CN105566174A - Method for synthesizing betaine by long-chain tertiary amine through normal-pressure anhydrous quaternization - Google Patents
Method for synthesizing betaine by long-chain tertiary amine through normal-pressure anhydrous quaternization Download PDFInfo
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- CN105566174A CN105566174A CN201510790110.7A CN201510790110A CN105566174A CN 105566174 A CN105566174 A CN 105566174A CN 201510790110 A CN201510790110 A CN 201510790110A CN 105566174 A CN105566174 A CN 105566174A
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- long
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- tertiary amine
- betaine
- carboxybetaine
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- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 42
- 150000003512 tertiary amines Chemical class 0.000 title claims abstract description 36
- 229960003237 betaine Drugs 0.000 title claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 title claims abstract 7
- 238000005956 quaternization reaction Methods 0.000 title abstract 2
- -1 betaine compound Chemical class 0.000 claims abstract description 36
- 239000012046 mixed solvent Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims abstract description 8
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 44
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 15
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 11
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 11
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 238000006073 displacement reaction Methods 0.000 abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 229940106681 chloroacetic acid Drugs 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- WGLGMILMHJAHCO-UHFFFAOYSA-M sodium;3-chloro-3-hydroxypropane-1-sulfonate Chemical compound [Na+].OC(Cl)CCS([O-])(=O)=O WGLGMILMHJAHCO-UHFFFAOYSA-M 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 18
- 239000002585 base Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000009466 transformation Effects 0.000 description 15
- 150000001412 amines Chemical class 0.000 description 12
- 239000003513 alkali Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 235000016068 Berberis vulgaris Nutrition 0.000 description 7
- 241000335053 Beta vulgaris Species 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000012190 activator Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001793 charged compounds Chemical class 0.000 description 4
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 235000021537 Beetroot Nutrition 0.000 description 3
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- ATACSYDDCNWCLV-UHFFFAOYSA-N 2-chloroacetic acid;sodium Chemical compound [Na].OC(=O)CCl ATACSYDDCNWCLV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 101710171220 30S ribosomal protein S12 Proteins 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000009096 changqing Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing betaine by long-chain tertiary amine anhydrous quaternization under normal pressure. The method comprises the following steps: in an anhydrous mixed solvent system, under the conditions of normal pressure and 110-150 ℃, long-chain tertiary amine reacts with sodium chlorohydroxypropylsulfonate or chloroacetic acid or sodium chloroacetate to generate a long-chain betaine compound. The method is particularly suitable for producing long-carbon-chain betaine compounds for oil displacement, adopts an anhydrous mixed solvent system to ensure that the reaction temperature can be increased to 110-150 ℃ under normal pressure, improves the reaction speed and the conversion rate, simultaneously inhibits the generation of hydrolysis products under the high-temperature condition, can ensure that the conversion rate is more than 95 percent within 4 hours of reaction time for quaternizing tertiary amine with a carbon chain of more than C18, effectively solves the defects of low flash point and incapability of assisting in dissolving the long-carbon-chain betaine of the conventional betaine synthesis process, and realizes the safe and efficient production of the long-carbon-chain betaine.
Description
Technical field
The invention belongs to technical field of surfactant, be specifically related to the method for the anhydrous quaternized synthesizing betaine of a kind of long chain tertiary amine normal pressure.
Background technology
Beet alkali surface activator is a kind of amphoterics, special structures shape its there is ability and the efficiency of excellent reduction surface and interface tension force, be with a wide range of applications in tertiary oil recovery field.The building-up reactions (i.e. quaterisation) of beet alkali surface activator refers to that tertiary amine and Mono Chloro Acetic Acid (sodium) or chlorine hydroxypropyl azochlorosulfonate acid sodium react to remove sodium-chlor in a solvent, generates target product beet alkali surface activator.Current industry commonly use trimethyl-glycine BS12 adopt dodecyl tertiary amine and Mono Chloro Acetic Acid (sodium) in isopropanol water solution about 80 DEG C react and form for 12 hours, transformation efficiency can reach about 90%.Shown by the research of a large amount of Structure-Property Relationships, adopt for three times trimethyl-glycine tertiary amine carbon number used at about 18-26.The tertiary amine of Long carbon chain like this reacts in isopropanol water solution, and because temperature is lower, long reaction time (being greater than 24 hours), transformation efficiency is lower (being less than 85%) also, cannot meet the quaternized processing requirement of long chain tertiary amine.Virahol makes system flash-point at about 30 DEG C as solvent simultaneously, and cannot meet rig-site utilization needs flash-point to be greater than the safety requirements of 60 DEG C.CN102618244A discloses a kind of synthetic method of beet alkali surface activator, have employed long chain tertiary amine high pressure quaterisation, and achieve long-chain trimethyl-glycine quaterisation, when the reaction times is 12 hours, transformation efficiency is greater than 90%.But this technique need be carried out in 3-10atm autoclave, and there is potential safety hazard, equipment requirements is high.
Summary of the invention
The object of the invention is to, for the shortcoming in the quaternized technique of long chain tertiary amine in above-mentioned prior art, provide the method for the anhydrous quaternized synthesizing betaine of a kind of long chain tertiary amine normal pressure.The method adopts anhydrous mixed solvent system to realize normal pressure and produces, and can ensure the safety of long-chain beet alkali surface activator, High-efficient Production.
For achieving the above object, the invention provides the method for the anhydrous quaternized synthesizing betaine of a kind of long chain tertiary amine normal pressure, it comprises the following steps: in anhydrous mixed solvent system, under normal pressure, the condition of 110 DEG C ~ 150 DEG C, long chain tertiary amine and chlorine hydroxypropyl azochlorosulfonate acid sodium or Mono Chloro Acetic Acid or sodium chloroacetate are reacted, generates long-chain betaine compound.
According to preferred specific embodiments of the present invention, in the methods described above, described anhydrous mixed solvent system was made up of several (i.e. two or more) in ethylene glycol, propylene glycol, butanols, amylalcohol, butanols Soxylat A 25-7 and hexanol Soxylat A 25-7 etc.
According to preferred specific embodiments of the present invention, in the methods described above, described anhydrous mixed solvent system was made up of several (i.e. two or more) in ethylene glycol, propylene glycol, butanols, amylalcohol and butanols Soxylat A 25-7 (2).
According to preferred specific embodiments of the present invention, in the methods described above, described anhydrous mixed solvent system is made up of ethylene glycol, propylene glycol (being preferably 1,2-PD) and amylalcohol (being preferably Pentyl alcohol); More preferably, the volume ratio of three is ethylene glycol: propylene glycol: amylalcohol=(2 ~ 4): (2 ~ 5): 1.
According to preferred specific embodiments of the present invention, in the methods described above, described anhydrous mixed solvent system is made up of ethylene glycol, propylene glycol (being preferably 1,2-PD) and butanols (being preferably propyl carbinol); More preferably, the volume ratio of three is ethylene glycol: propylene glycol: butanols=(2 ~ 5): (2 ~ 5): 1.
According to preferred specific embodiments of the present invention, in the methods described above, with the consumption of described long chain tertiary amine for 0.1mol is for benchmark, the consumption of described anhydrous mixed solvent system is 20-50mL, is more preferably 20-40mL, most preferably is 25-35mL.
According to preferred specific embodiments of the present invention, in the methods described above, temperature of reaction is 125 DEG C ~ 140 DEG C.
According to preferred specific embodiments of the present invention, in the methods described above, the reaction times is 2 hours ~ 4 hours.
According to preferred specific embodiments of the present invention, in the methods described above, the carbon number of described long chain tertiary amine is more than 18; More preferably, carbon number is 18-26.
According to preferred specific embodiments of the present invention, in the methods described above, the long-chain betaine compound generated comprises octadecyldimethyl carboxybetaine, octadecyldimethyl hydroxypropyl sultaine, docosyl dimethyl carboxybetaine, docosyl dimethyl hydroxypropyl sultaine, erucic acid acyl propyl-dimethyl carboxybetaine, erucic acid acyl propyl-dimethyl hydroxypropyl sultaine, m-xylene base hexadecyldimethylamine carboxybetaine, m-xylene base hexadecyldimethylamine hydroxypropyl sultaine, m-xylene base Eighteen alkyl acid amido propyl diformazan carboxybetaine, m-xylene base Eighteen alkyl acid amido propyl diformazan hydroxypropyl sultaine etc.More preferably, the long-chain betaine compound generated comprises octadecyldimethyl carboxybetaine, octadecyldimethyl hydroxypropyl sultaine, erucic acid acyl propyl-dimethyl carboxybetaine, erucic acid acyl propyl-dimethyl hydroxypropyl sultaine, m-xylene base hexadecyldimethylamine carboxybetaine, m-xylene base hexadecyldimethylamine hydroxypropyl sultaine etc.
In aforesaid method of the present invention, the compound that this area routine adopts is as the long chain tertiary amine (comprising fat tertiary amine, aryl tertiary aliphatic amine etc.) of raw material, chlorine hydroxypropyl azochlorosulfonate acid sodium or Mono Chloro Acetic Acid or sodium chloroacetate, its synthetic method can adopt the synthetic method of this area routine, such as method disclosed in CN102618244A, the application is quoted in full in this as a reference.In addition, the adding proportion of raw material long chain tertiary amine and chlorine hydroxypropyl azochlorosulfonate acid sodium or Mono Chloro Acetic Acid or sodium chloroacetate also can carry out conventional adjustment by those skilled in the art, and the mol ratio that such as can control long chain tertiary amine and chlorine hydroxypropyl azochlorosulfonate acid sodium or Mono Chloro Acetic Acid or sodium chloroacetate is 1:(1.1 ~ 1.3).
The method of the anhydrous quaternized synthesizing betaine of long chain tertiary amine normal pressure provided by the invention, be particularly suitable for the production of displacement of reservoir oil Long carbon chain betaine compound, under the method adopts anhydrous mixed solvent system to make normal pressure, temperature of reaction can be increased to 110 DEG C ~ 150 DEG C (preferably 125 DEG C ~ 140 DEG C), substantially increase speed of response and transformation efficiency, simultaneously anhydrous mixed solvent system effectively inhibits the generation of hydrolysate under hot conditions, tertiary amine (especially the Long carbon chain tertiary amine of C18-26) quaterisation carbochain being greater than to more than C18 can be greater than more than 95% by transformation efficiency in 4 little the reaction times, this anhydrous mixed solvent system also has the feature of high flash point and good lyotropy, product flash-point is more than 60 DEG C, efficiently solve conventional synthetic process for betaine as flash-point low, cannot the shortcoming of hydrotropy Long carbon chain trimethyl-glycine, achieve the safety of Long carbon chain trimethyl-glycine, High-efficient Production, and the trimethyl-glycine product prepared can be directly used in the displacement of reservoir oil, without the need to carrying out the steps such as solvent evaporated needed for conventional Betaine production technology.The Long carbon chain betaine type compound that this explained hereafter obtains has excellent properties, in tertiary oil recovery various fields, there is good application prospect, the composite oil-displacing system property indices of its preparation is excellent, can apply as effective oil-displacing agent in tertiary oil recovery.
Accompanying drawing explanation
Fig. 1 is the ESI-MS spectrogram of octadecyldimethyl hydroxypropyl sultaine prepared by the embodiment of the present invention 1.
Fig. 2 is the ESI-MS spectrogram of erucic acid acyl propyl-dimethyl hydroxypropyl sultaine prepared by the embodiment of the present invention 2.
Fig. 3 is the ESI-MS spectrogram of m-xylene base hexadecyldimethylamine carboxybetaine prepared by the embodiment of the present invention 3.
Fig. 4 is the ESI-MS spectrogram of m-xylene base Eighteen alkyl acid acyl dimethylamine hydroxypropyl sultaine prepared by the embodiment of the present invention 4.
Fig. 5 is the infrared figure of trimethyl-glycine prepared by comparative example 2.
Fig. 6 is the nuclear-magnetism figure of trimethyl-glycine prepared by comparative example 2.
Fig. 7 is the flooding system Daqing crude oil interfacial tension in the embodiment of the present invention 6.
Fig. 8 is the flooding system Yumen crude oil interfacial tension in the embodiment of the present invention 6.
Fig. 9 is the flooding system displacement test curve in the embodiment of the present invention 6.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
The anhydrous quaternized synthesis of embodiment 1 octadecyldimethyl hydroxypropyl sultaine normal pressure
0.1mol octadecyldimethyl tertiary amine 29.7g is added successively in the 250mL there-necked flask that thermometer, condensing reflux pipe are housed, 0.11mol trichlorine dihydroxyl propanesulfonate 21.6g, 10mL ethylene glycol, 10mL1,2-propylene glycol, 5mL propyl carbinol, then this there-necked flask is placed in 125 DEG C of oil baths, opens magnetic stirring apparatus, by measuring residual amine value detection reaction, measure amine value conversion transformation efficiency after 3 hours and be greater than 96%, close flash point is 75 DEG C.Fig. 1 is the ESI-MS spectrogram of product, and the molecular ion peak of 436m/z is the+H peak of octadecyldimethyl hydroxypropyl sultaine (Mw is 435).
The anhydrous quaternized synthesis of embodiment 2 erucic acid acyl propyl-dimethyl hydroxypropyl sultaine normal pressure
0.1mol octadecyldimethyl tertiary amine 42.2g is added successively in the 250mL there-necked flask that thermometer, condensing reflux pipe are housed, 0.12mol trichlorine dihydroxyl propanesulfonate 23.6g, 10mL ethylene glycol, 15mL1,2-propylene glycol, 3mL Pentyl alcohol, then this there-necked flask is placed in 135 DEG C of oil baths, opens magnetic stirring apparatus, by measuring residual amine value detection reaction, measure amine value conversion transformation efficiency after 2.5 hours and be greater than 95%, close flash point is 82 DEG C.Fig. 2 is the ESI-MS spectrogram of product, and the molecular ion peak of 561m/z is the+H peak of erucic acid acyl propyl-dimethyl hydroxypropyl sultaine (Mw is 560).
The anhydrous quaternized synthesis of embodiment 3 m-xylene base hexadecyldimethylamine carboxybetaine normal pressure
0.1mol m-xylene base hexadecyldimethylamine tertiary amine 40.1g is added successively in the 250mL there-necked flask that thermometer, condensing reflux pipe are housed, 0.13mol sodium chloroacetate 15.2g, 10mL ethylene glycol, 20mL1,2-propylene glycol, 4mL propyl carbinol, then this there-necked flask is placed in 140 DEG C of oil baths, opens magnetic stirring apparatus, by measuring residual amine value detection reaction, measure amine value conversion transformation efficiency after 3.5 hours and be greater than 98%, close flash point is 68 DEG C.Fig. 3 is the ESI-MS spectrogram of product, and the molecular ion peak of 460m/z is the+H peak of m-xylene base hexadecyldimethylamine carboxybetaine (Mw is 459).
The anhydrous quaternized synthesis of embodiment 4 m-xylene base Eighteen alkyl acid acyl dimethylamine hydroxypropyl sultaine normal pressure
0.1mol m-xylene base Eighteen alkyl acid acyl propyl-dimethyl tertiary amine 47.2g is added successively in the 250mL there-necked flask that thermometer, condensing reflux pipe are housed, 0.13mol trichlorine dihydroxyl propanesulfonate 25.5g, 10mL ethylene glycol, 20mL1,2-propylene glycol, 5mL Pentyl alcohol, then this there-necked flask is placed in 140 DEG C of oil baths, opens magnetic stirring apparatus, by measuring residual amine value detection reaction, measure amine value conversion transformation efficiency after 4 hours and be greater than 95%, close flash point is 70 DEG C.Fig. 4 is the ESI-MS spectrogram of product, and the molecular ion peak of 633m/z is the+Na peak of m-xylene base Eighteen alkyl acid acyl dimethylamine hydroxypropyl sultaine (Mw is 610).
Comparative example 1
0.1mol octadecyldimethyl tertiary amine 29.7g is added successively in the 250mL there-necked flask that thermometer, condensing reflux pipe are housed, 0.13mol sodium chloroacetate 15.2g, 100mL isopropanol water solution (volume ratio of Virahol and water is 2:1), then this there-necked flask is placed in 85 DEG C of oil baths, open magnetic stirring apparatus, by measuring residual amine value detection reaction, measuring amine value conversion transformation efficiency after 24 hours is about 83%, and close flash point is 26 DEG C.This shows, the tertiary amine of long-chain like this reacts in isopropanol water solution, and because temperature is lower, long reaction time, transformation efficiency is also lower, cannot meet the quaternized processing requirement of long chain tertiary amine.Virahol makes system flash-point at about 26 DEG C as solvent simultaneously, and cannot meet rig-site utilization needs flash-point to be greater than the safety requirements of 60 DEG C.
Comparative example 2
By dimethylbenzene α 18 tertiary amine (its preparation method can with reference to the embodiment 1 in CN102757775A), with chlorine hydroxypropyl azochlorosulfonate acid sodium, be that solvent is (with 0.1mol dimethylbenzene α 18 tertiary amine for benchmark with methyl alcohol, methanol usage is 100mL), 130 DEG C, react under 0.6MPa, by measuring residual amine value detection reaction, measuring amine value conversion transformation efficiency after 12 hours is about 90%, and close flash point is less than 20 DEG C.The structural identification collection of illustrative plates of the product trimethyl-glycine concrete structure of this product (can with reference to the structural formula in CN102757775A) as shown in Figure 5, Figure 6.
Infared spectrum: can see at 3421.18cm in Figure 5
-1there is association O-H stretching vibration of a larger alcohol at place.3008.96cm
-1for Ar-H stretching vibration; 1637.63cm
-1, 1463.22cm
-1for the skeletal vibration of phenyl ring; 816.42cm
-1for formation vibration outside Ar-H face of a disubstituted benzenes.2925.30cm
-1, 2853.57cm
-1for the saturated C-H stretching vibration of methyl.1199.82cm
-1for SO
3antisymmetric stretching vibration.1042.35cm
-1near be the C-N stretching vibration of tertiary amine.629.49cm
-1for SO
3out-of-plane deformation vibration.
1hNMR: as shown in Figure 6, multimodal ownership straight-chain methyl and methylene radical hydrogen near displacement 1.0-2.0, peak ownership aromatic ring methyl hydrogen near displacement 2.5, near displacement 2.7, peak ownership phenyl ring is connected methyne hydrogen, near displacement 3.3-3.5, ownership nitrogen be connected methylene radical hydrogen and the sulfonic group of methyl hydrogen, nitrogen that be connected in peak is connected methylene radical, and near displacement 3.9, peak returns hydroxyl to be connected peak ownership aromatic ring hydrogen near methyne hydrogen, displacement 7.0.Infrared and nuclear-magnetism detects and shows, synthetic product conforms to object construction.
The technique of this comparative example need be carried out in 3-10atm autoclave, and there is potential safety hazard, equipment requirements is high.Further, this technique when high pressure, temperature of reaction be 130 DEG C, the reaction times, when being 12 hours, transformation efficiency was not still more than 95%.And methyl alcohol makes system flash-point lower than 20 DEG C as solvent, cannot meet rig-site utilization needs flash-point to be greater than the safety requirements of 60 DEG C.In addition, the trimethyl-glycine product that this comparative example prepares can not be directly used in tertiary oil recovery, but needs evaporate to dryness methanol solvate, and residual methyl alcohol affects system flash-point.Also need to add other solvents for convenience of rig-site utilization, strengthen system solvability, to meet the requirement of the trimethyl-glycine oil-displacing agent for tertiary oil recovery.
The long-chain displacement of reservoir oil garden beet alkali-solubility contrast of embodiment 5 different process synthesis
The solvability of flooding system is the key index of oil-displacing agent rig-site utilization, and comparatively short carbon chain trimethyl-glycine is slightly poor for Long carbon chain trimethyl-glycine solvability, also has good solubilizing effect while the mixed solvent system that the present invention proposes meets the quaternized synthesis of normal pressure.Adopt the solvability (both carbon chain lengths are identical, solvability should quite) of Oil Field aquametry embodiment 4 and the long-chain trimethyl-glycine product of synthesis in comparative example 2, as shown in table 1.As can be seen from Table 1, the long-chain trimethyl-glycine product of synthesis in the embodiment of the present invention 4 significantly improves compared with the long-chain trimethyl-glycine product solubleness of synthesis in comparative example 2, substantially improves its solvability, improves long-chain displacement of reservoir oil garden beet alkali systems application performance.
Table 1 trimethyl-glycine solvability contrasts
The application of long-chain displacement of reservoir oil garden beet alkali in tertiary oil recovery of the anhydrous quaternized synthesis of embodiment 6 normal pressure
Water is injected at 1,600 ten thousand molecular weight partially hydrolyzed polyacrylamide polymkeric substance (product type is DQ1600) and the Changqing oilfields scene that m-xylene base hexadecyldimethylamine carboxybetaine oil-displacing agent embodiment 3 obtained, Daqing Refinery company produce, and to be mixed with trimethyl-glycine/polymkeric substance binary displacement oil system some, wherein, trimethyl-glycine active matter content is respectively 0.025wt%, 0.05wt%, 0.10wt%, 0.15wt%, 0.20wt%, and polymer content is 0.15%.As shown in Figure 7, the interface performance of visible alkali-free binary flooding system is excellent for the interfacial tension of alkali-free binary flooding system, remains ultralow, meet rig-site utilization requirement at the wider concentration window interface stress of beet alkali content 0.025-0.20wt%.
The 2500 ten thousand molecular weight partially hydrolyzed polyacrylamide polymkeric substance (product type is DQ2500) that m-xylene base Eighteen alkyl acid acyl dimethylamine hydroxypropyl sultaine oil-displacing agent embodiment 4 obtained, Daqing Refinery company produce, sodium carbonate and Yumen Oilfield be on-the-spot to be injected water to be mixed with trimethyl-glycine/polymkeric substance/sodium carbonate ternary oil displacement system some, wherein, trimethyl-glycine active matter content is respectively 0.05wt%, 0.10wt%, 0.15wt%, 0.20wt%, polymer content is 0.15%, and carbonate content is 0.5wt%.As shown in Figure 8, the interface performance of visible ternary oil displacement system is excellent for the interfacial tension of ternary oil displacement system, remains ultralow at the wider concentration window interface stress of beet alkali content 0.05-0.20wt%.Adopt trimethyl-glycine active matter content 0.20wt%, polymer content 0.15%, the ternary oil displacement system that carbonate content 0.5wt% prepares has carried out oil displacement experiment evaluation, table 2 is oil displacement experiment results, Fig. 9 is displacement of reservoir oil curve, can find out that ternary oil displacement system has good Oil Displacing Capacity, on the basis of water drive 35.4%, combination flooding improves recovery ratio and reaches 26.0%, is with a wide range of applications.
Table 2 flooding system combination flooding oil displacement experiment result
As can be seen from the above-described embodiment, the method of the anhydrous quaternized synthesizing betaine of long chain tertiary amine normal pressure provided by the invention, be particularly suitable for the production of displacement of reservoir oil Long carbon chain betaine compound, under the method adopts anhydrous mixed solvent system to make normal pressure, temperature of reaction can be increased to 110 DEG C ~ 150 DEG C (preferably 125 DEG C ~ 140 DEG C), substantially increase speed of response and transformation efficiency, simultaneously anhydrous mixed solvent system effectively inhibits the generation of hydrolysate under hot conditions, tertiary amine (especially the Long carbon chain tertiary amine of C18-26) quaterisation carbochain being greater than to more than C18 can be greater than more than 95% by transformation efficiency in 4 little the reaction times, this anhydrous mixed solvent system also has the feature of high flash point and good lyotropy, product flash-point is more than 60 DEG C, efficiently solve conventional synthetic process for betaine as flash-point low, cannot the shortcoming of hydrotropy Long carbon chain trimethyl-glycine, achieve the safety of Long carbon chain trimethyl-glycine, High-efficient Production, and the trimethyl-glycine product prepared can be directly used in the displacement of reservoir oil, without the need to carrying out the steps such as solvent evaporated needed for conventional Betaine production technology, this solvent system also has better solubilizing effect.The Long carbon chain betaine type compound that this explained hereafter obtains has excellent properties, and the composite oil-displacing system property indices of its preparation is excellent, can apply as effective oil-displacing agent in tertiary oil recovery.
Claims (10)
1. the method for the anhydrous quaternized synthesizing betaine of long chain tertiary amine normal pressure, it comprises the following steps: in anhydrous mixed solvent system, under normal pressure, the condition of 110 DEG C ~ 150 DEG C, long chain tertiary amine and chlorine hydroxypropyl azochlorosulfonate acid sodium or Mono Chloro Acetic Acid or sodium chloroacetate are reacted, generates long-chain betaine compound.
2. method according to claim 1, wherein, described anhydrous mixed solvent system is made up of several in ethylene glycol, propylene glycol, butanols, amylalcohol, butanols Soxylat A 25-7 and hexanol Soxylat A 25-7.
3. method according to claim 1 and 2, wherein, described anhydrous mixed solvent system is made up of several in ethylene glycol, propylene glycol, butanols, amylalcohol and butanols polyoxyethylene (2) ether.
4. the method according to any one of claim 1-3, wherein, described anhydrous mixed solvent system is made up of ethylene glycol, propylene glycol and amylalcohol, with volume basis, ethylene glycol: propylene glycol: amylalcohol=(2 ~ 4): (2 ~ 5): 1.
5. the method according to any one of claim 1-3, wherein, described anhydrous mixed solvent system is made up of ethylene glycol, propylene glycol and butanols, with volume basis, ethylene glycol: propylene glycol: butanols=(2 ~ 5): (2 ~ 5): 1.
6. the method according to any one of claim 1-5, wherein, with the consumption of described long chain tertiary amine for 0.1mol is for benchmark, the consumption of described anhydrous mixed solvent system is 20-50mL.
7. method according to claim 1, wherein, temperature of reaction is 125 DEG C ~ 140 DEG C.
8. method according to claim 1, wherein, the reaction times is 2 hours ~ 4 hours.
9. method according to claim 1, wherein, the long-chain betaine compound generated comprises octadecyldimethyl carboxybetaine, octadecyldimethyl hydroxypropyl sultaine, docosyl dimethyl carboxybetaine, docosyl dimethyl hydroxypropyl sultaine, erucic acid acyl propyl-dimethyl carboxybetaine, erucic acid acyl propyl-dimethyl hydroxypropyl sultaine, m-xylene base hexadecyldimethylamine carboxybetaine, m-xylene base hexadecyldimethylamine hydroxypropyl sultaine, m-xylene base Eighteen alkyl acid amido propyl diformazan carboxybetaine, m-xylene base Eighteen alkyl acid amido propyl diformazan hydroxypropyl sultaine.
10. the method according to claim 1 or 9, wherein, the long-chain betaine compound generated comprises octadecyldimethyl carboxybetaine, octadecyldimethyl hydroxypropyl sultaine, erucic acid acyl propyl-dimethyl carboxybetaine, erucic acid acyl propyl-dimethyl hydroxypropyl sultaine, m-xylene base hexadecyldimethylamine carboxybetaine, m-xylene base hexadecyldimethylamine hydroxypropyl sultaine.
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| CN115677542A (en) * | 2021-12-16 | 2023-02-03 | 上海银聪新材料科技有限公司 | Synthetic method of high-flash-point long-carbon-chain amidopropyl hydroxysulfobetaine |
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Application publication date: 20160511 |