CN108485735B - A kind of compound emulsifying agent of heavy oil, diesel oil in alcohol group - Google Patents

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

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CN108485735B
CN108485735B CN201810337611.3A CN201810337611A CN108485735B CN 108485735 B CN108485735 B CN 108485735B CN 201810337611 A CN201810337611 A CN 201810337611A CN 108485735 B CN108485735 B CN 108485735B
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parts
component
oil
heavy oil
emulsifying agent
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CN108485735A (en
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叶澄
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AVIC energy saving (Nanjing) environmental protection Co., Ltd
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Hangzhou Ding Hao New Materials Co Ltd
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    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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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 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 compound emulsifying agent of heavy oil, diesel oil in alcohol group
Technical field
The present invention relates to the high-efficiency environment friendly energy-conservation emulsifiers in emulsifier more particularly to a kind of heavy oil, diesel oil in alcohol group.
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: a kind of heavy oil, diesel oil in alcohol group environment-friendly type compound emulsifying agent, wherein component A includes such as The component of lower 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.
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.
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.
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 Fuel oil can more effectively burn, can fuel-economizing 35%-45%, reduction SO after heavy oil uses emulsifier of the invention2Discharge 90% More than, storage 1 year or more is not in water-oil separating, and performance is highly stable.The present invention by a part of conventional heavy oils emulsifier at Divide and form composite emulsifying system with new type resin emulsifier, heavy wool system can be emulsified, different oil products is made Dosage is small, and preparation method is simple, at low cost, can be recycled, and the stability of oil emulsion is good, not stratified, former taking into account many body system oil product While material, 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
Heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier, by component A and B component according to mass ratio 3:1 in organic solvent In be prepared, wherein component A includes styrene and methyl methacrylate 30-60 parts, Hexafluorobutyl mathacrylate 1-10 Part, 4,4- 1-3 parts of methyl diphenylene diisocyanates, 0.1-2 parts of fatty alcohol polyoxyethylene ether, methyl benzotriazazole 5-10 Part；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, 5-10 parts of ethylenediamine, 15-25 parts of phthalic anhydride, 4-8 parts of stearic acid.It prepares in accordance with the following methods: a, organic solvent being added in reaction kettle, is warming up to 50- 70 DEG C, then acrylate monomer, fluorochemical monomer are uniformly mixed, then is slowly dropped into organic solvent, control feed time, add Material, which finishes, continues insulation reaction 2-4h, stops reacting and is cooled to room temperature to obtain fluorine-containing oligomer resin solution；B, will In fatty alcohol polyoxyethylene ether, polyisocynate monomer investment fluorine-containing oligomer resin solution, 1~2h is sufficiently stirred Afterwards, methyl benzotriazazole, stirring is added, reaction 1h obtains mixed solution；C, by methyl sodium humate, sapn, cobalt naphthenate, Ethylenediamine is stirred evenly at 40-70 DEG C according to the proportion, and phthalic anhydride and stearic acid is then added, and is continued to stir 1h, is formed homogeneous 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, as needed, Excessive organic solvent is removed, mixed emulsifier is obtained.
Embodiment 2
Heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier, by component A and B component according to mass ratio 3:1 in organic solvent In be prepared, wherein component A includes 30 parts of styrene, 1 part of Hexafluorobutyl mathacrylate, 4,4- diphenyl methane, two isocyanide 1 part of acid esters, 0.1 part of fatty alcohol polyoxyethylene ether, 5 parts of methyl benzotriazazole；B component includes 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.It prepares: a, will have in accordance with the following methods Solvent is added in reaction kettle, is warming up to 50 DEG C, is then uniformly mixed acrylate monomer, fluorochemical monomer, then be slowly dropped into 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 third Olefin(e) acid oligomer resin solution；B, fatty alcohol polyoxyethylene ether, polyisocynate monomer are put into fluorine-containing propene acid oligomer tree In lipoprotein solution, after 1h is sufficiently stirred, methyl benzotriazazole, stirring is added, reaction 1h obtains mixed solution；C, by methyl humic Sour sodium, sapn, cobalt naphthenate, ethylenediamine are stirred evenly at 40 DEG C according to the proportion, and phthalic anhydride and stearic acid is then added, continues 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 of reactions 1h removes excessive organic solvent, obtains mixed emulsifier as needed.
Embodiment 3
Heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier, by component A and B component according to mass ratio 3:1 in organic solvent In be prepared, wherein component A includes 40 parts of methyl methacrylate, 5 parts of Hexafluorobutyl mathacrylate, 4,4- diphenylmethyls 2 parts of alkane diisocyanate, 1 part of fatty alcohol polyoxyethylene ether, 8 parts of methyl benzotriazazole；B component includes sulfomethylated humic acid sodium 5 parts, 10 parts of sorbester p17,10 parts of cobalt naphthenate, 6 parts of ethylenediamine, 20 parts of phthalic anhydride, 6 parts of stearic acid.It prepares in accordance with the following methods: A, organic solvent is added in reaction kettle, is warming up to 60 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 3h, stops reacting and is cooled to room temperature to obtain Fluorine-containing oligomer resin solution；B, fatty alcohol polyoxyethylene ether, polyisocynate monomer investment fluorine-containing is low In copolymer resin solution, after 1~2h is sufficiently stirred, methyl benzotriazazole, stirring is added, reaction 1h obtains mixed solution；c, By methyl sodium humate, sapn, cobalt naphthenate, ethylenediamine stirs evenly at 50 DEG C according to the proportion, and phthalic anhydride and tristearin is then added Acid continues to stir 1h, forms homogeneous solution；D, the homogeneous solution of step c is added in the mixed solution that step b is obtained, is protected 50 DEG C of reaction 2h are held, as needed, excessive organic solvent is removed, obtains mixed emulsifier.
Embodiment 4
Heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier, by component A and B component according to mass ratio 3:1 in organic solvent In be prepared, wherein component A includes styrene and 60 parts of methyl methacrylate, 10 parts of Hexafluorobutyl mathacrylate, 4, 3 parts of 4- methyl diphenylene diisocyanate, 2 parts of fatty alcohol polyoxyethylene ether, 10 parts of methyl benzotriazazole；B component includes sulphur 10 parts of methyl sodium humate, 20 parts of sorbester p17,30 parts of cobalt naphthenate, 10 parts of ethylenediamine, 25 parts of phthalic anhydride, 8 parts of stearic acid.According to Following methods preparation: a, organic solvent is added in reaction kettle, is warming up to 70 DEG C, then by acrylate monomer, fluorochemical monomer It is uniformly mixed, then is slowly dropped into organic solvent, control feed time, charging, which finishes, continues insulation reaction 4h, stops reaction simultaneously It is cooled to room temperature to obtain fluorine-containing oligomer resin solution；B, fatty alcohol polyoxyethylene ether, polyisocynate monomer are thrown Enter in fluorine-containing oligomer resin solution, after 2h is sufficiently stirred, methyl benzotriazazole, stirring is added, reaction 1h is obtained Mixed solution；C, by methyl sodium humate, sapn, cobalt naphthenate, ethylenediamine stirs evenly at 70 DEG C according to the proportion, is then added Phthalic anhydride and stearic acid continue to stir 1h, form homogeneous solution；D, the homogeneous solution of step c is added to the mixing that step b is obtained In solution, 60 DEG C of reaction 3h are kept, as needed, excessive organic solvent is removed, obtains mixed emulsifier.
Embodiment 5
Heavy oil, alcohol radical-diesel oil high efficiency composition emulsifier, by component A and B component according to mass ratio 2:1 in organic solvent In be prepared, wherein component A includes styrene and 50 parts of methyl methacrylate, 8 parts of Hexafluorobutyl mathacrylate, 4,4- 2 parts of methyl diphenylene diisocyanate, 1 part of fatty alcohol polyoxyethylene ether, 6 parts of methyl benzotriazazole；B component includes sulphur methyl 8 parts of sodium humate, 10 parts of sorbester p17,20 parts of cobalt naphthenate, 7 parts of ethylenediamine, 16 parts of phthalic anhydride, 6 parts of stearic acid.According to lower section Organic solvent: a, being added in reaction kettle, be warming up to 50-60 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 2-3h, and stopping reaction is simultaneously cold But fluorine-containing oligomer resin solution is obtained to room temperature；B, fatty alcohol polyoxyethylene ether, polyisocynate monomer are put into In fluorine-containing oligomer resin solution, after 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 40-50 DEG C according to the proportion, then plus Enter phthalic anhydride and stearic acid, continues to stir 1h, form homogeneous solution；D, by the homogeneous solution of step c be added to that step b obtains it is mixed It closes in solution, keeps 40-50 DEG C of reaction 1-3h, as needed, remove excessive organic solvent, obtain mixed emulsifier.
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 (1)

1. a kind of heavy oil, alcohol radical-diesel oil compound emulsifying agent, which is characterized in that existed by component A and B component according to mass ratio 3:1 It is prepared in organic solvent；
Wherein component A is grouped as by the group of following mass fraction:
40 parts of methyl methacrylate, 5 parts of Hexafluorobutyl mathacrylate, 4,4- 2 parts of methyl diphenylene diisocyanates, fat 1 part of alcohol polyoxyethylene ether, 8 parts of methyl benzotriazazole；
B component is grouped as by the group of following mass fraction:
5 parts of sulfomethylated humic acid 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.
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