CN113663598A - Preparation of composite lignin-based surfactant and application of composite lignin-based surfactant in treatment of oily sludge - Google Patents
Preparation of composite lignin-based surfactant and application of composite lignin-based surfactant in treatment of oily sludge Download PDFInfo
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- CN113663598A CN113663598A CN202110973868.XA CN202110973868A CN113663598A CN 113663598 A CN113663598 A CN 113663598A CN 202110973868 A CN202110973868 A CN 202110973868A CN 113663598 A CN113663598 A CN 113663598A
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- lignin
- amine
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- based surfactant
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 67
- 229920005610 lignin Polymers 0.000 title claims abstract description 61
- 239000010802 sludge Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 235000019357 lignosulphonate Nutrition 0.000 claims abstract description 36
- 150000001412 amines Chemical class 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 21
- -1 lignosulfonic acid amine Chemical class 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000003876 biosurfactant Substances 0.000 claims abstract description 13
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 17
- 239000004117 Lignosulphonate Substances 0.000 claims description 15
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- ZTOKUMPYMPKCFX-CZNUEWPDSA-N (E)-17-[(2R,3R,4S,5S,6R)-6-(acetyloxymethyl)-3-[(2S,3R,4S,5S,6R)-6-(acetyloxymethyl)-3,4,5-trihydroxyoxan-2-yl]oxy-4,5-dihydroxyoxan-2-yl]oxyoctadec-9-enoic acid Chemical compound OC(=O)CCCCCCC/C=C/CCCCCCC(C)O[C@@H]1O[C@H](COC(C)=O)[C@@H](O)[C@H](O)[C@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](COC(C)=O)O1 ZTOKUMPYMPKCFX-CZNUEWPDSA-N 0.000 claims description 4
- HVCOBJNICQPDBP-UHFFFAOYSA-N 3-[3-[3,5-dihydroxy-6-methyl-4-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyoxan-2-yl]oxydecanoyloxy]decanoic acid;hydrate Chemical compound O.OC1C(OC(CC(=O)OC(CCCCCCC)CC(O)=O)CCCCCCC)OC(C)C(O)C1OC1C(O)C(O)C(O)C(C)O1 HVCOBJNICQPDBP-UHFFFAOYSA-N 0.000 claims description 4
- 229930186217 Glycolipid Natural products 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical group CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 claims description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 3
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 claims description 3
- 229940043349 potassium metabisulfite Drugs 0.000 claims description 3
- 235000010263 potassium metabisulphite Nutrition 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000011121 hardwood Substances 0.000 claims description 2
- 229920005611 kraft lignin Polymers 0.000 claims description 2
- 239000011122 softwood Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000003921 oil Substances 0.000 abstract description 49
- 239000010779 crude oil Substances 0.000 abstract description 22
- 238000011084 recovery Methods 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- YHEWWEXPVKCVFY-UHFFFAOYSA-N 2,6-Dimethoxy-4-propylphenol Chemical group CCCC1=CC(OC)=C(O)C(OC)=C1 YHEWWEXPVKCVFY-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical group CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- PXIKRTCSSLJURC-UHFFFAOYSA-N Dihydroeugenol Chemical group CCCC1=CC=C(O)C(OC)=C1 PXIKRTCSSLJURC-UHFFFAOYSA-N 0.000 description 1
- 241000592342 Tracheophyta Species 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
Abstract
The invention provides a preparation method of a composite lignin-based surfactant and an application of the composite lignin-based surfactant in treating oily sludge; mixing lignin and an oxidizing reagent, and adding the mixture to react to obtain oxidized lignin; mixing the obtained oxidized lignin with a sulfonation reagent, adding the mixture to react to obtain oxidized sulfonated lignin; mixing propylene oxide and long-chain fatty amine substances and adding the mixture into a long-chain fatty quaternary ammonium salt intermediate; and mixing the oxidized sulfonated lignin and the long-chain fatty quaternary ammonium salt intermediate for reaction to obtain the lignosulfonic acid amine-based surfactant. Heating the oily sludge sample in an oil bath, adding the lignosulfonate amine-based surfactant and the biosurfactant, reacting under stirring, and then performing centrifugal separation. The recovery rate of crude oil can reach more than 77 percent and can reach as high as 94 percent.
Description
Technical Field
The invention belongs to the technical field of preparation of surfactants, and relates to preparation of a composite lignin-based surfactant and application thereof in treating oily sludge; in particular to a lignosulphonate amine surfactant and a small amount of biosurfactant composite system and application thereof in the aspect of strengthening the recovery of crude oil in oil-containing sludge.
Background
The surfactant can reduce the surface tension of a solution, change the interfacial state of the solution, and have the effects of emulsification, wetting, solubilization, penetration, and solubilization, etc. in use, thereby playing an important role in the industrial field. Most of the traditional surfactants are prepared by taking petroleum as a raw material, but the increasing exhaustion of petroleum resources causes the production cost of the surfactants to be remarkably increased, which is not favorable for the sustainable development of economy.
Lignin is an aromatic organic high polymer with a complex structure and is an important component of vascular plant cell walls. The lignin macromolecular structure is a three-dimensional space network structure formed by connecting three phenylpropane monomers (namely an syringyl propane structure S-unit, a p-hydroxyphenyl propane structure H-unit and a guaiacyl propane structure G-unit) through a large number of ether bonds (C-O) and carbon-carbon bonds (C-C). Meanwhile, lignin has many attractive advantages such as high carbon content, good thermal stability, biodegradability, excellent oxidation resistance, high hardness, low price, etc., which has led researchers to widely develop lignin in an attempt to apply its value-added products to various fields. Surfactants have received much attention from researchers as an important application area for lignin. Lignin is a natural surfactant, and has special structural properties, and contains both hydrophilic groups such as carboxyl, hydroxyl and carbonyl groups and lipophilic groups such as phenylpropane. Usually, lignin cannot be directly used as a surfactant to be applied to practice, and needs to be modified appropriately to increase the number of hydrophilic groups or lipophilic groups in lignin or enhance the hydrophilic-lipophilic strength so as to increase the surface activity of lignin. The application of the lignin in the field of the surfactant improves the use value of the lignin, relieves the problem of insufficient petroleum resources, and is beneficial to realizing the sustainable development of economy.
Oily sludge is a solid waste rich in mineral oil, which is generated in the petroleum exploration and development industry and the petrochemical industry production industry, and is not inherently present in nature. The oily sludge mainly comprises oil, silt and water, wherein the water content is 20-50%, the oil content is 30-60%, and the solid content is 10-40%. The crude oil yield is estimated to be 1.6 multiplied by 10 per year in China at present-8The oil-containing sludge produced by the method accounts for about 0.5-1% of the crude oil yield (nearly millions of tons of oil sludge, oil sand and the like are produced every year), and the oil-containing sludge and the like are accumulated in an oil tank for a long time due to the oil sludge discharge restriction policy of the environmental protection department, so that the operation device is not burdened, and the normal operation of oil field production is seriously hindered. In addition, the oily sludge has complex components, contains a large amount of organic pollutants, inorganic matters, heavy metals and even radioactive toxic substances, and is difficult to settle, so that the land structure and the underground water quality are deeply affected, the ecological structure is damaged, and the health of human bodies is seriously threatened. The oily sludge also contains various pathogenic bacteria, parasitic ova, homologues of benzene, anthracene, pyrene and other highly toxic substances, and the substances are exposed in the air for a long time and then can be infected infinitely. Fossil energy such as petroleum is a non-renewable resource, so that the efficient treatment of the oily sludge to obtain good oil recovery ratio not only conforms to the development concept of sustainable development, but also conforms to the development requirement of building an environment-friendly society.
The patent CN1360969A carries out electrode oxidation, alkylation and sulfonation modification operations on alkali lignin in sequence, and the oil-water surface tension of the modified lignin surfactant compounded with petroleum sulfonate under the alkali condition reaches 10-3mN/m, the oil content of the recovered oil reaches 78 percent; patent CN1327026A uses a long carbon chain-containing greaseThe fatty amide chemically modifies lignosulfonate, and the result shows that the lignosulfonate can enable the oil-water interfacial tension to reach 10-3mN/m; in patent CN1123620C, lignosulfonate is compounded with petroleum carboxylate and alkylbenzene sulfonate respectively, and it is found that the oil-water interfacial tension of the complex system can reach 10 under the alkali condition-3mN/m。
The composite surfactant provided by the invention aims to reduce the raw material cost, reduce the surface tension of oil and water to an ultra-low level without other specific conditions such as alkali and the like, and further improve the recovery rate of crude oil.
Disclosure of Invention
The invention aims to provide a method for preparing a lignosulphonate amine surfactant and a small amount of biosurfactant for recovering crude oil in oily sludge in a compounding way, the lignosulphonate amine surfactant takes lignin as a raw material, firstly reacts with an oxidant and a sulfonation reagent, hydrophilic groups are introduced to side chains of the lignin to obtain oxidized sulfonated lignin, then a long-chain quaternary ammonium salt substance, namely lipophilic group, is introduced into lignin molecules through alkylation reaction to obtain the lignosulphonate amine surfactant, and then the lignosulphonate amine surfactant and the small amount of biosurfactant are compounded to prepare the lignosulphonate amine surfactant,
the invention provides a preparation method of a composite lignin-based surfactant, which specifically comprises the following steps:
1) mixing and adding lignin and an oxidizing reagent for reaction, and reacting for 1-5 hours at the temperature of 50-100 ℃ to obtain oxidized lignin;
2) mixing the oxidized lignin obtained in the step 1) with a sulfonation reagent, adding the mixture into the mixture for reaction, and reacting the mixture for 1 to 12 hours at the temperature of between 50 and 300 ℃ to obtain oxidized sulfonated lignin;
3) mixing and adding propylene oxide and long-chain fatty amine substances, and reacting at the temperature of 20-120 ℃ for 1-10h to obtain a long-chain fatty quaternary ammonium salt intermediate;
4) mixing the oxidized sulfonated lignin obtained in the step 2) with the long-chain fatty quaternary ammonium salt intermediate obtained in the step 3), reacting at the temperature of 50-110 ℃ for 1-10h, and cooling to room temperature after the reaction is finished to obtain the lignosulfonic acid amine-based surfactant.
In the step 1), the lignin is specifically hardwood lignin and softwood lignin, and comprises lignosulfonate or kraft lignin.
In the step 1), the oxidizing reagent is hydrogen peroxide, sodium hypochlorite, potassium dichromate, sodium dichromate, potassium permanganate, nitric acid, chlorine or oxygen.
In the step 1), the mass ratio of the lignin to the oxidizing reagent is 0.1-4: 1.
In the step 2), the sulfonation reagent is sodium sulfite, sulfur trioxide, concentrated sulfuric acid, sulfur dioxide and oxygen, chlorosulfonic acid, potassium sulfite, sodium metabisulfite or potassium metabisulfite.
In the step 2), the mass ratio of the oxidized lignin to the sulfonation reagent is 0.1-6: 1.
In the step 3), the long-chain aliphatic amine substance is an organic amine compound with a carbon chain length within a range of 8-22, and is preferably dodecyl dimethyl primary amine, dodecyl dimethyl tertiary amine, tetradecyl dimethyl primary amine or tetradecyl dimethyl tertiary amine.
In the step 3), the mixing molar ratio of the epoxypropane to the long-chain aliphatic amine substance is 0.5-2:1
In the step 4), the molar ratio of the oxidized sulfonated lignin to the long-chain fatty quaternary ammonium salt intermediate is 0.5-2: 1.
The composite lignin-based surfactant prepared by the invention is applied to a method for treating oily sludge; uniformly stirring an oil-containing sludge sample, placing the sample in a container, and heating the sample by using an oil bath to perform reaction; adding lignosulphonate amine surfactant and biosurfactant, wherein the mass ratio of the lignosulphonate amine surfactant to the biosurfactant is 1-10:1, stirring at the stirring speed of 300r/min-5000r/min, and then reacting at the temperature of 60-120 ℃ for 1-12 h; after the reaction is finished, carrying out centrifugal separation on the reaction system, and carrying out subsequent content determination.
The biosurfactant is rhamnolipid, sophorolipid or seaweed glycolipid.
The principle of the invention is that the surface tension of an oil-water interface is reduced, the wettability of the interface surface is changed, and a surfactant can be adsorbed to certain components of the structural crude oil, the interaction of the components is weakened, the viscosity of the crude oil is promoted to be reduced, and the purpose of oil extraction is realized.
According to the characteristics of the natural lignin surfactant and the excellent characteristics of low cost, rich raw material sources and biodegradability, the high-efficiency lignin-based surfactant is prepared for treating the oily sludge, and the oil displacement effect is realized by reducing the surface tension of an oil-water interface.
The invention has the beneficial effects that: (1) the raw material lignin is nontoxic and harmless, has rich content and low cost, and relieves the pressure of shortage of petroleum resources; (2) provides a new way for the value-added utilization of lignin; (3) the composite use of the lignin-based surfactant and the biosurfactant can reduce the oil-water interfacial tension to an ultra-low level, and obviously improve the recovery ratio of crude oil in oil sludge; the invention provides a novel efficient environment-friendly lignin-based amphoteric surfactant for enhancing the recovery ratio of crude oil in oily sludge.
Detailed Description
Example 1
1. Firstly, carrying out oxidation reaction on 1g of alkali lignin and 10g of hydrogen peroxide at 50 ℃ for 1h to obtain oxidized lignin;
2. adding 0.4g of sodium sulfite and sulfonating for 1h at 50 ℃ to obtain oxidized sulfonated lignin;
3. mixing 0.53g of propylene oxide and 3.85g of dodecyl dimethyl primary amine, and reacting for 1h at the temperature of 20 ℃ to obtain a long carbon chain fatty quaternary ammonium salt intermediate;
4. 2.878g of quaternary ammonium salt intermediate and 1.445g of oxidized sulfonated lignin are mixed and reacted for 1h at 50 ℃, and after the reaction is finished, the temperature is cooled to room temperature to prepare the lignosulfonate amine-based surfactant.
Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulphonate amine surfactant and biosurfactant rhamnolipid according to the mass ratio of 10:1, stirring at the speed of 300r/min, and then reacting at the temperature of 60 ℃ for 1 h; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery rate of crude oil obtained by recovering and weighing the oil on the upper layer can reach 77%.
Example 2
1. Firstly, carrying out oxidation reaction on 1g of alkali lignin and 3.3g of sodium hypochlorite at 65 ℃ for 4h to obtain oxidized lignin;
2. adding 1.5g of concentrated sulfuric acid, and sulfonating at 90 ℃ for 3h to obtain oxidized sulfonated lignin;
3. mixing 1.23g of propylene oxide and 2.52g of dodecyl dimethyl tertiary amine, and reacting for 4 hours at the temperature of 60 ℃ to obtain a long-carbon-chain fatty quaternary ammonium salt intermediate;
4. mixing 4.637g of quaternary ammonium salt intermediate with 3.245g of oxidized sulfonated lignin, reacting for 5h at 70 ℃, cooling to room temperature after the reaction is finished, and preparing the lignosulfonate amine-based surfactant.
Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulphonate amine surfactant and biosurfactant rhamnolipid according to the mass ratio of 8:1, stirring at the speed of 1000r/min, and then reacting at the temperature of 80 ℃ for 6 h; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery ratio of crude oil obtained by recovering and weighing the oil on the upper layer can reach 80%.
Example 3
1. Firstly, carrying out oxidation reaction on 1g of alkali lignin and 2g of potassium dichromate at 80 ℃ for 4h to obtain oxidized lignin;
2. adding 2g of chlorosulfonic acid, and sulfonating at 135 ℃ for 3h to obtain oxidized sulfonated lignin;
3. mixing 1.75g of propylene oxide and 3.75g of dodecyl dimethyl tertiary amine, and reacting for 2 hours at 70 ℃ to obtain a long carbon chain fatty quaternary ammonium salt intermediate;
4. mixing 4.9g of quaternary ammonium salt intermediate with 4.8g of oxidized sulfonated lignin, reacting for 6h at 90 ℃, cooling to room temperature after the reaction is finished, and preparing the lignosulfonate amine-based surfactant.
Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulphonate amine surfactant and biological surfactant sophorolipid according to the mass ratio of 6:1, stirring at the speed of 2500r/min, and then reacting at the temperature of 75 ℃ for 6 h; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery ratio of crude oil obtained by recovering and weighing the oil on the upper layer can reach 87%.
Example 4
1. Firstly, carrying out oxidation reaction on 1g of lignosulfonate and 1g of sodium dichromate at 80 ℃ for 4 hours to obtain oxidized lignin;
2. adding 4g of potassium sulfite, and sulfonating at 200 ℃ for 8h to obtain oxidized sulfonated lignin;
3. mixing 2.188g of propylene oxide and 4.683g of tetradecyl dimethyl primary amine, and reacting at 90 ℃ for 7 hours to obtain a long-carbon-chain fatty quaternary ammonium salt intermediate;
4. 3.616g of quaternary ammonium salt intermediate and 5.424g of oxidized sulfonated lignin are mixed and reacted for 7 hours at the temperature of 90 ℃, and after the reaction is finished, the temperature is cooled to room temperature, so that the lignosulfonate amine-based surfactant is prepared.
Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulphonate amine surfactant and biological surfactant sophorolipid according to the mass ratio of 4:1, stirring at the speed of 3000r/min, and then reacting at the temperature of 120 ℃ for 12 hours; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery ratio of crude oil obtained by recovering and weighing the oil on the upper layer can reach 91%.
Example 5
1. Firstly, carrying out oxidation reaction on 1g of lignosulfonate and 0.67g of potassium permanganate at 90 ℃ for 5 hours to obtain oxidized lignin;
2. adding 0.2g of sodium metabisulfite and sulfonating for 10 hours at the temperature of 250 ℃ to obtain oxidized sulfonated lignin;
3. mixing 2.625g of propylene oxide and 5.615g of tetradecyl dimethyl tertiary amine, and reacting at 110 ℃ for 9h to obtain a long-carbon-chain fatty quaternary ammonium salt intermediate;
4. 4.485g of quaternary ammonium salt intermediate and 6.728g of oxidized sulfonated lignin are mixed and react for 8 hours at the temperature of 100 ℃, and after the reaction is finished, the temperature is cooled to room temperature to prepare the lignosulfonate amine-based surfactant.
Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulphonate amine surfactant and biological surfactant algal glycolipid according to the mass ratio of 3:1, stirring at the speed of 4500r/min, and then reacting at the temperature of 120 ℃ for 12 hours; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery rate of crude oil obtained by recovering and weighing the oil on the upper layer can reach 94 percent.
Example 6
1. Firstly, carrying out oxidation reaction on 1g of lignosulfonate and 0.25g of nitric acid at 100 ℃ for 5 hours to obtain oxidized lignin;
2. adding 0.2g of potassium metabisulfite, and sulfonating at 300 ℃ for 12 hours to obtain oxidized sulfonated lignin;
3. mixing 2.625g of propylene oxide and 5.615g of tetradecyl dimethyl tertiary amine, and reacting at 120 ℃ for 10h to obtain a long-carbon-chain fatty quaternary ammonium salt intermediate;
4. 3.613g of quaternary ammonium salt intermediate and 7.225g of oxidized sulfonated lignin are mixed and reacted for 10 hours at 110 ℃, and after the reaction is finished, the temperature is cooled to room temperature, so that the lignosulfonate amine-based surfactant is prepared.
Treating the oily sludge by using the prepared surfactant: uniformly stirring an oil-containing sludge sample, weighing 50g of oil sludge, placing the oil sludge in a beaker, and heating by utilizing an oil bath for reaction; adding lignosulfonate amine-based surfactant and biological surfactant trehalose glycolipid according to the mass ratio of 1:1, stirring at the speed of 5000r/min, and then reacting at the temperature of 120 ℃ for 12 hours; after the reaction is finished, moving the reaction system into a centrifugal tube for centrifugation, observing that the centrifugal tube is divided into three layers after the centrifugation is finished, wherein the crude oil to be recovered is positioned at the uppermost layer, the surfactant is positioned in the middle, and the lowermost layer is residual mud; the recovery ratio of crude oil obtained by recovering and weighing the oil on the upper layer can reach 89%.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention. The invention belongs to the known technology.
Claims (10)
1. A preparation method of a composite lignin-based surfactant specifically comprises the following steps:
1) mixing and adding lignin and an oxidizing reagent for reaction, and reacting for 1-5 hours at the temperature of 50-100 ℃ to obtain oxidized lignin;
2) mixing the oxidized lignin obtained in the step 1) with a sulfonation reagent, adding the mixture into the mixture for reaction, and reacting the mixture for 1 to 12 hours at the temperature of between 50 and 300 ℃ to obtain oxidized sulfonated lignin;
3) mixing and adding propylene oxide and long-chain fatty amine substances, and reacting at the temperature of 20-120 ℃ for 1-10h to obtain a long-chain fatty quaternary ammonium salt intermediate;
4) mixing the oxidized sulfonated lignin obtained in the step 2) with the long-chain fatty quaternary ammonium salt intermediate obtained in the step 3), reacting at the temperature of 50-110 ℃ for 1-10h, and cooling to room temperature after the reaction is finished to obtain the lignosulfonic acid amine-based surfactant.
2. The method as claimed in claim 1, wherein in step 1), the lignin is hardwood lignin, softwood lignin, including lignosulfonate or kraft lignin; the oxidizing agent is hydrogen peroxide, sodium hypochlorite, potassium dichromate, sodium dichromate, potassium permanganate, nitric acid, chlorine or oxygen.
3. The method as set forth in claim 1, wherein in the step 1), the mass ratio of the lignin to the oxidizing agent is 0.1-4: 1.
4. The method as set forth in claim 1, wherein in the step 2), the sulfonating agent is sodium sulfite, sulfur trioxide, concentrated sulfuric acid, sulfur dioxide plus oxygen, chlorosulfonic acid, potassium sulfite, sodium metabisulfite or potassium metabisulfite.
5. The method as set forth in claim 1, wherein in the step 2), the mass ratio of the oxidized lignin to the sulfonating agent is 0.1-6: 1.
6. The method as set forth in claim 1, wherein in the step 3), the long-chain aliphatic amine is an organic amine compound having a carbon chain length in the range of 8 to 22, and is preferably dodecyl dimethyl primary amine, dodecyl dimethyl tertiary amine, tetradecyl dimethyl primary amine, or tetradecyl dimethyl tertiary amine.
7. The method as set forth in claim 1, wherein in the step 3), the mixing ratio of the propylene oxide to the long-chain aliphatic amine is 0.5-2: 1.
8. The method as set forth in claim 1, wherein in the step 4), the molar ratio of the oxidized sulfonated lignin to the long-chain fatty quaternary ammonium salt intermediate is 0.5-2: 1.
9. The composite lignin-based surfactant prepared according to claim 1 is applied to a method for treating oil-containing sludge; the method is characterized in that an oily sludge sample is uniformly stirred and placed in a container, and is heated by an oil bath for reaction; adding lignosulphonate amine surfactant and biosurfactant, wherein the mass ratio of the lignosulphonate amine surfactant to the biosurfactant is 1-10:1, stirring at the stirring speed of 300r/min-5000r/min, and then reacting at the temperature of 60-120 ℃ for 1-12 h; after the reaction, the reaction system was centrifuged.
10. The method as claimed in claim 9, wherein the biosurfactant is rhamnolipid, sophorolipid or algal glycolipid.
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