CN115636767A - Biosurfactant for oil displacement and fracturing and preparation method thereof - Google Patents
Biosurfactant for oil displacement and fracturing and preparation method thereof Download PDFInfo
- Publication number
- CN115636767A CN115636767A CN202110818630.XA CN202110818630A CN115636767A CN 115636767 A CN115636767 A CN 115636767A CN 202110818630 A CN202110818630 A CN 202110818630A CN 115636767 A CN115636767 A CN 115636767A
- Authority
- CN
- China
- Prior art keywords
- biosurfactant
- substituted
- capsaicin
- unsubstituted
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003876 biosurfactant Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006073 displacement reaction Methods 0.000 title abstract description 18
- YKPUWZUDDOIDPM-SOFGYWHQSA-N capsaicin Chemical compound COC1=CC(CNC(=O)CCCC\C=C\C(C)C)=CC=C1O YKPUWZUDDOIDPM-SOFGYWHQSA-N 0.000 claims abstract description 53
- 229960002504 capsaicin Drugs 0.000 claims abstract description 28
- 235000017663 capsaicin Nutrition 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- -1 amino, phenyl Chemical group 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 150000003573 thiols Chemical class 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 40
- 230000009467 reduction Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000295 fuel oil Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000004094 surface-active agent Substances 0.000 description 33
- 239000010779 crude oil Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000000693 micelle Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 229940117986 sulfobetaine Drugs 0.000 description 3
- VQDQISMDUHBUFF-UHFFFAOYSA-N 4-phenylbutanoyl chloride Chemical compound ClC(=O)CCCC1=CC=CC=C1 VQDQISMDUHBUFF-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012457 nonaqueous media Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003079 shale oil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- CLHYKAZPWIRRRD-UHFFFAOYSA-N 1-hydroxypropane-1-sulfonic acid Chemical compound CCC(O)S(O)(=O)=O CLHYKAZPWIRRRD-UHFFFAOYSA-N 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OBKXEAXTFZPCHS-UHFFFAOYSA-N 4-phenylbutyric acid Chemical compound OC(=O)CCCC1=CC=CC=C1 OBKXEAXTFZPCHS-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 235000015076 Shorea robusta Nutrition 0.000 description 1
- 244000166071 Shorea robusta Species 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000004346 phenylpentyl group Chemical group C1(=CC=CC=C1)CCCCC* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a biosurfactant for oil displacement and fracturing and a preparation method thereof. The biosurfactant can be synthesized in one step through nucleophilic substitution reaction of capsaicin, and has the advantages of simple preparation method, mild reaction conditions, easiness in separation and purification and low cost. The biosurfactant has a very obvious viscosity reduction effect, is expected to be applied to oil-soluble viscosity reducers, oil displacement agents and microemulsions in tertiary oil recovery in the heavy oil recovery, and has a wide market prospect.
Description
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to a biosurfactant for oil displacement and fracturing and a preparation method thereof.
Background
In recent years, unconventional petroleum resources such as compact oil, shale oil and the like gradually become the field of major strategic and succeed energy, and long horizontal well and fracturing modification become the main development mode of unconventional oil reservoirs, but the yield is reduced rapidly, and the primary recovery rate is low. On the whole, unconventional reservoirs such as compact reservoirs and shales generally have the characteristics of low permeability, low porosity, low mobile fluid saturation and the like, crude oil has poor fluidity in the reservoirs, the fluidity in the reservoirs is close to that of thick oil and ultra-thick oil, and how to solve the problem that an injection medium effectively enters a nano-micron matrix of the reservoirs, reduce and eliminate association among components of the crude oil, improve the fluidity of the reservoirs of the crude oil, and realize the effects of permeation enhancement and oil displacement becomes the first technical problem in the high-efficiency development of unconventional reservoirs such as compact oil, shale oil and the like at home and abroad at present.
From 2000, north America companies such as Haributon and Nissan began to report microemulsion products, and the microemulsion products were applied to shale gas and compact oil reservoir reformation and synergism. However, the microemulsion product only solves the technical problem of the nano size of the existing liquid system, realizes the efficient entry of fine pores of a shale gas reservoir, but the surfactant component in the internal phase of the microemulsion does not have the characteristic of improving the flowability of crude oil. Therefore, the research of the surfactant has important significance for petroleum development.
The existing surfactants comprise water-soluble surfactants and oil-soluble surfactants, wherein the water-soluble surfactants have the problems of poor universality, serious emulsification, difficult subsequent treatment and the like, and have great difficulty in practical application. The oil soluble surfactant is mainly based on the development technology of crude oil pour point depressants, aims at the condition that colloid and asphaltene molecules are in a layered accumulation state, and ensures that the surfactant molecules penetrate into the layers of the colloid or asphaltene molecules by virtue of the characteristic of loose layer gaps accumulated under the action of high temperature or solvent to form small-size oil, thereby being a promising method for overcoming the technical defects of emulsification and viscosity reduction.
Much research is currently devoted to oil-soluble surfactants and their research in oil recovery, for example CN103030854A discloses a drag reducing composition and a preparation method thereof, the drag reducing composition is a suspension containing polyalphaolefin, silicone oil, surfactant and solvent; the surfactant is oil-soluble surfactant, and is selected from one or more of Tween surfactant, span surfactant or nonylphenol polyoxyethylene ether surfactant. CN103113869A discloses a double-long-chain alkyl hydroxy sulfobetaine surfactant and an oil displacement agent, wherein the double-long-chain alkyl hydroxy sulfobetaine surfactant is obtained by reacting double-long-chain alkyl methyl tertiary amine with 3-chloro-2-sodium hydroxypropanesulfonate, and each long-chain alkyl has 7-19 carbon atoms and good oil solubility; the oil displacement agent prepared from the double-long-chain alkyl hydroxy sulfobetaine surfactant can effectively reduce the interfacial tension between crude oil and water under the alkali-free condition. However, the types of surfactants suitable for oil and non-aqueous solutions developed at present are few, and only comprise mature products of OP-4, OP-7, span-20, span-80, tween-85 and the like; furthermore, it is customary to classify all common low hydrophilic-lipophilic balance (HLB) surfactants as oil-soluble surfactants, such as OP-4, span-80, etc., but such low HLB surfactants do not possess the ability to significantly alter the properties of both oil and non-aqueous solutions; meanwhile, the oil-soluble surfactant disclosed in the prior art has large molecular size, high dosage and poor surface activity, is difficult to enter the micro-nano pores of a compact shale reservoir, and limits the wide application of the oil-soluble surfactant in oil reservoir exploitation.
Therefore, the development of more types of oil-soluble surfactants with more excellent performance to meet the application requirements of viscosity-reducing oil displacement products in oil exploitation is an urgent problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a biosurfactant for oil displacement and fracturing and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a biosurfactant for flooding and fracturing, which has a structure as shown in formula I:
in the formula I, X is selected from substituted or unsubstituted C1-C10 straight-chain or branched-chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 straight-chain or branched-chain alkenyl,
Any one of the above;
* Represents the attachment site of a group;
r is selected from any one of C1-C10 straight chain or branched chain alkyl and C7-C20 aryl alkyl.
In the present invention, the C1 to C10 linear or branched alkyl groups may be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10 linear or branched alkyl groups, which illustratively include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl or n-heptyl and the like.
The C3 to C10 cycloalkyl group may be a C3, C4, C5, C6, C7, C8, C9 or C10 cycloalkyl group, and exemplary include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, and the like.
The C2 to C10 linear or branched alkenyl group may be a C2, C3, C4, C5, C6, C7, C8, C9 or C10 linear or branched alkenyl group, illustratively including but not limited to: vinyl, propenyl, allyl, 1-butenyl, 2-butenyl, 1, 3-butadienyl, 1-pentenyl, 1-hexenyl, or 2-hexenyl, and the like.
The C7 to C20 arylalkyl group may be a C7, C8, C9, C10, C12, C14, C16, C18, or C20, etc. arylalkyl group, illustratively including but not limited to: benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylpentyl, or phenylhexyl, and the like.
In the present invention, the substitution is mono-or poly-substituted, and the substituted site is any chemically allowable site that may be substituted.
The biosurfactant for oil displacement and fracturing has a structure shown in a formula I, has a molecular structure close to that of the saturated dense crude oil, has strong oleophylic characteristics, can be effectively dispersed in an aqueous solution, can effectively weaken the strong association effect among the components of the dense and shale crude oil to form a small-size oil effect, and has good oil washing capacity. The biosurfactant is used as a novel oil-soluble surfactant, the critical micelle concentration can be as low as 0.13-0.23%, the surface tension under the critical micelle concentration is 35-37 mN/m, the biosurfactant can have the effects of solubilization, disassociation, viscosity reduction and the like under the oil-soluble condition, the flowability characteristic of crude oil can be effectively changed, the oil washing capacity is strong, the viscosity reduction effect is obvious, and the biosurfactant has a wide application prospect.
Preferably, the substituted substituents in X are each independently selected from at least one of deuterium, carboxyl, hydroxyl, sulfonic acid, mercapto, amino, phenyl, C1-C6 alkoxy, C3-C6 cycloalkyl, or halogen.
Wherein, the C1 to C6 alkoxy group may be a C1, C2, C3, C4, C5 or C6 linear or branched alkoxy group, which exemplarily includes but is not limited to: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, or the like.
The C3 to C6 cycloalkyl group may be a C3, C4, C5 or C6 cycloalkyl group, and exemplary include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, and the like.
In the present invention, the halogen includes F, cl, br or I; the same description is referred to below, all having the same meaning.
Preferably, X is selected from the group consisting of substituted or unsubstituted C2 to C5 (e.g., C2, C3, C4, or C5) straight or branched alkyl, substituted or unsubstituted C3 to C6 (e.g., C3, C4, C5, or C6) cycloalkyl, and,
Any one of the above; wherein denotes the attachment site of the group.
The substituted substituents in X are each independently selected from at least one of deuterium, hydroxy, phenyl, C1-C4 (e.g., C1, C2, C3, or C4) alkoxy, C3-C6 (e.g., C3, C4, C5, or C6) cycloalkyl, or amino.
Preferably, R is selected from
Any one of C1-C5 (e.g., C1, C2, C3, C4 or C5) straight chain or branched alkyl; wherein, represents the attachment site of a group, R X Selected from C1-C5 linear or branched alkylene.
Wherein the C1 to C5 linear or branched alkylene group may be a C1, C2, C3, C4 or C5 linear or branched alkylene group, which exemplarily includes but is not limited to: methylene, ethylene, propylene, butylene, pentylene, and the like.
In a specific embodiment, the biosurfactant comprises any one of the following compounds:
in a second aspect, the present invention provides a process for the preparation of a biosurfactant according to the first aspect, which process comprises: reacting capsaicin with a halogen-containing reagent X-Z to obtain the biosurfactant; the reaction formula is as follows:
wherein X has the same limitations as in formula I and Z is selected from halogens (including F, cl, br or I).
In a specific embodiment, X is selected from any one of substituted or unsubstituted C1 to C10 linear or branched alkyl, substituted or unsubstituted C3 to C10 cycloalkyl, and substituted or unsubstituted C2 to C10 linear or branched alkenyl, and the molar ratio of the halogen-containing reagent X-Z to capsaicin is (1.4 to 2.0).
Preferably, Z is chloro or bromo, further preferably bromo; the reaction is a nucleophilic substitution reaction of capsaicin and a halogen-containing reagent X-Z.
Preferably, the reaction is carried out in the presence of a catalyst.
Preferably, the catalyst is a combination of potassium carbonate and potassium iodide.
Preferably, the molar ratio of capsaicin to potassium carbonate is 1 (3 to 3.5), and can be, for example, 1.
Preferably, the molar ratio of capsaicin to potassium iodide is 1 (1.5-2.0), and may be, for example, 1.
Preferably, the reaction temperature is 60 to 80 ℃, such as 61 ℃, 63 ℃, 65 ℃, 67 ℃, 69 ℃, 70 ℃, 71 ℃, 73 ℃, 75 ℃, 77 ℃ or 79 ℃ and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the reaction time is 4 to 6 hours, for example, 4.25 hours, 4.5 hours, 4.75 hours, 5 hours, 5.25 hours, 5.5 hours or 5.75 hours, and the specific values therebetween are not exhaustive, and for the sake of brevity, the invention is not intended to limit the scope to the specific values included in the ranges.
Preferably, the reaction is carried out in the presence of a solvent, which is acetonitrile.
Preferably, the reaction also comprises a post-treatment step after completion, wherein the post-treatment step comprises concentration, washing and purification.
In another specific embodiment, X is
The halogen-containing reagent X — Z is an acid halide, and the molar ratio thereof to capsaicin is (1.2 to 2.0) and can be, for example, 1.25; the reaction is nucleophilic substitution reaction of acyl halide and capsaicin.
Wherein the acid halide is available directly from the purchase or can be obtained from carboxylic acids
And halogenated sulfoxides (
For example thionyl chloride); the reaction is carried out in the presence of an acid-binding agent (such as triethylamine), the temperature of the reaction is 70-90 ℃ (preferably room temperature), and the time is 1-2 h; the molar ratio of the carboxylic acid compound to the halogenated sulfoxideIs 1 (1.2-1.5), and the molar ratio of the carboxylic acid compound to the acid-binding agent is 1 (0.2-0.5).
Preferably, the reaction is carried out in the presence of an acid scavenger.
Preferably, the acid scavenger comprises triethylamine and/or pyridine.
Preferably, the molar ratio of the capsaicin to the acid scavenger is 1 (1.3-1.6), and can be, for example, 1.
Preferably, the reaction is carried out in the presence of a solvent, which is dichloromethane.
Preferably, the reaction temperature is 15 to 40 ℃, for example, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃,30 ℃, 32 ℃, 35 ℃ or 38 ℃, and the specific values between the above values are limited by space and conciseness, and the invention does not exhaust the specific values included in the range, and further preferably room temperature.
Preferably, the reaction time is 0.5 to 3 hours, for example, 0.75 hour, 1 hour, 1.25 hour, 1.5 hour, 1.75 hour, 2 hours, 2.25 hours, 2.5 hours or 2.75 hours, and specific values therebetween, which are not exhaustive for the invention and for the sake of brevity.
Preferably, the reaction further comprises a post-treatment step, wherein the post-treatment step comprises washing, concentration and purification.
In a third aspect, the present invention provides the use of a biosurfactant according to the first aspect in an oil displacing agent, a fracturing fluid, a viscosity reducing agent or in a microemulsion.
In a fourth aspect, the present invention provides a viscosity reducing agent comprising a biosurfactant according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the biosurfactant provided by the invention is used as a novel oil-soluble surfactant, the critical micelle concentration of the biosurfactant is less than 0.24 percent and can be as low as 0.15 to 0.23 percent, the fluidity characteristic of crude oil can be effectively changed, and the oil washing capacity is strong. The biosurfactant can be synthesized in one step through nucleophilic substitution reaction of capsaicin, and has the advantages of simple preparation method, mild reaction conditions, easiness in separation and purification and low raw material cost. When the biosurfactant is used as a viscosity reducer, the viscosity reduction rate with the addition of 1% can reach 63-71%, the viscosity reduction effect is very obvious, the biosurfactant is expected to be applied to oil-soluble viscosity reducers, oil displacement agents in the heavy oil recovery, microemulsions in the tertiary oil recovery and the like, and the biosurfactant has a wide market prospect.
Drawings
FIG. 1 is a liquid chromatography mass spectrometry spectrum of the biosurfactant provided in example 1;
FIG. 2 is a nuclear magnetic spectrum of the biosurfactant provided in example 1;
FIG. 3 is a liquid chromatography-mass spectrometry spectrum of the biosurfactant provided in example 6;
fig. 4 is a nuclear magnetic spectrum of the biosurfactant provided in example 6.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A biosurfactant for oil displacement and fracturing, in particular to 3-butoxy capsaicin, which has the following structure:
the preparation method comprises the following steps:
at room temperature, 6.0g (19.65 mM) of capsaicin, 9.0g of potassium carbonate (65.12 mM), 6.0g (36.14 mM) of potassium iodide and 30mL of acetonitrile are added into a three-necked flask, after the completion of feeding, 4.5g (32.84 mM) of bromobutane is added dropwise with stirring, the temperature is raised to 70 ℃ with stirring, the reaction solution is kept for 5 hours, after the reaction solution is concentrated, the residue is sufficiently washed with Dichloromethane (DCM) and water, the obtained DCM solution is concentrated and purified by a chromatographic column (mobile phase n-hexane: ethyl acetate =20, volume ratio) to obtain 6.8g (18.81 mM) of the target product as a white solid with a yield of 95.7%.
Structural characterization:
the target product is characterized by liquid chromatography-mass spectrometry, an obtained liquid chromatography-mass spectrometry spectrogram is shown in figure 1, and as can be seen from figure 1, the theoretical molecular weight of the target product is 361.52mol/L, the actually measured molecular weight is 362.2-364.3 mol/L, the purity of a sample is more than 90%, and the synthesized compound conforms to the corresponding molecular weight of the target compound, namely 3-butoxy capsaicin.
The nuclear magnetic spectrum of the target product is shown in figure 2, 1 H-NMR(400MHz，CDCl 3 )：δ0.82-0.9(9H,(CH 3 ) 2 CH,CH 3 CH 2 )，1.12-1.65(10H,COCH 2 (CH 2 ) 3 ,CH 3 (CH 2 ) 2 CH 2 O)，2.09(2H,COCH 2 (CH 2 ) 3 )，2.18(1H,(CH 3 ) 2 CH)，3.70(3H,CH 3 O)，3.90(2H,CH 3 (CH 2 ) 2 CH 2 O)，4.16(2H,NHCH 2 )，5.32(2H,CH＝CH)，6.72-6.84(3H,C 6 H 3 )，8.2(1H,NH)。
example 2
A biosurfactant for oil displacement and fracturing, in particular to 3-ethoxy capsaicin, which has the following structure:
the preparation method comprises the following steps:
at room temperature, 6.0g (19.65 mM) of capsaicin, 9.0g of potassium carbonate (65.12 mM), 6.0g (36.14 mM) of potassium iodide and 30mL of acetonitrile are added into a three-necked flask, 3.58g (32.84 mM) of ethyl bromide is added dropwise with stirring after feeding, the temperature is raised to 70 ℃ with stirring, the temperature is kept for 5 hours, the reaction liquid is concentrated completely, the residue is fully washed with DCM and water, the obtained DCM solution is concentrated completely, and the obtained product is purified by a chromatographic column (the mobile phase is n-hexane: ethyl acetate =20, volume ratio is 1) to obtain 6.07g (18.2 mM) of the target product white solid with the yield of 93.04 percent.
Structural characterization:
1 H-NMR(400MHz，CDCl 3 )：δ0.86(6H,(CH 3 ) 2 CH)，1.19-2.1(9H,COCH 2 (CH 2 ) 3 ，CH 3 CH 2 O)，2.12(2H,COCH 2 (CH 2 ) 3 )，2.48(1H,(CH 3 ) 2 CH)，3.71(3H,CH 3 O)，3.98(2H,CH 3 CH 2 O)，4.22(2H,NHCH 2 )，5.43(2H,CH＝CH)，6.80-6.96(3H,C 6 H 3 )，8.2(1H,NH)。
examples 3 to 5
A biosurfactant for oil displacement and fracturing is prepared by nucleophilic substitution reaction of capsaicin and a bromine-containing reagent, and the specific synthetic route is the same as that in example 1; the structures of the starting material (bromine-containing reagent) and the target product are shown in table 1 below:
TABLE 1
Example 6
A biosurfactant for oil displacement and fracturing, in particular to 3- (4-phenylbutyl ester) capsaicin, which has the following structure:
the preparation method comprises the following steps:
4.25g of phenylbutyric acid (25.88 mM), 25mL of DCM, 0.6g of triethylamine (5.89 mM), 4.25g of thionyl chloride (35.72 mM) were added to a three-necked flask at room temperature and refluxed for 1.5h; the reaction mixture was concentrated by rotary evaporation to obtain 4-phenylbutyryl chloride, and 10mL of DCM was added to the concentrated residue, followed by cooling.
5.0g of capsaicin (16.37 mM) was dissolved in a mixture of 2 mL of DCM and 2.5g of triethylamine (24.54 mM) at room temperature, and the solution of 4-phenylbutyryl chloride in DCM obtained in step (1) was slowly added dropwise thereto under ice-bath conditions, followed by reaction at room temperature for 1.5 hours. The reaction was concentrated to completion, and the system was washed with water, saturated sodium bicarbonate solution, and water in this order, followed by separation into layers, and the resulting DCM layer was concentrated to completion by rotary evaporation and purified by chromatography (mobile phase n-hexane: ethyl acetate =20, volume ratio) to afford the desired product as a white paste 5.3g (11.74 mM) with a yield of 71.7%.
Structural characterization:
the target product is characterized by liquid chromatography-mass spectrometry, an obtained liquid chromatography-mass spectrometry spectrogram is shown in fig. 3, and as can be seen from fig. 3, the theoretical molecular weight of the target product is 451.6mol/L, the actually measured molecular weight is 452.2mol/L, the sample purity is more than 80%, and the synthesized compound conforms to the corresponding molecular weight of the target compound, namely 3- (4-phenylbutyl) capsaicin.
The nuclear magnetic spectrum of the target product is shown in figure 4, 1 H-NMR(400MHz，CDCl 3 )：δ0.82-0.9(6H,(CH 3 ) 2 CH)，1.12-1.52(6H,COCH 2 (CH 2 ) 3 )，1.81(1H,(CH 3 ) 2 CH)，2.09(2H,COCH 2 (CH 2 ) 3 )，2.51(2H,(CH 2 ) 2 CH 2 COO)，2.70(4H,C 6 H 5 (CH 2 ) 2 )，3.70(3H,CH 3 O)，4.24(2H,NHCH 2 )，5.32(2H,CH＝CH)，6.77-6.98(3H,C 6 H 3 )，7.23(5H,C 6 H 5 )，8.2(1H,NH)。
example 7
A biosurfactant for oil displacement and fracturing, in particular to 3- (4-phenylethyl ester) capsaicin, which has the following structure:
the preparation method comprises the following steps:
5.0g of capsaicin (16.37 mM) was dissolved in a mixture of 25mL of DCM and 2.5g of triethylamine (24.54 mM) at room temperature, and a solution of phenylacetyl chloride (24.5 mM) in DCM was slowly added dropwise thereto under ice-bath conditions, followed by reaction at room temperature for 1.5h. The reaction solution was concentrated to completion, the system was washed with water, saturated sodium bicarbonate solution and water in this order, the layers were separated, the obtained DCM layer was concentrated to completion by rotary evaporation and purified by chromatography (mobile phase n-hexane: ethyl acetate =20, volume ratio) to obtain the target product 5.29g (12.51 mM) as a white paste with a yield of 76.42%.
Structural characterization:
1 H-NMR(400MHz，CDCl 3 )：δ0.86-0.89(6H,(CH 3 ) 2 CH)，1.13-1.63(6H,COCH 2 (CH 2 ) 3 )，1.85(1H,(CH 3 ) 2 CH)，2.13(2H,COCH 2 (CH 2 ) 3 )，3.71(3H,CH 3 O)，3.91(2H,C 6 H 5 CH 2 COO)，4.24(2H,NHCH 2 )，5.41(2H,CH＝CH)，6.80-7.17(3H,C 6 H 3 )，7.24-7.26(5H,C 6 H 5 )，8.2(1H,NH)。
examples 8 to 9
A biosurfactant for oil displacement and fracturing is prepared by nucleophilic substitution reaction of capsaicin and acyl chloride compounds, and the specific synthetic route is the same as the step (2) in the embodiment 6; the structures of the raw material (acyl chloride compound) and the target product are shown in the following table 2:
TABLE 2
And (3) performance testing:
(1) Critical Micelle Concentration (CMC) and surface tension at critical micelle concentration (γ) CMC )
By Germany
The full-automatic surface tensiometer model K100 produced by the company carries out the test. Accurately weighing a certain amount of substances to be measured respectively, dissolving with deionized water, diluting into a series of water solutions with different concentrations, and mixing uniformly; and (3) keeping the prepared surfactant aqueous solutions with different concentrations at the constant temperature of 25 ℃ in a constant-temperature water bath kettle for 20min. After the surface tension meter is preheated for half an hour, the surface tension meter is corrected, then the surface tension of water at 25 ℃ is measured, and the measured value after correction is 72.0 +/-0.2 mN/m. And (3) measuring the surface tension of the surfactant solution one by one according to the sequence from low concentration to high concentration, recording data after the reading is stable, measuring each sample three times, and taking an average value. Drawing a relation curve of the surface tension and the concentration of the solution according to the surface tension data under each concentration, and obtaining the critical micelle concentration CMC of the substance to be detected and the surface tension gamma corresponding to the concentration from the turning point of the curve CMC 。
(2) Viscosity reduction effect test
The test was performed using an RS600 rotational rheometer. The crude oil is compact oil in a certain oil field at home, the testing temperature is 80 ℃, and the initial viscosity of the crude oil at 80 ℃ is 42mPa & s; adding the biosurfactants provided by the embodiments 1 to 9 into the crude oil, wherein the addition amount is 1 percent of the mass of the crude oil, uniformly mixing, testing the viscosity of the system by adopting a DG41Ti sleeve rotor, and calculating the viscosity reduction rate; viscosity reduction rate (%) =100% × (initial viscosity-post-viscosity reduction)/initial viscosity.
The biosurfactants provided in examples 1-9 were tested for performance according to the test methods described above, and the test data are shown in table 3, using the existing surfactants SDS and OP-10 as controls.
TABLE 3
According to the performance data in table 3, the biosurfactant provided by the invention is used as an oil-soluble surfactant, the critical micelle concentration can be as low as 0.13-0.23%, the surface tension under the critical micelle concentration is 35-37 mN/m, the fluidity characteristic of crude oil can be effectively changed, the viscosity of the crude oil is reduced, the viscosity reduction rate can reach 63-71%, and the viscosity reduction effect is superior to that of the traditional surfactants SDS (sodium dodecyl sulfate) and OP-10 (polyoxyethylene octylphenol ether-10).
The applicant states that the present invention is illustrated by the above examples, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A biosurfactant for flooding and fracturing, which is characterized by having a structure shown as a formula I:
wherein X is selected from substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 linear or branched alkenyl,
Any one of the above;
* Represents the attachment site of a group;
r is selected from any one of C1-C10 straight chain or branched chain alkyl and C7-C20 aryl alkyl.
2. The biosurfactant of claim 1 wherein the substituted substituents of X are each independently selected from at least one of deuterium, carboxyl, hydroxyl, sulfonic acid, thiol, amino, phenyl, C1-C6 alkoxy, C3-C6 cycloalkyl or halogen.
3. The biosurfactant of claim 1 or 2 wherein X is selected from the group consisting of substituted or unsubstituted C2-C5 linear or branched alkyl, substituted or unsubstituted C3-C6 cycloalkyl,
Any one of the above;
each of the substituted substituents in X is independently at least one of deuterium, hydroxyl, phenyl, C1-C4 alkoxy, C3-C6 cycloalkyl or amino;
preferably, R is selected from
Any one of C1-C5 straight chain or branched chain alkyl; wherein, represents the attachment site of the group, R X Selected from C1-C5 linear or branched alkylene.
4. A biosurfactant according to any one of claims 1 to 3 which comprises any one of the following compounds:
5. a process for the preparation of a biosurfactant according to any one of claims 1 to 4 which comprises: reacting capsaicin with a halogen-containing reagent X-Z to obtain the biosurfactant; the reaction formula is as follows:
wherein X has the same limits as in formula I and Z is selected from halogen.
6. The preparation method according to claim 5, wherein X is selected from any one of substituted or unsubstituted C1-C10 linear or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, and substituted or unsubstituted C2-C10 linear or branched alkenyl, and the molar ratio of the halogen-containing reagent X-Z to capsaicin is (1.4-2.0): 1;
preferably, the reaction is carried out in the presence of a catalyst;
preferably, the catalyst is a combination of potassium carbonate and potassium iodide;
preferably, the molar ratio of the capsaicin to the potassium carbonate is 1 (3-3.5);
preferably, the molar ratio of the capsaicin to the potassium iodide is 1 (1.5-2.0);
preferably, the temperature of the reaction is 60-80 ℃;
preferably, the reaction time is 4 to 6 hours.
7. The method according to claim 5, wherein X is
The molar ratio of the halogen-containing reagent X-Z to the capsaicin is (1.2-2.0): 1.
8. The method according to claim 5, wherein X is
The reaction is carried out in the presence of an acid-binding agent;
preferably, the acid scavenger comprises triethylamine and/or pyridine;
preferably, the molar ratio of the capsaicin to the acid-binding agent is 1 (1.3-1.6);
preferably, the temperature of the reaction is 15-40 ℃;
preferably, the reaction time is 0.5 to 3 hours.
9. Use of a biosurfactant according to any one of claims 1 to 4 in an oil displacing agent, a fracturing fluid, a viscosity reducing agent or in a microemulsion.
10. A viscosity reducing agent comprising the biosurfactant according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110818630.XA CN115636767A (en) | 2021-07-20 | 2021-07-20 | Biosurfactant for oil displacement and fracturing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110818630.XA CN115636767A (en) | 2021-07-20 | 2021-07-20 | Biosurfactant for oil displacement and fracturing and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115636767A true CN115636767A (en) | 2023-01-24 |
Family
ID=84940709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110818630.XA Pending CN115636767A (en) | 2021-07-20 | 2021-07-20 | Biosurfactant for oil displacement and fracturing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115636767A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55105601A (en) * | 1979-02-07 | 1980-08-13 | Saiden Kagaku Kk | Underwater antifouling agent |
| US20080020996A1 (en) * | 2006-07-24 | 2008-01-24 | Chandra Ulagaraj Singh | Esters of capsaicin for treating pain |
| US20080058362A1 (en) * | 2006-08-31 | 2008-03-06 | Singh Chandra U | Novel pharmaceutical compositions for treating chronic pain and pain associated with neuropathy |
| CN101208294A (en) * | 2005-04-25 | 2008-06-25 | 纽罗吉斯克斯公司 | TRPV1 agonist compounds and methods for making and using the same |
| US20100120912A1 (en) * | 2008-10-30 | 2010-05-13 | Trinity Laboratories Inc. | Esters of capsaicinoids as dietary supplements |
| WO2015160842A1 (en) * | 2014-04-14 | 2015-10-22 | Flex Pharma, Inc. | Methods and formulatiions of capsaicinoids and capsinoids |
-
2021
- 2021-07-20 CN CN202110818630.XA patent/CN115636767A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55105601A (en) * | 1979-02-07 | 1980-08-13 | Saiden Kagaku Kk | Underwater antifouling agent |
| CN101208294A (en) * | 2005-04-25 | 2008-06-25 | 纽罗吉斯克斯公司 | TRPV1 agonist compounds and methods for making and using the same |
| US20080020996A1 (en) * | 2006-07-24 | 2008-01-24 | Chandra Ulagaraj Singh | Esters of capsaicin for treating pain |
| US20080058362A1 (en) * | 2006-08-31 | 2008-03-06 | Singh Chandra U | Novel pharmaceutical compositions for treating chronic pain and pain associated with neuropathy |
| US20100120912A1 (en) * | 2008-10-30 | 2010-05-13 | Trinity Laboratories Inc. | Esters of capsaicinoids as dietary supplements |
| WO2015160842A1 (en) * | 2014-04-14 | 2015-10-22 | Flex Pharma, Inc. | Methods and formulatiions of capsaicinoids and capsinoids |
Non-Patent Citations (2)
| Title |
|---|
| ACS: "CAS: 1966925-45-0等", STN DATABASE, 4 August 2016 (2016-08-04) * |
| 张艳青: "CAS:1966925-45-0等", STN DATABASE, 4 August 2016 (2016-08-04) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7811473B2 (en) | Branched surfactant having fluoroalkyl group and hydrocarbon group | |
| CN101081976B (en) | Fire-resistant non-injury fracturing fluid thickening agent and preparation method and usage thereof | |
| CN105439885B (en) | A kind of fatty acid amide propyl glycine betaine foam discharging agent and its preparation method and application | |
| CN104609756B (en) | Cationic concrete mud inhibiting agent and preparation method thereof | |
| CN104371081B (en) | A kind of preparation method of rapid dispersion viscosity reduction type poly-carboxylic-acid cement dispersant | |
| CN109135709A (en) | A kind of viscosity reduction oil displacement agent and oil displacement system suitable for heavy crude reservoir | |
| CN109535016A (en) | A kind of novel gemini quaternary ammonium salt, preparation method and application | |
| CN106336350B (en) | Fluorine-containing dinaphthyl ethine liquid crystal compound and its preparation method and application | |
| US20150203736A1 (en) | Comb polymer, method of preparing the same, and use thereof | |
| CN100364650C (en) | Cation fluoride Gemini surface activator | |
| CN115636767A (en) | Biosurfactant for oil displacement and fracturing and preparation method thereof | |
| CN115636761A (en) | Oil-soluble surfactant, oil displacement agent and application thereof | |
| CN108623483A (en) | A kind of anti-mud agent and preparation method and application containing xenyl | |
| CN112175597A (en) | Well-flushing foam water shutoff agent and preparation method thereof | |
| CN115637142B (en) | Oil displacement agent containing fatty chain and preparation method and application thereof | |
| CN102351749A (en) | Benzenesulphonate anionic gemini surfactant and preparation method thereof | |
| CN110129020B (en) | Viscoelastic surfactant system and application thereof in exploitation of water-drive heavy oil reservoir | |
| CN113652236B (en) | Mudstone dispersant and preparation method thereof | |
| EP4177242A1 (en) | Alkylaniline polyether benzene sulfonate and preparation method therefor | |
| CN114685293B (en) | Aryl quaternary ammonium salt Gemini surfactant and preparation method and application thereof | |
| CN109679610B (en) | Solid foam drainage agent with pH value response, preparation method and application | |
| CN100408533C (en) | Twin diglycol compound, its preparation and use | |
| CN111087606A (en) | Double-long-chain alkyl polyoxyethylene-polyoxypropylene ether sulfate surfactant for oil displacement and preparation method thereof | |
| CN113897190B (en) | Surfactant for improving water injection efficiency of low-permeability reservoir and preparation method and application thereof | |
| CN112694881B (en) | Foam composition for enhanced oil recovery of fractured oil reservoir and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |