CN113801645B - Thickened oil viscosity reducing agent, preparation method thereof and thickened oil viscosity reducing method - Google Patents
Thickened oil viscosity reducing agent, preparation method thereof and thickened oil viscosity reducing method Download PDFInfo
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 18
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 16
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 244000226021 Anacardium occidentale Species 0.000 claims abstract description 16
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 16
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000020226 cashew nut Nutrition 0.000 claims abstract description 16
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 15
- 230000000149 penetrating effect Effects 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003921 oil Substances 0.000 claims description 145
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000000295 fuel oil Substances 0.000 claims description 7
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 3
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N octanoic acid methyl ester Natural products CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- YYZUSRORWSJGET-UHFFFAOYSA-N octanoic acid ethyl ester Natural products CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 claims description 2
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 30
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000005166 2-hydroxybenzoic acids Chemical class 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000008162 cooking oil Substances 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
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- 230000007774 longterm Effects 0.000 description 2
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- 229920002866 paraformaldehyde Polymers 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
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- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000002283 diesel fuel Substances 0.000 description 1
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- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- XOCNYZFAMHDXJK-UHFFFAOYSA-N methyl 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound COC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F XOCNYZFAMHDXJK-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- 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
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
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- 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
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- 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
- C09K8/588—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 polymers
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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- Mining & Mineral Resources (AREA)
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Abstract
The invention relates to the technical field of thickened oil viscosity reduction, and discloses a thickened oil viscosity reducing agent, a preparation method thereof and a thickened oil viscosity reducing method. The thickened oil viscosity reducer contains a biological phenol-aldehyde oligomer and a penetrating agent, the biological phenol-aldehyde oligomer is prepared by reacting cardanol and/or cashew nut shell oil with aldehydes in the presence of a catalyst, and the penetrating agent is a fluorocarbon surfactant. The thickened oil viscosity reducing agent disclosed by the invention is used for reducing the viscosity of thickened oil, so that the dynamic viscosity of the thickened oil can be effectively reduced, the thickened oil can be kept stable for a long time under a high-temperature condition after viscosity reduction, and the viscosity reducing agent has the characteristics of low use concentration, low cost, simplicity in preparation and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of thickened oil viscosity reduction, in particular to a thickened oil viscosity reducing agent, a preparation method thereof and a thickened oil viscosity reducing method.
Background
With the increasing demand of petroleum and the continuous consumption of common crude oil, the production of thick oil becomes more and more important. The thickened oil resource is abundant in storage capacity in the world, is a huge potential resource, and plays an increasingly important role in future crude oil production, wherein the geological resources of the thickened oil reservoir of the Shengli oil field, the Liaohe oil field, the Tahe oil field and the original oil field are very abundant, and the reduction of the viscosity of the thickened oil is a main problem to be solved in the processes of thickened oil development and lifting.
The chemical viscosity reducing method is one of the more common methods for exploiting thick oil, and mainly comprises two methods, namely emulsification viscosity reducing method and oil-soluble viscosity reducing method. The emulsification and viscosity reduction refers to that under the action of an emulsification and viscosity reduction agent (mainly a surfactant), a W/O type emulsion of thickened oil is converted into an O/W type emulsion, so that the purpose of viscosity reduction is achieved. The oil solubility viscosity reduction is realized by utilizing the interaction of polar groups in a molecular structure and asphaltene and colloid in the thickened oil to destroy the aggregation forms of the colloid and the asphaltene, so that the viscosity of the crude oil is reduced.
CN102585792A discloses a low-cost environment-friendly oil-soluble viscosity reducer for super heavy oil, which consists of a main agent, a solvent and an initiator, wherein the main agent consists of illegal cooking oil, aromatic hydrocarbon and olefin containing anhydride. The method reduces the cost of the viscosity reducer by taking the illegal cooking oil as the viscosity reducing component, and the viscosity reducer is used in the process of diluting and reducing viscosity by mixing with the thin oil, so that the viscosity reducing rate of the thick oil in the Tahe oil field reaches more than 90 percent.
CN104628934A discloses an anionic oil-soluble viscosity-reducing agent and a preparation method thereof, the oil-soluble viscosity-reducing agent is prepared by emulsion polymerization of octadecyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, styrene and acrylic acid through initiation by an oxidation-reduction initiator, and the viscosity-reducing rate of the viscosity-reducing agent to crude oil with viscosity of 17592-29353 mPa & s is up to 59.29%.
CN104629704A discloses a low molecular hyperbranched oil-soluble thickened oil viscosity reducer and a preparation method thereof, the viscosity reducer is composed of ethylenediamine, acetophenone, formaldehyde, butyl acrylate and a solvent 1, 4-dioxane, wherein the ethylenediamine, the acetophenone, the formaldehyde and the butyl acrylate are prepared into the hyperbranched oil-soluble viscosity reducer through mannich reaction, and the viscosity reducing rate of the viscosity reducer to the thickened oil in Xinjiang reaches 36.86%.
The existing oil-soluble viscosity reducer is mainly developed on the basis of a pour point reducer, takes the viscosity reduction and solvent dilution effects mainly based on high molecular polymers as main effects, is few in variety, is complex to operate in the polymer synthesis process, is difficult to control the polymerization degree, has certain influence on the viscosity reduction effect due to the polymers and the molecular weight, is high in preparation difficulty, and can generate adverse influence on the environment due to unreacted monomers.
Therefore, it is necessary to develop a viscosity reducer which can meet the requirement of thick oil exploitation and has the advantages of environmental protection, simple preparation and low cost.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a thickened oil viscosity reducing agent, a preparation method thereof and a thickened oil viscosity reducing method.
According to a first aspect of the invention, the invention provides a thickened oil viscosity reducing agent, which comprises a biological phenol-aldehyde oligomer and a penetrating agent, wherein the biological phenol-aldehyde oligomer is obtained by condensing cardanol and/or cashew nut shell oil and aldehydes, and the penetrating agent is a fluorocarbon surfactant.
In the biological phenol-aldehyde oligomer, the weight ratio of the biological phenol to the aldehyde is 10 to 30, preferably 12 to 20.
According to a second aspect of the present invention, the present invention provides a preparation method of a thickened oil viscosity reducer, comprising: (1) preparing a biological phenol-aldehyde oligomer; (2) mixing the biological phenol-aldehyde oligomer with a penetrant.
According to a third aspect of the invention, there is provided a method of viscosity reduction of thick oil, the method comprising: contacting the thickened oil with a thickened oil viscosity reducer, wherein the thickened oil viscosity reducer is the thickened oil viscosity reducer according to the first aspect of the invention.
According to a fourth aspect of the invention, the invention provides the application of the heavy oil viscosity reducer of the first aspect of the invention in heavy oil reservoir exploitation.
The thickened oil viscosity reducer disclosed by the invention is used for reducing viscosity of thickened oil, the dynamic viscosity of the thickened oil can be effectively reduced under the condition of low dosage, and the thickened oil (namely, mixed oil) after viscosity reduction can keep stability for a long time under the condition of high temperature, for example, in the embodiment 1-2, no solid matter is separated out after the mixed oil is aged for 10 days at 200 ℃, the mixed oil is still a uniform oil phase, and the thickened oil viscosity reducer is beneficial to smooth conveying and extraction of the thickened oil in a shaft after viscosity reduction in the exploitation of a thickened oil reservoir.
In addition, in the thickened oil viscosity reducer, the biological phenol-aldehyde oligomer is formed by condensation reaction of cardanol and/or cashew nut shell oil and aldehydes, and the raw materials are taken from cashew nut shell waste, so that the thickened oil viscosity reducer is wide in source, low in price, simple in preparation process, good in biodegradability and environment-friendly. The viscosity reducer can be prepared by simply mixing the biological phenol-aldehyde oligomer and the penetrating agent, so that the viscosity reducer has the characteristics of low cost, simplicity in preparation and environmental friendliness.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
According to a first aspect of the present invention, the present invention provides a thickened oil viscosity reducing agent, which comprises a biological phenol-aldehyde oligomer and a penetrant, wherein the mass ratio of the biological phenol-aldehyde oligomer to the penetrant can be 1:0.001 to 0.5, preferably 1:0.01 to 0.1.
In the invention, the biological phenol-aldehyde oligomer is formed by condensation reaction of cardanol and/or cashew nut shell oil and aldehydes. Wherein, the mass ratio of the biological phenol to the aldehyde is 10-30.
In the invention, the penetrating agent is a fluorocarbon surfactant, and the penetrating agent can play an effective wetting and impregnating role when being matched with the biological phenol-aldehyde oligomer for use, so that the solubility of the thickened oil viscosity reducer in thickened oil is improved. Further preferably, the penetrating agent is selected from at least one of perfluoro caprylic acid, perfluoro methyl caprylate and perfluoro ethyl caprylate.
The contents of the biological phenol-aldehyde oligomer and the penetrant are not particularly limited in the invention, as long as the specific viscosity reduction requirements of the thickened oil are met. According to an embodiment, in the thickened oil viscosity reducer, the mass ratio of the biological phenol-aldehyde oligomer to the penetrating agent may be 1:0.001 to 0.5, preferably 1:0.01 to 0.1.
The thickened oil viscosity reducer can also contain other conventional components, such as a stabilizer, a non-polar or weak-polar organic solvent and the like.
The inventor of the invention finds out through research that the biological phenol-aldehyde oligomer can obviously reduce the viscosity of the thick oil on one hand, and can replace the conventional polymer as the main component of the oil-soluble viscosity reducer. In addition, the biological phenol-aldehyde oligomer also has the function of inhibiting the precipitation of asphaltene from the thickened oil, and is beneficial to improving the long-term stability of the thickened oil after visbreaking.
In addition, when the biological phenol-aldehyde oligomer obtained by reacting cardanol and/or cashew nut shell oil with aldehydes is used as a thickened oil viscosity reducing main agent, compared with a composite viscosity reducing system only using cardanol and/or cashew nut shell oil as a main agent, the use amount of the viscosity reducing agent can be remarkably reduced, the biological phenol-aldehyde oligomer has the function of inhibiting asphaltene precipitation, the thickened oil system after viscosity reduction can be stabilized, and a stabilizing agent does not need to be additionally added.
According to a second aspect of the present invention, the present invention provides a preparation method of a thickened oil viscosity reducer, comprising: (1) preparing a biological phenol-aldehyde oligomer; and (2) mixing the biological phenol-aldehyde oligomer with a penetrant.
The preparation method of the biological phenol-aldehyde oligomer comprises the following steps: reacting a biological phenolic compound with aldehyde in the presence of a catalyst, wherein the mass ratio of the biological phenolic compound to the aldehyde is 10-30, and the preferable ratio is 12-20.
The biological phenol is cardanol and/or cashew nut shell oil. The aldehyde may be formaldehyde or paraformaldehyde.
It should be understood by those skilled in the art that cardanol is a mixture of phenol derivatives, mainly comprising a monohydric phenol of formula 1 and a dihydric phenol of formula 2;
in the formulas 1 and 2, R has a general formula of C 15 H 25～31 And R is a saturated straight-chain alkyl group or an unsaturated straight-chain alkyl group containing one, two or three double bonds, in particular, R has at least one of the following four carbon chain structures:
in the phenol derivative of cardanol, the mass content of monophenol shown in formula 1 is 85-90 wt%, and the mass content of dihydric phenol shown in formula 2 is 10-15 wt%. The cardanol is a mixture and contains a small amount of other components besides the structures shown in the formulas 1 and 2.
It will be understood by those skilled in the art that the cashew nut shell oil is a mixture of phenol derivatives, mainly comprising a monohydric phenol of formula 1, a dihydric phenol of formula 2 and 3, an alkyl-substituted o-hydroxybenzoic acid of formula 4:
in formulae 1 to 4, R is described as above.
In the phenol derivative of cashew nut shell oil, the mass content of monophenol shown in formula 1 is 2-7 wt%, the mass content of dihydric phenol shown in formula 2 is 15-20 wt%, the mass content of dihydric phenol shown in formula 3 is 2-5 wt%, and the mass content of alkyl-substituted o-hydroxybenzoic acid shown in formula 4 is 70-75 wt%. The cashew nut shell oil is a mixture, the main component of the cashew nut shell oil is a structure shown in a formula 1-4, and in addition, a small amount of other components are contained.
In the invention, the cardanol and cashew nut shell oil can be obtained commercially. In addition, the cardanol can also be prepared by refining cashew nut shell oil through decarboxylation acid.
According to the invention, the reaction temperature is 70 to 110 ℃ and preferably 80 to 90 ℃. The reaction time is 1 to 6 hours, preferably 2 to 3 hours. Preferably, after the reaction is finished, the temperature is raised to 120-140 ℃ to continue the reaction for 1-3 h, so as to remove the generated water, and obtain the water-free biological phenol-aldehyde oligomer.
The catalyst is acid or alkali, and can be organic acid or inorganic acid, organic alkali or inorganic alkali. For example, the acid may be p-toluenesulfonic acid, sulfuric acid, or the like; the alkali can be sodium hydroxide, potassium hydroxide, etc. The acid or base is a catalyst for the preparation process, and one of the acid or base can be selected optionally.
The total weight ratio of the catalyst to the biological phenol and the aldehyde is 0.5-2.5: 100, preferably in a ratio of 1 to 2.
According to the invention, the reaction can be carried out in the presence of an organic solvent or without a solvent. The organic solvent can be selected from benzene, toluene, xylene, industrial crude benzene, solvent oil or a mixture thereof, and the solvent is used for diluting a reaction product in the reaction process, improving the low-temperature fluidity of the prepared biological phenol-aldehyde oligomer and facilitating the use. The solvent is not particularly limited, but toluene or xylene is preferred, and the organic solvent can be separated off after the reaction is completed.
The total weight ratio of the solvent to the biological phenol to the aldehyde is 0-70: 100, preferably in a ratio of 30 to 50.
In the present invention, the thickened oil viscosity reducer can be prepared by mixing the biological phenol-aldehyde oligomer and the penetrating agent, and the conditions for the mixing are not particularly limited as long as the components can form a uniform oil phase. However, since the penetrant is generally solid at normal temperature, in order to further promote dissolution of the penetrant to achieve uniform mixing, it is preferable that the penetrant is dissolved by mixing the biological phenol-aldehyde oligomer and the penetrant under heating and stirring, and the mixing temperature may be 20 to 60 ℃ and the mixing time may be 10 to 30 minutes.
According to a third aspect of the invention, there is provided a method of viscosity reduction of thick oil, the method comprising: contacting the thickened oil with a thickened oil viscosity reducer, wherein the thickened oil viscosity reducer is the thickened oil viscosity reducer according to the first aspect of the invention.
The viscosity reduction method is suitable for processing thick oil with any viscosity, in particular for processing thick oil with high dynamic viscosity, and the dynamic viscosity of the thick oil at 50 ℃ is preferably 100-100000 mPa & s.
In the present invention, the amount of the viscous oil viscosity reducer can be selected according to the dynamic viscosity of the viscous oil, and generally, the mass ratio of the viscous oil viscosity reducer to the viscous oil can be 0.0005 to 0.1:1.
according to one embodiment, when the viscous oil has a dynamic viscosity of 100 to 10000 mPa-s at 50 ℃, the mass ratio of the viscous oil viscosity reducer to the viscous oil is 0.0005 to 0.01:1.
according to another embodiment, when the dynamic viscosity of the thickened oil at 50 ℃ is 10000-100000 mPa & s, the mass ratio of the thickened oil viscosity reducer to the thickened oil is 0.01-0.1: 1.
in the process of the present invention, the contacting may be carried out under stirring. The contact temperature can be 10-250 ℃, preferably 50-200 ℃, and more preferably 100-200 ℃; the contact time is not more than 7 days, preferably 0.1 to 4 hours.
According to a fourth aspect of the invention, the invention provides the use of the heavy oil viscosity reducer of the first aspect of the invention in heavy oil reservoir production.
The thickened oil viscosity reducer can effectively reduce the dynamic viscosity of thickened oil, and the recovery rate of the thickened oil can be improved by injecting the thickened oil viscosity reducer into a thickened oil reservoir. In addition, the thickened oil viscosity reducer can improve the long-term stability of thickened oil at high temperature after viscosity reduction, and is beneficial to smooth conveying and extraction of thickened oil in a shaft after viscosity reduction.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples,
the viscosities mentioned are dynamic viscosities measured with a rotational viscometer, model Hakke VT550, from Hakke, germany, according to SY/T6316-1997.
The viscosity reduction rate of the thickened oil is calculated according to the following formula:
viscosity reduction rate = (viscosity of thick oil before viscosity reduction-viscosity of thick oil after viscosity reduction)/viscosity of thick oil before viscosity reduction x 100%.
The stability of the thickened oil (i.e., the mixed oil) after viscosity reduction was judged according to the following method: observing whether solid matters are separated out after the mixed oil is aged under a certain condition by adopting a micro-particle analyzer with the model of UV-550, which is produced by Shanghai optical instrument six factories; if solid precipitates are observed, the stability of the thickened oil added with the viscosity reducer is poor; if no solid precipitate is observed, the stability of the thickened oil added with the viscosity reducer is good.
Perfluoro caprylic acid and perfluoro methyl caprylate are purchased from Beijing fluropont, and the GC purity is 96 percent;
cardanol and cashew nut shell oil are purchased from Shandong Haobo biological materials, inc.;
the other reactants for preparing the biological phenol-aldehyde oligomer, including the aldehyde, the solvent and the acid/base catalyst, are common chemical agents in the market and are purchased from Beijing YinuoKai science and technology Co., ltd or Beijing chemical reagent Co., ltd;
the treated thick oil-1, thick oil-2 and thick oil-3 are thick oil of Henan oilfield, and the dynamic viscosities of the thick oil-1, the thick oil-2 and the thick oil-3 at 50 ℃ are respectively 1.60 multiplied by 10 4 mPa·s、5.30×10 3 mPa·s、6.20×10 4 mPa·s。
Example 1
This example illustrates the viscosity reducing agent and viscosity reducing method for thick oil according to the present invention.
(1) Preparation of biological phenol-aldehyde oligomers
60g of cardanol and 4.0g of paraformaldehyde are added into a three-neck flask, and then 1.30g of p-toluenesulfonic acid and 32g of xylene are added. The biological phenol-aldehyde oligomer P2 was prepared under the same reaction conditions as in example 1.
(2) Preparation of viscous oil viscosity reducer
At 20 ℃, 0.1g of perfluorooctanoic acid was added to 10g of the biological phenol-aldehyde oligomer P2 prepared in step (1), and the mixture was stirred for 10 minutes to dissolve the same, thereby obtaining a viscous oil viscosity reducer A2.
(3) Viscosity reduction of thickened oil
0.05g of the thickened oil viscosity reducer A2 was added to 20g of the thickened oil-2, and then dissolved with stirring at 120 ℃ for 4 hours to obtain a mixed oil.
The kinematic viscosity of the oil blend at 50 ℃ and the stability results after 10 days aging at 200 ℃ are shown in Table 1.
Example 2
This example is used to illustrate the viscosity reducing agent and viscosity reducing method for thick oil of the present invention.
(1) Preparation of biological phenol-aldehyde oligomers
60g of cardanol and 8.2g of 36% formaldehyde aqueous solution are added into a three-neck flask, and then 1.36g of p-toluenesulfonic acid and 35g of xylene are added. Bio-phenol-aldehyde oligomer P3 was prepared under the same reaction conditions as in example 1.
(2) Preparation of viscous oil viscosity reducer
1.0g of methyl perfluorooctanoate was added to 10g of the biological phenol-aldehyde oligomer P3 at 30 ℃ and stirred for 30 minutes to dissolve it, to obtain a viscous oil viscosity reducer A3.
(3) Viscosity reduction of thickened oil
1g of the thickened oil viscosity reducer A3 is added into 20g of thickened oil-3, and then stirred and dissolved for 4 hours at the temperature of 200 ℃ to obtain mixed oil.
The kinematic viscosity of the oil blend at 50 ℃ and the stability results after 10 days aging at 200 ℃ are shown in Table 1.
Comparative example 1
CN104629704A oil soluble viscosity reducer prepared in example 1 and 0# diesel oil are prepared into viscosity reducer solution according to the mass ratio of 1.
The kinematic viscosity of the oil blend at 50 ℃ and the stability results after 10 days aging at 200 ℃ are shown in Table 1.
TABLE 1
Note:
1. the dosage of the viscosity reducer is the mass ratio of the viscosity reducer to the thickened oil.
2: stability of the mixed oil:
"homogeneous" means that no solids separation was found in the aged oil blend;
"slight phase separation" means that a small amount of solids are separated out from the aged mixed oil;
"significant phase separation" means that the aged mixed oil has a large amount of solids precipitated.
From the results in table 1, it can be seen that the kinetic viscosity of different thickened oils can be effectively reduced by using the thickened oil viscosity reducer provided by the invention.
As can be seen from comparative example 1, when the viscosity reduction of the thickened oil is performed by using the oil-soluble viscosity reducer disclosed in the prior art CN104629704A, the viscosity reduction rate of the thickened oil-1 is only 29.68%, and after the viscosity reduction, solids, phase separation and poor stability of mixed oil obviously exist in the thickened oil, which is not beneficial to the application of the viscosity reduction of the thickened oil.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. The thickened oil viscosity reducing agent comprises biological phenol-aldehyde oligomer and a penetrating agent, wherein the mass ratio of the biological phenol-aldehyde oligomer to the penetrating agent is 1: 0.001-0.5, the penetrating agent is at least one of perfluoro caprylic acid, perfluoro methyl caprylate and perfluoro ethyl caprylate, and the biological phenol-aldehyde oligomer is formed by condensation reaction of cardanol and/or cashew nut shell oil and aldehydes; the preparation method of the biological phenol-aldehyde oligomer comprises the following steps: reacting biological phenol and aldehyde at 70-110 ℃ for 1-6 hours in the presence of a catalyst, heating to 120-140 ℃ after the reaction is finished, and continuing to react for 1-3 hours to obtain a biological phenol-aldehyde oligomer, wherein the weight ratio of the biological phenol to the aldehyde is 12-20.
2. The adhesion reducing agent of claim 1, wherein the mass ratio of the bio-phenolic-aldehyde oligomer to the penetrant is 1:0.01 to 0.1.
3. A viscosity reducer according to claim 1 wherein the catalyst is an acid or a base.
4. The viscosity reducer according to claim 1, wherein the total mass ratio of the catalyst to the biological phenol and the aldehyde is 0.5-2.5: 100.
5. the viscosity reducer according to claim 1, wherein the total mass ratio of the catalyst to the biological phenol and the aldehyde is 1-2.
6. The viscosity reducer of claim 1 wherein the temperature at which the biological phenol-aldehyde oligomer and the penetrant are mixed is 20-60 ℃.
7. A method for reducing viscosity of thick oil, which comprises the following steps: contacting the thickened oil with the thickened oil viscosity reducer according to any one of claims 1 to 6.
8. The method according to claim 7, wherein the viscous oil has a dynamic viscosity of 100 to 100000 mPa-s at 50 ℃.
9. The method according to claim 7, wherein the mass ratio of the thick oil viscosity reducer to the thick oil is 0.0005-0.1: 1.
10. the method of claim 7, wherein the contacting temperature is from 10 to 250 ℃.
11. Use of the heavy oil viscosity reducer of any one of claims 1 to 6 in heavy oil reservoir recovery.
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