CN115141286B - Modified nanocellulose and preparation method and application thereof - Google Patents
Modified nanocellulose and preparation method and application thereof Download PDFInfo
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- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003921 oil Substances 0.000 claims abstract description 47
- 238000007385 chemical modification Methods 0.000 claims abstract description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000005886 esterification reaction Methods 0.000 claims description 36
- 239000003153 chemical reaction reagent Substances 0.000 claims description 30
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 28
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- 230000032050 esterification Effects 0.000 claims description 21
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 15
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- LACFLXDRFOQEFZ-UHFFFAOYSA-N 4-ethylbenzenesulfonyl chloride Chemical compound CCC1=CC=C(S(Cl)(=O)=O)C=C1 LACFLXDRFOQEFZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- VIVGANIZOCUFFE-UHFFFAOYSA-N 3-ethylbenzenesulfonyl chloride Chemical compound CCC1=CC=CC(S(Cl)(=O)=O)=C1 VIVGANIZOCUFFE-UHFFFAOYSA-N 0.000 claims description 6
- 229920000742 Cotton Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 229920002678 cellulose Polymers 0.000 abstract description 11
- 239000001913 cellulose Substances 0.000 abstract description 11
- 230000009467 reduction Effects 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010779 crude oil Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 13
- 230000032683 aging Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000003027 oil sand Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000013043 chemical agent Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229920002522 Wood fibre Polymers 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002025 wood fiber Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000010795 Steam Flooding Methods 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- -1 i.e. Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- CEMUQLXAOCBFNV-UHFFFAOYSA-N ethylbenzene;sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O.CCC1=CC=CC=C1 CEMUQLXAOCBFNV-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012533 medium component Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/592—Compositions used in combination with generated heat, e.g. by steam injection
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biochemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to modified nanocellulose and a preparation method and application thereof. A modified nano-cellulose is prepared from nano-cellulose through chemical modification and esterifying reaction. The modified nanocellulose has the advantage of balanced hydrophilic and lipophilic capability, and can be dissolved in water and interacted with crude oil. Meanwhile, the modified nano cellulose has the advantages of washable oil, high viscosity reduction rate and high temperature resistance.
Description
Technical Field
The invention belongs to the field of cellulose modification, and particularly relates to modified nanocellulose, and a preparation method and application thereof.
Background
Cellulose is a polymer material with the most abundant natural content, and widely exists in plants such as wood, cotton, sugarcane and the like. Cellulose has the advantages of reproducibility, multifunction and self-assembly, and is a renewable environment-friendly resource. Saito et al, university of Tokyo, used a 2, 6-tetramethylpiperidine nitroxide radical (TEMPO) mild oxidation system to pretreat cellulose by catalytic oxidation and then performed mechanical treatment to successfully produce nanocellulose with a diameter of 3-4 nm and a length of several microns, which was uniform in size and capable of long-term suspension in water. The TEMPO/NaBr/NaClO oxidation system is prepared by mixing C 6 Oxidation of primary hydroxy groups in position to carboxylate groups, C 2 、C 3 The hydroxyl group in the position remains unchanged. Due to C 6 A COONa group at position C 2 And C 3 The existence of the hydroxyl of the polar group makes the nano cellulose after TEMPO oxidation treatment have strong hydrophilicity, which limits the application of the nano cellulose.
Patent application CN 108219009A discloses a modified nanocellulose, a preparation method and application thereof, wherein sodium periodate is oxidized into nanocellulose to obtain aldehyde nanocellulose; the aldehyde nanocellulose is reacted with polyethyleneimine and sodium borohydride in sequence to obtain the modified nano-cellulose. The technology can improve the rigidity of polymer molecules and form a good intermolecular network structure of the polymer through stronger interaction between the nanocellulose and the polymer, thereby generating excellent performances of temperature resistance, salt resistance, ageing resistance and the like. The technology evaluates the viscosity change of the obtained product before and after aging at 90 ℃, and the retention rate can be more than 60%. The invention does not evaluate performance at higher temperature, and the nano material needs to react with the polymer, and the use mode is complex.
The energy problem is an important problem affecting the world and peace and development all the time, and petroleum has irreplaceable effects as a traditional energy source, but in the existing oil field, thick oil occupies a large proportion in world oil and gas resources. The main characteristics of the thick oil are: high viscosity, high density, temperature sensitivity, and low content of light and medium components. The thick oil exploitation is often assisted by using steam exploitation, and the main exploitation modes of the thick oil reservoirs at home and abroad are steam huff and puff and steam flooding at present.
However, due to the influences of the factors such as the heterogeneity of the oil reservoir, the difference of permeability, the fluidity ratio, the fluid saturation, the well spacing, the oil reservoir inclination and the like, the injected steam is subjected to steam channeling along the top of the oil reservoir and the high-permeability zone, so that the sweep coefficient of the injected steam is reduced. In order to solve the contradiction and improve the oil washing efficiency, research and application of adding chemical agents in the steam injection process are developed abroad.
However, the existing chemical agents have some defects: on the one hand, the temperature resistance is insufficient, the temperature resistance of the conventional alkyl carboxylate surfactant is lower than 120 ℃, even the sulfonate surfactant with better temperature resistance is difficult to keep stable under the steam flooding condition, and on the other hand, the polymer with relatively excellent temperature resistance has the problems that the surface activity is insufficient and thick oil cannot be effectively used. In addition, although the use of novel materials such as nanocellulose is desirable, the materials are limited by the problems of solubility, hydrophilic-lipophilic balance and the like of the materials, and the application field is limited.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the existing nanocellulose has over-strong hydrophilicity, which limits the application of the nanocellulose in the field of enhanced oil recovery of oil fields, especially in the field of thickened oil recovery, and provides a modified nanocellulose as well as a preparation method and application thereof. Meanwhile, the modified nano cellulose has the advantages of washable oil, high viscosity reduction rate and high temperature resistance.
The first aspect of the invention provides a modified nanocellulose, which is obtained by sequentially carrying out chemical modification and esterification reaction on nanocellulose raw materials, wherein the esterification reaction adopts an esterification reagent, and the esterification reagent has a structure shown in a formula (1):
wherein R is 1 Is C 1 ～C 8 Any one of alkyl and alkenyl;
R 2 is C 1 ～C 8 Any one of alkyl and hydrogen;
R 3 is C 1 ～C 8 Any one of alkyl and hydrogen.
In some embodiments, preferably, the esterification reagent has a structure represented by formula (2):
wherein R is 1 Is C 1 ～C 8 Any one of alkyl and alkenyl;
R 2 is C 1 ～C 8 Any one of alkyl and hydrogen;
R 3 is C 1 ～C 8 Any one of alkyl and hydrogen.
In some specific embodiments, preferably, the esterification reagent is selected from one or more of p-toluenesulfonyl chloride, p-ethylbenzenesulfonyl chloride, and m-ethylbenzenesulfonyl chloride. In the present invention, the esterification reagent can be obtained commercially.
In some specific embodiments, preferably, the chemical modification is selected from one or more of oxidative modification, alkylation modification, cationization modification, non-covalent surface adsorption modification, and graft copolymerization modification.
In some specific embodiments, still further preferred, the nanocellulose chemical modification comprises oxidative modification; more preferably, the chemical modification of the nanocellulose comprises oxidative modification with 2, 6-tetramethylpiperidine-1-oxyl.
In some specific embodiments, preferably, the nanocellulose raw material is plant nanocellulose. More preferably, the nanocellulose raw material is lignocellulose and/or cotton nanocellulose.
In some specific embodiments, preferably, the nanocellulose raw material has a particle size of 50 to 500nm.
The second aspect of the present invention provides a method for preparing modified nanocellulose, comprising the steps of:
step 1, chemically modifying a nano cellulose raw material to obtain chemically modified nano cellulose;
step 2, performing an esterification reaction on the obtained chemically modified nanocellulose, wherein the esterification reaction adopts an esterification reagent, and the esterification reagent has a structure shown in a formula (1):
wherein R is 1 Is C 1 ～C 8 Any one of alkyl and alkenyl;
R 2 is C 1 ～C 8 Any one of alkyl and hydrogen;
R 3 is C 1 ～C 8 Any one of alkyl and hydrogen.
In some embodiments, preferably, the esterification reagent has a structure represented by formula (2):
wherein R is 1 Is C 1 ～C 8 Any one of alkyl and alkenyl;
R 2 is C 1 ～C 8 Any one of alkyl and hydrogen;
R 3 is C 1 ～C 8 Any one of alkyl and hydrogen.
In some specific embodiments, preferably, the esterification reagent is selected from one or more of p-toluenesulfonyl chloride, p-ethylbenzenesulfonyl chloride, and m-ethylbenzenesulfonyl chloride.
In some specific embodiments, preferably, the chemical modification is selected from one or more of oxidative modification, alkylation modification, cationization modification, non-covalent surface adsorption modification, and graft copolymerization modification.
In some specific embodiments, preferably, the nanocellulose chemical modification comprises oxidative modification; more preferably, the chemical modification of the nanocellulose comprises oxidative modification with 2, 6-tetramethylpiperidine-1-oxyl.
In some specific embodiments, preferably, the chemical modification comprises: mixing a nanocellulose raw material, sodium bromide and 2, 6-tetramethylpiperidine-1-oxygen free radical, heating to 50-75 ℃, adding NaClO, regulating the pH value to 4-6, and filtering by adopting a filtering membrane to obtain the chemically modified nanocellulose.
In some specific embodiments, preferably, the nanocellulose raw material: sodium bromide: 2, 6-tetramethylpiperidine-1-oxyl radical: the weight ratio of NaClO is 1 (0.1-0.15) (0.05-0.1) (0.1-0.15).
In some specific embodiments, it is preferred to adjust the pH with a NaOH solution, more preferably, the concentration of the NaOH solution is 0.05 to 0.2mol/L, and still more preferably, 0.1mol/L.
In some specific embodiments, preferably, the pore size of the filter membrane is 200-500nm.
In some specific embodiments, preferably, the method of preparing further comprises formulating the chemically modified nanocellulose into a 1 wt% to 5 wt% suspension after adjusting the pH and before employing the filtration membrane. Preferably, water and chemically modified nanocellulose are used to make a 1 wt% to 5 wt% suspension.
In some specific embodiments, preferably, the esterification reaction comprises: dispersing the obtained chemically modified nano cellulose in N, N-dimethylacetamide, mixing with triethylamine, heating to 80-100 ℃, and adding an esterification reagent to perform esterification reaction.
In some embodiments, it is preferred that the weight ratio of chemically modified nanocellulose to N, N-dimethylacetamide is 1 (25 to 100).
In some specific embodiments, the weight ratio of the chemically modified nanocellulose to the triethylamine to the esterifying reagent is preferably 1 (0.1-0.8): 0.5-1.
In some specific embodiments, preferably, the esterification reaction conditions include: heating to 100-120 deg.c and constant temperature reaction for 4-8 hr.
In some embodiments, it is preferred that the esterification reaction is followed by centrifugation and washing of the product.
In some specific embodiments, preferably, the nanocellulose raw material is plant nanocellulose. More preferably, the nanocellulose raw material is lignocellulose and/or cotton nanocellulose.
In some specific embodiments, preferably, the nanocellulose raw material has a particle size of 50 to 500nm.
In some specific embodiments, the method of modifying nanocellulose according to the present disclosure may include the steps of:
1) Uniformly stirring nanofiber slurry (a nanocellulose raw material), sodium bromide and a TEMPO reagent, heating to 50-75 ℃, adding NaClO, adjusting pH value=4-6 by using NaOH in the reaction process until the dosage of NaOH is 0, preparing a suspension with the concentration of 1-5 wt% (the nanocellulose content is 1-5 wt%) and filtering by adopting a filtering membrane, and cleaning to obtain chemically modified nanocellulose;
2) Dispersing the chemically modified nano cellulose obtained in the step 1) in N, N-dimethylacetamide, adding triethylamine, heating to 80-100 ℃ after ultrasonic dispersion is uniform, adding an esterification reagent shown in the formula (1), heating to 100-120 ℃, reacting at constant temperature for 4-8 h, centrifuging and washing a product after the reaction is finished, and obtaining the modified nano cellulose.
The third aspect of the invention provides the modified nanocellulose or the application of the preparation method of the modified nanocellulose in the enhanced oil recovery of heavy oil reservoirs and oil fields.
The invention has the beneficial effects that:
(1) Compared with the prior art, the invention has the following beneficial effects: the inventor of the invention surprisingly found that the modified nanocellulose of the invention maintains the excellent temperature resistance of the nanocellulose itself, has a certain surface activity and can be directly applied to enhanced oil recovery, in particular to steam oil recovery in a high temperature environment.
(2) The preparation method improves the hydrophilic-lipophilic balance of the nanocellulose, and the obtained modified nanocellulose is used as a high-temperature-resistant chemical agent, has the advantages of high oil washing efficiency and high viscosity reduction rate, is simple and easy to carry out, and is suitable for large-scale production and application.
(3) The preparation method of the nanocellulose well improves the hydrophilic-lipophilic balance of the nanocellulose, and the obtained modified nanocellulose is used as a high-temperature-resistant chemical agent, so that the oil washing efficiency can reach 70% -78% and the viscosity reduction rate can reach 91% -96% respectively before and after aging for 7 days at 350 ℃. The better technical effect is achieved.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art. Wherein,,
the percentages and concentrations in the examples and comparative examples are by weight, unless otherwise specified.
The particle size of the wood fiber pulp is 50-500 nm.
The particle size of the cotton fiber pulp is 50-500 nm.
[ example 1 ]
Adding lignocellulose pulp (nano cellulose raw material) with the concentration of 1% by weight, sodium bromide and a 2, 6-tetramethyl piperidine-1-oxygen free radical (TEMPO) reagent into a reaction kettle, stirring for 0.5h at room temperature, then heating to 50 ℃ and adding NaClO, adjusting the pH value to be 4-6 by using 0.1mol/L NaOH in the reaction process until NaOH is not consumed, and ending the reaction. Wherein the fiber slurry: sodium bromide: TEMPO: the mass ratio of NaClO is 1:0.15:0.05:0.15. then, the mixture was mixed with water to prepare a 3 wt% suspension, and the solution was filtered using a 500nm filter membrane and repeatedly washed to obtain chemically modified nanocellulose a.
Dispersing the chemically modified nano cellulose A in N, N-dimethylacetamide, adding triethylamine, uniformly dispersing by ultrasonic, heating to 80 ℃, adding p-toluenesulfonyl chloride (esterification reagent), heating to 100 ℃, reacting at constant temperature for 5h, and finishing the reaction. Wherein the chemically modified nanocellulose: n, N-dimethylacetamide: triethylamine: the mass ratio of the p-toluenesulfonyl chloride is 1:100:0.5:0.5. and centrifuging and washing the product to obtain the modified nano-cellulose 1.
[ example 2 ]
Adding 1% weight concentration wood fiber pulp, sodium bromide and TEMPO reagent into a reaction kettle, stirring for 0.5h at room temperature, then heating to 50 ℃ and adding NaClO, and adjusting the pH value to be 4-6 by using 0.1mol/L NaOH in the reaction process until NaOH is not consumed, and ending the reaction. Wherein the fiber slurry: sodium bromide: TEMPO: the mass ratio of NaClO is 1:0.1:0.05:0.15. then, the mixture was mixed with water to prepare a suspension of 5 wt% and the solution was filtered using a 500nm filter membrane and repeatedly washed to obtain chemically modified nanocellulose B.
Dispersing the chemically modified nano cellulose B in N, N-dimethylacetamide, adding triethylamine, uniformly dispersing by ultrasonic, heating to 80 ℃, adding p-ethylbenzenesulfonyl chloride, heating to 110 ℃, reacting for 5 hours at constant temperature, and finishing the reaction. Wherein the chemically modified nanocellulose: n, N-dimethylacetamide: triethylamine: the mass ratio of the p-ethylbenzenesulfonyl chloride is 1:100:0.5:0.75. and centrifuging and washing the product to obtain the modified nano-cellulose 2.
[ example 3 ]
Adding 1% weight concentration cotton fiber pulp, sodium bromide and TEMPO reagent into a reaction kettle, stirring for 0.5h at room temperature, then heating to 50 ℃ and adding NaClO, and adjusting the pH value to 4-6 by using 0.1mol/L NaOH in the reaction process until NaOH is not consumed, and ending the reaction. Wherein the fiber slurry: sodium bromide: TEMPO: the mass ratio of NaClO is 1:0.1:0.05:0.15. then, the mixture was mixed with water to prepare a 1 wt% suspension, and the solution was filtered using a 200nm filtration membrane and repeatedly washed to obtain chemically modified nanocellulose C.
Dispersing the chemically modified nano cellulose C in N, N-dimethylacetamide, adding triethylamine, uniformly dispersing by ultrasonic, heating to 100 ℃, adding p-toluenesulfonyl chloride, heating to 120 ℃, reacting for 5 hours at constant temperature, and finishing the reaction. Wherein the chemically modified nanocellulose: n, N-dimethylacetamide: triethylamine: the mass ratio of the p-toluenesulfonyl chloride is 1:50:0.5:1. and centrifuging and washing the product to obtain the modified nano-cellulose 3.
[ example 4 ]
Adding 1% weight concentration wood fiber pulp, sodium bromide and TEMPO reagent into a reaction kettle, stirring for 0.5h at room temperature, then heating to 75 ℃ and adding NaClO, and adjusting the pH value to be 4-6 by using 0.1mol/L NaOH in the reaction process until NaOH is not consumed, and ending the reaction. Wherein the fiber slurry: sodium bromide: TEMPO: the mass ratio of NaClO is 1:0.15:0.1:0.15. then, the mixture was mixed with water to prepare a 3 wt% suspension, and the solution was filtered using a 500nm filter membrane and repeatedly washed to obtain chemically modified nanocellulose D.
Dispersing the chemically modified nano cellulose D in N, N-dimethylacetamide, adding triethylamine, uniformly dispersing by ultrasonic, heating to 80 ℃, adding m-ethyl benzenesulfonyl chloride, heating to 120 ℃, reacting for 5 hours at constant temperature, and finishing the reaction. Wherein the chemically modified nanocellulose: n, N-dimethylacetamide: triethylamine: the mass ratio of the m-ethyl benzene sulfonyl chloride is 1:100:0.5:0.75. and centrifuging and washing the product to obtain the modified nano-cellulose 4.
[ example 5 ]
The procedure of example 1 was followed except that p-toluenesulfonyl chloride (esterifying reagent) was replaced with p-ethylbenzenesulfonyl chloride, to finally obtain modified nanocellulose 5.
[ example 6 ]
Modified nanocellulose 6 was finally obtained following the procedure of example 1, except that p-toluenesulfonyl chloride (esterification reagent) was replaced with m-ethylbenzenesulfonyl chloride.
[ example 7 ]
The procedure of example 1 was followed, except that the chemically modified nanocellulose: n, N-dimethylacetamide: triethylamine: the mass ratio of the p-toluenesulfonyl chloride is 1:100:0.01: and 0.3, finally obtaining the modified nanocellulose 7.
[ example 8 ]
The procedure of example 1 was followed, except that the chemically modified nanocellulose: n, N-dimethylacetamide: triethylamine: the mass ratio of the p-toluenesulfonyl chloride is 1:100:1: and 1.5, finally obtaining the modified nanocellulose 8.
[ example 9 ]
The procedure of example 1 was followed, except that filtration was not performed using a filtration membrane, to finally obtain modified nanocellulose 9.
Test example 1
Modified nanocellulose wash oil experiment
Preparing oil sand with oil content of 20 wt% from formation sand of victory oil field and crude oil (10000 Pa.s), sealing, standing at 80deg.C for 7d, and mixing with mass m o The oil sand and the surfactant solution were added to a 100mL stoppered cylinder in a mass ratio of 1:10. Placing into an oven at 80deg.C, standing and heating for 24 hr, removing washed crude oil, cleaning oil sand with purified water, and oven drying oil sand to obtain mass m 1 . Thoroughly cleaning oil sand with petroleum ether, and oven drying to obtain mass m 2 Wash oil ratio= (m o -m 1 )/(m o -m 2 )×100％。
The chemically modified nanocellulose a-D obtained in examples 1-9 and the modified nanocellulose 1-9 were respectively formulated into 1% by weight aqueous solutions, i.e., surfactant solutions, respectively. The wash oil was tested as described above. The solution was then aged for 7d at 350 ℃. The wash oil ratio of the solution was measured after the aging was completed, and the experimental data are shown in table 1.
TABLE 1 nanocellulose wash oil test results
As can be seen from Table 1, the chemically modified nanocellulose cannot substantially elute crude oil, the washing ability of the modified nanocellulose of the invention is greatly improved, and the washing oil rate does not change obviously after aging at high temperature. Particularly, under the preferable conditions of the invention, the invention has better effect.
Test example 2
Viscosity reduction experiment of modified nanocellulose
Liquid samples were formulated with simulated saline to a concentration of 1.0% by weightAn aqueous solution. Placing dehydrated thick oil in beaker, placing in constant temperature water bath at 50deg.C, keeping constant temperature for 1 hr, and measuring its viscosity μ with viscometer 1 . Weighing 280g (accurate to 0.01 g) of the thick oil, adding 120g (accurate to 0.01 g) of the prepared sample solution into a beaker, placing into a constant-temperature water bath at 50 ℃ for 1h, taking out and fully stirring to form a uniform dispersion, and measuring the viscosity mu 2 . Sample viscosity reduction rate = (μ) 1 -μ 2 )/μ 1 ×100％。
The chemically modified nanocellulose a-D obtained in examples 1-8 and the modified nanocellulose 1-8 were respectively prepared into solutions with a concentration of 1% by weight, and the viscosity reduction rate was tested according to the above-described method. The solution was then aged for 7d at 350 ℃. The solution was tested for viscosity reduction after aging, and experimental data are shown in Table 2.
TABLE 2 results of nanocellulose viscosity reduction Rate test
As can be seen from table 2, the viscosity of the crude oil cannot be reduced, but the viscosity of the chemically modified nanocellulose is increased, but the viscosity reducing capability of the preferred modified nanocellulose is greatly improved, and the viscosity reducing rate is not obviously changed after high-temperature aging.
Thus, it can be seen from the results of test examples 1 and 2 that the modified nanocellulose of the present invention significantly improved the interaction with thick oil, whereas only the chemically modified nanocellulose was substantially incapable of eluting crude oil and would thicken the crude oil. Under the preferable condition, the washing oil rate of the modified nano cellulose is greatly improved to 70-78%, and the viscosity reduction rate is greatly improved to 91-96%.
[ comparative example 1 ]
Patent application CN 104164226a discloses a high-temperature oil washing agent, in particular to an oil washing agent compounded by decyl dimethyl hydroxypropyl sulfobetaine, solvent oil (such as diesel oil), a solubilizer, a dispersing agent and an emulsifying agent. The wash oil rate of the high-temperature wash oil agent at the concentration of 40mg/g is 72.6%, and the wash oil rate after aging for 12 hours at 350 ℃ is 71.8%.
Comparing comparative example 1 with the inventive example, comparative example 1 was used at a much higher concentration than inventive example 5 and had much less oil content (2.4 wt%) than example 5 (20 wt%), and comparative example 1 had insufficient aging of the oil sand, and the theoretical oil washing difficulty was much less than inventive example 5, but the oil washing rates were close, indicating that the oil washing effect of the modified nanocellulose of the invention was better. And after aging at high temperature, in the case that the aging time of comparative example 1 is smaller than that of example 5 of the present invention, the change in wash oil rate of comparative example 1 is larger than that of example 5 of the present invention, indicating that the modified nanocellulose of the present invention is more stable.
Claims (14)
1. The modified nanocellulose is prepared by sequentially carrying out chemical modification and esterification reaction on nanocellulose raw materials, wherein the esterification reaction adopts an esterification reagent, and the esterification reagent has a structure shown in a formula (1):
wherein R is 1 Is C 1 ～C 8 Any one of alkyl and alkenyl;
R 2 is C 1 ～C 8 Any one of alkyl and hydrogen;
R 3 is C 1 ～C 8 Any one of alkyl and hydrogen;
the chemical modification comprises oxidation modification by using 2, 6-tetramethyl piperidine-1-oxygen free radical.
2. The modified nanocellulose of claim 1, wherein said esterification reagent has a structure of formula (2):
wherein R is 1 Is C 1 ～C 8 Any one of alkyl and alkenyl;
R 2 is C 1 ～C 8 Any one of alkyl and hydrogen;
R 3 is C 1 ～C 8 Any one of alkyl and hydrogen.
3. The modified nanocellulose as claimed in claim 1 wherein the esterification reagent is selected from one or more of p-toluenesulfonyl chloride, p-ethylbenzenesulfonyl chloride and m-ethylbenzenesulfonyl chloride.
4. The preparation method of the modified nanocellulose comprises the following steps:
step 1, chemically modifying a nano cellulose raw material to obtain chemically modified nano cellulose; the chemical modification comprises oxidation modification by adopting 2, 6-tetramethyl piperidine-1-oxygen free radical;
step 2, performing an esterification reaction on the obtained chemically modified nanocellulose, wherein the esterification reaction adopts an esterification reagent, and the esterification reagent has a structure shown in a formula (1):
wherein R is 1 Is C 1 ～C 8 Any one of alkyl and alkenyl;
R 2 is C 1 ～C 8 Any one of alkyl and hydrogen;
R 3 is C 1 ～C 8 Any one of alkyl and hydrogen.
5. The process according to claim 4, wherein the esterifying reagent has a structure represented by formula (2):
wherein R is 1 Is C 1 ～C 8 Any one of alkyl and alkenyl;
R 2 is C 1 ～C 8 Any one of alkyl and hydrogen;
R 3 is C 1 ～C 8 Any one of alkyl and hydrogen.
6. The process according to claim 4, wherein the esterifying reagent is one or more selected from the group consisting of p-toluenesulfonyl chloride, p-ethylbenzenesulfonyl chloride and m-ethylbenzenesulfonyl chloride.
7. The method of any one of claims 4-6, wherein the chemical modification comprises: mixing a nanocellulose raw material, sodium bromide and 2, 6-tetramethylpiperidine-1-oxygen free radical, heating to 50-75 ℃, adding NaClO, regulating the pH value to 4-6, and filtering by adopting a filtering membrane to obtain the chemically modified nanocellulose.
8. The method of claim 7, wherein the nanocellulose material: sodium bromide: 2, 6-tetramethylpiperidine-1-oxyl radical: the weight ratio of NaClO is 1 (0.1-0.15): 0.05-0.1): 0.1-0.15; and/or
Adjusting the pH value by adopting NaOH solution; and/or
The pore diameter of the filtering membrane is 200-500nm.
9. The method according to claim 8, wherein the concentration of the NaOH solution is 0.05 to 0.2mol/L.
10. The production method according to any one of claims 4 to 6, wherein the esterification reaction comprises: dispersing the obtained chemically modified nano cellulose in N, N-dimethylacetamide, mixing with triethylamine, heating to 80-100 ℃, and adding an esterification reagent to perform esterification reaction.
11. The preparation method according to claim 10, wherein the weight ratio of the chemically modified nanocellulose to the N, N-dimethylacetamide is 1 (25-100); and/or
The weight ratio of the chemical modified nano cellulose to the triethylamine to the esterifying reagent is 1 (0.1-0.8) (0.5-1); and/or
The esterification conditions include: heating to 100-120 ℃, and reacting for 4-8 h at constant temperature; and/or
The esterification reaction is followed by centrifugation and washing of the product.
12. The method of any one of claims 4-6, wherein the nanocellulose material is plant nanocellulose; and/or
The particle size of the nano cellulose raw material is 50-500 nm.
13. The method of claim 12, wherein the nanocellulose raw material is lignocellulose and/or cotton nanocellulose.
14. Use of the modified nanocellulose of any of claims 1-3 or the modified nanocellulose of any of claims 4-13 in heavy oil reservoir recovery, enhanced oil recovery in oil fields.
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