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 PDFInfo
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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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- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 37
- 239000000295 fuel oil Substances 0.000 title claims abstract description 36
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 alcohol group compound Chemical class 0.000 title claims description 5
- 239000000178 monomer Substances 0.000 claims abstract description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011737 fluorine Substances 0.000 claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 17
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 16
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 16
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 16
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 16
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 16
- 239000008117 stearic acid Substances 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 13
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- 239000003921 oil Substances 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 125000003158 alcohol group Chemical group 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical class C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 abstract 1
- 150000002191 fatty alcohols Chemical class 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910003472 fullerene Inorganic materials 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 235000019476 oil-water mixture Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010729 system oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/328—Oil emulsions containing water or any other hydrophilic phase
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1608—Well defined compounds, e.g. hexane, benzene
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
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- C10L1/00—Liquid carbonaceous fuels
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- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1826—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms poly-hydroxy
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- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
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- C10L1/1886—Carboxylic acids; metal salts thereof naphthenic acid
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- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
- C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
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- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—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
- 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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- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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- C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
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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
Technical Field
The invention relates to an emulsifier, in particular to a preparation method of a high-efficiency environment-friendly energy-saving emulsifier in heavy oil and alcohol-based diesel oil.
Background
Energy is the life line of national safety, with non-renewable petroleum resources being one of the most important energy supply safety issues. In order to effectively construct energy safety, all countries pay attention to petroleum consumption and storage, and various methods are adopted to actively research and reduce or replace the consumption of petroleum resources. With the rapid development of science and technology and economy, the actual automobile possession in China and the petroleum demand caused by the actual automobile possession are rapidly increasing. The automobile industry is one of the mainstay industries of national economy in China, and since 2010, the automobile industry accounts for more than 5.5 percent of the proportion of GDP, and the automobile output in China has leaped the third world and accounts for about 6 to 8 percent of the total automobile output in the world. According to statistics, the total consumption of gasoline and diesel oil for automobiles in 2018 in China is increased by nearly 1 time to about 3 hundred million tons compared with that in 2014, so that the problem of short supply of gasoline and diesel oil is more serious.
Heavy oil and alcohol-based diesel oil are important fuels, and the heavy oil is generally used as the fuel in oil refineries, chemical plants, steel plants, power plants and other places, but because the heavy oil is residual substances in petroleum deep processing, the heavy oil is directly combusted no matter what combustion equipment with high thermal effect is adopted, the combustion reaction is inevitably incomplete, black smoke, coking and carbon deposition are formed, a great deal of fuel waste is caused, and meanwhile, the problem of environmental pollution is also caused. Usually, excess air is injected to ensure sufficient combustion, and the discharge of this excess air carries away heat, resulting in heat losses.
At present, heavy oil is generally emulsified and then combusted to solve the problems, but an emulsifier which can effectively combust the emulsified heavy oil and can protect the environment and reduce emission is not available.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the high-efficiency environment-friendly energy-saving emulsifier in the heavy oil and the diesel oil, which has stable performance, can efficiently synthesize the heavy oil and has the effects of energy conservation and environmental protection, and the preparation method thereof. In addition, the compound emulsifier can also be used for emulsifying an alcohol-based diesel oil system, so that the alcohol-based diesel oil is always stably in an oil-in-alcohol type state and does not generate layering within the effective period.
The technical scheme of the invention is as follows: a preparation method of an environment-friendly composite emulsifier for heavy oil and alcohol-based diesel oil comprises the following steps:
a. adding an organic solvent into a reaction kettle, heating to 50-70 ℃, then uniformly mixing an acrylate monomer and a fluorine-containing monomer, slowly dripping the mixture into the organic solvent, controlling the feeding time, continuing to perform heat preservation reaction for 2-4 hours after the feeding is finished, stopping the reaction, and cooling to room temperature to obtain a fluorine-containing acrylic oligomer resin solution;
b. putting fatty alcohol-polyoxyethylene ether and a polyisocyanate monomer into a fluorine-containing acrylic oligomer resin solution, fully stirring for 1-2 h, adding methylbenzotriazole, stirring, and reacting for 1h to obtain a component A mixed solution;
c. uniformly stirring sodium sulfomethylhumate, span, cobalt naphthenate and ethylenediamine at 40-70 ℃ according to the proportion, then adding phthalic anhydride and stearic acid, and continuously stirring for 1h to form a B component uniform solution;
d. c, adding the uniform solution of the component B in the step c into the mixed solution of the component A obtained in the step B, keeping the temperature at 40-60 ℃ for reaction for 1-3h, and removing the redundant organic solvent to obtain a compound emulsifier, wherein the reaction condition is preferably 50 ℃ for 2 h;
wherein,
the component A comprises the following components in parts by mass:
about 30 to 60 parts of acrylic monomer,
1 to 10 parts of a fluorine-containing component,
1-3 parts of polyisocyanate monomer,
0.1 to 2 portions of fatty alcohol-polyoxyethylene ether,
5-10 parts of methylbenzotriazole;
the component B comprises the following components in parts by mass:
0.5 to 10 portions of sodium sulfomethyl humate,
805-20 parts of span-pan (805-20),
1 to 30 parts of cobalt naphthenate,
5-10 parts of ethylene diamine,
15-25 parts of phthalic anhydride, namely,
4-8 parts of stearic acid.
Preferably, the mass ratio of the component A to the component B of the composite emulsifier is 3-5: 1, wherein the component and the weight portion ratio of the group A agent are as follows: 40-50 parts of acrylic monomer, 5-10 parts of fluorine-containing component, 1-2 parts of polyisocyanate monomer, 0.1-1 part of fatty alcohol-polyoxyethylene ether and 5-8 parts of methylbenzotriazole;
the component and the weight portion ratio of the B group agent are as follows: 0.5-3 parts of sodium sulfomethylhumate, 808-10 parts of span, 10-20 parts of cobalt naphthenate, 8-10 parts of ethylenediamine, 15-20 parts of phthalic anhydride and 4-6 parts of stearic acid.
Wherein the acrylate monomer is styrene, methyl methacrylate or the mass ratio of styrene to methyl methacrylate is 1: (2-20); the fluorine-containing component is hexafluorobutyl methacrylate.
The polyisocyanate monomer is one or a combination of toluene diisocyanate and polymers thereof, and 4, 4-diphenylmethane diisocyanate.
The organic solvent is propylene glycol or ethylene glycol.
In the invention, the acrylic ester monomer and the fluorine-containing monomer in the component A are polymerized to generate the fluorine-containing acrylic acid oligomer, so that the polymer shows certain physicochemical properties of the fluorine-containing compound to a certain extent. Therefore, the oil-repellent emulsion has excellent hydrophobicity and certain oil repellency, can stably emulsify an alcohol-oil interface or a heavy oil and diesel oil system, increases the intersolubility of alcohol and diesel oil, and has wide application system and stable effect; because of adopting naphthenic acid compound in the component B and proper feeding proportion, the emulsifier has the function of catalytic combustion supporting, thereby greatly reducing the emission of heavy oil combustion and SO after the emulsifier emulsifies the heavy oil2The emission of the methyl benzotriazole can be reduced by more than 90 percent, and the methyl benzotriazole also has the function of preventing equipment of a gasoline engine or a diesel engine from being corroded; the emulsifier of the invention has strong emulsifying capacity due to the emulsifier of the component B, the proportion of the heavy oil and water can reach 1:1 when the heavy oil is emulsified, the emulsified heavy oil is of a water-in-oil molecular structure, the emulsified heavy oil can not be subjected to oil-water separation after being stored for more than one year, and the performance is very stable.
The emulsifier of the invention can be applied to emulsifying heavy oil, emulsified diesel oil or a system containing alcohol group-diesel oil, and a composite system, and has good applicability, and the formed composite emulsifier has the advantages of good stability, easy recovery and repeated utilization.
The emulsifier of the invention can effectively emulsify heavy oil, diesel oil or fuel oil, SO that the emulsified heavy oil, diesel oil or fuel oil can be more effectively combusted, the heavy oil can save 35 to 45 percent of oil and reduce SO after being emulsified by the emulsifier of the invention2Discharge 90% of the total weight of the oil-water mixture is higher than that of the total weight of the oil-water mixture, oil-water separation cannot occur after the oil-water mixture is stored for more than one year, and the performance is very stable. According to the invention, a part of traditional heavy oil emulsifier components and the novel resin emulsifier form a composite emulsification system, so that a multi-oil system can be emulsified, the use amount of different oil products is small, the preparation method is simple, the cost is low, the oil product can be recovered, the stability of the emulsified oil is good, no layering is generated, and a good emulsification effect can be realized while the multi-system oil product raw materials are considered.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1
The preparation method of the high-efficiency composite emulsifier of heavy oil and alcohol-based diesel oil comprises the following steps of mixing the component A and the component B according to the mass ratio of 3: 1 in an organic solvent, wherein the component A comprises 30-60 parts of styrene and methyl methacrylate, 1-10 parts of hexafluorobutyl methacrylate, 1-3 parts of 4, 4-diphenylmethane diisocyanate, 0.1-2 parts of fatty alcohol-polyoxyethylene ether and 5-10 parts of methylbenzotriazole; the component B comprises 0.5-10 parts of sodium sulfomethylhumate, 805-20 parts of span, 1-30 parts of cobalt naphthenate, 5-10 parts of ethylenediamine, 15-25 parts of phthalic anhydride and 4-8 parts of stearic acid. The preparation method comprises the following steps: a. adding an organic solvent into a reaction kettle, heating to 50-70 ℃, then uniformly mixing an acrylate monomer and a fluorine-containing monomer, slowly dripping the mixture into the organic solvent, controlling the feeding time, continuing to perform heat preservation reaction for 2-4 hours after the feeding is finished, stopping the reaction, and cooling to room temperature to obtain a fluorine-containing acrylic oligomer resin solution; b. putting fatty alcohol-polyoxyethylene ether and a polyisocyanate monomer into a fluorine-containing acrylic oligomer resin solution, fully stirring for 1-2 h, adding methylbenzotriazole, stirring, and reacting for 1h to obtain a mixed solution; c. uniformly stirring sodium methyl humate, span, cobalt naphthenate and ethylenediamine at 40-70 ℃ according to the proportion, then adding phthalic anhydride and stearic acid, and continuously stirring for 1h to form a uniform solution; d. and c, adding the uniform solution obtained in the step c into the mixed solution obtained in the step b, keeping the temperature of 40-60 ℃ for reaction for 1-3h, and removing redundant organic solvent according to needs to obtain the compound emulsifier.
Example 2
The preparation method of the high-efficiency composite emulsifier of heavy oil and alcohol-based diesel oil comprises the following steps of mixing the component A and the component B according to the mass ratio of 3: 1 in an organic solvent, wherein the component A comprises 30 parts of styrene, 1 part of hexafluorobutyl methacrylate, 1 part of 4, 4-diphenylmethane diisocyanate, 0.1 part of fatty alcohol-polyoxyethylene ether and 5 parts of methylbenzotriazole; the component B comprises 0.5 part of sodium sulfomethylhumate, 805 parts of span, 1 part of cobalt naphthenate, 5 parts of ethylenediamine, 15 parts of phthalic anhydride and 4 parts of stearic acid. The preparation method comprises the following steps: a. adding an organic solvent into a reaction kettle, heating to 50 ℃, then uniformly mixing an acrylate monomer and a fluorine-containing monomer, slowly dripping the mixture into the organic solvent, controlling the feeding time, continuing to perform heat preservation reaction for 2 hours after the feeding is finished, stopping the reaction, and cooling to room temperature to obtain a fluorine-containing acrylic oligomer resin solution; b. putting fatty alcohol-polyoxyethylene ether and a polyisocyanate monomer into a fluorine-containing acrylic oligomer resin solution, fully stirring for 1h, adding methylbenzotriazole, stirring, and reacting for 1h to obtain a mixed solution; c. uniformly stirring sodium methyl humate, span, cobalt naphthenate and ethylenediamine at 40 ℃ according to the proportion, then adding phthalic anhydride and stearic acid, and continuously stirring for 1h to form a uniform solution; d. and c, adding the uniform solution obtained in the step c into the mixed solution obtained in the step b, keeping the temperature of 40 ℃ for reaction for 1 hour, and removing the redundant organic solvent according to the requirement to obtain the compound emulsifier.
Example 3
The preparation method of the high-efficiency composite emulsifier of heavy oil and alcohol-based diesel oil comprises the following steps of mixing the component A and the component B according to the mass ratio of 3: 1 in an organic solvent, wherein the component A comprises 40 parts of methyl methacrylate, 5 parts of hexafluorobutyl methacrylate, 2 parts of 4, 4-diphenylmethane diisocyanate, 1 part of fatty alcohol-polyoxyethylene ether and 8 parts of methylbenzotriazole; the component B comprises 5 parts of sodium sulfomethylhumate, 8010 parts of span, 10 parts of cobalt naphthenate, 6 parts of ethylenediamine, 20 parts of phthalic anhydride and 6 parts of stearic acid. The preparation method comprises the following steps: a. adding an organic solvent into a reaction kettle, heating to 60 ℃, then uniformly mixing an acrylate monomer and a fluorine-containing monomer, slowly dripping the mixture into the organic solvent, controlling the feeding time, continuing to perform heat preservation reaction for 3 hours after the feeding is finished, stopping the reaction, and cooling to room temperature to obtain a fluorine-containing acrylic oligomer resin solution; b. putting fatty alcohol-polyoxyethylene ether and a polyisocyanate monomer into a fluorine-containing acrylic oligomer resin solution, fully stirring for 1-2 h, adding methylbenzotriazole, stirring, and reacting for 1h to obtain a mixed solution; c. uniformly stirring sodium methyl humate, span, cobalt naphthenate and ethylenediamine at 50 ℃ according to the proportion, then adding phthalic anhydride and stearic acid, and continuously stirring for 1h to form a uniform solution; d. and c, adding the uniform solution obtained in the step c into the mixed solution obtained in the step b, keeping the temperature of 50 ℃ for reaction for 2 hours, and removing the redundant organic solvent according to the requirement to obtain the compound emulsifier.
Example 4
The preparation method of the high-efficiency composite emulsifier of heavy oil and alcohol-based diesel oil comprises the following steps of mixing the component A and the component B according to the mass ratio of 3: 1 in an organic solvent, wherein the component A comprises 60 parts of styrene and methyl methacrylate, 10 parts of hexafluorobutyl methacrylate, 3 parts of 4, 4-diphenylmethane diisocyanate, 2 parts of fatty alcohol-polyoxyethylene ether and 10 parts of methylbenzotriazole; the component B comprises 10 parts of sodium sulfomethylhumate, 8020 parts of span, 30 parts of cobalt naphthenate, 10 parts of ethylenediamine, 25 parts of phthalic anhydride and 8 parts of stearic acid. The preparation method comprises the following steps: a. adding an organic solvent into a reaction kettle, heating to 70 ℃, then uniformly mixing an acrylate monomer and a fluorine-containing monomer, slowly dripping the mixture into the organic solvent, controlling the feeding time, continuing to perform heat preservation reaction for 4 hours after the feeding is finished, stopping the reaction, and cooling to room temperature to obtain a fluorine-containing acrylic oligomer resin solution; b. putting fatty alcohol-polyoxyethylene ether and a polyisocyanate monomer into a fluorine-containing acrylic oligomer resin solution, fully stirring for 2 hours, adding methylbenzotriazole, stirring, and reacting for 1 hour to obtain a mixed solution; c. uniformly stirring sodium methyl humate, span, cobalt naphthenate and ethylenediamine at 70 ℃ according to the proportion, then adding phthalic anhydride and stearic acid, and continuously stirring for 1h to form a uniform solution; d. and c, adding the uniform solution obtained in the step c into the mixed solution obtained in the step b, keeping the temperature at 60 ℃ for reaction for 3 hours, and removing the redundant organic solvent according to the requirement to obtain the compound emulsifier.
Example 5
The preparation method of the high-efficiency composite emulsifier of heavy oil and alcohol-based diesel oil comprises the following steps of mixing the component A and the component B according to the mass ratio of 2: 1 in an organic solvent, wherein the component A comprises 50 parts of styrene and methyl methacrylate, 8 parts of hexafluorobutyl methacrylate, 2 parts of 4, 4-diphenylmethane diisocyanate, 1 part of fatty alcohol-polyoxyethylene ether and 6 parts of methylbenzotriazole; the component B comprises 8 parts of sodium sulfomethylhumate, 8010 parts of span, 20 parts of cobalt naphthenate, 7 parts of ethylenediamine, 16 parts of phthalic anhydride and 6 parts of stearic acid. The preparation method comprises the following steps: a. adding an organic solvent into a reaction kettle, heating to 50-60 ℃, then uniformly mixing an acrylate monomer and a fluorine-containing monomer, slowly dripping the mixture into the organic solvent, controlling the feeding time, continuing to perform heat preservation reaction for 2-3 hours after the feeding is finished, stopping the reaction, and cooling to room temperature to obtain a fluorine-containing acrylic oligomer resin solution; b. putting fatty alcohol-polyoxyethylene ether and a polyisocyanate monomer into a fluorine-containing acrylic oligomer resin solution, fully stirring for 2 hours, adding methylbenzotriazole, stirring, and reacting for 1 hour to obtain a mixed solution; c. uniformly stirring sodium methyl humate, span, cobalt naphthenate and ethylenediamine at 40-50 ℃ according to the proportion, then adding phthalic anhydride and stearic acid, and continuously stirring for 1h to form a uniform solution; d. and c, adding the uniform solution obtained in the step c into the mixed solution obtained in the step b, keeping the temperature of 40-50 ℃ for reaction for 1-3h, and removing redundant organic solvent according to needs to obtain the compound emulsifier.
Mixing oil products: compound emulsifier: solvent: graphene or fullerene is obtained according to the following formula of 100-: 10-20: 5-10: the emulsified oil is obtained after mixing in a weight ratio of 0.1-1, and experiments show that the emulsified oil can be stable and does not delaminate after standing; for the emulsification of heavy oil, still do not appear oil-water separation more than a year, and can save oil 30%, reduce the discharge of sulfur-containing material, for alcohol group diesel oil, owing to have partial resin effect, alcohol group diesel oil can fine mutual solubility, less carbon discharges, and component A and component B can play the synergistic effect, can greatly reduced diesel oil or the consumption of heavy oil, and can reduce petrochemical industry cost, be suitable for a plurality of systems simultaneously, have good emulsification effect to the system that has diesel oil and/or alcohol group diesel oil simultaneously.
Application example 1
Heating 100kg heavy oil to 60 deg.C, stirring, adding 10 kg emulsifier, 5g solvent, and 0.1g fullerene, stirring at high speed for 5-15min, adding appropriate amount of 60 deg.C water, and standing for 24 hr.
Application example 2
Heating 120kg of alcohol-based diesel oil to 60 ℃, uniformly stirring, adding 10 kg of emulsifier, 10g of solvent and 0.5g of fullerene, stirring at a high speed for 5-15min, adding 70 ℃ water according to needs, uniformly mixing and stirring to obtain the high-efficiency environment-friendly emulsified oil, and standing for 24 hours for use.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be made by those skilled in the art without inventive work within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (2)
1. A preparation method of a composite emulsifier for heavy oil and alcohol-based diesel oil is characterized by comprising the following steps:
a. adding an organic solvent into a reaction kettle, heating to 50-70 ℃, then uniformly mixing styrene and hexafluorobutyl methacrylate, slowly dripping into the organic solvent, controlling the feeding time, continuing to perform heat preservation reaction for 2-4h after the feeding is finished, stopping the reaction, and cooling to room temperature to obtain a fluorine-containing acrylic oligomer resin solution;
b. putting fatty alcohol-polyoxyethylene ether and a polyisocyanate monomer into a fluorine-containing acrylic oligomer resin solution, fully stirring for 1-2 h, adding methylbenzotriazole, stirring, and reacting for 1h to obtain a component A mixed solution;
c. uniformly stirring sodium sulfomethylhumate, span, cobalt naphthenate and ethylenediamine at 40-70 ℃ according to the proportion, then adding phthalic anhydride and stearic acid, and continuously stirring for 1h to form a B component uniform solution;
d. c, adding the component B uniform solution obtained in the step c into the component A mixed solution obtained in the step B, keeping the temperature at 50 ℃ for reacting for 2 hours, and removing the redundant organic solvent to obtain a composite emulsifier;
wherein,
the component A comprises the following components in parts by mass:
30 parts of styrene and 30 parts of styrene,
1 part of hexafluorobutyl methacrylate, namely,
1 part of polyisocyanate monomer(s),
0.1 part of fatty alcohol-polyoxyethylene ether,
5 parts of methylbenzotriazole;
the component B comprises the following components in parts by mass:
0.5 part of sodium sulfomethyl humate,
805 parts of span-pan (a), 805 parts of,
1 part of cobalt naphthenate, and the balance of cobalt naphthenate,
5 parts of ethylene diamine, namely 5 parts of ethylene diamine,
15 parts of phthalic anhydride, namely benzene anhydride,
4 parts of stearic acid;
the polyisocyanate monomer is one or a combination of toluene diisocyanate and polymers thereof and 4, 4-diphenylmethane diisocyanate, and the organic solvent is propylene glycol or ethylene glycol.
2. The method according to claim 1, wherein the mass ratio of the component a to the component B is 3 to 5: 1.
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| 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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| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105802682B (en) | 2018-07-06 |
| CN105802682A (en) | 2016-07-27 |
| CN108277052A (en) | 2018-07-13 |
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