CN103396515A - High temperature resistant modified starch filtration reducing agent and preparation method thereof - Google Patents
High temperature resistant modified starch filtration reducing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high temperature resistant modified starch filtration reducing agent and a preparation method thereof. The modified starch filtration reducing agent and the preparation method comprise that: with starch, a phenolic compound, alkenyl amide and alkenyl sulfonic acid as raw materials, an oil phase solution as a continuous phase and a nonionic surfactant as an emulsifying agent, and under catalytic actions of a reduction substrate and a hydrogen acceptor substrate, a starch graft copolymer is generated through a reaction. The filtration reducing agent provided by the invention is resistant to temperature of up to 175 DEG C, and simultaneously also has good salt and calcium resistance capabilities; and the preparation method is simple and easy to implement, and has mild and controllable reaction conditions, high grafting efficiency, fast reaction speed and low cost.
Description
Technical field
Fluid loss agent that the present invention relates to use in oil/gas drilling and preparation method thereof, relate in particular to treated starch fluid loss agent and preparation method thereof.
Background technology
Along with the continuous increase of world energy sources demand, exploitation deep formation hydrocarbon resources has become inevitable, and this just has higher requirement to drilling technology.Drilling Fluid is as integral part important in drilling technology, and the quality of its performance is directly connected to drilling quality and drilling cost, even drilling well success or failure.Under the deep formation high-temperature and high-pressure conditions, the filtration property of drilling fluid is the integral part of drilling fluid over-all properties, and under high-temperature and high-pressure conditions, the control of drilling fluid filtration is to rely on the fluid loss agent of high temperature resistance to realize.The starch based fluid loss agent has asepsis environment-protecting, with low cost, source is wide, the anti-calcium and anti-salt ability is strong, as filtrate reducer for drilling fluid, uses very early.But if temperature surpasses 120 ℃, starch will lose efficacy because of high temperature degradation, thereby had greatly limited its use range.At present, the method that improves the heat-resisting property of starch based fluid loss agent mainly realizes by graft copolymerization vinyl monomer and etherificate, but the temperature resistance ability of these fluid loss agents of starch by modification in fresh-water drilling fluid still is difficult to break through 140 ℃, but and the domestic and international treated starch fluid loss agent product of 140 ℃ of rare several temperature resistances, under its hot conditions, the anti-calcium and anti-salt performance is poor.
Therefore, need to utilize new method of modifying to improve the high temperature resistance of starch based fluid loss agent, anti-salt and anticalcium ability, to adapt to the needs of high temperature deep well probing.
Summary of the invention
For solving the problems of the technologies described above, the purpose of this invention is to provide a kind of high temperature resistance treated starch fluid loss agent and preparation method thereof, described technical scheme is as follows:
A kind of high temperature resistance treated starch fluid loss agent, described treated starch fluid loss agent is to be raw material by starch, phenolic compound, alkenyl amide and olefin sulfonic acid, oil-phase solution is external phase, nonionogenic tenside is emulsifying agent, and under the katalysis of reduction substrate and hydrogen acceptor substrate, a kind of starch graft copolymer that reaction generates.
Described starch is enzymolysis under the effect of α-amylase, obtains enzymatic degradation of starch, and described enzymolysis process comprises as follows:
In the starch that takes, add distilled water, compound concentration is the starch milk of 20.0wt%～50.0wt%, and starch milk is heated in the water-bath of 25～96 ℃;
In starch milk after heating, add α-amylase, stir and evenly, after sustained reaction 60～120min, be warming up to 105～118 ℃, deactivation 60～120min obtains the enzymatic degradation of starch emulsion.
A kind of preparation method of high temperature resistance treated starch fluid loss agent comprises:
Alkenyl amide and alkenyl sulphonate are dissolved in deionized water solvent, and be 6.0～8.0 with NaOH or the KOH aqueous solution adjusting lysate pH of 2.0wt%, obtaining concentration is 20.0wt%～50.0wt% mixed monomer solution;
Oil-phase solution and nonionogenic tenside are joined in reactor, and being uniformly mixed and obtaining having oleophilic hydrophil balance value HLB scope is 7.0～9.0 emulsion;
The enzymatic degradation of starch emulsion is joined in emulsion, and add phenolic compound, biological enzyme and reduction substrate, stir and obtain the microemulsion that oil/water volume ratio is 2～5:1;
Microemulsion slowly was warming up to 20～86 ℃ in 0.5～3.0 hour, and be that 20.0wt%～50.0wt% mixed monomer solution and molar weight are that the hydrogen acceptor substrate of 0.2～1.0 times of phenolic compound molar weight joins in the microemulsion reaction system by concentration, react and obtained the thick product of high temperature resistance treated starch fluid loss agent in 1.0～3.0 hours, then described thick product is obtained after precipitation, washing, extracting, vacuum-drying to high temperature resistance treated starch fluid loss agent.
Compared with prior art, one or more embodiment of the present invention can have following advantage:
The present invention is to provide a kind of novel high temperature resistance modified starch series fluid loss agent, first phenolic compound is incorporated in starch molecular structure, by strengthening molecular rigidity, improved the heat-resisting property of modified starch series fluid loss agent, and anti-salt and anticalcium ability; And what the preparation method adopted is the conversed phase micro emulsion copolymerization method, and this preparation method is simple, and the reaction conditions gentleness is controlled, and speed of response is fast, and percentage of grafting is high, is applicable to industrial applications and promotes.
Other features and advantages of the present invention will be set forth in the following description, and, partly from specification sheets, becoming apparent, or understand by implementing the present invention.Purpose of the present invention and other advantages can realize and obtain by specifically noted technology in specification sheets, claims.
Embodiment
Easily understand, according to technical scheme of the present invention, do not changing under connotation of the present invention, one of ordinary skill in the art can propose a plurality of frame mode of the present invention and making method.Therefore following embodiment is only illustrating of technical scheme of the present invention, and should not be considered as of the present invention all or be considered as restriction or the restriction of technical solution of the present invention.
A kind of high temperature resistance treated starch fluid loss agent, described treated starch fluid loss agent is to be raw material by starch, phenolic compound, alkenyl amide and olefin sulfonic acid, oil-phase solution is external phase, nonionogenic tenside is emulsifying agent, and under the katalysis of reduction substrate and hydrogen acceptor substrate, a kind of starch graft copolymer that reaction generates.
Above-mentioned starch is enzymolysis under the effect of α-amylase, obtains enzymatic degradation of starch, and described enzymolysis process comprises as follows:
In the starch that takes, add distilled water, compound concentration is the starch milk of 20.0wt%～50.0wt%, and starch milk is heated in the water-bath of 25～96 ℃;
In starch milk after heating, add α-amylase, stir and evenly, after sustained reaction 60～120min, be warming up to 105～118 ℃, deactivation 60～120min obtains the enzymatic degradation of starch emulsion.
Above-mentioned starch is one or more in cereal starch, potato starch and legume starch;
Above-mentioned phenolic compound is one or more in following chemical general formula material scope,
Above-mentioned alkenyl amide is acrylamide, N, N-DMAA, N, N-diethyl acrylamide, N-ethylene vinyl amine, N-vinyl methylacetamide, N-vinyl ethyl acetamide, diacetone-acryloamide(DAA), N, one or more in N-methylene-bis the third ethernamine, N hydroxymethyl acrylamide;
Above-mentioned olefin sulfonic acid is one or more among vinyl sulfonic acid, allyl sulphonic acid, styrene sulfonic acid, acryloyl-oxy butyl sulfonic acid, 2-acrylamido dodecyl sodium sulfonate, 2-acrylamido tetradecyl sulfonic acid, 2-acrylamido hexadecyl sulfonic acid, 2-acryloxy-2-methyl propane sulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid.
R in above-mentioned phenolic compound chemical general formula
1, R
2, R
3, R
4, R
6And R
8For H, OH, CH
3, CF
3, C
2H
5, C
2F
5, NH
2, NHCH
3, N (CH
3)
2, OCH
3, NHCOCH
3, Cl, Br, I; R
5And R
7For N
+(CH
3)
3, NO
2, CN, CONH
2, SO
3H, SO
3Na, SO
3K, CHO, COOH, COONa, COOK.
Above-mentioned starch is 5～10:1 with the molar mass ratio of phenolic compound;
The molar mass ratio of above-mentioned phenolic compound, alkenyl amide and olefin sulfonic acid is 1～5:2～10:3～15.
A kind of preparation method of high temperature resistance treated starch fluid loss agent comprises:
Alkenyl amide and alkenyl sulphonate are dissolved in deionized water solvent, and be 6.0～8.0 with NaOH or the KOH aqueous solution adjusting lysate pH of 2.0wt%, obtaining concentration is 20.0wt%～50.0wt% mixed monomer solution;
Oil-phase solution and nonionogenic tenside are joined in reactor, and being uniformly mixed and obtaining having oleophilic hydrophil balance value HLB scope is 7.0～9.0 emulsion;
The enzymatic degradation of starch emulsion is joined in emulsion, and add phenolic compound, biological enzyme and reduction substrate, stir and obtain the microemulsion that oil/water volume ratio is 2～5:1;
Microemulsion slowly was warming up to 20～86 ℃ in 0.5～3.0 hour, and be that 20.0wt%～50.0wt% mixed monomer solution and molar weight are that the hydrogen acceptor substrate of 0.2～1.0 times of phenolic compound molar weight joins in the microemulsion reaction system by concentration, react and obtained the thick product of high temperature resistance treated starch fluid loss agent in 1.0～3.0 hours, then described thick product is obtained after precipitation, washing, extracting, vacuum-drying to high temperature resistance treated starch fluid loss agent.
Below will resist high temperature modified starch fluid loss agent preparation method by following examples is elaborated:
Embodiment 1
The 40g W-Gum is added in the beaker that 100mL distilled water is housed, pour in reactor after fully stirring into pasty state, in the water-bath of 65 ℃, heat.Under agitation condition, add the 0.04g α-amylase, constant temperature keeps 120min, intensification oil bath temperature to 110 ℃, and constant temperature keeps 60min, namely obtains the enzymatic degradation of starch emulsion.
The 2-acrylamide-2-methylpro panesulfonic acid is made into to the solution of 15.0wt% in water, with the KOH solution of 50.0wt%, is neutralized to pH=6.0, be placed under 20 ℃ of vacuum drying ovens and dry to constant weight.
5.61 gram acrylamides and 19.34g2-acrylamide-2-methylpro panesulfonic acid potassium are dissolved in the water of 60mL, with the KOH aqueous solution of 2.0wt%, regulate pH to 7.5 and namely obtain mixed monomer solution.
In the reactor that temperature regulating device, reflux condensate device and constant voltage feeding device are housed, add the 400mL cyclohexane, add again 35.0g Span80 and 12.0g Tween80, stir 30min, under agitation condition, in reactor, slowly add enzymatic degradation of starch emulsion, 6.0g2,4-dihydroxy benzenes sulfonic acid potassium, 0.08g horseradish peroxidase and 0.96g methyl ethyl diketone.In 1 hour, the temperature to 50 ℃ of reaction system in the reactor that slowly raises, and the while at the uniform velocity drips mixed monomer solution and concentration is the H of 5.0wt%
2O
210.0mL to reaction system, continue reaction 3 hours, namely obtain the thick product of high temperature resistance treated starch fluid loss agent.
After adding 350mL dehydrated alcohol precipitation, filter, successively use the washing with acetone product each 3 times, again the Glacial acetic acid take volume ratio as 3:2-ethylene glycol mixed solvent as extractant to product with Soxhlet extractor extracting 24 hours, 25 ℃ of lower vacuum-dryings are to constant weight, namely obtain high temperature resistance treated starch fluid loss agent product, its molecular structure is as follows:
Embodiment 2
The 40g tapioca (flour) is added in the beaker that 40mL distilled water is housed, after fully stirring into pasty state, pour in reactor, in the water-bath of 96 ℃, heat, under agitation condition, add the 0.008g α-amylase, constant temperature keeps 120min, intensification oil bath temperature to 118 ℃, constant temperature keeps 60min, namely obtains the enzymatic degradation of starch emulsion.
Styrene sulfonic acid is made into to the solution of 15.0wt% in water, with the NaOH solution of 50.0wt%, is neutralized to pH=6.0, be placed under 20 ℃ of vacuum drying ovens and dry to constant weight.
6.61g N,N-DMAA and 20.62g sodium p styrene sulfonate are dissolved in the water of 100mL, with the NaOH aqueous solution of 2.0wt%, regulate pH to 7.0 and obtain mixed monomer solution.
In the reactor that temperature regulating device, reflux condensate device and constant voltage feeding device are housed, add 480mL toluene, then add 26.91g Span60 and 21.03g OP-10, stir 60min.Under agitation condition, in reactor, slowly add enzymatic degradation of starch emulsion, 4.20g pyrogallol, 0.06g soybean peroxidase and 1.2g methyl ethyl diketone.In 3 hours, the temperature to 86 ℃ of reaction system in the reactor that slowly raises, and the while at the uniform velocity drips mixed monomer solution and concentration is the H of 5.0wt%
2O
210.0mL to reaction system, continue reaction 1 hour, namely obtain the thick product of high temperature resistance treated starch fluid loss agent.
After adding 350mL dehydrated alcohol precipitation, filter, successively use the washing with acetone product each 3 times, again the Glacial acetic acid take volume ratio as 3:2-ethylene glycol mixed solvent as extractant to product with Soxhlet extractor extracting 24 hours, 25 ℃ of lower vacuum-dryings are to constant weight, namely obtain high temperature resistance treated starch fluid loss agent product, its molecular structure is as follows:
Embodiment 3
The 40g wheat starch is added in the beaker that 160mL distilled water is housed, after fully stirring into pasty state, pour in reactor, in the water-bath of 25 ℃, heat, under agitation condition, add the 0.2g α-amylase, constant temperature keeps 120min, intensification oil bath temperature to 105 ℃, very surely keep 120min, namely obtain the enzymatic degradation of starch emulsion.
The 2-acrylamide-2-methylpro panesulfonic acid is made into to the solution of 15.0wt% in water, with the NaOH solution of 50.0wt%, is neutralized to pH=7.0, be placed under 20 ℃ of vacuum drying ovens and dry to constant weight.
5.0gN-n-methylolacrylamide and 11.46g2-acrylamide-2-methylpro panesulfonic acid sodium are dissolved in the water of 50mL, with the NaOH aqueous solution of 2.0wt%, regulate pH to 8.0 and namely obtain mixed monomer solution.
In the reactor that temperature regulating device, reflux condensate device and constant voltage feeding device are housed, add the 600mL o-Xylol, then add 62.52g Span60 and 18.20g Tween60, stir 90min.Under agitation condition, in reactor, slowly add enzymatic degradation of starch emulsion, 8.0g P-hydroxybenzoic acid sodium, 0.096g horseradish peroxidase and 1.5g methyl ethyl diketone.In 0.5 hour, the temperature to 45 ℃ of reaction system in the reactor that slowly raises, and the while at the uniform velocity drips mixed monomer solution and concentration is the H of 5.0wt%
2O
213.6mL to reaction system.Continue reaction 3.0 hours, namely obtain the thick product of high temperature resistance treated starch fluid loss agent.
After adding 350mL dehydrated alcohol precipitation, filter, successively use the washing with acetone product each 3 times, again the Glacial acetic acid take volume ratio as 3:2-ethylene glycol mixed solvent as extractant to product with Soxhlet extractor extracting 24 hours, 25 ℃ of lower vacuum-dryings are to constant weight, namely obtain high temperature resistance treated starch fluid loss agent product, its molecular structure is as follows:
Embodiment 4
The heat-resisting property of treated starch fluid loss agent product, anti-salt contamination and anticalcium are invaded merit rating.Testing method: adopt ZB/TE13004-90: the drilling fluid test procedure
1, test in the fresh water-based slurry
Fresh water-based slurry: stir in cup and add the 400mL tap water at height, quantitatively add 16.0 calcium bentonites and 0.8g Na under constantly stirring
2CO
3.Stirred 20 minutes, and stopped at least twice therebetween, to scrape the wilkinite that sticks on wall of container, maintenance is 24 hours in sealed vessel.
Treated starch-fresh-water drilling fluid system: quantitatively take the treated starch fluid loss agent, it is joined in fresh water-based slurry, maintenance 24 hours in sealed vessel after fully stirring.
Fresh water-based slurry and treated starch-fresh-water drilling fluid system high-speed stirring are packed into after 5 minutes in the high temperature ageing tank, 175 ℃ boiling hot 16 hours, with commit a breach of etiquette filter loss with high pressure high temperature filter tester mensuration drilling fluid of press filtration in normal temperature, its result such as following table 1:
Table 1
| The experiment slurry | 175 ℃/16 hours |
| ? | FL API | FL HTHP |
| The fresh water-based slurry | 86.0 | The full leakage |
| Fresh water-based slurry+1.8wt% embodiment 1 sample | 13.2 | 28.4 |
| Fresh water-based slurry+2.5wt% embodiment 2 samples | 14.8 | 34.0 |
| Fresh water-based slurry+2.8wt% embodiment 2 samples | 13.8 | 29.6 |
| Fresh water-based slurry+2.8wt% embodiment 3 samples | 14.6 | 29.8 |
In table, FL
APIPress filtration vector in-normal temperature; FL
HTHP-high temperature and high pre ssure filtration, measure temperature identical with corresponding aging temperature, and test pressure is 3.5MPa.
2, in the water base slurry of saturated salt, test
The water base slurry of saturated salt: stir in cup and add the 400mL tap water at height, constantly adding 144.0g, 16.0g calcium bentonite and 0.8g Na under agitation condition
2CO
3.Stirred 20 minutes, and stopped at least twice therebetween, to scrape the wilkinite that sticks on wall of container, maintenance is 24 hours in sealed vessel.
Treated starch-saturated salt-water drilling fluid system: quantitatively take the treated starch fluid loss agent, it is joined in the water base slurry of saturated salt, maintenance 24 hours in sealed vessel after fully stirring.
The water base slurry of saturated salt and treated starch-saturated salt-water drilling fluid system high-speed stirring are packed into after 5 minutes in the high temperature ageing tank, 175 ℃ boiling hot 16 hours, with press filtration in normal temperature, commit a breach of etiquette and high pressure high temperature filter tester is measured the filter loss of drilling fluid, its result such as following table 2:
Table 2
3, test in calcic base slurry
Calcic base slurry: stir in cup and add the 400mL tap water at height, constantly adding 2.0gCaCl under agitation condition
2, 16.0g calcium bentonite and 0.8g Na
2CO
3.Stirred 20 minutes, and stopped at least twice therebetween, to scrape the wilkinite that sticks on wall of container, maintenance is 24 hours in sealed vessel.
Treated starch-calcic drilling fluid system; Quantitatively take the treated starch fluid loss agent, it is joined in calcic base slurry, maintenance 24 hours in sealed vessel after fully stirring.
Calcic base slurry and treated starch-calcic drilling fluid system high-speed stirring are packed into after 5 minutes in the high temperature ageing tank, 175 ℃ boiling hot 16 hours, with commit a breach of etiquette filter loss with high pressure high temperature filter tester mensuration drilling fluid of press filtration in normal temperature, its result such as following table 3:
Table 3
Above test result shows, in treated starch-fresh-water drilling fluid system, and after 175 ℃ of aging 16h, when the concentration of the treated starch fluid loss agent of preparation is respectively 1.8wt%, 2.5wt% and 2.8wt% in adding above-described embodiment 1～3, can be by the FL of drilling fluid
APIBe reduced to below 15.0mL; When interpolation concentration is respectively 1.8wt%, 2.8wt% and 2.8wt%, can be by the FL of drilling fluid
HTHPBe reduced to below 30.0mL.Compare treated starch-fresh-water drilling fluid system, improve in right amount the high temperature resistance treated starch at treated starch-saturated salt-water drilling fluid system and treated starch-calcic (0.5wt%CaCl
2) dosage of drilling fluid system, can effectively reduce the filter loss of drilling fluid system.It can be said that brightly, the temperature resistance ability of the heat resisting fluid loss reducing agent that this patent provides can reach 175 ℃, and has good anti-salt and anticalcium ability.Therefore, under the geologic condition of the suitable deep-well of this fluid loss agent product, the high temperature of ultra deep well, high salt or high calcium, use.
From above embodiment, can draw the principal feature of high temperature resistant anti-calcium and anti-salt rigidity fluid loss agent: the starch structure unit, introduce phenyl ring as rigid radical, weakened the attached effect of desorption under high temperature that the fluid loss agent molecule causes because of thermal motion, improved the performance of treated starch fluid loss agent under hot conditions, and anti-salt and anticalcium ability.In addition, on the order of addition of synthesis material, take the expedite that the starch structure unit is preferential and phenolic compound reacts, thereby the Sauerstoffatom in the starch structure unit directly is connected with carbon atom on phenyl ring in phenolic compound, on Sauerstoffatom, the orphan is pi-conjugated to the generation of the π-electron on p electronics and phenyl ring p-, thereby has improved the thermostability of molecule integral body.In addition, the conversed phase micro emulsion copolymerization method impels the free radical in reaction system steadily to generate fast, improved stability and the speed of reaction of polyreaction, and its reaction conditions gentleness is controlled, and grafting efficiency is high.
Although the disclosed embodiment of the present invention as above, the embodiment that described content just adopts for the ease of understanding the present invention, not in order to limit the present invention.Technician in any the technical field of the invention; under the prerequisite that does not break away from the disclosed spirit and scope of the present invention; can do any modification and variation what implement in form and on details; but scope of patent protection of the present invention, still must be as the criterion with the scope that appending claims was defined.
Claims (9)
1. high temperature resistance treated starch fluid loss agent, it is characterized in that, described treated starch fluid loss agent is to be raw material by starch, phenolic compound, alkenyl amide and olefin sulfonic acid, oil-phase solution is external phase, nonionogenic tenside is emulsifying agent, and under the katalysis of reduction substrate and hydrogen acceptor substrate, a kind of starch graft copolymer that reaction generates.
2. high temperature resistance treated starch fluid loss agent according to claim 1, is characterized in that, described starch is enzymolysis under the effect of α-amylase, obtains enzymatic degradation of starch, and described enzymolysis process comprises as follows:
In the starch that takes, add distilled water, compound concentration is the starch milk of 20.0wt%～50.0wt%, and starch milk is heated in the water-bath of 25～96 ℃;
In starch milk after heating, add α-amylase, stir and evenly, after sustained reaction 60～120min, be warming up to 105～118 ℃, deactivation 60～120min obtains the enzymatic degradation of starch emulsion.
3. high temperature resistance treated starch fluid loss agent according to claim 1, is characterized in that,
Described starch is one or more in cereal starch, potato starch and legume starch;
Described phenolic compound is one or more in following chemical general formula material scope,
Described alkenyl amide is acrylamide, N, N-DMAA, N, N-diethyl acrylamide, N-ethylene vinyl amine, N-vinyl methylacetamide, N-vinyl ethyl acetamide, diacetone-acryloamide(DAA), N, one or more in N-methylene-bis the third ethernamine, N hydroxymethyl acrylamide;
Described olefin sulfonic acid is one or more among vinyl sulfonic acid, allyl sulphonic acid, styrene sulfonic acid, acryloyl-oxy butyl sulfonic acid, 2-acrylamido dodecyl sodium sulfonate, 2-acrylamido tetradecyl sulfonic acid, 2-acrylamido hexadecyl sulfonic acid, 2-acryloxy-2-methyl propane sulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid;
Described reduction substrate is methyl ethyl diketone; Described hydrogen acceptor substrate is H
2O
2.
4. high temperature resistance treated starch fluid loss agent according to claim 3, is characterized in that, R in described phenolic compound chemical general formula
1, R
2, R
3, R
4, R
6And R
8For H, OH, CH
3, CF
3, C
2H
5, C
2F
5, NH
2, NHCH
3, N (CH
3)
2, OCH
3, NHCOCH
3, Cl, Br, I; R
5And R
7For N
+(CH
3)
3, NO
2, CN, CONH
2, SO
3H, SO
3Na, SO
3K, CHO, COOH, COONa, COOK.
5. high temperature resistance treated starch fluid loss agent according to claim 1, is characterized in that,
Described starch is 5～10:1 with the molar mass ratio of phenolic compound;
The molar mass ratio of described phenolic compound, alkenyl amide and olefin sulfonic acid is 1～5:2～10:3～15.
6. the preparation method of a high temperature resistance treated starch fluid loss agent, is characterized in that, described method comprises:
Alkenyl amide and alkenyl sulphonate are dissolved in deionized water solvent, and be 6.0～8.0 with NaOH or the KOH aqueous solution adjusting lysate pH of 2.0wt%, obtaining concentration is 20.0wt%～50.0wt% mixed monomer solution;
Oil-phase solution and nonionogenic tenside are joined in reactor, and being uniformly mixed and obtaining having oleophilic hydrophil balance value HLB scope is 7.0～9.0 emulsion;
The enzymatic degradation of starch emulsion is joined in emulsion, and add phenolic compound, biological enzyme and reduction substrate, stir and obtain the microemulsion that oil/water volume ratio is 2～5:1;
Microemulsion slowly was warming up to 20～86 ℃ in 0.5～3.0 hour, and be that 20.0wt%～50.0wt% mixed monomer solution and molar weight are that the hydrogen acceptor substrate of 0.2～1.0 times of phenolic compound molar weight joins in the microemulsion reaction system by concentration, react and obtained the thick product of high temperature resistance treated starch fluid loss agent in 1.0～3.0 hours, then described thick product is obtained after precipitation, washing, extracting, vacuum-drying to high temperature resistance treated starch fluid loss agent.
7. the preparation method of high temperature resistance treated starch fluid loss agent according to claim 6, is characterized in that,
Described alkenyl sulphonate is olefin sulfonic acid to be configured to the solution of 15.0wt% in water, and is neutralized to pH=6.0～7.0 with the KOH solution of 50.0wt%, is placed under 20 ℃ of vacuum drying ovens to dry to constant weight to obtain;
The concentration of described nonionogenic tenside in oil-phase solution is 10.0wt%～20.0wt%;
The concentration of described biological enzyme in microemulsion is 0.005wt%～0.05wt%, and the molar weight of reduction substrate is alkenyl amide, olefin sulfonic acid and phenolic compound integral molar quantity 0.05～0.2 times.
8. the preparation method of high temperature resistance treated starch fluid loss agent according to claim 6, is characterized in that,
Described oil-phase solution is one or more in benzene, toluene, o-Xylol, silicone oil, white oil, kerosene, normal heptane, cyclohexane, normal hexane, octane-iso;
Described nonionogenic tenside is one or more in Determination of Polyoxyethylene Non-ionic Surfactants, polyol-based non-ionic surfactant, alkylol amide type nonionogenic tenside;
Described biological enzyme is one or more in plant peroxidases, animal peroxidase and fungi peroxidase.
9. the preparation method of high temperature resistance treated starch fluid loss agent according to claim 6, is characterized in that, described reduction substrate is methyl ethyl diketone; Described hydrogen acceptor substrate is H
2O
2.
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