CN101880523B - Enzyme-microbe coupled fracturing fluid system and preparation method and applications thereof - Google Patents
Enzyme-microbe coupled fracturing fluid system and preparation method and applications thereof Download PDFInfo
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- Detergent Compositions (AREA)
- Enzymes And Modification Thereof (AREA)
Abstract
The invention relates to a fracturing fluid system, in particular to a new aqueous fracturing enzyme-microbe coupled fracturing fluid system used in the petroleum and natural gas exploitation, wherein the chemical additives in the original aqueous fracturing fluid are replaced by the biological additives with the same function, and inoculating microbe degrading residue and gel are added to react so as to greatly increase the gel-breaking efficiency and reduce formation damage. The fracturing fluid system comprises the following components: 0.30-0.55wt% of vegetable gum polymer, 0.002-0.2wt% of biological bactericide, 0.025-0.05wt% of biological cleanup additive, 0.05-0.1wt% of ahead fluid biological optimizer, 0.05-0.1wt% of microbial enhanced production-increasing agent, 1-3wt% of clay stabilizer, pH regulator, 10-30mg/L of enzyme breaker and the balance water. The fracturing fluid system of the invention uses non-toxic and harmless natural products to the maximum to replace toxic and harmful chemical additives, achieves the aims of degradable working fluid creatures which are injected in the formation, energy conservation and emission reduction and environmental protection and is an ideal fracturing fluid system.
Description
Technical field
The present invention relates to biological fracturing fluid system, specifically a kind of novel oil field vegetable jelly environmental protection and the available water-based fracturing liquid system of biomass and preparation thereof.
Background technology
The oil field waterfrac treatment is to cause one of operation of a large amount of chemical pollutions in stratum and polymer damage.Will add the number of chemical additive in the construction in fracturing liquid, larger to the injury of stratum indigenous microorganism, bioavailability is low, and broken glue effect is bad.The analysis of carrying out according to 150 waterfrac treatment operations of the U.S. shows, the polymkeric substance that pressure break pumps into the on average row of returning leads 35%-45% is only arranged, and remains in the polymkeric substance of bottom, forms easily filter cake, stops up pore throat, and the stratum is damaged.This injury is difficult to remove, and such as water-sensitive type stratum, also can form dead pressure, has a strong impact on the fracturing yield increasing effect.
Since the eighties in 20th century, many countries have carried out the exploration of promoting MEOR method raising oil recovery factor, and through the effort of more than ten years, technique has been obtained very big progress.U.S. 1991 MEOR classify that traditional heat is driven as, the 4th kind of method that improves recovery ratio after the chemical flooding, gas drive, and in many field use, obtained input-output ratio and be 1: 5 good result.China in some oil fields, such as huge port, the Liaohe River, triumph, has carried out research and the application of MEOR since the nineties in 20th century in succession, has also obtained certain effect.Its principle be microorganism in the growth metabolism process, with the carbon source of the normal paraffin in external source carbohydrate or the crude oil as self growth, perhaps produce the carbochain that bio-surfactant changes crude oil and form; On the other hand, the biological enzyme that discharges during microorganism growth can degrading crude oil, make the fracture of crude oil carbochain, high carbon chain crude oil becomes low carbon chain crude oil, restructuring minute minimizing, light constituent increases, zero pour and reduced viscosity, thus play the effect that viscosity reduction, wax control improve crude oil fluidity.
Summary of the invention
The object of the present invention is to provide and a kind ofly can efficiently reduce formation damage, improve the pressure break system of fracturing yield increasing effect.It should have the degraded cull, reduce residue, thereby breaking glue solution can be reached characteristics such as removing formation damage, technique simple possible by origin and inoculating microbe utilization behind the broken glue.
For achieving the above object, the technical solution used in the present invention is:
Enzyme-enzyme-microbe coupled fracturing fluid system, it is formulated for the water-based fracturing liquid system mainly contains vegetable jelly, biological assistant, linking agent, microorganism, water.Said components by weight, by vegetable jelly polymkeric substance 0.30-0.55%, biological bactericide 0.002-0.2%, biological cleanup additive 0.025-0.05%, spearhead Biological optimization agent 0.05-0.1%, microbial augmentation increasing agent 0.05-0.1%, clay stabilizer 1-3%, pH value conditioning agent, biological enzyme gel breaker 10-30mg/L, surplus is water.Said components according to a conventional method mix and blend gets final product.Rock core infiltration recovery rate of the present invention can reach 92%, uses six rotating speed viscometer 170S
-1Shearing rate shear that viscosity is greater than 100mpa.s in the 1h, level of residue is less than 80mg/L behind the broken glue, after vexed well 5-10 days, level of residue is less than 20mg/L.Less than 10%, downhole temperature all can use below 80 ℃ enzyme-enzyme-microbe coupled fracturing fluid to the injury rate of rate of permeation, need not the row of returning after the pressure break or postpones the row of returning.
The vegetable jelly polymkeric substance is one or more in guar gum, hydroxypropylguar gum or other guar derivative;
Biological bactericide is: one or more in the microorganism of bacitracin, polymyxin, product fungistat or other biological bactericide with same effect;
Biological cleanup additive is: Lipopeptide Biosurfactants, Glycolipids Biosurfactants via, phospholipid tensio-active agent or other have one or more in the bio-surfactant of same effect;
Enzyme breaker is the 'beta '-mannase, cellulase, laccase of acid-fast alkali-proof, heatproof or in other biological enzyme with same effect one or more; Clay stabilizer is KCl.
PH adjusting agent is citric acid or sodium bicarbonate, and it is adjusted to 8.5-9.5 with fracturing fluid system final pH value.
Add the spearhead Biological optimization agent that is beneficial to volume increase in the pressure break system, its consumption is counted the 0.05-0.1% of pressure break system by weight;
Its composition is counted in mass ratio: potassium primary phosphate 8-12%, dipotassium hydrogen phosphate 3-8%, ammoniacal liquor 1-3%, phosphoric acid 0.5-3%; Its preparation method is:
1) press concentration ratio weighing potassium primary phosphate 8-12g, dipotassium hydrogen phosphate 3-8g is for subsequent use in beaker;
2) measure in mass ratio ammoniacal liquor 1-3g, phosphoric acid 0.5-3g, add water 50g and in beaker, mix.
3) load weighted potassium primary phosphate in 1 and dipotassium hydrogen phosphate are added 2) system in, add again 50g water to medicine and dissolve fully.
Add the microbial augmentation increasing agent that is beneficial to volume increase in the pressure break system, its consumption is counted 0.05-0.1% by weight; Composition is: subtilis, Bacillus licheniformis or other have the single bacterium of the broken glue residue effect of identical degraded guar gum or the composite microbial inoculum of multiple bacterium.
For obtaining to have certain viscoelastic frozen glue shape water-based fracturing liquid system, employed linking agent is borax or organic boron in the pressure break system, and its consumption is: the aqueous solution of 1-1.5wt% borax or organic boron, crosslinked ratio is 100: 5-100: 10.
The preparation method of described water-based fracturing liquid system, at first preparing mass concentration is the guar gum base fluid of 0.3-0.55%, again biological cleanup additive, biological bactericide, biological enzyme, the agent of spearhead Biological optimization, microbial augmentation increasing agent are added in ratio claimed in claim 1, add at last linking agent and carry out crosslinkedly, it is become have certain viscoelastic frozen glue.
The application of described water-based fracturing liquid system in the oil and natural gas pressure break, it is characterized in that: utilize this fracturing fluid system to break the glue experiment, be incubated 1h under the pressure break temperature, fracturing liquid viscosity 〉=100mpa.s, its broken glue level of residue≤80mg/L, the broken glue time is 2-3h, and breaking glue solution viscosity is 1-5mpas.
Utilize this fracturing fluid system to carry out pressing crack construction, fracturing liquid need not the row of returning or postpones the row of returning after the construction, and after vexed well 5-10 days, further cull, residue are degraded by microorganisms, level of residue≤20mg/L after the degraded;
Wherein the microbial augmentation increasing agent can utilize cull, residue to generate the material that organic acid, organic ketone, organic ester and bio-surfactant etc. are conducive to the crude oil volume increase;
And used bacterium is conducive to the natural bacteria that crude oil increases production material for forming organic acid, organic ester, organic ketone or bio-surfactant etc.;
But used bacterium tolerable temperature scope is: 20～80 ℃, the salinity scope is: 0～100000mg/L, and facultative aerobic.
The present invention substitutes the chemistry aiding discharging agent in original aqueous fracturing fluid with biological cleanup additive, chemical bactericide substitutes with biological bactericide, chemical gel breaker substitutes with the biological enzyme gel breaker, and add clay stabilizer and pH adjusting agent and be beneficial to the agent of spearhead Biological optimization and the microbial augmentation increasing agent that hydrocarbon-bearing pool is increased production, then carry out crosslinked, can form the visco-elasticity frozen glue body of composite fracturing requirement, i.e. enzyme and enzyme-microbe coupled fracturing fluid; Utilize this fracturing fluid system that the well temperature is carried out pressing crack construction for 30-80 ℃ Oil/gas Well, it is few to reach level of residue, and the pressure break injury is low, enters the not row of returning of well fracturing fluid, improves the purpose of effect of increasing production.
The invention has the advantages that:
The made green fracturing fluid system of the present invention is with the technical superiority of the traditional chemical system of the at present existing use in oil field: all characteristics that 1) have the crosslinked and rheological of traditional fracturing fluid gel; 2) used alternative biological assistant (gel breaker, cleanup additive, sterilant, flow improver, emulsion splitter, emulsifying agent) is biodegradable low toxicity or nontoxic green bio preparation; 3) broken glue is thorough, and the broken glue time is controlled; 4) contain the agent of nitrogen phosphorus spearhead Biological optimization and not only have the frictional resistance of falling effect, also provide necessary nutrition for origin and inoculating microbe, promote the degraded of pressure break cull, and generate bio-surfactant.5) this System On Core injury is less than 10% (chemical method 30-37%, enzyme process 21-27%), in the recovery process, the sustainable reduction pressure break injury of the inoculating microbe that injects and the indigenous microorganism of activation, generate the materials such as organic acid, organic ketone, organic ester, bio-surfactant, sustainable raising fracture flow capacity; 6) behind this fracturing fluid system pressing crack construction, the row of returning or postpone the row of returning not.
Description of drawings
Fig. 1 guar gum rheological figure.
Embodiment
Embodiment 1
A kind of novel water-based of the fracturing fluid preparation for the oil and natural gas exploitation is achieved in the following ways:
1) takes by weighing by weight vegetable jelly polymkeric substance 0.45g, under the condition of high-speed stirring, at the uniform velocity add in the water of 100mL, be mixed with the guar gum base fluid.
2) add biological bactericide 0.02g, biological cleanup additive 0.025g, spearhead Biological optimization agent 0.05g, microbial augmentation increasing agent 0.1g, clay stabilizer 2g, biological enzyme gel breaker 30mg/L.
3) add pH adjusting agent and regulate the pH value to 8.5-9.5.
4) add linking agent and carry out crosslinkedly, linking agent is the 1.5wt% borax solution, and add-on is 5mL, stirs gently simultaneously, can obtain the frozen glue for pressure break.
The preparation method of a kind of spearhead Biological optimization agent, its effect is to activate the oil well indigenous microorganism, and for inoculating microbe provides nutrition source, its preparation is achieved in the following ways:
1) weighing potassium primary phosphate 8g, dipotassium hydrogen phosphate 3g places for subsequent use;
2) get by volume ammoniacal liquor 1mL, phosphoric acid 0.5mL, add water 50mL and mix.
3) with 1) in load weighted potassium primary phosphate and dipotassium hydrogen phosphate add 2) system in, add again 50g water to medicine and dissolve fully.
The construction idiographic flow:
1, by above-mentioned recipe configuration guar gum base fluid 40m
3
2, sneak into the grains of sand at truck-mounted blender, slowly add gel breaker simultaneously, consumption is about the 2kg/ well.Crosslinkedly pump into the down-hole with pump truck afterwards.
3, the breaking glue solution row of returning not behind the broken glue, vexed well 5～10 days.
Its construction results is as follows:
Shown by above-mentioned experimental data, adopt the well of the pressure break system of enzyme of the present invention-microbe coupled, behind the broken glue not in the situation of the row of returning, daily oil production can reach 3-10 doubly more than, as seen this invention increase oil recovery effect is very obvious.
Embodiment 2
Reagent is prepared as described in example 1 above, arrangement and method for construction:
1, by above-mentioned recipe configuration guar gum base fluid 40m
3
2, sneak into the grains of sand at truck-mounted blender, slowly add gel breaker simultaneously, consumption is about the 2kg/ well.Crosslinkedly pump into the down-hole with pump truck afterwards.
3, breaking glue solution delay 2-3h returns row, and its construction results is as follows:
Shown that by above-mentioned experimental data adopts the well of the pressure break system of enzyme of the present invention-microbe coupled, in the situation of the delay row of returning behind the broken glue, daily oil production obviously increases, as seen the operational version of this invention can increase the petroleum production of half.
Embodiment 3
Reduce level of residue, do following test with core permeability determinator, core porosity determinator, rock core vacuum pressed saturation device etc.The reagent preparation is selected the rock core on three same stratum as described in Example 1, and the rock core primary data is as follows:
Rock core physical parameter table
Breaking glue solution by the 1# rock core is take ammonium persulphate as gel breaker, and the breaking glue solution by the 2# rock core is only take biological enzyme as gel breaker, and the breaking glue solution by the 3# rock core is as gel breaker take enzyme-microbe coupled system.Use the Instrument measuring core damage.Experiment flow is as follows:
1, the rock core forward injects kerosene, until saturated.Intake pressure remains on
About 20MPa, top hole pressure remains on
0.2MPa aboutMeasure rate of permeation.
2, after breaking glue solution filters, the inverse injection rock core, injection rate reaches 2PV.
3, forward injects kerosene again, until saturated.Measure rate of permeation.
4, calculate core damage by front and back permeability variation relation.
Evaluation and level of residue result are as follows:
| The rock core numbering | Rate of permeation mD before the infringement | Rate of permeation mD after the infringement | Injury rate η d/(％) | Level of residue mg/L |
| 1 | 0.001059 | 0.000724 | 31.6 | 548 |
| 2 | 0.008732 | 0.007796 | 10.7 | 234 |
| 3 | 0.043240 | 0.040181 | 7.07 | 117 |
Shown by above-mentioned experimental data, adopt enzyme of the present invention-microbe coupled pressure break system to do the core damage experiment, the injury rate has dropped to 7.07% from original 31.6%, level of residue from before 548mg/L drop to 117mg/L, as seen this invention is very obvious to reducing rock stratum injury effect.
Embodiment 4
For prove this invention system on the rheological of thickening material without impact, reagent is pressed embodiment 1 preparation:
1) takes by weighing by weight vegetable jelly polymkeric substance 0.45g, under the condition of high-speed stirring, at the uniform velocity add in the water of 100mL, be mixed with the guar gum base fluid.
2) add biological bactericide 0.02g, biological cleanup additive 0.025g, spearhead Biological optimization agent 0.05g, microbial augmentation increasing agent 0.1g, clay stabilizer 2g, biological enzyme gel breaker 30mg/L.
3) add pH adjusting agent and regulate the pH value to 8.5-9.5.
4) add linking agent and carry out crosslinkedly, linking agent is the 1.5wt% borax solution, and add-on is 5mL, adds simultaneously to stir gently, can obtain the frozen glue for pressure break.
With rheometer measurement guar gum frozen glue rheological, its result such as Fig. 1.
Shown by above-mentioned experimental data, adopt the rheological experiment that enzyme of the present invention-microbe coupled pressure break system is done, the time during to 1h of the fracturing fluid viscosity still can remain to more than the 100mpaS, as seen this invents and meets the fracturing liquid requirement fully.
Claims (3)
1. preparation method who is used for the aqueous fracturing fluid of oil and natural gas exploitation: it is characterized in that:
1) takes by weighing by weight vegetable jelly polymkeric substance 0.45g, under the condition of high-speed stirring, at the uniform velocity add in the water of 100mL, be mixed with the guar gum base fluid;
2) add biological bactericide 0.02g, biological cleanup additive 0.025g, spearhead Biological optimization agent 0.05g, microbial augmentation increasing agent 0.1g, clay stabilizer 2g, biological enzyme gel breaker 30mg/L;
3) add pH adjusting agent and regulate the pH value to 8.5-9.5;
4) add linking agent and carry out crosslinkedly, linking agent is the 1.5wt% borax solution, and add-on is 5mL, stirs gently simultaneously, can obtain the frozen glue for pressure break;
The preparation method of described spearhead Biological optimization agent is:
A) weighing potassium primary phosphate 8g, dipotassium hydrogen phosphate 3g places for subsequent use;
B) get by volume ammoniacal liquor 1mL, phosphoric acid 0.5mL, add water 50mL and mix;
C) load weighted potassium primary phosphate in a) and dipotassium hydrogen phosphate are added b) system in, add again 50g water to medicine and dissolve fully;
Wherein, the vegetable jelly polymkeric substance is one or more in guar gum, hydroxypropylguar gum or other guar derivative;
Biological bactericide is: one or more in the microorganism of bacitracin, polymyxin, product fungistat or other biological bactericide with same effect;
Biological cleanup additive is: Lipopeptide Biosurfactants, Glycolipids Biosurfactants via, phospholipid tensio-active agent or other have one or more in the bio-surfactant of same effect;
Enzyme breaker is the 'beta '-mannase, cellulase, laccase of acid-fast alkali-proof, heatproof or in other biological enzyme with same effect one or more; Clay stabilizer is KCl; PH adjusting agent is citric acid or sodium bicarbonate;
The microbial augmentation increasing agent, its consumption is counted 0.05-0.1% by weight; Composition is: subtilis, Bacillus licheniformis or other have the single bacterium of the broken glue residue effect of identical degraded guar gum or the composite microbial inoculum of multiple bacterium.
2. the preparation method of described aqueous fracturing fluid for oil and natural gas exploitation according to claim 1, it is characterized in that: utilize this fracturing fluid system to break the glue experiment, be incubated 1h under the pressure break temperature, fracturing liquid viscosity 〉=100mpa.s, its broken glue level of residue≤80mg/L, the broken glue time is 2-3h.
3. the preparation method of described aqueous fracturing fluid for oil and natural gas exploitation according to claim 1 and 2, it is characterized in that: utilize this fracturing fluid system to carry out pressing crack construction, fracturing liquid need not the row of returning or postpones the row of returning after the construction, after vexed well 5-10 days, broken glue cull, residue are degraded by microorganisms, level of residue≤20mg/L after the degraded;
Wherein microbial augmentation increasing agent degradable cull, residue and generate the material that organic acid, organic ketone, organic ester and bio-surfactant microbial secondary meta-bolites are conducive to crude oil volume increase;
But used bacterium tolerable temperature scope is: 20～80 ℃, the salinity scope is: 0～100000mg/L, and facultative aerobic.
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| CN102877815A (en) * | 2011-07-15 | 2013-01-16 | 中国石油天然气股份有限公司 | Method for reducing guargum fracturing fluid residues |
| CN103573238A (en) * | 2012-07-26 | 2014-02-12 | 中国石油天然气股份有限公司 | Method for degrading oil well fracturing fluid through biological enzyme |
| CN103912254B (en) * | 2013-01-09 | 2016-11-16 | 中国石油化工股份有限公司 | A kind of method utilizing compounding activation agent to improve fracturing well capacity |
| CN103305571B (en) * | 2013-06-09 | 2015-03-18 | 郑建立 | Preparation method of low-molecular-weight plant gelatin powder |
| CN103555629B (en) * | 2013-11-04 | 2015-11-11 | 赵静 | A kind of bacterial strain and application thereof of producing middle low temperature 'beta '-mannase |
| CN106893573A (en) * | 2015-12-17 | 2017-06-27 | 大连百奥泰科技有限公司 | A kind of biological fracturing fluid system and its preparation and application |
| CN108728058A (en) * | 2018-06-29 | 2018-11-02 | 长江大学 | A kind of drilling fluid inhibitor and its application |
| CN111793490A (en) * | 2019-04-08 | 2020-10-20 | 中国石油天然气股份有限公司 | Vegetable gum fracturing fluid microorganism composite viscosity reduction system and application thereof in field of thick oil exploitation |
| CN112778991B (en) * | 2021-01-08 | 2022-12-06 | 中国石油天然气集团公司 | Biological enzyme composite blocking remover and preparation method thereof |
| CN113685163A (en) * | 2021-08-26 | 2021-11-23 | 杜海峰 | Novel process for microbial agent oil well fracturing prepad fluid |
| CN114686199A (en) * | 2022-04-22 | 2022-07-01 | 大庆华理生物技术股份有限公司 | Composite fracturing fluid system slickwater |
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| WO2007067668A1 (en) * | 2005-12-08 | 2007-06-14 | Hercules Incorporated | Solvent free fluidized polymer suspensions for oilfield servicing fluids |
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