CN108277052B - A kind of heavy oil, diesel oil in alcohol group compound emulsifying agent preparation method - Google Patents

A kind of heavy oil, diesel oil in alcohol group compound emulsifying agent preparation method Download PDF

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CN108277052B
CN108277052B CN201810337464.XA CN201810337464A CN108277052B CN 108277052 B CN108277052 B CN 108277052B CN 201810337464 A CN201810337464 A CN 201810337464A CN 108277052 B CN108277052 B CN 108277052B
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parts
component
oil
added
organic solvent
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CN108277052A (en
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叶澄
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Zhuhai Sanyue Petrochemical Co ltd
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Zhuhai Sanyue Petrochemical Co Ltd
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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

The present invention discloses a kind of preparation method for heavy oil, the compound emulsifying agent of diesel oil in alcohol group, mass ratio including component A and B component is 3-5:1, wherein, wherein component A includes 30-60 parts of acrylic monomers, 1-10 parts of fluorine component, 1-3 parts of polyisocynate monomer, 0.1-2 parts of fatty alcohol polyoxyethylene ether, 5-10 parts of methyl benzotriazazole；B component includes 0.5-10 parts of sulfomethylated humic acid sodium, 5-20 parts of sorbester p17,1-30 parts of cobalt naphthenate, 5-10 parts of ethylenediamine, 15-25 parts of phthalic anhydride, 4-8 parts of stearic acid.The compound emulsifying agent of this technology production can be used for oil products system, be widely used, and production is simple, and cost is relatively low, and stability is good.

Description

A kind of heavy oil, diesel oil in alcohol group compound emulsifying agent preparation method
Technical field
The present invention relates to a kind of systems of the high-efficiency environment friendly energy-conservation emulsifier in emulsifier more particularly to heavy oil, diesel oil in alcohol group Preparation Method.
Background technique
The energy is the lifeline of national security, wherein non-renewable petroleum resources are that most important the energy safety of supply is asked One of topic.In order to effectively construct energy security, each state all attaches great importance to oil consumption and deposit, and various methods is taken actively to grind Study carefully reduction or substitutes the consumption of petroleum resources.With science and technology and economic rapid development, the practical owning amount of the automobile in China and by This caused oil demand is always in rapid growth.Auto industry is one of the mainstay of the national economy industry in China, since Since 2010, auto industry accounts for 5.5% or more of the specific gravity of GDP, and China's auto output has leapt to third place in the world, accounted for about The 6%~8% of world car total output.According to statistics, China is in motor benzines in 2018 and diesel consumption total amount than 2014 It nearly doubles, reaches 300,000,000 tons or so, therefore petrol and diesel oil problem in short supply will be more serious.
Heavy oil and diesel oil in alcohol group are all a kind of important fuel, many in oil plant, chemical plant, steel mill and power plant etc. Place generally all uses heavy oil as fuel, still, since heavy oil is petroleum deep processing surplus materials, no matter which kind of high fever is used The combustion apparatus of effect, direct combusting heavy oil inevitably cause combustion reaction incomplete, form black smoke, coking and carbon deposit, The problem of causing fuel largely to waste, while also bringing environmental pollution.It is abundant generally for burning is guaranteed, excessive sky need to be injected Gas, and heat has been taken away in the discharge of these excess airs, causes thermal loss.
To generally burn after heavy oil emulsive to solve the above problems at present, but do not have also it is a kind of effectively can make emulsification after Heavy oil active combustion, while can also environmental emission reduction emulsifier.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides that a kind of performance is stable, can efficiently synthesize heavy oil, also has section It can the heavy oil of environment protecting, the high-efficiency environment friendly energy-conservation emulsifier in diesel oil and preparation method thereof.In addition, the composite milk of the application Agent can be also used for emulsification alcohol radical-diesel oil system, so that diesel oil in alcohol group is steadily in the state of alcohol oil-in always, effective It is not layered in time limit.
The technical solution of the present invention is as follows: the preparation method of a kind of heavy oil, diesel oil in alcohol group environment-friendly type compound emulsifying agent, including with Lower step:
A, organic solvent is added in reaction kettle, is warming up to 50-70 DEG C, then mix acrylate monomer, fluorochemical monomer It closes uniformly, then is slowly dropped into organic solvent, control feed time, charging, which finishes, continues insulation reaction 2-4h, stops reaction simultaneously It is cooled to room temperature to obtain fluorine-containing oligomer resin solution；
B, it by fatty alcohol polyoxyethylene ether, polyisocynate monomer investment fluorine-containing oligomer resin solution, fills After dividing 1~2h of stirring, methyl benzotriazazole, stirring is added, reaction 1h obtains component A mixed solution；
C, by sulfomethylated humic acid sodium, sapn, cobalt naphthenate, ethylenediamine stirs evenly at 40-70 DEG C according to the proportion, then Phthalic anhydride and stearic acid is added, continues to stir 1h, forms B component homogeneous solution；
D, the B component homogeneous solution of step c is added in the component A mixed solution that step b is obtained, is kept for 40-60 DEG C 1-3h is reacted, excessive organic solvent is removed, obtains mixed emulsifier, preferably 50 DEG C of reaction condition, 2h；
Wherein,
Component A includes the component of following mass fraction:
About 30-60 parts of acrylic monomers,
1-10 parts of fluorine component,
1-3 parts of polyisocynate monomer,
0.1-2 parts of fatty alcohol polyoxyethylene ether,
5-10 parts of methyl benzotriazazole；
B component includes the component of following mass fraction:
0.5-10 parts of sulfomethylated humic acid sodium,
5-20 parts of sorbester p17,
1-30 parts of cobalt naphthenate,
5-10 parts of ethylenediamine,
15-25 parts of phthalic anhydride,
4-8 parts of stearic acid.
Preferably, the mass ratio of compound emulsifying agent of the present invention, component A and B component is 3-5:1, wherein A group agent Component and its weight fraction ratio are as follows: 40-50 parts of acrylic monomers, 5-10 parts of fluorine component, 1-2 parts of polyisocynate monomer, 0.1-1 parts of fatty alcohol polyoxyethylene ether, 5-8 parts of methyl benzotriazazole；
The component and its weight fraction ratio of B group agent are as follows: 0.5-3 parts of sulfomethylated humic acid sodium, 8-10 parts of sorbester p17, cycloalkanes Sour cobalt 10-20 parts, 8-10 parts of ethylenediamine, 15-20 parts of phthalic anhydride, 4-6 parts of stearic acid.
Wherein, it according to mass ratio is 1:(2- that the acrylate monomer, which is styrene, methyl methacrylate or the two, 20) it forms；The fluorine component is Hexafluorobutyl mathacrylate.
The polyisocynate monomer is toluene di-isocyanate(TDI) and its polymer, 4,4- diphenylmethane diisocyanate One of ester or its multiple combinations.
The organic solvent is propylene glycol or ethylene glycol.
In the present invention, because generating fluorine-containing propene acid oligomer using acrylate monomer in component A and fluorochemical monomer polymerization, So that polymer shows certain physico-chemical properties of fluorochemical to a certain extent.Therefore, to have excellent hydrophobicity same When, it is also equipped with certain oil repellency, can steadily emulsify alcohol-containing-oil interface or heavy oil, diesel oil system, increases alcohols and bavin The intersolubility of oil, application system is extensive, and effect stability；Because feeding intake using the naphthenic compound in group agent B and suitably Proportion, has the function of catalytic combustion-supporting, to make emulsifier of the invention by after heavy oil emulsive, the discharge of heavy oil combustion subtracts significantly It is few, SO2Discharge can reduce 90% or more, the work that methyl benzotriazazole also prevents gasoline engine or diesel-engine equipment from corroding With；The emulsifiers such as component B stearic acid, phthalic anhydride, make emulsifier of the invention have very strong emulsifying capacity, heavy oil emulsification when, The ratio of heavy oil and water can reach 1:1, and the heavy oil after emulsification is the molecular structure of water-in-oil type, and the heavy oil storage one after emulsification Year or more be for a long time not in water-oil separating, performance is highly stable.
Emulsifier of the invention can be applied not only to emulsification heavy oil, while can also be applied to diesel oil emulsification or contain alcohol Base-diesel oil system combines compound system, and application is good, and the compound emulsifying agent of formation has stability good, is easy recycling, The advantages of recycling.
Emulsifier of the invention can effectively emulsify heavy oil, diesel oil or fuel oil, make emulsification after heavy oil, diesel oil or It can more effectively burn, it, can fuel-economizing 35%-45%, reduction SO after heavy oil uses emulsifier of the invention290% or more discharge, storage Depositing 1 year or more is not in water-oil separating, and performance is highly stable.The present invention is by a part of conventional heavy oils emulsifier component and newly Type resin emulsifier forms composite emulsifying system, heavy wool system can be emulsified, small for different oil product usage amounts, Preparation method is simple, at low cost, can be recycled, and the stability of oil emulsion is good, not stratified, is taking into account the same of many body system oil product raw material When, good emulsifying effectiveness may be implemented.
Specific embodiment
The present invention will be further described in detail with reference to the specific embodiments.
Embodiment 1
The preparation method of heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier, by component A and B component according to mass ratio 3:1 It is prepared in organic solvents, wherein component A includes styrene and methyl methacrylate 30-60 parts, methacrylic acid six 1-10 parts of fluorine butyl ester, 4,4- 1-3 parts of methyl diphenylene diisocyanates, 0.1-2 parts of fatty alcohol polyoxyethylene ether, methyl benzo three 5-10 parts of nitrogen azoles；B component includes 0.5-10 parts of sulfomethylated humic acid sodium, and 5-20 parts of sorbester p17,1-30 parts of cobalt naphthenate, second two 5-10 parts of amine, 15-25 parts of phthalic anhydride, 4-8 parts of stearic acid.It prepares: organic solvent being added in reaction kettle in accordance with the following methods a, It is warming up to 50-70 DEG C, is then uniformly mixed acrylate monomer, fluorochemical monomer, then be slowly dropped into organic solvent, control adds Expect the time, charging, which finishes, continues insulation reaction 2-4h, stops reacting and is cooled to room temperature to obtain fluorine-containing oligomer resin Solution；B, it by fatty alcohol polyoxyethylene ether, polyisocynate monomer investment fluorine-containing oligomer resin solution, sufficiently stirs After mixing 1~2h, methyl benzotriazazole, stirring is added, reaction 1h obtains mixed solution；C, by methyl sodium humate, sapn, ring Alkanoic acid cobalt, ethylenediamine are stirred evenly at 40-70 DEG C according to the proportion, and phthalic anhydride and stearic acid is then added, and continue to stir 1h, are formed equal Even solution；D, the homogeneous solution of step c is added in the mixed solution that step b is obtained, keeps 40-60 DEG C of reaction 1-3h, root According to needs, excessive organic solvent is removed, mixed emulsifier is obtained.
Embodiment 2
The preparation method of heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier, by component A and B component according to mass ratio 3:1 It is prepared in organic solvents, wherein component A includes 30 parts of styrene, and 1 part of Hexafluorobutyl mathacrylate, 4,4- diphenyl 1 part of methane diisocyanate, 0.1 part of fatty alcohol polyoxyethylene ether, 5 parts of methyl benzotriazazole；B component includes sulphur methyl humic 0.5 part of sour sodium, 5 parts of sorbester p17,1 part of cobalt naphthenate, 5 parts of ethylenediamine, 15 parts of phthalic anhydride, 4 parts of stearic acid.It makes in accordance with the following methods It is standby: a, organic solvent is added in reaction kettle, is warming up to 50 DEG C, is then uniformly mixed acrylate monomer, fluorochemical monomer, then It is slowly dropped into organic solvent, controls feed time, charging, which finishes, continues insulation reaction 2h, stops reacting and being cooled to room temperature To fluorine-containing oligomer resin solution；B, fatty alcohol polyoxyethylene ether, polyisocynate monomer are put into fluorine-containing In oligomer resin solution, after 1h is sufficiently stirred, methyl benzotriazazole, stirring is added, reaction 1h obtains mixed solution；C, will Methyl sodium humate, sapn, cobalt naphthenate, ethylenediamine are stirred evenly at 40 DEG C according to the proportion, and phthalic anhydride and stearic acid is then added, Continue to stir 1h, forms homogeneous solution；D, the homogeneous solution of step c is added in the mixed solution that step b is obtained, keeps 40 DEG C reaction 1h, as needed, remove excessive organic solvent, obtain mixed emulsifier.
Embodiment 3
The preparation method of heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier, by component A and B component according to mass ratio 3:1 It is prepared in organic solvents, wherein component A includes 40 parts of methyl methacrylate, and 5 parts of Hexafluorobutyl mathacrylate, 4, 2 parts of 4- methyl diphenylene diisocyanate, 1 part of fatty alcohol polyoxyethylene ether, 8 parts of methyl benzotriazazole；B component includes sulphur first 5 parts of base sodium humate, 10 parts of sorbester p17,10 parts of cobalt naphthenate, 6 parts of ethylenediamine, 20 parts of phthalic anhydride, 6 parts of stearic acid.According to following Organic solvent: a, being added in reaction kettle, be warming up to 60 DEG C by method preparation, then mixes acrylate monomer, fluorochemical monomer Uniformly, it then is slowly dropped into organic solvent, controls feed time, charging, which finishes, continues insulation reaction 3h, and stopping reaction is simultaneously cooling Fluorine-containing oligomer resin solution is obtained to room temperature；B, fatty alcohol polyoxyethylene ether, polyisocynate monomer investment are contained In perfluoroalkyl acrylate oligomer resin solution, after 1~2h is sufficiently stirred, methyl benzotriazazole, stirring is added, reaction 1h is mixed Close solution；C, by methyl sodium humate, sapn, cobalt naphthenate, ethylenediamine stirs evenly at 50 DEG C according to the proportion, and benzene is then added Acid anhydride and stearic acid continue to stir 1h, form homogeneous solution；D, that the homogeneous solution of step c is added to the mixing that step b is obtained is molten In liquid, 50 DEG C of reaction 2h are kept, as needed, excessive organic solvent is removed, obtains mixed emulsifier.
Embodiment 4
The preparation method of heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier, by component A and B component according to mass ratio 3:1 It is prepared in organic solvents, wherein component A includes styrene and 60 parts of methyl methacrylate, methacrylic acid hexafluoro fourth 10 parts of ester, 4,4- 3 parts of methyl diphenylene diisocyanates, 2 parts of fatty alcohol polyoxyethylene ether, 10 parts of methyl benzotriazazole；B group Point include 10 parts of sulfomethylated humic acid sodium, 20 parts of sorbester p17,30 parts of cobalt naphthenate, 10 parts of ethylenediamine, 25 parts of phthalic anhydride, stearic acid 8 parts.Prepare: organic solvent being added in reaction kettle in accordance with the following methods a, be warming up to 70 DEG C, then by acrylate monomer, Fluorochemical monomer is uniformly mixed, then is slowly dropped into organic solvent, and feed time is controlled, and charging, which finishes, continues insulation reaction 4h, is stopped It only reacts and is cooled to room temperature to obtain fluorine-containing oligomer resin solution；B, by fatty alcohol polyoxyethylene ether, polyisocyanic acid Ester monomer is put into fluorine-containing oligomer resin solution, and after 2h is sufficiently stirred, methyl benzotriazazole is added, stirs, instead 1h is answered to obtain mixed solution；C, by methyl sodium humate, sapn, cobalt naphthenate, ethylenediamine stirs evenly at 70 DEG C according to the proportion, Then phthalic anhydride and stearic acid is added, continues to stir 1h, forms homogeneous solution；D, the homogeneous solution of step c step b is added to obtain To mixed solution in, keep 60 DEG C of reaction 3h, as needed, remove excessive organic solvent, obtain mixed emulsifier.
Embodiment 5
The preparation method of heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier, by component A and B component according to mass ratio 2:1 It is prepared in organic solvents, wherein component A includes styrene and 50 parts of methyl methacrylate, methacrylic acid hexafluoro fourth 8 parts of ester, 4,4- 2 parts of methyl diphenylene diisocyanates, 1 part of fatty alcohol polyoxyethylene ether, 6 parts of methyl benzotriazazole；B component Including 8 parts of sulfomethylated humic acid sodium, 10 parts of sorbester p17,20 parts of cobalt naphthenate, 7 parts of ethylenediamine, 16 parts of phthalic anhydride, 6 parts of stearic acid. Prepare: organic solvent being added in reaction kettle in accordance with the following methods a, be warming up to 50-60 DEG C, then by acrylate monomer, contain Fluorine monomer is uniformly mixed, then is slowly dropped into organic solvent, and feed time is controlled, and charging, which finishes, continues insulation reaction 2-3h, is stopped It only reacts and is cooled to room temperature to obtain fluorine-containing oligomer resin solution；B, by fatty alcohol polyoxyethylene ether, polyisocyanic acid Ester monomer is put into fluorine-containing oligomer resin solution, and after 2h is sufficiently stirred, methyl benzotriazazole is added, stirs, instead 1h is answered to obtain mixed solution；C, by methyl sodium humate, sapn, cobalt naphthenate, ethylenediamine stirs at 40-50 DEG C equal according to the proportion It is even, phthalic anhydride and stearic acid is then added, continues to stir 1h, forms homogeneous solution；D, the homogeneous solution of step c is added to step In the mixed solution that b is obtained, 40-50 DEG C of reaction 1-3h is kept, as needed, excessive organic solvent is removed, obtains composite milk Agent.
By oil product: compound emulsifying agent: solvent: graphene or fullerene are according to 100-120:10-20:5-10:0.1-1 weight Than obtaining oil emulsion after mixing, our experiments show that, it can stablize after oil emulsion is static not stratified；For heavy oil emulsive, by one Year or more still there is not water-oil separating, and sulphur-containing substance discharge can be reduced with fuel-economizing 30%, for diesel oil in alcohol group, due to tool There is the effect of part resin, diesel oil in alcohol group can dissolve each other very well, less carbon emission, and component A can be played with component B and be cooperateed with work With the consumption of diesel oil or heavy oil can be substantially reduced, and can reduce petrochemical industry cost, while being applicable in multiple systems, to simultaneously System with diesel oil and/or diesel oil in alcohol group has good emulsifying effectiveness.
Application examples 1
100kg heavy oil is taken, 60 DEG C is heated to and stirs evenly, adds 10 kg emulsifiers, 5g solvent, 0.1g fullerene, warp Appropriate 60 DEG C of water is added in high-speed stirred 5-15min as needed, uses after standing 24 hours.
Application examples 2
120kg diesel oil in alcohol group is taken, 60 DEG C is heated to and stirs evenly, adds 10 kg emulsifiers, 10g solvent, 0.5g fowler Alkene, through high-speed stirred 5-15min, the water of 70 DEG C of addition, which is mixed evenly, as needed becomes high-efficiency environment friendly oil emulsion, quiet It is used after setting 24 hours.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any Those skilled in the art within the technical scope disclosed by the invention, can without the variation that creative work is expected or Replacement, should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be limited with claims Subject to fixed protection scope.

Claims (2)

1. a kind of preparation method for heavy oil, the compound emulsifying agent of diesel oil in alcohol group, which comprises the following steps:
A, organic solvent is added in reaction kettle, is warming up to 50-70 DEG C, then mix styrene, Hexafluorobutyl mathacrylate It closes uniformly, then is slowly dropped into organic solvent, control feed time, charging, which finishes, continues insulation reaction 2-4h, stops reaction simultaneously It is cooled to room temperature to obtain fluorine-containing oligomer resin solution；
B, it by fatty alcohol polyoxyethylene ether, polyisocynate monomer investment fluorine-containing oligomer resin solution, sufficiently stirs After mixing 1~2h, methyl benzotriazazole, stirring is added, reaction 1h obtains component A mixed solution；
C, by sulfomethylated humic acid sodium, sapn, cobalt naphthenate, ethylenediamine stirs evenly at 40-70 DEG C according to the proportion, is then added Phthalic anhydride and stearic acid continue to stir 1h, form B component homogeneous solution；
D, the B component homogeneous solution of step c is added in the component A mixed solution that step b is obtained, keeps 50 DEG C of reaction 2h, Excessive organic solvent is removed, compound emulsifying agent is obtained；
Wherein,
Wherein component A is grouped as by the group of following mass fraction:
30 parts of styrene,
1 part of Hexafluorobutyl mathacrylate,
1 part of polyisocynate monomer,
0.1 part of fatty alcohol polyoxyethylene ether,
5 parts of methyl benzotriazazole；
B component is grouped as by the group of following mass fraction:
0.5 part of sulfomethylated humic acid sodium,
5 parts of sorbester p17,
1 part of cobalt naphthenate,
5 parts of ethylenediamine,
15 parts of phthalic anhydride,
4 parts of stearic acid;
The polyisocynate monomer is in toluene di-isocyanate(TDI) and its polymer, 4,4- methyl diphenylene diisocyanate One kind or its multiple combinations, organic solvent be propylene glycol or ethylene glycol.
2. preparation method according to claim 1, which is characterized in that the mass ratio of component A and B component is 3-5:1.
CN201810337464.XA 2016-03-24 2016-03-24 A kind of heavy oil, diesel oil in alcohol group compound emulsifying agent preparation method Expired - Fee Related CN108277052B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1153203A (en) * 1995-12-08 1997-07-02 刘志强 Fuel oil emulsifying agent
CN102226117A (en) * 2011-05-12 2011-10-26 周鼎力 Preparation method of diesel emulsifier and emulsified diesel for vehicles and ships
CN102676249A (en) * 2012-06-05 2012-09-19 广州埃尔辟能源科技有限公司 High-efficiency environment-friendly energy-saving emulsifier for heavy oil, diesel oil or fuel oil and preparation method of emulsifier
CN104818057A (en) * 2015-04-10 2015-08-05 中山职业技术学院 Automobile alcohol-based diesel oil composite resin type emulsifier, preparation method and auxiliary agent with application of emulsifier

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1153203A (en) * 1995-12-08 1997-07-02 刘志强 Fuel oil emulsifying agent
CN102226117A (en) * 2011-05-12 2011-10-26 周鼎力 Preparation method of diesel emulsifier and emulsified diesel for vehicles and ships
CN102676249A (en) * 2012-06-05 2012-09-19 广州埃尔辟能源科技有限公司 High-efficiency environment-friendly energy-saving emulsifier for heavy oil, diesel oil or fuel oil and preparation method of emulsifier
CN104818057A (en) * 2015-04-10 2015-08-05 中山职业技术学院 Automobile alcohol-based diesel oil composite resin type emulsifier, preparation method and auxiliary agent with application of emulsifier

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