CN102746875B - New method for preparation of gasoline from ethanol - Google Patents
New method for preparation of gasoline from ethanol Download PDFInfo
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- CN102746875B CN102746875B CN201110100013.2A CN201110100013A CN102746875B CN 102746875 B CN102746875 B CN 102746875B CN 201110100013 A CN201110100013 A CN 201110100013A CN 102746875 B CN102746875 B CN 102746875B
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Abstract
The invention relates to a method for preparation of gasoline from ethanol and light petroleum distillates, and aims to mainly solve the problems that light petroleum distillates are unable or difficult to be prepared into gasoline, ethanol composite gasoline has a low heat value and is easy to deteriorate and undergo layering, and direct doping of ethanol into gasoline has an amount restriction and is easy to corrode equipment in the prior art. The method of the invention adopts a technical scheme composed of: taking ethanol or ethyl ether and light petroleum distillates as raw materials, under the conditions of a reaction temperature of 50-500DEG C, a reaction pressure of 0.02-15.0MPa, and a raw material weight hourly space velocity of 0.3-20h<-1>, contacting the raw materials with a solid acid catalyst, and making the ethanol and the petroleum distillates undergo an alkylation reaction on the catalyst so as to obtain a gasoline product having a oxygen-containing compound weight concentration of less than 1000ppm. The technical scheme of the invention well solves the problems, and can be used in the industrial production of gasoline.
Description
Technical field
The present invention relates to a kind of method of ethanol and primary flash distillate gasoline processed.
Background technology
Gasoline is a large class of oil product, is transparent liquid, is mainly by C5～C12Ge family hydrocarbon composition, has good vapo(u)rability and incendivity, can guarantee that running of an engine is steady, burning is complete, carbon deposit is few; There is good stability, in storing and use procedure, be not prone to early oxidation rotten, to engine parts and oil pot non-corrosiveness, mainly as the fuel of vehicular engine.
In prior art, gasoline is generally made by petroleum distillation or heavy ends cracking.Because petroleum resources are limited, reserves decline increasingly, and many oil fields enter the exploitation later stage, and cost of winning raises, and causes gasoline in short supply, and price is surging, and the technical study of gasoline energy substitution receives increasing concern.
In petroleum distillation and scission reaction process, can generate the primary flash distillate that a large amount of carbonatomss are 1～12, in these primary flash distillates, the C1 of molecular weight, C2 are difficult to utilize, generally directly enter fuel gas pipe network as geseous fuel, C3, C4, often as civil liquefied gas, are having in relevant corollary apparatus situation, also can be used as cracking ethylene preparation or steam and transform preparing synthetic gas raw material.
The above primary flash distillate of C5 is complicated mixture, octane value is generally lower, and often contain more benzene, along with strict new gasoline standard is put into effect, it is directly subject to strict restriction as gasoline blend component consumption, need carry out the following process such as benzene extracting or Aromatics Extractive Project and isomerization, catalytic reforming and could be used as gasoline through being in harmonious proportion.
Ethanol is a kind of inflammable, volatile colourless transparent liquid under normal temperature, normal pressure, has many uses, and can be used for manufacturing acetic acid, beverage, essence, dyestuff, fuel and sterilizing agent etc.In recent years, along with oil price raises, ethanol is mixed to gasoline formation ethanol composite gasoline becomes a kind of trend.
Chinese patent CN101812332A discloses a kind of ethanol petrol scheme, it is characterized in that being comprised of the raw material of following parts by volume: 60～70 parts of regular price gasolines; 2～10 parts of dehydrated alcohols; 10～20 parts of solubility promoters; 13～23 parts, tensio-active agent; 10～15 parts of ignition dopes; 3～10 parts of corrosion inhibitors; 7～15 parts of detergent-dispersant additives, octane value meets or exceeds 93#, 95# white gasoline standard, and its overall performance meets the standard-required of 93# white gasoline.
Chinese patent CN200810140881.1 discloses a kind of ethanol petrol scheme, by volume per-cent gasoline accounts for 81%～94%, synthesizing alcohol or fermenting alcohol 5%～18%, solubility promoter 0.5%～3%, oxidation inhibitor 0.4%～0.1%, anti-corrosion additive 0.1%～0.01%.The ethanol petrol of allotment compares power with white gasoline and oil consumption is suitable, and engine is had no side effect, and energy-saving and emission-reduction, are applicable to temperature and use in more than-10 ℃ area.
Yet, because the latent heat of vaporization of ethanol is large, vaporization temperature under chemically correct fuel is greater than regular price gasoline, affect formation and the combustionvelocity of gas mixture, during large the or low temperature of incorporation, automobile is difficult to starting, easily produce vapour lock, be unfavorable for the accelerating ability of automobile, so the general ethanol content of ethanol petrol is controlled at below 10%.
Ethanol is a kind of fine solvent, easily the caulking gum of automobile and other synmetal is produced to slight corrosion, swelling, softening or be full of cracks effect.Ethanol, in storage and combustion processes, can produce acetic acid, and the special copper of automobile metal is had to corrosive nature, have test to show, in gasoline, ethanol content, does not have to corrode to metal when following 10% substantially, but when ethanol surpasses 15%, must add effective corrosion inhibitor.
Once ethanol composite gasoline is met water, liquid phase separation will occur, impact is used, and ethanol is as a kind of good tensio-active agent, and the very easily moisture absorption, so ethanol petrol has strict restriction to water-content, cannot adopt the pipeline that cost is very low to carry.
The accumulating cycle of ethanol composite gasoline only has 4-5 days, quality guaranteed period only has one month, easily there is demixing phenomenon in the ethanol petrol of having spent the quality guaranteed period, in oil tank fuel tank, easily become muddy, beat missing of ignition, therefore must transform or build specialize in vehicle-use alcohol gasoline use storage tank, tank car, be in harmonious proportion and add wet goods facility, increased use cost.
Ethanol oxygen level is up to 34.7%, and calorific value is 60% of traditional motor spirit, and the composite gasoline oxygen level that contains 10% ethanol just can reach 3.5%.According to pertinent data, if automobile does not make any changes while just using the blend gasoline containing ethanol 10%, the oil consumption meeting of engine increases by 5%.
Ethanol composite gasoline must be raw material by dehydrated alcohol and high-quality gasoline product, cannot utilize cheap coarse ethanol and low-quality primary flash distillate, and cost is relatively high.
Although there is many defects in ethanol petrol, especially current ethanol technology too relies on grain, make country carry out certain restriction to the development of ethanol petrol, yet because gasoline consumption increases sharply, petroleum resources are exhausted at last, and renewable substitute energy is imperative, once Mierocrystalline cellulose ethanol technology processed obtains, break through, when the matter such as stalk, cassava can become ethanol main raw material, the production capacity of ethanol will sharply be expanded.
It is raw material that this technology be take primary flash distillate and ethanol, by chemical reaction, obtains conventional gasoline product, in use without existing storage, transportation, engine system and using method are carried out to any change.Can also further improve the utilization ratio of primary flash distillate by the measure lower than the component circulating reaction of benzene by benzene and boiling point aborning, benzene is converted into other aromatic hydrocarbons such as ethylbenzene, propyl benzene simultaneously, thereby without carrying out benzene extracting.
This technology can realize and make ethanol conversion is conventional gasoline component, make the reactions such as primary flash distillate generation alkylation, aromizing, isomerization simultaneously, the object that quality significantly promotes, thereby greatly expand gasoline stocks source, biochemical industry and petroleum refining industry are combined closely, produce high-quality high heating value gasoline products.
Adopting ethanol and primary flash distillate gasoline processed is the new way of ethanol gasoline processed, belongs to brand-new research field, has not yet to see research report in this respect.
Summary of the invention
Technical problem to be solved by this invention is that the primary flash distillate existing in prior art can not or be difficult to make gasoline, and ethanol composite gasoline calorific value is low, perishable, layering, directly mixes gasoline consumption limited, the problem of corrosive equipment.A kind of novel method of new ethanol gasoline processed is provided, it is high that the method has the gasoline products octane value and the calorific value that obtain, without using method, engine, storage and handling facility, accumulating mode are carried out to any change, primary flash distillate can access better utilization, ethanol utilization is large, the feature that available low-quality ethanol or bio-ethanol work in-process are raw material.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of ethanol and primary flash distillate gasoline processed, take ethanol or ether and primary flash distillate as raw material, at temperature of reaction 50-500 ℃, reaction pressure 0.02～15.0MPa, raw material weight air speed 0.3～20h
-1under condition, raw material contacts with solid acid catalyst, obtains gasoline fraction.
In technique scheme, said primary flash distillate comprises that all final boiling point, not higher than the petroleum fractions of 205 ℃, also comprise dry gas and liquefied gas; In raw material, ethanol or ether content are 1～100% by weight percentage, and preferable range is 5～85%; By weight, in gasoline products, oxygenates level is less than 1000ppm; Solid acid catalyst used is selected from least one in silico-aluminate, molecular sieve, immobilized mineral acid, heteropolyacid or solid super-strong acid; Temperature of reaction preferable range is 80-480 ℃, and more preferably scope is 150-450 ℃; Reaction pressure preferable range is 0.05～10.0MPa, and more preferably scope is 0.5～3.0MPa; Raw material weight air speed preferable range is 0.5～10.0h
-1preferable range is 1.5～5.0h
-1; The weight concentration of ethanol raw material is at least 30%, and all the other compositions are water or alcohol, ether, ketone or aldehydes organism.
In primary flash distillate, often there is a large amount of alkene, naphthenic hydrocarbon and aromatic hydrocarbons, these are all the good acceptors of ethyl, thereby can with a large amount of ethanol or ether generation alkylated reaction, carbochain is extended, thereby realizes light petroleum fraction heaviness and become qualified gasoline component.
Easily there is molecule inner dewatering reaction generation small-numerator olefin in ethanol or ether under catalyst action, when alcohol concn is higher, also can there is intermolecular dehydration and generate more macromolecular alkene in ethanol, these alkene character are active, be very easy to react with petroleum fractions generation alkylation, superimposed etc., self also may there is the reactions such as superimposed, aromatization, can reach equally the object that carbochain lengthens, make ethanol and primary flash distillate be converted into high-quality gasoline.
Due to reactions such as alkylation, superimposed, cyclisation, aromizing and hydrogen transferences, the alkene in raw material can significantly reduce, thereby in the gasoline product obtaining, olefin(e) centent is lower.
With ethanol generation alkylated reaction in, between primary flash distillate, also can there is the reactions such as superimposed, isomerization, aromizing, make light petroleum fraction heaviness and become qualified gasoline component, branched-chain hydrocarbon and aromatic hydrocarbon content increase simultaneously, alkene reduces, thereby obtains the gasoline of higher quality.
The reaction that ethanol gasoline processed relates to is acid catalyzed reaction, the Surface acidity of catalyzer and strength of acid have material impact to this reaction, strong acid is conducive to isomerization and aromatization, generate stop bracket gasoline, but because ethanol character is active, easily cause coking and deactivation, decaying catalyst can be by burning activity recovery.
Compare with ethanol composite gasoline, the present invention is owing to adopting the method for chemical reaction, oxygen in ethanol or ether is removed with the form of water, thereby make the content of oxygenatedchemicals in the finished product be less than 1000ppm, guarantee that its calorific value and conventional gasoline are basic identical, in use without carrying out special disposal.
The technical program is by special catalyst effect, and control main reaction is alkylated reaction, and primary flash distillate plays diluting effect to ethanol, and liquid is received and significantly improved, and shows that the utilization ratio of ethanol is higher, while carbon distribution rate reduction, and catalyst life extends.
The technical program ethanol used allows to contain a large amount of fusels, assorted ether, water, aldehyde, ester and ketone and other nonnitrogenous organic impurities, therefore can be with the work in-process ethanol that does not carry out in bio-ethanol production process fully purifying as raw material, greatly reduce production cost, applying of bio-ethanol technology also had to very large promoter action.
Use our legal system gasoline, can take the non-gasoline blend component of C1-C4 and C5-C12 low octane value gasoline blend component and ethanol or ether is raw material, and product octane value can reach more than 93, and ethanol or the ether ratio in raw material can reach 85%.The oil product olefin(e) centent making is few, and stability and oil product anti-knocking property are good, thereby reach, utilizes cheaply, and the ethanol of wide material sources and primary flash distillate are produced the object of high-quality gasoline.
The present invention has realized usings ethanol and originates as gasoline, and biochemical industry and petroleum refining industry are combined, and has obtained good technique effect, has good prospects for commercial application.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
In weight, consist of 3.5%ZrO
2-0.5%H
2sO
4/ 70%ZSM-5/30%Al
2o
3solid acid catalyst effect under, take light naphthar and dehydrated alcohol reacts as raw material, reaction conditions and the results are shown in Table 1:
Table 1 ethanol and light naphthar be reaction result under molecular sieve catalyst effect
| Raw material forms | 0.7A/0.3B | 0.8A/0.2B | 0.9A/0.1B |
| Raw material bromine valency, g/100g | 13.1 | 14.9 | 16.8 |
| Temperature of reaction, ℃ | 150 | 80 | 50 |
| Weight space velocity, h -1 | 25.0 | 15.0 | 5.0 |
| System pressure, MPa | 0.5 | 0.05 | 0.02 |
| Liquid yield, wt% | 98.5 | 98.1 | 98.3 |
| Yield of gasoline, wt% | 79.1 | 89.4 | 96.5 |
| Diesel yield, wt% | 1.3 | 0.5 | 0.2 |
| Organon gasoline octane rating | 90 | 91 | 90 |
| Oxygenatedchemicals, ppm | 321 | 525 | 738 |
| Gasoline bromine valency, g/100g | 0.8 | 1.2 | 1.3 |
Note: A represents petroleum naphtha, B represents ethanol.
Component in product liquid outside gasoline and diesel oil is the water deviate from reaction process of ethanol and the ethanol of traces of unreacted.From table 1, adopt the present invention program, the light naphthar of inferior quality can be converted into octane value high, the high-quality gasoline of good security.
[embodiment 2]
In weight, consist of 5% phospho-wolframic acid/100%Al
2o
3solid acid catalyst effect under, take and do as the heavy naphtha of 205 ℃ and moisture 30%, containing acetaldehyde 2%, containing the ethanol of ethyl acetate 0.5%, be that raw material reacts, reaction conditions and the results are shown in Table 2:
Table 2 ethanol and heavy naphtha is reaction result under the aluminium oxide catalyst effect of load 5% phospho-wolframic acid
| Raw material forms | 0.3A/0.7B | 0.7A/0.3B | 0.9A/0.1B |
| Raw material bromine valency, g/100g | 5.5 | 12.8 | 16.5 |
| Temperature of reaction, ℃ | 650 | 550 | 450 |
| Weight space velocity, h -1 | 5.0 | 1.5 | 0.3 |
| System pressure, MPa | 150 | 10 | 3 |
| Liquid yield, wt% | 91.3 | 96.9 | 98.2 |
| Yield of gasoline, wt% | 67.1 | 85.4 | 91.5 |
| Diesel yield, wt% | 3.5 | 2.6 | 1.3 |
| Organon gasoline octane rating | 94 | 94 | 92 |
| Oxygenatedchemicals, ppm | 21 | 33 | 19 |
| Gasoline bromine valency, g/100g | 1.0 | 1.2 | 1.5 |
Note: A represents heavy naphtha, B represents ethanol.
[embodiment 3]
In weight, consist of 1.5%Co-1.0%Mo/70%USY/30%A
12o
3solid acid catalyst effect under, take and do as the catalytic cracking raw gasline of 202 ℃ and moisture 20%, containing the ethanol of acetic acid 3%, be that raw material reacts, reaction conditions and the results are shown in Table 3:
Table 3 ethanol and catalytic cracking raw gasline reaction result under molecular sieve catalyst effect
| Raw material forms | 0.7A/0.3B | 0.8A/0.2B | 0.9A/0.1B |
| Raw material bromine valency, g/100g | 14.6 | 16.7 | 18.8 |
| Temperature of reaction, ℃ | 300 | 250 | 150 |
| Weight space velocity, h -1 | 10.0 | 5.0 | 1.0 |
| System pressure, MPa | 0.5 | 0.05 | 0.02 |
| Liquid yield, wt% | 98.6 | 98.8 | 99.2 |
| Yield of gasoline, wt% | 85.1 | 87.3 | 89.8 |
| Diesel yield, wt% | 1.5 | 1.0 | 0.2 |
| Organon gasoline octane rating | 91 | 89 | 89 |
| Oxygenatedchemicals, ppm | 417 | 556 | 491 |
| Gasoline bromine valency, g/100g | 1.4 | 1.9 | 2.6 |
Note: A represents catalytic cracking raw gasline, and B represents ethanol.
[embodiment 4]
In weight, consist of under the solid acid catalyst effect of 1.5%Mo-0.5%Ni-3.0%P/100% pure aluminium silicate, with dry gas, raffinate oil and moisture 60%, containing methyl alcohol 1%, containing acetone 0.5%, containing the ethanol of amylalcohol 8.5%, be that raw material reacts, reaction conditions and the results are shown in Table 4:
Table 4 ethanol and dry gas, the reaction result under composite oxide catalysts effect of raffinating oil
| Raw material forms | 0.5A/0.2B/0.3C | 0.6A/0.2B/0.2C | 0.7A/0.2B/0.1C |
| Raw material bromine valency, g/100g | 1.3 | 1.6 | 1.8 |
| Temperature of reaction, ℃ | 550 | 450 | 400 |
| Weight space velocity, h -1 | 1.5 | 0.75 | 0.3 |
| System pressure, MPa | 15.0 | 10.0 | 5.0 |
| Liquid yield, wt% | 89.7 | 90.3 | 93.4 |
| Yield of gasoline, wt% | 70.2 | 75.2 | 80.6 |
| Diesel yield, wt% | 2.1 | 1.2 | 0.7 |
| Organon gasoline octane rating | 94 | 92 | 92 |
| Oxygenatedchemicals, ppm | 54 | 32 | 26 |
| Gasoline bromine valency, g/100g | 1.0 | 1.4 | 1.8 |
Note: A representative is raffinated oil, and B represents dry gas, and C represents ethanol, and dry gas is with gaseous feed, and raw material bromine valency is not containing dry gas.
[embodiment 5]
In weight, consist of 3.0%Ga-3.0%B/50% mordenite/25% β zeolite/25%SiO
2solid acid catalyst effect under, with liquefied gas, condensed oil, tops and moisture 10%, containing the ethanol of Virahol 1%, be that raw material reacts, reaction conditions and the results are shown in Table 5:
Table 5 ethanol and compound material are being loaded with reaction result under the catalyst action of metal
| Raw material forms | 0.15A/0.4B/0.15C/0.3D | 0.2A/0.4B/0.2C/0.2D |
| Raw material bromine valency, g/100g | 23.9 | 32.6 |
| Temperature of reaction, ℃ | 350 | 200 |
| Weight space velocity, h -1 | 20.0 | 10.0 |
| System pressure, MPa | 18.0 | 12.0 |
| Liquid yield, wt% | 92.1 | 94.3 |
| Yield of gasoline, wt% | 75.6 | 79.2 |
| Diesel yield, wt% | 28 | 1.6 |
| Organon gasoline octane rating | 92 | 90 |
| Oxygenatedchemicals, ppm | 319 | 554 |
| Gasoline bromine valency, g/100g | 2.5 | 3.9 |
Note: A represents liquefied gas, B represents condensed oil, and C represents tops, and D represents ethanol.
[embodiment 6]
In weight, consist of 2%Zn-1%Ca/70%SAPO-34/30%Al
2o
3solid acid catalyst effect under, take and do cracking of ethylene raw gasline, carbon 5 distillates and dehydrated alcohol as 203 ℃ and react as raw material, reaction conditions and the results are shown in Table 6:
Table 6 ethanol and compound material be reaction result under dual-function catalyst effect
| Raw material forms | 0.2A/0.5B/0.3C | 0.5A/0.3B/0.2C |
| Raw material bromine valency, g/100g | 33.2 | 34.1 |
| Temperature of reaction, ℃ | 450 | 380 |
| Weight space velocity, h -1 | 5.0 | 3.0 |
| System pressure, MPa | 5.0 | 3.0 |
| Liquid yield, wt% | 94.2 | 95.0 |
| Yield of gasoline, wt% | 78.4 | 80.3 |
| Diesel yield, wt% | 2.6 | 20 |
| Organon gasoline octane rating | 94 | 91 |
| Oxygenatedchemicals, ppm | 159 | 244 |
| Gasoline bromine valency, g/100g | 2.5 | 2.9 |
Note: A represents cracking of ethylene raw gasline, and B represents carbon 5 distillates, and C represents ethanol.
[embodiment 7]
Consisting of 1.0%La/5% silicotungstic acid/65%MCM-41/35%Al
2o
3solid acid catalyst effect under, take light naphthar and anhydrous but react as raw material containing the ethanol of fusel, by weight percentage, in fusel, methyl alcohol: acetone: acetic acid: amylalcohol=12%: 10%: 20%: 52%, reaction conditions and the results are shown in Table 7:
The ethanol that table 7 contains fusel and light naphthar be reaction result under molecular sieve catalyst effect
| Raw material forms | 0.5A/0.5B | 0.3A/0.7C | 0.2A/0.8D |
| Raw material bromine valency, g/100g | 9.4 | 5.6 | 3.7 |
| Temperature of reaction, ℃ | 450 | 480 | 420 |
| Weight space velocity, h -1 | 15 | 0.5 | 0.2 |
| System pressure, MPa | 3.0 | 1.5 | 1.0 |
| Liquid yield, wt% | 97.6 | 96.4 | 98.2 |
| Yield of gasoline, wt% | 82.3 | 78.6 | 83.0 |
| Diesel yield, wt% | 1.9 | 1.4 | 1.0 |
| Organon gasoline octane rating | 91 | 92 | 90 |
| Oxygenatedchemicals, ppm | 317 | 325 | 274 |
| Gasoline bromine valency, g/100g | 1.2 | 1.4 | 1.0 |
Note: A represents light naphthar, B representative is containing the ethanol of 30% fusel, and C representative is containing the ethanol of 50% fusel, and D represents the ethanol of 70% fusel.
[embodiment 8]
In weight, consist of 5%H
3pO
4/ 60%EU-1/40%Al
2o
3solid acid catalyst effect under, take to do as the ethanol of the heavy naphtha of 210 ℃ and moisture 30% as raw material and react, reaction conditions and the results are shown in Table 8:
Table 8 aqueous ethanol and light naphthar be reaction result under molecular sieve catalyst effect
| Raw material forms | 0.2A/0.8B | 0.5A/0.5C | 0.3A/0.7D |
| Raw material bromine valency, g/100g | 4.6 | 11.5 | 6.9 |
| Temperature of reaction, ℃ | 120 | 90 | 45 |
| Weight space velocity, h -1 | 2.5 | 2.0 | 1.5 |
| System pressure, MPa | 20.0 | 10 | 3 |
| Liquid yield, wt% | 98.7 | 99.4 | 99.7 |
| Yield of gasoline, wt% | 88.1 | 90.7 | 94.2 |
| Diesel yield, wt% | 0.5 | 0.3 | 0.1 |
| Organon gasoline octane rating | 89 | 86 | 82 |
| Oxygenatedchemicals, ppm | 648 | 819 | 1054 |
| Gasoline bromine valency, g/100g | 1.7 | 3.5 | 2.9 |
Note: A represents light naphthar, B representative is containing the ethanol of 15% water, and C representative is containing the ethanol of 35% water, and D represents the ethanol of 60% water.
[embodiment 9]
In weight, consist of 1.2%H
2sO
4/ 60% beta-molecular sieve/40%SiO
2solid acid catalyst effect under, take dry gas, light naphthar and ethanol reacts as raw material, dry gas, liquefied gas, diesel component and micro-ether recycle, reaction conditions and the results are shown in Table 9:
Table 9 ethanol and dry gas, light naphthar reaction result under molecular sieve catalyst effect
| Raw material forms | 0.1A/0.5B/0.3C/0.1D | 0.2A/0.4B/0.2C/0.2D |
| Raw material bromine valency, g/100g | 10.4 | 8.5 |
| Temperature of reaction, ℃ | 400 | 450 |
| Weight space velocity, h -1 | 7.5 | 5.0 |
| System pressure, MPa | 15.0 | 3 |
| Liquid yield, wt% | 90.3 | 87.5 |
| Yield of gasoline, wt% | 74.2 | 72.5 |
| Diesel yield, wt% | 2.1 | 2.8 |
| Organon gasoline octane rating | 96 | 94 |
| Oxygenatedchemicals, ppm | 107 | 76 |
| Gasoline bromine valency, g/100g | 0.5 | 0.3 |
Note: A represents dry gas, B represents light naphthar, and C represents ethanol, and D represents cycle stock.
[embodiment 10]
In weight, consist of 1.5%B-1.5F/60% mordenite/40%Al
2o
3solid acid catalyst effect under, take liquefied gas, do as the heavy naphtha of 210 ℃ and ether as raw material and react, reaction conditions and the results are shown in Table 10:
Table 10 ether and liquefied gas, heavy naphtha reaction result under molecular sieve catalyst effect
| Raw material forms | 0.1A/0.5B/0.4C | 0.2A/0.6B/0.2C |
| Raw material bromine valency, g/100g | 20.4 | 36.2 |
| Temperature of reaction, ℃ | 500 | 650 |
| Weight space velocity, h -1 | 15 | 25 |
| System pressure, MPa | 5.0 | 3.0 |
| Liquid yield, wt% | 92.8 | 90.3 |
| Yield of gasoline, wt% | 73.8 | 71.4 |
| Diesel yield, wt% | 3.5 | 4.1 |
| Organon gasoline octane rating | 94 | 96 |
| Oxygenatedchemicals, ppm | 54 | 18 |
| Gasoline bromine valency, g/100g | 0.4 | 0.2 |
Note: A represents liquefied gas, B represents heavy naphtha, C represents ether.
Claims (8)
1. a method for ethanol and primary flash distillate gasoline processed, take ethanol or ether and primary flash distillate as raw material, at temperature of reaction 50-500 ℃, and reaction pressure 0.02～15.0MPa, raw material weight air speed 0.3～20h
-1under condition, raw material contacts with solid acid catalyst, obtains gasoline fraction; Wherein, solid acid catalyst used is selected from least one in silico-aluminate, immobilized mineral acid or solid super-strong acid.
2. the method for ethanol and primary flash distillate gasoline processed according to claim 1, is characterized in that primary flash distillate comprises that all final boiling point are not higher than petroleum fractions or dry gas or the liquefied gas of 205 ℃.
3. the method for ethanol and primary flash distillate gasoline processed according to claim 1, is characterized in that by weight percentage in raw material that ethanol or ether content are 1～100%.
4. the method for ethanol and primary flash distillate gasoline processed according to claim 3, is characterized in that by weight percentage in raw material that ethanol or ether content are 5～85%.
5. the method for ethanol and primary flash distillate gasoline processed according to claim 1, is characterized in that by weight in gasoline products, oxygenates level is less than 1000ppm.
6. the method for ethanol and primary flash distillate gasoline processed according to claim 1, is characterized in that temperature of reaction is 80-480 ℃, and reaction pressure is 0.05～10.0MPa, raw material weight air speed 0.5～10.0h
-1.
7. the method for ethanol and primary flash distillate gasoline processed according to claim 6, is characterized in that temperature of reaction is 150-450 ℃, and reaction pressure is 0.5～3.0MPa, raw material weight air speed 1.5～5.0h
-1.
8. the method for ethanol and primary flash distillate gasoline processed according to claim 1, the weight concentration that it is characterized in that ethanol is at least 30%, all the other are alcohol, ether, ketone, ester or aldehydes and other nonnitrogenous organism.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110100013.2A CN102746875B (en) | 2011-04-20 | 2011-04-20 | New method for preparation of gasoline from ethanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110100013.2A CN102746875B (en) | 2011-04-20 | 2011-04-20 | New method for preparation of gasoline from ethanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102746875A CN102746875A (en) | 2012-10-24 |
| CN102746875B true CN102746875B (en) | 2014-08-13 |
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| CN1580199A (en) * | 2003-08-05 | 2005-02-16 | 中国科学院大连化学物理研究所 | Process for modifying petrol by etherification and aromatization |
| CN101081995A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Method for reducing sulfur content of catalytically cracked gasoline |
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| CN1580199A (en) * | 2003-08-05 | 2005-02-16 | 中国科学院大连化学物理研究所 | Process for modifying petrol by etherification and aromatization |
| CN101081995A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Method for reducing sulfur content of catalytically cracked gasoline |
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