CN101906296B - Camellia saponin type oilfield foaming agent and preparation method and application thereof - Google Patents
Camellia saponin type oilfield foaming agent and preparation method and application thereof Download PDFInfo
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- CN101906296B CN101906296B CN2010101823281A CN201010182328A CN101906296B CN 101906296 B CN101906296 B CN 101906296B CN 2010101823281 A CN2010101823281 A CN 2010101823281A CN 201010182328 A CN201010182328 A CN 201010182328A CN 101906296 B CN101906296 B CN 101906296B
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Abstract
The invention relates to a camellia saponin type oilfield foaming agent and a preparation method and application thereof. The oilfield foaming agent comprises the following components in part by mass: 100 parts of camellia saponin based on the solid content, 1 to 10 parts of cocoanut oil diethanol amide, 1 to 10 parts of amine ether alkyl glucoside, 1 to 10 parts of dodecyl betaine, and 0.5 to 2 parts of lauryl dimethy amine oxide, wherein the camellia saponin is natural plant source camellia saponin or structure-modified camellia saponin. The camellia saponin type oilfield foaming agent is used as an oilfield foaming agent in oil recovery, has the characteristics of acid, alkali and salt resistance, temperature resistance, high foam expansion ratio, long stable foam time and the like, can meet oil extraction requirements under different geological and weather conditions, cannot pollute an oilfield soil layer employing the foaming agent, can prevent a chemically synthesized foaming agent from harming the oilfield stratum, and has remarkable environmental protection characteristic.
Description
(1) technical field
The present invention relates to the oil field chemical technical field, be specifically related to a kind of novel oilfield foaming agent and its preparation method and application, employing is take the sasanguasaponin of natural plant～sasanguasaponin or modification as base starting material, through compatibility optimization, the camellia saponin type oilfield foaming agent that is composited, be applied in the processes such as oil drilling, completion, oil recovery, water filling, raising recovery ratio and collection be defeated.
(2) background technology
Petroleum resources are a kind of important strategic resources, intensification along with the exploratory development degree, the exploitation difficulty progressively strengthens, oil reservoir (relies on the oil reservoir primary energy through primary oil recovery, general recovery ratio only is 5%-10%, make the verified oil reserves about 90% be left on underground), secondary oil recovery is (by the water filling supplementing energy, make oil recovery rate bring up to 30%-40%, but still have the 60%-70% remaining residue at underground mining not out) after, take physics one chemical process, change the character of fluid, phase and change gas one liquid, liquid-liquid, liquid one solid interphase interface effect, what enlarge notes people water involves scope to improve oil displacement efficiency, becomes tertiary oil recovery thereby increase substantially again recovery ratio.Therefore in the situation that be becoming tight energy day, improve the key subjects that tar productivity has become oil production research, tertiary oil recovery then is a kind of method that especially effectively improves tar productivity.Tertiary oil recovery technology is a new and high technology growing up over past ten years of China, it apply improving oil recovery factor, stablizing the maturing field crude production rate and play an important role.The requirement of the development Surfactant of tertiary oil recovery technology is more and more higher, not only requires it to have low oil water interfacial tension and low adsorptive value, and requires it and reservoir fluid compatibility and cheapness.At present the oil reservoir situation of China's high temperature, high salinity has proposed anti-supersalinity, the requirement that high temperature resistant, adsorption losses is low, cost is low to surface active agent for tertiary oil recovery
The method of enhancing crude oil recovery efficiency in tertiary recovery mainly is divided into chemical method, mixed phase method, heating power method and microbial method etc.Especially obtain people's generally attention with chemical method and microbe oil production, and chemical rule demonstrates obvious superiority.
Chemical method mainly contains with tensio-active agent: (1) anion surfactant (sulfonated petro-leum, alkylbenzene sulfonate, sulfonated lignin, a one alkene sulfonate, fatty alcohol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene vitriol, fatty alcohol-polyoxyethylene ether shuttle hydrochlorate, polyoxyethylene polyoxypropylene alkane ether sulfate, the many vitriol of alkylphenol-polyethenoxy polyoxypropylene etc.); (2) nonionogenic tenside (Fatty Alcohol(C12-C14 and C12-C18) series Soxylat A 25-7, alkylphenol system, Soxylat A 25-7, alkylphenol are Soxylat A 25-7 formaldehyde condensation products, polyoxyethylene polyoxypropylene block copolymer, alkyl acid amine type, the inferior maple of polyoxyethylene poly-oxygen propylene aether, alkyl (gathering) glycoside, oleic acid polyoxyethylene phenol etc.); (3) amphoterics.
China is very fast in the development of the aspects such as exploitation, surface chemical property research, broadened application scope, but with larger gap is abroad still arranged, although they have the interfacial activity advantages of higher, but all there are respectively temperature tolerance, salt tolerance, acid resistance and the shortcomings such as poor stability in the stratum, and price is generally higher, particularly these tensio-active agents mainly are to obtain by chemical synthesis process, and long-term a large amount of the use causes comparatively serious environmental pollution to underground water, geology etc.
Therefore, go deep into development research solubilising, alkaline-resisting, anti-salt, heatproof, Oil Displacing Capacity good tensio-active agent and flooding system efficient, cheap, non-environmental-pollution extremely urgent, further improve recovery ratio to adapt to water filling later stage maturing field, this is the cutting edge technology of the world today.
(3) summary of the invention
The object of the invention is to propose that a kind of surface tension is low, that the anti-salt of stable performance, alkaline-resisting, heatproof, Oil Displacing Capacity are good is efficient, cheap, the new type natural green oilfield foaming agent of non-environmental-pollution, can be used as oil field chemical is applied in the processes such as oil drilling, completion, oil recovery, water filling, raising recovery ratio and collection be defeated, to in oil field chemical, increase environmentally friendly, ecophene, the foaming agent of diverse in function type.
The oilfield foaming agent that the present invention proposes is according to the structure activity study result to the active analysis of the body structure surface of natural plant sasanguasaponin and oil exploration and extraction technological process, adopting the natural plant sasanguasaponin or repairing structural modification type cameclia oleifera saponin is base starting material, through compatibility optimization, natural green camellia saponin type oilfield foaming agent prescription and clearer production technology route are composited.The natural plant sasanguasaponin obtains the natural plant sasanguasaponin of structure shown in the formula (1) usually take the tea dregs of rice as raw material through process for refining such as extraction, high efficiency separation.
For achieving the above object, the present invention adopts following technical scheme:
A kind of camellia saponin type oilfield foaming agent, described oilfield foaming agent is made by the component of following mass parts:
The solid content that sasanguasaponin is pressed sasanguasaponin measures 100 parts
1～10 part of Oleum Cocois diethanolamine
1～10 part of amidogen ether alkyl polyglycosides
1～10 part of empgen BB
0.5～2 part of dimethyl dodecyl amine oxide
Described sasanguasaponin is natural plant sasanguasaponin or structural modification type cameclia oleifera saponin; Described sasanguasaponin can be liquid state or solid-state, sasanguasaponin of the present invention all is that the solid content by sasanguasaponin measures, described structural modification type cameclia oleifera saponin, prepare in accordance with the following methods: sasanguasaponin and propyl carbinol are at catalyzer 4～Dimethylamino pyridine, dewatering agent N, under the effect of N '～dicyclohexylcarbodiimide, stir under the normal temperature and carry out esterification, react after 4～8 hours, add the mixture of 14～Stearyl alcohol or its arbitrary proportion, after mixing, be heated to 70～100 ℃, the control reaction pressure is 0.005～0.015MPa, stirs and carries out transesterification reaction, reacts after 1～5 hour, reacting liquid filtering, get the washing of liquor B water or 0.5～2%wt sodium chloride solution, removing catalyzer, water-soluble little because of propyl carbinol and high fatty alcohol, can use the salt water washing, but can not stir; Get organic layer and filter after with anhydrous sodium sulfate drying, get liquor C, get the liquor C underpressure distillation and reclaim propyl carbinol, residuum is described structural modification type cameclia oleifera saponin; Described natural plant sasanguasaponin, propyl carbinol, N, the mass ratio of N '～dicyclohexylcarbodiimide, cetyl alcohol is 100: 100～200: 50～90: 10～30, the mass ratio of described sasanguasaponin, catalyzer 4～Dimethylamino pyridine is 100: 1～8, and described natural plant sasanguasaponin is by its solid content metering.
The preferred described camellia saponin type oilfield foaming agent of the present invention, made by the component of following mass parts:
Sasanguasaponin is by 100 parts of the solid contents of sasanguasaponin
8～10 parts of Oleum Cocois diethanolamine
8～10 parts of amidogen ether alkyl polyglycosides
6～8 parts of empgen BBs
1～1.5 part of dimethyl dodecyl amine oxide
Further, described camellia saponin type oilfield foaming agent is recommended to be made by the component of following mass parts:
The natural plant sasanguasaponin is by 100 parts of natural plant sasanguasaponin solid contents
8 parts of Oleum Cocois diethanolamine
10 parts of amidogen ether alkyl polyglycosides
8 parts of empgen BBs
1.5 parts of dimethyl dodecyl amine oxides
Further again, described oilfield foaming agent is made by the component of following mass parts:
Structural modification type cameclia oleifera saponin is by 100 parts of structural modification type cameclia oleifera saponin solid contents
10 parts of Oleum Cocois diethanolamine
8 parts of amidogen ether alkyl polyglycosides
6 parts of empgen BBs
1 part of dimethyl dodecyl amine oxide
Natural plant sasanguasaponin of the present invention can come from commercially available, also can obtain by self-control, concrete natural plant sasanguasaponin can make as follows: got grain diameter less than the tea seed grouts particle of 2.5mm, normal temperature dipping 1～3 hour, described alcoholic solvent was methyl alcohol or ethanol take mass concentration as 50%～80% alcoholic solvent; Filter to such an extent that get filtrate and get tea seed grouts extracting solution, described tea seed grouts extracting solution is concentrated under 50～100 ℃ of conditions, when being concentrated into solid content in the enriched material and being 30～50%, takes out enriched material and is the natural plant sasanguasaponin.The present invention measures solid content by the tracking and measuring degree Beaume.
The preparation method of camellia saponin type oilfield foaming agent of the present invention, component is as follows: 100 parts of sasanguasaponins (by the sasanguasaponin solid content), 1～10 part of Oleum Cocois diethanolamine, 1～10 part of amidogen ether alkyl polyglycosides, 1～10 part of empgen BB, 0.5～2 part of dimethyl dodecyl amine oxide; The preparation method is:
(a) get sasanguasaponin, Oleum Cocois diethanolamine, amidogen ether alkyl polyglycosides, the empgen BB of prescription amount, 50～80 ℃ of temperature, stirred under the normal pressure 0.5～3 hour, mix, get mixed solution.
(b) dimethyl dodecyl amine oxide of adding prescription amount in (a) gained mixed solution, under 70～100 ℃ of temperature, stir about 0.5～2 hour, make it full and uniform, when cooling to 40～60 ℃, drip water, when the control solid content is 20～60%, namely obtain camellia saponin type oilfield foaming agent.It is terminal point that the present invention reaches the solid content requirement by the tracking and measuring degree Beaume
The preferred technical scheme of the present invention is as follows, and above-mentioned steps (a) is recommended in 60～70 ℃ of temperature, stirs under the normal pressure 1～2 hour, gets reaction solution.Described step (b) stirred 1～2 hour 70～80 ℃ of temperature.When described step (b) cools to 40～50 ℃, drip water, the control solid content is 30～50%.
Concrete, the preferred preparation method of the present invention is:
(a) get sasanguasaponin, Oleum Cocois diethanolamine, amidogen ether alkyl polyglycosides, the empgen BB of prescription amount, 65～70 ℃ of temperature, stirred 2 hours under the normal pressure, mix, get mixed solution.
(b) dimethyl dodecyl amine oxide of adding prescription amount in (a) gained mixed solution, under 75～80 ℃ of temperature, stir about 1.5 hours, when cooling to 45～50 ℃, drip water, when the control solid content is 30%, namely obtain camellia saponin type oilfield foaming agent.
The present invention is by studying active analysis of the body structure surface of natural plant sasanguasaponin and structural modification type cameclia oleifera saponin, find out the structure activity relationship with the oil exploration and extraction technological process, according to this structure activity relationship, employing is take natural plant sasanguasaponin and structural modification type cameclia oleifera saponin as base starting material, through compatibility optimization, be combined into the natural green camellia saponin type oilfield foaming agent.Described camellia saponin type oilfield foaming agent in oil recovery as the application of oilfield foaming agent.
Beneficial effect of the present invention is embodied in: the oilfield foaming agent that the present invention is compound has the characteristics such as acidproof, alkaline-resisting, heatproof, anti-salt, expansion ratio are high, surely the bubble time is long, can adapt to the oil recovery requirement under different geology and weather condition, can not produce the oil field soil layer behind the use foaming agent and pollute, can avoid the chemosynthesis foaming agent to the injury of oil field stratum, the environmental protection characteristic remarkable.
Can adopt ordinary method to be applied in the operations such as aerated fluid sand washing, aerated fluid acidifying, aerated fluid mixing, foam drilling, profile control and water plugging, foam drainage gas recovery in oil field, thereby reach the target that improves oil recovery.
(4) description of drawings
Accompanying drawing 1 be camellia saponin type oilfield foaming agent that embodiment 6 makes be applied to aerated fluid acidifying in oblique 313 wells of careless 4-8-of Shengli Oil Field day produce graphic representation; As seen from Figure 1: volume increase is apparent in view behind this well foam acidizing, construction effect is remarkable, this has also proved absolutely the superiority of the performance of this oilfield foaming agent, can be adapted to the technique such as aerated fluid sand washing, aerated fluid acidifying, aerated fluid mixing in the oil well.
(5) embodiment
The invention will be further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited to this.
The natural plant sasanguasaponin of the embodiment of the invention 1～3 derives from commercially available, by Changshan branch office of Zhejiang Orient Tea Development Co., Ltd., the liquid oils TS of producing, its solid content are that the natural plant sasanguasaponin of many 50%, embodiment 4～15 derives from self-control: make as follows from method:
Got grain diameter less than the tea seed grouts particle of 2.5mm, take mass concentration as 70% alcohol solvent normal temperature dipping 2 hours, cross leaching filtrate and get tea seed grouts extracting solution, abandon filter residue, concentrated under 80 ℃ of conditions of described tea seed grouts extracting solution, when being concentrated into solid content in the enriched material and being 50% (reaching requirement as terminal point take the tracking and measuring degree Beaume), take out enriched material and be sasanguasaponin.
Embodiment 1:
(a) in the 1500L reactor, add respectively 300 kilograms of commercially available liquid natural plant-sourced sasanguasaponins (in solid content), 15 kilograms of Oleum Cocois diethanolamine, 30 kilograms of amidogen ether alkyl polyglycosides, 15 kilograms of empgen BBs, be heated to 60-70 ℃ of temperature, stirred 2 hours under the normal pressure, mix, get mixed solution.
(b) in the mixed solution that (a) obtains, add 3 kilograms of dimethyl dodecyl amine oxides, be heated to 70-80 ℃ of temperature, stir about 1 hour, when cooling to 40-50 ℃, drip and to add water to when measuring degree Beaume and reaching requirement and be terminal point, namely obtain solid content and be approximately 1210 kilograms of 30% natural green camellia saponin type oilfield foaming agents.
Embodiment 2:
(a) in the 1500L reactor, add respectively 300 kilograms of commercially available liquid natural plant-sourced sasanguasaponins (in solid content), 3 kilograms of Oleum Cocois diethanolamine, 30 kilograms of amidogen ether alkyl polyglycosides, 30 kilograms of empgen BBs, be heated under the 70-80 ℃ of temperature, stirred 2 hours under the normal pressure, mix, get mixed solution.
(b) in the mixed solution that (a) obtains, add 1.5 kilograms of dimethyl dodecyl amine oxides, be heated to 80-90 ℃ of temperature, stir about 1 hour, when cooling to 40-50 ℃, drip and to add water to when measuring degree Beaume and reaching requirement and be terminal point, namely obtain solid content and be approximately 1215 kilograms of 30% natural green camellia saponin type oilfield foaming agents.
Embodiment 3:
(a) in the 1500L reactor, add respectively 300 kilograms of commercially available liquid natural plant-sourced sasanguasaponins (in solid content), 30 kilograms of Oleum Cocois diethanolamine, 3 kilograms of amidogen ether alkyl polyglycosides, 30 kilograms of empgen BBs, be heated under the 70-80 ℃ of temperature, stirred 2 hours under the normal pressure, mix, get mixed solution.
(b) in the mixed solution that (a) obtains, add 6 kilograms of dimethyl dodecyl amine oxides, be heated to 90-100 ℃ of temperature, stir about 0.5 hour, when cooling to 50-60 ℃, drip and to add water to when measuring degree Beaume and reaching requirement and be terminal point, namely obtain solid content and be approximately 1230 kilograms of 30% natural green camellia saponin type oilfield foaming agents.
Embodiment 4:
(a) in the 1500L reactor, add respectively 300 kilograms of self-control liquid natural plant-sourced sasanguasaponins (in solid content), 30 kilograms of Oleum Cocois diethanolamine, 3 kilograms of amidogen ether alkyl polyglycosides, 15 kilograms of empgen BBs, be heated under the 50-60 ℃ of temperature, stirred 3 hours under the normal pressure, mix, get mixed solution.
(b) in the mixed solution that (a) obtains, add 3 kilograms of dimethyl dodecyl amine oxides, be heated to 90-100 ℃ of temperature, stir about 0.5 hour, when cooling to 50-60 ℃, drip and to add water to when measuring degree Beaume and reaching requirement and be terminal point, namely obtain solid content and be approximately 1170 kilograms of 30% natural green camellia saponin type oilfield foaming agents.
Embodiment 5:
(a) in the 1500L reactor, add respectively 300 kilograms of self-control liquid natural plant-sourced sasanguasaponins (in solid content), 30 kilograms of Oleum Cocois diethanolamine, 15 kilograms of amidogen ether alkyl polyglycosides, 15 kilograms of empgen BBs, be heated under the 70-80 ℃ of temperature, stirred 0.5 hour under the normal pressure, mix, get mixed solution.
(b) in the mixed solution that (a) obtains, add 1.5 kilograms of dimethyl dodecyl amine oxides, be heated to 90-100 ℃ of temperature, stir about 1 hour, when cooling to 50-60 ℃, drip and to add water to when measuring degree Beaume and reaching requirement and be terminal point, namely obtain solid content and be approximately 904 kilograms of 40% natural green camellia saponin type oilfield foaming agents.
Embodiment 6:
(a) in the 1500L reactor, add respectively 300 kilograms of self-control liquid natural plant-sourced sasanguasaponins (in solid content), 30 kilograms of Oleum Cocois diethanolamine, 30 kilograms of amidogen ether alkyl polyglycosides, 30 kilograms of empgen BBs, be heated under the 70-80 ℃ of temperature, stirred 2 hours under the normal pressure, mix, get mixed solution.
(b) in the mixed solution that (a) obtains, add 5 kilograms of dimethyl dodecyl amine oxides, be heated to 90-100 ℃ of temperature, stir about 2 hours, when cooling to 50-60 ℃, drip and to add water to when measuring degree Beaume and reaching requirement and be terminal point, approximately 1317 kilograms of the natural green camellia saponin type oilfield foaming agents when namely obtaining solid content and being 30%.
Embodiment 7:
(a) condition is with example 5;
(b) in the mixed solution that (a) obtains, add 4.5 kilograms of dimethyl dodecyl amine oxides, be heated to 80-90 ℃ of temperature, stir about 2 hours, when cooling to 40-50 ℃, drip and to add water to when measuring degree Beaume and reaching requirement and be terminal point, approximately 729 kilograms of the natural green camellia saponin type oilfield foaming agents when namely obtaining solid content and being 50%.
Embodiment 8:
(a) condition is with example 5;
(b) in the mixed solution that (a) obtains, add 4.5 kilograms of dimethyl dodecyl amine oxides, be heated to 80-90 ℃ of temperature, stir about 2 hours, when cooling to 55-60 ℃, drip and to add water to when measuring degree Beaume and reaching requirement and be terminal point, namely obtain solid content and be approximately 607.5 kilograms of 60% natural green camellia saponin type oilfield foaming agents.
Embodiment 9 is with the preparation of the preparation camellia saponin type oilfield foaming agent structural modification type cameclia oleifera saponin of structural modification type cameclia oleifera saponin:
(1) in 10000L reactor A, add respectively base starting material--2000 kilograms of the self-control sasanguasaponins (in solid content) described in the present invention (five) embodiment, 3000 kilograms of propyl carbinols, be steam heated to 60～70 ℃ of temperature, stirred 60 minutes under the normal pressure, sasanguasaponin is fully dissolved, be cooled to 50 ℃ of filtrations, filtrate is pumped among another 10000L reactor B.
(2) in reactor B, add 1500 kilograms of N, N '-dicyclohexylcarbodiimide (DCC), double centner DMAP (DMAP) stirred 5 hours at normal temperatures.
(3) in reactor, add 400 kilograms of cetyl alcohols again, stirred at normal temperatures 3 hours.Be steam heated to 80～90 ℃, be decompressed to 0.01MPa, stirred 2 hours.Filter, keep filtrate.
(4) add 3000 kilogram of 1% salt solution washing to filtrate, repeat to wash 1 time with 3000 kilogram of 1% salt solution again, discard water layer.The upper strata organic layer adds the anhydrous sodium sulphate double centner, stirs 30 minutes, filters, and keeps filtrate.Filtrate is heated to 100 ℃, is decompressed to 0.01MPa, stirs 2 hours, reclaims propyl carbinol and catalyzer and applies mechanically, and gets residuum after the cooling and namely gets 2800 kilograms of structural modification type cameclia oleifera saponins, and solid content is 50%.
The preparation of camellia saponin type oilfield foaming agent:
(a) in the 1500L reactor, add respectively the above-mentioned structural modification type cameclia oleifera saponin that makes by 300 kilograms of solid contents, 3 kilograms of Oleum Cocois diethanolamine, 30 kilograms of amidogen ether alkyl polyglycosides, 30 kilograms of empgen BBs, be heated under the 70-80 ℃ of temperature, stirred 2 hours under the normal pressure, mix, get mixed solution.
(b) in the mixed solution that (a) obtains, add 1.5 kilograms of dimethyl dodecyl amine oxides, be heated to 80-90 ℃ of temperature, stir about 1 hour, when cooling to 40-50 ℃, drip and to add water to when measuring degree Beaume and reaching requirement and be terminal point, namely obtain solid content and be approximately 1215 kilograms of 30% camellia saponin type oilfield foaming agents.
The preparation of structural modification type cameclia oleifera saponin:
(1) in 10000L reactor A, add respectively base starting material--2000 kilograms of the self-control sasanguasaponins (in solid content) described in the present invention (five) embodiment, 2000 kilograms of propyl carbinols, be steam heated to 50～70 ℃ of temperature, stirred 60 minutes under the normal pressure, sasanguasaponin is fully dissolved, be cooled to 20 ℃ of filtrations, filtrate is pumped among another 10000L reactor B.
(2) in reactor B, add 1000 kilograms of N, N '-dicyclohexylcarbodiimide (DCC), 20 kilograms of DMAPs (DMAP) stirred 4 hours at normal temperatures;
(3) in reactor, add 400 kilogram 16 to the Stearyl alcohol mixture again, stirred at normal temperatures 3 hours.Be steam heated to 80～90 ℃, be decompressed to 0.01MPa, stirred 2 hours.Filter, keep filtrate.
(4) add 3000 kilogram of 1% salt solution washing to filtrate, repeat to wash again 1 time, discard water layer.The upper strata organic layer adds the anhydrous sodium sulphate double centner, stirs 30 minutes, filters, and keeps filtrate.Filtrate is heated to 100 ℃, is decompressed to 0.01MPa, stirs 2 hours, reclaims propyl carbinol and catalyzer and applies mechanically, and gets residuum after the cooling and namely gets 2800 kilograms of structural modification type cameclia oleifera saponins, and solid content is 60%.
The preparation of camellia saponin type oilfield foaming agent:
(a) in the 1500L reactor, add respectively the above-mentioned structural modification type cameclia oleifera saponin that makes in 300 kilograms of solid contents, 30 kilograms of Oleum Cocois diethanolamine, 3 kilograms of amidogen ether alkyl polyglycosides, 15 kilograms of empgen BBs, be heated under the 50-60 ℃ of temperature, stirred 3 hours under the normal pressure, mix, get mixed solution.
(b) in the mixed solution that (a) obtains, add 3 kilograms of dimethyl dodecyl amine oxides, be heated to 90-100 ℃ of temperature, stir about 0.5 hour, when cooling to 50-60 ℃, drip and to add water to when measuring degree Beaume and reaching requirement and be terminal point, namely obtain solid content and be approximately 1170 kilograms of 30% camellia saponin type oilfield foaming agents.
Embodiment 11:
The characteristic index evaluation of the camellia saponin type oilfield foaming agent that embodiment 6 is made, carry out in China University Of Petroleum Beijing aerated fluid research centre, particularly its characteristic index of transformation period (transformation period that heatproof is forward and backward) of surface tension, foaming volume (foam height that heatproof is forward and backward), foam is estimated, the evaluation code name of natural green camellia saponin type oilfield foaming agent is " the special-purpose foaming agent in natural plant ZYH-0860 oil field ", and evaluation result sees Table one:
Word is commented in oily research centre in table one, the sample appraisal report: UPC-FRC-J-0011 number
China University Of Petroleum Beijing aerated fluid research centre
Evaluation result shows: the characteristic index of natural green camellia saponin type oilfield foaming agent, particularly surface tension obviously reduce than compatibility optimization, compound front sasanguasaponin (surface tension 47-51mN/m), all meet the requirement of the special-purpose foaming agent in oil field.
Embodiment 12:
The camellia saponin type oilfield foaming agent that embodiment 6 is made is to improving the important indicator evaluation of oil recovery, carry out in China University Of Petroleum Beijing aerated fluid research centre, adopt single tube model and two kinds of method comparative evaluations of parallel two-tube model, the condition of single tube model: Φ 25 * 600mm, rate of permeation 915 * 10
-3μ m
2, porosity 31.5%, simulated oil viscosity 10.8mPas, rate of displacement 0.2mL/min, foaming agent concentration 0.3%, foam vapour-liquid ratio 1: 1.The condition of parallel two-tube model: (model A: Φ 25 * 600mm, rate of permeation 987 * 10
-3μ m
2, porosity 31.9%, Model B: Φ 25 * 600mm, rate of permeation 4006 * 10
-3μ m
2, porosity 35.6%), simulated oil viscosity 10.8mPas, rate of displacement 0.4mL/min, foaming agent concentration 0.3%, foam vapour-liquid ratio 1: 1.
Adopt single tube model and parallel two-tube model trial, can improve respectively oil recovery 20.6% and 24.1%, improve oil recovery obvious, the auspicious table one of seeing among the embodiment 11 of evaluation result.
Embodiment 13:
The camellia saponin type oilfield foaming agent that embodiment 6 makes (application code name: the special-purpose foaming agent in natural plant ZYH-0860 oil field), converge construction application in rich Petroleum Technology Co., Ltd some oil wells at Shengli Oil Field through Dongying, such as the aerated fluid sand washing at wells such as the aerated fluid acidifying of oblique 313 wells of careless 4-8-, Zheng 411-flat 3, flat 4, flat 5, flat 63, the aerated fluid mixing of GDGB1X9, B3X35 well etc. all use this foaming agent to finish smoothly to construct and is obtained good effect.Day as an example of the oblique 313 well aerated fluid acidifyings of careless 4-8-example is produced graphic representation as shown in Figure 1:
As seen from Figure 1: volume increase is apparent in view behind this well foam acidizing, construction effect is remarkable, this has also proved absolutely the superiority of the performance of this oilfield foaming agent, can be adapted to the technique such as aerated fluid sand washing, aerated fluid acidifying, aerated fluid mixing in the oil well.
Embodiment 14:
To embodiment 2 and the embodiment 9 effect comparative experiments as oilfield foaming agent.
The effect of the camellia saponin type oilfield foaming agent that embodiment 2 and embodiment 9 are made as: characteristic index and the oil displacement efficiency of the transformation period (transformation period that heatproof is forward and backward) of surface tension, foaming volume (foam height that heatproof is forward and backward), foam compare experiment, and it the results are shown in Table two:
The oilfield foaming agent effect comparison sheet that table two embodiment 2 and embodiment 9 make
Can be found out by table two: the performance of the camellia saponin type oilfield foaming agent that embodiment 2 and embodiment 9 make is close, and surface tension and transformation period (transformation period after the heatproof), embodiment 9 slightly was better than embodiment 2; But oil displacement efficiency is consistent.
Embodiment 15:
To embodiment 4 and the embodiment 10 effect comparative experiments as oilfield foaming agent.
The effect of the camellia saponin type oilfield foaming agent that embodiment 4 and embodiment 10 are made as: characteristic index and the oil displacement efficiency of the transformation period (transformation period that heatproof is forward and backward) of surface tension, foaming volume (foam height that heatproof is forward and backward), foam compare experiment, and it the results are shown in Table three:
The oilfield foaming agent effect comparison sheet that table three embodiment 4 and embodiment 10 make
Can be found out by table three: the performance of the camellia saponin type oilfield foaming agent that embodiment 4 and embodiment 10 make is close, surface tension, foaming volume (foam height after the heatproof) and the transformation period (transformation period after the heatproof) embodiment 10 slightly be better than embodiment 4; But oil displacement efficiency is consistent.
Claims (11)
1. a camellia saponin type oilfield foaming agent is characterized in that, described oilfield foaming agent is made by the component of following mass parts:
Described sasanguasaponin is natural plant sasanguasaponin or structural modification type cameclia oleifera saponin;
Described structural modification type cameclia oleifera saponin, prepare in accordance with the following methods: natural plant oil tea sasanguasaponin and propyl carbinol are at the catalyzer DMAP, dewatering agent N, under the effect of N '-dicyclohexylcarbodiimide, stir under the normal temperature and carry out esterification, react after 4～8 hours, the mixture that adds 14～Stearyl alcohol or its arbitrary proportion, after mixing, be heated to 70～100 ℃, the control reaction pressure is 0.005～0.015MPa, stirs and carries out transesterification reaction, reacts after 1～5 hour, reacting liquid filtering, get the washing of liquor B water or 0.5～2%wt sodium chloride solution, get organic layer and filter after with anhydrous sodium sulfate drying, get liquor C, get the liquor C underpressure distillation and reclaim propyl carbinol and catalyzer, residuum is described structural modification type cameclia oleifera saponin; Described natural plant sasanguasaponin, propyl carbinol, N, the mass ratio of the mixture of N '-dicyclohexylcarbodiimide, 14～Stearyl alcohol or its arbitrary proportion is 100:100～200:50～90:10～30, the mass ratio of described natural plant sasanguasaponin, catalyzer DMAP is 100:1～8, and described natural plant sasanguasaponin is by its solid content metering.
2. camellia saponin type oilfield foaming agent as claimed in claim 1 is characterized in that, described oilfield foaming agent is made by the component of following mass parts:
3. camellia saponin type oilfield foaming agent as claimed in claim 1 is characterized in that, described oilfield foaming agent is made by the component of following mass parts:
4. camellia saponin type oilfield foaming agent as claimed in claim 1 is characterized in that described oilfield foaming agent made by the component of following mass parts:
5. such as the described camellia saponin type oilfield foaming agent of one of claim 1～3, it is characterized in that described natural plant sasanguasaponin makes as follows: get grain diameter less than the tea seed grouts particle of 2.5mm, normal temperature dipping 1～3 hour, described alcoholic solvent was methyl alcohol or ethanol take mass concentration as 50%～80% alcoholic solvent; Cross leaching filtrate and get tea seed grouts extracting solution, described tea seed grouts extracting solution is concentrated under 50～100 ℃ of conditions, is concentrated into consolidating in the enriched material and contains when being 30～50%, takes out enriched material and is natural plant oil sasanguasaponin.
6. the preparation method of a camellia saponin type oilfield foaming agent as claimed in claim 1, it is characterized in that, described oilfield foaming agent is made by the component of following mass parts: sasanguasaponin is by 100 parts of its solid content meterings, 1～10 part of Oleum Cocois diethanolamine, 1～10 part of amidogen ether alkyl polyglycosides, 1～10 part of empgen BB, 0.5～2 part of dimethyl dodecyl amine oxide; Described preparation method is:
(a) get sasanguasaponin, Oleum Cocois diethanolamine, amidogen ether alkyl polyglycosides, the empgen BB of prescription amount, 50～80 ℃ of temperature, stirred under the normal pressure 0.5～3 hour, mix, get mixed solution;
(b) dimethyl dodecyl amine oxide of adding prescription amount in (a) gained mixed solution under 70～100 ℃ of temperature, stirred 0.5～2 hour, make abundant mixing, when cooling to 40～60 ℃, drip water, when the control solid content is 20～60 %, namely obtain camellia saponin type oilfield foaming agent.
7. the preparation method of camellia saponin type oilfield foaming agent as claimed in claim 6 is characterized in that described step (a) 60～70 ℃ of temperature, stirred under the normal pressure 1～2 hour, gets mixed solution.
8. the preparation method of camellia saponin type oilfield foaming agent as claimed in claim 6 is characterized in that described step (b) stirred 1～2 hour 70～80 ℃ of temperature.
9. the preparation method of camellia saponin type oilfield foaming agent as claimed in claim 6 is characterized in that described step (b) drips water, and the control solid content is 30～50 %.
10. the preparation method of camellia saponin type oilfield foaming agent as claimed in claim 6 is characterized in that described preparation method is:
(a) get sasanguasaponin, Oleum Cocois diethanolamine, amidogen ether alkyl polyglycosides, the empgen BB of prescription amount, 65～70 ℃ of temperature, stirred 2 hours under the normal pressure, get mixed solution;
(b) dimethyl dodecyl amine oxide of adding prescription amount in (a) gained mixed solution under 75～80 ℃ of temperature, stirred 1.5 hours, when cooling to 45～50 ℃, dripped water, when the control solid content is 30 %, namely obtained camellia saponin type oilfield foaming agent.
11. camellia saponin type oilfield foaming agent as claimed in claim 1 in oil recovery as the application of oilfield foaming agent.
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| CN104403653A (en) * | 2014-11-17 | 2015-03-11 | 合肥学院 | Environment-friendly tertiary oil recovery oil-displacing agent based on biosurfactant |
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| CN107236529A (en) * | 2014-12-01 | 2017-10-10 | 程叶红 | Tea saponin modification agent and its oil displacement agent of preparation |
| CN104874329A (en) * | 2015-06-03 | 2015-09-02 | 中国科学院沈阳应用生态研究所 | Application of plant source surface active agent |
| CN109943307B (en) * | 2019-04-26 | 2020-04-03 | 中国石油大学(华东) | Foam solution for profile control plugging in thick oil thermal recovery process, preparation method thereof, foam system and profile control plugging method |
| CN114958328B (en) * | 2022-04-29 | 2023-09-19 | 常州大学 | Application of tea-oil saponin foaming agent in tertiary oil recovery |
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