CN107663447A - A kind of hydrate inhibitor and its application - Google Patents
A kind of hydrate inhibitor and its application Download PDFInfo
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- CN107663447A CN107663447A CN201610615975.4A CN201610615975A CN107663447A CN 107663447 A CN107663447 A CN 107663447A CN 201610615975 A CN201610615975 A CN 201610615975A CN 107663447 A CN107663447 A CN 107663447A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
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Abstract
The present invention provides a kind of hydrate inhibitor and its application.The hydrate inhibitor of the present invention includes proline；Hydrate Suppression includes using the generation of the hydrate in the hydrate inhibitor inhibition system, wherein, the system is profit system, air water system or oil-water-gas system.The hydrate inhibitor of the present invention not only has hypotoxicity, non-volatile, degradable, advantages of environment protection, is furthermore possible to greatly improve the equilibrium condition of hydrate generation, has good thermodynamics inhibitory action.
Description
Technical field
The invention belongs to production of hydrocarbons field, and in particular to a kind of hydrate inhibitor and its application.
Background technology
The gas of some low molecule amounts and some volatile liquids, such as C1~C4 lighter hydrocarbons, N2、O2、CO2、H2S, epoxy second
It is brilliant that alkane, tetrahydrofuran and halogenated alkane etc. can form non-stoichiometry caged under the conditions of certain temperature and pressure with water
Body, commonly referred to as clathrate hydrate (Clathrate Hydrates), referred to as hydrate, its structure type mainly have I types, knot
Three kinds of structure II types and H types.For a long time, line clogging caused by gas hydrate generation is puzzlement production of hydrocarbons and transportation department
Thorny problem；Particularly, the deep-sea of the exploitation for offshore oil and gas field and oil gas is transported, and hydrate problems are especially prominent, main
Want the generation that reason is the water temperature in seabed and pressure condition is all well suited for hydrate.Therefore, how to prevent hydrate from generating one
Directly paid close attention to by oil and gas industry, and be badly in need of the problem broken through in industry.
Hydrate Suppression has traditional thermodynamics suppressing method and new dynamic control method two types.Heat
The characteristics of mechanics suppressing method is by being dehydrated, heating, depressurizing and adding thermodynamic inhibitor, system is hydrated without generation
The thermodynamic condition of thing, is currently widely used.Traditional thermodynamics suppresses method, presses down typically by enough thermodynamics is added
Preparation (such as methanol, ethanol, ethylene glycol, triethylene glycol etc.), the balance generation pressure of hydrate is set to be higher than the operating pressure of pipeline
Or the balance generation temperature of hydrate is less than the operation temperature of pipeline, so as to avoid the generation of hydrate.However, this method because
Using methanol, ethylene glycol, as the usage amount of the thermodynamic inhibitor of representative, big (usage amount is usually the quality of system reclaimed water
40wt%-60wt%), cost is high, reclaims the problems such as difficult and is restricted.Particularly, methanol is because toxicity is big, volatile, pollution
The defects of property is strong is gradually eliminated, and using sodium chloride as the electrolyte salt of representative because of corrosive pipeline the problems such as also can only be limited
In the range of apply.
Dynamic control method is developed by kinetic inhibition method, including kinetic inhibition and dynamic control two
Approach.Kinetic inhibition method adds the hydrate inhibitor of low dosage, and it does not change the thermodynamic condition of hydrate generation, but
The dynamic conditions generated by changing hydrate, the nucleation for such as postponing hydrate, the growth rate for slowing down hydrate crystal, resistance
Sealing solvate crystal assembles the purpose for reaching preventing and treating hydrate such as blocking.Low dosage hydrate inhibitor includes hydrate kinetic
Inhibitor and anti polymerizer；Wherein, kinetic inhibitor is primarily adapted for use in air water two-phase system, using PVC as generation
The kinetic inhibitor of table exist inhibitory activity it is not high, generally under the conditions of degree of supercooling using, be easy to more than 10 DEG C failure etc.
Defect, particularly its biological degradability is poor, therefore many offshore oilfield limitations use；And anti polymerizer can only be sent out in the presence of oil phase
The effect of waving, when the moisture content in system is more than 50wt%, prevent poly- effect will fail, in addition anti polymerizer also exist synthesis into
The problems such as this is higher, toxicity is big, so as to gradually be used by limitation.
The content of the invention
The present invention provides a kind of hydrate inhibitor and its application, and the hydrate inhibitor not only has hypotoxicity, do not waved
Hair, degradable, advantages of environment protection, it is furthermore possible to greatly improve the equilibrium condition of hydrate generation, there is good heating power
Learn inhibitory action.
A kind of hydrate inhibitor of present invention offer, including proline, its structural formula are as follows：
In the present invention, the hydrate inhibitor can be only proline；Now, proline presses down directly as hydrate
Preparation.
In addition, the hydrate inhibitor of the present invention can also be proline and the other Conventional Hydrate inhibitor in this area
Mixture；Wherein, proline can be mixed with other Conventional Hydrate inhibitor with arbitrary proportion.
The present invention also provides application of the described hydrate inhibitor on hydrate is suppressed.
The present invention also provides a kind of Hydrate Suppression, including uses in described hydrate inhibitor inhibition system
The generation of hydrate.
The present invention is not limited strictly system used in hydrate inhibitor, such as can be profit system, air water
System, oil-water-gas system etc..Specifically, profit system can be the system of water and oily (such as water and gasoline) composition；Air water body
System can be water and C1~C4 lighter hydrocarbons (such as methane, ethane etc.), N2、O2、CO2、H2The system of the gases such as S composition；Profit gas
System can be the three-phase system being made up of water, above-mentioned oil and above-mentioned gas.
The present invention can be without strict demand, the volume content of the system reclaimed water to the volume content of the system reclaimed water
1%-99%, it is further 50-99%.
In the present invention, the usage amount of the hydrate inhibitor can be the 0.001%- of the quality of the system reclaimed water
70%, it is further 10-70%, is further 30-70%.
The present invention is not limited strictly the condition of the generation using the hydrate in the hydrate inhibitor inhibition system
System, the suppression can be for example 0.1-35MPa in absolute pressure, temperature is carried out under conditions of being -30-25 DEG C；Further may be used
To carry out under conditions of being 5-10 DEG C as 9-15MPa, temperature in absolute pressure.
The present invention is not limited strictly the hydrate；In concrete scheme, the hydrate can be gas hydrate
Thing, such as methane hydrate etc..
Hydrate inhibitor provided by the invention at least has the advantage that：
(1) non-volatility：The hydrate inhibitor of the present invention exists with solidapowder form at normal temperatures, will not volatilize and make
Sucked into staff；In addition, the hydrate inhibitor will not also produce volatilization when being dissolved in various systems, therefore make
Used time only needs simple anti-dust measure.
(2) hypotoxicity：The hydrate inhibitor of the present invention belongs to biological micromolecule, can be metabolized completely by animals and plants, its
It is small to the harmfulness of human body to the dangerous low of skin, and without cumulative effect, usual industrial treatment.
(3) it is pollution-free：The hydrate inhibitor of the present invention is to form one kind in 20 kinds of amino acid of organism, is had close
100% biological degradability, its contaminative to environment is small, thus overcome current most of hydrate inhibitor difficult degradation,
The shortcomings of toxicity is big.
(4) versatility is good：The hydrate inhibitor of the present invention can be widely used for profit system, air water system, profit gas
The condition such as system etc., concentration, temperature, pressure during its water content and use to system without strict demand, application not by
Limitation.
(5) high efficiency：The hydrate inhibitor of the present invention has good thermodynamics inhibition and kinetic inhibition effect
Fruit, under equivalent molar concentration, its inhibition is significantly higher than other Conventional Hydrate inhibitor (such as methanol of this area
Deng)；Especially for methane hydrate, it can improve balance pressure 6.68MPa or so at 10 DEG C.
Brief description of the drawings
Fig. 1 is the structural representation for carrying out the reaction system that hydrate of the present invention suppresses experiment.
Description of reference numerals：
1：Vavuum pump；2：Reactor；3：Gas cylinder；4：Air bath temperature control equipment；5：Air bath；6：Magnetic agitation fills
Put；7：Manual pump；8：Piston；9：Visual windows；10：Temperature indicating device；11：Pressure-display device.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with embodiments of the invention, to this
Technical scheme in inventive embodiments is clearly and completely described, it is clear that described embodiment is that a part of the invention is real
Apply example, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making creation
Property work under the premise of the every other embodiment that is obtained, belong to the scope of protection of the invention.
Embodiment 1
The hydrate inhibitor of the present embodiment is proline, and carrying out the method for hydrate suppression using it includes following step
Suddenly：
1st, solution is prepared
Proline is dissolved completely in deionized water, the proline solution that molar concentration is 3mol/L is made, and (quality is dense
Spend for 34.5%).
2nd, hydrate suppresses
Hydrate is carried out using the reaction system shown in Fig. 1 and suppresses experiment, wherein：System is gas used by the present embodiment
Aqueous systems, hydrate inhibitor be 3mol/L proline solution, gas CH4, water is obtained using constant temperature and pressure search method
The equilibrium condition of compound, experimental temperature are arranged to 9.99 DEG C, comprised the following steps that：
1) reactor 2 is vacuumized using vavuum pump 1, reactor 2 carried out clearly followed by negative pressure suction deionized water
Wash, until cleaning up；
2) by the above-mentioned proline solution rinse reactor 2 prepared three times, then appropriate proline solution is sucked to reaction
In kettle 2；
3) methane gas that would be stored in gas cylinder 3 is filled with reactor 2 to be purged to reactor 2 on a small quantity, then right
Reactor 2 vacuumizes, repeatedly for three times after, be filled with the methane gas of appropriate pressure；
4) start and adjust air bath temperature control equipment 4, the temperature of reactor 2 is reached 9.99 DEG C by air bath 5
And keep constant, later on magnetic stirring apparatus 6, constant speed stirring is carried out in suitable mixing speed；
5) manually pump 7 and piston 8 pressurize to reactor 2, the pressure inside reactor 2 is given birth to higher than hydrate
Whether into pressure, being observed using cold light source by the visual windows 9 of reactor 2 in reactor 2 has hydrate to generate (generally 1
Hydrate is generated within hour, heat release when generating hydrate, the temperature of reactor 2 has certain increase)；
6) when having observed hydrate generation, the manual pump 5 of quick rotation makes generation to reduce the pressure of reactor 2
Hydrate is partly dissolved as early as possible；
7) after the temperature stabilization of reactor 2 is in experimental temperature, repeat the above steps 4), when there is trace hydrate crystal
When (only several hydrate crystal grain) generates at gas-liquid interface and is adhered to the visual windows 9 of reactor 2, maintenance reaction kettle 2
Temperature and pressure is constant, stablizes 4 hours.
8) after 4 hours, if the hydrate crystal of trace still has in reactor 2, pressure now is to test temperature
Hydrate generation pressure under degree；If the trace hydrate crystal generated in 4 hours is all dissolved, illustrate pressure now
Pressure need to be adjusted to a high value (amplification 0.02MPa), given birth to again in reactor 2 less than hydrate generation pressure by power
Into trace hydrate and ensure that it is stabilized 4 hours, finally give experimental system under experimental temperature hydrate generation
Pressure.
During above-mentioned experiment, temperature can be shown that pressure can be shown by pressure by temperature indicating device 10
Showing device 11 is shown.
After testing, the present embodiment is stabilized in trace hydrate and after pressure stability 4h, resulting balance pressure value
For 13.93Mpa；Meanwhile blank control test (above-mentioned proline solution is replaced with the deionized water without proline) gained
The balance pressure value arrived is 7.25Mpa.
It is indicated above：At 10 DEG C or so, the hydrate inhibitor of the present embodiment can improve when concentration is 3mol/L
Pressure value 6.68Mpa is balanced, illustrates that the hydrate inhibitor can significantly improve the formation condition of hydrate, so as to suppress air water
The generation of hydrate in system.
Embodiment 2
System is air water system used by the present embodiment, and hydrate inhibitor is 3mol/L proline solution, gas
For CH4, the equilibrium condition of hydrate is obtained using constant temperature and pressure search method, experimental temperature is arranged to 6.11 DEG C, using with reality
Apply the identical step of example 1 and carry out hydrate suppression experiment.
After testing, the present embodiment is stabilized in trace hydrate and after pressure stability 4h, resulting balance pressure value
For 9.0Mpa；Meanwhile obtained by blank control test (replacing above-mentioned proline solution with the deionized water without proline)
Balance pressure value be 4.69Mpa.
It is indicated above：At 6 DEG C or so, the hydrate inhibitor of the present embodiment can improve flat when concentration is 3mol/L
Weigh pressure value 4.31Mpa, illustrates that the hydrate inhibitor can significantly improve the formation condition of hydrate, so as to suppress air water body
The generation of hydrate in system.
Embodiment 3
System is air water system used by the present embodiment, and hydrate inhibitor is mass concentration 21.9wt% proline
Solution, gas CH4, the equilibrium condition of hydrate is obtained using constant temperature and pressure search method, experimental temperature is arranged to 10.0 DEG C,
Hydrate is carried out using step same as Example 1 and suppresses experiment.
After testing, the present embodiment is stabilized in trace hydrate and after pressure stability 4h, resulting balance pressure value
For 9.36Mpa；Meanwhile obtained by blank control test (replacing above-mentioned proline solution with the deionized water without proline)
Balance pressure value be 7.25Mpa.
It is indicated above：At 10 DEG C or so, the hydrate inhibitor of the present embodiment energy when mass concentration is 21.9wt%
It is enough to improve balance pressure value 2.11Mpa, illustrate that the hydrate inhibitor can significantly improve the formation condition of hydrate, so as to press down
The generation of hydrate in air water system processed.
Reference examples 1
System is air water system used by this reference examples, and hydrate inhibitor is 3mol/L methanol solution, and gas is
CH4, the equilibrium condition of hydrate is obtained using constant temperature and pressure search method, experimental temperature is arranged to 9.99 DEG C, using with implementation
The identical step of example 1 carries out hydrate and suppresses experiment.
After testing, at 10 DEG C or so, the hydrate inhibitor of this reference examples is stabilized and pressure in trace hydrate
After stable 4h, resulting balance pressure value is 12.14Mpa, balance pressure value 4.89Mpa is only improved, well below the present invention
Hydrate inhibitor, thus illustrate the present invention hydrate inhibitor inhibition be much better than this area tradition suppression
Agent.
Reference examples 2
System is air water system used by this reference examples, and hydrate inhibitor is 3mol/L glycine solution, gas
For CH4, the equilibrium condition of hydrate is obtained using constant temperature and pressure search method, experimental temperature is arranged to 9.99 DEG C, using with reality
Apply the identical step of example 1 and carry out hydrate suppression experiment.
After testing, at 10 DEG C or so, the hydrate inhibitor of this reference examples is stabilized and pressure in trace hydrate
After stable 4h, resulting balance pressure value is 9.75Mpa, balance pressure value 2.5Mpa is only improved, well below the present invention's
Hydrate inhibitor, thus explanation is not that arbitrary amino acid is necessarily of good hydrate inhibition effect.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (9)
1. a kind of hydrate inhibitor, it is characterised in that including proline.
2. application of the hydrate inhibitor on hydrate is suppressed described in claim 1.
3. a kind of Hydrate Suppression, it is characterised in that including suppressing body using the hydrate inhibitor described in claim 1
The generation of hydrate in system.
4. Hydrate Suppression according to claim 3, it is characterised in that the system is profit system, air water body
System or oil-water-gas system.
5. the Hydrate Suppression according to claim 3 or 4, it is characterised in that the volume content of the system reclaimed water
For 1%-99%.
6. the Hydrate Suppression according to claim 3 or 4, it is characterised in that the use of the hydrate inhibitor
Measure the 0.001%-70% of the quality for the system reclaimed water.
7. the Hydrate Suppression according to claim 3 or 4, it is characterised in that the suppression in absolute pressure is
0.1-35MPa, temperature are carried out under conditions of being -30-25 DEG C.
8. the Hydrate Suppression according to claim 3 or 4, it is characterised in that the hydrate is gas hydrate.
9. Hydrate Suppression according to claim 8, it is characterised in that the gas hydrate is hydrated for methane
Thing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610615975.4A CN107663447A (en) | 2016-07-28 | 2016-07-28 | A kind of hydrate inhibitor and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610615975.4A CN107663447A (en) | 2016-07-28 | 2016-07-28 | A kind of hydrate inhibitor and its application |
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| Publication Number | Publication Date |
|---|---|
| CN107663447A true CN107663447A (en) | 2018-02-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610615975.4A Pending CN107663447A (en) | 2016-07-28 | 2016-07-28 | A kind of hydrate inhibitor and its application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023122947A1 (en) * | 2021-12-28 | 2023-07-06 | 大连理工大学 | Environmentally-friendly natural gas hydrate inhibitor and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0536950A1 (en) * | 1991-10-10 | 1993-04-14 | The British Petroleum Company P.L.C. | Method for inhibiting hydrate formation |
| KR20130058483A (en) * | 2011-11-25 | 2013-06-04 | 재단법인 포항산업과학연구원 | Environmental thermodynamic hydrate formation inhibitors |
| 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 |
-
2016
- 2016-07-28 CN CN201610615975.4A patent/CN107663447A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0536950A1 (en) * | 1991-10-10 | 1993-04-14 | The British Petroleum Company P.L.C. | Method for inhibiting hydrate formation |
| KR20130058483A (en) * | 2011-11-25 | 2013-06-04 | 재단법인 포항산업과학연구원 | Environmental thermodynamic hydrate formation inhibitors |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 刘倩: "水溶液中单糖与脯氨酸相互作用的体积、粘度性质", 《河南师范大学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023122947A1 (en) * | 2021-12-28 | 2023-07-06 | 大连理工大学 | Environmentally-friendly natural gas hydrate inhibitor and application |
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