CN1152607A - Heavy oil-water suspensoid fuel and preparation thereof - Google Patents
Heavy oil-water suspensoid fuel and preparation thereof Download PDFInfo
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- CN1152607A CN1152607A CN 95114269 CN95114269A CN1152607A CN 1152607 A CN1152607 A CN 1152607A CN 95114269 CN95114269 CN 95114269 CN 95114269 A CN95114269 A CN 95114269A CN 1152607 A CN1152607 A CN 1152607A
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Abstract
The present invention relates to a heavy oil-water suspensoid fuel and its preparation method. It is characterized by that the heavy oil is pulverized into the particles with grain size of 0.1-100 micrometers, then the particles are uniformly distributed in water-based continuous phase as disperse phase, and then a polar organic matter with 0.05-5% water-solubility at normal temp. is added in the course of emulsification by adding emulsifying agent at 50-95 deg.C so as to make the above-mentioned material into the micro emulsifiable solution which is thermodynamically stable, then the obtained micro emulsifiable solution is cooled, and can be converted into the invented water suspensoid solution. Said invented fuel possesses good flowability under the solidification point of heavy oil, stability, burning performance, and its viscosity is 0.2-0.9 Pa.s.
Description
The present invention relates to a kind of heavy oil---water suspended colloid fuel and preparation method thereof provides a kind of and has been lower than the fuel that has good fluidity under the heavy oil freezing point temperature.
Characteristics such as heavy oil has the calorific value height, ash content is low, volatile matter is high, burning-point is low than coal, price is more honest and cleaner are the conventional fuels of non-ferrous metal metallurgy, steel ingot heater and multiple Industrial Stoves.Because furol viscosity is big, zero pour is high, therefore when storing and use, must have boiler, steam-pipe or electric heater unit, so that the heavy oil heat tracing is kept liquid state.Like this, increased investment, the maintenance of auxiliary facility, cost rises, workload strengthens, also must consumes energy and cause the loss through volatilization of hanging down the boiling range material in the heavy oil.In order to improve heavy oil viscosity and combustion position at normal temperatures, a lot of technology have been developed both at home and abroad, for example Japanese kokai publication hei 4-20593,4-20594,1-313594 etc., generally be in heavy oil, to add entry and emulsifying agent, heating emulsification, be formed with the water-in-oil or the O/w emulsion of particle diameter 1-100 μ m disperse phase, after emulsification, directly enter burner to improve the combustion position of heavy oil, or improve the emulsifying agent kind and increase consumption, make heavy oil emulsion that lower viscosity and the stability of long period be arranged at normal temperatures.But all measures all are only limited to and make heavy oil become oil in water emulsion, oil in water emulsion is a unsettled system on thermodynamics, moreover always use under gravity field, gravity has quickened this unstable, can engender newborn interface, water-oil interface after a couple of days and breakdown of emulsion.In case the profit layering occurs, will cause combustion instability, operational outfit easily breaks down.The oil in water emulsion that has improved can flow more than 30 ℃, and preservation period can reach one month, still have significant limitation.
In order to solve the low and mobile bad problem below 30 ℃ of heavy oil emulsive liquid stability, the present invention initiates a kind of different with heavy oil emulsive liquid form, still has heavy oil---the water suspended colloid fuel and the method for making thereof of good fluidity and stability under the temperature that is lower than the heavy oil zero pour.The present invention is ground into heavy oil with high-shear or spray method the particulate of particle diameter 0.1～100 μ m, be uniformly distributed in the aqueous based continuous phase as disperse phase, again at the oil in water emulsion factors of instability---interfacial tension and gravity, add water, emulsifying agent in 50～95 ℃ of emulsion processes at heavy oil, added the 3rd class material---0.05～5% water miscible polar organic matter is arranged under the normal temperature, make system median surface tension force become zero, become micro emulsion oil highly stable on the thermodynamics, transform to such an extent that heavy oil---the water suspended colloid fuel has reached the object of the invention through cooling.
Heavy oil of the present invention---water suspended colloid fuel is characterised in that and contains the water of 24～70% (weight) as external phase, 29～75% (weight) are as the heavy oil of disperse phase, 0.01～3.0% (weight) is applicable to that heavy oil forms the polar organic matter of the emulsifying agent and 0.01～5.0% (weight) of O/w emulsion as cosurfactant, described polar organic matter have at normal temperatures 0.05～5% water-soluble, assembly is divided into 100%, and described disperse phase is the particulate of particle diameter 0.1～100 μ m at normal temperatures.
Emulsifying agent of the present invention is that all are applicable to that heavy oil forms the emulsifying agent of O/w emulsion, for example:
(a) aniorfic surfactant: metal carboxylate tensio-active agent, sulfonate surfactant;
(b) cationic surfactant: alkyl propylene diamine class tensio-active agent, quaternary ammonium salts tensio-active agent;
(c) hydrophilic---the nonionic surface active agent of lipophilic balance value (HLB) in 8～20 scopes.
Can choose above-mentioned one or more tensio-active agent as emulsifying agent of the present invention, consider from the angle that improves stability and reduce cost, can be by (a) with (c) by (a): (c)=2: 98～75: 25 (weight ratio) or (b) with (c) by (b): C=2: 98～75: 25 (weight ratios) be formed emulsifying agent of the present invention, and described (a) and (b), (c) can select one or more material respectively for use.The use of mentioned emulsifier sees embodiment for details, and its total content accounts for 0.01～3% (weight) of the total composition of the present invention.
Cosurfactant of the present invention is exactly the 3rd class material that the present invention adds, be intended to overcome water and interfacial tension and the gravity of emulsifying agent in the heavy oil emulsive process, make interfacial tension become zero, the median size of dispersed phase particles is below 0.1 μ m at this moment, this process is called the micro emulsion process, and the oil in water emulsion of formation is a micro emulsion oil, because interfacial tension is zero, thereby be steady state on thermodynamics, place for a long time and do not produce demulsifying phenomenon.The used cosurfactant of the present invention is a polar organic matter, is characterized in having the limit water-soluble, at room temperature should have 0.05～5% water-soluble.Preferably select one or more the material in alcohols (for example amylalcohol, Virahol are contour, lower aliphatic alcohols and other), amine (for example diethanolamine, Yi Bingchunan etc.), the acids for use.In addition, the polar organic matter that can also select other for use is ether, ester, ketone and one or more materials in the organic compound (containing two or more hydroxyls, epoxy group(ing), aldehyde radical, amino, chloro base and similar group) of 4～8 carbon atoms are arranged for example, sees embodiment for details.The total content of above-mentioned auxiliary surface activator accounts for 0.01～5.0% (weight) of the total composition of the present invention.
Heavy oil of the present invention---can also add 0～0.1% ethylene glycol mono-ether (for example ethylene glycol monomethyl ether, ethanol list ether etc.) and glycerol in the water suspended colloid fuel, press ethylene glycol mono-ether: glycerol=7: 3～9: 1 (weight ratio) makes up as frostproofer, makes this fuel also can keep good flowability in the temperature below 0 ℃.If glycerol can no longer add here as cosurfactant of the present invention.
Heavy oil of the present invention---in the water suspended colloid fuel, described heavy oil can replace for solid-state or full-bodied hydrocarbon polymer down with normal temperature.
Heavy oil of the present invention---the preparation method of water suspended colloid fuel is: 1. the water with the heavy oil and 24～70% (weight) of 29～75% (weight) is preheated to 50～95 ℃ respectively, then the cosurfactant of the emulsifying agent of 0.01～3.0% (weight) and 0.01～5.0% (weight) is added in the entry, after fully mixing dissolving with high-shear machine (more than the rotating speed 15000r/min), add above-mentioned heavy oil, proceed high-shear emulsifying, form micro emulsion oil; Or available following method: the cosurfactant of the emulsifying agent of 0.01～3.0% (weight) and 0.01～5.0% (weight) is added in the water of 24～70% (weight), stirring and dissolving, then 29～75% (weight) be preheated to 75～95 ℃ heavy oil with the oil pump pump to spraynozzle (require ejection fogdrop diameter be about 0.1～50 μ m), directly spray in the water, and constantly stir, make micro emulsion oil; 2. the micro emulsion oil cooling that will 1. make makes the micro-droplet of oil in the micro emulsion oil be frozen into small particle to normal temperature, makes the normal temperature suspension.
Emulsifying agent described in the preparation method of the present invention is that all are applicable to that heavy oil forms emulsifying agents of O/w emulsion, and described cosurfactant is that 0.05～5% water miscible polar organic matter is arranged under the normal temperature, detailed all as previously mentioned; When adding above-mentioned two kinds of materials, also can add 0～0.1% ethylene glycol mono-ether (for example ethylene glycol monomethyl ether, second diether list ether etc.) and glycerol makes up as frostproofer by 7: 3～9: 1 (weight ratio).
Heavy oil of the present invention---water suspended colloid fuel has good flowability in temperature more than 0 ℃, viscosity is 0.2～0.9Pas, and is not stratified in 3-6 month, and temperature is not being freezed below 0 ℃ behind the adding frostproofer, and keeps good flowability.Because fuel water of the present invention and heavy oil uniform mixing, heavy oil is ground into median size and reaches micron-sized minimum particulate, and the burning that is highly advantageous to is carried out, and makes burning more abundant thoroughly.The carbon residue that cracking produces in the heavy oil combustion generates CO and H owing to there being the water vapor existence can produce water-gas reaction
2Thereby one side can reduce the temperature of flame kernel, makes burning more complete on the other hand again, and efficiency of combustion is further improved; Flue dust, NO have also been reduced simultaneously
xAnd the quantity discharged of CO.
Except that heavy oil, all are solid-state or full-bodied hydrocarbon polymer such as wax and pitch etc. at normal temperatures, and all available aforesaid method is made suspended colloid fuel.Heavy oil described in the preparation method of the present invention can replace for solid-state or full-bodied hydrocarbon polymer down with normal temperature.
Provide the embodiment of the invention below, emulsifying agent used in the present invention and cosurfactant are not limited to embodiment certainly.
Embodiment one
Heavy oil and water are heated to 75 ℃ respectively, tensio-active agent and cosurfactant are added in the hot water, in high-speed shearing machine (rotating speed 15000r/min), fully mix dissolving, and then heavy oil adding the carrying out emulsify at a high speed that has heated, form microemulsion, be cooled to room temperature by water cooler then, form suspension.Used heavy oil in the present embodiment, water, tensio-active agent, cosurfactant use and account for total composition per-cent such as following table, each total composition is respectively 100%.
| The content of oil and water | Surfactant content | Cosurfactant content | The fuel rerum natura | Viscosity (Pas) | ||
| Negatively charged ion | Nonionic | Positively charged ion | ||||
| Oil 75% water 24% | Sodium lignosulfonate 0.20% | The polyoxyethylene nonylphenol ether 0.40% of HLB=15.5 | ????0％ | Amylalcohol 0.40% | The not stratified few sediment of profit | 0.36 |
| Oil 72.5% water 24% | Sulfosalicylic stearate methyl ester sodium salt 3% | 0％ | ????0％ | Virahol 0.25% amylalcohol 0.25% | The not stratified few sediment of profit | 0.72 |
| Oil 75% water 24% | Lignosulfonic acid formaldehyde condensation products sodium salt 0.25% | The ethylene oxide 0.40% of the nonyl phenol formaldehyde condensation products of HLB=15.2 | ????0％ | Virahol 0.35% | The not stratified few sediment of profit | 0.62 |
| Oil 75% water 24% | 0％ | 0％ | Tallow Pn 0.99% | Yi Bingchunan 0.01% | Profit is not sent out a layer few sediment | 0.78 |
Embodiment two
Respectively tensio-active agent, cosurfactant according to the form below ratio are added in the entry stirring and dissolving.Heating heavy oil to 95 ℃, with oil pump with petroleum pump to spraynozzle, directly mist of oil is sprayed in the water and constantly and stirs, require the scope of the diameter of atomizing rear nozzle ejection droplet at 0.1 μ m～50 μ n, can obtain heavy oil after the cooling---the water suspension.
The weight percent that uses and account for total composition of heavy oil, water, tensio-active agent and cosurfactant sees the following form in an embodiment, and each total composition is respectively 100%.
| The content of heavy oil and water | Surfactant content | Cosurfactant content | The fuel rerum natura | Viscosity (Pas) | ||
| Negatively charged ion | Nonionic | Positively charged ion | ||||
| Oil 29% water 70% | 0％ | HLB=15.0 polyoxyethylene lauryl ether 0.6% | 0％ | Amylalcohol 0.4% | The not stratified few sediment of profit | 0.50 |
| Oil 29% water 70% | 0％ | HLB=20 polyoxyethylene alkylphenol ether 0.3% | N-alkyl propylene diamine 0.4% | Yi Bingchunan 0.15% amylalcohol 0.15% | The not stratified few sediment of profit | 0.40 |
| Oil 29% water 70% | The misery basic sodium salt 0.6% of nutmeg ester | 0％ | 0％ | Virahol 0.4% | The not stratified few sediment of profit | 0.38 |
| Oil 29% water 70% | 0％ | 0％ | C 7～9Alkyl propylene diamine dihydrochloride 0.8% | Yi Bingchunan 0.2% | The not stratified few sediment of profit | 0.35 |
| Oil 70% water 26% | Palmitinic acid methyl sodium salt 1.0% | 0％ | 0％ | Amylalcohol 3% | The not stratified few sediment of profit | 0.28 |
| Oil 65% water 31.7% | Dibutyl naphthalene sulfonic formaldehyde condensation compound sodium salt 0.005% | HLB=15.0 styryl phenol formaldehyde resin Soxylat A 25-7 0.005% | 0％ | Virahol 1.2% amylalcohol 2% | The not stratified few sediment of profit | 0.41 |
| Oil 65% water 29% | Sodium polystyrene sulfonate (molecular weight 8,000) 0.5% | HLB=16.0 polyoxyethylene oleate 0.5% | 0％ | Amylalcohol 5% | The not stratified few sediment of profit | 0.23 |
| Oil 65% water 29.5% | Octene is along divinyl acid cointegrates sodium salt 1.0% | HLB=13.0 castor oil polyoxyethylene ether 0.55% | 0％ | Amylalcohol 3.95% | The not stratified few sediment of profit | 0.26 |
Top embodiment is and preserves the situation of measuring after 3 months under the normal temperature in the time of 25 ℃
Embodiment three: the heavy oil that accounts for total composition 70% (weight), the water of point assembly part 24.4% (weight), account for molecular weight 3.5 ten thousand polyoxyethylene---polyoxypropylene---the polyoxy butylene blocks type polyethers of total composition 0.5% (weight), account for the Span20 of total composition 0.05% (weight), account for the octylame of total composition 0.05% (weight), the amylalcohol that accounts for total composition 5% (weight) is heated to 50 ℃ respectively, mix then, stir, put into high-speed shearing machine (15000r/min) emulsification again, form microemulsion, be cooled to 15 ℃, form suspension, preserve under 15 ℃ of conditions and measured rerum natura in 3 months, this suspended colloid fuel is not stratified, and viscosity is 0.45Pas.The present embodiment assembly is divided into 100%.
Embodiment four: each component is (except that amylalcohol is 4.9% (weight) in the last example, all the other and last routine same ratio) be preheated to 70 ℃ respectively, as above example is mixed stirring then, again the ethylene glycol monoethyl ether of 0.09% (accounting for gross weight) and 0.01% glycerol are added respectively, high speed shear emulsification is chilled to subzero-5 ℃ then and preserves that to measure viscosity after 3 months be 0.56Pas.
Embodiment five:
Hydrocarbon polymer Yatall MA 70% (gross weight meter with viscosity under the normal temperature, down together), water 25% is heated to 50 ℃ respectively, add sodium lauryl sulphate 1.7%, ethoxylated dodecyl alcohol 0.8%, amylalcohol 2.5% mixes, and then high speed (15000r/min) emulsification pretreatment, the milk sap that makes is cooled to normal temperature, forms suspension, and 3 months measure its viscosity 30 ℃ the time is 0.21Pas.
Embodiment six:
With fusing point 75～95 ℃ paraffin (C
35～50Chloroflo) 70% (gross weight meter, down together), water 25%, sodium lauryl sulphate 2%, polyoxyethylene nonylphenol ether (HLB=15) 0.5%, amylalcohol 2.5% preheating respectively, in the time of 95 ℃, stir mixed, carry out high speed shear emulsification then, be chilled to normal temperature after forming milk sap, measuring its viscosity 30 ℃ the time after 3 months is 0.30Pas.
Embodiment seven:
With pitch 69.0% (gross weight meter, down together), water 28%, tallow Pn 1.5%, alkylphenol polyoxyethylene (HLB=13) 0.5%, amylalcohol 1%, respectively preheating is stirred mixedly in the time of 90 ℃, carries out emulsify at a high speed then, form milk sap, be chilled to normal temperature, measuring its viscosity 30 ℃ the time after 3 months is 0.21Pas.
The various embodiments described above assembly is divided into 100%.
Claims (9)
1, a kind of heavy oil---water suspended colloid fuel, it is characterized in that containing the water of 24～70% (weight) as external phase, 29～75% (weight) are as the heavy oil of disperse phase, 0.01～3.0% (weight) is suitable for heavy oil and forms the polar organic matter of the emulsifying agent and 0.01～5.0% (weight) of O/w emulsion as cosurfactant, described polar organic matter have at normal temperatures 0.05～5% water-soluble, total composition is 100%, and described disperse phase is the particulate of particle diameter 0.1～100 μ m at normal temperatures.
2, heavy oil according to claim 1---water suspended colloid fuel is characterized in that described heavy oil replaces for solid-state or full-bodied hydrocarbon polymer down with normal temperature.
3, heavy oil according to claim 1---water suspended colloid fuel is characterized in that described emulsifying agent is: (a) aniorfic surfactant: metal carboxylate tensio-active agent, sulfonate surfactant; (b) cationic surfactant: alkyl propylene diamine class surfactant, quaternary ammonium salts tensio-active agent; (c) hydrophilic---the nonionic surface active agent of lipophilic balance value (HLB) in 8～20 scopes, one or more in the mentioned emulsifier.
4, heavy oil according to claim 3---water suspended colloid fuel, it is characterized in that described emulsifying agent is (a) and (c) by (a): (c)=2: 98～75: 25 (weight ratio) or (b) with (c) by (b): (c)=2: 98～75: 25 (weight ratio) form, described (a) and (b), (c) are respectively one or more materials.
5,, it is characterized in that described polar organic matter as cosurfactant is one or more the material in alcohols, amine, acids, ether, ketone, ester and the organic compound that 4～8 carbon atoms are arranged (containing two or more hydroxyls, epoxy group(ing), aldehyde radical, amino, chloro base and similar group) according to the described heavy oil of claim r---water suspended colloid fuel.
6, heavy oil according to claim 1---water suspended colloid fuel is characterized in that also containing ethylene glycol mono-ether and the glycerol of 0～0.1% (weight) as frostproofer, presses ethylene glycol mono-ether: glycerol=7: 3～combination in 9: 1.
7, a kind of claim 1,3,4,5 or 6 described heavy oil---method of water suspended colloid fuel of preparing, it is characterized in that: 1. heavy oil and water are preheated to 50～95 ℃ respectively, then emulsifying agent and cosurfactant are added in the entry, after fully mixing dissolving with high-shear machine (more than the rotating speed 15000r/min), add above-mentioned heavy oil, proceed high-shear emulsifying, form micro emulsion oil; 2. the micro emulsion oil cooling that will 1. make makes the micro-droplet of oil in the micro emulsion oil be frozen into small particle to normal temperature, makes the normal temperature suspension.
8, a kind of claim 1,3,4,5 or 6 described heavy oil---method of water suspended colloid fuel of preparing, it is characterized in that: 1. emulsifying agent and auxiliary surface activator are added stirring and dissolving in the entry, then be preheated to 50～95 ℃ heavy oil with the oil pump pump to spraynozzle (require ejection fogdrop diameter be about 0.1～50 μ m), directly spray in the water and constantly and stir, make micro emulsion oil; 2. the micro emulsion oil cooling that will 1. make makes the micro-droplet of oil in the micro emulsion oil be frozen into particulate to normal temperature, makes the normal temperature suspension.
9,, it is characterized in that described heavy oil can replace for solid-state or full-bodied hydrocarbon polymer down with normal temperature according to claim 7,8 described claim 1,3,4,5 or 6 described heavy oil---the methods of water suspended colloid fuel of preparing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95114269A CN1052748C (en) | 1995-12-18 | 1995-12-18 | Heavy oil-water suspensoid fuel and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95114269A CN1052748C (en) | 1995-12-18 | 1995-12-18 | Heavy oil-water suspensoid fuel and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1152607A true CN1152607A (en) | 1997-06-25 |
| CN1052748C CN1052748C (en) | 2000-05-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95114269A Expired - Fee Related CN1052748C (en) | 1995-12-18 | 1995-12-18 | Heavy oil-water suspensoid fuel and preparation thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107172A (en) * | 2010-11-01 | 2011-06-29 | 深圳市华星光电技术有限公司 | Frame sealant coating device and sealant supply method thereof |
| CN105316048A (en) * | 2014-07-24 | 2016-02-10 | 田永峰 | Heavy fuel oil effect improving agent |
| CN106544069A (en) * | 2015-09-17 | 2017-03-29 | 张宇 | A kind of production technology of energy-conserving and environment-protective emulsification, combustion oil |
| CN110869474A (en) * | 2017-05-11 | 2020-03-06 | 跨瑞丝国际有限责任公司 | Oil-in-water emulsions |
| US10704003B2 (en) | 2015-11-06 | 2020-07-07 | Quadrise International Limited | Oil-in-water emulsions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ226638A (en) * | 1987-10-23 | 1990-04-26 | Harrier Gmbh | Producing oil-water emulsion: circulating mixture through vortex chambers |
| CN1067593A (en) * | 1991-06-10 | 1993-01-06 | 湖南日用化工总厂 | Multifunctiuonal emulsifying agent for adding water in heavy oil |
| CN1035439C (en) * | 1993-11-12 | 1997-07-16 | 中国科学院化学研究所 | Emulsified heavy oil, its prepn. and application |
-
1995
- 1995-12-18 CN CN95114269A patent/CN1052748C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107172A (en) * | 2010-11-01 | 2011-06-29 | 深圳市华星光电技术有限公司 | Frame sealant coating device and sealant supply method thereof |
| WO2012058824A1 (en) * | 2010-11-01 | 2012-05-10 | 深圳市华星光电技术有限公司 | Sealant spreading device and sealant ejection method thereof |
| CN102107172B (en) * | 2010-11-01 | 2013-01-09 | 深圳市华星光电技术有限公司 | Frame sealant coating device and sealant supply method thereof |
| CN105316048A (en) * | 2014-07-24 | 2016-02-10 | 田永峰 | Heavy fuel oil effect improving agent |
| CN106544069A (en) * | 2015-09-17 | 2017-03-29 | 张宇 | A kind of production technology of energy-conserving and environment-protective emulsification, combustion oil |
| US10704003B2 (en) | 2015-11-06 | 2020-07-07 | Quadrise International Limited | Oil-in-water emulsions |
| CN110869474A (en) * | 2017-05-11 | 2020-03-06 | 跨瑞丝国际有限责任公司 | Oil-in-water emulsions |
| US11268040B2 (en) | 2017-05-11 | 2022-03-08 | Quadrise International Limited | Oil-in-water emulsions |
| CN110869474B (en) * | 2017-05-11 | 2022-06-21 | 跨瑞丝国际有限责任公司 | Oil-in-water emulsions |
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|---|---|
| CN1052748C (en) | 2000-05-24 |
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