CN108570150A - Elasticity adjusts stream particle and preparation method thereof - Google Patents

Elasticity adjusts stream particle and preparation method thereof Download PDF

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Publication number
CN108570150A
CN108570150A CN201810310358.2A CN201810310358A CN108570150A CN 108570150 A CN108570150 A CN 108570150A CN 201810310358 A CN201810310358 A CN 201810310358A CN 108570150 A CN108570150 A CN 108570150A
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sulphur
elasticity
oil
preparation
hour
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CN108570150B (en
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杨祖国
高秋英
何龙
赵海洋
任波
焦保雷
曹畅
张亚刚
刘磊
艾克热木·牙生
程仲富
邢钰
范伟东
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China Petroleum and Chemical Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/14Polysulfides
    • C08G75/16Polysulfides by polycondensation of organic compounds with inorganic polysulfides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504Compositions based on water or polar solvents
    • C09K8/506Compositions based on water or polar solvents containing organic compounds
    • C09K8/508Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/5086Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/516Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/18Bridging agents, i.e. particles for temporarily filling the pores of a formation; Graded salts

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Fats And Perfumes (AREA)

Abstract

The present invention provides a kind of elasticity to adjust stream, is the substance of logical formula (I), and Gt is triglyceride fat acid, and n is 1 to 6.The present invention also provides the preparation methods that elasticity adjusts stream particle, include the following steps:(1) it is liquid to be heated to melting completely by sulphur, obtains Molten sulphur;(2) Molten sulphur is uniformly mixed with vegetable crude oil or oil foot, then heating is reacted, and solid sulphur rubber grain is obtained;(3) solid sulphur rubber grain is granulated and is sorted, obtained elasticity and adjust stream particle.

Description

Elasticity adjusts stream particle and preparation method thereof
Technical field
The present invention relates to a kind of oilfield chemistry agent, in particular it relates to a kind of elasticity for fracture-pore reservoir Adjust stream particle and preparation method thereof.
Background technology
Based on surface layer weathering crust, underground underground river solution cavity, disconnected control karst, oil reservoir has Carbonate Reservoir Reservoir Body The feature that depth, anisotropism are strong, bottom water is strong, Tibetan oil mass natural depletion is fast is buried, causes two to adopt limitation, overall recovery ratio It is low.It is that flush stage is short, water-free oil production period is short, energy declines that Carbonate Oil, which ensconces aggregate performance in natural energy recovery process, Soon.Secondary oil recovery mainly supplements stratum energy by gas injection, water filling, and by well group gas injection, water filling come remaining between well of taping the latent power Oil.Secondary oil recovery middle and later periods well group forms predominant pathway, and easily form has channeling or water after excessive round water filling, gas injection between well It alters, gas injection or water filling can be caused to fail, even if still relatively low if having the whole recovery percent of reserves of abundant remaining oil between well.
There are two ways to exploiting remaining oil between such well at present:First, improving water injection pressure, start advantage water stream channel Neighbouring secondary channel improves sweep efficiency;Second is that advantage water stream channel is blocked successively to nearly well band in water injection well distal end, by Grade improves water injection pressure, starts secondary oil flow channel, to greatest extent Remaining Oil.Water injection pressure is improved, to pipeline requirements Height, tubing string is impaired serious, and of high cost, easy water breakthrough improves recovery ratio limitation.From far near, adjustment flow is logical for water injection well Road can improve oil recovery factor to the maximum extent under the execution conditions of mitigation.Thus, it invents and is suitble to reservoir high temperature, high mineralization The runner adjustment agent system of degree, realizes step by step closure of the water injection well to producing well advantage water stream channel, is to realize fracture hole type oil Hide the key of improving ecology effect.
Invention content
The object of the present invention is to provide a kind of elasticity to adjust stream particle and preparation method thereof, to solve fracture hole type carbonate Shale oil hides surface layer crust reservoirs of weathering water breakthrough problem.
On the one hand, the present invention provides a kind of elasticity to adjust stream particle, is the substance of logical formula (I):
Wherein, Gt is triglyceride fat acid, and n is 1 to 6.
Elasticity above-mentioned adjusts stream particle, and it is 1mm to 2mm, 3mm to 5mm or 5mm that the elasticity, which adjusts the grain size of stream particle, To 8mm.
On the other hand, the present invention provides the preparation method that a kind of elasticity adjusts stream particle, include the following steps:
(1) it is liquid to be heated to melting completely by sulphur, obtains Molten sulphur;
(2) Molten sulphur is uniformly mixed with vegetable crude oil or oil foot, then heating is reacted, and solid sulphur is obtained Rubber grain;
(3) solid sulphur rubber grain is granulated and is sorted, obtained elasticity and adjust stream particle.
Sulphur is heated to 130 DEG C to 150 DEG C by preparation method above-mentioned in step (1).
Preparation method above-mentioned, in step (2), Molten sulphur and the mass ratio of vegetable crude oil or oil foot are 1:1.5 extremely 1:0.7 (preferably 1:1.05).
Preparation method above-mentioned, in step (2), after Molten sulphur is mixed with vegetable crude oil or oil foot extremely at 130 DEG C 160 DEG C (preferably 150 DEG C) stir 0.3 hour to 0.8 hour (preferably 0.5 hour).
Molten sulphur is uniformly mixed by preparation method above-mentioned in step (2) with vegetable crude oil or oil foot, is then risen Temperature to 160 DEG C to 200 DEG C (preferably 180 DEG C) carry out reaction 0.3 hour to 0.6 hour (preferably 0.45 hour).
Preparation method above-mentioned obtains elasticity and adjusts the grain size of stream particle to be 1mm to 2mm, 3mm is extremely in step (3) 5mm or 5mm to 8mm.
Compared with the existing technology, elasticity of the invention adjusts stream particle and preparation method thereof to have the advantages that:
(1) preparation method is simple, easy to operate, is suitable for industrialized production and field application.
(2) raw material sources are wide, and vegetable crude oil is that edible oil processes first squeezing product, and major oil-fat plant all has abundant Storage level;Sulphur is available in major high-hydrogen sulfide oil gas field desulfurization process and recycling.
(3) of low cost, vegetable crude oil can extend further to oil foot, be Oil processing link low value product, and sulphur is The self-produced byproduct in oil field processes the sulphur caoutchouc elasticity tune stream particle of preparation, can greatly improve value of the product.
(4) particle prepared is that one kind can be in 120 DEG C of temperature, salinity 22 × 104Under the conditions of mg/L keep elasticity and Intensity can reach 10Mpa by compressive deformation, plugging strength, as the change of water injection pressure is migrated in duct, administer seam Hole type reservoir surface layer crust reservoirs of weathering water breakthrough problem.
Description of the drawings
Fig. 1 is that the high temperature and pressure used in embodiment 4 measures tune stream solid particle intensity device, wherein each label table Show:
1- high pressure water-injection pumps, 2- pressure gauges, 3- valves, 4- high temperature and pressure intensity pressure measurement cabin, 5- pistons, 6- hole patterns, 7- oil Bath, 8- hand pumps, 9- back-pressure valves.
Fig. 2 shows the performance test results of embodiment 4.
Specific implementation mode
In order to fully understand the purpose of the present invention, feature and effect, by following specific implementation modes, the present invention is made It is described in detail.For the process of the present invention in addition to following the description, remaining is all made of the conventional method or device of this field.Unless It is otherwise noted, otherwise the term involved in the present invention all has the normally understood meaning of those skilled in the art.
The first aspect of the present invention provides a kind of elasticity tune stream particle, belongs to sulphur caoutchouc elasticity tune stream particle, Structure with logical formula (I):
Wherein, Gt is triglyceride fat acid, and n is 1 to 6.
Preferably, it is 1mm to 2mm, 3mm to 5mm or 5 mm to 8mm which, which adjusts the grain size of stream particle,.More preferably Ground, it is best to 6mm holes blocking effects when it is 1mm to 2mm that elasticity, which adjusts the grain size of stream particle,;When elasticity adjusts stream particle It is best to 10mm holes blocking effects when grain size is 3mm to 5mm;When it is 5mm to 8mm that elasticity, which adjusts the grain size of stream particle, It is best to 16mm holes blocking effects.
The elasticity adjusts stream particle in 120 DEG C of temperature, salinity 22 × 104Elasticity modulus and intensity are kept under the conditions of mg/L, Can be by compressive deformation, plugging strength is up to 10MPa.
The sulphur caoutchouc elasticity tune stream particle for fractured-cavernous carbonate reservoir of the present invention is suitble to reservoir high temperature (example Such as 120 DEG C), high salinity (such as 22 × 104Mg/L runner) can realize water injection well to producing well advantage water stream channel Closure step by step, be the key that realize fracture-pore reservoir improving ecology effect.
The fracture-pore reservoir sulphur caoutchouc elasticity tune stream particle of the present invention can be applicable to the water filling well group of failure, Neng Gouyou The deep adjustment of advantage water stream channel between well group is realized on effect ground, expands floood conformance range, starts secondary seepage channel step by step, Remaining Oil to the maximum extent improves fracture-pore reservoir ultimate recovery.When specifically used, according to strata pressure, crack Water absorbing capacity in width, pit shaft bearing capacity and the well the injecting process is strong and weak, and the particle of appropriate particle size is selected to inject into well, After injection, with the oilfield injection water of more times of hole volumes (such as three hole volumes) it is flat-pushing enter stratum.
The second aspect of the present invention provides the preparation method that elasticity adjusts stream particle, including:(1) sulphur has been heated to Full-fusing is liquid, obtains Molten sulphur;(2) Molten sulphur is uniformly mixed with vegetable crude oil or oil foot, then heating carries out Reaction, obtains solid sulphur rubber grain;(3) solid sulphur rubber grain is granulated and is sorted, obtained elasticity and adjust stream Grain.
In a kind of preferred embodiment, it includes following step that elasticity of the invention, which adjusts the preparation method of stream particle, Suddenly:
The first step, by sulphur be heated to 130 DEG C to 150 DEG C so that its completely melting be liquid, obtain Molten sulphur.
Sulphur is that appearance is the crystallization of faint yellow brittleness or powder, is derived from a wealth of sources, de- in major high-hydrogen sulfide oil gas field It is available in sulphuring treatment and recycling.The present invention does not have particular/special requirement to sulphur, is returned after regular industrial sulphur, oil gas field desulfurization The sulphur of receipts, is used equally in the present invention.
Second step, Molten sulphur is with vegetable crude oil or oil foot according to mass ratio 1:1.5 to 1:0.7 (preferably 1:1.05) into Row mixing, and 0.3 hour to 0.8 hour (preferably 0.5 hour) is stirred at 130 DEG C to 160 DEG C (preferably 150 DEG C), it then will be warm Degree rises to 160 DEG C to 200 DEG C (preferably 180 DEG C), and the reaction was continued 0.3 hour to 0.6 hour (preferably 0.45 hour), to obtain Solid sulphur rubber grain.
Vegetable crude oil refers to the pre- squeezing or extracted plant oil fat without refining, and main component is triglyceride fat acid Mixture.Oil foot refers to the byproduct that refining vegetable oil generates, and main component is the aliphatic acid as soda soap form in Property grease, be Oil processing link low value product.
Following reaction mainly has occurred in this step:
When Molten sulphur and vegetable crude oil or oil foot are according to mass ratio 1:1.5 to 1:0.7 when being mixed, sulphur concentration Between 40% to 60%, the solid rubber elasticity and moderate strength of formation can effectively realize water injection well in actual use To the closure step by step of producing well advantage water stream channel.
Third walks, and solid sulphur rubber grain is imported in rubber grain machine, is granulated and is sorted, and it is 1 that grain size, which is made, The various sizes of sulphur caoutchouc elasticity tune stream particle such as~2mm, 3~5mm, 5~8mm.
Embodiment
It further illustrates the present invention, but does not therefore limit the present invention to described below by the mode of embodiment Among scope of embodiments.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or presses It is selected according to product manual.
Embodiment 1
Industrial sulphur 50g is added in 250mL beakers, starts blender, temperature is raised to 140 DEG C, is melt into liquid completely Afterwards, the vegetable crude oil that 52.5g is preheated to 140 DEG C is added, continues stirring 0.5 hour at 140 DEG C, is warming up to 180 DEG C of (heating frequencies 2.0 DEG C/min of rate), isothermal reaction 0.45h obtains sulphur rubber solids, and after cooling, crushing sub-elects grain size 1~2mm particles, Obtain sulphur caoutchouc elasticity tune stream particle 1.
Embodiment 2
Industrial sulphur 60g is added in 250mL beakers, starts blender, temperature is raised to 150 DEG C, is melt into liquid completely Afterwards, the vegetable crude oil that 40g is preheated to 150 DEG C is added, continues stirring 0.3 hour at 150 DEG C, is warming up to 180 DEG C of (heating frequencies 3.0 DEG C/min), isothermal reaction 0.5h obtains sulphur rubber solids, and after cooling, crushing sub-elects grain size 3~5mm particles, i.e., Obtain sulphur caoutchouc elasticity tune stream particle 2.
Embodiment 3
Industrial sulphur 50g is added in 250mL beakers, starts blender, temperature is raised to 130 DEG C, is melt into liquid completely Afterwards, the vegetable crude oil that 75g is preheated to 130 DEG C is added, continues stirring 0.8 hour at 130 DEG C, is warming up to 180 DEG C of (heating frequencies 3.0 DEG C/min), isothermal reaction 0.3h obtains sulphur rubber solids, and after cooling, crushing sub-elects grain size 5~8mm particles, i.e., Obtain sulphur caoutchouc elasticity tune stream particle 3.
Embodiment 4:Performance test
It adjusts the intensity of stream particle to evaluate the elasticity of embodiment 1 to embodiment 3 respectively using following methods, uses Equipment is that high temperature and pressure measures tune stream solid particle intensity device (as shown in Figure 1).
(1) blank assay is carried out, testing process frictional resistance reduces pressure error;
(2) hole pattern size is selected according to fractured-cavernous carbonate reservoir situation, selects granular size (1 evaluation experimental of particle Select 6mm hole patterns, 2 evaluation experimental of particle that 10mm hole patterns, 3 evaluation experimental of particle is used to use 16mm hole patterns);
(3) candidate particles are put into high temperature and pressure intensity pressure measurement cabin, addition is high temperature and pressure intensity pressure measurement volume of compartment product One third, and will be hydraulically full in high temperature and pressure intensity pressure measurement cabin;
(4) back-pressure valve is set into 2MPa, and heats oil bath to setting value (i.e. reservoir temperature);
(5) high pressure water-injection pump observation pressure gauge variation is opened, rapid increase occurs, until under pressure is occurred by peak Drop, i.e. particle are broken through, and plateau pressure at this time is granule strength.
Test results are shown in figure 2.As seen from Figure 2,1~2mm sulphur caoutchouc elasticity tune stream particles of embodiment 1 To 6mm holes blocking excellent effects, 1000s can start accumulation and block, and 1200s is up to plugging strength 10MPa;Embodiment 2 3~5mm sulphur caoutchouc elasticity tune stream particles are to 10mm holes blocking excellent effects, and 400s can start accumulation and block, 1200s Up to plugging strength 10MPa;5~8mm sulphur caoutchouc elasticity tune stream particles of embodiment 3 to 16mm holes blocking excellent effects, 200s can start accumulation and block, and 1000s is up to plugging strength 10MPa.
The present invention is hereinbefore disclosed with preferred embodiment, but it should be understood by those skilled in the art that, these Embodiment is only used for describing the present invention, and should not be construed as limiting the scope of the invention.It should be noted that every and these realities Example equivalent variation and displacement are applied, should all be set as being covered by scope of the presently claimed invention.Therefore, protection of the invention Range should be subject to the range defined in claims.

Claims (8)

1. a kind of elasticity adjusts stream particle, which is characterized in that it is the substance of logical formula (I):
Wherein, Gt is triglyceride fat acid, and n is 1 to 6.
2. elasticity according to claim 1 adjusts stream particle, which is characterized in that it is 1mm that the elasticity, which adjusts the grain size of stream particle, To 2mm, 3mm to 5mm or 5mm to 8mm.
3. elasticity as claimed in claim 1 or 2 adjusts the preparation method of stream particle, which is characterized in that include the following steps:
(1) it is liquid to be heated to melting completely by sulphur, obtains Molten sulphur;
(2) Molten sulphur is uniformly mixed with vegetable crude oil or oil foot, then heating is reacted, and solid sulphur rubber is obtained Grain;
(3) solid sulphur rubber grain is granulated and is sorted, obtained elasticity and adjust stream particle.
4. preparation method according to claim 3, which is characterized in that in step (1), sulphur is heated to 130 DEG C extremely 150℃。
5. preparation method according to claim 3, which is characterized in that in step (2), Molten sulphur and vegetable crude oil or The mass ratio of oil foot is 1:1.5 to 1:0.7 (preferably 1:1.05).
6. preparation method according to claim 3, which is characterized in that in step (2), by Molten sulphur and vegetable crude oil Or 0.3 hour to 0.8 hour (preferably 0.5 hour) is stirred at 130 DEG C to 160 DEG C (preferably 150 DEG C) after oil foot mixing.
7. preparation method according to claim 3, which is characterized in that in step (2), by Molten sulphur and vegetable crude oil Or oil foot is uniformly mixed, and is then raised temperature to 160 DEG C to 200 DEG C (preferably 180 DEG C) and is carried out reaction 0.3 hour to 0.6 hour (preferably 0.45 hour).
8. preparation method according to claim 3, which is characterized in that in step (3), obtain the grain that elasticity adjusts stream particle Diameter is 1mm to 2mm, 3mm to 5mm or 5mm to 8mm.
CN201810310358.2A 2018-04-09 2018-04-09 Elastic flow-regulating granule and preparation method thereof Active CN108570150B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113309500A (en) * 2020-02-26 2021-08-27 中国石油化工股份有限公司 Tahe carbonate reservoir water injection well group flow channel adjusting method
CN113309505A (en) * 2020-02-26 2021-08-27 中国石油化工股份有限公司 Adjusting method for flow channel of water injection well of weathering crust karst reservoir
CN114686194A (en) * 2020-12-25 2022-07-01 中国石油化工股份有限公司 Vegetable oil byproduct oil residue blocking agent and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113309500A (en) * 2020-02-26 2021-08-27 中国石油化工股份有限公司 Tahe carbonate reservoir water injection well group flow channel adjusting method
CN113309505A (en) * 2020-02-26 2021-08-27 中国石油化工股份有限公司 Adjusting method for flow channel of water injection well of weathering crust karst reservoir
CN113309505B (en) * 2020-02-26 2022-10-04 中国石油化工股份有限公司 Weathered crust karst reservoir water injection well flow passage adjusting method
CN113309500B (en) * 2020-02-26 2022-10-04 中国石油化工股份有限公司 Tahe carbonate reservoir water injection well group flow channel adjusting method
CN114686194A (en) * 2020-12-25 2022-07-01 中国石油化工股份有限公司 Vegetable oil byproduct oil residue blocking agent and preparation method thereof

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