoxy methylal by using ionic liquid |
| CN102249868A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Technical process for preparing polymethoxy dimethyl ether by subjecting formaldehyde and methanol to acetalation reaction |
| CN102120728A (en) * | 2011-01-10 | 2011-07-13 | 常州大学 | Sulfonic- functionalized caprolactam acidic ion liquid and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106635249A (en) * | 2016-10-17 | 2017-05-10 | 江苏高科石化股份有限公司 | Method for preparing bio-lubricant base oil through hydrosilylation of biodiesel |
| CN106635249B (en) * | 2016-10-17 | 2019-08-30 | 江苏高科石化股份有限公司 | A kind of method that the hydrogenation of biodiesel silicon prepares Biolubrication oil base oil |
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Effective date of registration: 20201113 Address after: 226408 Xinjian West Road, Fengli Town, Rudong County, Nantong City, Jiangsu Province Patentee after: Rudong Wenyuan investment and Development Co., Ltd Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: CHANGZHOU University |