CN101608112A - A kind of efficient hydrate inhibitor - Google Patents
A kind of efficient hydrate inhibitor Download PDFInfo
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- CN101608112A CN101608112A CNA2009100408448A CN200910040844A CN101608112A CN 101608112 A CN101608112 A CN 101608112A CN A2009100408448 A CNA2009100408448 A CN A2009100408448A CN 200910040844 A CN200910040844 A CN 200910040844A CN 101608112 A CN101608112 A CN 101608112A
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Abstract
The invention provides a kind of hydrate inhibitor efficiently, relate to technical field of oil-gas hydrate.Hydrate inhibitor of the present invention is the mixture of anti polymerizer and ethylene glycol or Virahol.Described hydrate forms the inhibitor applying pressure at 1.5～25MPa, and temperature is at-20～25 ℃.Inhibitor of the present invention can overcome the prior art shortcoming, mixes with lower concentration, injects the petroleum fluids of producing or carrying, and reduces hydrate nucleation, growth and coalescent speed, and it is wide to have suitability, characteristics with low cost.
Description
Technical field
The present invention relates to technical field of oil-gas hydrate, relate in particular to a kind of hydrate inhibitor efficiently.
Technical background
In the line of pipes of Sweet natural gas and petroleum fluids, various low boiling point hydrocarbons such as methane, ethane, propane and carbonic acid gas, hydrogen sulfide etc. exist simultaneously with water, under the cryogenic high pressure condition, can form gas hydrate, i.e. the cage type crystal of micro-molecular gas such as water and lighter hydrocarbons formation.Because of the generation hydrate causes the obstruction of Sweet natural gas/crude production device and line of pipes is the thorny problem of a long-term puzzlement production of hydrocarbons, freight department.For offshore oil and gas field exploitation and territory, deep-sea pipe-line transportation, because submarine water temperature and pressure condition all are well suited for the generation of hydrate, hydrate problems is particularly outstanding.For example under the pressure of about 1MPa, ethane can form hydrate being lower than under 4 ℃ the temperature, is being lower than under 14 ℃ the temperature with regard to able to generate hydrate at ethane under the 3MPa pressure.And this type of temperature, pressure condition are not rare in the oil-gas mining of reality, many operating environments of conveying yet.How to prevent that the generation of hydrate from becoming the emphasis problem of the concern that always is subjected to oil and gas industry.
Hydrate commonly used is prevented and treated method, mainly is by dehydration, heating, decompression and adding thermodynamics inhibitor, makes system not possess the thermodynamic condition that generates hydrate, perhaps one or several methods is joined together.Though these traditional methods have obtained certain inhibition or preventive effect, need to drop into substantial contribution, and need the very big energy of input to carry out subsequent disposal, especially a large amount of uses of thermodynamics inhibitor such as methyl alcohol bring very big negative impact to environment.
At present, research emphasis is concentrated on the low dosage hydrate inhibitor both at home and abroad, comprise kinetic inhibitor and anti polymerizer.The adding of kinetic inhibitor can suppress or postpone the growth time of hydrate, suppresses the purpose that hydrate generates thereby reach.Its adding concentration is low, does not influence the thermodynamic condition that hydrate generates, and can postpone the nucleation of hydrate and the time of crystal growth under the thermodynamic condition that hydrate forms.Yet kinetic inhibitor action effect under the situation that pipeline (or oil well) seals or condensate depression is bigger is poor, so range of application is restricted.Anti polymerizer is to prevent the coalescent of hydrate crystal grain by adding very low tensio-active agent of some concentration or polymkeric substance, guarantees the safe fluid conveying.Though anti polymerizer can not stop the formation of gas hydrate in the pipeline, can make hydrate be difficult to be agglomerated into piece.Than kinetic inhibitor, can under the situation that pipeline (or oil well) seals or condensate depression is bigger, use, but its effect of using separately is not really desirable.
Summary of the invention:
The objective of the invention is to overcome the defective of prior art, a kind of efficient hydrate inhibitor is provided, inhibitor of the present invention is subjected to the restriction of condensate depression and operational condition little, be applicable to oil gas water three phase or profit two-phase coexistent system, can give full play to anti polymerizer and suppress the coalescent effect of hydrate, it is wide to have suitability, characteristics with low cost.
The object of the invention is achieved through the following technical solutions:
A kind of hydrate inhibitor efficiently is the mixture of anti polymerizer and solubility alcohols.
A kind of hydrate inhibitor efficiently is to be mixed by anti polymerizer and solubility alcohols.The mass ratio of water in anti polymerizer and the system wherein, anti polymerizer is adapted at 0.05～5%, and is excellent in 0.2～2.5%, optimum 0.5～1%; The mass ratio of water in solubility alcohols and the system, the solubility alcohols is adapted at 1～35%, and is excellent in 5～25%, optimum 10～20%.Described system is oil gas water three phase or profit two-phase coexistent system.
Wherein, anti polymerizer can adopt quaternary ammonium salt surface active agent, as TBAB (Tetrabutyl amonium bromide), four pentyl brometo de amonio and have quaternary ammonium salt of 2～3 normal-butyls, n-pentyl or isopentyl etc.
Anti polymerizer also can adopt common polymerization inhibition effect one or more mixtures in Span20 (sorbitol anhydride mono-laurate), Span65 (anhydrous sorbitol tristearate), Span80 (sorbitan monooleate), the glyceryl monostearate preferably.
The mixture of one of perhaps above four kinds (Span20, Span65, Span80, glyceryl monostearates) and Tween65 (polyoxyethylene 20 sorbitan tristearate) or Tween85 (polyoxyethylene 20 sorbitan trioleate).Alcohol makes spent glycol, Virahol.
Hydrate inhibitor of the present invention is suitable for pressure at 1.5～25MPa, and temperature is at-20～25 ℃.Be to be under 5%～50% condition, use in oil or oil and the Sweet natural gas polyphasic flow system at water, oil volume per-cent.
Principal feature of the present invention is that the adding of alcohol has reduced hydrate generation temperature or improved hydrate generation pressure, has reduced condensate depression to a certain extent, and anti polymerizer is better played effectiveness.Anti polymerizer has restraining effect to hydrate simultaneously, and has stoped hydrate to be gathered into piece.
The present invention considers the problem of operating cost, and the consumption of pure and mild anti polymerizer is less, and subsequent treatment process is simple.
The present invention has overcome the shortcoming of traditional water compound inhibition method preferably, has overcome simultaneously that thermodynamics inhibitor consumption is big, expense is high, and the expensive many drawbacks of anti polymerizer.Mix the petroleum fluids that injects production or carry with lower concentration, reduce hydrate nucleation, growth and coalescent speed, it is wide to have suitability, characteristics with low cost.
Advantage and beneficial effect that the present invention has with respect to prior art:
(1) action effect is good: independent alcohols can only influence the thermodynamic property that hydrate generates as the thermodynamics inhibitor, having reduced hydrate generates temperature or has improved hydrate generation pressure, can suppress the generation of hydrate, but, can not play preventing that it is coalescent, the effect of blocking pipeline for the hydrate that has formed.Assemble though anti polymerizer can prevent hydrate, result of use is not ideal enough separately.With alcohols inhibitor and the compound use of anti polymerizer, the adding of alcohol improves surroundings to a certain extent, creates surroundings preferably for anti polymerizer plays a role.The two is used, and can better bring into play inhibition, anti-accumulative effect.
(2) consumption is little, and cost is low: tradition adding thermodynamics inhibitor consumption is big, and operation is expensive, and the anti polymerizer price is also higher simultaneously.The pure and mild anti polymerizer that the present invention selects cheapness for use, is easy to get, and addition is low, can compositely reach the economic proportioning of ideal.Can reduce the cost that gas industries is used for hydrate control so greatly.
Embodiment:
Below the present invention is further described in detail, but embodiments of the present invention are not limited to this.
The used experiment porch of following examples is described as follows:
The present invention adopts the cryogenic high pressure reactor of external chuck band double vision window and magnetic stirring apparatus as experimental installation, and this equipment mainly is made up of double vision window chuck autoclave, magnetic stirring apparatus, reometer, temperature and pressure transmitter, low temperature thermostat bath, vacuum pump and data collecting instrument.Low temperature thermostat bath can be reacting kettle jacketing and provides-30～100 ℃ refrigerant circulation fluid, and agitator at the uniform velocity stirs.Hydrate can generate in autoclave, can observe hydrate generation situation in the still by form.Can be by temperature and pressure transmitter and data collecting instrument with temperature, pressure data transmission in the hydro-combination process to computer, by form directly and reometer survey the hydrate generation whether fully as can be known of magnetic stirring apparatus electric current change intensity.The operating pressure of this system is at 0～20MPa, and working temperature is at-20～100 ℃.Anti polymerizer can be weighed by the hydrate rise time the inhibition effect of hydrate in the reactor with the hydrate inhibitor that alcohol is formed, and anti-poly-effect generates fully by hydrate to be weighed.The hydrate rise time is long more, and it is good more to suppress effect; The complete rise time of hydrate is long more, and anti-poly-effect is good more.
Reactor is cleaned up vacuum-drying with deionized water before the reaction beginning.The reaction initial temperature is made as 3 ℃, feeds the gas mixture that methane, ethane and propane are formed, and original pressure is 6MPa, and the setting stir speed (S.S.) is 300rmp.
The generation of hydrate changes by reacting kettle inner pressure to be judged, the still internal pressure all maintains 6MPa all the time before the reaction beginning, and after the reaction beginning, the unexpected drop point of still internal pressure is exactly the starting point that hydrate generates.The hydrate rise time promptly is that to feed gas and constant pressure in the still be 6MPa to the time that the pressure drop point is experienced.The generation fully of hydrate is judged by direct viewing and the required current value of agitator motor, can be observed hydrate by form generates and the gathering situation, under stir speed (S.S.) one stable condition, stir required strength of current before and after the reaction and change above 50mA, promptly think and assemble.Therefore, the complete rise time is defined as hydrate generation point and reaches the time that 50mA experiences to stir current, in addition, adopts observation and electric current determining method to improve result's accuracy simultaneously.The action effect of inhibitor of the present invention can according to the rise time of hydrate and the rise time be judged fully.The inhibition effect that the hydrate rise time generates hydrate in order to reaction suppressor, the hydrate rise time is long more, and it is good more to suppress effect; The complete rise time of hydrate, the complete rise time of hydrate was long more in order to the anti-poly-effect of reaction suppressor to the hydrate that generated, and anti-poly-effect is good more.
Comparative Examples 1
Add the 150mL crude oil sample in reactor, the question response temperature in the kettle is stabilized in about 3 ℃, feeds gas (CH
491.05%, C
2H
66.05%, C
3H
82.90%), experimental result is 35min for the hydrate rise time, and the rise time is 140min fully.
Comparative Examples 2
In reactor, add the 150mL crude oil sample, in crude oil sample, add span20, the mass ratio 0.7% of water in the quality of Span20 and the crude oil sample; Experimental technique and step such as Comparative Examples 1, result show that the system hydrate rise time that contains span20 is 47min, and the complete rise time of hydrate is 236min.Has anti-preferably poly-effect.
Comparative Examples 3
Add the 150mL crude oil sample in reactor, add ethylene glycol in crude oil sample, the mass ratio of water is 20% in the quality of ethylene glycol and the crude oil sample; Experimental technique and step such as Comparative Examples 1, result show that the system hydrate rise time that contains ethylene glycol is 100min, and the complete rise time of hydrate is 163min.It is obvious that it suppresses effect, but do not have significantly anti-poly-effect.
Comparative Examples 4
In reactor, add the 150mL crude oil sample, in crude oil sample, add Span65 and Tween85, the mass ratio of water is 0.3% in Span65 (anhydrous sorbitol tristearate) and the crude oil sample, the mass ratio of water is 0.3% in Tween85 (polyoxyethylene 20 sorbitan trioleate) and the crude oil sample, experimental technique and step are as above, the result shows that the hydrate rise time is 40min, and the complete rise time of hydrate is 285min.Its anti-poly-effect is obvious, but does not have the obvious suppression effect.
Embodiment 1
The same Comparative Examples of experimental technique and step, in reactor, add the 150mL crude oil sample, in crude oil sample, add inhibitor of the present invention, the mass ratio of water is 10.5% in inhibitor and the crude oil sample, and wherein the mass ratio of span20 and water is 0.5%, and the mass ratio of ethylene glycol and water is 10%, the reaction initial temperature is made as 3 ℃, feeds gas (CH
491.05%, C
2H
66.05%, C
3H
82.90%), makes pressure reach 6MPa, open magnetic stirring apparatus and begin reaction.Reaction finishes to be measured as hydrate, and to begin the rise time be 148min, and the rise time is 294min fully.The result shows that Span20 with 0.5% and 10% ethylene glycol are used, and has obviously prolonged the rise time and the complete rise time of hydrate, and the anti-poly-and rejection of Span20 and ethylene glycol all obviously improves.
Embodiment 2
In reactor, add the 150mL crude oil sample, in crude oil sample, add inhibitor of the present invention, with respect to the quality of water in the crude oil sample, the mass ratio of inhibitor of the present invention and water is 21%, and wherein Span 20 (sorbitol anhydride mono-laurate) is 1% with the mass ratio of water, the mass ratio of ethylene glycol and water is 20%, experimental technique and step such as embodiment 1, the hydrate rise time is 170min, the rise time is 417min fully.The result shows that Span 20 with 1% and 20% ethylene glycol are used, and has obviously prolonged the rise time and the complete rise time of hydrate, and the anti-poly-and rejection of Span20 and ethylene glycol all obviously improves.
Embodiment 3
In reactor, add the 150mL crude oil sample, in crude oil sample, add inhibitor of the present invention, with respect to the quality of water in the crude oil sample, the mass ratio of inhibitor of the present invention and water is 5.2%, and wherein Span 20 (sorbitol anhydride mono-laurate) is 0.2% with the mass ratio of water, the mass ratio of ethylene glycol and water is 5%, experimental technique and step such as embodiment 1, the hydrate rise time is 118min, the rise time is 250min fully.The result shows that Span 20 with 0.2% and 5% ethylene glycol are used, and has prolonged the rise time and the complete rise time of hydrate to a certain extent, but the ethylene glycol working concentration is on the low side, Span 20 consumptions are higher, not in the optimum amount scope, improve limited so suppress effect.
Embodiment 4
In reactor, add the 150mL crude oil sample, in crude oil sample, add inhibitor of the present invention, with respect to the quality of water in the crude oil sample, the mass ratio of inhibitor of the present invention and water is 27.5%, and wherein Span 20 (sorbitol anhydride mono-laurate) is 2.5% with the mass ratio of water, the mass ratio of ethylene glycol and water is 25%, experimental technique and step such as embodiment 1, the hydrate rise time is 207min, the rise time is 430min fully.The result shows that Span 20 with 2.5% and 25% ethylene glycol are used, and has to suppress preferably and prevent poly-effect.
Embodiment 5
In reactor, add the 150mL crude oil sample, in crude oil sample, add inhibitor of the present invention, with respect to the quality of water in the crude oil sample, the mass ratio of inhibitor of the present invention and water is 1.05%, and wherein the mass ratio of Span 20 (sorbitol anhydride mono-laurate) and water is for being 0.05%, the mass ratio of Virahol and water is 1%, experimental technique and step such as embodiment 1, the hydrate rise time is 57min, the rise time is 190min fully.The result shows that span20 with 0.05% and 1% Virahol are used, because the two consumption is all on the low side, the rise time of hydrate and complete rise time are not all obviously prolonged, and does not reach ideal inhibition and anti-poly-effect.
Embodiment 6
In reactor, add the 150mL crude oil sample, in crude oil sample, add inhibitor of the present invention, with respect to the quality of water in the crude oil sample, the mass ratio of inhibitor of the present invention and water is 40%, and wherein the mass ratio of TBAB (Tetrabutyl amonium bromide) and water is for being 5%, the mass ratio of ethylene glycol and water is for being 35%, experimental procedure such as embodiment 1, the hydrate rise time is 230min, the rise time is 450min fully.The result shows that TBAB with 5% and 35% ethylene glycol are used, and has obviously prolonged the rise time and the complete rise time of hydrate, and inhibitor has obvious suppression and anti-poly-effect in this system.
Embodiment 7
In reactor, add the 150mL crude oil sample, in crude oil sample, add inhibitor of the present invention, with respect to the quality of water in the crude oil sample, the mass ratio of inhibitor of the present invention and water is 20.5%, and wherein TBAB (Tetrabutyl amonium bromide) is 0.5% with the mass ratio of water, the mass ratio of Virahol and water is 20%, experimental technique and step such as embodiment 1, the hydrate rise time is 190min, the rise time is 275min fully.The result shows that TBAB with 0.5% and 20% Virahol are used, and has obviously prolonged the rise time and the complete rise time of hydrate, and inhibitor has obvious suppression and anti-poly-effect in this system.
Embodiment 8
In reactor, add the 150mL crude oil sample, in crude oil sample, add inhibitor of the present invention, quality with respect to water in the crude oil sample, the mass ratio of inhibitor of the present invention and water is 11%, wherein Span65 (anhydrous sorbitol tristearate) is 1% with the mass ratio of water, the mass ratio of ethylene glycol and water is 10%, experimental technique and step such as embodiment 1, the hydrate rise time is 140min, the rise time is 387min fully, the result shows, Span65 with 1% and 10% ethylene glycol are used, and have obviously prolonged the rise time and the complete rise time of hydrate, and inhibitor has obvious suppression and anti-poly-effect in this system.
Embodiment 9
In reactor, add the 150mL crude oil sample, in crude oil sample, add inhibitor of the present invention, with respect to the quality of water in the crude oil sample, the mass ratio of inhibitor of the present invention and water is 25.2%, and wherein Span80 (sorbitan monooleate) is 0.2% with the mass ratio of water, the mass ratio of Virahol and water is 25%, experimental technique and step such as embodiment 1, the hydrate rise time is 201min, the rise time is 386min fully.The result shows that inhibitor has obvious suppression and anti-poly-effect in this system.
Embodiment 10
In reactor, add the 150mL crude oil sample, in crude oil sample, add inhibitor of the present invention, quality with respect to water in the crude oil sample, the mass ratio of inhibitor of the present invention and water is 3%, wherein Span20 (sorbitol anhydride mono-laurate) is 2.2% with the mass ratio of water, Tween65 (anhydrous sorbitol tristearate) is 0.3% with the mass ratio of water, the mass ratio of ethylene glycol and water is 5%, experimental technique and step such as embodiment 1, the hydrate rise time is 132min, and the rise time is 459min fully.The result shows, the Span20 with 2.2%, and 0.3% Tween65 and 5% ethylene glycol are used, and have prolonged the rise time of hydrate and complete rise time, and inhibitor has and suppresses preferably and prevent gathering effect in this system.
Embodiment 11
In reactor, add the 150mL crude oil sample, in crude oil sample, add inhibitor of the present invention, quality with respect to water in the crude oil sample, the mass ratio of inhibitor of the present invention and water is 15.6%, wherein Span65 (anhydrous sorbitol tristearate) is 0.3% with the mass ratio of water, Tween85 (polyoxyethylene 20 sorbitan trioleate) is 0.3% with the mass ratio of water, the mass ratio of Virahol and water is 15%, experimental technique and step such as embodiment 1, the hydrate rise time is 172min, and the rise time is 413min fully.The result shows, the Span65 with 0.3%, and 0.3% Tween85 and 15% Virahol are used, and have obviously prolonged the rise time of hydrate and complete rise time, and inhibitor has and suppresses preferably and prevent gathering effect in this system.
Claims (9)
1, a kind of hydrate inhibitor efficiently is characterized in that, described hydrate inhibitor is the mixture of anti polymerizer and solubility alcohols.
2, hydrate inhibitor according to claim 1 is characterized in that the quality with respect to water in the system, and the mass ratio of anti polymerizer and water is 0.05～5%, and the mass ratio of solubility alcohols and water is 1～35%.
3, hydrate inhibitor according to claim 2 is characterized in that the quality with respect to water in the system, and the mass ratio of anti polymerizer and water is 0.2～2.5%, and the mass ratio of solubility alcohols and water is 5～25%.
4, hydrate inhibitor according to claim 3 is characterized in that the quality with respect to water in the system, and the mass ratio of anti polymerizer and water is 0.5～1%, and the mass ratio of solubility alcohols and water is 10～20%.
According to the described hydrate inhibitor of one of claim 2-4, it is characterized in that 5, described system is oil gas water three phase or profit two-phase coexistent system.
6, hydrate inhibitor according to claim 1 is characterized in that, described solubility alcohols comprises ethylene glycol or Virahol.
7, hydrate inhibitor according to claim 1 is characterized in that, described anti polymerizer adopts quaternary ammonium salt surface active agent, comprises the quaternary ammonium salt, Tetrabutyl amonium bromide or the four pentyl brometo de amonio that contain 2～3 normal-butyls, n-pentyl or isopentyl.
8, hydrate inhibitor according to claim 1, it is characterized in that the mixture of one or more in described anti polymerizer employing sorbitol anhydride mono-laurate, anhydrous sorbitol tristearate, sorbitan monooleate, the glyceryl monostearate.
9, hydrate inhibitor according to claim 1, it is characterized in that the mixture of a kind of and polyoxyethylene 20 sorbitan tristearate or polyoxyethylene 20 sorbitan trioleate in described anti polymerizer employing sorbitol anhydride mono-laurate, anhydrous sorbitol tristearate, sorbitan monooleate, the glyceryl monostearate.
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| AR001674A1 (en) * | 1995-04-25 | 1997-11-26 | Shell Int Research | Method to inhibit gas hydrate clogging of ducts |
| CN101109481A (en) * | 2007-07-04 | 2008-01-23 | 中国海洋石油总公司 | Method for preventing hydrate polymerization inhibitor from being disabled |
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