CN103305200A - Compound type hydrate inhibitor - Google Patents
Compound type hydrate inhibitor Download PDFInfo
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- CN103305200A CN103305200A CN2013101700139A CN201310170013A CN103305200A CN 103305200 A CN103305200 A CN 103305200A CN 2013101700139 A CN2013101700139 A CN 2013101700139A CN 201310170013 A CN201310170013 A CN 201310170013A CN 103305200 A CN103305200 A CN 103305200A
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Abstract
The invention belongs to the field of gas storage and transportation, and specifically relates to a compound type gas hydrate inhibitor. The inhibitor consists of the following components in percentage by mass: 0.1-0.5% of polyvinyl caprolactam, 1-5% of alcohol or salt and the balance of water. According to the inhibitor provided by the invention, by adding a certain amount of salt or alcohol into the existing dynamic inhibitor, the generation time of a hydrate can be increased, and the generation amount of the hydrate can be reduced; and moreover, the inhibition effect of the dynamic inhibitor is greatly improved so that the dynamic inhibitor has a better effect and is more stable and wider in range of application.
Description
Technical field
The invention belongs to the gas storage and transportation field, refer in particular to and suppress the additive that hydrate takes place in the gas storage and transportation process.
Background technology
In oil, gas extraction, transportation, because its special high pressure and low temperature environment, various lower boiling hydro carbons gases (as methane, ethane, propane) and non-hydrocarbon gases (carbonic acid gas, hydrogen sulfide) be easy to petroleum fluids in water formation gas hydrate.Gas hydrate is the cage structure that is connected to form by hydrogen bond by water molecules, and gas molecules is enclosed in the cage structure by the Van der Waals force effect, the ice shape compound of formation.It flocks together under certain condition, forms bulk, equipment such as meeting blocking pipe, pit shaft, valve and instrument when serious, and this causes very big threat to oil and gas industry production and accumulating, mainly shows following three aspects:
(1) hydrate generates in pipeline, then can blocking pipe, increase pipeline pressure reduction, damage pipe fitting etc.;
(2) hydrate forms in the porous medium of stratum, then can stop up hydrocarbon occurrence, the reduction oil gas well production rate of oil gas well, the porosity that lowers hydrocarbon-bearing pool and relative permeability, change hydrocarbon-bearing pool;
(3) hydrate forms in pit shaft, then can stop up pit shaft, damage the pit shaft internal part, reduces oil and gas production even stopping production.
Since Hammersdhmidt in 1934 finds that hydrate stops up natural gas line, how in production of hydrocarbons and transportation, to suppress the formation of hydrate, become oil, gas industry urgent problem.
The underlying condition that gas hydrate form is: the water content of (1) Sweet natural gas is in state of saturation, and the existence of liquid phase water is the prerequisite that produces hydrate; (2) sufficiently high pressure and enough low temperature, different components forms the top temperature that the critical temperature of hydrate is this component hydrate existence in the Sweet natural gas; (3) when possessing above-mentioned condition, the formation of hydrate, also requiring has some subsidiary conditions, as the fluctuation of gas pressure, the stirring that gas produces because of the sudden change that flows to, and the existence of crystal seed etc.
At the hydrate formation condition, the effective means that suppresses that hydrate generates destroys its formation condition exactly, generally speaking, the hydrate prophylactico-therapeutic measures is to create with hydrate to form opposing condition: high temperature, low pressure, remove Bai Youshui (or reduce water dew point).Mainly contain according to the prophylactico-therapeutic measures to the research hydrate of gas hydrate formation condition: heating method, evaporation, step-down control method, add the chemical inhibitor method.
By pipeline is heated, the hydrate that system temperature is higher than under the system pressure generates temperature, avoids blocking pipeline.But difficult point is position that be difficult to determine that hydrate stops up, in case and hydrate has generated and has carried out heat treated again, can cause decomposition of hydrate and cause partial high pressure, cause line fracture.Dehydration technique is to cause that by removal the moisture that hydrate generates eliminates the risk that generates hydrate, is the preventive measures that adopt usually before the present natural gas transport.Gas dehydration can significantly reduce water dew point, is exactly branch fugacity or the activity that has reduced water from the thermodynamics angle, and the generation temperature of hydrate is significantly descended, thereby eliminates the risk that generates hydrate in the pipe conveying procedure.But difficult point is to be subjected to seasonal effect and restive, and risk is bigger.
Because in order to keep certain transport capacity, so the reduction that the pressure of pipeline generally can not be random is a kind of method that step-down control just can realize theoretically.
Adding that the chemical inhibitor method has simply, advantage such as economic, effective, is to prevent that hydrate from generating most popular method.In view of the limitation that serious harm and other three kinds of hydrates of hydrate are prevented and treated method, developing efficiently, hydrate inhibitor is significant.
In actual the generation for reaching effective hydrate inhibition effect, the normal method that adopts the chemical additive that adds capacity, the balance that improves hydrate generates pressure (working pressure that is higher than pipeline), or the balance that reduces hydrate generates temperature (being lower than the service temperature of pipeline), suppress the generation of hydrate with this, change the thermodynamic condition that hydrate forms, crystallization rate or accumulation shape, reach the purpose that keeps fluid flow, the hydrate inhibitor type mainly is divided into the thermodynamics inhibitor, kinetic inhibitor and anti polymerizer, methyl alcohol, traditional hot mechanics inhibitor such as alcohols such as ethylene glycol or ionogen can change the hydrate equilibrium conditions, but adopt the thermodynamics inhibitor, add-on is big, concentration in the aqueous solution (massfraction) generally need reach 10%-60%, that have even reach 50%, cost is higher, and the loss of inhibitor simultaneously is also bigger, and brings problem of environmental pollution.Anti polymerizer can make the gas hydrate of generation be difficult to be agglomerated into piece, can still have limitation in sealing pipeline or the bigger situation work of condensate depression, only just works when You Heshui exists simultaneously.Therefore, from the nineties in 20th century, the begin one's study kinetic inhibitor of low dosage of Chinese scholars is in order to replace the use of thermodynamics inhibitor.Kinetic inhibitor is by suppressing or delay the growth time of hydrate, generating thereby suppress hydrate, and can not influence the thermodynamic condition that hydrate generates.But kinetic inhibitor is subjected to the influence of condensate depression bigger, and the high supercooling degree that current driving force learns that inhibitor is suitable for has only 10-12 ℃, under higher condensate depression, suppresses active on the low side, must with the thermodynamics inhibitor unite use just economical, effective.In view of above reason, the present invention is on the basis of the advantage that takes into full account various hydrate inhibitor for natural gas methods and deficiency, and we propose a kind of composite hydrate inhibitor preparation method.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide that a kind of investment cost is little, economical operation, be not subjected to the efficient composite hydrate inhibitor preparation method of condensate depression restriction.
For achieving the above object, the present invention adopts following technical scheme:
A kind of compound gas hydrate inhibitor is made up of kinetic inhibitor, alcohol or salt and water, wherein each component by mass percentage, kinetic inhibitor accounts for 0.1%～0.5%, alcohol or salt account for 1%～5%, all the other are water.。
Wherein, kinetic inhibitor is selected Vinylcaprolactam homopolymer (PVCap) for use.
Salt is selected Potassium ethanoate and saltpetre for use.
Alcohols is selected ethylene glycol for use.
Beneficial effect of the present invention:
(1) action effect is good: kinetic inhibitor can only prolong the rise time of hydrate, can not reduce the growing amount of hydrate, and the present invention generates kinetics and the generation of two aspects inhibition of thermodynamics hydrate from hydrate, except prolonging the rise time of hydrate, can also change the hydrate phase balance point, reduce the growing amount of hydrate.
(2) application is more extensive: the problem that kinetic inhibitor faces in application is to suppress active on the low side, it is bigger to be affected by the external environment, versatility is poor, application has limitation, because the effect of compound inhibitor improves greatly, and can also reduce the generation of hydrate, therefore more stable, versatility is stronger.
(3) cost is lower, more economical environmental protection: the selected additive of the present invention is some cheapnesss, be easy to get and salt and alcohol that corrodibility is low, and addition is also little, the consumption of composite back kinetic inhibitor can be lower, so just greatly reduces gas industries and be used for suppressing the cost that hydrate generates.
The present invention adds certain salt or alcohols in the available dynamic inhibitor, can not only prolong the rise time of hydrate, and can also reduce the growing amount of hydrate, improved the inhibition of kinetic inhibitor widely, make kinetic inhibitor better effects if, more stable, range of application is more extensive.
Description of drawings
Fig. 1 is that hydrate generates the experimental installation schema
1, gas cylinder; 2, relief valve; 3, mass flowmeter; 4, check valve; 5, gate valve; 6, vacuum pump; 7, pressure, temperature transmitter; 8, circulation groove; 9, water bath with thermostatic control; 10, reactor; 11, data collecting system; 12, computer; 13, photocell lens.
Embodiment
Below the present invention is further described in detail, but embodiments of the present invention are not limited in this.
The experimental installation that the present invention adopts as shown in Figure 1, by gas cylinder 1; Relief valve 2; Mass flowmeter 3; Check valve 4; Gate valve 5; Vacuum pump 6; Pressure, temperature transmitter 7; Circulation groove 8; Water bath with thermostatic control 9; Reactor 10; Data collecting system 11; Computer 12 grades are partly formed.As source of the gas, be transferred to suitable pressure through relief valve 2 with gas cylinder 1, with mass flowmeter 3 stoichiometric consumption Sweet natural gases.By the temperature and pressure in pressure, the temperature transmitter 7 monitoring reaction stills 10.Control fluid temperature in the water bath with thermostatic control 9 by circulation groove 8, thus the conditioned reaction temperature in the kettle.Also form situation by hydrate in the photocell lens 13 monitoring reaction stills by data collecting system 11 and computer 12 image data.Vacuum pump 6 is used for aspirating liquid in the reactor.This system works pressure is 0-30MPa, and temperature range is-10 ℃-25 ℃.
Concrete preparation process:
1) with vacuum pump 6 reactor 10, piping system are vacuumized, the pumpdown time is 40-50min.
2) for getting rid of the air in reactor 10 and the piping system as far as possible, with experimental gas they are replaced twice, and then vacuumize.
3) the compound inhibitor aqueous solution with the different concns for preparing injects reactor 10, stirs 3-5min, and is pre-chilled to certain temperature earlier.
4) open check valve 4, High-Voltage Experimentation gas is charged into reactor 10, by relief valve 2 reacting system pressure is maintained the required pressure of experiment.
5) set experimental temperature, start the temperature controlling system of experimental installation.Utilize 8 pairs of reactors 10 of circulation groove to cool off, the temperature in reactor 10 reaches design temperature.
6) carry out hydrate and generate experiment.
The compound inhibitor of selecting for use consists of: aqueous solution quality is 200g, and the Vinylcaprolactam homopolymer of adding (PVCap) mass concentration is between 0.1%-0.5%, and the salt of adding or alcohols mass percent are between 1%-5%, and it is the same to see Table 1. experimental procedures.The PVCap of three kinds of concentration mixes with three kinds of salt or the alcohol of different concns respectively, draws inhibition time and pressure by experiment and falls and compare, thereby filter out the optimum concn ratio of composite inhibitor.
Table 1 composite inhibitor prepares concentration
Comparative Examples (pure water)
The condition of reaction beginning is 2 ℃, the pressure of 5MPa, and the equilibrium pressure that the methane hydrate of reaction generates in the time of 2 ℃ is 4.6MPa.Experimental procedure is the same.When the temperature in the reactor is cooled to 2 ℃, feed methane (purity 99.99%) gas, make the pressure in the still reach 5Mpa, begin to stir and make it to keep 500rmp, because methane is water-soluble, pressure slightly descends, when pressure reaches 3.4MPa, reaction reaches balance, reacts the methane gas scale of construction that consumes by pressure drop.It is 45min that pure water hydrate under these conditions generates required induction time, and the reaction deadline is 157min, and the pressure in the reaction is reduced to 0.7MPa.
Embodiment 1
0.1% PVCap and 1% ethylene glycol are compound, and experimental procedure is the same, and the result shows that its induction time is 65min, reaction deadline 180min, and the pressure of methane gas is reduced to 0.6MPa, and it is more obvious that its rejection is compared pure water.
Embodiment 2
0.1% PVCap and 3% ethylene glycol are compound, and experimental procedure is the same, and the result shows that its induction time is 78min, reaction deadline 200min, and the pressure of methane gas is reduced to 0.5MPa, and its rejection obviously improves.
0.1% PVCap and 5% ethylene glycol are compound, and experimental procedure is the same, and the result shows that its induction time is 85min, reaction deadline 215min, and the pressure of methane gas is reduced to 0.45MPa, and its rejection obviously improves.
Embodiment 4
0.3% PVCap and 1% ethylene glycol are compound, and experimental procedure is the same, and the result shows that its induction time is 90min, reaction deadline 225min, and the pressure of methane gas is reduced to 0.35MPa, and its rejection obviously improves.
Embodiment 5
0.3% PVCap and 3% ethylene glycol are compound, and experimental procedure is the same, and the result shows that its induction time is 105min, reaction deadline 245min, and the pressure of methane gas is reduced to 0.35MPa, and its rejection obviously improves.
Embodiment 6
0.3% PVCap and 5% ethylene glycol are compound, and experimental procedure is the same, and the result shows that its induction time is 120min, reaction deadline 276min, and the pressure of methane gas is reduced to 0.3MPa, and its rejection obviously improves.
0.5% PVCap and 1% ethylene glycol are compound, and experimental procedure is the same, and the result shows that its induction time is 127min, reaction deadline 289min, and the pressure of methane gas is reduced to 0.32MPa, and its rejection obviously improves.
0.5% PVCap and 3% ethylene glycol are compound, and experimental procedure is the same, and the result shows that its induction time is 135min, reaction deadline 334min, and the pressure of methane gas is reduced to 0.25MPa, and its rejection obviously improves.
0.5% PVCap and 5% ethylene glycol are compound, and experimental procedure is the same, and the result shows that its induction time is 156min, reaction deadline 377min, and the pressure of methane gas is reduced to 0.2MPa, and its rejection obviously improves.
Composite gas hydrate is generated of ethylene glycol that is drawn 0.1%～0.5%PVCap and 1%～5% by above example has the obvious suppression effect, and the compound inhibition the best of the ethylene glycol of 0.5% PVCap and 5%.Equally, Potassium ethanoate, saltpetre also have the obvious suppression effect with PVCap composite generation to hydrate in identical concentration range respectively.
Claims (2)
1. a compound gas hydrate inhibitor is characterized in that being made up of Vinylcaprolactam homopolymer, alcohol or salt and water, wherein each component by mass percentage, Vinylcaprolactam homopolymer accounts for 0.1% ~ 0.5%, alcohol or salt account for 1% ~ 5%, all the other are water.
2. according to the described compound gas hydrate inhibitor of claim, it is characterized in that alcohols is ethylene glycol, salt is Potassium ethanoate or saltpetre.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221685A (en) * | 2016-07-21 | 2016-12-14 | 常州大学 | A kind of composite hydrate inhibitor |
| CN106468395A (en) * | 2016-09-09 | 2017-03-01 | 常州大学 | A kind of gas hydrate inhibitor and preparation method thereof |
| CN106589994A (en) * | 2016-11-24 | 2017-04-26 | 常州大学 | Composite hydrate anti-agglomerant containing attapulgite |
| CN107903884A (en) * | 2017-10-31 | 2018-04-13 | 常州大学 | A kind of combined gas hydrate inhibitor and preparation method thereof |
| CN113462370A (en) * | 2021-05-20 | 2021-10-01 | 无锡雪浪康威环保科技有限公司 | Hydrate inhibitor |
| CN115595127A (en) * | 2022-09-19 | 2023-01-13 | 中海油海南能源有限公司（Cn） | Deepwater shallow gas hydrate multi-layer combined production drilling fluid system and hydrate inhibition performance regulation and control method |
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| WO2005005567A1 (en) * | 2003-07-02 | 2005-01-20 | Exxonmobil Upstream Research Company | A method for inhibiting hydrate formation |
| WO2006110192A1 (en) * | 2005-04-07 | 2006-10-19 | Exxonmobil Upstream Research Company | Recovery of kinetic hydrate inhibitor |
| CN101074361A (en) * | 2007-05-25 | 2007-11-21 | 东莞理工学院 | Efficient composite hydrate inhibitor |
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2013
- 2013-05-09 CN CN2013101700139A patent/CN103305200A/en active Pending
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221685A (en) * | 2016-07-21 | 2016-12-14 | 常州大学 | A kind of composite hydrate inhibitor |
| CN106468395A (en) * | 2016-09-09 | 2017-03-01 | 常州大学 | A kind of gas hydrate inhibitor and preparation method thereof |
| CN106589994A (en) * | 2016-11-24 | 2017-04-26 | 常州大学 | Composite hydrate anti-agglomerant containing attapulgite |
| CN106589994B (en) * | 2016-11-24 | 2019-05-28 | 常州大学 | One kind containing attapulgite clay compounded type hydrate anticoagulant |
| CN107903884A (en) * | 2017-10-31 | 2018-04-13 | 常州大学 | A kind of combined gas hydrate inhibitor and preparation method thereof |
| CN113462370A (en) * | 2021-05-20 | 2021-10-01 | 无锡雪浪康威环保科技有限公司 | Hydrate inhibitor |
| CN115595127A (en) * | 2022-09-19 | 2023-01-13 | 中海油海南能源有限公司（Cn） | Deepwater shallow gas hydrate multi-layer combined production drilling fluid system and hydrate inhibition performance regulation and control method |
| CN115595127B (en) * | 2022-09-19 | 2024-01-26 | 中海油海南能源有限公司 | Deep water shallow gas hydrate multi-layer joint production drilling fluid system and hydrate inhibition performance regulation and control method |
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Application publication date: 20130918 |