CN114426655A - Novel lignin-based oil-in-water emulsion demulsifier, preparation method thereof and treatment method of crude oil-in-water emulsion - Google Patents
Novel lignin-based oil-in-water emulsion demulsifier, preparation method thereof and treatment method of crude oil-in-water emulsion Download PDFInfo
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- CN114426655A CN114426655A CN202011081739.1A CN202011081739A CN114426655A CN 114426655 A CN114426655 A CN 114426655A CN 202011081739 A CN202011081739 A CN 202011081739A CN 114426655 A CN114426655 A CN 114426655A
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- lignin
- initiator
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- demulsifier
- hydrophobic monomer
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- 229920005610 lignin Polymers 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007764 o/w emulsion Substances 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims abstract description 73
- 229920001577 copolymer Polymers 0.000 claims abstract description 47
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 41
- 239000003921 oil Substances 0.000 claims abstract description 32
- 230000007071 enzymatic hydrolysis Effects 0.000 claims abstract description 20
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims abstract description 20
- 239000010779 crude oil Substances 0.000 claims abstract description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- 239000007762 w/o emulsion Substances 0.000 claims abstract description 12
- -1 2-ethylhexyl Chemical group 0.000 claims abstract description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 239000003999 initiator Substances 0.000 claims description 51
- 239000000839 emulsion Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229920006243 acrylic copolymer Polymers 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 5
- 230000033116 oxidation-reduction process Effects 0.000 claims description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 238000010526 radical polymerization reaction Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- ZAVUGVPMYAZPGN-UHFFFAOYSA-N benzoyl benzenecarboperoxoate;n,n-dimethylaniline Chemical group CN(C)C1=CC=CC=C1.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 ZAVUGVPMYAZPGN-UHFFFAOYSA-N 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000002569 water oil cream Substances 0.000 claims 5
- 239000000243 solution Substances 0.000 description 14
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- GDNCXORZAMVMIW-UHFFFAOYSA-N dodecane Chemical compound [CH2]CCCCCCCCCCC GDNCXORZAMVMIW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000010946 mechanistic model Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of demulsifiers, and discloses a novel lignin-based oil water-in-oil emulsion demulsifier, a preparation method thereof and a treatment method of a crude oil water-in-oil emulsion. The demulsifier comprises an acrylate copolymer containing a lignin structure, wherein the acrylate copolymer is formed by polymerizing enzymatic hydrolysis lignin, a hydrophobic monomer and a hydrophilic monomer; the structural formula of the acrylate copolymer comprises a structural unit shown as a formula M, N, X, Y, wherein in the formula N, R1Is methyl, 2-ethylhexyl or dodecyl, R2Is H or AA group; in the formula X, R3Is H or methyl.
Description
Technical Field
The invention belongs to the technical field of demulsifiers, and particularly relates to a novel lignin-based oil water-in-oil emulsion demulsifier, a preparation method thereof and a treatment method of a crude oil water-in-oil emulsion.
Background
The addition of chemicals to the crude oil emulsion to break the emulsion is known as chemical demulsification and can be used either alone or in combination with other methods. Demulsifiers have been studied and used for over 80 years. At present, most of crude oil demulsifiers used in oil fields in China are ethylene oxide and propylene oxide block polyether demulsifiers. The main types of the demulsifier can be summarized as block polyether using alcohols as an initiator, block polyether using amines as an initiator, alkyl phenolic resin block polyether, phenolic amine aldehyde resin block polyether, silicon-containing demulsifier, ultrahigh relative molecular weight demulsifier, polyphosphate ester and modified products of block polyether. The emulsion breaking effect is poor due to large consumption when the emulsion breaking is carried out at low temperature. From the research and development trends of domestic and foreign crude oil demulsifiers, the non-polyether demulsifier is a demulsifier which is developed rapidly in recent ten years, and has the characteristics of clear water color, small dosage and lasting medicament dehydration performance on crude oil emulsion, particularly thick oil emulsion.
Nowadays, social fossil energy is increasingly exhausted, and as the second most abundant renewable resource in nature, lignin is regarded as a potential substitute of the fossil energy. From the mechanistic model of lignin, it can be found that lignin has a large number of hydroxyl groups on its molecule. Based on the characteristics, lignin molecules can react with other functional molecules, and a precondition basis is provided for preparing high-value lignin-based materials.
Disclosure of Invention
The invention aims to provide a novel lignin-based oil water-in-emulsion demulsifier, a preparation method thereof and a treatment method of a crude oil water-in-oil emulsion.
The invention provides a novel lignin-based oil water-in-emulsion demulsifier, which comprises an acrylate copolymer containing a lignin structure, wherein the acrylate copolymer is formed by polymerizing enzymatic hydrolysis lignin, a hydrophobic monomer and a hydrophilic monomer;
the structural formula of the acrylate copolymer comprises a structural unit shown as a formula M, N, X, Y:
in the formula N, R1Is methyl, 2-ethylhexyl or dodecyl, R2Is H or methyl;
in the formula X, R3Is H or methyl.
The second aspect of the present invention provides a preparation method of the above novel lignin-based oil water-in-emulsion demulsifier, comprising: in the presence of an initiator and a solvent, carrying out solution free radical polymerization reaction on the enzymatic hydrolysis lignin, the hydrophobic monomer and the hydrophilic monomer to prepare the acrylate copolymer.
A third aspect of the present invention provides a method of treating a crude oil-in-water emulsion, the method comprising: the crude oil water-in-oil emulsion is contacted with the novel lignin-based oil water-in-emulsion demulsifier or the novel lignin-based oil water-in-emulsion demulsifier prepared by the preparation method.
The acrylic ester copolymer containing the lignin structure is prepared by adopting enzymolysis lignin, a hydrophobic monomer and a hydrophilic monomer through a solution free radical polymerization method and using a composite initiator system consisting of calcium chloride/hydrogen peroxide, an oxidation-reduction initiator or an azo initiator, a reproducible and biodegradable lignin structure unit is introduced into the molecular structure of the demulsifier, and the introduction of a large number of benzene ring structures can enhance the affinity of demulsifier molecules with crude oil, particularly thickened oil, enhance the surface activity of the demulsifier and improve the demulsification and dehydration performances of the demulsifier on crude oil-in-water emulsion.
The invention can select the acrylate copolymers containing the lignin structure with different proportions to prepare the corresponding demulsifier according to different crude oil water-in-oil emulsions, and can also improve the broad-spectrum performance of the reverse demulsifier by compounding with other demulsifiers.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a novel lignin-based oil water-in-emulsion demulsifier comprising an acrylate copolymer comprising a lignin structure, the acrylate copolymer being polymerized from enzymatically hydrolyzed lignin, a hydrophobic monomer, and a hydrophilic monomer;
the structural formula of the acrylate copolymer comprises a structural unit shown as a formula M, N, X, Y:
in the formula N, R1Is methyl, 2-ethylhexyl or dodecyl, R2Is H or methyl;
in the formula X, R3Is H or methyl.
According to the invention, M accounts for more than or equal to 0 in weight percentage of the acrylate copolymer, N accounts for more than or equal to 0 in weight percentage of the acrylate copolymer, and M + N is more than or equal to 20% and less than or equal to 95.5%, preferably, M + N is more than or equal to 70% and less than or equal to 90%, and M is more than or equal to 0, N is more than or equal to 0;
x accounts for 0 to 15 percent of the weight of the acrylic copolymer, preferably 6 to 12 percent of the weight of the acrylic copolymer;
y accounts for 0.5-10% of the weight percentage of the acrylic copolymer, preferably 2-10%.
The appearance of the acrylic ester copolymer containing the lignin structure is light brown to dark brown viscous liquid.
According to a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned novel lignin-based oil water-in-emulsion demulsifier, the method comprising: in the presence of an initiator and a solvent, carrying out solution free radical polymerization reaction on the enzymatic hydrolysis lignin, the hydrophobic monomer and the hydrophilic monomer to prepare the acrylate copolymer.
In the invention, the enzymatic hydrolysis lignin comprises the following components: the content of lignin is more than or equal to 90 wt%, the content of residual sugar is less than or equal to 5 wt%, the content of ash is less than or equal to 5 wt%, and the content of phenolic hydroxyl is more than or equal to 10 wt%.
The hydrophobic monomer can be one or more selected from butyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate and dodecyl acrylate.
The hydrophilic monomer may be acrylic acid or methacrylic acid.
Preferably, the initiator comprises initiator A and initiator B;
the initiator A is calcium chloride and hydrogen peroxide;
the initiator B is an azo initiator, a peroxide initiator or an oxidation-reduction initiator;
further preferably, the azo initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate.
Further preferably, the peroxide initiator is benzoyl peroxide.
Further preferably, the oxidation-reduction initiator is benzoyl peroxide-dimethylaniline.
According to the invention, the dosage of the enzymatic hydrolysis lignin is 0.5-10 parts by weight; the dosage of the hydrophobic monomer is 20-95.5 parts; the using amount of the hydrophilic monomer is 0-10 parts;
the dosage of the initiator A is 0.2-5 parts, and the weight ratio of the calcium chloride to the hydrogen peroxide is 1: 0.5-2; the using amount of the initiator B is 0.2-1.5 parts.
Preferably, the solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and dioxane. The solvent may be used in an amount such that the solid content of the reaction system is from 10 to 50% by weight.
According to a preferred embodiment of the invention, the preparation method comprises the following steps:
1) dissolving part of hydrophobic monomer in part of solvent to prepare hydrophobic monomer solution;
2) dissolving enzymolysis lignin and an initiator A in a part of solvent to prepare an enzymolysis lignin solution;
3) under the protection of nitrogen, heating the hydrophobic monomer solution and heating and activating the enzymatic hydrolysis lignin solution respectively, then mixing the hydrophobic monomer solution and the enzymatic hydrolysis lignin solution, and adding part of the initiator B for reaction;
4) uniformly mixing part of hydrophobic monomer, part of hydrophilic monomer, part of initiator B and part of solvent, and adding the mixture into the reaction system obtained in the step 3) for reaction;
5) uniformly mixing the rest reaction monomer, the initiator B and the solvent, and adding the mixture into the reaction system obtained in the step 4) for reaction, wherein the reaction monomer comprises a hydrophilic monomer and an optional hydrophobic monomer;
6) cooling, purifying and drying the mixture obtained by the reaction in the step 5) to obtain the acrylic ester copolymer containing the lignin structure.
Preferably, the amount of the hydrophobic monomer in the step 1) is 60-95% of the total weight of the hydrophobic monomer, and the amount of the hydrophobic monomer in the step 4) is 5-20% of the total weight of the hydrophobic monomer;
the using amount of the hydrophilic monomer in the step 4) is 20-70% of the total weight of the hydrophilic monomer;
the dosage of the solvent in the step 1) is 40-70% of the total weight of the solvent, the dosage of the solvent in the step 2) is 10-30% of the total weight of the solvent, and the dosage of the solvent in the step 4) is 5-15% of the total weight of the solvent;
the dosage of the initiator B in the step 3) is 40-70% of the total weight of the initiator B, and the dosage of the initiator B in the step 4) is 15-40% of the total weight of the initiator B.
According to the invention, in the step 3), the temperature of the hydrophobic monomer solution is 60-80 ℃, the temperature of the enzymatic hydrolysis lignin solution is 45-55 ℃ and the time is 10-40 min.
Preferably, the reaction temperature in each step is 60-90 ℃, the reaction time in step 3) is 0.5-2h, the reaction time in step 4) is 1-3h, and the reaction time in step 5) is 4-10 h.
According to the invention, the purification in step 6) comprises: the mixture was subjected to rotary evaporator to remove most of the solvent and unreacted monomers, precipitated with deionized water, and repeatedly washed with absolute ethanol or acetone.
The acrylic ester copolymer can be directly discharged as a solution product to obtain the acrylic ester copolymer aqueous solution.
According to a third aspect of the present invention, the present invention is a method for treating a water-in-oil emulsion of crude oil, the method comprising: the crude oil water-in-oil emulsion is contacted with the novel lignin-based oil water-in-emulsion demulsifier or the novel lignin-based oil water-in-emulsion demulsifier prepared by the preparation method.
The novel lignin-based oil water-in-emulsion demulsifier can be an aqueous solution containing the acrylate copolymer, and can also be an aqueous solution product prepared by the preparation method or an aqueous solution of a prepared solid product. In general, the acrylic copolymer of the present invention is used in the form of a solution when used for treating a water-in-oil emulsion of crude oil, and the concentration of the solution may be 0.5 to 30% by weight, and the specific concentration is set as required.
In the present invention, the amount of the novel lignin-based oil water-in-emulsion demulsifier may be the same as or different from the prior art. Preferably, the amount of the acrylate copolymer in the novel lignin-based water-in-oil emulsion demulsifier is 30-200mg, preferably 50-150mg, relative to 1L of the crude oil-in-water emulsion.
The acrylic ester copolymer can be used as a demulsifier independently, and can also be used as one of the components of the demulsifier to be matched with other conventional demulsifiers for use, so that the broad-spectrum performance of the demulsifier is improved. The prior other demulsifiers can be various polyoxyethylene polyoxypropylene ethers with different initiators, or non-polyether acrylate demulsifiers, special surfactants containing silicon and phosphorus, and the like.
In the invention, the contact temperature can be 50-90 ℃, and different temperatures are selected according to different properties of the crude oil emulsion; the contact time is 0.5 to 8 hours, preferably 1 to 6 hours.
The crude oil water-in-oil emulsion of the present invention may be an oil well production fluid in the oil field, and may contain water in an amount of 20% to 70% by volume.
The remaining parameters not defined in the present invention can be routinely selected according to the state of the art.
The present invention will be further described with reference to the following examples. But is not limited by these examples.
Examples 1-3 illustrate the novel lignin-based oil water-in-emulsion demulsifiers and methods for their preparation of the present invention.
Example 1
A preparation method of a novel lignin-based oil water-in-emulsion demulsifier comprises the following steps:
step 1, 15 grams of hydrophobic monomers (10 grams of butyl acrylate and 5 grams of methyl methacrylate) and 25 grams of N, N-dimethylformamide were weighed into reactor 1 and stirred well until completely dissolved.
Step 2, weighing 1.6 g of enzymatic hydrolysis lignin, 0.2 g of calcium chloride, 0.2 g of hydrogen peroxide and 10 g of N, N-dimethylformamide, adding into the reactor 2, and fully stirring until the materials are completely dissolved.
And 3, replacing air in the reactors 1 and 2 with nitrogen, continuously introducing the nitrogen, heating the reactor 1 to 80 ℃, and heating the reactor 2 to 50 ℃. After 20 minutes, the mixture in reactor 2 was added to reactor 1 and mixed well. The reaction was started by continuing the nitrogen flow into the reactor 1 and by adding 0.14 g of benzoyl peroxide. The reaction was carried out at 80 ℃ for 1 hour.
Step 4, weighing 2 g of hydrophobic monomer (butyl acrylate), 0.4 g of hydrophilic monomer (acrylic acid), 0.09 g of benzoyl peroxide and 5 g of N, N-dimethylformamide, uniformly mixing, adding into the reactor 1, and continuously reacting for 2 hours at 80 ℃.
Step 5, weighing 3 g of hydrophobic monomer (2 g of butyl acrylate and 1 g of methyl methacrylate), 1 g of hydrophilic monomer (acrylic acid), 0.09 g of benzoyl peroxide and 14 g of N, N-dimethylformamide, uniformly mixing, adding into the reactor 1, and continuously reacting for 4 hours at 80 ℃.
And 6, cooling, removing most of the solvent and unreacted monomers from the reaction mixture by using a rotary evaporator, precipitating by using deionized water, repeatedly washing by using absolute ethyl alcohol, and drying to obtain brown viscous liquid.
According to the added raw materials, the structural formula of the prepared acrylate copolymer comprises a structural unit shown as a formula M, N, X, Y, wherein in the formula N, R is1Is methyl, R2Is methyl, in the formula X, R3Is H. The content of each structural unit in the acrylate copolymer is obtained by calculation according to the adding amount of the raw materials, which is also a conventional representation method in the field, wherein M accounts for 60.9 wt% of the prepared acrylate copolymer, N accounts for 26.1 wt% of the acrylate copolymer, X accounts for 6.1 wt% of the acrylate copolymer, and Y accounts for 6.9 wt% of the acrylate copolymer.
Example 2
A preparation method of a novel lignin-based oil water-in-emulsion demulsifier comprises the following steps:
step 1, a mixture of 30 g of hydrophobic monomers (15 g of butyl acrylate and 15 g of 2-ethylhexyl acrylate) and 40 g of N, N-dimethylacetamide was weighed into a reactor 1 and stirred well until completely dissolved.
Step 2, weighing 1 g of enzymatic hydrolysis lignin, 0.1 g of calcium chloride, 0.1 g of hydrogen peroxide and 10 g of N, N-dimethylacetamide, adding into the reactor 2, and fully stirring until the enzymatic hydrolysis lignin, the calcium chloride, the hydrogen peroxide and the N, N-dimethylacetamide are completely dissolved.
And 3, replacing air in the reactors 1 and 2 with nitrogen, continuously introducing the nitrogen, heating the reactor 1 to 68 ℃, and heating the reactor 2 to 50 ℃. After 15 minutes, the mixture in reactor 2 was added to reactor 1 and mixed well. The reaction was started by continuing the nitrogen gas introduction into the reactor 1 and adding 0.22 g of azobisisobutyronitrile. The reaction was carried out at 68 ℃ for 1.5 hours.
Step 4, weighing 2.5 g of hydrophilic monomer (methacrylic acid), 5 g of hydrophobic monomer (2-ethylhexyl acrylate), 0.15 g of azobisisobutyronitrile and 10 g of N, N-dimethylacetamide, uniformly mixing, adding into the reactor 1, and continuously reacting for 2 hours at 68 ℃.
Step 5, weighing 2.5 g of hydrophilic monomer (methacrylic acid), 0.05 g of azobisisobutyronitrile and 2 g of N, N-dimethylacetamide, uniformly mixing, adding into the reactor 1, and continuously reacting for 8 hours at 68 ℃.
And 6, cooling, removing most of the solvent and unreacted monomers from the reaction mixture by using a rotary evaporator, precipitating by using deionized water, repeatedly washing by using absolute ethyl alcohol, and putting the mixture into a vacuum oven to be dried in vacuum at 40 ℃ to constant weight to obtain light brown yellow viscous liquid.
According to the added raw materials, the structural formula of the prepared acrylate copolymer comprises a structural unit shown as a formula M, N, X, Y, wherein in the formula N, R is1Is ethylhexyl, R2Is H, in the formula X, R3Is methyl. The content of each structural unit in the acrylate copolymer is obtained by calculation according to the adding amount of the raw materials, which is also a conventional representation method in the field, wherein M accounts for 36.6 wt% of the prepared acrylate copolymer, N accounts for 48.8 wt% of the acrylate copolymer, X accounts for 12.2 wt% of the acrylate copolymer, and Y accounts for 2.4 wt% of the acrylate copolymer.
Example 3
A preparation method of a novel lignin-based oil water-in-emulsion demulsifier comprises the following steps:
step 1, 10 grams of hydrophobic monomer (8 grams of butyl acrylate and 2 grams of dodecyl acrylate) and 40 grams of dioxane were weighed into a reactor and stirred well until completely dissolved.
Step 2, weighing 2 g of enzymatic hydrolysis lignin, 0.4 g of calcium chloride, 0.6 g of hydrogen peroxide and 20 g of dioxane, adding into the reactor 2, and fully stirring until the materials are completely dissolved.
And 3, replacing air in the reactors 1 and 2 with nitrogen, continuously introducing the nitrogen, heating the reactor 1 to 75 ℃, and heating the reactor 2 to 50 ℃. After 30 minutes, the mixture in reactor 2 was added to reactor 1 and mixed well. The reaction was started by continuing the nitrogen flow into the reactor 1 and by adding 0.2 g of benzoyl peroxide. The reaction was carried out at 75 ℃ for 2 hours.
Step 4, weighing 3 g of hydrophobic monomer (2 g of butyl acrylate and 1 g of lauryl acrylate), 1 g of hydrophilic monomer (acrylic acid), 0.06 g of benzoyl peroxide and 10 g of dioxane, uniformly mixing, adding into the reactor 1, and continuously reacting for 2 hours at 75 ℃.
Step 5, weighing 3 g of hydrophobic monomer (2 g of butyl acrylate and 1 g of dodecyl acrylate), 1 g of hydrophilic monomer (acrylic acid), 0.04 g of benzoyl peroxide and 10 g of dioxane, uniformly mixing, adding into the reactor 1, and continuously reacting for 5 hours at 75 ℃.
And 6, cooling, removing most of the solvent and unreacted monomers from the reaction mixture by using a rotary evaporator, precipitating by using deionized water, repeatedly washing by using absolute ethyl alcohol, and drying to obtain brown viscous liquid.
According to the added raw materials, the structural formula of the prepared acrylate copolymer comprises a structural unit shown as a formula M, N, X, Y, wherein in the formula N, R is1Is dodecyl radical, R2Is H, in the formula X, R3Is H. Calculating the content of each structural unit in the acrylate copolymer according to the adding amount of the raw materials, which is also a conventional expression method in the field, wherein M accounts for 60 wt%, N accounts for 20 wt%, and X accounts for 20 wt% of the prepared acrylate copolymerThe weight percentage of the polymer is 10 percent, and Y accounts for 10 percent of the weight percentage of the acrylate copolymer.
Comparative example 1
The demulsifier was prepared according to the method of example 1 of patent document CN 102399576A.
Comparative example 2
The demulsifier is a polyether demulsifier and is provided by the victory chemical industry.
Application examples
The acrylate copolymer demulsifier prepared in the embodiment 1-3 and the demulsifier prepared in the comparative example 1-2 are respectively used for demulsifying the heavy oil emulsion in the victory oil field island oil production six-island combined station, and the demulsification performance of the heavy oil emulsion is evaluated by an evaluation method specified by a service performance detection method (bottle test method) of a crude oil demulsifier in a petroleum and natural gas industry standard SY-Y5281-2000. The oil sample name is crude oil with water content of 40% (volume), field demulsification temperature of 75 ℃, test temperature of 75 ℃, and the results are shown in Table 1.
TABLE 1
*: the dosage of the demulsifier refers to the mass of the demulsifier added in each liter of oil sample.
As can be seen from the data in Table 1, the demulsifying effect of the demulsifier prepared by the method of the invention is obviously higher than that of the demulsifier prepared by the method of patent CN102399576A and the demulsifier used in the field of the Saturo combined station.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A novel lignin-based oil water-in-emulsion demulsifier is characterized by comprising an acrylate copolymer containing a lignin structure, wherein the acrylate copolymer is formed by polymerizing enzymatic hydrolysis lignin, a hydrophobic monomer and a hydrophilic monomer;
the structural formula of the acrylate copolymer comprises a structural unit shown as a formula M, N, X, Y:
in the formula N, R1Is methyl, 2-ethylhexyl or dodecyl, R2Is H or methyl;
in the formula X, R3Is H or methyl.
2. The novel lignin-based oil water-in-emulsion demulsifier of claim 1, wherein M is not less than 0% by weight of the acrylate copolymer, N is not less than 0% by weight of the acrylate copolymer, and M + N is not less than 20% and not more than 95.5%;
x accounts for 0-15% of the weight percentage of the acrylic copolymer;
y accounts for 0.5-10% of the weight percentage of the acrylate copolymer;
preferably, m + n is more than or equal to 70% and less than or equal to 90%, m is more than or equal to 0, and n is more than or equal to 0; x is more than or equal to 6 percent and less than or equal to 12 percent; y is more than or equal to 2 percent and less than or equal to 10 percent.
3. The method of preparing the novel lignin-based oil water-in-emulsion demulsifier of claim 1 or 2, wherein the method comprises: in the presence of an initiator and a solvent, carrying out solution free radical polymerization reaction on the enzymatic hydrolysis lignin, the hydrophobic monomer and the hydrophilic monomer to prepare the acrylate copolymer.
4. The method of preparing the novel lignin-based oil water emulsion demulsifier of claim 3 wherein the enzymatic hydrolysis of lignin comprises: the content of lignin is more than or equal to 90 wt%, the content of residual sugar is less than or equal to 5 wt%, the content of ash is less than or equal to 5 wt%, and the content of phenolic hydroxyl is more than or equal to 10 wt%;
the hydrophobic monomer is selected from one or more of butyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate and dodecyl acrylate;
the hydrophilic monomer is acrylic acid or methacrylic acid.
5. The method of preparing a novel lignin-based oil water emulsion demulsifier according to claim 3 wherein the initiator comprises initiator A and initiator B;
the initiator A is calcium chloride and hydrogen peroxide;
the initiator B is an azo initiator, a peroxide initiator or an oxidation-reduction initiator;
preferably, the azo initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate; the peroxide initiator is benzoyl peroxide; the oxidation-reduction initiator is benzoyl peroxide-dimethylaniline.
6. The preparation method of the novel lignin-based oil water emulsion demulsifier according to claim 5, wherein the enzymatic hydrolysis lignin is used in an amount of 0, 5-10 parts by weight; the dosage of the hydrophobic monomer is 20-95.5 parts; the using amount of the hydrophilic monomer is 0-10 parts;
the dosage of the initiator A is 0.2-5 parts, and the weight ratio of the calcium chloride to the hydrogen peroxide is 1: 0.5-2; the using amount of the initiator B is 0.2-1.5 parts.
7. The method for preparing a novel lignin-based oil water emulsion demulsifier according to claim 3, wherein the solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and dioxane; the amount of the solvent used is such that the solid content of the reaction system is from 10 to 50% by weight.
8. The method of preparing a novel lignin-based oil water emulsion breaker according to claim 5 or 6, wherein said method of preparation comprises the steps of:
1) dissolving part of hydrophobic monomer in part of solvent to prepare hydrophobic monomer solution;
2) dissolving enzymolysis lignin and an initiator A in a part of solvent to prepare an enzymolysis lignin solution;
3) under the protection of nitrogen, heating the hydrophobic monomer solution and heating and activating the enzymatic hydrolysis lignin solution respectively, then mixing the hydrophobic monomer solution and the enzymatic hydrolysis lignin solution, and adding part of the initiator B for reaction;
4) uniformly mixing part of hydrophobic monomer, part of hydrophilic monomer, part of initiator B and part of solvent, and adding the mixture into the reaction system obtained in the step 3) for reaction;
5) uniformly mixing the rest reaction monomer, the initiator B and the solvent, and adding the mixture into the reaction system obtained in the step 4) for reaction;
6) cooling, purifying and drying the mixture obtained by the reaction in the step 5) to obtain the acrylic ester copolymer containing the lignin structure;
preferably, the amount of the hydrophobic monomer in the step 1) is 60-95% of the total weight of the hydrophobic monomer, and the amount of the hydrophobic monomer in the step 4) is 5-20% of the total weight of the hydrophobic monomer;
the using amount of the hydrophilic monomer in the step 4) is 20-70% of the total weight of the hydrophilic monomer;
the dosage of the solvent in the step 1) is 40-70% of the total weight of the solvent, the dosage of the solvent in the step 2) is 10-30% of the total weight of the solvent, and the dosage of the solvent in the step 4) is 5-15% of the total weight of the solvent;
the dosage of the initiator B in the step 3) is 40-70% of the total weight of the initiator B, and the dosage of the initiator B in the step 4) is 15-40% of the total weight of the initiator B.
9. The preparation method of the novel lignin-based oil water-in-emulsion demulsifier according to claim 8, wherein in step 3), the temperature of the hydrophobic monomer solution is raised to 60-80 ℃, the temperature of the enzymatic hydrolysis lignin solution is raised to 45-55 ℃ and the time is 10-40 min;
the reaction temperature in each step is 60-90 ℃, the reaction time in step 3) is 0.5-2h, the reaction time in step 4) is 1-3h, and the reaction time in step 5) is 4-10 h.
10. A method for treating a crude oil-in-water emulsion, the method comprising: contacting a crude oil water-in-oil emulsion with the novel lignin-based oil water-in-emulsion demulsifier according to claim 1 or 2 or the novel lignin-based oil water-in-emulsion demulsifier prepared by the preparation method according to any one of claims 3 to 9;
preferably, the contact time is 0.5-8h, and the contact temperature is 50-90 ℃; the amount of the acrylate copolymer in the novel lignin-based oil-in-water emulsion demulsifier is 30-200mg, preferably 50-150mg, relative to 1L of crude oil-in-water emulsion.
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