CN102925126B - Saponin-containing composite type hydrate anti-agglomerant - Google Patents
Saponin-containing composite type hydrate anti-agglomerant Download PDFInfo
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Abstract
The present invention relates to a saponin-containing composite type hydrate anti-agglomerant, which comprises a saponin plant extract and an auxiliary anti-agglomerant. Compared to the existing anti-agglomerant, the saponin-containing composite type hydrate anti-agglomerant of the present invention has the following characteristics that: an initial generation state of a hydrate can be effectively controlled so as to effectively avoid possibly-generated hydrate aggregation when water content is high, such that dynamic control of the hydrate is easily achieved, it is ensured that hydrate crystals exist in an oil-gas-water multiphase mixing transportation pipeline in a small particle form, and accumulation and deposition phenomena can not be generated so as to effectively solve the flow safety assurance problem of the multiphase mixing transportation pipeline; the saponin plant extract in the hydrate anti-agglomerant is a nature plant extract, does not have toxicity, and is easily biodegraded, and the selected raw materials of the auxiliary anti-agglomerant are non-toxic; and the hydrate anti-agglomerant has characteristics of no toxicity, economy, environment protection, good action effect, uniform generated hydrate particle distribution, and the like.
Description
Technical field
The present invention relates to a kind of hydrate anticoagulant, relate in particular to a kind of composite hydrate anticoagulant containing saponin(e, belong to oil gas conveying technology field.
Background technology
Gas hydrate be a kind of by water and some gas molecules (for example: CH
4, C
2h
6, C
3h
8) the nonstoichiometry solid crystals material that forms under low temperature and high pressure.Gas hydrate is present in liquid with solid form conventionally; therefore the formation of hydrate solids can impact the production of Gas Company, transportation etc. conventionally; for example hydrate solids blocking pipeline or transport line, valve, safety can and other devices; cause the underproduction, the even line fracture that stops production, cause oil and gas leakage contaminate environment.The research of gas hydrate has caused the attention of many companies, particularly some oil and gas companies.
At present mainly by thermodynamic control method and two kinds of technology of dynamic control method, control or solve the harm that hydrate causes in industrial production.
Thermodynamic control method mainly contains dehydration technique, pipeline heating technique, reduction technology, interpolation thermodynamics inhibitor (as methyl alcohol, ethanol, ethylene glycol etc.) etc.First three cost of planting technology is too high, the oil gas that is not suitable for small field and long distance is carried, to adding thermodynamics inhibitor in hydrate, be in order to change the partial potential of the aqueous solution or hydrate phase, the phase equilibrium line of hydrate is moved to lower temperature or higher pressure direction, thereby reach, suppress the object that hydrate generates, but, because thermodynamics inhibitor has the features such as consumption is large, cost is high, difficulty reclaims, toxicity is large, can not meet the actual demand of current industrial transport.
Dynamic control method mainly comprises kinetic inhibition and dynamically controls two kinds of approach.Wherein, not change of kinetic inhibition method system generates the thermodynamic condition of hydrate, but significantly reduces the speed that hydrate generates, and guarantees in course of conveying not blockage phenomenon; Dynamically controlling is by controlling generation form and the growing amount of hydrate, makes it have with the even mixing of fluid-phase and with its mobile feature, thereby avoids blocking pipeline.The key of above-mentioned two kinds of methods is all the suitable chemical additive of exploitation, the former is called kinetic inhibitor (KHI or KI), the latter is called anti polymerizer (AA), because both additions are generally all lower, is therefore referred to as low dosage hydrate inhibitor (LDHI).Add after KHI, hydrate just starts to form over time, and fluid can be carried not forming under hydrate situation, thereby avoids stopping up, hydrate crystal is first form be called during this period of time inductive phase.AA is different, allows hydrate to form, but can prevent hydrate accumulation agglomerating.Can make the adding of AA hydrate as movable non-stickiness slurries be dispersed in liquid hydrocarbon mutually in, thereby guarantee that convey materials has flowable in line of pipes.
At present, it has been found that a lot of these class anti polymerizers (AA), such as IFP (I.F.P.), in its a series of patent, (Fr Pats.2625527,2625547,2625548,2697264 etc.) described large quantities of tensio-active agents that can be used as gas hydrate anti polymerizer in detail.In the patent application of having announced at present, related anti polymerizer mainly comprises the tensio-active agents such as senior phosphoric acid ester of acyl ammoniac compounds, quaternary ammonium compound, (gathering) phosphoric acid salt (ester) compounds, polyoxyethylene.But these current anti polymerizers mostly have certain toxicity, and price is also higher, is unfavorable for promoting and a large amount of use, also has some anti polymerizers also to exist the shortcomings such as effect is unstable.
Saponin(e is a kind of bio-surfactant, is distributed widely in plant, it is reported in nearly 100 various plants and contains saponin(e.Saponin(e is that a class glucosides is mainly distributed in the higher plant of land, is also present on a small quantity in rudimentary marine organisms, and it is to consist of the aglycon without sugar chain and sugar chain, according to the sugar chain connecting number be divided into monoterpene, diterpene or triterpenoid saponin.Saponin(e has been widely used in food, makeup, agricultural and medicine now, is to be mainly used as emulsifying agent, whipping agent, washing composition, foodstuff additive, bacterium and microbial culture medium, soil improvement agent, hormone raw material, immune drug auxiliary agent etc.
In Chinese patent application 201110096579.2, disclose a kind of saponins plant extract type hydrate anticoagulant, it is that extract with saponins plant is directly used as hydrate anticoagulant.Above-mentioned anti polymerizer has nontoxic, economic environmental protection, action effect is good, generate the features such as even particle distribution of hydrate, but this anti polymerizer can not make water be dispersed in oil phase, when stirring, can only disperse with fine granularity, in addition, when hydrate initially generates hydrate, generation state is platy shaped particle, when water-content is too high, the hydrate generating at first can absorb free-water around, platy shaped particle is constantly increased, although can be smashed by rotor gradually after hydrate generates completely, but hydrate not too large or that generate when static most probably can be coalescent in system disturbance, therefore be necessary further to improve.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of novel hydrate anticoagulant, take saponins plant milk extract as main raw material, add one or more complementary anti polymerizers, obtain a kind of composite hydrate anticoagulant, to reach, prevent that better hydrate is agglomerated into the object of piece.
The present invention also aims to provide a kind of method that in the mixed defeated system of oil-gas-water, hydrate is built up that suppresses, by add above-mentioned hydrate anticoagulant in the mixed defeated system of oil-gas-water, can reach the effect that good inhibition hydrate is built up.
For achieving the above object, first the present invention provides a kind of composite hydrate anticoagulant containing saponin(e, and it is comprised of saponins plant milk extract and complementary anti polymerizer.
According to concrete technical scheme of the present invention, preferably, in the gross weight of saponins plant milk extract, the saponins plant milk extract adopting in composite hydrate anticoagulant provided by the present invention is containing the saponin(e of the 5.0-30.0% that has an appointment.
In above-mentioned composite hydrate anticoagulant provided by the invention, the mass ratio of saponins plant milk extract and complementary anti polymerizer may be controlled to about 0.01-100: 1, be preferably about 0.1-10: and 1, about 0.5-7 more preferably: 1.
According to concrete technical scheme of the present invention, preferably, saponins plant milk extract of the present invention is one or more extractions in branches and leaves, rhizome and the fruit etc. of the plant that contains saponin(e.Saponin(e is extensively present in plant, all has distribution in monocotyledons and dicotyledons.Once there were 1730 kind of plant in Ren Dui104Ge section to analyze, find wherein 860 kind of plant containing the You79Ge section of saponin(e, as the plant that contains saponin(e (or claiming saponins plant) of the extraction source of saponins plant milk extract of the present invention, can comprise one or more in the plants such as the Rosaceae, Caryophyllaceae, Sapindaceae, potato preparatory course, Polygalaceae, Araeceae, Liliaceae, scrophulariaceae, pulse family, Araliaceae, Curcurbitaceae, Ranunculaceae, umbelliferae, Rhamnaceae and Primulaceae; Preferably, the above-mentioned plant that contains saponin(e comprises one or more in the plants such as the Rosaceae, Caryophyllaceae, potato preparatory course, Polygalaceae, scrophulariaceae, pulse family, Curcurbitaceae, Rhamnaceae and Primulaceae; More preferably, the above-mentioned plant that contains saponin(e comprise that Chinese honey locust, balloonflower root, potato are auspicious, one or more in ginseng, pseudo-ginseng, the wind-weed, polygala root, Radix Glycyrrhizae, tealeaves and radix bupleuri etc.
According to concrete technical scheme of the present invention, saponins plant milk extract of the present invention can be to adopt alcohol or water as solvent extraction, extracting process comprises and directly leaches or adopt the extractors such as apparatus,Soxhlet's to extract, particularly, above-mentioned saponins plant milk extract can be extracted and be obtained by following steps;
Utilize alcohol (such as dehydrated alcohol, propyl alcohol etc., wherein take dehydrated alcohol as good) plant that contains saponin(e is extracted, obtain mixed solution, mixed solution is filtered, then filtrate is carried out to underpressure distillation and obtain saturated solution, obtain saponins plant milk extract; Or, adopt water to extract the plant that contains saponin(e, obtain mixed solution, mixed solution is filtered, then filtrate is carried out to underpressure distillation to dry, will be dried thing and be dissolved in alcoholic solvent and obtain saturated solution, obtain saponins plant milk extract.
Wherein, while adopting anhydrous alcohols to extract, underpressure distillation proceeds to while there is solid and just can stop, and resulting saponins plant milk extract is a kind of concentrated saturated liquid, can be used as the saponins plant milk extract of composite hydrate anticoagulant provided by the present invention.
While adopting water to extract, underpressure distillation stops in the time of need to proceeding to water evaporate to dryness, resulting saponins plant milk extract is solid, be dissolved in solvent (such as alcoholic solvents such as ethanol) afterwards, the saturated solution obtaining can be used as the saponins plant milk extract of composite hydrate anticoagulant provided by the present invention.
While adopting alcohol solution to extract, but the concentration any concentration of alcohols, experimentation is same with employing water extraction phase, need first that extracting solution underpressure distillation is extremely dry, obtain the saponin(e plant milk extract of solid, be dissolved in solvent (such as alcoholic solvents such as ethanol) afterwards, the saturated solution obtaining can be used as the saponins plant milk extract of composite hydrate anticoagulant provided by the present invention.
In the preparation process of saponins extract, when adopting water or alcohol etc. to leach, can carry out leaching repeatedly to improve productive rate, be generally more than 2 times, preferably more than 3 times.
According to concrete technical scheme of the present invention, preferably, saponins plant milk extract can obtain by following concrete steps extraction:
The plant that contains saponin(e is ground and obtains powder;
Powder is mixed with the water of 3-10 times of (being preferably 4-6 doubly) weight, carry out 2-8 time (being preferably 3-5 time) leaching, leaching temperature is controlled as 20-100 ℃ (being preferably 50-80 ℃), each leaching time is controlled as within 1-30 hour, (the higher leaching time of temperature is shorter, and oversize meeting of time causes the decomposition of effective constituent; Adopt less powder particle and when leaching, carry out disturbance (for example suitable stirring) and can improve dissolved efficiency, reduce leaching time), obtain mixed solution, or, powder is placed in to apparatus,Soxhlet's or other extractor, to account for the water of powder weight 2-10 times (being preferably 3-5 doubly), extract, extraction time is controlled as 1-10 hour, obtains mixed solution;
Mixed solution is filtered, filtrate is carried out to underpressure distillation, until stop obtaining solid product during water evaporate to dryness;
Solid product is dissolved in to solvent (can be alcoholic solvent, such as dehydrated alcohol, glycerol, ethylene glycol etc.) and obtains saturated solution, obtain saponins plant milk extract.
According to concrete technical scheme of the present invention, preferably, saponins plant milk extract also can obtain by following concrete steps extraction:
The plant that contains saponin(e is ground and obtains powder;
The alcohol of powder and the 3-10 weight that doubly (is preferably 4-7 doubly) (such as dehydrated alcohol etc.) is mixed, carry out 2-8 time (being preferably 3-5 time) leaching, leaching temperature is controlled as 20-90 ℃ (being preferably 50-80 ℃), each leaching time is controlled as within 1-200 hour, (the higher leaching time of temperature is shorter, for example under room temperature, can adopt ethanol to leach one week, generally can not make effective constituent decompose; While adopting less powder particle and leaching, carry out disturbance (for example suitable stirring) and can improve dissolved efficiency, reduce leaching time), obtain mixed solution, or, powder is placed in to apparatus,Soxhlet's or other extractor, to account for the alcohol of powder weight 2-10 times (being preferably 3-6 doubly), extract, extraction time is controlled as 1-10 hour, obtains mixed solution;
Mixed solution is filtered, filtrate is carried out to underpressure distillation, until stop while there is solid, obtain saturated solution, obtain saponins plant milk extract.
According to concrete technical scheme of the present invention, the complementary anti polymerizer adopting in composite hydrate anticoagulant can be nonionogenic tenside; Preferably, above-mentioned ionic surfactant pack is drawn together one or more in Determination of Polyoxyethylene Non-ionic Surfactants and/or polyol-based non-ionic surfactant etc.; More preferably, above-mentioned ionic surfactant pack is drawn together one or more in high-carbon fatty alcohol polyoxyethylene ether (AEO) and/or sorbitan ester (Span series and Tween series) etc.
The present invention also provides a kind of method that in the mixed defeated system of oil-gas-water, hydrate is built up that suppresses, and it comprises that adding the above-mentioned composite hydrate anticoagulant containing saponin(e to oil-gas-water mixes the step in defeated system.
The present invention also provides the application that the hydrate in suppressing the mixed defeated system of oil-gas-water is built up of the above-mentioned composite hydrate anticoagulant containing saponin(e.
When recovering the oil, the gases such as some low-carbon alkanes that can contain part water in the oil of extraction and dissolve due to high pressure, alkene, in oily course of conveying, these water, gas all can be along with oil is carried together, therefore, generally the mixture of the oil being transferred, G&W is called to the mixed defeated system of oil-gas-water, is called for short mixed defeated system.
The effect of the composite hydrate anticoagulant containing saponin(e provided by the invention is mainly to prevent hydrate accumulation, is beneficial to improve conveying and the production effect of crude oil.In order to realize pulpous state, carry, in system, must contain a certain amount of water, when air content one regularly, the water of enough or small amount can be all for generating hydrate, and the mobility of system is declined; Although increasing, water content is conducive to improve mobility, but can greatly reduce transport efficiency, therefore, the ratio that the volume content that aforesaid method provided by the invention is particularly suitable for water accounts for oil-water two-phase cumulative volume, higher than 50.0% the mixed defeated system of oil-gas-water, is not preferably 5.0%-30.0%.
For composition and the character of delivery system, and the situation of line of pipes, can suitably adjust this containing the add-on of the composite hydrate anticoagulant of saponin(e, generally should control the more than 1.0% of mass content into water in system; The consumption that increases within the specific limits anti polymerizer is conducive to improve anti-poly-effect, in aforesaid method provided by the invention, preferably, the addition that contains the composite hydrate anticoagulant of saponin(e may be controlled to the 1.0-10.0% of the quality of water in the mixed defeated system of oil-gas-water oil-gas-water, is preferably 1.0-5.0%.
By adopting anti polymerizer provided by the invention, make the requirement of aforesaid method provided by the invention environmental aspect in pipeline course of conveying for oil-gas-water delivery system looser, for example, the temperature of the mixed defeated system of oil-gas-water may be controlled to 0-20 ℃, pressure-controlling can be 0.5-20.0MPa, thus, can produce more easily and carry.
In oil gas transportation art, three-phase mixed transferring can significantly reduce conveying cost, mixed defeated main difficulty is the generation meeting blocking pipeline of hydrate, thermodynamics inhibitor and kinetic inhibitor are mainly by preventing that the generation of hydrate from avoiding blocking pipeline, the temperature range that does not generate hydrate that anti-condensate depression degree (condensate depression) thermodynamics of reactions inhibitor and kinetic inhibitor can bear in actual fed process, the condensate depression of mixed defeated system is general all lower than 10 ℃, in carrying, oil gas generally all adds a large amount of methyl alcohol (add-on 10%-50%, poisonous, condensate depression that can anti-3-8 ℃ left and right) as thermodynamics inhibitor, also seldom there is line clogging, but, this method is not only poisonous but also price is higher, pay attention to day by day with environmental problem, this method will inevitably be eliminated, and gas extraction now also develops to deep-sea gradually, the anti-condensate depression degree of current inhibitor (comprising existing anti polymerizer) is below 15 ℃, the oil gas that is difficult to adapt to completely in the recovery process of deep-sea is carried requirement, and composite hydrate anticoagulant provided by the present invention is a kind of low dosage hydrate inhibitor---the highest can the reaching more than 20 ℃ of anti-condensate depression degree of anti polymerizer, the oil gas that can adapt to deep-sea exploitation is carried requirement, anti polymerizer does not stop the generation of hydrate in addition, the hydrate generating can absorb a large amount of gas (volume ratio 140-176: 1, generate the Sweet natural gas that 1 volume hydrate approximately consumes 140-176 volume, therefore can significantly reduce the volume of delivering gas), thereby reduce the ratio of gas in mixed defeated system, thereby can improve transport efficiency and gas volume, have broad application prospects.
Than existing anti polymerizer, composite hydrate anticoagulant containing saponin(e provided by the invention, can effectively control hydrate and initially generate state, thereby the hydrate that may occur while effectively avoiding water ratio high is coalescent, be more conducive to realize hydrate dynamic control technology, guarantee that in oil-gas-water Multi phase pipeline, hydrate crystal is present in pipeline with fine granularity, accumulation and depositional phenomenon do not occur, thereby effectively solve the mobile safety control problem of Multi phase pipeline.In this hydrate anticoagulant, containing saponins plant milk extract, be natural plant extracts, there is no toxicity and be easy to biological degradation, complementary anti polymerizer all select for poisonous material, should there is the features such as even particle distribution that nontoxic, economic environmental protection, action effect are good, generate hydrate containing saponin(e composite hydrate anticoagulant.
Accompanying drawing explanation
The following drawings is only intended to the present invention to schematically illustrate and explain, not delimit the scope of the invention.Wherein:
Fig. 1 is for evaluating the circulation line test set of the anti-poly-performance of hydrate anticoagulant;
Fig. 2 adds the online particle laser visual fractional analysis instrument of rear hydrate form for evaluating hydrate anticoagulant;
Hydrate form when the mixed defeated system of bavin oil-gas-water that Fig. 3 is 15% for the water ratio that provides in embodiment 3 adopts static that camera arrives in sapphire still;
The mixed flow of defeated system of bavin oil-gas-water and the variation relation curve of time that the water ratio that Fig. 4 provides for embodiment 7 is 10%;
Hydrate form and size picture that the mixed defeated system of bavin oil-gas-water that the water ratio that Fig. 5 provides for embodiment 9 is 20% adds the hydrate of anti polymerizer formation to adopt PVM to collect.
Drawing reference numeral explanation:
Mixing kettle 101 compressor 102 impeller pump 103 under meter 104 differential manometer 105 scanning thermometer 106 temperature sensor 107 circulating cooling pipeline 108 hydrate circulation line 109 form 110 circulator bath 111 data collecting system 112 gas cylinder 113 cooling system 114 condenser 115 autoclave 201 real-time online particle laser visual fractional analysis instrument 202 data collecting system 203 pressure transmitter 204 temperature sensor 205 gas cylinder 206 rotor 207 vapor pipe 208 magnetic stirring apparatus 209 airbaths 210
Embodiment
For technical characterictic of the present invention, object and beneficial effect being had more clearly, understand, referring now to Figure of description, technical scheme of the present invention is carried out to following detailed description, but can not be interpreted as restriction that can practical range of the present invention.
Anti-poly-performance test
1, in sapphire still, evaluate hydrate form
For the impact of the composite hydrate anticoagulant containing saponin(e provided by the invention on hydrate form is described, adopt visual transparent sapphire autoclave to test its performance, this visual transparent sapphire autoclave and corollary system thereof are mainly comprised of five parts such as high pressure sapphire still, constant temperature air bath, temperature, pressure measuring instruments, stirring system and computer data automated collection systems.The maximum functional volume of high pressure sapphire still is 78cm
3(comprising piston and stirrer), maximum working pressure is 20MPa, and operating temperature range is-90 ℃ to 150 ℃.Autoclave is furnished with LGY150A type cold light source outward, and still internal pressure can free adjustment, and the maximum working pressure (MWP) of pump is 50MPa.In still, with a packed-piston, charging fluid and experimental system can be separated.Above-mentioned transparent sapphire autoclave is the conventional device of research Hydrate Technology, and for example the shown device of Fig. 1 of Chinese patent application CN200710178198.2 (CN101377487A), is incorporated herein by reference the full text of above-mentioned patent application here.
Test procedure:
Before reaction starts, with deionized water, whole experimental system is cleaned, after vacuum-drying, by the oil-in-water emulsions preparing altogether 10mL and the composite hydrate anticoagulant containing saponin(e for preparing be in advance placed in sapphire still, setting air bath temperature is 277.2K;
When system temperature was stablized after 2 hours, (the composition gas of this experimental gas all samples from test site to pass into experimental gas, the combination of simulation Sweet natural gas, it forms in Table 1, adopt the analysis of HP6890 gas chromatograph), in displacement still, air is 3-4 time, and (hydrate being less than at this temperature generates equilibrium pressure to pass into certain pressure, the calculating of hydrate equilibrium pressure employing Chen-Guo New Hydrate Model) experimental gas makes it to reach dissolution equilibrium, forms the mixed defeated system of oil-gas-water of simulation;
Then, pass into experimental gas and make system pressure rise to 6.5MPa, close intake valve, open agitator, whole experimentation stirring velocity is invariable; Along with the carrying out of reaction, gas constantly consumes, and after pressure-stabilisation, promotes packed-piston make still internal pressure again maintain 6.5MPa by manual pump, observes the form of hydrate crystal in still by form.
Table 1, test the composition of simulation Sweet natural gas used
| Gas | CH 4 | C 2H 6 | C 3H 8 | i-C 4H 10 | n-C 4H 10 | C 5+ | C0 2 |
| Form (mol) | 0.8384 | 0.0166 | 0.0364 | 0.0076 | 0.0030 | 0.0151 | 0.0829 |
Anti polymerizer can effectively prevent that the performance that hydrate is built up from being: under predetermined temperature and pressure condition, in whole reaction process, there is not hydrate accumulation phenomenon, stirrer can freely stir all the time in still, and the most of hydrate in reactor all becomes pulpous state or cotton-shaped (concrete state changes with the variation of water ratio).
2, anti polymerizer effect and stability test in circulation line
For investigating effect and the stability of anti polymerizer in actual oil-gas-water three-phase mixed transferring process, this hydrate anticoagulant to be tested in hydrate circulation line test set, the structural representation of this device is shown in Fig. 1.This apparatus main body is the U-shaped pipe (by DB Robinson Corp., Canada manufactures) of 20m length, and its inner tube is to be by internal diameter
casting propylene acid tube form, as hydrate pipeline, can bear the pressure of 4MPa; Adopt two water-baths to carry cooling fluid (ethylene glycol solution) to circulate cooling by double-deck clamp, adopt thermopair that six precision are ± 0.1K to be arranged on and in circulation line, to measure temperature as temperature sensor 107, by precision pressure gauge, measure the pressure of system, by domestic impeller pump 103, slurries are flowed in hydrate circulation line 109, maximum delivery flow is 3000L/h.This hydrate circulation line test set detailed components and purposes are as follows: mixing kettle 101 (for holding oil-water mixture and anti polymerizer), compressor 102 (refrigeration for 115), pump 103 (for the transmitting power of system slurries), under meter 104 (measuring system slurry flow), differential manometer 105 (signal piping entrance and top hole pressure are poor), scanning thermometer 106 (showing pipeline temperature), temperature sensor 107 (temperature survey and collection), circulating cooling pipeline 108 (water coolant compound circulation line 109), hydrate circulation line 109 (hydrate conveying), form 110 (observing hydrate state), circulator bath 111, data collecting system 112 (is collected the temperature that temperature sensor 107 detects, the flow that under meter 104 detects, the pressure difference that pressure in mixing kettle 101 and differential manometer 105 detect, analyzes and provides detected result), gas cylinder 113 (for to mixing kettle 101 air feed), cooling system 114 (carrying out cooling to mixing kettle 101), condenser 115 (carrying out cooling to the pipeline except hydrate circulation line 109).
Specific experiment operation steps is as follows:
(1), prepare the experimental system of different profit volume ratios, liquid phase volume total amount is 16L;
(2), with sherwood oil and water, hydrate circulation line 109 is cleaned up successively, toward the oil solution of anti polymerizer that added the interpolation for preparing in mixing kettle 101;
(3), open temperature controlling instruments, adjust temperature to set(ting)value, and mixing kettle 101 vacuumized, remove air residual in system;
(4), when temperature, be down to and specify after experimental temperature, open intake valve, by gas cylinder 113, to slow input gas in mixing kettle 101, until system pressure, rise to while approaching experimental pressure, start impeller pump 103;
(5), in reaction process by reducing valve hierarchy of control pressure, guarantee that fluid circulates under constant pressure and steady temperature, gas flow is measured by mass-flow gas meter;
(6), whole system is by computer data acquisition system 112 automatic data collections, changes different experiment condition repetition tests.
3, PVM test water compound graininess
For investigating the graininess after the mixed defeated system hydrate of the oil-gas-water injecting after anti polymerizer forms, by online sreen analysis system (PVM), test, the test set that the present invention adopts is that the real-time online particle laser visual fractional analysis instrument of manufacturing based on German Mettler Toledo Inc. is set up, this device is mainly by autoclave 201, real-time online particle laser visual fractional analysis instrument 202, data collecting system 203 forms (seeing Fig. 2), PVM technical testing principle is: by the small portion region of six bundle illuminated with laser light detecting probe surfaces, computer is taken and be sent to the digital picture that probe is formed in real time by camera, the picture gathering by computer carries out online visual analyzing to measurement system, can see very intuitively the changing conditions of tested systems like this.Evaluating the composition of the simulation Sweet natural gas adopting forms identical with the Sweet natural gas shown in table 1.Evaluation procedure is as follows:
Before reaction starts, with deionized water, whole autoclave 201 is cleaned, after vacuum-drying, the composite hydrate anticoagulant containing saponin(e that the oil-in-water emulsions preparing is total to 400mL and prepares is in advance placed in autoclave 201, this autoclave 201 is placed in airbath 210, and the temperature of setting air bath 210 is 277.2K;
When system temperature is stablized 2 hours, (temperature is detected by temperature sensor 205, and be transferred to data collecting system 203) after, by gas cylinder 206, pass into experimental gas (in Table 1), in displacement still, air is 3-4 time, (hydrate being less than at this temperature generates equilibrium pressure to pass into certain pressure, hydrate equilibrium pressure adopts Chen-Guo New Hydrate Model to calculate, pressure value is detected by pressure transmitter 204, and be transferred to data collecting system 203) experimental gas make it to reach dissolution equilibrium, form the mixed defeated system of oil-gas-water of simulation;
Then, pass into experimental gas and make system pressure rise to 6.5MPa, close intake valve, open agitator 209, whole experimentation stirring velocity is invariable; Carrying out along with reaction, gas constantly consumes, hydrate starts to generate over time, now in the terminal of data gathering, can show the variation of slurries in reactor, state and size that hydrate can be observed hydrate after generating, in whole process, picture is gathered automatically by data collecting system 203, and acquisition rate is 5/minute.
Embodiment 1
The present embodiment provides a kind of saponins plant milk extract, and it prepares by following steps:
First choose Chinese honey locust skin (remaining skin after Chinese honey locust pod removal fruit) 100g, adopt pulverizer that Chinese honey locust shelling is broken to powdery, obtain spaonin powder;
Spaonin powder is injected to apparatus,Soxhlet's, add 600g dehydrated alcohol to carry out the extraction of 3 hours, obtain mixed solution;
Adopt Büchner funnel to carry out suction filtration to mixed solution, filtrate adopts Rotary Evaporators underpressure distillation to stop when having solid to separate out, and the concentrated solution now obtaining is saturated solution (brown liquid), i.e. saponins plant milk extract.
After measured, in the saponins plant milk extract extracting at the present embodiment, total saponin content is 21% of Chinese honey locust cortex amount, and in saponins plant milk extract, saponin(e effective concentration is 19%.
Embodiment 2
The present embodiment provides a kind of saponins plant milk extract, and it prepares by following steps:
Choose 100g Radix Glycyrrhizae, adopt mortar to be milled to powdery, obtain licorice powder;
Licorice powder is injected to flask, add 300g water at 70 ℃, to carry out the leaching of 4 hours, adopt Büchner funnel to carry out suction filtration, filter residue carries out the leaching of 4 hours again with 300g water, suction filtration is total to leaching repeatedly and suction filtration four times, obtain mixed solution, mixed solution is to leach the summation of the liquid obtaining four times;
Filter mixed solution, filtrate is concentrated and adopted vacuum distillation method by moisture evaporate to dryness wherein, obtain saponins plant milk extract solid;
Adopt anhydrous alcohol solution reconcentration to till having solid to separate out above-mentioned solid, concentrated solution is now saponins plant milk extract.
After measured, in the saponins plant milk extract extracting at the present embodiment, total saponin content is 5.1% of Radix Glycyrrhizae quality, and in saponins plant milk extract, saponin(e effective concentration is 18%.
Embodiment 3
The present embodiment provides a kind of composite hydrate anticoagulant containing saponin(e, and it is prepared by following steps:
The saponins plant milk extract extracting in embodiment 1 is mixed according to the mass ratio of 3: 1 with complementary anti polymerizer Span20, stir, obtain the composite hydrate anticoagulant containing saponin(e.
Adopt the above-mentioned anti-poly-effect that contains the composite hydrate anticoagulant of saponin(e that visual transparent sapphire autoclave and corollary system provide the present embodiment to carry out the test of hydrate form.Wherein, the oil-in-water emulsions of the mixed defeated system of oil-gas-water is formulated by 0.5mL deionized water and 9.5mL diesel oil, the volume content that is water in the mixed defeated system of oil-gas-water is 5% (Yi Shui and oily volume sum are benchmark), the total amount that adds of anti polymerizer is that 2.0wt% is (with respect to the mass content of water, as follows), the gas composition passing into is identical with the gas composition shown in table 1, and test evaluation step is identical with the test procedure of recording in anti-poly-performance test above.
Test evaluation result:
Before test, it is finely dispersed milk sap that observation adds the slurries that form after the composite hydrate anticoagulant containing saponin(e, and this expression adds the slurries original state forming after the composite hydrate anticoagulant containing saponin(e better than adding separately containing saponin(e plant extract type anti polymerizer effect; In whole test process, hydrate forms microparticle shape, there is not to build up caking, show that the composite hydrate anticoagulant containing saponin(e that the present embodiment provides has good anti-poly-effect when for water ratio being the mixed defeated system of oil-gas-water of 5% (volume), after generating hydrate, stop stirring, after 2 hours, open and stir, hydrate is caking not, this shows the hydrate good stability generating, in disturbance compared with little or all can not lump while stopping stirring and cause blocking pipeline.
Adopting the composite hydrate anticoagulant containing saponin(e that identical method provides the present embodiment is respectively 10% at water ratio, 15%, 20%, 25%, anti-poly-effect in 30% the mixed defeated system of oil-gas-water is carried out the test of hydrate form, the add-on that contains the composite hydrate anticoagulant of saponin(e is 2.0wt%, test evaluation result shows that the hydrate in above-mentioned mixed defeated system all can keep good state, and there is not to build up caking, two of water ratio 10% and 25% groups of experiments are stopped stirring restarting above for 2 hours the phenomenon that hydrate lumps does not all occur, wherein by note propane, the mode of pressurization and cooling increases condensate depression test to one of 10% water ratio group, when being 19.5 ℃, high supercooling degree there is not yet hydrate caking, more than illustrate that the composite hydrate anticoagulant containing saponin(e that the present embodiment provides all has good anti-poly-effect in water ratio is the mixed defeated system of oil-gas-water of 5-30% (volume), can bear higher condensate depression.
The hydrate slurry picture that Fig. 3 photographs while being static in 18 ℃ of jewel stills in condensate depression for the anti polymerizer that provides in this example is provided in the water ratio mixed defeated system of oil-gas-water that is 15%, hydrate is now dispersed in system with the form (can show the rough and uneven in surface particulate state that is defined as by static rear layering top) of microparticle as seen from Figure 3, do not lump, again starting to stir does not have bulk hydrate to occur yet.
Embodiment 4
The present embodiment provides a kind of composite hydrate anticoagulant containing saponin(e, and it is prepared by following steps:
Mass ratio by the saponins plant milk extract extracting in embodiment 2 and complementary anti polymerizer high-carbon fatty alcohol polyoxyethylene ether (AEO) according to 7: 1 mixes, and stirs, and obtains the composite hydrate anticoagulant containing saponin(e.
Adopting the above-mentioned composite hydrate anticoagulant containing saponin(e that visual transparent sapphire autoclave and corollary system provide the present embodiment is respectively that anti-poly-effect in 5%, 10%, 15%, 20%, 25%, 30% the mixed defeated system of oil-gas-water is carried out the test of hydrate form at water ratio, test evaluation step is identical with embodiment 3, wherein, the add-on containing the composite hydrate anticoagulant of saponin(e is 3.0wt%.
Test evaluation result: in whole test process, hydrate forms microparticle shape, do not occur to build up caking, show that the composite hydrate anticoagulant containing saponin(e that the present embodiment provides has good anti-poly-effect when for water ratio being the mixed defeated system of oil-gas-water of 5-30% (volume).
Embodiment 5
The present embodiment provides a kind of composite hydrate anticoagulant containing saponin(e, and it is prepared by following steps:
The saponins plant milk extract extracting in embodiment 1 is mixed according to the mass ratio of 2: 1 with complementary anti polymerizer Tween40, stir, obtain the composite hydrate anticoagulant containing saponin(e.
Adopting the above-mentioned composite hydrate anticoagulant containing saponin(e that visual transparent sapphire autoclave and corollary system provide the present embodiment is respectively that anti-poly-effect in 5%, 10%, 15%, 20%, 25%, 30% the mixed defeated system of oil-gas-water is carried out the test of hydrate form at water ratio, test evaluation step is identical with embodiment 3, wherein, the add-on containing the composite hydrate anticoagulant of saponin(e is 3.0wt%.
Test evaluation result: in whole test process, hydrate forms microparticle shape, do not occur to build up caking, show that the composite hydrate anticoagulant containing saponin(e that the present embodiment provides has good anti-poly-effect when for water ratio being the mixed defeated system of oil-gas-water of 5-30% (volume).
Embodiment 6
The present embodiment provides a kind of preparation method and performance evaluation containing saponin(e composite hydrate anticoagulant.
The saponins plant milk extract extracting in embodiment 1 is mixed according to the mass ratio of 2: 1 with complementary anti polymerizer Span60, stir, obtain the composite hydrate anticoagulant containing saponin(e.
Adopt the above-mentioned anti-poly-effect that contains the composite hydrate anticoagulant of saponin(e that visual transparent sapphire autoclave and corollary system provide the present embodiment to carry out test evaluation.Wherein, the oil-in-water emulsions of the mixed defeated system of oil-gas-water is formulated by 0.5mL deionized water and 9.5mL condensate oil, the volume content that is water in the mixed defeated system of oil-gas-water is 5% (Yi Shui and oily volume sum are benchmark), the total amount that adds of anti polymerizer is 1.6wt% (with respect to the mass content of water), the gas composition passing into is identical with the gas composition shown in table 1, and test evaluation step is identical with the test procedure of recording in anti-poly-performance test above.
Test evaluation result: in whole test process, hydrate forms microparticle shape, do not occur to build up caking, show that the composite hydrate anticoagulant containing saponin(e that the present embodiment provides has good anti-poly-effect when for water ratio being the mixed defeated system of oil-gas-water of 5% (volume).
Adopting the composite hydrate anticoagulant containing saponin(e that identical method provides the present embodiment is respectively 10% at water ratio, 15%, 20%, 25%, anti-poly-effect in 30% the mixed defeated system of oil-gas-water is carried out test evaluation, the add-on that contains the composite hydrate anticoagulant of saponin(e is 2.0wt%, test evaluation result shows that the hydrate in above-mentioned mixed defeated system all can keep good state, and there is not to build up caking, illustrate that the composite hydrate anticoagulant containing saponin(e that the present embodiment provides all has good anti-poly-effect in water ratio is the mixed defeated system of oil-gas-water of 5-30% (volume).
Embodiment 7
It is example that the present embodiment be take the composite hydrate anticoagulant containing saponin(e that embodiment 3 provides, and test is containing the anti-poly-effect of the composite hydrate anticoagulant of saponin(e.
Test procedure: the oil-in-water emulsions of the mixed defeated system adopting is formulated by water and the diesel oil of 1: 9 (volume ratio), the volume content that is water in system is 10% the volume sum of water and diesel oil (take be benchmark), add the hydrate anticoagulant containing saponin(e, it adds total amount is 3.0wt% (with respect to the mass content of water), obtains mixed solution;
Above-mentioned mixed solution is joined in the hydrate circulation line test set shown in Fig. 1, then pass into simulation Sweet natural gas (its composition is identical with the component shown in table 1) circular flow 24 hours, its anti-poly-effect and stability are tested.
Test result: find that by the flow of measuring in pipeline hydrate, at pipeline run duration, Hydrate Plugging phenomenon does not occur, in operational process, stop again opening after pump several minutes, by front and back fluctuations in discharge, can find out, there is not bust in its flow, this explanation is within the time out of service, and hydrate stable existence, is not gathered into piece, after apparent viscosity calculation result shows to generate hydrate, viscosity is lower, has good mobility.
Fig. 4 is that water ratio is the variation relation curve of flow, apparent viscosity and the time of the mixed defeated system of 10% bavin oil-gas-water.Flow represents the mobile speed of hydrate slurry, and apparent viscosity is an important indicator of examination hydrate slurry state system flow characteristics.The gas that carries out along with reaction is consumed fast as shown in Figure 4, and its wear rate is much larger than polishing speed.After make-up gas in system, system flow presents the state of rising, but with gas again consume and flow decline gradually, compare with the Schwellenwert that fluid after first set reaction declines, the Schwellenwert that after reaction, fluid flow rate declines is for the second time compared smaller for the first time.Generation along with hydrate, system flow reduces, by apparent viscosity curve, can see that the reduction of outflow rate is that rising due to apparent viscosity causes, after hydrate slurry stable system, flow by stopping, after in half an hour, again opening water pump and recover to flow, basic state before recovering to stop to carry after system stability of flow, this explanation stops stirring and does not occur hydrate caking, not blocking pipeline.After long-play, flow presents the trend rising by a small margin, shows thus to present for the hydrate slurry fluid containing this anti polymerizer system the characteristic of shear shinning.System is lowered the temperature to operation to improve the condensate depression of system, and result shows to reduce with the reduction system flow of temperature, and apparent viscosity raises.The system flow that does not occur to cause because of hydrate caking in whole service process reduces suddenly or blocking pipeline, and this shows containing composite hydrate anticoagulant evaluation effect in cycle of higher pressure pipeline of saponin(e better, has well anti-poly-effect.
Adopting the composite hydrate anticoagulant containing saponin(e that identical method provides the present embodiment is respectively 5% at water ratio, 10%, 15%, 20%, 25%, anti-poly-effect in 30% the mixed defeated system of oil-gas-water is carried out test evaluation, the add-on that contains the composite hydrate anticoagulant of saponin(e is 3.0wt%, test evaluation result shows to generate the phenomenon that flow bust and blocking pipeline do not occur after hydrate, the oil-gas-water that the above-mentioned composite hydrate anticoagulant containing saponin(e of this explanation is 5-30% (volume) at water ratio all has good anti-poly-effect in mixing defeated system.
Embodiment 8
It is example that the present embodiment be take the composite hydrate anticoagulant containing saponin(e that embodiment 3,4 and 5 provides, and test is containing the toxicity of the composite hydrate anticoagulant of saponin(e.
This toxotest adopts the goldfish of viewing and admiring of market sale, in test process, to the composite hydrate anticoagulant containing saponin(e that adds respectively 2000ppm embodiment 3,4 and 5 to provide in the water that has goldfish, the survival condition of then observing the goldfish in water after a week are provided.
In test process, added containing the goldfish in the water of the composite hydrate anticoagulant of saponin(e and there is no death, composite hydrate anticoagulant that contains saponin(e that this explanation embodiment 3,4 and 5 provides do not have toxicity or toxicity minimum.
Embodiment 9
It is example that the present embodiment be take the composite hydrate anticoagulant containing saponin(e that embodiment 3 provides, and measures the state generating after hydrate.
The oil-in-water emulsions of the mixed defeated system adopting is formulated by water and the diesel oil of 2: 8 (volume ratio), and in system, the volume content of water is 20%, and the composition of the Sweet natural gas passing into is identical with the composition shown in table 1.In above-mentioned mixed defeated system, add the composite hydrate anticoagulant containing saponin(e that embodiment 3 provides, adding total amount is 2.0wt%, adopts the PVM device shown in Fig. 2 to carry out hydrate granularity and morphological analysis test.
By PVM, measure, can clearly find to add the hydrate generating after the composite hydrate anticoagulant containing saponin(e block for thering is crystalline structure taper, granular size is between 30-90 μ m, with 70 about μ m at most, be uniformly dispersed, there is no large caking, see Fig. 5, this explanation is added containing the composite hydrate anticoagulant of saponin(e can effectively control the granular size that ground hydrate generates, and suppresses hydrate and is agglomerated into piece.Comparing particle with independent use saponin(e anti polymerizer bigger may be that polymerization due to the inside Span20 causes, and causes whole system to be uniformly dispersed in generating hydrate process just because of the emulsifying effectiveness of Span 20 always, is not agglomerated into piece.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the foregoing is only specific embodiments of the invention; the protection domain being not intended to limit the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (12)
1. containing a composite hydrate anticoagulant for saponin(e, it is comprised of saponins plant milk extract and complementary anti polymerizer;
Wherein, in the gross weight of described saponins plant milk extract, the saponin(e that described saponins plant milk extract contains 5.0-30.0%; The mass ratio of described saponins plant milk extract and described complementary anti polymerizer is 0.01-100:1;
Described saponins plant milk extract is that one or more extractions in branches and leaves, rhizome and the fruit of the plant that contains saponin(e obtain, described in contain saponin(e plant comprise that Chinese honey locust, balloonflower root, potato are auspicious, one or more in ginseng, pseudo-ginseng, the wind-weed, polygala root, Radix Glycyrrhizae, tealeaves and radix bupleuri.
2. composite hydrate anticoagulant according to claim 1, wherein, the mass ratio of described saponins plant milk extract and described complementary anti polymerizer is 0.1-10:1.
3. composite hydrate anticoagulant according to claim 1, wherein, described saponins plant milk extract extracts by following steps:
Utilize alcohol to extract the plant that contains saponin(e, obtain mixed solution, mixed solution is filtered, then filtrate is carried out to underpressure distillation and obtain saturated solution, obtain described saponins plant milk extract; Or,
Adopt water to extract the plant that contains saponin(e, obtain mixed solution, mixed solution is filtered, then filtrate is carried out to underpressure distillation to dry, will be dried thing and be dissolved in solvent and obtain saturated solution, obtain described saponins plant milk extract.
4. composite hydrate anticoagulant as claimed in claim 3, wherein, described saponins plant milk extract extracts by following steps:
The plant that contains saponin(e is ground and obtains powder;
Powder is mixed with the water of 3-10 times of weight, carry out 2-8 leaching, leaching temperature is controlled as 20-100 ℃, each leaching time is controlled as 1-30 hour, obtains mixed solution, or, powder is placed in to apparatus,Soxhlet's or other extractor, to account for powder weight 2-10 water doubly, extract, extraction time is controlled as 1-10 hour, obtains mixed solution;
Mixed solution is filtered, filtrate is carried out to underpressure distillation, until stop obtaining solid product during water evaporate to dryness;
Solid product is dissolved in to alcoholic solvent and obtains saturated solution, obtain described saponins plant milk extract.
5. composite hydrate anticoagulant as claimed in claim 3, wherein, described saponins plant milk extract extracts by following steps:
The plant that contains saponin(e is ground and obtains powder;
Powder is mixed with the alcohol of 3-10 times of weight, carry out 2-8 leaching, leaching temperature is controlled as 20-90 ℃, each leaching time is controlled as 1-200 hour, obtains mixed solution, or, powder is placed in to apparatus,Soxhlet's, to account for powder weight 2-10 alcohol doubly, extract, extraction time is controlled as 1-10 hour, obtains mixed solution;
Mixed solution is filtered, then filtrate is carried out to underpressure distillation, until stop while there is solid, obtain saturated solution, obtain described saponins plant milk extract.
6. composite hydrate anticoagulant according to claim 1, wherein, described complementary anti polymerizer is nonionogenic tenside.
7. composite hydrate anticoagulant according to claim 6, wherein, described ionic surfactant pack is drawn together one or more in Determination of Polyoxyethylene Non-ionic Surfactants and/or polyol-based non-ionic surfactant.
8. composite hydrate anticoagulant according to claim 7, wherein, described ionic surfactant pack is drawn together one or more in high-carbon fatty alcohol polyoxyethylene ether and/or sorbitan ester.
9. suppress the method that in the mixed defeated system of oil-gas-water, hydrate is built up, it comprises that adding the composite hydrate anticoagulant containing saponin(e described in claim 1-8 any one to described oil-gas-water mixes the step in defeated system.
10. method according to claim 9, wherein, mixes in defeated system at described oil-gas-water, and the volume content of described water accounts for the ratio of oil-water two-phase cumulative volume not higher than 50.0%.
11. methods according to claim 10, wherein, the addition of the described composite hydrate anticoagulant containing saponin(e is controlled the 1.0-10.0% for the quality of water in the mixed defeated system of described oil-gas-water.
The application that the hydrate of the composite hydrate anticoagulant containing saponin(e described in 12. claim 1-8 any one in suppressing the mixed defeated system of oil-gas-water built up.
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| CN104927821B (en) * | 2015-06-08 | 2018-03-09 | 苏州冰之火能源科技有限公司 | A kind of green compound type hydrate inhibitor and preparation method thereof |
| CN106381125B (en) * | 2016-08-26 | 2021-03-30 | 华南理工大学 | Chinese herbal medicine extract and application thereof in preparation of gas hydrate with high gas storage density |
| CN107011880B (en) * | 2017-05-22 | 2018-03-23 | 任丘市力科节能材料有限公司 | A kind of high temperature resistance pressure-bearing retaining wall agent and preparation method thereof of drilling fluid, application |
| CN109705925A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | One kind for absorb-hydration method separation gas working solution and preparation method |
| CN109135702B (en) * | 2018-09-07 | 2020-09-11 | 湘南学院 | Hydrate inhibitor and application thereof |
| CN111189957A (en) * | 2018-11-14 | 2020-05-22 | 中国石油化工股份有限公司 | Gas hydrate inhibitor performance evaluation system |
| CN111189746A (en) * | 2018-11-14 | 2020-05-22 | 中国石油化工股份有限公司 | Performance evaluation method and application of gas hydrate inhibitor |
| CN113817444B (en) * | 2020-06-18 | 2022-11-22 | 中国石油化工股份有限公司 | Composition capable of promoting hydrate formation and hydrate formation method for inhibiting hydrate aggregation |
| CN113214815B (en) * | 2021-05-07 | 2023-06-23 | 大庆永铸石油技术开发有限公司 | Nanometer microemulsion oil displacement agent and preparation method thereof |
| CN113416529A (en) * | 2021-07-07 | 2021-09-21 | 西南石油大学 | Preparation method of gas hydrate anti-agglomerant |
| CN115678514A (en) * | 2022-08-25 | 2023-02-03 | 西安石油大学 | Application of plant extract as shale hydration inhibitor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863949A (en) * | 2010-05-25 | 2010-10-20 | 青田中野天然植物科技有限公司 | Structural modification type cameclia oleifera saponin and preparation method and application thereof |
-
2011
- 2011-08-09 CN CN201110227519.XA patent/CN102925126B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863949A (en) * | 2010-05-25 | 2010-10-20 | 青田中野天然植物科技有限公司 | Structural modification type cameclia oleifera saponin and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 廖久明.皂角提取液的纯化研究.《精细石油化工》.2003,(第2期),第50-53页. * |
| 皂角提取液的纯化研究;廖久明;《精细石油化工》;20030331(第2期);第50-53页 * |
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