CN103450950B - Efficient environment-friendly fuel oil and preparing method thereof - Google Patents
Efficient environment-friendly fuel oil and preparing method thereof Download PDFInfo
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- CN103450950B CN103450950B CN201310431311.9A CN201310431311A CN103450950B CN 103450950 B CN103450950 B CN 103450950B CN 201310431311 A CN201310431311 A CN 201310431311A CN 103450950 B CN103450950 B CN 103450950B
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Abstract
The invention discloses efficient environment-friendly fuel oil and a preparing method thereof. According to the preparing method of the efficient environment-friendly fuel oil, a nonionic surface active agent and a compound enzyme solution prepared from Aspergillus oryzae, cellulose, glutaminase, glucose isomerase and water are added into an oil product, uniform mixing is carried out at a normal temperature, and then centrifugal separation is carried out to obtain the efficient environment-friendly fuel oil. Due to the fact that the compound enzyme is added to be combined with the oil product under a specific condition, mutual transformation of isomers is promoted, rearrangement reaction inside substrate molecules is catalyzed, and modification of traditional fuel oil is achieved. Compared with the traditional fuel oil product, the modified fuel oil product has the advantages that increment is obtained, sulphur content is greatly reduced, the quantity of carbon residues on residua is reduced, ash content is greatly reduced, the cetane number is increased, emission of Sox and NOx is greatly reduced, efficiency is high, cleanness is achieved, and the environment is protected. The production of the modified efficient environment-friendly fuel oil is carried out at the normal temperature, operation such as hydrogenation, high-temperature cracking and desulfuration is simplified, energy consumption for production is low, the number of steps is small, and practicality is strong.
Description
Technical field
The present invention relates to a kind of fuel oil and preparation method thereof, specifically a kind of Efficient environment-friendlyfuel fuel oil and preparation method thereof.
Background technology
Along with the continuous increase of the day by day serious of energy dilemma and consumption of petroleum amount; cost, the price of oil fuel also go up thereupon; and the discharge produced due to the burning of fuel oil and pollution problem thereof also develop into global problem gradually, improve oil inflame quality, emphasis that emissions reduction becomes various countries' oil industry research.Save energy, realize the reasonable application to the energy, reduce motor vehicle exhaust, reduce topsoil to being the Main way that people solve that the energy and the energy use the problem of environmental pollution brought at present, solve problem of environmental pollution that the energy causes at present mainly by improve oil refining process, improvement engine or combustion equipment, in fuel oil, add these three kinds of methods of suitable additive carry out.
Correlative study shows, fuel oil additive can to raising fuel qualities, improve combustioncharacteristics and have significant effect.Fuel dope, except to the raising of fuel qualities and the improvement of combustioncharacteristics, also needs the requirement of the engine technology meeting development.
Existing fuel oil additive adopts Emulsified Fuel Technology at Power.Past so-called emulsion fuel is in fuel oil, add water and interfacial agent, is uniformly mixed and makes its emulsification after emulsification, final water or water, oily or oily, without any the change of matter, so through after a period of time maybe when being warmed to certain temperature, You Heshui will start to be separated.Because its essence is exactly water and oil mixt, such emulsion fuel, along with the increase of water, can cause the decline of fuel value, affect efficiency of combustion, and at present, emulsion fuel is progressively by market.Such as, methyl alcohol is a kind of clean fuel substitute of generally acknowledged oil engine, for being methyl alcohol and diesel oil be mixed with methyl alcohol-diesel blended fuel or use with M100 fuel during oil engine.When carrying out the preparation of methyl alcohol-diesel blended fuel, adopt Emulsified Fuel Technology at Power exactly, as patent CN1431280, CN1339576 are just referred to this type of emulsion fuel and preparation thereof, but due to the system that obtained emulsion is unstable on thermodynamics, there is the problem of above-mentioned oily water separation, make this class A fuel A fail to promote the use of.And patent CN100398631C discloses a kind of environment-friendly methanol diesel oil, its be by modified biofuel and methyl alcohol, petrifaction diesel at normal temperatures and pressures mix and blend obtain.The environment-friendly methanol diesel oil of this patent is by first enabling modification biological diesel oil and these two kinds of polar materials of methyl alcohol dissolve each other with arbitrary proportion when not adding assistant to existing biofuel modification, but due to methanol content more than 45% time, needing to carry out transforming to existing diesel engine the environment-friendly methanol diesel oil described in this patent of application to be the normal operation ensureing diesel engine, therefore, its application receives certain restriction.
United States Patent (USP) once disclosed and was added in fuel oil with the mixture of tricarboxylic acid acid amides or tetracarboxylic acid acid amides and basic metal or earth alkali inorganic salt, can play the anti-attrition to engine and etch-proof effect at work.Patent CN100460487C discloses a kind of oil-soluble organic acids metal-salt fuel oil additive added containing MR general formula, in formula, R is organic acid, and its corresponding organic acid is containing the saturated of 1-40 carbon atom or unsaturated fatty acids, naphthenic acid, aromatic acid or alkylphenol; M is the metallic cation of basic metal, alkaline-earth metal, rare earth metal, transition metal.But the use of aminated compounds, due to the content adding nitride in membership increase motor vehicle discharged tail gas of nitrogen-atoms, causes larger atmospheric pollution.
Utilize enzyme to prepare have promote fuel power, energy-saving function fuel oil additive also have report, as patent CN101240201 B discloses a kind of gasoline, the diesel-dope with lifting power and energy-saving function, its component comprises hydrogenated vegetable oil Witepsol W-S 55, biological lipase, dimethyl formamide, N-BUTYL ACETATE.Dimethyl formamide composition is employed in this patent additive, dimethyl formamide is mainly used as industrial solvent, there is pungency, it is a kind of inflammable liquid, chance naked light, Gao Re can cause combustion explosion, even can blast with the vitriol oil, nitrosonitric acid vigorous reaction, danger is higher, and dimethyl formamide add the air pollution problems inherent that still really cannot solve nitride in tail gas and cause.Have no a kind of modification utilizing enzyme to realize to conventional fuel oil at present, to obtain the relevant report of the fuel oil of efficient, clean environment firendly.
Advocate environmental protection, improving Air quality is the emphasis that global human is paid close attention to, and affects the per minute of the mankind just energy demand all be unable to do without per second of Air quality, because do not have the fuel oil of high-efficiency cleaning, cause day by day serious topsoil haze phenomenon, extremely affect the healthy of the mankind.Therefore, a kind of clean, environmental protection, efficient modern fuel oil is urgently provided.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of Efficient environment-friendlyfuel fuel oil is provided, this fuel oil adds complex enzyme liquid and nonionogenic tenside in traditional fuel oil oil product, be mixed at normal temperatures, pass through prozyme: aspergillus oryzae, cellulase, L-Glutamine deaminase, the katalysis of glucose isomerase, make substrate molecule inside that molecular rearrangement reaction occur, and then the modification realized conventional fuel oil, modified fuel oil is compared with before modified, obtain increment, reach the effect of saving fuel oil, sulphur content reduces greatly, steam excess carbon residue, ash content declines to a great extent, cetane value improves, there is the feature of high-efficiency cleaning environmental protection, traditional emulsified fuel oil or other deficiencies that modified fuel oil adding methyl alcohol exists oil, water is separated can be overcome, realize, only by the eco-friendly material of interpolation, producing under the environment of gentleness, production process clean environment firendly.
Another object of the present invention is to provide the preparation method of above-mentioned a kind of Efficient environment-friendlyfuel fuel oil.
The technical solution adopted in the present invention is: a kind of preparation method of Efficient environment-friendlyfuel fuel oil, comprises following concrete steps:
(1) preparation of complex enzyme liquid: in steam-operating stirred pot, adds aspergillus oryzae, cellulase, L-Glutamine deaminase, glucose isomerase and water, carries out steam-operating at normal temperatures and stirs 24-36 hour, obtained complex enzyme liquid; The consumption proportion of described aspergillus oryzae, cellulase, L-Glutamine deaminase, glucose isomerase and water is: every 1 ton of water adds 1-1.5kg aspergillus oryzae, 1-1.5kg cellulase, 1-1.5kg L-Glutamine deaminase, 1-1.5kg glucose isomerase;
(2) oil product pre-treatment: add the nonionogenic tenside accounting for oil quality 0.8-1.5 ‰ in oil product, stirs and makes nonionogenic tenside be well dispersed in oil product;
(3) by complex enzyme liquid and pretreated oil product according to the ratio of mass ratio 3:7 or 4:6, mix 1-2min at normal temperatures, blend pressure is at 0.6 below MPa, after mixing, through centrifugation, namely obtain Efficient environment-friendlyfuel fuel oil, be separated simultaneously and obtain enzyme liquid residuum.
Described fuel oil oil product is aviation kerosene or diesel oil or heavy oil.
Described nonionogenic tenside is Span series emulsifying agent.
Preparation method of the present invention is adopted to prepare in the process of Efficient environment-friendlyfuel fuel oil, the enzyme liquid residuum separated can be recycled, its Land use systems is: mixed through mixing tank with the heavy oil being heated to 35-45 DEG C by enzyme liquid residuum, then obtains efficient and environment-friendly type heavy oil through centrifugation; Described enzyme liquid residuum and the blending ratio of the heavy oil being heated to 35-45 DEG C are that 3:7 or 4:6 mixes in mass ratio.
The present invention mainly realizes the modification to conventional fuel oil by biotechnological formulation prozyme, its action principle is: under the effect of prozyme, in reaction system, the double bond of oil product substrate molecule chain there occurs and add group or de-radical reaction, namely hydrolysis reaction RCOOR '+H occurs
2o → RCOOH+R ' OH or building-up reactions RCOOH+R ' OH → RCOOR '+H
2o, promote that a kind of compound is split into two kinds of compounds, or by a kind of compound of two kinds of compou nd synthesis, promote that isomers transforms mutually, the i.e. intramolecular rearrangement reaction of catalytic substrate, its essence is under the katalysis of enzyme, there occurs hydrolysis and building-up reactions, realize the modification to conventional fuel oil thus, modified fuel oil is compared with before modified, and performance index improve, be embodied in sulphur content greatly to reduce, steam excess carbon residue, ash content declines to a great extent, cetane value improves, thus improve efficiency of combustion, there is the advantage of high-efficiency cleaning environmental protection.
The aspergillus oryzae that the present invention adopts is a kind of fungi, for producing the bacterial strain of prozyme, can produce proteolytic enzyme amylase, saccharifying enzyme, cellulase, phytase etc., have special catalysis; Cellulase is primarily of compositions such as circumscribed beta-glucanase, Endo-β-glucanase and beta-glucosidases, one that is made up of multiple lytic enzyme complicated enzyme system, there is very high vigor, the cellulase playing katalysis in the present invention can be adsorbed on substrate Mierocrystalline cellulose specifically, then promotes substrate molecule chain rupture and rearrangement reaction under the synergy of several component.Adopt complex enzyme liquid of the present invention, its catalytic efficiency is much higher than traditional organic catalyst or single enzyme catalyst about 10 to 18 times, and catalyzed reaction can be carried out under the normal temperature and pressure of gentleness, catalyzed reaction terminates its character and does not change also without destruction, can realize regeneration and utilize.
Compared with prior art, the present invention has following beneficial effect:
(1) the modified fuel oil oil product adopting method of the present invention to obtain is compared to unmodified oil product of the same type, increment can be obtained: modified aviation kerosene increment 10% ~ 15%, modified diesel oil increment 10% ~ 20%, modification heavy oil increment 10% ~ 20%, and the modified fuel oil oil product obtained, its property indices can be improved, particularly sulphur content declines, steam excess carbon residue to decline to a great extent, ash content is zero, cetane value is improved, and can stand the test of time and temperature variation and engine apparatus operation during application;
(2) complex enzyme liquid is added, catalysis is carried out by enzyme, make the double bond of fuel oil oil product substrate molecule chain to be carried out add group or de-radical reaction, promote that a kind of compound is split into two kinds of compounds, or by a kind of compound of two kinds of compou nd synthesis, promote that isomers transforms mutually, the i.e. intramolecular rearrangement reaction of catalytic substrate, its essence is that conventional fuel oil obtains modification, obtain increment, the modified fuel product property indices obtained is improved, and significantly reduces SOx, the discharge of NOx under to a certain degree; Meanwhile, because enzyme molecular surface has hole or the crack of three-D space structure, the substrate molecule entered can be held and combine with it, and catalytic substrate changes product into, make production process of the present invention have high efficiency;
(3) there is not the reaction of pyrolytic cracking in Efficient environment-friendlyfuel fuel oil production process of the present invention, do not need to add other harmful additive, whole production process is all carry out at normal temperatures, do not need pyroprocessing, thus simplify hydrogenation, pyrolytic cracking and desulfurization etc. are a series of had not only consumed energy but also complicated program, and production energy consumption is low, and production process is clean, environmental protection.
figure of description
Fig. 1 is that embodiment 1 is prepared efficient and environment-friendly type diesel oil of the present invention and the enzyme liquid residuum in preparation process carried out to the schema of recycle.
Fig. 2 is that the performance index of the efficient and environment-friendly type diesel oil that embodiment 1 prepares detect data.
Embodiment
Explain the present invention further below in conjunction with embodiment, but embodiment does not limit in any form to the present invention.
Embodiment 1 adopts following steps to prepare Efficient environment-friendlyfuel fuel oil of the present invention and carries out recycle to the enzyme liquid residuum in preparation process, preparation flow as shown in Figure 1:
(1) preparation of complex enzyme liquid: add 1.5kg aspergillus oryzae, 1.5kg cellulase, 1.5kg L-Glutamine deaminase, 1.5kg glucose isomerase liquid by every 1 ton of water, aspergillus oryzae, cellulase, L-Glutamine deaminase, glucose isomerase amount ratio are the ratio of 1:1:1:1, at normal temperatures, aspergillus oryzae, cellulase, L-Glutamine deaminase, glucose isomerase liquid and water are added in steam-operating stirred pot, carry out steam-operating and stir 30 hours, obtained complex enzyme liquid;
(2) for standard diesel oil (No. 0), adopt the method for production Efficient environment-friendlyfuel fuel oil of the present invention to carry out modification and obtain efficient and environment-friendly type derv fuel oil: in commercially available No. 0 standard diesel oil, add the nonionogenic tenside sapn emulsifying agent accounting for its quality 1.0 ‰, stirring makes sapn be well dispersed in diesel oil, obtains pretreated diesel oil; Get the obtained complex enzyme liquid of step (1) and pretreated diesel oil at normal temperatures, by complex enzyme liquid with pretreated diesel quality than 3:7 mixing 2min, blend pressure is 0.5 MPa, through centrifugation after mixing, obtain efficient guarantor's type diesel oil, be separated simultaneously and obtain enzyme liquid residuum;
(3) recycle of enzyme liquid residuum: the weight ratio of enzyme liquid residuum and heavy oil being pressed 3:7, mixes through mixing tank with No. 180 heavy oil being heated to 40 DEG C, then through centrifugation, obtains environment-friendly type heavy oil.
Adopt the efficient and environment-friendly type diesel oil that aforesaid method is produced, through the repeated detection indices of Guangzhou energy detecting institute
Qualified, meet GB19147-2009 standard-required, and be better than GB diesel oil
,examining report is shown in Fig. 2.
Contrast from Fig. 2: high-efficiency cleaning type environment-friendly type diesel oil of the present invention, compared with GB, it declines 50% containing sulphur content, 10% steams excess carbon residue declines to a great extent, and ash content is zero, and cetane value improves 10%, the improvement of several index highlights the high-efficiency cleaning type environment-friendly type diesel oil adopting the inventive method to obtain above, meet the standard of derv fuel oil completely, and reach the requirement of the energy-saving and emission-reduction that country advocates, the raising of cetane value, ash content are zero object having reached oil plant perfect combustion.
The efficient and environment-friendly type diesel oil adopting aforesaid method to produce is as shown in the table in the oil consumption of east wind pick up (2.8L).Monitor through travelling, result shows, and after using the efficient and environment-friendly type diesel oil of the present embodiment, oil consumption declines, and after traveling 100km, its exhaust gas smoke decline 11.35%, CO, HC value also have remarkable reduction, and obviously feel that automobile power improves after travelling.High-efficiency cleaning environment friendly fuel of the present invention can save the energy more than 10%, that is cargo truck needed the distance that use 10 kilograms of regular fuels can be covered originally, only need less than 9 kilograms of high-efficiency cleaning type fuel oils now, high-efficiency cleaning environment friendly fuel of the present invention can be society and brings pure and fresh air, there is huge potential economic benefit.
Table 1 oil consumption (L/100 kilometer) contrasts
| Car number | Use regular fuel | Use the present embodiment efficient and environment-friendly type diesel oil | Average oil-saving rate |
| 1 | 7.21 | 6.46 | 10.40% |
| 2 | 7.10 | 6.38 | 10.14% |
| 3 | 6.98 | 6.27 | 10.13% |
| 4 | 7.33 | 6.52 | 11.05% |
Embodiment 2 adopts following steps to prepare Efficient environment-friendlyfuel fuel oil of the present invention and the recycling with the enzyme liquid residuum in preparation process:
(1) preparation of complex enzyme liquid: add 1.2kg aspergillus oryzae, 1.2kg cellulase, 1.2kg L-Glutamine deaminase, 1.2kg glucose isomerase liquid by every 1 ton of water, aspergillus oryzae, cellulase, L-Glutamine deaminase, glucose isomerase amount ratio are the ratio of 1:1:1:1, at normal temperatures, aspergillus oryzae, cellulase, L-Glutamine deaminase, glucose isomerase liquid and water are added in steam-operating stirred pot, carry out steam-operating and stir 36 hours, obtained complex enzyme liquid;
(2) for aviation kerosene, the method of production Efficient environment-friendlyfuel fuel oil of the present invention is adopted to carry out modification: in aviation kerosene, add the nonionogenic tenside sapn accounting for its quality 1.5 ‰, stirring makes sapn be well dispersed in aviation kerosene, obtains pretreated aviation kerosene; Get the obtained complex enzyme liquid of step (1) and pretreated aviation kerosene at normal temperatures, by complex enzyme liquid and pretreated aviation kerosene mass ratio 4:6 mixing 2min, blend pressure is 0.3MPa, through centrifugation after mixing, obtain efficient and environment-friendly type aviation kerosene, be separated simultaneously and obtain enzyme liquid residuum;
(3) recycle of enzyme liquid residuum: the weight ratio of enzyme liquid residuum and heavy oil being pressed 4:6, mixes through mixing tank with No. 180 heavy oil being heated to 45 DEG C, then through centrifugation, obtains environment-friendly type heavy oil.
Embodiment 3 adopts following steps to prepare the recycling of the enzyme liquid residuum in Efficient environment-friendlyfuel fuel oil of the present invention and preparation process:
(1) preparation of complex enzyme liquid: add 1.0kg aspergillus oryzae, 1.5kg cellulase, 1.0kg L-Glutamine deaminase, 1.5kg glucose isomerase liquid by every 1 ton of water, at normal temperatures, aspergillus oryzae, cellulase, L-Glutamine deaminase, glucose isomerase liquid and water are added in steam-operating stirred pot, carry out steam-operating and stir 24 hours, obtained complex enzyme liquid;
(2) for heavy oil, the method of production Efficient environment-friendlyfuel fuel oil of the present invention is adopted to carry out modification: in commercially available heavy oil, add the nonionogenic tenside sapn emulsifying agent accounting for its quality 1.5 ‰, stirring makes sapn emulsifying agent be well dispersed in heavy oil, obtains pretreated heavy oil; Get the obtained complex enzyme liquid of step (1) and pretreated heavy oil at normal temperatures, by complex enzyme liquid and pretreated heavy oil mass ratio 4:6 mixing 2min, blend pressure is 0.4MPa, through centrifugation after mixing, obtain efficient and environment-friendly type heavy oil, be separated simultaneously and obtain enzyme liquid residuum;
(3) recycle of enzyme liquid residuum: the weight ratio of enzyme liquid residuum and heavy oil being pressed 3:7, mixes through mixing tank with No. 180 heavy oil being heated to 35 DEG C, then through centrifugation, obtains environment-friendly type heavy oil.
Claims (5)
1. a preparation method for Efficient environment-friendlyfuel fuel oil, is characterized in that: comprise following concrete steps:
(1) preparation of complex enzyme liquid: in steam-operating stirred pot, adds aspergillus oryzae, cellulase, L-Glutamine deaminase, glucose isomerase and water, carries out steam-operating at normal temperatures and stirs 24-36 hour, obtained complex enzyme liquid; The consumption proportion of described aspergillus oryzae, cellulase, L-Glutamine deaminase, glucose isomerase and water is: every 1 ton of water adds 1-1.5kg aspergillus oryzae, 1-1.5kg cellulase, 1-1.5kg L-Glutamine deaminase, 1-1.5kg glucose isomerase;
(2) oil product pre-treatment: add the nonionogenic tenside accounting for oil quality 0.8-1.5 ‰ in oil product, stirs and makes nonionogenic tenside be well dispersed in oil product;
(3) by complex enzyme liquid and pretreated oil product according to the ratio of mass ratio 3:7 or 4:6, mix 1-2min at normal temperatures, blend pressure is at 0.6 below MPa, after mixing, through centrifugation, namely obtain Efficient environment-friendlyfuel fuel oil, be separated simultaneously and obtain enzyme liquid residuum.
2. the preparation method of Efficient environment-friendlyfuel fuel oil according to claim 1, is characterized in that: described fuel oil oil product is aviation kerosene or diesel oil or heavy oil.
3. the preparation method of Efficient environment-friendlyfuel fuel oil according to claim 1, is characterized in that: described nonionogenic tenside is Span series emulsifying agent.
4. the preparation method of Efficient environment-friendlyfuel fuel oil according to claim 1, it is characterized in that: the recycling mode of described enzyme liquid residuum is: mixed through mixing tank with the heavy oil being heated to 35-45 DEG C by enzyme liquid residuum, then obtain efficient and environment-friendly type heavy oil through centrifugation; Described enzyme liquid residuum is mass ratio 3:7 or 4:6 with the blending ratio of the heavy oil being heated to 35-45 DEG C.
5. an Efficient environment-friendlyfuel fuel oil, is characterized in that: adopt preparation method described in claim 1 to prepare.
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| JP2001342470A (en) * | 2000-06-01 | 2001-12-14 | Sun Life Kagaku Kk | Combustion promotion solution, combustion promotion granule and method for producing the solution and the granule |
| CN101798542A (en) * | 2009-02-10 | 2010-08-11 | 范明星 | Energy saving additive for industrial fuel oil and production process |
| KR101011724B1 (en) * | 2009-06-29 | 2011-01-31 | 김상규 | A Fuel Additive and Manufacturing Method For the Same |
| CN102250653A (en) * | 2011-05-20 | 2011-11-23 | 黄龙哲 | Energy-saving agent for biomass fuel oil |
| CN102703143A (en) * | 2012-05-30 | 2012-10-03 | 荆门市浩吉星生物科技有限公司 | High-efficiency energy-saving and environment-friendly catalyst for fuel oil |
| CN103194283B (en) * | 2013-04-15 | 2015-09-09 | 东木奥森科技（天津）有限公司 | A kind of Micell activity bio-enzyme fuel oil synergist |
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