CN108277052A - 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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CN108277052A
CN108277052A CN201810337464.XA CN201810337464A CN108277052A CN 108277052 A CN108277052 A CN 108277052A CN 201810337464 A CN201810337464 A CN 201810337464A CN 108277052 A CN108277052 A CN 108277052A
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parts
component
oil
organic solvent
added
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CN108277052B (en
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叶澄
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Zhuhai Sanyue Petrochemical Co ltd
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Wenzhou Hongchengxiang Technology Co Ltd
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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • 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, including the mass ratio of component A and B component is 35：1, wherein wherein component A includes 30 60 parts of acrylic monomers, 1 10 parts of fluorine component, 13 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, 48 parts of stearic acid.The compound emulsifying agent of this technology production can be used for oil products system, be widely used, and make simply, 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 technology
The energy is the lifeline of national security, is asked wherein non-renewable petroleum resources are most important the energy safety of supply 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 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 proportion 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 ratio 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 oil 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 ensured, 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.
Invention content
For overcome the deficiencies in the prior art, a kind of performance of present invention offer is stable, can efficiently synthesize heavy oil, also has section High-efficiency environment friendly energy-conservation emulsifier and preparation method thereof that can be in the heavy oil of environment protecting, diesel oil.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 scheme is that：A kind of preparation method 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 mixed acrylate monomer, fluorochemical monomer equal It is even, then be slowly dropped into organic solvent, feed time is controlled, charging, which finishes, continues insulation reaction 2-4h, and stopping reaction is simultaneously cooling Fluorine-containing oligomer resin solution is obtained to room temperature；
B, it by fatty alcohol polyoxyethylene ether, polyisocynate monomer input fluorine-containing oligomer resin solution, fully 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 proportioning, 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 40-60 DEG C of reaction 1-3h removes excessive organic solvent, 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 part ratio be：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 part ratio of B group agent be：0.5-3 parts of sulfomethylated humic acid sodium, 8-10 parts of sorbester p17, cobalt naphthenate 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 that the acrylate monomer, which is styrene, methyl methacrylate or the two,：（2- 20）Composition；The fluorine component is Hexafluorobutyl mathacrylate.
The polyisocynate monomer is toluene di-isocyanate(TDI) and its polymer, 4,4- diphenylmethane diisocyanates One kind in 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 containing alcohol-oil interface or heavy oil, diesel oil system, increases alcohols and bavin The intersolubility of oil, application system is extensive, and effect stability；Because using the naphthenic compound in group agent B and suitably feeding intake Proportioning, has the function of catalytic combustion-supporting, and to make the emulsifier of the present invention by after heavy oil emulsive, the discharge of heavy oil combustion subtracts significantly It is few, SO2Discharge can reduce 90% or more, methyl benzotriazazole also has the work for preventing gasoline engine or diesel-engine equipment from corroding With；The emulsifiers such as component B stearic acid, phthalic anhydride, make the present invention emulsifier have very strong emulsifying capacity, heavy oil emulsification when, The ratio of heavy oil and water can reach 1:1, 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 not in water-oil separating for a long time, performance is highly stable.
The emulsifier of the present 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, while compound system is taken into account, application is good, and the compound emulsifying agent of formation has stability good, is easy recycling, The advantages of recycling.
The present invention emulsifier effectively heavy oil, diesel oil or fuel oil can be emulsified, make the heavy oil after emulsification, diesel oil or It can more effectively burn, it, can fuel-economizing 35%-45%, reduction SO after heavy oil emulsifier using the present invention290% or more discharge, storage It is not in water-oil separating to deposit 1 year or more, 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, and heavy wool system can be emulsified, small for different oil product usage amounts, Preparation method is simple, at low cost, recyclable, 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 implementation mode
The present invention will be further described in detail with reference to the specific embodiments.
Embodiment 1
Heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier preparation method, by component A and B component according to mass ratio 3：1 is having It is prepared in solvent, wherein component A includes 30-60 parts of styrene and methyl methacrylate, methacrylic acid hexafluoro fourth 1-10 parts of ester, 4,4- 1-3 parts of methyl diphenylene diisocyanates, 0.1-2 parts of fatty alcohol polyoxyethylene ether, methyl benzotriazazole 5-10 parts；B component includes 0.5-10 parts of sulfomethylated humic acid sodium, 5-20 parts of sorbester p17,1-30 parts of cobalt naphthenate, ethylenediamine 5- 10 parts, 15-25 parts of phthalic anhydride, 4-8 parts of stearic acid.It prepares in accordance with the following methods：A, organic solvent is added in reaction kettle, is heated up To 50-70 DEG C, then acrylate monomer, fluorochemical monomer are uniformly mixed, then is slowly dropped into organic solvent, when control feeds Between, charging, which finishes, continues insulation reaction 2-4h, stops reacting and is cooled to room temperature to obtain fluorine-containing oligomer resin solution； B, 1 will be sufficiently stirred in fatty alcohol polyoxyethylene ether, polyisocynate monomer input fluorine-containing oligomer resin solution~ After 2h, methyl benzotriazazole, stirring is added, reaction 1h obtains mixed solution；C, by methyl sodium humate, sapn, aphthenic acids Cobalt, ethylenediamine are stirred evenly according to proportioning at 40-70 DEG C, and phthalic anhydride and stearic acid is then added, and continue to stir 1h, are formed uniformly molten Liquid；D, the homogeneous solution of step c is added in the mixed solution that step b is obtained, 40-60 DEG C of reaction 1-3h is kept, according to need It wants, removes excessive organic solvent, obtain mixed emulsifier.
Embodiment 2
Heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier preparation method, by component A and B component according to mass ratio 3：1 is having It is prepared in solvent, wherein component A includes 30 parts of styrene, 1 part of Hexafluorobutyl mathacrylate, 4,4- diphenyl methanes 1 part of diisocyanate, 0.1 part of fatty alcohol polyoxyethylene ether, 5 parts of methyl benzotriazazole；B component includes sulfomethylated humic acid sodium 0.5 part, 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 prepares in accordance with the following methods： A, organic solvent is added in reaction kettle, is warming up to 50 DEG C, be then uniformly mixed acrylate monomer, fluorochemical monomer, then delay It is slow to instill in organic solvent, feed time is controlled, charging, which finishes, continues insulation reaction 2h, stops reacting and is cooled to room temperature to obtain Fluorine-containing oligomer resin solution；B, fatty alcohol polyoxyethylene ether, polyisocynate monomer input fluorine-containing is low In copolymer resin solution, after being sufficiently stirred 1h, methyl benzotriazazole, stirring is added, reaction 1h obtains mixed solution；C, Jiang Jia Base sodium humate, sapn, cobalt naphthenate, ethylenediamine are stirred evenly according to proportioning at 40 DEG C, and phthalic anhydride and stearic acid is then added, after Continuous stirring 1h, forms homogeneous solution；D, the homogeneous solution of step c is added in the mixed solution that step b is obtained, is kept for 40 DEG C 1h is reacted, as needed, excessive organic solvent is removed, obtains mixed emulsifier.
Embodiment 3
Heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier preparation method, by component A and B component according to mass ratio 3：1 is having It being prepared in solvent, wherein component A includes 40 parts of methyl methacrylate, 5 parts of Hexafluorobutyl mathacrylate, and 4,4- bis- 2 parts of methylenebis phenyl isocyanate, 1 part of fatty alcohol polyoxyethylene ether, 8 parts of methyl benzotriazazole；B component includes that sulphur methyl is rotten Grow 5 parts of sour sodium, 10 parts of sorbester p17,10 parts of cobalt naphthenate, 6 parts of ethylenediamine, 20 parts of phthalic anhydride, 6 parts of stearic acid.In accordance with the following methods It prepares：A, organic solvent is added in reaction kettle, is warming up to 60 DEG C, be then uniformly mixed acrylate monomer, fluorochemical monomer, It is slowly dropped into organic solvent again, controls feed time, charging, which finishes, continues insulation reaction 3h, stops reacting and being cooled to room temperature Obtain fluorine-containing oligomer resin solution；B, fatty alcohol polyoxyethylene ether, polyisocynate monomer are put into fluorine-containing propene In acid oligomer resin solution, after being sufficiently stirred 1~2h, methyl benzotriazazole, stirring is added, reaction 1h obtains mixing molten Liquid；C, by methyl sodium humate, sapn, cobalt naphthenate, ethylenediamine stirs evenly according to proportioning at 50 DEG C, be then added phthalic anhydride and Stearic acid continues to stir 1h, forms homogeneous solution；D, the homogeneous solution of step c is added to the mixed solution that step b is obtained In, keep 50 DEG C of reaction 2h to remove excessive organic solvent as needed, obtain mixed emulsifier.
Embodiment 4
Heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier preparation method, by component A and B component according to mass ratio 3：1 is having It is prepared in solvent, wherein component A includes 60 parts of styrene and methyl methacrylate, Hexafluorobutyl mathacrylate 10 Part, 4,4- 3 parts of methyl diphenylene diisocyanates, 2 parts of fatty alcohol polyoxyethylene ether, 10 parts of methyl benzotriazazole；B component packet 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, 8 parts of stearic acid. It prepares in accordance with the following methods：A, organic solvent is added in reaction kettle, is warming up to 70 DEG C, then by acrylate monomer, fluorine-containing Monomer is uniformly mixed, then is slowly dropped into organic solvent, and feed time is controlled, and charging, which finishes, continues insulation reaction 4h, stops anti- It should and be cooled to room temperature to obtain fluorine-containing oligomer resin solution；B, by fatty alcohol polyoxyethylene ether, polyisocyanates list Body is put into fluorine-containing oligomer resin solution, after being sufficiently stirred 2h, methyl benzotriazazole is added, 1h is reacted in stirring Obtain mixed solution；C, by methyl sodium humate, sapn, cobalt naphthenate, ethylenediamine stirs evenly according to proportioning at 70 DEG C, then Phthalic anhydride and stearic acid is added, continues to stir 1h, forms homogeneous solution；D, the homogeneous solution of step c is added to what step b was obtained In mixed solution, 60 DEG C of reaction 3h is kept to remove excessive organic solvent as needed, obtain mixed emulsifier.
Embodiment 5
Heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier preparation method, by component A and B component according to mass ratio 2：1 is having It is prepared in solvent, wherein component A includes 50 parts of styrene and methyl methacrylate, Hexafluorobutyl mathacrylate 8 Part, 4,4- 2 parts of methyl diphenylene diisocyanates, 1 part of fatty alcohol polyoxyethylene ether, 6 parts of methyl benzotriazazole；B component packet Include 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.It presses It is prepared according to following methods：A, organic solvent is added in reaction kettle, is warming up to 50-60 DEG C, then by acrylate monomer, fluorine-containing 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, stops It reacts and is cooled to room temperature to obtain fluorine-containing oligomer resin solution；B, by fatty alcohol polyoxyethylene ether, polyisocyanates Monomer is put into fluorine-containing oligomer resin solution, and after being sufficiently stirred 2h, methyl benzotriazazole is added, stirs, reaction 1h obtains mixed solution；C, by methyl sodium humate, sapn, cobalt naphthenate, ethylenediamine stirs according to proportioning at 40-50 DEG C equal 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 to remove excessive organic solvent as needed, obtain 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 are the effect of part resin, diesel oil in alcohol group that can dissolve each other very well, less carbon emission, and also 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, pair simultaneously System with diesel oil and/or diesel oil in alcohol group is with 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 solvents, 0.1g fullerenes, through high speed 5-15min is stirred, appropriate 60 DEG C of water is added as needed, is used 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 solvents, 0.5g fullerenes, 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, stands It is used after 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 It replaces, 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 domain.

Claims (2)

1. a kind of preparation method for heavy oil, the compound emulsifying agent of diesel oil in alcohol group, which is characterized in that include 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 reacting simultaneously It is cooled to room temperature to obtain fluorine-containing oligomer resin solution；
B, it by fatty alcohol polyoxyethylene ether, polyisocynate monomer input fluorine-containing oligomer resin solution, fully 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 about stirs evenly at 40-70 DEG C according to proportioning, then plus Enter phthalic anhydride and stearic acid, continues 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 diisocyanates 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.
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