CN102925126A - Saponin-containing composite type hydrate anti-agglomerant - Google Patents
Saponin-containing composite type hydrate anti-agglomerant Download PDFInfo
- Publication number
- CN102925126A CN102925126A CN201110227519XA CN201110227519A CN102925126A CN 102925126 A CN102925126 A CN 102925126A CN 201110227519X A CN201110227519X A CN 201110227519XA CN 201110227519 A CN201110227519 A CN 201110227519A CN 102925126 A CN102925126 A CN 102925126A
- Authority
- CN
- China
- Prior art keywords
- hydrate
- saponin
- water
- gas
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Medicines Containing Plant Substances (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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 that contains 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 under low temperature and high pressure, forms.Gas hydrate is present in the liquid with solid form usually; therefore the formation of hydrate solids can impact the production of Gas Company, transportation etc. usually; for example hydrate solids blocking pipeline or transport line, valve, safety can and other devices; cause the underproduction, stopping production even line fracture, cause the 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 control or solve the harm that hydrate causes by thermodynamic control method and two kinds of technology of dynamic control method in industrial production.
The thermodynamic control method mainly contains dehydration technique, pipeline heating technique, reduction technology, interpolation thermodynamics inhibitor (such 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, adding the thermodynamics inhibitor in the hydrate is in order to change the partial potential of the aqueous solution or hydration phase, so that the phase equilibrium line of hydrate moves to lower temperature or higher pressure direction, suppress the purpose that hydrate generates thereby reach, but the characteristics such as consumption is large, cost is high because the thermodynamics inhibitor has, difficulty reclaims, toxicity is large can not satisfy the actual demand of present 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 the speed that the decrease hydrate generates, and guarantees in course of conveying not blockage phenomenon; Dynamically control is generation form and the growing amount by the control hydrate, it is had with the even mixing of fluid-phase and with its characteristics that flow, thereby avoid blocking pipeline.The key of above-mentioned two kinds of methods all is 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, therefore is referred to as low dosage hydrate inhibitor (LDHI).After adding KHI, hydrate just begins to form over time, and fluid can be carried not forming under the hydrate situation, thereby avoids stopping up, hydrate crystal is first form be called during this period of time inductive phase.AA is then different, allows hydrate to form, but can prevent hydrate accumulation and agglomerating.The adding of AA can make 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), 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 the gas hydrate anti polymerizer in detail such as IFP (I.F.P.).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 in the patent application of having announced at present.But these present anti polymerizers mostly have certain toxicity, and price is also higher, are unfavorable for promoting and a large amount of the use, also have 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 the plant, it is reported to contain saponin(e in nearly 100 various plants.Saponin(e is that a class glucosides mainly is distributed in the higher plant of land, also is present on a small quantity in the rudimentary marine organisms, and it is to be made of aglycon and sugar chain without sugar chain, how much is divided into monoterpene, diterpene or triterpenoid saponin according to the sugar chain that connects.Saponin(e has been widely used in food, makeup, agricultural and the medicine now, mainly is to be 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.
Disclose a kind of saponins plant extract type hydrate anticoagulant in Chinese patent application 201110096579.2, it is that extract with the saponins plant directly is used as hydrate anticoagulant.Above-mentioned anti polymerizer has nontoxic, economic environmental protection, action effect is good, generate the characteristics such as even particle distribution of hydrate, but this anti polymerizer can not make water be dispersed in the oil phase, when stirring, can only disperse with fine granularity, in addition, when hydrate initially generates hydrate, the generation state is platy shaped particle, when water-content is too high, free-water around the hydrate that generates at first can absorb, platy shaped particle is constantly increased, although can be smashed by rotor gradually after hydrate generates fully, the hydrate that generates when the system disturbance is not too large or static most probably can be coalescent, therefore is 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 the saponins plant milk extract as main raw material, add one or more complementary anti polymerizers, obtain a kind of composite hydrate anticoagulant, prevent better that to reach hydrate is agglomerated into the purpose of piece.
The present invention also aims to provide a kind of method that hydrate is built up in the mixed defeated system of oil-gas-water that suppresses, by in the mixed defeated system of oil-gas-water, adding above-mentioned hydrate anticoagulant, can reach the effect that good inhibition hydrate is built up.
For achieving the above object, the present invention at first provides a kind of composite hydrate anticoagulant that contains 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 that adopts in the composite hydrate anticoagulant provided by the present invention contains 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 by one or more extractions in branches and leaves, rhizome and the fruit etc. of the plant that contains saponin(e.Saponin(e extensively is present in the plant, and distribution is all arranged in monocotyledons and the dicotyledons.Once there was the people that 1730 kind of plant in 104 sections are analyzed, find wherein to contain 860 kind of plant that 79 sections are arranged of saponin(e, 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 as the plant that contains saponin(e (or claiming saponins plant) of the extraction source of saponins plant milk extract of the present invention; 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, in ginseng, pseudo-ginseng, the wind-weed, polygala root, Radix Glycyrrhizae, tealeaves and radix bupleuri etc. one or more.
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 obtain by the following steps extraction;
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 underpressure distillation and obtain saturated solution, namely obtain the saponins plant milk extract; Perhaps, adopt water that the plant that contains saponin(e is extracted, obtain mixed solution, mixed solution is filtered, then filtrate is carried out underpressure distillation to dry, dry thing is dissolved in obtains saturated solution in the alcoholic solvent, namely obtain the saponins plant milk extract.
Wherein, when adopting anhydrous alcohols to extract, underpressure distillation proceeds to when solid occurring and just can stop, and resulting saponins plant milk extract is a kind of concentrated saturated liquid, namely can be used as the saponins plant milk extract of composite hydrate anticoagulant provided by the present invention.
When adopting water to extract, underpressure distillation stops in the time of need to proceeding to the water evaporate to dryness, resulting saponins plant milk extract is solid, it is dissolved in solvent (such as alcoholic solvents such as ethanol) afterwards, and the saturated solution that obtains can be used as the saponins plant milk extract of composite hydrate anticoagulant provided by the present invention.
When adopting alcohol solution to extract, but the concentration any concentration of alcohols, experimentation and employing water extraction phase are together, namely need first that the extracting solution underpressure distillation is extremely dry, obtain the saponin(e plant milk extract of solid, it is dissolved in solvent (such as alcoholic solvents such as ethanol) afterwards, and the saturated solution that obtains 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 to wait to leach, can carry out repeatedly leaching with the raising productive rate, be generally more than 2 times, preferably more than 3 times.
According to concrete technical scheme of the present invention, preferably, the saponins plant milk extract can obtain by following concrete steps extraction:
The plant that will contain saponin(e grinds and obtains powder;
The water of powder with 3-10 times of (being preferably 4-6 doubly) weight is mixed, carry out 2-8 time (being preferably 3-5 time) leaching, leaching temperature is controlled to be 20-100 ℃ (being preferably 50-80 ℃), each leaching time is controlled to be 1-30 hour, and (the higher leaching time of temperature is shorter, and the time, oversize meeting caused the decomposition of effective constituent; Adopt less powder particle and carry out disturbance (for example suitable stirring) in when leaching and can improve dissolved efficiency, reduce leaching time), obtain mixed solution, perhaps, powder is placed apparatus,Soxhlet's or other extractor, extract with the water that accounts for powder weight 2-10 times (being preferably 3-5 doubly), extraction time is controlled to be 1-10 hour, obtains mixed solution;
Mixed solution is filtered, filtrate is carried out underpressure distillation, until stop to obtain solid product during the water evaporate to dryness;
Solid product is dissolved in solvent (can be alcoholic solvent, such as dehydrated alcohol, glycerol, ethylene glycol etc.) obtains saturated solution, namely obtain the saponins plant milk extract.
According to concrete technical scheme of the present invention, preferably, the saponins plant milk extract also can obtain by following concrete steps extraction:
The plant that will contain saponin(e grinds 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 to be 20-90 ℃ (being preferably 50-80 ℃), each leaching time is controlled to be 1-200 hour, and (the higher leaching time of temperature is shorter, for example can adopt ethanol to leach a week under the room temperature, effective constituent is decomposed; Carry out disturbance (for example suitable stirring) when adopting less powder particle and leaching and can improve dissolved efficiency, reduce leaching time), obtain mixed solution, perhaps, powder is placed apparatus,Soxhlet's or other extractor, extract with the alcohol that accounts for powder weight 2-10 times (being preferably 3-6 doubly), extraction time is controlled to be 1-10 hour, obtains mixed solution;
Mixed solution is filtered, filtrate is carried out underpressure distillation, until stop when solid occurring, obtain saturated solution, namely obtain the saponins plant milk extract.
According to concrete technical scheme of the present invention, the complementary anti polymerizer that adopts 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 the 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 the sorbitan ester (Span series and Tween series) etc.
The present invention also provides a kind of method that hydrate is built up in the mixed defeated system of oil-gas-water that suppresses, and it comprises and adds the above-mentioned composite hydrate anticoagulant that contains saponin(e in the mixed defeated system of oil-gas-water step.
The application that the present invention also provides the above-mentioned hydrate of composite hydrate anticoagulant in suppressing the mixed defeated system of oil-gas-water that contains saponin(e to build up.
When recovering the oil, the gases such as some low-carbon alkanes that can contain part water in the oil of extraction and dissolve owing to high pressure, alkene, in the course of conveying of oil, these water, gas all can be along with oil is carried together, therefore, the oil that generally will be transferred, the mixture of G﹠W are called the mixed defeated system of oil-gas-water, are called for short mixed defeated system.
The effect that contains the composite hydrate anticoagulant of saponin(e provided by the invention mainly is to prevent the hydrate accumulation, is beneficial to improve conveying and the production effect of crude oil.In order to realize that pulpous state carries, must contain a certain amount of water in the system, when air content one regularly, the water of capacity or small amount can all be used for the generation hydrate, and makes the flowability decline of system; Although increasing, water content is conducive to improve flowability, 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 is not higher than 50.0% the mixed defeated system of oil-gas-water, is preferably 5.0%-30.0%.
For composition and the character of delivery system, and the situation of line of pipes, can suitably adjust the add-on that this contains the composite hydrate anticoagulant of saponin(e, generally should be controlled to be more than 1.0% of mass content of water in the 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 aforesaid method provided by the invention looser for the requirement of the environmental aspect of oil-gas-water delivery system in the pipeline course of conveying, 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 the oil gas transportation art, three-phase mixed transferring can significantly reduce the conveying cost, mixed defeated main difficulty is the generation meeting blocking pipeline of hydrate, thermodynamics inhibitor and kinetic inhibitor are mainly avoided blocking pipeline by the generation that prevents hydrate, 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 the actual fed process, the condensate depression of mixed defeated system generally all is 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 about anti-3-8 ℃) as the thermodynamics inhibitor, line clogging also seldom appears, 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 now gas extraction also develops to the deep-sea gradually, the anti-condensate depression degree of present inhibitor (comprising existing anti polymerizer) is below 15 ℃, the oil gas that is difficult to adapt to fully 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 the deep-sea exploitation is carried requirement, anti polymerizer does not stop the generation of hydrate in addition, the hydrate that generates can absorb a large amount of gas (volume ratio 140-176: 1, namely generate the Sweet natural gas that 1 volume hydrate approximately consumes the 140-176 volume, therefore can significantly reduce the volume of delivering gas), thereby reduce the ratio of gas in the mixed defeated system, thereby can improve transport efficiency and gas volume, have broad application prospects.
Than existing anti polymerizer, the composite hydrate anticoagulant that contains saponin(e provided by the invention, can effectively control hydrate and initially generate state, thereby the hydrate that may occur when effectively avoiding water ratio high is coalescent, be more conducive to realize the hydrate dynamic control technology, guarantee that hydrate crystal is present in the pipeline with fine granularity in the oil-gas-water Multi phase pipeline, accumulation and depositional phenomenon do not occur, thereby effectively solve the mobile safety control problem of Multi phase pipeline.Containing the saponins plant milk extract in this hydrate anticoagulant is natural plant extracts, do not have toxicity and be easy to biological degradation, complementary anti polymerizer all select for poisonous material, this contains the saponin(e composite hydrate anticoagulant and has the characteristics such as even particle distribution that nontoxic, economic environmental protection, action effect are good, generate hydrate.
Description of drawings
The following drawings only is intended to the present invention done and schematically illustrates and explain, not delimit the scope of the invention.Wherein:
Fig. 1 is for estimating 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 estimating hydrate anticoagulant;
Fig. 3 is the mixed defeated system of diesel oil-air-water of 15% hydrate form when adopting static that camera arrives in the sapphire still for the water ratio that provides among the embodiment 3;
The water ratio that Fig. 4 provides for embodiment 7 is 10% the mixed flow of system and the variation relation curve of time failed of diesel oil-air-water;
The water ratio that Fig. 5 provides for embodiment 9 is that the mixed defeated system of diesel oil-air-water of 20% adds hydrate form and the size picture that hydrate that anti polymerizer forms adopts PVM to collect.
The drawing reference numeral explanation:
209 airbaths 210 of mixing kettle 101 compressors 102 impeller pumps 103 under meters 104 differential manometers 105 scanning thermometers 106 temperature sensors 107 circulating cooling pipelines 108 hydrate circulation lines 109 forms 110 circulator baths 111 data collecting systems 112 gas cylinders 113 cooling systems 114 condensers 115 autoclaves 201 real-time online particle laser visual fractional analysis instrument 202 data collecting systems 203 pressure transmitters 204 temperature sensors 205 gas cylinders 206 rotors 207 vapor pipes 208 magnetic stirring apparatuss
Embodiment
Understand for technical characterictic of the present invention, purpose and beneficial effect being had more clearly, referring now to Figure of description technical scheme of the present invention is carried out following detailed description, but but can not be interpreted as restriction to practical range of the present invention.
Anti-poly-performance test
1, estimates the hydrate form in the sapphire still
In order to illustrate that the composite hydrate anticoagulant of saponin(e that contains provided by the invention is on the impact of hydrate form, adopt visual transparent sapphire autoclave that its performance is tested, this visual transparent sapphire autoclave and corollary system thereof mainly are 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, but still internal pressure free adjustment, and the maximum working pressure (MWP) of pump is 50MPa.With a packed-piston, charging fluid and experimental system can be separated in the still.Above-mentioned transparent sapphire autoclave is research Hydrate Technology device commonly used, the shown device of Fig. 1 of Chinese patent application CN200710178198.2 (CN101377487A) for example, and the full text with above-mentioned patent application is incorporated herein by reference here.
Test procedure:
Before the reaction beginning, with deionized water whole experimental system is cleaned, after the vacuum-drying, with the oil-in-water emulsions for preparing altogether 10mL and the composite hydrate anticoagulant that contains saponin(e for preparing in advance place the sapphire still, the setting air bath temperature is 277.2K;
After system temperature is stablized 2 hours, (the composition gas of this experimental gas is all taken a sample from test site to pass into experimental gas, the combination of simulation Sweet natural gas, its composition sees Table 1, adopt the analysis of HP6890 gas chromatograph), air is 3-4 time in the displacement still, passes into certain pressure and (generates equilibrium pressure less than the hydrate under this temperature, the calculating of hydrate equilibrium pressure employing Chen-Guo New Hydrate Model) experimental gas makes it to reach dissolution equilibrium, forms the mixed system of failing 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 by manual pump and makes the still internal pressure again maintain 6.5MPa, observes the form of hydrate crystal in the still by form.
The composition of table 1, the used simulation Sweet natural gas of experiment
| 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 prevent effectively that the performance that hydrate is built up from being: under predetermined temperature and pressure condition, do not occur hydrate in the whole reaction process and build up phenomenon, stirrer can freely stir in still all the time, and the most of hydrate in the 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 the 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 seen Fig. 1.This apparatus main body is the U-shaped pipe (by DB Robinson Corp., Canada makes) of 20m length, and its inner tube is to be by internal diameter
Casting propylene acid tube consist of, as the hydrate pipeline, can bear the pressure of 4MPa; Adopt two water-baths to carry cooling fluid (ethylene glycol solution) to circulate to cool off by double-deck clamp, adopt six precision to be installed in as temperature sensor 107 and to measure temperature in the circulation line for the ± thermopair of 0.1K, measure the pressure of system by precision pressure gauge, by domestic impeller pump 103 slurries are flowed in hydrate circulation line 109, the maximum delivery flow is 3000L/h.This hydrate circulation line test set detailed components and purposes are as follows: mixing kettle 101 (being used for holding oil-water mixture and anti polymerizer), compressor 102 (being used for 115 refrigeration), pump 103 (transmitting power that is used for the 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 the 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 the 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, detected result is analyzed and provided to the pressure difference that pressure in the mixing kettle 101 and differential manometer 105 detect), gas cylinder 113 (being used for to mixing kettle 101 air feed), cooling system 114 (mixing kettle 101 is cooled off), condenser 115 (pipeline except hydrate circulation line 109 is cooled off).
Concrete experimental implementation step is as follows:
(1), the preparation different profit volume ratios experimental system, the liquid phase volume total amount is 16L;
(2), with sherwood oil and water hydrate circulation line 109 is cleaned up successively, the oil solution of anti polymerizer that added the interpolation for preparing in the mixing kettle 101;
(3), open temperature controlling instruments, adjust temperature to set(ting)value, and mixing kettle 101 vacuumized, remove air residual in the system;
(4), when temperature be down to specify experimental temperature after, open intake valve, by gas cylinder 113 slow input gas in the mixing kettle 101, when treating that system pressure rises near experimental pressure, start impeller pump 103;
(5), in the 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
Be the mixed graininess of failing after the system hydrate forms of the oil-gas-water behind the investigation injection anti polymerizer, test by online sreen analysis system (PVM), the test set that the present invention adopts is based on that real-time online particle laser visual fractional analysis instrument that German Mettler Toledo Inc. makes sets up, this device is mainly by autoclave 201, real-time online particle laser visual fractional analysis instrument 202, data collecting system 203 consists of (seeing Fig. 2), PVM technical testing principle is: by the small portion zone of six bundle illuminated with laser light detecting probe surfaces, computer is taken and be sent to the digital picture that probe forms in real time by camera, picture by the computer collection carries out online visual analyzing to the measurement system, can see very intuitively like this changing conditions of tested systems.Estimating the composition of the simulation Sweet natural gas that adopts forms identical with the Sweet natural gas shown in the table 1.Evaluation procedure is as follows:
Before the reaction beginning, with deionized water whole autoclave 201 is cleaned, after the vacuum-drying, 400mL and the composite hydrate anticoagulant that contains saponin(e for preparing in advance place autoclave 201 altogether with the oil-in-water emulsions for preparing, this autoclave 201 places airbath 210, and the temperature of setting air bath 210 is 277.2K;
(temperature is detected by temperature sensor 205 when system temperature is stablized 2 hours, and be transferred to data collecting system 203) after, pass into experimental gas (seeing Table 1) by gas cylinder 206, air is 3-4 time in the displacement still, pass into certain pressure and (generate equilibrium pressure less than the hydrate under this temperature, the hydrate equilibrium pressure adopts the 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 begins to generate over time, can show at this moment the variation of slurries in the reactor in the terminal of data gathering, state and size that hydrate can be observed hydrate after generating, picture is gathered automatically by data collecting system 203 in whole process, and acquisition rate is 5/minute.
Present embodiment provides a kind of saponins plant milk extract, and it prepares by following steps:
At first choose Chinese honey locust skin (remaining skin behind the Chinese honey locust pod removal fruit) 100g, adopt pulverizer that the Chinese honey locust shelling is broken to powdery, obtain spaonin powder;
Spaonin powder is injected apparatus,Soxhlet's, add the 600g dehydrated alcohol and carry out 3 hours extraction, obtain mixed solution;
Adopt Büchner funnel that mixed solution is carried out suction filtration, filtrate adopts the Rotary Evaporators underpressure distillation to stop when having solid to separate out, and the concentrated solution that obtain this moment is saturated solution (brown liquid), i.e. saponins plant milk extract.
After measured, in the saponins plant milk extract that present embodiment extracts, total saponin content is 21% of Chinese honey locust cortex amount, and saponin(e effective concentration is 19% in the saponins plant milk extract.
Embodiment 2
Present embodiment provides a kind of saponins plant milk extract, and it prepares by following steps:
Choose the 100g Radix Glycyrrhizae, adopt mortar to be milled to powdery, obtain licorice powder;
Licorice powder is injected flask, add 300g water and under 70 ℃, carry out 4 hours leaching, adopt Büchner funnel to carry out suction filtration, filter residue carries out 4 hours leaching again with 300g water, suction filtration is total to repeatedly leaching and suction filtration four times, obtain mixed solution, mixed solution is the summation of four liquid of obtaining of leaching;
Filter mixed solution, filtrate is concentrated and adopted vacuum distillation method general moisture evaporate to dryness wherein, obtain saponins plant milk extract solid;
Adopt the anhydrous alcohol solution reconcentration till have solid to separate out above-mentioned solid, the concentrated solution of this moment is the saponins plant milk extract.
After measured, in the saponins plant milk extract that present embodiment extracts, total saponin content is 5.1% of Radix Glycyrrhizae quality, and saponin(e effective concentration is 18% in the saponins plant milk extract.
Embodiment 3
Present embodiment provides a kind of composite hydrate anticoagulant that contains saponin(e, and it prepares by following steps:
The saponins plant milk extract that extracts among the embodiment 1 is mixed according to 3: 1 mass ratio with complementary anti polymerizer Span20, stir, obtain containing the composite hydrate anticoagulant of saponin(e.
Adopt visual transparent sapphire autoclave and corollary system that the above-mentioned anti-poly-effect that contains the composite hydrate anticoagulant of saponin(e that present embodiment provides is carried 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% (the volume sum of Yi Shui and oil is benchmark), the adding total amount of anti polymerizer is that 2.0wt% is (with respect to the mass content of water, as follows), the gas composition that passes into is identical with the gas composition shown in the table 1, and the test procedure of putting down in writing in test evaluation step and the anti-poly-performance test above is identical.
The test evaluation result:
Before test, observe adding and containing the slurries that form behind the composite hydrate anticoagulant of saponin(e is finely dispersed milk sap, and this expression adds and contains the slurries original state that forms behind the composite hydrate anticoagulant of saponin(e to contain saponin(e plant extract type anti polymerizer effect than independent adding good; In whole test process, hydrate forms the microparticle shape, caking does not occur to build up, show that the composite hydrate anticoagulant that contains saponin(e that present embodiment provides has good anti-poly-effect when for water ratio being the mixed defeated system of oil-gas-water of 5% (volume), stop to stir after generating hydrate, opened after 2 hours and stir, hydrate is caking not, this shows the hydrate good stability of generation, and is less or all can not lump when stopping to stir and cause blocking pipeline in disturbance.
Adopting identical method is 10% to the composite hydrate anticoagulant that contains saponin(e that present embodiment provides at water ratio respectively, 15%, 20%, 25%, anti-poly-effect in the mixed defeated system of 30% 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%, the test evaluation result shows that the hydrate in the above-mentioned mixed defeated system all can keep good state, and caking does not occur to build up, water ratio 10% and 25% two groups experiments are stopped to stir restart the phenomenon that the hydrate caking does not all occur more than 2 hours, wherein by annotating propane, the mode of pressurization and cooling increases the condensate depression test to a group of 10% water ratio, the hydrate caking does not appear when high supercooling degree is 19.5 ℃ yet, more than the composite hydrate anticoagulant that contains saponin(e that provides of explanation present embodiment 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 when being static in 18 ℃ of jewel stills in condensate depression for the anti polymerizer that provides in this example is provided in the mixed defeated system of 15% oil-gas-water for water ratio, the hydrate of this moment is dispersed in the 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 the bulk hydrate to occur yet.
Present embodiment provides a kind of composite hydrate anticoagulant that contains saponin(e, and it prepares by following steps:
The saponins plant milk extract that extracts among the embodiment 2 and complementary anti polymerizer high-carbon fatty alcohol polyoxyethylene ether (AEO) mass ratio according to 7: 1 is mixed, stir, obtain containing the composite hydrate anticoagulant of saponin(e.
Adopting the above-mentioned composite hydrate anticoagulant that contains saponin(e that visual transparent sapphire autoclave and corollary system provide present embodiment respectively is 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, the test evaluation step is identical with embodiment 3, wherein, the add-on that contains the composite hydrate anticoagulant of saponin(e is 3.0wt%.
Test evaluation result: in whole test process, hydrate forms the microparticle shape, occur to build up caking, show that the composite hydrate anticoagulant that contains saponin(e that 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
Present embodiment provides a kind of composite hydrate anticoagulant that contains saponin(e, and it prepares by following steps:
The saponins plant milk extract that extracts among the embodiment 1 is mixed according to 2: 1 mass ratio with complementary anti polymerizer Tween40, stir, obtain containing the composite hydrate anticoagulant of saponin(e.
Adopting the above-mentioned composite hydrate anticoagulant that contains saponin(e that visual transparent sapphire autoclave and corollary system provide present embodiment respectively is 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, the test evaluation step is identical with embodiment 3, wherein, the add-on that contains the composite hydrate anticoagulant of saponin(e is 3.0wt%.
Test evaluation result: in whole test process, hydrate forms the microparticle shape, occur to build up caking, show that the composite hydrate anticoagulant that contains saponin(e that 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).
Present embodiment provides a kind of preparation method and performance evaluation that contains the saponin(e composite hydrate anticoagulant.
The saponins plant milk extract that extracts among the embodiment 1 is mixed according to 2: 1 mass ratio with complementary anti polymerizer Span60, stir, obtain containing the composite hydrate anticoagulant of saponin(e.
Adopt visual transparent sapphire autoclave and corollary system that the above-mentioned anti-poly-effect that contains the composite hydrate anticoagulant of saponin(e that present embodiment provides is carried 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% (the volume sum of Yi Shui and oil is benchmark), the adding total amount of anti polymerizer is 1.6wt% (with respect to the mass content of water), the gas composition that passes into is identical with the gas composition shown in the table 1, and the test procedure of putting down in writing in test evaluation step and the anti-poly-performance test above is identical.
Test evaluation result: in whole test process, hydrate forms the microparticle shape, occur to build up caking, show that the composite hydrate anticoagulant that contains saponin(e that 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 identical method is 10% to the composite hydrate anticoagulant that contains saponin(e that present embodiment provides at water ratio respectively, 15%, 20%, 25%, anti-poly-effect in the mixed defeated system of 30% oil-gas-water is carried out test evaluation, the add-on that contains the composite hydrate anticoagulant of saponin(e is 2.0wt%, the test evaluation result shows that the hydrate in the above-mentioned mixed defeated system all can keep good state, and occur to build up caking, illustrate that the composite hydrate anticoagulant that contains saponin(e that present embodiment provides all has the good anti-effect of gathering in water ratio is the mixed defeated system of oil-gas-water of 5-30% (volume).
Embodiment 7
The composite hydrate anticoagulant that contains saponin(e that present embodiment provides take embodiment 3 is as example, and test contains the anti-poly-effect of the composite hydrate anticoagulant of saponin(e.
Test procedure: the oil-in-water emulsions of the mixed defeated system that adopts is formulated by water and the diesel oil of 1: 9 (volume ratio), the volume content that is water in the system is 10% (take the volume sum of water and diesel oil as benchmark), add the hydrate anticoagulant that contains 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 Figure 1, then pass into simulation Sweet natural gas (its composition is identical with the component shown in the table 1) circular flow 24 hours, its anti-poly-effect and stability are tested.
Test result: find that by the flow of measuring in the pipeline hydrate at the pipeline run duration Hydrate Plugging phenomenon does not occur, in operational process, stop again to open behind the pump several minutes, can find out by the front and back fluctuations in discharge, bust does not occur in its flow, this explanation is within the time out of service, and the hydrate stable existence is not gathered into piece, viscosity was lower after apparent viscosity calculation result showed the generation hydrate, had mobile preferably.
Fig. 4 is that water ratio is 10% the mixed variation relation curve of failing flow, apparent viscosity and the time of system of diesel oil-air-water.Flow represents the mobile speed of hydrate slurry, and apparent viscosity then is an important indicator of examination hydrate slurry attitude 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, the system flow presents the state of rising, but with gas again consume and flow descend gradually, compare with the Schwellenwert that fluid behind the first set reaction descends, the Schwellenwert that fluid flow rate descends after the reaction is for the second time compared for the first time smaller.Generation along with hydrate, the system flow reduces, can see that by the apparent viscosity curve reduction of outflow rate is because the rising of apparent viscosity causes, behind the hydrate slurry stable system, flow by stopping, again opening water pump after in half an hour recovers to flow, basic state before recovering to stop to carry behind the system stability of flow, this explanation stops stirring and hydrate caking, not blocking pipeline do not occur.Flow presents the trend that rises by a small margin behind the long-play, shows thus the characteristic that presents shear shinning for the hydrate slurry fluid that contains this anti polymerizer system.System is lowered the temperature operation to improve the condensate depression of system, and the result shows that the reduction system flow with temperature reduces, and apparent viscosity raises.The system flow that does not occur to cause because of the hydrate caking in the whole service process reduces suddenly or blocking pipeline, and this shows that the composite hydrate anticoagulant evaluation effect in the cycle of higher pressure pipeline that contains saponin(e is better, has well anti-poly-effect.
Adopting identical method is 5% to the composite hydrate anticoagulant that contains saponin(e that present embodiment provides at water ratio respectively, 10%, 15%, 20%, 25%, anti-poly-effect in the mixed defeated system of 30% oil-gas-water is carried out test evaluation, the add-on that contains the composite hydrate anticoagulant of saponin(e is 3.0wt%, the test evaluation result shows and generates the phenomenon that flow bust and blocking pipeline do not occur behind the hydrate, and the composite hydrate anticoagulant that this explanation is above-mentioned to contain saponin(e all has good anti-poly-effect in water ratio is the mixed defeated system of oil-gas-water of 5-30% (volume).
The composite hydrate anticoagulant that contains saponin(e that present embodiment provides take embodiment 3,4 and 5 is as example, and test contains 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, add respectively the composite hydrate anticoagulant that contains saponin(e that 2000ppm embodiment 3,4 and 5 provides to supporting in the water that goldfish is arranged, the survival condition of then after a week, observing the goldfish in the water.
In test process, the goldfish of having added in the water of the composite hydrate anticoagulant that contains saponin(e does not have death, and composite hydrate anticoagulant that contains saponin(e that this explanation embodiment 3,4 and 5 provides does not have toxicity or toxicity minimum.
Embodiment 9
The composite hydrate anticoagulant that contains saponin(e that present embodiment provides take embodiment 3 is as example, measures the state that generates behind the hydrate.
The oil-in-water emulsions of the mixed defeated system that adopts is formulated by water and the diesel oil of 2: 8 (volume ratio), and namely the volume content of water is 20% in the system, and the composition of the Sweet natural gas that passes into is identical with the composition shown in the table 1.Add the composite hydrate anticoagulant that contains saponin(e that embodiment 3 provides in above-mentioned mixed defeated system, the adding total amount is 2.0wt%, adopts PVM device shown in Figure 2 to carry out hydrate granularity and morphological analysis test.
Measure by PVM, it is block for having the crystalline structure taper clearly to find to add the hydrate that generates behind the composite hydrate anticoagulant that contains saponin(e, granular size is between 30-90 μ m, with about 70 μ m at most, be uniformly dispersed, do not have large caking, see Fig. 5, the composite hydrate anticoagulant that contains saponin(e is added in this explanation can effectively control the granular size that the ground hydrate generates, and suppresses hydrate and is agglomerated into piece.Comparing particle with independent use saponin(e anti polymerizer bigger may be because the polymerization of the inside Span20 causes, and causes whole system to be uniformly dispersed in generating the hydrate process just because of the emulsifying effectiveness of Span 20 always, is not agglomerated into piece.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; the protection domain that is 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., all should be included within protection scope of the present invention.
Claims (10)
1. composite hydrate anticoagulant that contains saponin(e, it is comprised of saponins plant milk extract and complementary anti polymerizer.
2. composite hydrate anticoagulant according to claim 1, wherein, in the gross weight of described saponins plant milk extract, described saponins plant milk extract contains the saponin(e of 5.0-30.0%.
3. composite hydrate anticoagulant according to claim 1 and 2, wherein, the mass ratio of described saponins plant milk extract and described complementary anti polymerizer is 0.01-100: 1, be preferably 0.1-10: 1.
4. each described composite hydrate anticoagulant according to claim 1-3, wherein, described saponins plant milk extract is to be obtained by one or more extractions in branches and leaves, rhizome and the fruit of the plant that contains saponin(e, and the described plant that contains saponin(e comprises one or more in the Rosaceae, Caryophyllaceae, Sapindaceae, potato preparatory course, Polygalaceae, Araeceae, Liliaceae, scrophulariaceae, pulse family, Araliaceae, Curcurbitaceae, Ranunculaceae, umbelliferae, Rhamnaceae and the Ofthe Primulaceae; Preferably, the described plant that contains saponin(e comprises one or more in the Rosaceae, Caryophyllaceae, potato preparatory course, Polygalaceae, scrophulariaceae, pulse family, Curcurbitaceae, Rhamnaceae and the Ofthe Primulaceae; More preferably, the described plant that contains saponin(e comprise that Chinese honey locust, balloonflower root, potato are auspicious, in ginseng, pseudo-ginseng, the wind-weed, polygala root, Radix Glycyrrhizae, tealeaves and the radix bupleuri one or more.
5. according to claim 2 or 4 described composite hydrate anticoagulants, wherein, described saponins plant milk extract extracts by following steps:
Utilize alcohol that the plant that contains saponin(e is extracted, obtain mixed solution, mixed solution is filtered, then filtrate is carried out underpressure distillation and obtain saturated solution, namely obtain described saponins plant milk extract; Perhaps,
Adopt water that the plant that contains saponin(e is extracted, obtain mixed solution, mixed solution is filtered, then filtrate is carried out underpressure distillation to dry, dry thing is dissolved in obtains saturated solution in the solvent, namely obtain described saponins plant milk extract.
6. composite hydrate anticoagulant as claimed in claim 5, wherein, described saponins plant milk extract extracts by following steps:
The plant that will contain saponin(e grinds and obtains powder;
The water of powder with 3-10 times of weight is mixed, carry out 2-8 leaching, leaching temperature is controlled to be 20-100 ℃, each leaching time is controlled to be 1-30 hour, obtains mixed solution, perhaps, powder is placed apparatus,Soxhlet's or other extractor, extract to account for powder weight 2-10 water doubly, extraction time is controlled to be 1-10 hour, obtains mixed solution;
Mixed solution is filtered, filtrate is carried out underpressure distillation, until stop to obtain solid product during the water evaporate to dryness;
Solid product is dissolved in alcoholic solvent obtains saturated solution, namely obtain described saponins plant milk extract.
7. composite hydrate anticoagulant as claimed in claim 5, wherein, described saponins plant milk extract extracts by following steps:
The plant that will contain saponin(e grinds and obtains powder;
The alcohol of powder with 3-10 times of weight is mixed, carry out 2-8 leaching, leaching temperature is controlled to be 20-90 ℃, each leaching time is controlled to be 1-200 hour, obtains mixed solution, perhaps, powder is placed apparatus,Soxhlet's, extract to account for powder weight 2-10 alcohol doubly, extraction time is controlled to be 1-10 hour, obtains mixed solution;
Mixed solution is filtered, then filtrate is carried out underpressure distillation, until stop when solid occurring, obtain saturated solution, namely obtain described saponins plant milk extract.
8. according to claim 3 or 4 described composite hydrate anticoagulants, wherein, described complementary anti polymerizer is nonionogenic tenside; Preferably, described ionic surfactant pack is drawn together one or more in Determination of Polyoxyethylene Non-ionic Surfactants and/or the polyol-based non-ionic surfactant; More preferably, described ionic surfactant pack is drawn together one or more in high-carbon fatty alcohol polyoxyethylene ether and/or the sorbitan ester.
9. one kind is suppressed the method that hydrate is built up in the mixed defeated system of oil-gas-water, and it comprises and adds each described composite hydrate anticoagulant that contains saponin(e of claim 1-8 in the mixed defeated system of described oil-gas-water step; Preferably, in the mixed defeated system of described oil-gas-water, the ratio that the volume content of described water accounts for oil-water two-phase cumulative volume is not higher than 50.0%; More preferably, the described addition that contains the composite hydrate anticoagulant of saponin(e is controlled to be the 1.0-10.0% of the quality of water in the mixed defeated system of described oil-gas-water.
10. each described application that contains hydrate accumulation of composite hydrate anticoagulant in suppressing the mixed defeated system of oil-gas-water of saponin(e of claim 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110227519.XA CN102925126B (en) | 2011-08-09 | 2011-08-09 | Saponin-containing composite type hydrate anti-agglomerant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110227519.XA CN102925126B (en) | 2011-08-09 | 2011-08-09 | Saponin-containing composite type hydrate anti-agglomerant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102925126A true CN102925126A (en) | 2013-02-13 |
| CN102925126B CN102925126B (en) | 2014-11-05 |
Family
ID=47640060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110227519.XA Active CN102925126B (en) | 2011-08-09 | 2011-08-09 | Saponin-containing composite type hydrate anti-agglomerant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102925126B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927821A (en) * | 2015-06-08 | 2015-09-23 | 苏州冰之火能源科技有限公司 | Environment-friendly composite hydrate inhibitor and preparation method thereof |
| CN106381125A (en) * | 2016-08-26 | 2017-02-08 | 华南理工大学 | Chinese herb extract and application thereof in preparing gas hydrate of high gas storage density |
| CN107011880A (en) * | 2017-05-22 | 2017-08-04 | 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 |
| CN109135702A (en) * | 2018-09-07 | 2019-01-04 | 湘南学院 | A kind of hydrate inhibitor and its 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 |
| 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 |
| 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 |
| CN113214815A (en) * | 2021-05-07 | 2021-08-06 | 大庆永铸石油技术开发有限公司 | Nano 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 |
| CN113817444A (en) * | 2020-06-18 | 2021-12-21 | 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 |
| 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 (1)
| Title |
|---|
| 廖久明: "皂角提取液的纯化研究", 《精细石油化工》, no. 2, 31 March 2003 (2003-03-31), pages 50 - 53 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104927821A (en) * | 2015-06-08 | 2015-09-23 | 苏州冰之火能源科技有限公司 | Environment-friendly composite hydrate inhibitor and preparation method thereof |
| CN106381125A (en) * | 2016-08-26 | 2017-02-08 | 华南理工大学 | Chinese herb extract and application thereof in preparing gas hydrate of high gas storage density |
| CN107011880A (en) * | 2017-05-22 | 2017-08-04 | 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 |
| CN109135702A (en) * | 2018-09-07 | 2019-01-04 | 湘南学院 | A kind of hydrate inhibitor and its application |
| 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 |
| 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 |
| CN113817444A (en) * | 2020-06-18 | 2021-12-21 | 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 |
| 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 |
| CN113214815A (en) * | 2021-05-07 | 2021-08-06 | 大庆永铸石油技术开发有限公司 | Nano microemulsion oil displacement agent and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102925126B (en) | 2014-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102925126B (en) | Saponin-containing composite type hydrate anti-agglomerant | |
| CN105670591B (en) | Anti-freezing foam drainage agent and preparation method and application thereof | |
| CN102746361B (en) | Saponin plant extract type hydrate anti-agglomerant | |
| CN103865505B (en) | Non-ionic composite Anti-agglomerates of Gas Hydrate | |
| CN103937479A (en) | Foaming material for gas field foam discharging agent, slow dissolving foam discharging agent, and preparation method of slow dissolving foam discharging agent | |
| CN104390137A (en) | Environment-friendly gas hydrate polymerization inhibitor and preparation method thereof | |
| CN103852359A (en) | Method for extracting soil heavy metal ion | |
| CN107828402B (en) | Improve deep viscous crude CO2Chemical additive for recovery ratio in gas flooding process | |
| CN105771827A (en) | Method for preparing water-soluble plant essential oil nanoparticles | |
| CN110054727A (en) | A kind of preparation method and device of polyacrylamide nano microballoon | |
| CN104447295B (en) | The preparation method of a kind of fire-resistant oxidation resistant agent improving fried food product storage quality | |
| CN101731578A (en) | Extract of carica papaya L. seeds produced in Hainan, preparation method and application thereof | |
| CN103185772A (en) | Hydrate phase transition solid-liquid-gas multiphase flow experimental facility and testing method | |
| CN102451640B (en) | Non-ionic compound hydrate anti-agglomerant | |
| CN104873469B (en) | A kind of preparation method of aescin for injection freeze-dried emulsion | |
| CN104857891A (en) | Hydrate promoter and preparation method thereof | |
| CN106667833B (en) | Camellia oleifera seed coat extract and preparation method and application thereof | |
| CN107314247B (en) | Environmental protection compound type hydrate polymerization inhibitor composition and application thereof | |
| Azcan et al. | Fatty acids of the seeds of Origanum onites L. and O. vulgare L. | |
| Tao et al. | A new process of extracting oleoresin ginger from ginger by critical-state liquid CO2 | |
| CN205133473U (en) | A equipment for extracting tea saponin | |
| CN1332687C (en) | Fatty acid synthetic enzyme inhibitor and its production method and application | |
| Iversen | Epidermal chalones and squamous cell carcinomas: The growth inhibitory effects of aqueous epidermal extracts (G 1 and G 2 chalones) on the epidermis and on a transplantable keratinizing carcinoma in nude mice | |
| CN103202289A (en) | 1,2-dihydroxy-hexacosan-4-keton water suspending agent and preparation method thereof | |
| CN103349785A (en) | Traditional Chinese medicine volatile oil complex and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |