CN104789203B - A kind of biological enzyme pressure break detergent and its application - Google Patents
A kind of biological enzyme pressure break detergent and its application Download PDFInfo
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- CN104789203B CN104789203B CN201410025827.8A CN201410025827A CN104789203B CN 104789203 B CN104789203 B CN 104789203B CN 201410025827 A CN201410025827 A CN 201410025827A CN 104789203 B CN104789203 B CN 104789203B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
- C09K8/905—Biopolymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/26—Gel breakers other than bacteria or enzymes
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Abstract
The present invention provides a kind of biological enzyme pressure break detergents, are formulated by cellulase, pentosanase, pectase and water.It is preferred that the cellulase is 10~20 weight %, pentosanase is 10~20 weight %, and pectase is 10~20 weight %, and surplus is water.The application of the biological enzyme pressure break detergent is that the biological enzyme fracturing fluid detergent is added to in liquid water before fracturing fluid base fluid is prepared, and the various additives that fracturing fluid base fluid is then added by recipe requirements use after plastic as fracturing fluid.The detergent can be in selective removal fracturing fluid base fluid water-insoluble, it is Chong Die with natural plant gum aquation dissolution time on the reaction time, without carrying out special modification process to natural plant gum, and the glue performance that can improve that treated, it is safe and environment-friendly, efficient.
Description
Technical field
The present invention relates to a kind of biological enzyme pressure break detergent and its applications.
Background technology
Natural plant gum used in petroleum industry field is mainly galactomannans（Poly-galactomannan, PGM）
The more carbohydrates and their derivatives of class.Galactomannans is a kind of polysaccharide containing mannose backbone and galactose side, more acurrate
A little for, galactomannans be by threadiness link（Isosorbide-5-Nitrae-β-D type mannoses, β-Isosorbide-5-Nitrae-D-mannopyranose）
The polysaccharide of main chain and 1, the 6- α-D type galactolipins being connected on main chain, i.e., 1, the α-D type galactopyranoses of 6 connections（α-1,6-
D-galactopyranose）Side chain.According to the ratio of mannose and galactolipin, by galactomannans type by ratio by small
To longer spread：Fenugreek gum（Fenugreek gum）, mannose is about 1 than galactolipin:1, guanidine glue（Guar gum）And sesbania gum
（Sesbania Gum）, mannose is about 2 than galactolipin:1, tara gum（Tara gum）, mannose is about than galactolipin
3:1, locust bean gum（Locust bean gum）Or carob（Carob gum）, mannose is about 4 than galactolipin:1.Guanidine glue
Endosperm, is separated crushing by the endosperm from annual herb plant melon beans from seed, and guanidine rubber powder is just made.Due to
Guanidine collagen powder water-insoluble is higher, larger to formation damage, therefore, need to carry out hydroxypropylation or carboxymethyl-modification to it, from
And its water insoluble matter content is made to be greatly lowered, in China, large area is promoted and applied at present.Sesbania gum is in domestic natural plant gum
The kind of the closest guanidine glue of molecular structure, physicochemical property, since the growth of sesbania adapts to salt, flood, lean natural environment, and
Value with comprehensive utilization, thus sesbania gum resource can be developed rapidly.Daqing oil field, Shengli Oil Field use sesbania gum once
Carry out fracturing work, after abandoned because the higher residue of water-insoluble is larger.Fenugreek gum is that performance is more excellent in domestic natural plant gum
Kind, because its strand have larger proportion galactose side, so water-soluble speed, water-soluble adhesiveness are all higher.Its water
Insolubles content is even lower than the guanidine glue of import, natural plant gum of the thermal stability also superior to other kinds.
In oil and gas exploitation field, natural plant gum is typically used as the thickening agent of hydrofrac fluid, and and crosslinking agent（If any
Machine boron）, pH adjusting agent, the formation such as gel breaker there is the viscoelasticity frozen glue of multiple functions.Water-soluble colloid is removed in natural plant gum
Group further includes some water-insoluble components exceptionally, such as cellulose and pectic substance from plant cell wall.
In order to improve water solubility, the temperature stability of natural plant gum, water insoluble matter content is reduced, is started in the seventies in last century
To the chemical modification of guanidine glue, including prepare hydroxypropyl guar（HPG）, carboxy-methyl hydroxy propyl guanidine glue（CMHPG）Deng passing through hydroxypropyl
Change or carboxylic first hydroxypropylation makes cellulose, pectin in natural plant gum etc. be converted into soluble matter, but the reaction turn property is poor, plants
The reaction can equally occur for the galactomannans in object glue, due to facing a cis hydroxyl groups caused by natural plant gum side chain addition reaction
Structural damage can influence the thickening properties of natural plant gum thickening agent to a certain degree.Therefore, the degree of substitution of the reactions such as hydroxypropylation is more
It controls the rubber powder obtained after 0.3 or so, reaction and still contains a certain amount of water-insoluble.In addition, in the chemical modification of natural plant gum
In technology, used raw material and intermediate reaction process need the participation of a large amount of organic solvents, wherein hydroxypropylation, hydroxyl second
Propylene oxide, ethylene oxide needed for glycosylation reaction are the explosive materials of danger, and the security risk of production has been significantly greatly increased；Synthesis is anti-
Isopropanol etc. is also usually used in answering and is used as solvent, and the energy is not only consumed, but also dispose by repeatedly eluting separation after reaction
Cause outer excretion leakage that can cause huge environment hidden danger accidentally.Piece alkali, glacial acetic acid etc. are also potential as pH adjusting agent itself
Environmental contaminants, meanwhile, it is also a degree of to increase production cost.Therefore one kind is needed to reduce fracturing fluid in a mild condition
The cleaning agents of the water insoluble matter content of middle natural plant gum.
Invention content
The present invention provides one for higher, larger to the reservoir damage feature of existing natural plant gum thickener water-insoluble
Kind biological enzyme fracturing fluid detergent, can be with the water-insoluble in selective removal glue.
To achieve the goals above, the concrete scheme that the present invention takes is as follows：
A kind of biological enzyme pressure break detergent, is formulated by cellulase, pentosanase, pectase and water.
In one particular embodiment of the present invention, each component content is as follows：The cellulase is 10~20 weight %,
Pentosanase is 10~20 weight %, and pectase is 10~20 weight %, and surplus is water.
In one particular embodiment of the present invention, the cellulase preferably is selected from Novi letter Carezyme4500L, outstanding energy
At least one of section Promafast200, AB enzyme KRX-300, Royal DSM DSM-HSP6000 and Dan Niyue Denpill66L.
In one particular embodiment of the present invention, the pentosanase preferably is selected from Novi letter Pentopan
MonoBG2500F, Jie Neng section Laminex, AB enzyme Finase L, Royal DSM DSM Bakerzyme6000 and Dan Niyue
At least one of Denykem1500L.
In one particular embodiment of the present invention, the pectase preferably is selected from letter Pectin16000U, Jie Neng sections of Novi
At least one of P200, AB Pectina, Royal DSM DSM Rapidasepress and Dan Niyue Denykem PAP-4.
The present invention also provides a kind of fracturing fluids, including biological enzyme pressure break detergent as previously described.
The preparation method of the fracturing fluid, be included in fracturing fluid base fluid prepare before, by the biological enzyme fracturing fluid detergent with
Certain proportion is preferably added to in liquid water with 0.1%~0.5% volume ratio, fracturing fluid base fluid then is added by recipe requirements
Various additives, such as thickener, crosslinking agent, demulsifier, cleanup additive use after plastic as fracturing fluid.
In one embodiment of the invention, the formula of the fracturing fluid base fluid is as follows：1.0~2.0 weight % of potassium chloride,
0.05~0.2 weight % of 0.3~0.4 weight % of natural plant gum, 0.05~0.2 weight % of demulsifier and cleanup additive, surplus is water.
The natural plant gum can be the common natural plant gum in fracturing fluid field, such as fenugreek gum, guanidine glue, sesbania gum, tara gum, thorn
Locust bean gum and/or carob.Preferably fenugreek gum, the reason is as follows that：Main water-insoluble in fenugreek gum is residual in seed endosperm
The plant cell wall stayed is removed by the compound biological enzyme, achievees the purpose that fenugreek gum water-insoluble of degrading.Meanwhile by
The hydrolysis and destruction of cell wall in fenugreek gum endosperm so that increasing stick process colloid release rate has obtained a degree of raising,
The final performance for substantially improving fracturing fluid.
The demulsifier and cleanup additive are that aqueous fracturing fluid field is general, the crosslinking and broken glue process with fracturing fluid without
It closes, mainly the needs of fracturing fluid recovery (backflow).Typical demulsifier such as polyoxyethylene polyoxypropylene polyoxypropylene octadecyl alcolol ether, polyoxy
Ethylene detergent alkylate fluosite sodium sulfovinate salt, polyxyethylated toluene phenolic ether, polyoxyethylene polyoxypropylene the third two
Alcohol ether etc., cleanup additive such as Sodium perfluorooctanoate, perfluoro-octanoyl ethylene aminomethyl diethyl ammonium iodide etc..
It is to pass through addition in fracturing fluid base fluid process for preparation the present invention provides a kind of biological enzyme fracturing fluid detergent
Compound bio enzyme solution to the water-insoluble in natural plant gum rubber powder carry out degradation and minimizing, the process on the reaction time with plant
Glue dissolution time is overlapped, and need not separately increase processing cost and time cost, without carrying out special change to natural plant gum
Property treatment process, and the glue performance that can greatly improve that treated, are a kind of very safe and environment-friendly, efficient methods.
With using biological enzyme as gel breaker, i.e., be added crosslinking agent in fracturing fluid base fluid, carry out brokenly glue after forming frozen glue
The prior art is different.It is fully sharp present invention is mainly applied in the process for preparation of fracturing fluid base fluid, have chosen specific enzyme preparation
The time being swollen with natural plant gum realizes the purpose for reducing natural plant gum water-insoluble.Since enzyme preparation is only in natural plant gum
Contained water-insoluble component has carried out the degradation of selectivity, therefore does not interfere with the crosslinking of natural plant gum and broken colloidality energy, after
Continuous fracturing fluid can apply enzyme or oxidized form gel breaker to be broken glue.Due to the addition of detergent, although not influencing fracturing fluid
Broken glue process, but the broken glue residue of system can be greatly lowered with the reduction of water-insoluble, to improve whole pressure break
Liquid quality.
Specific implementation mode
With reference to specific embodiment, the present invention is described further, however these embodiments are used for the purpose of saying
It is bright rather than limit the scope of the invention.
Demulsifier in embodiment and comparative example is polyoxyethylene polyoxypropylene polyoxypropylene octadecyl alcolol ether, and cleanup additive is equal
For the mixture of 1.0 weight % of Sodium perfluorooctanoate, 35 weight % of lauryl sodium sulfate, 64 weight % of isopropanol.
Embodiment 1
Using institute of Novozymes Company cellulase-producing, pentosanase and pectase as raw material, it is 10% to prepare weight content
Carezyme4500L, 10%Pentopan MonoBG2500F and 10% Pectin16000U compound bio enzyme solution, it is spare.
500mL water is added in Xiang Wuyin mixed adjust in device, holding rotating speed is 1000r/min, and above-mentioned compound bio enzyme solution is added
0.5mL is added potassium chloride 5.0g, is then slowly added into 1.5g fenugreek gums, stirs 5 minutes, be then added 0.1mL demulsifiers and
0.1mL cleanup additives continue stirring 2 minutes, then prepared fracturing fluid base fluid are transferred in beaker, is placed in 30 DEG C of water-baths 4
Hour.Embodiment 2
Using institute of Genencor Company cellulase-producing, pentosanase and pectase as raw material, it is 12% to prepare weight content
Promafast200,12% Laminex and 12% P200 compound bio enzyme solution, it is spare.
500mL water is added in Xiang Wuyin mixed adjust in device, keep 1000r/min, above-mentioned compound bio enzyme solution 1.0mL is added, adds
Enter potassium chloride 5.0g, be then slowly added into 1.5g fenugreek gums, stirs 5 minutes, 0.1mL demulsifiers then are added and 0.1mL helps row
Agent continues stirring 2 minutes, then prepared fracturing fluid base fluid is transferred in beaker, is placed in 30 DEG C of water-baths 4 hours.
Embodiment 3
Using German AB enzymes industry institute cellulase-producing, pentosanase and pectase as raw material, it is 15% to prepare weight content
KRX-300,15% Finase L and 15% Pectina compound bio enzyme solution, it is spare.
500mL water is added in Xiang Wuyin mixed adjust in device, keep 1000r/min, above-mentioned compound bio enzyme solution 1.5mL is added, adds
Enter potassium chloride 5.0g, be then slowly added into 1.5g fenugreek gums, stirs 5 minutes, 0.1mL demulsifiers then are added and 0.1mL helps row
Agent continues stirring 2 minutes, then prepared fracturing fluid base fluid is transferred in beaker, is placed in 30 DEG C of water-baths 4 hours.
Embodiment 4
Using institute of Royal DSM company cellulase-producing, pentosanase and pectase as raw material, it is 18% to prepare weight content
DSM-HSP6000,18% Bakerzyme6000 and 18% DSM Rapidasepress compound bio enzyme solution, it is spare.
500mL water is added in Xiang Wuyin mixed adjust in device, keep 1000r/min, above-mentioned compound bio enzyme solution 2.0mL is added, adds
Enter potassium chloride 5.0g, be then slowly added into 1.5g fenugreek gums, stirs 5 minutes, 0.1mL demulsifiers then are added and 0.1mL helps row
Agent continues stirring 2 minutes, then prepared fracturing fluid base fluid is transferred in beaker, is placed in 30 DEG C of water-baths 4 hours.
Embodiment 5
Using institute of Dan Niyue companies cellulase-producing, pentosanase and pectase as raw material, it is 20% to prepare weight content
Denpill66L, 20% Denykem1500L and 20% Denykem PAP-4 compound bio enzyme solution, it is spare.
500mL water is added in Xiang Wuyin mixed adjust in device, keep 1000r/min, above-mentioned compound bio enzyme solution 2.5mL is added, adds
Enter potassium chloride 5.0g, be then slowly added into 1.5g fenugreek gums, stirs 5 minutes, 0.1mL demulsifiers then are added and 0.1mL helps row
Agent continues stirring 2 minutes, then prepared fracturing fluid base fluid is transferred in beaker, is placed in 30 DEG C of water-baths 4 hours.
Comparative example 1
500mL water is added in Xiang Wuyin mixed adjust in device, keep 1000r/min, potassium chloride 5.0g is added, is then slowly added into
1.5g fenugreek gums stir 5 minutes, 0.1mL demulsifiers and 0.1mL cleanup additives are then added, continue stirring 2 minutes, then by institute
The fracturing fluid base fluid of preparation is transferred in beaker, is placed in 30 DEG C of water-baths 4 hours.
Fracturing fluid base fluid 50mL prepared by above-described embodiment and comparative example is taken with the Centrifuge Cup of pre- constant weight respectively, is placed in
It is centrifuged 30 minutes in 3000r/min centrifuges, after carefully toppling over supernatant, takes 50mL distilled water by sediment resuspension at uniform
Dispersed phase, then system is placed in 3000r/min centrifuges and is centrifuged 20 minutes, after toppling over supernatant again, Centrifuge Cup is placed in
105 DEG C drying to constant weight, calculates the water insoluble matter content in fracturing fluid base fluid with reference to following formula, the results are shown in Table 1.
Water insoluble matter content（%）=（Centrifuge Cup quality-Centrifuge Cup original quality after drying）/ [0.5 × (1- natural plant gum is aqueous
Rate)]
The fenugreek gum moisture content is by moisture teller SH10A types or similar product, according to SYT5764-2007 standards
Test obtains, and measurement process is as follows：Moisture teller weighs 5.00g rubber powders and is laid in the scale pan after 105 DEG C of preheatings, correction,
0.5h is heated at 105 DEG C, unlatching instrument readings switch, observation projection screen, when readings amplitude is less than 0.2% in 10min, instrument
The reading of device is the moisture content of rubber powder.
Each 300mL of fracturing fluid base fluid for taking above-described embodiment and comparative example to prepare is placed in the fast viscosimeter of Fann formulas six, will
Rotating speed is adjusted to 100r/min, measures the viscosity number of fracturing fluid base fluid, the results are shown in Table 1.
Water insoluble matter content and viscosity number in 1 embodiment and comparative example fracturing fluid base fluid of table
| Water insoluble matter content（%） | Viscosity（mPa·s） | |
| Embodiment 1 | 1.02 | 16.88 |
| Embodiment 2 | 2.32 | 16.90 |
| Embodiment 3 | 1.65 | 16.87 |
| Embodiment 4 | 1.71 | 16.83 |
| Embodiment 5 | 2.55 | 16.85 |
| Comparative example 1 | 6.78 | 16.86 |
As can be seen from the above table, after the processing of compound bio enzyme solution, water-insoluble in the fracturing fluid base fluid that fenugreek gum is prepared
Content（Based on fenugreek gum quality）1.02%, 2.32%, 1.65%, 1.71 and 2.55% is dropped to by 6.78%.And fracturing fluid base fluid
Viscosity does not change substantially, experimental result explanation：This method can effectively reduce plant gum fracturing fluid water-insoluble, and to fracturing fluid
Performance does not make significant difference.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (5)
1. a kind of method of natural plant gum water-insoluble in removal fracturing fluid, is included in biological enzyme pressure break before fracturing fluid base fluid is prepared
Liquid detergent is added to 0.1%~0.5% volume ratio in liquid water, and the various additives of fracturing fluid base fluid are then added,
It is used as fracturing fluid after plastic；
Wherein, the biological enzyme pressure break detergent, is formulated by cellulase, pentosanase, pectase and water；
The biological enzyme pressure break detergent cellulase is 10~20 weight %, and pentosanase is 10~20 weight %, pectin
Enzyme is 10~20 weight %, and surplus is water；
The natural plant gum is fenugreek gum.
2. according to the method described in claim 1, it is characterized in that, the cellulase is selected from Novi letter Carezyme 4500L
Or Royal DSM DSM-HSP 6000.
3. according to the method described in claim 1, it is characterized in that, the pectase is selected from AB Pectina and Dan Niyue
At least one of Denykem PAP-4.
4. according to the method described in claim 1, it is characterized in that, the formula of the fracturing fluid base fluid is as follows：Potassium chloride 1.0~
2.0 weight %, 0.05~0.2 weight % of 0.3~0.4 weight % of natural plant gum, 0.05~0.2 weight % of demulsifier and cleanup additive,
Surplus is water.
5. according to the method described in claim 4, it is characterized in that, the demulsifier is polyoxyethylene polyoxypropylene polyoxypropylene
Octadecyl alcolol ether, the cleanup additive are 1.0 weight % of Sodium perfluorooctanoate, 35 weight % of lauryl sodium sulfate and 64 weight of isopropanol
Measure the mixture of %.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1844299A (en) * | 2006-04-17 | 2006-10-11 | 大庆沃太斯采油工程技术研究所 | Composition for treating guar gum in oil field stratum |
| CN101608113A (en) * | 2009-06-30 | 2009-12-23 | 东营盛世石油科技有限责任公司 | A kind of prescription that utilizes the biological enzyme formulation preparing fracturing fluid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1844299A (en) * | 2006-04-17 | 2006-10-11 | 大庆沃太斯采油工程技术研究所 | Composition for treating guar gum in oil field stratum |
| CN101608113A (en) * | 2009-06-30 | 2009-12-23 | 东营盛世石油科技有限责任公司 | A kind of prescription that utilizes the biological enzyme formulation preparing fracturing fluid |
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