CN101942349B - High-environmental-protection clean gasoline additive and preparation method thereof - Google Patents
High-environmental-protection clean gasoline additive and preparation method thereof Download PDFInfo
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- CN101942349B CN101942349B CN 201010272930 CN201010272930A CN101942349B CN 101942349 B CN101942349 B CN 101942349B CN 201010272930 CN201010272930 CN 201010272930 CN 201010272930 A CN201010272930 A CN 201010272930A CN 101942349 B CN101942349 B CN 101942349B
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Abstract
The invention relates to a high-environmental-protection clean gasoline additive and a preparation method thereof. The gasoline additive is prepared from the following components in percentage by weight: 89-95 percent of clean antiknock, 3-5 percent of carboxylic aromatic ester and 2-6 percent of arylamine which sum up to 100 percent. The preparation method of the high-environmental-protection clean gasoline additive comprises the following steps of: respectively taking one of methylal or acetal, C1-C10 saturated alcohol and a catalyst according to a weight ratio of 0.55-0.75:1:0.05; carryingout a reflux reaction at 60+/-5 DEG C for 5-6 h; rectifying and recycling the liquid at 60-90 DEG C to prepare a clean antiknock; adding the carboxylic aromatic ester and the arylamine to the clean antiknock, slowly stirring, evenly mixing, filtering and collecting the filtrate to obtain the high-environmental-protection clean gasoline additive. The gasoline additive of the invention can improve the octane value of the gasoline and decrease the production cost without containing banned substances.
Description
Technical field
The invention belongs to energy technology field, relate to a kind of additive that can improve gasoline octane rating, the enhancing gasoline capability of antidetonance, reduce objectionable impurities in the tail gas, be specifically related to a kind of high-environmental-protection clean gasoline additive, the invention still further relates to the preparation method of this gasoline dope.
Background technology
Gasoline is as the fuel that generally uses, be widely used in the various vehicles, for it provides power, but gasoline produces a large amount of objectionable impuritiess in combustion processes, atmospheric environment has been caused serious pollution, in order to reduce the pollution that produces when fuel oil uses, people have carried out strict control to the discharging of vehicle fuel tail gas, and require unleaded gasoline, low alkene, low emission, high grade.A lot of countries have spent many manpowers, financial resources are carried out the research that fuel oil hangs down pollution, low emission.Simultaneously, adopt " double fuel ", with dynamic performance (raising power), reduction fuel consumption, the minimizing exhaust emissions that improves fuel.But adopt " double fuel " to need the combustion system of engine of vehicle is changed accordingly, also need existing service station is transformed, not only need to drop into a large amount of funds, and effect is not fully up to expectations.
As everyone knows, the usefulness of fuel oil on engine is fixed with the compression ratio of engine, and larger its usefulness of compression ratio is also higher, and power also improves thereupon.And engine compression ratio just increases the requirement of fuel after improving thereupon.Modern Automobile Engine must have high-octane gasoline to match for raising the efficiency.But the octane value in the gasoline that the employing prior art makes is decided by the factory state of refinery.Refinery adopt more the methods such as base oil catalysis, hot tearing, reformation, isomerization with produce the saturated alkane that more has fork chain or with the compound of this saturated alkane similar, increase the ratio of these compounds in gasoline, thereby improve the octane value of gasoline.But these methods are time-consuming, power consumption, effect are very unobvious, and increased cost.At present, by improve the dispatch from the factory octane value of gasoline of refinery with additive, as in gasoline, adding tetraethyllead, methyl tertiary butyl ether (MTBE) etc., but there is following problem in these additives: tetraethyllead has severe toxicity, now forbid, methyl tertiary butyl ether (MTBE) pollutes underground water, and developed country also forbids, and the content of manganese metal, iron in the gasoline is also had clearly restriction.
Summary of the invention
In order to overcome above-mentioned problems of the prior art, the purpose of this invention is to provide a kind of high-environmental-protection clean gasoline additive, can not only improve the octane value of gasoline, reduce production costs, and do not contain banned substance.
Another object of the present invention provides a kind of preparation method of above-mentioned gasoline dope.
For achieving the above object, the technical solution adopted in the present invention is, high-environmental-protection clean gasoline additive, can improve the octane value of gasoline, and do not contain banned substance, this gasoline dope, by weight percentage, cleaning octane promoter by 89%～95%, 3%～5% carboxy acid aromatic ester and 2%～6% arylamine form each component total amount 100%.
The cleaning octane promoter adopts following method to make: by weight 0.55～0.75: 1: 0.05, get respectively a kind of, C1～C10 saturated alcohol and catalyzer in methylal〔Su〕 or the acetal, place under 60 ± 5 ℃ the temperature, back flow reaction 5 hours～6 hours, 60 ℃～90 ℃ liquid is reclaimed in rectifying, and this liquid is the cleaning octane promoter that makes.
Catalyzer adopts sulfuric acid, hydrochloric acid, phosphoric acid or sulfonic acid.
The carboxy acid aromatic ester adopts formic acid-2,4-Dimethoxyphenyl ester.
Arylamine adopts DMA or 2,4-xylidine.
Another technical scheme of the present invention is, a kind of preparation method of above-mentioned gasoline dope carries out according to the following steps:
Step 1: by weight 0.55～0.75: 1: 0.05, get respectively a kind of, C1～C10 saturated alcohol and catalyzer in methylal〔Su〕 or the acetal, place under 60 ± 5 ℃ the temperature back flow reaction 5 hours～6 hours, 60 ℃～90 ℃ liquid is reclaimed in rectifying, makes the cleaning octane promoter;
Step 2: by weight percentage, get respectively the cleaning octane promoter 89%～95% that carboxy acid aromatic ester 3%～5%, arylamine 2%～6% and step 1 make, each component total amount 100%;
Step 3: carboxy acid aromatic ester and arylamine are added in the cleaning octane promoter, slowly stir, make liquid mixing even;
Step 4: the liquid that mixes in the step 3 is filtered, collect filtrate, make high-environmental-protection clean gasoline additive.
Stirring velocity in the step 3 is 400 rev/mins～600 rev/mins.
Gasoline dope of the present invention has the following advantages:
1. simple, little, easy to operate, the high efficiency of investment of preparation technology.
2. nontoxic, the stable performance of each component, use are safe, economical.Only there are anti-knocking property, not environmental protection to have obvious superiority than traditional tetraethyllead (severe toxicity).
3. compare with methyl tertiary butyl ether, cost is low, and environmental protection.
4. the main raw material of cleaning octane promoter is methyl alcohol, and 1.5 tons of methyl alcohol can be produced 1 ton of cleaning octane promoter, and the cleaning octane promoter is addition large (15～25%) in gasoline component, has realized that truly coal-based alternative fuel engineering is newly selected.
5. not needing to rely on petroleum products can finish, and not only is petroleum industry, and has opened up extremely wide prospect for the development of Coal Chemical Industry industry.
Description of drawings
Fig. 1 is that motor speed is 2000 rev/mins, when adopting respectively gasoline, propellant combination 1 or propellant combination 2 to act as a fuel, and engine effective thermal efficiency and mean effective pressure relation curve comparison diagram.
Fig. 2 is that motor speed is 4000 rev/mins, when adopting respectively gasoline, propellant combination 1 or propellant combination 2 to act as a fuel, the engine effective thermal efficiency with mean effective pressure relation curve comparison diagram.
Fig. 3 is that motor speed is 2000 rev/mins, when adopting respectively gasoline, propellant combination 1 or propellant combination 2 to act as a fuel, and the relation curve comparison diagram of the hydrocarbon of discharging and mean effective pressure.
Fig. 4 is that motor speed is 2000 rev/mins, when adopting respectively gasoline, propellant combination 1 or propellant combination 2 to act as a fuel, and the relation curve comparison diagram of the carbon monoxide of discharging and mean effective pressure.
Fig. 5 is that motor speed is 2000 rev/mins, when adopting respectively gasoline, propellant combination 1 or propellant combination 2 to act as a fuel, and the relation curve comparison diagram of the nitride of discharging and mean effective pressure.
Fig. 6 is that motor speed is 4000 rev/mins, when adopting respectively gasoline, propellant combination 1 or propellant combination 2 to act as a fuel, and the relation curve comparison diagram of the hydrocarbon of discharging and mean effective pressure.
Fig. 7 is that motor speed is 4000 rev/mins, when adopting respectively gasoline, propellant combination 1 or propellant combination 2 to act as a fuel, and the relation curve comparison diagram of the carbon monoxide of discharging and mean effective pressure.
Fig. 8 is that motor speed is 4000 rev/mins, when adopting respectively gasoline, propellant combination 1 or propellant combination 2 to act as a fuel, and the relation curve comparison diagram of the nitride of discharging and mean effective pressure.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
High-environmental-protection clean gasoline additive of the present invention (HLK) can be used in refinery; improve gasoline octane rating; reduce the olefin(e) centent in the gasoline, further reduce the tooling cost of refinery, improve engine power, save energy, minimizing pollution, protection of the environment.
Gasoline dope of the present invention, by weight percentage, the cleaning octane promoter by 89～95%, 3～5% carboxy acid aromatic ester and 2～6% arylamine form each component total amount 100%.
Wherein, the cleaning octane promoter adopts following methods to make: by weight 0.55～0.75: 1: 0.05, get respectively a kind of, C1～C10 saturated alcohol and catalyzer in methylal〔Su〕 or the acetal, back flow reaction is 5～6 hours under 60 ℃ ± 5 ℃ temperature, 60 ℃～90 ℃ liquid are reclaimed in rectifying, and this liquid is the cleaning octane promoter.
Catalyzer adopts sulfuric acid, hydrochloric acid, phosphoric acid or sulfonic acid, preferred sulfonic acid.
The carboxy acid aromatic ester adopts formic acid-2,4-Dimethoxyphenyl ester.
Arylamine adopts DMA or 2,4-xylidine.
This gasoline dope is in cylinder during pyrolytic decomposition, the chain that the chain of the free radical of active gene and pinking reaction becomes reaction produces rapidly chemical reaction variation, thereby it is strongly active to eliminate it, the free radical that suppresses superoxide, generate stable isomeric compound, weaken cool flame intensity, the pinking fission reaction is stopped.
Free radical chain oxidizing reaction change procedure is as follows:
RH+O
2→RO-O-H→RO+OH
RO+O
2→RO
2
RO
2+RH→ROOH+R
ROOH→RO+OH
Above-mentioned various in, R, HO
2With RO be free radical, ROOH is organo-peroxide.
The reaction that adds behind the additive of the present invention is:
RO→O→H+RO+OH+R→O→O→
ROOH+CnO
2--→CnO+H
2O
Can find out from following formula, add that the resultant of free radical chain oxidizing reaction is behind the gasoline dope of the present invention: alcohol, aldehyde, acid, nitrogen peroxide, water etc.
The present invention also provides a kind of preparation method of above-mentioned gasoline dope, specifically carries out according to the following steps:
Step 1: by weight 0.55～0.75: 1: 0.05, get respectively a kind of, C1～C10 saturated alcohol and catalyzer in methylal〔Su〕 or the acetal, place under 60 ± 5 ℃ the temperature back flow reaction 5～6 hours, 60 ℃～90 ℃ liquid is reclaimed in rectifying, makes the cleaning octane promoter;
Step 2: by weight percentage, get respectively the cleaning octane promoter 89～95% that carboxy acid aromatic ester 3～5%, arylamine 2～6% and step 1 make, the each component total amount is 100%;
Step 3: the cleaning octane promoter that adopts explosion-proof pump that step 2 is got is squeezed into enamel (stainless steel) mediation still, then, add carboxy acid aromatic ester and arylamine that step 2 is got, slowly stir, 400～600 rev/mins of stirring velocitys mix the liquid in the mediation still fully;
Step 4: the liquid that mixes in the step 3 is filtered with filter, collect filtrate, make high-environmental-protection clean gasoline additive.
1: 3 in mass ratio～5, get respectively this gasoline dope and GB 90# gasoline, after the employing ordinary method is in harmonious proportion, can use.
Embodiment 1
By weight 0.55: 1: 0.05, get respectively methylal〔Su〕, C1 saturated alcohol and sulfonic acid, under 60 ℃ condition, back flow reaction 5 hours, 60 ℃ liquid is reclaimed in rectifying, makes the cleaning octane promoter; Get respectively formic acid-2,4-Dimethoxyphenyl ester 3 grams, DMA 2 grams and cleaning octane promoter 95 grams that make; Adopt explosion-proof pump will clean octane promoter and squeeze into enamel mediation still, then, add the formic acid-2 of getting, 4-Dimethoxyphenyl ester and DMA slowly stir, and 500 rev/mins of stirring velocitys mix the liquid in the mediation still fully; This liquid is filtered with filter, collect filtrate, make high-environmental-protection clean gasoline additive.
With 15 restrain gasoline dope add in the 85 gram GB 90# gasoline, mix and be 93# gasoline; With 20 restrain gasoline dope add in the 80 gram GB 90# gasoline, mix and be 97# gasoline; With 15 restrain gasoline dope add in the 85 gram direct current gasoline, mix, obtain composite fuels 1; With 20 restrain gasoline dope add in the 80 gram direct current gasoline, mix, obtain composite fuels 2.The octane value of 93# gasoline, 97# gasoline, composite fuels 1 and the composite fuels 2 that preparation is obtained is measured respectively, and the measurement result of octane value is as shown in table 1.
The octane value of the sample gasoline that table 1 obtains after adopting gasoline dope of the present invention and regular price gasoline to prepare
Table 1 shows, behind the adding gasoline dope of the present invention, so that the octane value of gasoline increases, illustrates that this gasoline dope can improve the octane value of gasoline in regular price gasoline.
The physical parameter of regular price gasoline and additive of the present invention, as shown in table 2.
The physical parameter of table 2 regular price gasoline and gasoline dope of the present invention
By calculating the significant parameter of regular price gasoline, composite fuels 1 and composite fuels 2, as shown in table 3.
The significant parameter of table 3 regular price gasoline, composite fuels 1 and composite fuels 2
As can be seen from Table 3, along with the increase of gasoline dope consumption in the propellant combination, the latent heat of vaporization value of fuel increases, and low heat value reduces.
When motor speed is respectively 2000 rev/mins, 4000 rev/mins, adopt gasoline, propellant combination 1 or propellant combination 2 to act as a fuel, the engine effective thermal efficiency that obtains and the relation curve comparison diagram of mean effective pressure, as depicted in figs. 1 and 2.As can be seen from Figure, compare with gasoline, the effective thermal efficiency of propellant combination is improved, more obvious during high rotating speed, the rate of consumption of explanation propellant combination under identical mean effective pressure increases to some extent than gasoline, but the specific fuel oil consumption that is converted to when petrol reduces the effective thermal efficiency raising.
When motor speed is 2000 rev/mins, adopt respectively gasoline, propellant combination 1 or propellant combination 2 to act as a fuel, the relation curve of the hydrocarbon of discharging, carbon monoxide and nitride and mean effective pressure is such as Fig. 3, Fig. 4, shown in Figure 5; When motor speed is 4000 rev/mins, adopt respectively gasoline, propellant combination 1 or propellant combination 2 to act as a fuel, the relation curve of the hydrocarbon of discharging, carbon monoxide, nitride and mean effective pressure is such as Fig. 6, Fig. 7, shown in Figure 8.Show among the figure, the discharging of the hydrocarbon of propellant combination and carbon monoxide emission are all lower than gasoline under the high rotating speed, and emitting nitride does not significantly change.Illustrate under the identical mean effective pressure, the hydrocarbon during the gasoline propellant combination, carbon monoxide emission reduce with the increase of oxygen level in the fuel, have improved on the whole the discharging of petrol motor tail gas.
Embodiment 2
By weight 0.75: 1: 0.05, get respectively acetal, C10 saturated alcohol and sulfuric acid, under 65 ℃ temperature, back flow reaction 6 hours, 90 ℃ liquid is reclaimed in rectifying, makes the cleaning octane promoter; By weight percentage, get respectively formic acid-2,4-Dimethoxyphenyl ester 3%, DMA 2% and the cleaning octane promoter 95% that makes; Adopt explosion-proof pump will clean octane promoter and squeeze into stainless steel mediation still, then, add formic acid-2,4-Dimethoxyphenyl ester and DMA slowly stir with 400 rev/mins rotating speeds, and the liquid in the mediation still is mixed fully; This liquid that mixes is filtered with filter, collect filtrate, make high-environmental-protection clean gasoline additive.
Embodiment 3
By weight 0.65: 1: 0.05, get respectively methylal〔Su〕, C5 saturated alcohol and hydrochloric acid, under 55 ℃ temperature, back flow reaction 5.5 hours, 75 ℃ liquid is reclaimed in rectifying, makes the cleaning octane promoter; By weight percentage, get respectively formic acid-2,4-Dimethoxyphenyl ester 5%, 2,4-xylidine 6% and the cleaning octane promoter 89% that makes; Adopt explosion-proof pump will clean octane promoter and squeeze into enamel mediation still, then, add formic acid-2,4-Dimethoxyphenyl ester and 2,4-xylidine slowly stir with 600 rev/mins rotating speeds, and the liquid in the mediation still is mixed fully; This liquid that mixes is filtered with filter, collect filtrate, make high-environmental-protection clean gasoline additive.
Embodiment 4
By weight 0.6: 1: 0.05, get respectively acetal, C2 saturated alcohol and phosphoric acid, place under 60 ℃ the temperature, back flow reaction 5.25 hours, 67.5 ℃ liquid is reclaimed in rectifying, makes the cleaning octane promoter; By weight percentage, get respectively formic acid-2,4-Dimethoxyphenyl ester 4%, 2,4-xylidine 4% and the cleaning octane promoter 92% that makes; Adopt explosion-proof pump will clean octane promoter and squeeze into enamel mediation still, then, add formic acid-2,4-Dimethoxyphenyl ester and 2,4-xylidine slowly stir with 500 rev/mins rotating speeds, and the liquid in the mediation still is mixed fully; This liquid that mixes is filtered with filter, collect filtrate, make high-environmental-protection clean gasoline additive.
Claims (7)
1. a high-environmental-protection clean gasoline additive can improve the octane value of gasoline, and does not contain banned substance, it is characterized in that, this gasoline dope, by weight percentage, cleaning octane promoter by 89%～95%, 3%～5% carboxy acid aromatic ester and 2%～6% arylamine form each component total amount 100%;
Described cleaning octane promoter adopts following method to make: by weight 0.55～0.75:1:0.05, get respectively a kind of, C1～C10 saturated alcohol and catalyzer in methylal〔Su〕 or the acetal, place under 60 ± 5 ℃ the temperature, back flow reaction 5 hours～6 hours, 60 ℃～90 ℃ liquid is reclaimed in rectifying, and this liquid is the cleaning octane promoter that makes;
Described catalyzer adopts sulfuric acid, hydrochloric acid, phosphoric acid or sulfonic acid.
2. according to gasoline dope claimed in claim 1, it is characterized in that, described carboxy acid aromatic ester adopts formic acid-2,4-Dimethoxyphenyl ester.
3. according to gasoline dope claimed in claim 1, it is characterized in that, described arylamine adopts DMA or 2,4-xylidine.
4. the preparation method of the described gasoline dope of claim 1 is characterized in that, this preparation method carries out according to the following steps:
Step 1: by weight 0.55～0.75:1:0.05, get respectively a kind of, C1～C10 saturated alcohol and catalyzer in methylal〔Su〕 or the acetal, place under 60 ± 5 ℃ the temperature back flow reaction 5 hours～6 hours, 60 ℃～90 ℃ liquid is reclaimed in rectifying, makes the cleaning octane promoter;
Step 2: by weight percentage, get respectively the cleaning octane promoter 89%～95% that carboxy acid aromatic ester 3%～5%, arylamine 2%～6% and step 1 make, each component total amount 100%;
Step 3: carboxy acid aromatic ester and arylamine are added in the cleaning octane promoter, slowly stir, make liquid mixing even;
Step 4: the liquid that mixes in the step 3 is filtered, collect filtrate, make high-environmental-protection clean gasoline additive;
Catalyzer in the described step 1 adopts sulfuric acid, hydrochloric acid, phosphoric acid or sulfonic acid.
5. according to preparation method claimed in claim 4, it is characterized in that, the carboxy acid aromatic ester in the described step 2 adopts formic acid-2,4-Dimethoxyphenyl ester.
6. according to gasoline dope claimed in claim 4, it is characterized in that, the arylamine in the described step 2 adopts DMA or 2,4-xylidine.
7. according to preparation method claimed in claim 4, it is characterized in that, the stirring velocity in the described step 3 is 400 rev/mins～600 rev/mins.
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| CN102154042A (en) * | 2011-02-21 | 2011-08-17 | 于涛 | Gasoline standard upgrading agent and preparation method thereof |
| CN104449893B (en) * | 2014-12-28 | 2016-05-04 | 山西华顿实业有限公司 | Low ratio methanol gasoline compound additive in one |
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|---|---|---|---|---|
| US6392102B1 (en) * | 1998-11-12 | 2002-05-21 | Bp Corporation North America Inc. | Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of formaldehyde formed by oxidation of dimethyl ether |
| CN1389546A (en) * | 2001-06-06 | 2003-01-08 | 姜皓 | Anti-knock agent for gasoline |
| CN101193948A (en) * | 2005-06-15 | 2008-06-04 | 巴斯福股份公司 | Process for preparing polyoxymethylene dimethyl ethers from methanol and formaldehyde |
| CN101671583A (en) * | 2009-10-19 | 2010-03-17 | 张淑蓉 | High cleanness energy-saving unleaded gasoline standard increasing agent |
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2010
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6392102B1 (en) * | 1998-11-12 | 2002-05-21 | Bp Corporation North America Inc. | Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of formaldehyde formed by oxidation of dimethyl ether |
| CN1389546A (en) * | 2001-06-06 | 2003-01-08 | 姜皓 | Anti-knock agent for gasoline |
| CN101193948A (en) * | 2005-06-15 | 2008-06-04 | 巴斯福股份公司 | Process for preparing polyoxymethylene dimethyl ethers from methanol and formaldehyde |
| CN101671583A (en) * | 2009-10-19 | 2010-03-17 | 张淑蓉 | High cleanness energy-saving unleaded gasoline standard increasing agent |
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