CN110746943A - Non-fluorine silicon supercritical carbon dioxide fluid tackifier, preparation method and application - Google Patents
Non-fluorine silicon supercritical carbon dioxide fluid tackifier, preparation method and application Download PDFInfo
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- CN110746943A CN110746943A CN201911006084.9A CN201911006084A CN110746943A CN 110746943 A CN110746943 A CN 110746943A CN 201911006084 A CN201911006084 A CN 201911006084A CN 110746943 A CN110746943 A CN 110746943A
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- carbon dioxide
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- supercritical carbon
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- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention belongs to the technical field of tackifying agents, and discloses a non-fluorinated silicone supercritical carbon dioxide fluid tackifying agent, a preparation method and application thereof, wherein cyclodextrin and derivatives thereof are used as main compounds, and alkyl, aryl or ether compounds are used as guest compounds; synthesizing a polymer having suitable backbone units and carbon dioxide-philic units; respectively grafting a host unit and a guest unit to obtain a host polymer and a guest polymer; self-assembling the host polymer and the guest polymer to synthesize the host polymer and the guest polymer to obtain the non-fluorine-silicon supercritical carbon dioxide fluid tackifier. The invention can convert greenhouse effect gas CO into CO2The resource is utilized, the waste is changed into valuable, and economy is created; the comprehensive benefits of oil and gas drilling development can be improved, including loss reduction by increasing drilling speed, oil and gas production increase by protecting the reservoir and increasing oil and gas recovery. Therefore, the expected economic and social benefits after industrialization are considerable.
Description
Technical Field
The invention belongs to the technical field of tackifying agents, and particularly relates to a non-fluorosilicone supercritical carbon dioxide fluid tackifying agent, a preparation method and application.
Background
Currently, the closest prior art: with the rapid increase of the demand of national economy on oil and gas resources and the implementation of new national oil and gas energy strategies, China is increasing the exploration and development strength of unconventional oil and gas resources such as compact oil and gas reservoirs, shale gas, coal bed gas, heavy oil and the like. The supercritical carbon dioxide fluid has the characteristics of density close to water, diffusion coefficient larger than water, surface tension close to zero, strong solvation capacity and the like, can obviously improve the mechanical drilling speed, has no damage and pollution to a reservoir, is easy to enter capillary pores of the reservoir to displace and replace methane, has strong flowback capacity and can dissolve heavy oil components, and is considered as the most suitable working fluid for yield increasing technologies such as a continuous pipe drilling technology, a shale gas reservoir fracturing technology, a compact oil and gas reservoir fracturing technology, heavy oil displacement even a conventional sandstone reservoir and the like by experts at home and abroad.
2018, CO in China2Annual emissions reach 100 million tons, of which about 15% come from gas field exploitation, but a large amount of CO2Is not recycled, one of the main reasons being the recovered CO2The method has no market, direct burial and no economic value, and cannot stimulate the enthusiasm of recovery enterprises. If the method can be successfully applied to oil field construction such as oil and gas drilling, fracturing, displacement and the likeA large market not only promoting CO2The rapid development of the recovery industry can improve the development benefit of the oil and gas field and simultaneously lead CO to be used2Buried underground, realizes the emission reduction and the efficiency improvement and the green development of fossil energy.
But in the presence of supercritical CO2① has technical bottlenecks that the annular rock carrying capacity in drilling and the sand carrying capacity in fracturing need to be enhanced due to low viscosity of fluid used for oil and gas drilling and production, and that 'fingering' is easily caused in displacement ② CO2Has greenhouse effect, and needs to be added with a recycling device in construction. For supercritical CO2The technical problems of low fluid viscosity and insufficient rock carrying and sand suspending capabilities are solved by foreign experts, and corresponding measures are developed and successively screened out to be used for supercritical CO2Fluid-viscosifying shear-promoting high molecular weight polymers, fluorocarbon surfactants, and carbo-silicone surfactants. However, these two types of supercritical CO2The viscosity increasing and cutting ability of the fluid viscosity increasing and cutting agent needs to be further improved, and the high molecular polymer is not beneficial to improving the mechanical drilling speed, has large damage to a reservoir stratum and is not beneficial to CO2The separation and recovery are realized, the dosage of the fluorocarbon and carbon silicon surfactants is large, the cost is high, and the industrial use value is not realized.
The difficulty in viscosity enhancement of supercritical carbon dioxide fluids is that most polymers and surfactants (especially ionic surfactants) have very low solubility in supercritical carbon dioxide due to their weak van der waals forces and low dielectric constant, and cannot form network structures in supercritical carbon dioxide fluids. The polar cosurfactant can make polar compound in nonpolar supercritical CO2The solubility is increased, and the interaction between the surfactant and the cosolvent plays an important role, especially the hydrogen bond formed between the surfactant and the cosolvent can obviously improve the solubility. When CO is present2When used as a continuous phase in a dispersion system, the surfactant is required to be in supercritical CO2Has a certain solubility, and the tail part of the nano-silver-nickel composite material can be sufficiently solvated by carbon dioxide so as to reduce the interaction between liquid drops. Surfactant in supercritical CO2Phase state studies in the system showed that at the tail of the surfactantIncorporating a low solubility parameter, low polarity or electron donating Lewis basic group (CO)2Is a weak Lewis acid) to improve its solubility. Carbon dioxide-philic functional groups containing these properties include siloxanes, perfluorinated ethers and perfluoroalkanes, tertiary amines, fatty ethers, acetylenic alcohols and acetylenic diols, and the like.
Therefore, the research on the development and the action mechanism of the supercritical carbon dioxide fluid tackifier which has strong tackifying and shearing improving capability, small damage to a reservoir stratum, contribution to improving the mechanical drilling speed and low price has important theoretical and technical values on the aspects of applying the supercritical carbon dioxide to underbalanced drilling of a continuous pipe, fracturing of an oil-gas layer (particularly shale gas and compact oil-gas reservoir), carbon dioxide flooding and the like.
In conclusion, the research and development of the current supercritical carbon dioxide fluid tackifier still have the following problems that the solubility and the tackifying performance of ① non-fluorinated silicone polymer in the supercritical carbon dioxide fluid are in outstanding contradiction, the dosage of ② fluorinated silicone polymer, surfactant and the like is too large, the price is high, the application prospect is not good, the non-covalent interaction between the polymers reported by ③ is weak, the tackifying effect is poor, and the viscosity of the thickened supercritical carbon dioxide fluid reported abroad at present is not higher than 5mPa.s, so that the requirements of the supercritical carbon dioxide fluid for coiled tubing drilling, sand fracturing and efficient displacement of unconventional oil and gas reservoirs cannot be met.
In summary, the problems of the prior art are as follows:
(1) the prior supercritical carbon dioxide fluid tackifier has the outstanding contradiction between the solubility and the tackifying performance of non-fluorinated silicone high polymer in the supercritical carbon dioxide fluid.
(2) The prior supercritical carbon dioxide fluid tackifier has large dosage of fluorine-containing silicon polymer, surfactant and the like, high price and poor application prospect.
(3) The existing supercritical carbon dioxide fluid tackifier has the problems that the non-covalent interaction between polymers is weak, and the tackifying effect is poor; the viscosity of the thickened supercritical carbon dioxide fluid is not higher than 5mPa.s at present, and the requirement of the supercritical carbon dioxide fluid for coiled tubing drilling, sand fracturing of unconventional oil and gas reservoirs and efficient displacement cannot be met.
The difficulty of solving the technical problems is that ① non-fluorine silicon type polymer molecular structure which can be dissolved in supercritical carbon dioxide fluid is designed and synthesized, ② polymer which can be dissolved in supercritical carbon dioxide fluid host and guest are optimized, and ③ host and guest assembling and action strength control method.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a non-fluorine silicon supercritical carbon dioxide fluid tackifier, a preparation method and application thereof.
The invention is realized in such a way that the non-fluorine silicon supercritical carbon dioxide fluid tackifier takes cyclodextrin and derivatives thereof as main compounds and takes alkyl, aryl or ether compounds as guest compounds. The molar ratio of the host compound to the guest compound is 1: 1.
The host compound adopts polystyrene- β -cyclodextrin, and the guest compound adopts polyethylene oxide-ferrocene.
Further, β -cyclodextrin dimer was used as the host compound, and adamantane was used as the guest compound.
Further, the main compound adopts β -CD modified chitosan, and the guest compound adopts ferrocene modified polyethylene glycol.
Further, the host compound is a linear copolymer synthesized by β -CD and epichlorohydrin, and the guest compound is a copolymer of ferrocene and polyethylene glycol containing polymerizable double bonds.
Further, the host compound is methyl β -CD, and the guest compound is polypropylene glycol.
Another objective of the present invention is to provide a method for preparing a non-fluorinated silicone supercritical carbon dioxide fluid tackifier, wherein the method for preparing a non-fluorinated silicone supercritical carbon dioxide fluid tackifier comprises the following steps:
a first step of synthesizing a polymer having a suitable backbone unit and a carbon dioxide-philic unit;
and secondly, respectively grafting the host unit and the guest unit to respectively obtain a host polymer and a guest polymer.
And thirdly, self-assembling the host polymer and the guest polymer to synthesize the host polymer and the guest polymer, thereby obtaining the non-fluorine-silicon supercritical carbon dioxide fluid tackifier.
Further, the synthesis method of the host polymer comprises the following steps:
dissolving 10g of β -CD in 15mL of NaOH aqueous solution, stirring for 3h until the solution is clear, adding 2mL of toluene, continuing stirring for 2h, and adding 1.85g of epichlorohydrin;
after 3.5h, the reaction is ended, the solution is completely poured into 200mL of isopropanol at room temperature for precipitation, and the precipitate is dissolved in water;
adjusting pH to neutral with hydrochloric acid, placing into dialysis bag, dialyzing in water for 3 days, changing water every 12h for 1 time, and vacuum drying to obtain main polymers A and B.
Further, the synthesis method of the host-guest polymer comprises the following steps:
respectively dissolving the synthesized main polymers A and B in distilled water by a saturated aqueous solution method to form saturated solutions, and cooling to 25 ℃;
according to the molar ratio of the host to the guest of 1:1, weighing polypropylene glycol; respectively slowly adding polypropylene glycol into the saturated solution of the main polymer A and the saturated solution of the main polymer B at 60 ℃, and stirring for 3 hours at constant temperature; cooling the stirred solution to room temperature, and refrigerating the solution at 4-5 ℃ for 24 hours;
filtering out solid by reduced pressure suction filtration, and drying the solid at 40 ℃ for 6 h; the final product is a milky viscous substance which is a linear host-guest polymer A-PPG and an irregular host-guest polymer B-PPG.
The invention also aims to provide an application of the non-fluorinated silicone supercritical carbon dioxide fluid tackifier in coiled tubing drilling.
The invention also aims to provide an application of the non-fluorinated silicone supercritical carbon dioxide fluid tackifier in sand fracturing of unconventional oil and gas reservoirs.
In summary, the advantages and positive effects of the invention are:
aiming at the defects of poor tackifying effect, large using amount, high cost and the like of the prior fluorosilicone polymer type supercritical carbon dioxide tackifier, the invention develops the efficient non-fluorosilicone supercritical carbon dioxide fluid tackifier based on the effects of a host and an object, reveals the action mechanism of the tackifier at multiple angles, forms an efficient supercritical carbon dioxide rheological property regulation chemical method, and lays theoretical and material foundation for the application of supercritical carbon dioxide in coiled tubing drilling, unconventional oil and gas reservoir fracturing, displacement and natural gas hydrate exploitation.
The invention also considers the focus problems in the development of oil and gas fields, such as efficient drilling, oil and gas recovery ratio improvement, reservoir protection, environmental protection, natural gas hydrate exploitation and the like, and the research result provides technical guarantee for efficient and green development of oil and gas resources.
Currently, 6% silicon-based polymer and toluene can increase the viscosity of supercritical carbon dioxide fluid from 0.04mpa.s to 3.48mpa.s, and 4% fluoropolymer can increase the viscosity to 0.22 mpa.s. The viscosity of the supercritical carbon dioxide can be increased by 10% by the tackifier of the invention2And the magnitude order is more than that of the supercritical carbon dioxide fluid, so that the supercritical carbon dioxide fluid is promoted to be industrially utilized as the working fluid for petroleum engineering construction. The synthesis process, the research of action mechanism and the formed chemical method for regulating and controlling the rheological property of the supercritical carbon dioxide fluid tackifier based on the host-object action provide a new idea for the resource utilization of the carbon dioxide and provide a new way for reducing the greenhouse effect and strengthening the environmental protection.
With the enhancement of environmental awareness and the fluctuation of international oil and gas prices, how to 'environment-friendly, safe, efficient and low-cost' drill and exploit oil and gas resources is the current and even long-term strategic target and technical requirement of the oil industry. And at present, the fields of oil and gas exploration, forward ocean deep water development, deep stratum, unconventional oil and gas resources and the like are expanded. The supercritical carbon dioxide can be used for the aspects of coiled tubing underbalanced drilling, oil-gas reservoir (particularly shale gas and compact oil-gas reservoir) fracturing, carbon dioxide flooding, natural gas hydrate exploitation and the like, and is also beneficial to environmental protection. Therefore, the oil and gas field has wide push in home and abroadHas wide application prospect. On the one hand, the greenhouse effect gas CO can be used2The resource is utilized, the waste is changed into valuable, and economy is created; on the other hand, the comprehensive benefits of oil and gas drilling development can be improved, including loss reduction by increasing the drilling speed, and oil and gas production increase by protecting the reservoir and increasing the oil and gas recovery rate. Therefore, the expected economic and social benefits after industrialization are considerable.
Drawings
Fig. 1 is a flow chart of a method for preparing a non-fluorinated silicone supercritical carbon dioxide fluid tackifier according to an embodiment of the present invention.
Fig. 2 is a schematic diagram of a synthetic route of a non-fluorinated silicone supercritical carbon dioxide fluid tackifier according to an embodiment of the present invention.
Fig. 3 is a schematic diagram of host-guest interactions of tackifier molecules in a supercritical carbon dioxide fluid according to an embodiment of the present invention.
FIG. 4 is a schematic diagram of the synthesis of host-guest polymers of polystyrene- β -cyclodextrin and polyethylene oxide-ferrocene provided by the embodiment of the present invention.
FIG. 5 is a schematic diagram of the synthesis of β -cyclodextrin dimer and adamantane host-guest polymer provided by the examples of the present invention.
FIG. 6 is a schematic diagram of the synthesis of β -CD modified chitosan and ferrocene modified polyethylene glycol host-guest polymer provided in the embodiment of the present invention.
FIG. 7 is a schematic diagram of the synthesis of β -CD and epichlorohydrin linear copolymer provided by the embodiment of the invention.
FIG. 8 is a schematic diagram of the synthesis of ferrocene and polyethylene glycol copolymer provided by the embodiment of the present invention.
FIG. 9 is a schematic diagram of the synthesis of host-guest polymers of methyl β -CD and polypropylene glycol according to the embodiment of the present invention.
FIG. 10 is a schematic diagram of the synthesis of the host polymer, 21- β -cyclodextrin, 22-epichlorohydrin, 23-linear copolymer (A), and 24-random copolymer (B), according to the embodiment of the present invention.
Figure 11 is a block diagram of a cyclodextrin provided in accordance with an embodiment of the present invention.
FIG. 12 is a block diagram of β -cyclodextrin provided by an embodiment of the present invention.
FIG. 13 is a dew point pressure plot of CO2 for three cyclodextrins provided by an example of the present invention, testing cyclodextrins for CO2Solubility of (b) in (c), experiment temperature: 298K (solid line), 313K (dotted line), experiment articles: α -cyclodextrin (▲, Mn ═ 1729), β -cyclodextrin (◆, Mn ═ 2017), γ -cyclodextrin (■, Mn ═ 2305).
FIG. 14 is a process for synthesizing host and guest polymers by a saturated aqueous solution method according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a non-fluorinated silicone supercritical carbon dioxide fluid tackifier, a preparation method and application thereof, and the invention is described in detail with reference to the accompanying drawings 1 to 14.
The non-fluorinated silicone supercritical carbon dioxide fluid tackifier provided by the embodiment of the invention takes cyclodextrin and derivatives thereof as main compounds and takes alkyl, aryl or ether compounds as guest compounds. The molar ratio of the host compound to the guest compound is 1: 1.
As shown in fig. 1, a method for preparing a non-fluorinated silicone supercritical carbon dioxide fluid tackifier provided by an embodiment of the present invention includes the following steps:
s101: a polymer having suitable backbone units and carbon dioxide-philic units is synthesized.
S102: and respectively grafting the host unit and the guest unit to obtain a host polymer and a guest polymer.
S103: the host polymer and the guest polymer are self-assembled to synthesize the host polymer and the guest polymer, and the non-fluorine-silicon supercritical carbon dioxide fluid tackifier is obtained.
The technical solution of the present invention is further described below with reference to experiments.
Binding of monomers in ScCO2Solubility in fluids and molecular structure, interactions, etc., to be CO-philic2The monomer β -cyclodextrin and polypropylene glycol are used for designing ScCO2The host molecule is β -CD and epichlorohydrin linear copolymer or irregular copolymer, and the object molecule is polypropylene glycol.
Selecting and CO2The compound with high affinity and good flexibility is used as a main body, and cyclodextrin is selected primarily as the main body compound through analysis.
Cyclodextrin (CD for short) generally contains 6-12D-glucopyranose units, the molecules of the cyclodextrin are wide at the upper part and narrow at the lower part, two ends of the cyclodextrin are opened, the cyclodextrin is a hollow cylindrical object, all hydrocarbon groups are distributed outside the molecules, so that the cyclodextrin is hydrophobic in a cavity and hydrophilic outside the cavity, can form an inclusion compound with guest molecules, and is a good load material, α -cyclodextrin (α -CD), β -cyclodextrin (β -CD) and gamma-cyclodextrin (gamma-CD) have the property parameters shown in table 1, the structure is shown in figure 11, and the specific structure of β -cyclodextrin is shown in figure 12.
TABLE 1 Cyclodextrin Property parameters
Uses α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin in CO2The common method for measuring the solubility of highly carbon dioxide-philic oligomeric and polymeric materials, α -cyclodextrin, gamma-cyclodextrin, gave a clear, free-flowing liquid phase in the two-phase region β -cyclodextrin is more viscous, consistent with its high dissolution pressure relative to the other two cyclodextrins.
The cavity of a-CD is small, when the complex is used as a carrier, some guest molecules are difficult to enter the cavity and only can be included with the guest molecules with small sizes, the cavity of gamma-CD is too large, the guest molecules are easy to dissociate after entering the cavity, the inclusion compound is unstable and only can be used for including some guest molecules with large sizes, and the cavity of β -CD is moderate in size and can form a stable inclusion compound with the guest molecules, so β -CD is selected as a monomer for synthesizing a host polymer.
The particular structure of the cyclodextrin molecule gives it some unique physical and chemical properties. The cavity of the cyclodextrin has certain rigidity due to the action of a hydrogen bond network between edges, so that molecules with the size matched with that of the cavity, such as benzene and naphthalene, can selectively form a stable compound to play a role in molecular recognition.
Natural cyclodextrin is insoluble in ScCO2However, the functional β -cyclodextrin, polyether-carbonate, polyvinyl acetate with higher solubility and the addition of acetic acid side chain can improve the performance of the polymer in ScCO2Solubility in (c). The 1-octylamine is subjected to ring opening reaction of amino and glucolactone, and then is subjected to peracetylation reaction with acetic anhydride to prepare the fully acetylated amine which is easily soluble in CO at 298K2Acetylation of all hydroxyl groups present on native β -cyclodextrin greatly increases the solubility of macromolecules.
When cyclodextrin macromolecules are peracetylated, the cavity is rather distorted and it is difficult to accommodate a guest molecule. The cavity was found to be self-closing at the broad edge, which was associated with a conformational change of one glucose unit (from chair to deflection), pushing some of the acetyl groups into the cavity. Self-closing of the narrow edge was also observed, but over a smaller range and for a shorter time.
The main body is designed to be a long-chain molecule or a ring-shaped molecule with a plurality of (at least 3-5) cyclodextrin molecules. In addition, the hydroxyl group of cyclodextrin can be used as a nucleophilic reagent under certain conditions to activate or intervene certain bonds of the guest molecule, thereby playing a catalytic role.
Selecting and CO2The compound has high affinity and can perform host-guest action with a host compound.
Molecular based on ScCO2The host-guest polymer of the cyclodextrin β -cyclodextrin is taken as the single molecule of the host molecule, and the host-guest polymer is researched and researched5 schemes of supramolecular polymers formed by the interaction between a host and a guest by taking cyclodextrin and derivatives thereof as the host are summarized, and the schemes are analyzed and compared.
Scheme 1, synthesizing a host-guest polymer by taking polystyrene- β -cyclodextrin as a host and polyethylene oxide-ferrocene as a guest, and testing shows that the host and the guest in the scheme are ScCO2All of them have better solubility.
Scheme 2, the host is β -cyclodextrin dimer, and the guest is adamantane.
Scheme 3, β -CD modified chitosan is used as a host, ferrocene modified polyethylene glycol is used as a guest, the chitosan is insoluble in ScCO2 fluid, but the solubility of the guest polyethylene glycol in ScCO2 fluid is higher.
Scheme 4, the linear copolymer synthesized from β -CD and epichlorohydrin is taken as a main body, and the ferrocene and polyethylene glycol copolymer containing polymerizable double bonds is taken as an object for synthesis.
The object is a copolymer which can enter a cyclodextrin cavity, the size of the phenyl is consistent with that of the cavity from the viewpoint of the size of the cavity, and in the research, benzoic acid (BEA) is taken as a main component, and in ScCO2According to the extraction technique, the BEA starts extraction at 40 ℃ and 80bar, the solubility of which increases with the increase in pressure, but attention is paid to the phenomenon of "reverse dissolution" of benzoic acid, the reaction temperature is 60 ℃, the reaction time is 120min, the inclusion rate is the greatest at a charge ratio n (β cyclodextrin): n (benzoic acid) ═ 1.0: 2.0.
The guest should have at least two monomers, a portion of which can penetrate into the cyclodextrin cavity and a portion of which is soluble in supercritical CO2. In aqueous media, the driving force for host-guest recognition is usually hydrophilic/hydrophobicBalance of sexuality. Applying this mechanism to SCCO2In, the host-guest identification should be parent CO2Hydrophobic CO2Balancing of (1). Thus, a synthetic host with multiple cyclodextrins should be CO-philic2Structure, while in the synthesized object, the structure entering into the cyclodextrin cavity should be relatively hydrophobic to CO2The portion of the structure not entering the cavity is preferably relatively CO-philic2And (5) structure.
Methyl- β -cyclodextrin (MBCD) has different clathration effects on two polypropylene glycols (PPG), a plurality of MBCD rings can penetrate to a PPG chain in a solvent-free state to form a cylindrical clathrate compound, and the clathration degree between the MBCD and the PPG can be further increased after the hydroxyl groups at both ends of the PPG chain are changed into acrylate groups.
The main body synthesis method comprises the following steps of dissolving 10g of β -CD (8.8mmol) in 15mL of aqueous solution of NaOH (15%), stirring for 3h until the solution is clear, adding 2mL of toluene (8.8mmol) (no toluene to obtain irregular polymer (B)), continuing stirring for 2h, adding 1.85g of epoxy chloropropane (20mmol), finishing the reaction after 3.5h, pouring all the solution into 200mL of isopropanol at room temperature (-15 ℃) to precipitate, dissolving the precipitate in water, adjusting the pH to be neutral by using hydrochloric acid (1mol/L), then putting the solution into a dialysis bag (MWCO 8000-14000), dialyzing in water for 3 days, changing water every 12h for 1 time, and then carrying out vacuum drying to obtain final products A and B, wherein the final products are white crystalline powder.
The synthesis of host and guest polymers generally does not require a solvent. For sublimable materials, powdered crystalline CD can be mixed with powdered guest to make CD inclusions. But for materials that do not readily sublime, water or other materials are required as a solvent. Most studies on inclusion complexation of cyclodextrins have been performed in aqueous solutions, however, there have been some reports on organic solvent-water mixed systems or pure organic solvents. At present, many experimental results show that the solvent can influence the inclusion coordination ability of cyclodextrin on guest molecules, and can change the inclusion coordination mode between hosts and guests in some cases.
In cyclodextrin supramolecular systems, as the polarity of the solvent decreases, a decrease in the stability of the complexes formed between the host and the guest is often observed. The stability of the host-guest complex is also affected by the pH of the solvent. The cyclodextrin polymer forming the inclusion compound is obtained by forming the inclusion compound between the polymer and cyclodextrin or a plurality of cyclodextrin arm chain steric structures through complexation. The polymer has unique structure and performance superior to cyclodextrin and polymer, and can raise the solubility of guest molecule obviously. The subject and object synthesis method comprises a saturated aqueous solution method, an ultrasonic method, a grinding method, a colloid grinding method, a freeze drying method and a spray drying method, wherein the saturated aqueous solution method with higher inclusion rate is selected.
The saturated aqueous solution method comprises the steps of dissolving a synthesized β -CD host in distilled water to form a saturated solution, cooling to 25 ℃, weighing polypropylene glycol according to the ratio of the host to the guest being 1:1, respectively and slowly adding the polypropylene glycol into the saturated solution of the host (A) and the saturated solution of the guest being (B) at 60 ℃, stirring at constant temperature for 3h, cooling the stirred solution to room temperature, refrigerating at 4-5 ℃ for 24h, filtering out solids by using reduced pressure suction filtration, drying the solids at 40 ℃ for 6h, and finally obtaining milky viscous substances (a linear host-guest polymer A-PPG and an irregular host-guest polymer B-PPG) as shown in figure 14.
1. Establishment of supercritical carbon dioxide fluid performance test method
(1) Method for establishing supercritical carbon dioxide fluid viscosity and shear force test
The method comprises the steps of improving a test part of an autoclave body of a drilling fluid natural gas hydrate inhibition evaluation simulation device independently developed by a research laboratory, increasing a heating system, enhancing the sensitivity of a torque tester, and calculating the viscosity and the shear force of supercritical carbon dioxide fluid by testing torque values at different shear rates.
(2) Method for establishing test of solubility of supercritical carbon dioxide fluid to compound
Designing a stainless steel high-temperature autoclave with a visual window, and testing the dissolution characteristics of the compound at different temperatures and pressures by a cloud point pressure method. The principle is as follows: if the compound is soluble in the supercritical carbon dioxide fluid, at a certain combination of temperature and pressure, the test system will change from a turbid state to a clear state, obtaining a cloud point pressure for the compound at that temperature; if the compound is not soluble in the supercritical carbon dioxide fluid, the test system is always in a cloudy state, and there is no cloud point pressure.
2. Synthesis and mechanism of supercritical carbon dioxide fluid tackifier based on host-guest polymer
(1) Host-guest compound screening with interaction in supercritical carbon dioxide fluid
The cyclodextrin and the derivatives thereof are used as host compounds, alkyl, aryl or ether compounds are used as guest compounds, and the host compounds and the guest compounds with better interaction are screened out through the change of the solubility before and after the two compounds are mixed, and are used as reactants for the synthesis of the tackifier for later use.
(2) Synthesis and characterization of supercritical carbon dioxide fluid tackifier
The synthetic route of the adhesion promoter is shown in FIG. 2. Synthesizing a polymer with a proper framework unit and a carbon dioxide-philic unit, grafting a host unit and a guest unit respectively on the basis of the polymer, obtaining a host polymer and a guest polymer respectively, and self-assembling the host polymer and the guest polymer to form the host-guest polymer. In the reaction process, the molecular weight and the molecular structure of the polymer are controlled by controlling the reaction conditions and the addition of reactants, so that the solubility of the product in the supercritical carbon dioxide and the strength of the interaction between the host polymer and the guest polymer are controlled. The structure and purity of the product of each step of reaction are represented by analytical means such as gel permeation chromatography, nuclear magnetic resonance, infrared spectrum and element analysis.
(3) Supercritical carbon dioxide fluid tackifier action mechanism analysis
Adding the tackifier into the supercritical carbon dioxide fluid, testing the viscosity and the shear force of the system at different temperatures and pressures, and simultaneously, investigating the influence of the molecular structure and the concentration of the tackifier on the rheological property of the system. During the regulation process, it is presumed that the adhesion promoter molecules will have host-guest interactions in the supercritical carbon dioxide fluid as shown in fig. 3.
The evaluation data of the tackifying effect of the tackifier is explained by researching the relationship among the temperature, the molecular structure of the tackifier, the dissolving performance of the tackifier and the aggregation behavior, and the rheological regulation mechanism of the tackifier is discussed.
① characterization of tackifier dissolution Properties
And testing the solubility of the polymers with different framework units, carbon dioxide-philic units and host-guest units in supercritical carbon dioxide at the same temperature to establish the relationship between the polymer structure and the solubility property of the polymer. Meanwhile, the solubility of the polymer in the supercritical carbon dioxide is tested along with the change of the temperature, and key factors influencing the solubility of the polymer are found out.
② host-guest interactions
Synthesizing a polymer which is similar to the molecular weight and the molecular structure of the tackifier but does not contain a host-guest unit as a comparison sample, researching the influence of different polymers on the viscosity and the shear force of supercritical carbon dioxide, and qualitatively analyzing the relationship between the content and the proportion of the host-guest unit and the interaction of the host and the guest. Meanwhile, the grid structure form of the tackifier and the interaction sites of the host and the object are inspected through test methods such as an atomic force microscope, a transmission electron microscope, environmental scanning electron microscope analysis and the like.
3. Evaluation of Performance of densified supercritical carbon dioxide fluid
(1) Reservoir protection performance evaluation
And evaluating the damage to the reservoir through a high-pressure core displacement experiment.
(2) Evaluation and optimization of rock-carrying sand-suspending capacity of thickened supercritical carbon dioxide fluid
A research room supercritical carbon dioxide drilling fluid circulation simulation experiment system is adopted to experimentally evaluate the rock-carrying and sand-suspending capacity of the thickened supercritical carbon dioxide fluid under different temperature and pressure conditions and well inclination, and the optimal rock-carrying and sand-suspending capacity is obtained through the optimization of parameters such as injection flow, pressure and the like.
The invention discloses an action mechanism of a tackifier based on supercritical carbon dioxide fluid tackifying effect evaluation at multiple angles, has important theoretical guidance effect on supercritical carbon dioxide rheological control and related research, and has the key points that: the characterization of the dissolving performance of the tackifier in the supercritical carbon dioxide fluid and the influence factors thereof. And (3) the interaction between the subject and the object, including the relationship between the content and the proportion of the subject and the object units and the interaction between the subject and the object units, the testing and the characterization of the grid structure form of the tackifier and the analysis of the interaction sites of the subject and the object.
Firstly, establishing a method for testing the viscosity and the shear force of a supercritical carbon dioxide fluid and a method for testing the solubility of the supercritical carbon dioxide fluid to a compound; based on molecular structure design, synthesizing a polymer with a proper framework unit and a carbon dioxide-philic unit, preferably and grafting a host and an object to obtain a host polymer and an object polymer, further optimizing the assembly conditions of the host and the object polymer, and developing a high-efficiency non-fluorinated silicone supercritical carbon dioxide fluid tackifier; the structure of the material is represented by gel chromatography, mass spectrometry, nuclear magnetic resonance, infrared spectroscopy, element analysis and the like, and the action mechanism of the material is revealed by the researches of dissolution characteristic test, grid structure form, subject-object interaction site analysis and the like; the method is characterized in that the harmfulness of the viscous supercritical carbon dioxide fluid to a reservoir is evaluated by a high-pressure core displacement experiment means, and the viscous supercritical carbon dioxide fluid is evaluated and optimized under different temperature and pressure conditions and well deviation by adopting a supercritical carbon dioxide drilling fluid circulation simulation experiment system. Finally, a feasible and efficient chemical regulation and control method is formed.
Analyzing the action mechanism of the supercritical carbon dioxide tackifier: the molecular structure and concentration of the supercritical carbon dioxide viscosifier have influence on the rheological property of the system, and during the regulation and control process, the viscosifier molecules have host-guest interaction in the supercritical carbon dioxide fluid as shown in figure 3. The evaluation data of the effect of the tackifier is explained through the relationship among the temperature, the molecular structure of the tackifier, the dissolving performance of the tackifier and the aggregation behavior, and the rheological regulation mechanism of the tackifier is discussed.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a non-fluorosilicone supercritical carbon dioxide fluid tackifier is characterized by comprising the following steps:
a first step of synthesizing a polymer having a suitable backbone unit and a carbon dioxide-philic unit;
secondly, respectively grafting a host unit and an object unit to respectively obtain a host polymer and an object polymer;
and thirdly, self-assembling the host polymer and the guest polymer to synthesize the host polymer and the guest polymer, thereby obtaining the non-fluorine-silicon supercritical carbon dioxide fluid tackifier.
2. The method of claim 1, wherein the second step of synthesizing the host polymer comprises:
dissolving 10g of β -CD in 15mL of NaOH aqueous solution, stirring for 3h until the solution is clear, adding 2mL of toluene, continuing stirring for 2h, and adding 1.85g of epichlorohydrin;
after 3.5h, the reaction is ended, the solution is completely poured into 200mL of isopropanol at room temperature for precipitation, and the precipitate is dissolved in water;
adjusting pH to neutral with hydrochloric acid, placing into dialysis bag, dialyzing in water for 3 days, changing water every 12h for 1 time, and vacuum drying to obtain main polymers A and B;
the third step, the synthesis method of the host-guest polymer adopts a saturated aqueous solution method, and comprises the following steps:
respectively dissolving the synthesized main polymers A and B in distilled water to form saturated solution, and cooling to 25 ℃;
according to the molar ratio of the host to the guest of 1:1, weighing polypropylene glycol; slowly adding polypropylene glycol into the saturated solution of the main polymer A and the saturated solution of the main polymer B respectively at 60 ℃, and stirring for 3 hours at constant temperature; cooling the stirred solution to room temperature, and refrigerating the solution at 4-5 ℃ for 24 hours;
filtering out solid by reduced pressure suction filtration, and drying the solid at 40 ℃ for 6 h; the final product is a milky viscous substance which is a linear host-guest polymer A-PPG and an irregular host-guest polymer B-PPG.
3. The non-fluorosilicone supercritical carbon dioxide fluid tackifier is characterized in that cyclodextrin and derivatives thereof are used as main compounds, and alkyl, aryl or ether compounds are used as guest compounds; the molar ratio of the host compound to the guest compound is 1: 1.
4. The non-fluorosilicone supercritical carbon dioxide fluid tackifier of claim 3, wherein the host compound is polystyrene- β -cyclodextrin and the guest compound is polyethylene oxide-ferrocene.
5. The non-fluorinated silicone supercritical carbon dioxide fluid viscosifier of claim 3, in which said host compound comprises β -cyclodextrin dimer and said guest compound comprises adamantane.
6. The non-fluorosilicone supercritical carbon dioxide fluid tackifier of claim 3, wherein the host compound is β -CD modified chitosan, and the guest compound is ferrocene modified polyethylene glycol.
7. The non-fluorosilicone supercritical carbon dioxide fluid tackifier of claim 3, wherein the host compound is a linear copolymer synthesized from β -CD and epichlorohydrin, and the guest compound is a copolymer of ferrocene and polyethylene glycol containing a polymerizable double bond.
8. The non-fluorosilicone supercritical carbon dioxide fluid viscosifier of claim 3, wherein said host compound comprises methyl β -CD and said guest compound comprises polypropylene glycol.
9. Use of a non-fluorosilicone supercritical carbon dioxide fluid viscosifier according to any one of claims 1 to 7 in coiled tubing drilling.
10. Use of a non-fluorosilicone supercritical carbon dioxide fluid viscosifier according to any one of claims 1 to 7 in sand fracturing of unconventional hydrocarbon reservoirs.
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