CN104449898B - A kind of automobile-used ethers is mixed fuel burning and preparation method thereof - Google Patents

A kind of automobile-used ethers is mixed fuel burning and preparation method thereof Download PDF

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CN104449898B
CN104449898B CN201410679719.2A CN201410679719A CN104449898B CN 104449898 B CN104449898 B CN 104449898B CN 201410679719 A CN201410679719 A CN 201410679719A CN 104449898 B CN104449898 B CN 104449898B
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dmm
automobile
fuel burning
dimethoxymethane
metaformaldehyde
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CN104449898A (en
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刘锦超
张斌
李华
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Chengdu Green Innovation Energy Technology Group Co ltd
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SICHUAN AIR INVESTMENT Co Ltd
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Abstract

The invention discloses a kind of automobile-used ethers and mix fuel burning, belong to clean fuel for vehicle field, it is polymethoxy dimethyl ether DMM that described automobile-used ethers is mixed fuel burningn, wherein, 1≤n≤7, described polymethoxy dimethyl ether DMMnPrepared by dimethoxymethane and metaformaldehyde, preparation method reacts for dimethoxymethane, metaformaldehyde and catalyst by proportion are put into reaction vessel, after metaformaldehyde reacts completely, isolate unreacted dimethoxymethane and product DMM1-2With DMM3-7, the whole preparation process of the present invention is simpler, greatly reduces preparation cost, and catalyst of the present invention is less for the corrosivity of equipment, and productive rate can reach more than 95%.

Description

A kind of automobile-used ethers is mixed fuel burning and preparation method thereof
Technical field
The present invention relates to clean fuel for vehicle field, particularly a kind of automobile-used ethers of being prepared by dimethoxymethane and metaformaldehyde is mixed fuel burning and preparation method thereof.
Background technology
Along with society and expanding economy, the recoverable amount of automobile is increasing; Meanwhile, the ratio that emission from vehicles accounts in atmosphere pollution factor for the pollution of air is increasing. In order to alleviate the air pollution day by day increasing the weight of, clean fuel oil becomes the important directions of people's research.
In existing research and application, except the discharge of the improvement by PETROLEUM PROCESSING technique with less Vehicular exhaust, another important direction is to add and mix fuel burning in existing fuel oil, promotes on the one hand automobile power retrieval fuel consume, can reduce on the other hand exhaust emissions.
Existing research shows, polymethoxy dimethyl ether (DMMn), have that [molecular formula is CH with diesel oil core component alkane3(CH2)nCH3] closely similar molecular structure, polymethoxy dimethyl ether general structure is CH3O(CH2O)nCH3, according to the similar general principle mixing, the intersolubility of itself and diesel oil is good;
Meanwhile, DMMnThere is higher oxygen content (42%~49%) and higher Cetane number (DMM3~8Cetane number all more than 78); Polymethoxy dimethyl ether (DMMn) oxygen atom be combined with singly-bound with carbon atom, in conjunction with can be higher, easily activation forms the molecule with oxidative function, mixes at diesel oil the difficulty that has overcome burning anoxic and few oxygen in burning process, makes the engine combustion efficiency and heat utilization efficiency increase of motor vehicles. Causing carbon monoxide, hydrocarbon and soot decline in the tail gas of motor vehicles discharges, is a kind of clean energy resource of energy-saving and emission-reduction;
So lot of documents has been reported DMMn, wherein n >=3, especially DMM3~8Being suitable as the fuel burning of mixing of diesel oil, is that the diesel oil that a class is good is mixed burning component.
So far, there is the multiple polymethoxy dimethyl ether (DMM for preparingn) method be in the news (as US2008/0221368Al, US.Pat.No.6166266, US.PalNo.6160174, US.Pat.No.6265828Bl, CN.10199266.4, CN.10190967.1, CN10397887.3, CN.101110297908.X etc.). By polymethoxy dimethyl ether (DMMn) molecular formula [CH3O(CH2O)nCH3] known, its building-up process is mainly synthesized by the compound (formaldehyde, metaformaldehyde and paraformaldehyde etc.) of paraformaldehyde and the compound (methyl alcohol, dimethyl ether and dimethoxymethane etc.) of sealing end of its interlude.
There is following shortcoming in above method:
(1) above method is all to mix the DMM of fuel burning with combined diesel oiln(n >=3) are object, and in course of reaction, all can produce a certain amount of DMM1And DMM2, and DMM1-2Be not suitable as diesel oil because flash-point is low and mix fuel burning, need to be by DMM1And DMM2After separation, again react, to remove DMM1And DMM2, cause production process to extend, production efficiency is low;
(2) above method all has water byproduct to generate in process of production, and water easily decomposes synthetic polymethoxy dimethyl ether under acidic catalyst, forms unsettled hemiacetal, has increased the purification difficulty of polymethoxy dimethyl ether.
Summary of the invention
One of goal of the invention of the present invention, is to provide a kind of new automobile-used ethers to mix fuel burning, to address the above problem.
The technical solution used in the present invention is such: a kind of automobile-used ethers is mixed fuel burning, and it is polymethoxy dimethyl ether DMM that described automobile-used ethers is mixed fuel burningn, wherein, 1≤n≤7.
As preferred technical scheme, described polymethoxy dimethyl ether DMMn is prepared by dimethoxymethane and metaformaldehyde.
As preferred technical scheme, described DMM1-2With DMM3-7Ratio, count by weight DMM1-2:DMM3-7=2:8~3:7。
As further preferred technical scheme, described DMM1With DMM2Ratio, count by weight DMM1:DMM2=2:8~3:7。
As further preferred technical scheme, described DMM3、DMM4、DMM5、DMM6With DMM7Ratio, count by weight DMM3:DMM4:DMM5:DMM6:DMM7=25:30:25:15:5。
Two of goal of the invention of the present invention, the preparation method who provides a kind of above-mentioned automobile-used ethers to mix fuel burning is provided.
The technical scheme adopting is: dimethoxymethane, metaformaldehyde and catalyst by proportion are put into reaction vessel and react, after metaformaldehyde reacts completely, isolate unreacted dimethoxymethane and product DMM1-2With DMM3-7
After metaformaldehyde reacts completely, remaining reactant is dimethoxymethane, is easier to separate.
As preferred technical scheme: the additional proportion of described dimethoxymethane and metaformaldehyde, is calculated in molar ratio as dimethoxymethane: metaformaldehyde=1:2~2:3.
React with metaformaldehyde because dimethoxymethane in course of reaction has enough amounts, dimethoxymethane is excessive, and metaformaldehyde is at DMMnO'clock almost complete reaction of polymerization degree n≤7, be difficult to polymerization again and form the DMM of n > 7n
As preferred technical scheme: described dimethoxymethane and metaformaldehyde are taked intermittent reaction, and wherein reaction temperature is 50 DEG C~130 DEG C, and reaction pressure is 0.8MPa~2.0MPa.
As preferred technical scheme: described dimethoxymethane takes continuation mode to react with metaformaldehyde, and wherein reaction temperature is 60 DEG C~120 DEG C, and reaction pressure is 1.0MPa~1.8MPa.
Under this temperature and pressure, metaformaldehyde early reacts with excessive dimethoxymethane, forms the DMM of n≤7n
As preferred technical scheme: the purity of described reactant dimethoxymethane is more than 99.0%. Avoid moisture in reactant and cause the generation of hemiacetal.
As preferred technical scheme: the purity of described reactant metaformaldehyde is more than 99.5%. Avoid moisture in reactant and cause the generation of hemiacetal.
As preferred technical scheme: the addition of described catalyst, by weight, reactant: catalyst=100:10~100:5.
As preferred technical scheme: described catalyst is acid cation catalyst, described acid cation catalyst is the mixture of styrene type cation exchange resin and sulfonation fluoroolefins resin derivative, by weight, styrene type cation exchange resin: sulfonation fluoroolefins resin derivative=5:5~4:6. This ratio catalytic efficiency is high.
As further preferred technical scheme: described acid cation catalyst uses high activity resin fixed bed reactors, and one of its resin is following kind: (1) sulfonation tetrafluoroethene and styrene, divinyl benzene copolymer (2) acrylic acid, divinyl benzene copolymer (3) methacrylic acid, divinyl benzene copolymer. Resin is little to equipment corrosion, and catalytic efficiency is high.
The present invention adopts above-mentioned preparation method to prepare DMM1-7, and separation obtains DMM1And DMM2, and the present inventor is by experimental results demonstrate: DMM1And DMM2Can be used as gasoline and mix fuel burning, can greatly improve the quality of gasoline, thereby can make full use of the DMM that needs to separate removal in prior art1And DMM2, especially DMM1Thereby, simplify preparation process, and the added value of product is promoted greatly.
In sum, owing to having adopted technique scheme, the invention has the beneficial effects as follows:
(1) due to DMM1-2Be one of target product of the present invention, because the present invention is by the control to reaction raw materials and condition, only generate DMM1-7, reaction finishes only need be to DMM1-2And DMM3-7Separate, so whole preparation process is simpler, greatly reduce preparation cost;
(2) the present invention can be by the addition of reaction raw materials, thereby can select the wherein one in reaction raw materials dimethoxymethane and metaformaldehyde to recycle, and reaction raw materials utilization rate is high,
(3) catalyst of the present invention catalytic activity in reaction of the present invention is strong, and catalytic efficiency is high, less for the corrosivity of equipment.
(4) reaction yield of the present invention is high, and its productive rate can reach more than 95%.
Detailed description of the invention
The present invention is described in detail below.
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated. Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1:
Intermittent reaction is prepared DMM1-7
Preparation process is:
220 grams of high activity acid cation catalyst styrene type cation exchange resins and sulfonation fluoroolefins resin derivative 220 grams (weight ratio is 5:5) are fixed on resin bed;
The dimethoxymethane 1520g that is 99.2% by purity and 99.6% metaformaldehyde 2700g(mol ratio are 2:3) send into reactor;
The temperature of reactor is controlled between 50 DEG C and 120 DEG C;
The pressure of reactor is controlled between 1.0MPa and 2.0MPa;
In detection reaction device, after metaformaldehyde complete reaction, stop reaction;
All mixtures in reactor are carried out to board-like rectification under vacuum one-level and separate, isolate respectively polymethoxy dimethyl ether DMMn(1≤n≤7) and unreacted dimethoxymethane;
Then by DMMn(1≤n≤7) mixture carries out board-like rectification under vacuum the second-order separation, isolates respectively DMM1-2And DMM3-7
DMM1-2Middle DMM2Component exceed 30%(mass fraction) time, set it as reactant and enter again reaction system, until DMM2Content be 20%; This ratio is more suitable for DMM1-2Mix fuel burning as gasoline;
And then separate respectively DMM1-2And DMM3-7, obtain DMM1、DMM2、DMM3、DMM4、DMM5、DMM6With DMM7
Result: the DMM obtaining1、DMM2、DMM3、DMM4、DMM5、DMM6With DMM7Weight ratio be respectively: 5:15:25:25:15:10:5;
Productive rate is: 95.3%.
Embodiment 2:
Intermittent reaction is prepared DMM1-7
Preparation process is:
100 grams of high activity acid cation catalyst styrene type cation exchange resins and sulfonation fluoroolefins resin derivative 250 grams (weight ratio is 4:6) are fixed on resin bed;
The dimethoxymethane 760g that is 99.3% by purity and 99.8% metaformaldehyde 1800g(mol ratio are 1:2) send into reactor;
The temperature of reactor is controlled between 60 DEG C and 130 DEG C;
The pressure of reactor is controlled between 1.1MPa and 2.1MPa;
In detection reaction device, after metaformaldehyde complete reaction, stop reaction;
All mixtures in reactor are carried out to board-like rectification under vacuum one-level and separate, isolate respectively polymethoxy dimethyl ether DMMn(1≤n≤7) and unreacted dimethoxymethane;
Then by DMMn(1≤n≤7) mixture carries out board-like rectification under vacuum the second-order separation, isolates respectively DMM1-2And DMM3-7
And then separate respectively DMM1-2And DMM3-7, obtain DMM1、DMM2、DMM3、DMM4、DMM5、DMM6With DMM7
Result: the DMM obtaining1、DMM2、DMM3、DMM4、DMM5、DMM6With DMM7Weight ratio be respectively: 5:10:25:30:10:10:10;
Productive rate is: 95.4%.
Embodiment 3:
Continuous reaction is prepared DMM1-7
Preparation process is:
330 grams of high activity acid cation catalyst styrene type cation exchange resins and sulfonation fluoroolefins resin derivative 330 grams (weight ratio is 5:5) are fixed on resin bed;
The dimethoxymethane 2280g that is 99.2% by purity and 99.7% metaformaldehyde 4500g(mol ratio are 3:5) send into reactor;
The temperature of reactor is controlled between 70 DEG C and 120 DEG C;
The pressure of reactor is controlled between 1.0MPa and 1.6MPa;
The reaction velocity of dimethoxymethane and metaformaldehyde is 50h-1~500h-1
All mixtures in reactor are carried out to board-like rectification under vacuum one-level and separate, isolate respectively polymethoxy dimethyl ether DMMn(1≤n≤7) and unreacted dimethoxymethane;
Then by DMMn(1≤n≤7) mixture carries out board-like rectification under vacuum the second-order separation, isolates respectively DMM1-2And DMM3-7
DMM1-2Middle DMM2Component exceed 30%(mass fraction) time, set it as reactant and enter again reaction system, until DMM2Content be 20%; This ratio is more suitable for DMM1-2Mix fuel burning as gasoline;
And then separate respectively DMM1-2And DMM3-7, obtain DMM1、DMM2、DMM3、DMM4、DMM5、DMM6With DMM7
Result: the DMM obtaining1、DMM2、DMM3、DMM4、DMM5、DMM6With DMM7Weight ratio be respectively: 5:15:30:30:10:5:5;
Productive rate is: 95.7%.
Embodiment 4:
Continuous reaction is prepared DMM1-7
Preparation process is:
168 grams of high activity acid cation catalyst styrene type cation exchange resins and sulfonation fluoroolefins resin derivative 252 grams (weight ratio is 4:6) are fixed on resin bed;
The dimethoxymethane 1520g that is 99.2% by purity and 99.7% metaformaldehyde 2700g(mol ratio are 2:3) send into reactor;
The temperature of reactor is controlled between 50 DEG C and 110 DEG C;
The pressure of reactor is controlled between 1.2MPa and 1.8MPa;
The reaction velocity of dimethoxymethane and metaformaldehyde is 50h-1~500h-1
All mixtures in reactor are carried out to board-like rectification under vacuum one-level and separate, isolate respectively polymethoxy dimethyl ether DMMn(1≤n≤7) and unreacted dimethoxymethane;
Then by DMMn(1≤n≤7) mixture carries out board-like rectification under vacuum the second-order separation, isolates respectively DMM1-2And DMM3-7
And then separate respectively DMM1-2And DMM3-7, obtain DMM1、DMM2、DMM3、DMM4、DMM5、DMM6With DMM7
Result: the DMM obtaining1、DMM2、DMM3、DMM4、DMM5、DMM6With DMM7Weight ratio be respectively: 5:10:30:30:15:5:5;
Productive rate is: 95.2%.
Embodiment 5
The present embodiment is by DMM1And DMM2Add in gasoline and mix fuel burning as gasoline, for improving the test of gasoline quality, its concrete test procedure and result are as follows:
By DMM1And DMM2Be that 8:2 adds 93 to according to weight ratio#In gasoline, addition is 93#20% of gasoline volume, the clean gasoline of concocting by mixture technique carries out platform experiment, power performance and 93#Gasoline is substantially suitable, and discharge performance result is: pollutants of idle speed emission CO is compared with 93#Gasoline reduces by 35.67%, and pollutants of idle speed emission HC is compared with 93#Gasoline reduces by 32.6%, NOXAll inspection is not shown in.

Claims (12)

1. automobile-used ethers is mixed a fuel burning, it is characterized in that, it is polymethoxy dimethyl ether DMMn that described automobile-used ethers is mixed fuel burning, wherein, and 1≤n≤7;
The ratio of described DMM1-2 and DMM3-7, counts by weight, DMM1-2:DMM3-7=2:8~3:7;
The ratio of described DMM1 and DMM2, counts by weight, DMM1:DMM2=2:8~3:7.
2. the automobile-used ethers of one according to claim 1 is mixed fuel burning, it is characterized in that, described polymethoxy dimethyl ether DMMn is prepared by dimethoxymethane and metaformaldehyde.
3. the automobile-used ethers of one according to claim 1 is mixed fuel burning, it is characterized in that, the ratio of described DMM3, DMM4, DMM5, DMM6, DMM7, counts by weight, DMM3:DMM4:DMM5:DMM6:DMM7=25:30:25:15:5.
4. the preparation method that the automobile-used ethers described in claims 1 to 3 any one is mixed fuel burning, it is characterized in that, dimethoxymethane, metaformaldehyde and catalyst by proportion are put into reaction vessel reacts, after metaformaldehyde reacts completely, isolate unreacted dimethoxymethane and product DMM1-2 and DMM3-7.
5. the preparation method that automobile-used ethers according to claim 4 is mixed fuel burning, is characterized in that: the additional proportion of described dimethoxymethane and metaformaldehyde, is calculated in molar ratio as dimethoxymethane: metaformaldehyde=1:2~2:3.
6. the preparation method that automobile-used ethers according to claim 4 is mixed fuel burning, is characterized in that: described dimethoxymethane and metaformaldehyde are taked intermittent reaction, and wherein reaction temperature is 50 DEG C~130 DEG C, and reaction pressure is 0.8MPa~2.0MPa.
7. the preparation method that automobile-used ethers according to claim 4 is mixed fuel burning, is characterized in that: described dimethoxymethane takes continuation mode to react with metaformaldehyde, and wherein reaction temperature is 60 DEG C~120 DEG C, and reaction pressure is 1.0MPa~1.8MPa.
8. the preparation method that automobile-used ethers according to claim 4 is mixed fuel burning, is characterized in that: the purity of described reactant dimethoxymethane is more than 99.0%.
9. the preparation method that automobile-used ethers according to claim 4 is mixed fuel burning, is characterized in that: the purity of described reactant metaformaldehyde is more than 99.5%.
10. the preparation method that automobile-used ethers according to claim 4 is mixed fuel burning, is characterized in that: the addition of described catalyst, by weight, reactant: catalyst=100:10~100:5.
The preparation method that 11. automobile-used ethers according to claim 4 are mixed fuel burning, it is characterized in that: described acid cation catalyst is the mixture of styrene type cation exchange resin and sulfonation fluoroolefins resin derivative, by weight, styrene type cation exchange resin: sulfonation fluoroolefins resin derivative=5:5~4:6.
The preparation method that 12. automobile-used ethers according to claim 11 are mixed fuel burning, it is characterized in that: described acid cation catalyst uses high activity resin fixed bed reactors, and one of its resin is following kind: (1) sulfonation tetrafluoroethene and styrene, divinyl benzene copolymer (2) acrylic acid, divinyl benzene copolymer (3) methacrylic acid, divinyl benzene copolymer.
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US5746785A (en) * 1997-07-07 1998-05-05 Southwest Research Institute Diesel fuel having improved qualities and method of forming
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CN103420817B (en) * 2012-05-16 2016-05-18 中国石油化工股份有限公司 By the method for dimethoxym ethane and paraformaldehyde synthesizing polyoxymethylene dimethyl ether
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