CN104789203A - Biological enzyme fracturing cleaner and application thereof - Google Patents
Biological enzyme fracturing cleaner and application thereof Download PDFInfo
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- CN104789203A CN104789203A CN201410025827.8A CN201410025827A CN104789203A CN 104789203 A CN104789203 A CN 104789203A CN 201410025827 A CN201410025827 A CN 201410025827A CN 104789203 A CN104789203 A CN 104789203A
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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 invention provides a biological enzyme fracturing cleaner. The biological enzyme fracturing cleaner is prepared from cellulase, pentosanase, pectase and water, and preferably 10-20wt% of cellulase, 10-20wt% of pentosanase, 10-20wt% of pectase, and the balance of water. An application of the biological enzyme fracturing cleaner is characterized in that the biological enzyme fracturing cleaner is added to fluid preparation water before a fracturing fluid base fluid is prepared, and various additives of the fracturing fluid base fluid are added according to formula requirements in order to form an adhesive which is used as a fracturing fluid. The cleaner has the advantages of selective removal of water-insoluble substances in the fracturing fluid base fluid, overlapping of the reaction time with plant glue hydration dissolving time, no need of special modifying treatment technologies of plant glue, improvement of the performance of treated glue, safety, environmental protection and high efficiency.
Description
Technical field
The present invention relates to a kind of biological enzyme pressure break sanitising agent and application thereof.
Background technology
The vegetable jelly that petroleum industry field uses is the many carbohydrates and their derivative of polygalactomannan (Poly-galactomannan, PGM) class mainly.Polygalactomannan is a kind of polysaccharide containing mannose backbone and galactose side, 1 more accurately, polygalactomannan links (1 by wire, 4-β-D type seminose, β-Isosorbide-5-Nitrae-D-mannopyranose) main chain be connected to 1 on main chain, the polysaccharide of 6-α-D type semi-lactosi, i.e. 1,6 α-D type galactopyranose (α-1,6-D-galactopyranose) side chains linked.According to the ratio of seminose and semi-lactosi, polygalactomannan kind is arranged from small to large by ratio: fenugreek gum (Fenugreek gum), seminose is approximately 1:1 than semi-lactosi, guanidine glue (Guar gum) and sesbania gum (Sesbania Gum), seminose is approximately 2:1 than semi-lactosi, tara gum (Tara gum), and seminose is approximately 3:1 than semi-lactosi, Viscogum BE (Locust bean gum) or carob bean gum (Carob gum), seminose is approximately 4:1 than semi-lactosi.Endosperm, from the endosperm of annual herb plant melon beans, is separated pulverizing by guanidine glue from seed, just makes guanidine rubber powder.Because guanidine collagen powder water-insoluble is higher, formation injury is comparatively large, therefore, need carry out hydroxypropylation or carboxymethyl-modification to it, thus its water insoluble matter content is greatly reduced, apply at present in China's big area.Sesbania gum be domestic vegetable jelly Middle molecule structure, physico-chemical property the most close to the kind of guanidine glue, the growth due to sesbania can adapt to salt, flood, lean physical environment, and has the value of comprehensive utilization, and thus sesbania gum resource can be developed rapidly.Daqing oil field, Shengli Oil Field used sesbania gum to carry out frac job once, abandoned because the higher residue of water-insoluble is comparatively large afterwards.Fenugreek gum is the kind that in domestic vegetable jelly, performance is comparatively excellent, because its molecular chain has the galactose side of larger proportion, so water-soluble speed, water-sol viscosity are all higher.Its water insoluble matter content is even lower than the guanidine glue of import, and thermostability is also better than the vegetable jelly of other kinds.
In oil and gas exploitation field, vegetable jelly is typically used as the viscosifying agent of hydrofrac fluid, and forms the viscoelasticity frozen glue with several functions with linking agent (as organic boron), pH value regulator, gel breaker etc.In vegetable jelly except water miscible glial component, also comprise some water-insoluble components, as from the Mierocrystalline cellulose of plant cell wall and pectic substance.
In order to improve the water-soluble of vegetable jelly, temperature stability, reduce water insoluble matter content, the chemical modification to guanidine glue is started in the seventies in last century, comprise and prepare hydroxypropyl guar (HPG), carboxy-methyl hydroxy propyl guanidine glue (CMHPG) etc., the Mierocrystalline cellulose in vegetable jelly is made by hydroxypropylation or carboxylic first hydroxypropylation, pectin etc. are converted into solvend, but it is poor that this reaction turns a property, this reaction can be there is equally in the polygalactomannan in vegetable jelly, that causes due to the addition reaction of vegetable jelly side chain faces the thickening properties that a cis hydroxyl groups structural damage to a certain degree can affect vegetable jelly viscosifying agent.Therefore, the substitution value of the reaction such as hydroxypropylation is multi-control about 0.3, and the rubber powder obtained after reaction is still containing a certain amount of water-insoluble.In addition, in the chemical modification technique of vegetable jelly, the participation of the raw material used and a large amount of organic solvent of intermediate reaction process need, wherein, propylene oxide needed for hydroxypropylation, ethoxyl etherification, oxyethane are dangerous explosive materials, greatly add the security risk of production; Also usually use Virahol etc. in building-up reactions as solvent, will be separated by repeatedly wash-out after reaction, not only consume the energy, and dispose and accidentally cause outer excretion leakage can cause huge environment hidden danger.Sheet alkali, Glacial acetic acid etc. are also potential environmental pollutant as pH adjusting agent itself, meanwhile, also to a certain degree add production cost.Therefore a kind of cleaning agents reducing the water insoluble matter content of vegetable jelly in fracturing liquid is in a mild condition needed.
Summary of the invention
The present invention is directed to the feature that existing vegetable jelly thickening material water-insoluble is higher, larger to reservoir damage, provide a kind of biological enzyme fracturing liquid sanitising agent, can water-insoluble in selective removal glue.
To achieve these goals, the concrete scheme taked of the present invention is as follows:
A kind of biological enzyme pressure break sanitising agent, formulated by cellulase, pentosanase, polygalacturonase and water.
In one particular embodiment of the present invention, each component content is as follows: described cellulase is 10 ~ 20 % by weight, and pentosanase is 10 ~ 20 % by weight, and polygalacturonase is 10 ~ 20 % by weight, and surplus is water.
In one particular embodiment of the present invention, at least one of described cellulase preferably in Novi letter Carezyme4500L, Jie Neng section Promafast200, AB enzyme KRX-300, DSM DSM-HSP6000 and Dan Niyue Denpill66L.
In one particular embodiment of the present invention, at least one of described pentosanase preferably in Novi letter Pentopan MonoBG2500F, Jie Neng section Laminex, AB enzyme Finase L, DSM DSM Bakerzyme6000 and Dan Niyue Denykem1500L.
In one particular embodiment of the present invention, at least one of described polygalacturonase preferably in Novi letter Pectin16000U, Jie Neng section P200, AB Pectina, DSM DSM Rapidasepress and Dan Niyue Denykem PAP-4.
Present invention also offers a kind of fracturing liquid, comprise biological enzyme pressure break sanitising agent as previously mentioned.
Described of the fracturing fluid preparation method, before being included in the preparation of fracturing liquid base fluid, by this biological enzyme fracturing liquid sanitising agent with certain proportion, preferably join in dosing water with the volume ratio of 0.1% ~ 0.5%, then the various additives of fracturing liquid base fluid is added by recipe requirements, as thickening material, linking agent, emulsion splitter, cleanup additive etc., use as fracturing liquid after plastic.
In one embodiment of the invention, the formula of described fracturing liquid base fluid is as follows: Repone K 1.0 ~ 2.0 % by weight, vegetable jelly 0.3 ~ 0.4 % by weight, emulsion splitter 0.05 ~ 0.2 % by weight and cleanup additive 0.05 ~ 0.2 % by weight, surplus is water.
The vegetable jelly that described vegetable jelly can be commonly used for fracturing liquid field, as fenugreek gum, guanidine glue, sesbania gum, tara gum, Viscogum BE and/or carob bean gum.Be preferably fenugreek gum, reason is as follows: the main water-insoluble in fenugreek gum is plant cell wall residual in seed endosperm, is removed by this compound biological enzyme, reaches the object of degraded fenugreek gum water-insoluble.Meanwhile, due to hydrolysis and the destruction of cell walls in fenugreek gum endosperm, make to increase glutinous process colloid release rate and obtain raising to a certain degree, finally substantially improve of the fracturing fluid performance.
Described emulsion splitter and cleanup additive are that aqueous fracturing fluid field is general, have nothing to do with of the fracturing fluid crosslinked and broken glue process, the mainly needs of fracturing fluid recovery (backflow).Typical emulsion splitter is as polyoxyethylene polyoxypropylene polyoxypropylene stearyl alcohol ether, polyoxyethylene lauryl base phenol formaldehyde resin sulfuric ester sodium salt, polyxyethylated toluene phenolic ether, polyoxyethylene polyoxypropylene propylene glycol etc., and cleanup additive is as Sodium perfluorooctanoate, perfluoro-octanoyl ethyleneamines ylmethyl diethyl ammonium iodide etc.
The invention provides a kind of biological enzyme fracturing liquid sanitising agent, in fracturing liquid base fluid process for preparation, by adding compound biological enzyme liquid, the water-insoluble in vegetable jelly rubber powder is degraded and minimizing, this process is overlapping with vegetable jelly aquation dissolution time on the reaction times, do not need to increase processing costs and time cost separately, without the need to carrying out special modification process to vegetable jelly, and greatly can improve the glue performance after process, be that one is very safe, environmental protection, efficiently method.
With using biological enzyme as gel breaker, namely in fracturing liquid base fluid, add linking agent, form the prior art of carrying out brokenly glue after frozen glue different.The present invention is mainly used in the process for preparation of fracturing liquid base fluid, have chosen specific zymin, takes full advantage of the time that vegetable jelly is swelling, achieves the object reducing vegetable jelly water-insoluble.Because zymin has just carried out optionally degrading to water-insoluble component contained in vegetable jelly, therefore can not affect the crosslinked of vegetable jelly and broken colloidality energy, follow-up fracturing liquid can apply enzyme or oxidized form gel breaker gives brokenly glue.Due to the interpolation of sanitising agent, although do not affect of the fracturing fluid broken glue process, the broken glue residue of system significantly can reduce with the minimizing of water-insoluble, thus improves overall fracturing liquid quality.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but these embodiments are only used to illustrate instead of limit the scope of the invention.
Emulsion splitter in embodiment and comparative example is polyoxyethylene polyoxypropylene polyoxypropylene stearyl alcohol ether, and cleanup additive is the mixture of Sodium perfluorooctanoate 1.0 % by weight, sodium lauryl sulphate 35 % by weight, Virahol 64 % by weight.
Embodiment 1
With institute of Novozymes Company cellulase-producing, pentosanase and polygalacturonase for raw material, preparation weight content is the compound biological enzyme liquid of the Pectin16000U of Carezyme4500L, 10%Pentopan MonoBG2500F and 10% of 10%, for subsequent use.
The mixed tune in device of Xiang Wuyin adds 500mL water, maintenance rotating speed is 1000r/min, add above-mentioned compound biological enzyme liquid 0.5mL, add Repone K 5.0g, then slowly add 1.5g fenugreek gum, stir 5 minutes, then 0.1mL emulsion splitter and 0.1mL cleanup additive is added, continue stirring 2 minutes, then prepared fracturing liquid base fluid is transferred in beaker, is placed in 30 DEG C of water-baths 4 hours.Embodiment 2
With institute of Genencor Company cellulase-producing, pentosanase and polygalacturonase for raw material, preparation weight content is the compound biological enzyme liquid of P200 of the Promafast200 of 12%, the Laminex of 12% and 12%, for subsequent use.
The mixed tune in device of Xiang Wuyin adds 500mL water, keep 1000r/min, add above-mentioned compound biological enzyme liquid 1.0mL, add Repone K 5.0g, then slowly add 1.5g fenugreek gum, stir 5 minutes, then 0.1mL emulsion splitter and 0.1mL cleanup additive is added, continue stirring 2 minutes, then prepared fracturing liquid base fluid is transferred in beaker, is placed in 30 DEG C of water-baths 4 hours.
Embodiment 3
With German AB enzyme industry institute cellulase-producing, pentosanase and polygalacturonase for raw material, preparation weight content is the compound biological enzyme liquid of Pectina of the KRX-300 of 15%, the Finase L and 15% of 15%, for subsequent use.
The mixed tune in device of Xiang Wuyin adds 500mL water, keep 1000r/min, add above-mentioned compound biological enzyme liquid 1.5mL, add Repone K 5.0g, then slowly add 1.5g fenugreek gum, stir 5 minutes, then 0.1mL emulsion splitter and 0.1mL cleanup additive is added, continue stirring 2 minutes, then prepared fracturing liquid base fluid is transferred in beaker, is placed in 30 DEG C of water-baths 4 hours.
Embodiment 4
With institute of DSM company cellulase-producing, pentosanase and polygalacturonase for raw material, preparation weight content is the compound biological enzyme liquid of DSM Rapidasepress of the DSM-HSP6000 of 18%, the Bakerzyme6000 of 18% and 18%, for subsequent use.
The mixed tune in device of Xiang Wuyin adds 500mL water, keep 1000r/min, add above-mentioned compound biological enzyme liquid 2.0mL, add Repone K 5.0g, then slowly add 1.5g fenugreek gum, stir 5 minutes, then 0.1mL emulsion splitter and 0.1mL cleanup additive is added, continue stirring 2 minutes, then prepared fracturing liquid base fluid is transferred in beaker, is placed in 30 DEG C of water-baths 4 hours.
Embodiment 5
With institute of Dan Niyue company cellulase-producing, pentosanase and polygalacturonase for raw material, preparation weight content is the compound biological enzyme liquid of Denykem PAP-4 of the Denpill66L of 20%, the Denykem1500L of 20% and 20%, for subsequent use.
The mixed tune in device of Xiang Wuyin adds 500mL water, keep 1000r/min, add above-mentioned compound biological enzyme liquid 2.5mL, add Repone K 5.0g, then slowly add 1.5g fenugreek gum, stir 5 minutes, then 0.1mL emulsion splitter and 0.1mL cleanup additive is added, continue stirring 2 minutes, then prepared fracturing liquid base fluid is transferred in beaker, is placed in 30 DEG C of water-baths 4 hours.
Comparative example 1
The mixed tune in device of Xiang Wuyin adds 500mL water, keep 1000r/min, add Repone K 5.0g, then 1.5g fenugreek gum is slowly added, stir 5 minutes, then add 0.1mL emulsion splitter and 0.1mL cleanup additive, continue stirring 2 minutes, then prepared fracturing liquid base fluid is transferred in beaker, is placed in 30 DEG C of water-baths 4 hours.
Fracturing liquid base fluid 50mL prepared by above-described embodiment and comparative example is got respectively with the Centrifuge Cup of pre-constant weight, be placed in 3000r/min whizzer centrifugal 30 minutes, after carefully toppling over supernatant liquor, get 50mL distilled water by throw out resuspension uniformly disperse phase, again system is placed in 3000r/min whizzer centrifugal 20 minutes, after again toppling over supernatant liquor, Centrifuge Cup is placed in 105 DEG C and dries to constant weight, with reference to the water insoluble matter content in following formulae discovery fracturing liquid base fluid, the results are shown in Table 1.
Water insoluble matter content (%)=(after drying Centrifuge Cup quality-Centrifuge Cup original quality)/[0.5 × (1-vegetable jelly water ratio)]
Described fenugreek gum water ratio is by moisture content tester SH10A type or like product, obtain according to SYT5764-2007 standard testing, measuring process is as follows: moisture content tester is after 105 DEG C of preheatings, correcting, taking 5.00g rubber powder is laid in the scale pan, heat 0.5h at 105 DEG C, open instrument readings switch, observe projection screen, when in 10min, readings amplitude is less than 0.2%, the reading of instrument is the water ratio of rubber powder.
Get each 300mL of fracturing liquid base fluid prepared by above-described embodiment and comparative example, be placed in the fast viscometer of Fann formula six, rotating speed is adjusted to 100r/min, measure the viscosity number of fracturing liquid base fluid, the results are shown in Table 1.
Water insoluble matter content in table 1 embodiment and comparative example fracturing liquid base fluid and viscosity number
| Water insoluble matter content (%) | Viscosity (mPas) | |
| 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 process of compound biological enzyme liquid, in the fracturing liquid base fluid of fenugreek gum preparation, water insoluble matter content (by fenugreek gum quality) drops to 1.02%, 2.32%, 1.65%, 1.71 and 2.55% by 6.78%.And the viscosity of fracturing liquid base fluid does not change substantially, experimental result illustrates: present method can effectively reduce plant gum fracturing fluid water-insoluble, and does not make significant difference to fracturing fluid property.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (10)
1. a biological enzyme pressure break sanitising agent, formulated by cellulase, pentosanase, polygalacturonase and water.
2. biological enzyme pressure break sanitising agent according to claim 1, is characterized in that, described cellulase is 10 ~ 20 % by weight, and pentosanase is 10 ~ 20 % by weight, and polygalacturonase is 10 ~ 20 % by weight, and surplus is water.
3. biological enzyme pressure break sanitising agent according to claim 1 and 2, it is characterized in that, described cellulase is selected from least one in Novi letter Carezyme4500L, Jie Neng section Promafast200, AB enzyme KRX-300, DSM DSM-HSP6000 and Dan Niyue Denpill66L.
4. biological enzyme pressure break sanitising agent according to claim 1 and 2, it is characterized in that, described pentosanase is selected from least one in Novi letter Pentopan MonoBG2500F, Jie Neng section Laminex, AB enzyme Finase L, DSM DSM Bakerzyme6000 and Dan Niyue Denykem1500L.
5. biological enzyme pressure break sanitising agent according to claim 1 and 2, it is characterized in that, described polygalacturonase is selected from least one in Novi letter Pectin16000U, Jie Neng section P200, AB Pectina, DSM DSM Rapidasepress and Dan Niyue Denykem PAP-4.
6. a fracturing liquid, comprises biological enzyme pressure break sanitising agent described in any one of Claims 1 to 5.
7. an of the fracturing fluid preparation method as claimed in claim 6, before being included in the preparation of fracturing liquid base fluid, described biological enzyme fracturing liquid sanitising agent is joined in dosing water, then the various additives of fracturing liquid base fluid is added, after plastic as fracturing liquid use, preferably by described biological enzyme fracturing liquid sanitising agent with 0.1% ~ 0.5% volume ratio join in dosing water.
8. method according to claim 7, is characterized in that, the formula of described fracturing liquid base fluid is as follows: Repone K 1.0 ~ 2.0 % by weight, vegetable jelly 0.3 ~ 0.4 % by weight, emulsion splitter 0.05 ~ 0.2 % by weight and cleanup additive 0.05 ~ 0.2 % by weight, surplus is water.
9. method according to claim 8, is characterized in that, described vegetable jelly is fenugreek gum, guanidine glue, sesbania gum, tara gum, Viscogum BE and/or carob bean gum, is preferably fenugreek gum.
10. method according to claim 8, it is characterized in that, described emulsion splitter is polyoxyethylene polyoxypropylene polyoxypropylene stearyl alcohol ether, and described cleanup additive is the mixture of Sodium perfluorooctanoate 1.0 % by weight, sodium lauryl sulphate 35 % by weight and Virahol 64 % by weight.
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| CN201410025827.8A CN104789203B (en) | 2014-01-20 | 2014-01-20 | A kind of biological enzyme pressure break detergent and its application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107989587A (en) * | 2017-10-27 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of method that the injury of cellulose fracturing fluid is reduced using microorganism |
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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Patent 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107989587A (en) * | 2017-10-27 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of method that the injury of cellulose fracturing fluid is reduced using microorganism |
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