CN101906296A - 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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- CN101906296A CN101906296A CN2010101823281A CN201010182328A CN101906296A CN 101906296 A CN101906296 A CN 101906296A CN 2010101823281 A CN2010101823281 A CN 2010101823281A CN 201010182328 A CN201010182328 A CN 201010182328A CN 101906296 A CN101906296 A CN 101906296A
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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 production and application, employing is a base starting material with the sasanguasaponin of natural plant～sasanguasaponin or modification, 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 to adopt to come out underground) after, take physics one chemical process, change fluidic character, phase and change gas one liquid, liquid-liquid, interface effect between liquid one solid phase, what enlarge notes people water involves scope to improve oil displacement efficiency, becomes tertiary oil recovery thereby increase substantially recovery ratio again.Therefore under situation about being 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.Development of Tertiary Oil Recovery Technology is more and more higher to the requirement of tensio-active agent, 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, high temperature resistant, adsorption losses is low, cost is low requirement to the used for tertiary oil recovery tensio-active agent
The method that tertiary oil recovery improves oil recovery factor 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 aspects such as exploitation, surface chemical property research, broadened application scope, but with big gap is abroad still arranged, though they have the interfacial activity advantages of higher, but all there are temperature tolerance, salt tolerance, acid resistance and the shortcomings such as poor stability in the stratum respectively, 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 that to underground water, geology etc. comparatively serious environmental is polluted.
Therefore, it is extremely urgent to go deep into development research solubilising, alkaline-resisting, anti-salt, heatproof, displacement of reservoir oil performance good tensio-active agent and flooding system efficient, cheap, non-environmental-pollution, 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 objective of the invention is to propose that a kind of surface tension is low, the anti-salt of stable performance, alkaline-resisting, heatproof, the good green oilfield foaming agent of new type natural efficient, cheap, non-environmental-pollution of displacement of reservoir oil performance, 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 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 is a raw material with the tea dregs of rice usually, obtains the natural plant sasanguasaponin of structure shown in the formula (1) 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 glucoside
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 '～dicyclohexyl carbon imide, normal temperature stirs down and carries 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 anhydrous sodium sulfate drying after-filtration, 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 '～dicyclohexyl carbon imide, 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, make 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 glucosides
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 glucosides
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 glucosides
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 the tea seed grouts particle of grain diameter less than 2.5mm, with mass concentration is 50%～80% alcoholic solvent normal temperature dipping 1～3 hour, and described alcoholic solvent is methyl alcohol or ethanol; Filter to such an extent that get filtrate and get tea seed grouts extracting solution, described tea seed grouts extracting solution concentrates under 50～100 ℃ of conditions, and the solid content that is concentrated in the enriched material is 30～50% o'clock, 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 glucoside, 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 glucoside, the empgen BB of prescription amount, 50～80 ℃ of temperature, normal pressure stirred 0.5～3 hour down, mix, 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, the control solid content is 20～60% o'clock, promptly obtains 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
Optimized technical scheme of the present invention is as follows, and above-mentioned steps (a) is recommended in 60～70 ℃ of temperature, and normal pressure stirred 1～2 hour down, 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, preferred manufacturing procedure of the present invention is:
(a) get sasanguasaponin, Oleum Cocois diethanolamine, amidogen ether alkyl glucoside, the empgen BB of prescription amount, 65～70 ℃ of temperature, normal pressure stirred 2 hours down, mix, 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 ℃, drips water, and the control solid content is 30% o'clock, promptly obtains 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 structure activity relationship with the oil exploration and extraction technological process, according to this structure activity relationship, employing is a base starting material with natural plant sasanguasaponin and structural modification type cameclia oleifera saponin, 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: compound oilfield foaming agent of the present invention has characteristics such as acidproof, alkaline-resisting, heatproof, anti-salt, expansion ratio height, surely the bubble time is long, can adapt to the oil recovery requirement under different geology and weather condition, can not produce and pollute the oil field soil layer behind the use foaming agent, can avoid of the injury of chemosynthesis foaming agent, the environmental protection characteristic remarkable to oil field stratum.
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, foaming water discharge gas production in oil field, thereby reach the target that improves oil recovery.
(4) description of drawings
Accompanying drawing 1 is that camellia saponin type oilfield foaming agent that embodiment 6 makes is applied to aerated fluid acidifying day produce graphic representation in oblique 313 wells of careless 4-8-of Shengli Oil Field; As seen from Figure 1: volume increase is apparent in view after this well foam acidifying, construction effect is remarkable, this has also proved absolutely the superiority of the performance of this oilfield foaming agent, can be adapted to the technology 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 thereto.
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 sasanguasaponin of producing, its solid content are many 50%, and the natural plant sasanguasaponin of embodiment 4～15 derives from self-control: make as follows from method:
Got the tea seed grouts particle of grain diameter less than 2.5mm, with mass concentration is 70% alcohol solvent normal temperature dipping 2 hours, cross leaching filtrate and get tea seed grouts extracting solution, abandon filter residue, concentrate under 80 ℃ of conditions of described tea seed grouts extracting solution, the solid content that is concentrated in the enriched material is 50% o'clock (reaching requirement with the tracking and measuring degree Beaume is terminal point), takes out enriched material and is sasanguasaponin.
Embodiment 1:
(a) in the 1500L reactor, add 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 glucosides, 15 kilograms of empgen BBs respectively, be heated to 60-70 ℃ of temperature, normal pressure stirred 2 hours down, 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, promptly obtain solid content and be about 1210 kilograms of 30% natural green camellia saponin type oilfield foaming agent.
Embodiment 2:
(a) in the 1500L reactor, add 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 glucosides, 30 kilograms of empgen BBs respectively, be heated under the 70-80 ℃ of temperature, normal pressure stirred 2 hours down, 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, promptly obtain solid content and be about 1215 kilograms of 30% natural green camellia saponin type oilfield foaming agent.
Embodiment 3:
(a) in the 1500L reactor, add 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 glucosides, 30 kilograms of empgen BBs respectively, be heated under the 70-80 ℃ of temperature, normal pressure stirred 2 hours down, 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, promptly obtain solid content and be about 1230 kilograms of 30% natural green camellia saponin type oilfield foaming agent.
Embodiment 4:
(a) in the 1500L reactor, add 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 glucosides, 15 kilograms of empgen BBs respectively, be heated under the 50-60 ℃ of temperature, normal pressure stirred 3 hours down, 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, promptly obtain solid content and be about 1170 kilograms of 30% natural green camellia saponin type oilfield foaming agent.
Embodiment 5:
(a) in the 1500L reactor, add 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 glucosides, 15 kilograms of empgen BBs respectively, be heated under the 70-80 ℃ of temperature, normal pressure stirred 0.5 hour down, 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, promptly obtain solid content and be about 904 kilograms of 40% natural green camellia saponin type oilfield foaming agent.
Embodiment 6:
(a) in the 1500L reactor, add 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 glucosides, 30 kilograms of empgen BBs respectively, be heated under the 70-80 ℃ of temperature, normal pressure stirred 2 hours down, 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, promptly obtain solid content and be 30% o'clock about 1317 kilograms of natural green camellia saponin type oilfield foaming agent.
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, promptly obtain solid content and be 50% o'clock about 729 kilograms of natural green camellia saponin type oilfield foaming agent.
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, promptly obtain solid content and be about 607.5 kilograms of 60% natural green camellia saponin type oilfield foaming agent.
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 base starting material respectively--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, normal pressure stirred 60 minutes down, 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 '-dicyclohexyl carbon imide (DCC), double centner 4-Dimethylamino pyridine (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 promptly 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 the above-mentioned structural modification type cameclia oleifera saponin that makes respectively by 300 kilograms of solid contents, 3 kilograms of Oleum Cocois diethanolamine, 30 kilograms of amidogen ether alkyl glucosides, 30 kilograms of empgen BBs, be heated under the 70-80 ℃ of temperature, normal pressure stirred 2 hours down, 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, promptly obtain solid content and be about 1215 kilograms of 30% camellia saponin type oilfield foaming agent.
The preparation of structural modification type cameclia oleifera saponin:
(1) in 10000L reactor A, add base starting material respectively--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, normal pressure stirred 60 minutes down, 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 '-dicyclohexyl carbon imide (DCC), 20 kilograms of 4-Dimethylamino pyridines (DMAP) stirred 4 hours at normal temperatures;
(3) in reactor, add 400 kilogram 16 again to the Stearyl alcohol mixture, 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 promptly 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 the above-mentioned structural modification type cameclia oleifera saponin that makes respectively in 300 kilograms of solid contents, 30 kilograms of Oleum Cocois diethanolamine, 3 kilograms of amidogen ether alkyl glucosides, 15 kilograms of empgen BBs, be heated under the 50-60 ℃ of temperature, normal pressure stirred 3 hours down, 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, promptly obtain solid content and be about 1170 kilograms of 30% camellia saponin type oilfield foaming agent.
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 surface tension, foaming volume (foam height that heatproof is forward and backward), the characteristic index of foamy transformation period (transformation period that heatproof is forward and backward) are 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 preceding 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 oil recovery 20.6% and 24.1% respectively, it is obvious to improve oil recovery, the auspicious table of seeing among the embodiment 11 one 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 through Dongying at Shengli Oil Field, 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.With the oblique 313 well aerated fluid acidifyings of careless 4-8-be example day produce graphic representation as shown in Figure 1:
As seen from Figure 1: volume increase is apparent in view after this well foam acidifying, construction effect is remarkable, this has also proved absolutely the superiority of the performance of this oilfield foaming agent, can be adapted to the technology such as aerated fluid sand washing, aerated fluid acidifying, aerated fluid mixing in the oil well.
Embodiment 14:
To embodiment 2 and 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: surface tension, foaming volume (foam height that heatproof is forward and backward), characteristic index and the oil displacement efficiency of foamy transformation period (transformation period that heatproof is forward and backward) 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
By table two as can be seen: 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 unanimity.
Embodiment 15:
To embodiment 4 and 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: surface tension, foaming volume (foam height that heatproof is forward and backward), characteristic index and the oil displacement efficiency of foamy transformation period (transformation period that heatproof is forward and backward) 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
By table three as can be seen: 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 unanimity.
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:
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 glucoside
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 structural modification type cameclia oleifera saponin, prepare in accordance with the following methods: natural plant oil tea sasanguasaponin and propyl carbinol are at catalyzer 4～Dimethylamino pyridine, dewatering agent N, under the effect of N '～dicyclohexyl carbon imide, normal temperature stirs down and carries 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 anhydrous sodium sulfate drying after-filtration, 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 '～dicyclohexyl carbon imide, 14～Stearyl alcohol or its arbitrary proportion is 100: 100～200: 50～90: 10～30, the mass ratio of described natural plant sasanguasaponin, catalyzer 4～Dimethylamino pyridine 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:
The solid content that sasanguasaponin is pressed sasanguasaponin measures 100 parts
8～10 parts of Oleum Cocois diethanolamine
8～10 parts of amidogen ether alkyl glucosides
6～8 parts of empgen BBs
1～1.5 part of dimethyl dodecyl amine oxide
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:
The solid content that the natural plant sasanguasaponin is pressed the natural plant sasanguasaponin measures 100 parts
8 parts of Oleum Cocois diethanolamine
10 parts of amidogen ether alkyl glucosides
8 parts of empgen BBs
1.5 parts of dimethyl dodecyl amine oxides
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:
The solid content that structural modification type cameclia oleifera saponin is pressed structural modification type cameclia oleifera saponin measures 100 parts
10 parts of Oleum Cocois diethanolamine
8 parts of amidogen ether alkyl glucosides
6 parts of empgen BBs
1 part of dimethyl dodecyl amine oxide
5. 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 the tea seed grouts particle of grain diameter less than 2.5mm, with mass concentration is 50%～80% alcoholic solvent normal temperature dipping 1～3 hour, and described alcoholic solvent is methyl alcohol or ethanol; Cross leaching filtrate and get tea seed grouts extracting solution, described tea seed grouts extracting solution concentrates under 50～100 ℃ of conditions, and being concentrated into that consolidating in the enriched material contain is 30～50% o'clock, 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 glucoside, 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 glucoside, the empgen BB of prescription amount, 50～80 ℃ of temperature, normal pressure stirred 0.5～3 hour down, mix, 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 abundant mixing, when cooling to 40～60 ℃, drip water, the control solid content is 20～60% o'clock, promptly obtains camellia saponin type oilfield foaming agent.
7. the preparation method of described camellia saponin type oilfield foaming agent as claimed in claim 6 is characterized in that described step (a) 60～70 ℃ of temperature, and normal pressure stirred 1～2 hour down, gets mixed solution.
8. the preparation method of described camellia saponin type oilfield foaming agent as claimed in claim 1 is characterized in that described step (b) stirred 1～2 hour 70～80 ℃ of temperature.
9. the preparation method of described 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 described camellia saponin type oilfield foaming agent as claimed in claim 61 is characterized in that described preparation method is:
(a) get sasanguasaponin, Oleum Cocois diethanolamine, amidogen ether alkyl glucoside, the empgen BB of prescription amount, 65～70 ℃ of temperature, normal pressure stirred 2 hours down, mixed solution;
(b) dimethyl dodecyl amine oxide of adding prescription amount in (a) gained mixed solution under 75～80 ℃ of temperature, was mixed about 1.5 hours, when cooling to 45～50 ℃, dripped water, and the control solid content is 30% o'clock, promptly obtains 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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