CN102199222A - Amphiphilic starch and preparation method thereof - Google Patents
Amphiphilic starch and preparation method thereof Download PDFInfo
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- CN102199222A CN102199222A CN2010101332129A CN201010133212A CN102199222A CN 102199222 A CN102199222 A CN 102199222A CN 2010101332129 A CN2010101332129 A CN 2010101332129A CN 201010133212 A CN201010133212 A CN 201010133212A CN 102199222 A CN102199222 A CN 102199222A
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Abstract
The invention relates to an amphiphilic starch and a preparation method thereof. The preparation method comprises the following steps: carrying out hydrophilic modification on starch so as to obtain hydrophilic starch, wherein the molar ratio of the starch to alkali to a hydrophilic reagent is 1.0:(0.5-1.5):(1.0-3.0); and then carrying out hydrophobic modification on the hydrophilic starch serving as a raw material so as to obtain the amphiphilic starch, wherein the molar ratio of the a hydrophilic starch to alkali to a lyophobic reagent is 1.0:(0.2-2.5):(0.2-2.5). The hydrophobic starch prepared by the method has certain hydrophobicity, and the water-solubility of the hydrophobic starch is also obviously improved relatively. The amphiphilic starch can be used as a drilling fluid auxiliary; a drilling fluid added with the auxiliary has the advantages of good filter loss reduction property, good salt resistance and good temperature resistance; and the amphiphilic functional requirement of oil-gas storage layer protection on a plugging material is met, the defects that the use temperature of the traditional modified starch is low and the functionality of the traditional modified starch is poor are overcome, and the recontamination of the storage layer is reduced so as to improve the recovery efficiency of oil and gas.
Description
Technical field
The present invention relates to a kind of parents' starch and preparation method thereof, this technology is used in modified starch manufacturing enterprise, and the amphoteric starch product of Sheng Chaning then can be applicable to extensively industry and field such as papermaking, weaving, chemical industry, pharmacy, oil, environmental protection, agricultural and mining industry thus.
Background technology
The tradition treated starch mainly is to introduce hydrophilic radical in starch molecule, and the hydrophilic nmature of starch itself makes the single wetting ability of a product tool in addition.If on the starch molecule chain backbone, introduce hydrophobic grouping with hydrophobic property, can make starch molecule have " parents' structure ", this is the hydrophilic trunk-hydrophobic branched polymer tensio-active agent of a quasi-representative.Introduce lipophilic group can make starch character be improved significantly, have many new particular performances, as significant tackifying, heat-resistant salt-resistant, Stability Analysis of Structures, good biocompatibility, emulsification, solubilising etc.But be introduced separately into the hydrophobization starch that strong hydrophobic grouping obtains,, bring inconvenience, limited its range of application to product application because the introducing of hydrophobic grouping causes the decreased solubility of starch.By the hydrophobic modification water soluble starch, can not only obtain having the modified starch of certain hydrophobic performance, and its water-soluble also raising greatly, make product obtain better application performance.
Treated starch has been used for drilling fluid in the fifties in last century, China is used for additive for drilling fluid with treated starch and starts from the phase at the beginning of the eighties in last century.In recent years, China's grain yield constantly increases, and drilling fluid is swift and violent with the research and development of treated starch.Because modified starch series treatment agent raw material sources are abundant, low price, dehydration is fallen, anti sloughing effectiveness is good, its outstanding saline-alkaline tolerance has become salt solution and saturated salt-water drilling fluid high-quality fluid loss agent in addition, progressively becomes one of main treatment agent kind of drilling fluid.Treated starch is as additive for drilling fluid landing leak-off, tackify, stabilizing borehole and effect such as anti-collapse, but its shortcoming is a poor heat stability, is subjected to degradation by bacteria to produce CO
2Cause that bubble fermentation is smelly, the crosslinked drilling speed that causes of easy and drilling cuttings descends.In order fully to excavate starch property, the expanded application scope need be carried out modification to starch, is included in to introduce on the starch skeleton to have multiple functional group and side chain to improve the product temperature resistance, to fall leak-off, erosion resistant and solvability.
The present invention introduces hydrophilic radical and makes the starch dissolution increase on conventional starch molecule skeleton, introduce hydrophobic grouping again simultaneously and make it have certain hydrophobicity.It has good leak-off, anti-salt and the temperature resistance of falling as drilling fluid additive, overcomes the limitation of traditional modified starch to a certain extent, strengthens its reservoir protection performance.
Summary of the invention
The object of the invention provides a kind of preparation method of parents' starch.Feature is earlier starch to be carried out hydrophilic modifying to obtain hydrophilic starch, is that raw material carries out hydrophobic modification and obtains amphipathic starch with hydrophilic starch again.This parents' starch not only has certain hydrophobicity but also has good solvability.The object of the invention realizes by following measure:
The present invention relates to a kind of amphipathic starch and preparation method thereof, it is characterized in that introducing hydrophilic radical and hydrophobic grouping respectively on the starch molecule skeleton, it is hydrophilic and oil loving amphiphilic that the starch derivative that obtains is had simultaneously.
A kind of parents' starch of the present invention is characterized in that:
(1) adopting water-alcohol is reaction medium, and alkali is catalyzer, and halohydrocarbon or epoxide are hydrophilic reagent, and starch is carried out hydrophilic modification, obtain hydrophilic starch.
(2) be raw material with hydrophilic starch again, water-alcohol is reaction medium, and alkali is catalyzer, and aliphatics acyl chlorides or acid anhydrides are hydrophobization reagent, with hydrophilic starch reaction, obtain hydrophobization starch, i.e. amphipathic starch.
A kind of parents' starch of the present invention is characterized in that described starch is one or more in conventional corn, potato, cassava, wheat, the sweet potato.
A kind of parents' starch of the present invention, the introducing that it is characterized in that hydrophilic radical is that 20 ~ 80% alcoholic solutions are as reaction medium with volume fraction, the massfraction that starch accounts for total system is 5 ~ 35%, in starch emulsion, add a certain amount of alkali earlier in 20 ~ 30 ℃ of following quaternization 30min, be warming up to 35 ~ 75 ℃ then and add hydrophilic reagent and remaining alkali continuation reaction 100 ~ 300min again, reaction finishes to drip a certain amount of protonic acid solution is neutralized to neutrality, filter, wash, 60 ℃ of vacuum-drying 24h, crushing screening gets hydrophilic starch.
A kind of parents' starch of the present invention is characterized in that hydrophilic radical is halohydrocarbon or epoxide, and the part of hydroxyl of starch polymer is replaced by carboxyl or hydroxyalkyl.
A kind of parents' starch of the present invention, the introducing that it is characterized in that hydrophilic radical be with certain volume fractional alcoholic solution as reaction medium, its alcohol may be one or more in methyl alcohol, ethanol, the Virahol.
A kind of amphipathic starch of the present invention is characterized in that starch, alkali, hydrophilic reagent are 1.0: 0.1 ~ 5.0: 1.0 ~ 10.0(preferred 1.0: 0.5 ~ 1.5: 1.0 ~ 3.0 according to mol ratio).Wherein, the molar weight of starch is pressed dehydrated glucose unit calculating.
A kind of parents' starch of the present invention, the introducing that it is characterized in that hydrophobic grouping are to be raw material with hydrophilic starch, carry out in water-pure reaction medium.The massfraction that hydrophilic starch accounts for total system is 5 ~ 25%, in starch emulsion, add a certain amount of alkali earlier in 20 ~ 30 ℃ of following quaternization 30min, be warming up to 25 ~ 55 ℃ then and add hydrophobic agents and remaining alkali continuation reaction 60 ~ 180min, reaction finishes to drip a certain amount of protonic acid solution is neutralized to neutrality, product precipitates in ethanol separates out, filter, wash, 60 ℃ of vacuum-drying 24h, crushing screening gets parents' starch.
A kind of parents' starch of the present invention is characterized in that hydrophobic grouping is aliphatics acyl chlorides or acid anhydrides, and the part of hydroxyl of starch polymer is replaced by chain alkyl or phenyl ring.
A kind of parents' starch of the present invention, the introducing that it is characterized in that hydrophobic grouping are to be reaction medium with certain volume fractional alcoholic solution, and its alcohol may be one or more mixing in methyl alcohol, ethanol, the Virahol.
A kind of amphipathic starch of the present invention is characterized in that hydrophilic starch, alkali, hydrophobic agents are preferred 1.0: 0.2 ~ 2.5:0.2 of 1.0: 0.1 ~ 25:0.1 ~ 25(~ 2.5 according to mol ratio).Wherein, hydrophilic starch calculates by the glucose unit that is connected to hydrophilic radical.
A kind of parents' starch of the present invention is characterized in that hydrophilic radical and hydrophobic grouping introduce respectively, can control the size of hydrophilic substitution value and hydrophobic substitution value respectively, guarantees that it is amphiphilic.
A kind of parents' starch of the present invention is characterized in that prepared parents' starch has 100 ~ 200 ℃ high-temperature stability.
A kind of parents' starch of the present invention, it is water-soluble to it is characterized in that prepared parents' starch has, and the water filter loss of its drilling fluid is less than 10 ml/30 minute.
A kind of parents' starch of the present invention is characterized in that NaCl, the CaCl of prepared parents' starch at 1000 ~ 100000mg/L
2Perhaps has very high stability in their blended salt solution.
A kind of parents' starch of the present invention is characterized in that the hydrocarbon flow duct of the protection of shutoff when prepared parents' starch is used to bore out hydrocarbon zone reservoir, stops water intrusion and damages hydrocarbon zone.And when hydrocarbon zone is produced, do not need de-plugging just can make hydrocarbon flow enter recovery well smoothly, improve the rate of oil and gas recovery.
Embodiment
Embodiment 1
In volume fraction is in the 80% 1458.0ml ethanolic soln, adds 40.0g NaOH solid and stirs dissolving fully, adds the 162.0g W-Gum, stirs into starch emulsion and pours in the 2.0L there-necked flask, in 30 ℃ of stirred in water bath alkalization 30min.Take by weighing the 103.9g hydrophilic reagent and be dissolved in the ethanol, it is soluble in water to take by weighing 44.0g NaOH, and both hybrid reactions generate the sodium solution of hydrophilic reagent, are poured into the there-necked flask bath temperature and are elevated to 55 ℃, add remaining 12.8g NaOH, etherification reaction 140min.Reaction finishes with the Glacial acetic acid neutralization, filter, washing, dry, pulverize hydrophilic starch powder.Recording hydrophilic substitution value with the copper sulfate volumetry is 1.061.Its solvability and hydrophobicity see Table 1.
Embodiment 2
Take by weighing 2.0g sodium hydroxide and be added in the ethanolic soln of 15% 1110.9ml, add the hydrophilic starch of 123.4g, pour in the there-necked flask of 2.0L in 25 ℃ of stirred in water bath alkalization 20min; Add the 11.6ml hydrophobic agents, be warming up to 30 ℃, add 5.0mol/L sodium hydroxide solution 10.0ml.Reaction finishes with the Glacial acetic acid neutralization, and product precipitates in ethanol, washing, filter, dry, pulverize parents' starch powder.Adopting ultraviolet spectrophotometer method to measure hydrophobic substitution value is 0.1071.Its solvability and hydrophobicity see Table 1.
Embodiment 3
Take by weighing 5.0g sodium hydroxide and be added in the ethanolic soln of 15% 1110.9ml, add the hydrophilic starch of 123.4g, pour in the there-necked flask of 2.0L in 25 ℃ of stirred in water bath alkalization 20min; Add the 29.0ml hydrophobic agents, be warming up to 30 ℃, add 5.0mol/L sodium hydroxide solution 25.0ml.Reaction finishes with the Glacial acetic acid neutralization, and product precipitates in ethanol, washing, filter, dry, pulverize parents' starch powder.Adopting ultraviolet spectrophotometer method to measure hydrophobic substitution value is 0.1594.Its solvability and hydrophobicity see Table 1.
Embodiment 4
Take by weighing 8.0g sodium hydroxide and be added in the ethanolic soln of 15% 1110.9ml, add the hydrophilic starch of 123.4g, pour in the there-necked flask of 2.0L in 25 ℃ of stirred in water bath alkalization 20min; Add the 46.4ml hydrophobic agents, be warming up to 30 ℃, add 5.0mol/L sodium hydroxide solution 40.0ml.Reaction finishes with the Glacial acetic acid neutralization, and product precipitates in ethanol, washing, filter, dry, pulverize parents' starch powder.Adopting ultraviolet spectrophotometer method to measure hydrophobic substitution value is 0.3056.Its solvability and hydrophobicity see Table 1.
Embodiment 5
Take by weighing 10.0g sodium hydroxide and be added in the ethanolic soln of 15% 1110.9ml, add the hydrophilic starch of 123.4g, pour in the there-necked flask of 2.0L in 25 ℃ of stirred in water bath alkalization 20min; Add the 58.0ml hydrophobic agents, be warming up to 30 ℃, add 5mol/L sodium hydroxide solution 50.0ml.Reaction finishes with the Glacial acetic acid neutralization, and product precipitates in ethanol, washing, filter, dry, pulverize parents' starch powder.It is 0.5285 that the method for employing ultraviolet spectrophotometer is measured hydrophobic substitution value.Its solvability and hydrophobicity see Table 1.
Embodiment 6
Take by weighing 15.0g sodium hydroxide and be added in the ethanolic soln of 15% 1110.9ml, add the hydrophilic starch of 123.4g, pour in the there-necked flask of 2.0 L in 25 ℃ of stirred in water bath alkalization 20min; Add the 87.0ml hydrophobic agents, be warming up to 30 ℃, add 5.0mol/L sodium hydroxide solution 75.0ml.Reaction finishes with the Glacial acetic acid neutralization, and product precipitates in ethanol, washing, filter, dry, pulverize parents' starch.It is 0.7091 that the method for employing ultraviolet spectrophotometer is measured hydrophobic substitution value.Its solvability and hydrophobicity see Table 1.
Embodiment 7
Take by weighing 25.0g sodium hydroxide and be added in the ethanolic soln of 15% 1110.9ml, add the hydrophilic starch of 123.4g, pour in the there-necked flask of 2.0L in 25 ℃ of stirred in water bath alkalization 20min; Add the 145.0ml hydrophobic agents, be warming up to 30 ℃, add 5.0mol/L sodium hydroxide solution 125.0ml.Reaction finishes with the Glacial acetic acid neutralization, and product precipitates in ethanol, washing, filter, dry, pulverize parents' starch powder.Adopting ultraviolet spectrophotometer method to measure hydrophobic substitution value is 0.8522.Its solvability and hydrophobicity see Table 1.
Embodiment 8-23
Preparation parents' starch solution of 3.0% is packed digestion tank into behind room temperature, 120 ℃, 140 ℃, 160 ℃ following rolling 16h, be cooled to room temperature after, 8000 r/min height stir 10min, with rotation six fast viscometer viscosimetrics.The results are shown in Table 2.
Embodiment 24-51
Parents' starch solution of preparation 4.0% adds certain mass fractional NaCl, and the 8000r/min height stirs 10min, with rotation six fast viscometer viscosimetrics.The results are shown in Table 3.
Embodiment 52-79
Parents' starch solution of preparation 4.0% adds certain mass fractional CaCl
2, the 8000r/min height stirs 10min, with rotation six fast viscometer viscosimetrics.The results are shown in Table 4.
Embodiment 80-94
The yellow soda ash of adding 0.3% in 6.0% polynite base slurry, the 8000r/min height stirs the 20min aquation and disperses 24h, add a certain amount of parents' starch, the 8000r/min height stirs 5min, the 8000r/min height stirs 5min after placing maintenance 24h under the room temperature, with the filter loss of middle pressure filter press mensuration mud, with rotation six fast viscometer viscosimetrics.The results are shown in Table 5.
Embodiment 95-112
The yellow soda ash of adding 0.3% in 6.0% polynite base slurry, the 8000r/min height stirs the 20min aquation and disperses 24h, parents' starch of adding 2.0%, add a certain amount of NaCl, high-speed stirring 5min, 8000r/min high-speed stirring 5min after placing maintenance 24h under the room temperature is with the filter loss of filter press mensuration mud, with the viscosity of rotary viscosity design determining mud.The results are shown in Table 6.
Embodiment 113-130
The yellow soda ash of adding 0.3% in 6.0% polynite base slurry, the 8000r/min height stirs the 20min aquation and disperses 24h, adds parents' starch of 2.0%, adds a certain amount of CaCl
2, high-speed stirring 5min, the 8000r/min height stirs 5min under room temperature after placing maintenance 24h under the room temperature, with the filter loss of filter press mensuration mud, with the viscosity of rotary viscosity design determining mud.The results are shown in Table 7.
Embodiment 131 – 142
The yellow soda ash of adding 0.3% in 6.0% polynite base slurry, the 8000r/min height stirs the 20min aquation and disperses 24h, parents' starch of adding 2.0%, height stirs 5min, digestion tank pack into behind room temperature, 120 ℃, 140 ℃, 160 ℃ following rolling 16h, the 8000r/min height stirs 10min after being cooled to room temperature, with the filter loss of filter press mensuration mud, with the viscosity of rotary viscosity design determining mud.The results are shown in Table 8.
Comparative example 1
Ative starch (starch of non-modified), its solvability and hydrophobicity see Table 1.
Comparative example 2
Take by weighing 10.0g sodium hydroxide and be added in the ethanolic soln of 15% 729.0ml, add the 81.0g W-Gum, pour in the there-necked flask of 1.0L in 25 ℃ of stirred in water bath alkalization 20min; Add the 29.0ml hydrophobic agents, be warming up to 30 ℃, add 5.0mol/L sodium hydroxide solution 50.0ml.Reaction finishes with the Glacial acetic acid neutralization, and product precipitates in ethanol, washing, filter, dry, pulverize product.Adopting ultraviolet spectrophotometer method to measure hydrophobic substitution value is 0.2110.
Comparative example 3-8
A kind of reservoir protection starch according to the literature.Add 40.0g wilkinite and 6.0g yellow soda ash in 1.0L water, height stirs 20min, places maintenance 24h under the room temperature and obtains testing the base slurry, adds 2.0% modified starch, adds certain mass fractional NaCl, and the 8000r/min height stirs 10min.The 8000r/min height stirs 5min under room temperature after placing maintenance 24h under the room temperature, with the filter loss of filter press mensuration mud, with the viscosity of rotary viscosity design determining mud.The results are shown in Table 6.
Comparative example 9-13
A kind of reservoir protection starch according to the literature.Add 40.0g wilkinite and 6.0g yellow soda ash in 1.0L water, height stirs 20min, places maintenance 24h under the room temperature and obtains testing the base slurry, adds 2.0% modified starch, adds certain mass fractional CaCl
2, stir 10min at the 8000r/min height.The 8000r/min height stirs 5min under room temperature after placing maintenance 24 h under the room temperature, with the filter loss of filter press mensuration mud, with the viscosity of rotary viscosity design determining mud.The results are shown in Table 7.
Comparative example 14-17
A kind of reservoir protection starch according to the literature.In 1.0L water, add 40.0g wilkinite and 6.0g yellow soda ash, high-speed stirring 20min, place maintenance 24h under the room temperature and obtain testing the base slurry, the modified starch of adding 2.0%, height stirs 5min, packs digestion tank into behind 25 ℃, 90 ℃, 110 ℃, 130 ℃ following rolling 16h, be cooled to room temperature after the 8000r/min height stir 10min, with the filter loss of filter press mensuration mud, with the viscosity of rotary viscosity design determining mud.The results are shown in Table 8.
Table 1 substitution value is to modified starch solvability and hydrophobic influence
| Comparative example | Solvability | Hydrophobic substitution value | Oil-absorption(number)/ml/100g | Remarks |
| 1 | Good | 0.000 | 32.0 | Hydrophilic starch |
| 2 | Good | 0.1071 | 33.0 | Parents' starch |
| 3 | Good | 0.1594 | 37.0 | Parents' starch |
| 4 | Good | 0.3056 | 36.0 | Parents' starch |
| 5 | Better | 0.5285 | 33.0 | Parents' starch |
| 6 | Better | 0.7091 | 32.5 | Parents' starch |
| 7 | Difference | 0.8522 | 32.0 | Parents' starch |
| Comparative example 1 | Difference | 0.000 | 69.0 | Ative starch |
Table 2 temperature is to the influence of modified starch solution apparent viscosity
| Comparative example | Substitution value | Apparent viscosity/mp.s | Temperature/℃ |
| 8 | 0.1071 | 63.0 | Room temperature |
| 9 | 0.1071 | 57.0 | 120.0 |
| 10 | 0.1071 | 41.0 | 140.0 |
| 11 | 0.1071 | 33.0 | 160.0 |
| 12 | 0.1594 | 79.0 | Room temperature |
| 13 | 0.1594 | 58.0 | 120.0 |
| 14 | 0.1594 | 47.0 | 140.0 |
| 15 | 0.1594 | 36.0 | 160.0 |
| 16 | 0.3056 | 61.0 | Room temperature |
| 17 | 0.3056 | 43.0 | 120.0 |
| 18 | 0.3056 | 35.0 | 140.0 |
| 19 | 0.3056 | 30.0 | 160.0 |
| 20 | 0.5285 | 46.0 | Room temperature |
| 21 | 0.5285 | 40.0 | 120.0 |
| 22 | 0.5285 | 33.0 | 140.0 |
| 23 | 0.5285 | 22.0 | 160.0 |
Table 3 NaCl content is to the influence of modified starch solution apparent viscosity
| Comparative example | Substitution value | NaCl/wt% | Apparent viscosity/mp.s |
| 24 | 0.1071 | 0.0 | 85.0 |
| 25 | 0.1071 | 0.5 | 69.0 |
| 26 | 0.1071 | 1.0 | 61.0 |
| 27 | 0.1071 | 2.0 | 52.0 |
| 28 | 0.1071 | 3.0 | 47.0 |
| 29 | 0.1071 | 5.0 | 43.0 |
| 30 | 0.1071 | 7.0 | 41.0 |
| 31 | 0.1594 | 0.0 | 95.0 |
| 32 | 0.1594 | 0.5 | 70.0 |
| 33 | 0.1594 | 1.0 | 63.0 |
| 34 | 0.1594 | 2.0 | 49.0 |
| 35 | 0.1594 | 3.0 | 48.0 |
| 36 | 0.1594 | 5.0 | 42.0 |
| 37 | 0.1594 | 7.0 | 37.0 |
| 38 | 0.3056 | 0.0 | 73.0 |
| 39 | 0.3056 | 0.5 | 55.0 |
| 40 | 0.3056 | 1.0 | 47.0 |
| 41 | 0.3056 | 2.0 | 40.0 |
| 42 | 0.3056 | 3.0 | 38.0 |
| 43 | 0.3056 | 5.0 | 36.0 |
| 44 | 0.3056 | 7.0 | 33.0 |
| 45 | 0.5285 | 0.0 | 65.0 |
| 46 | 0.5285 | 0.5 | 55.0 |
| 47 | 0.5285 | 1.0 | 51.0 |
| 48 | 0.5285 | 2.0 | 48.0 |
| 49 | 0.5285 | 3.0 | 43.0 |
| 50 | 0.5285 | 5.0 | 30.0 |
| 51 | 0.5285 | 7.0 | 25.0 |
Table 4 CaCl
2Content is to the influence of modified starch solution apparent viscosity
| Comparative example | Substitution value | CaCl 2/wt% | Apparent viscosity/mp.s |
| 52 | 0.1071 | 0.00 | 85.0 |
| 53 | 0.1071 | 0.05 | 77.0 |
| 54 | 0.1071 | 0.10 | 66.0 |
| 55 | 0.1071 | 0.15 | 62.0 |
| 56 | 0.1071 | 0.20 | 56.0 |
| 57 | 0.1071 | 0.30 | 47.0 |
| 58 | 0.1071 | 0.50 | 35.0 |
| 59 | 0.1594 | 0.00 | 95.0 |
| 60 | 0.1594 | 0.05 | 86.0 |
| 61 | 0.1594 | 0.10 | 80.0 |
| 62 | 0.1594 | 0.15 | 77.0 |
| 63 | 0.1594 | 0.20 | 73.0 |
| 64 | 0.1594 | 0.30 | 61.0 |
| 65 | 0.1594 | 0.50 | 37.0 |
| 66 | 0.3056 | 0.00 | 73.0 |
| 67 | 0.3056 | 0.05 | 72.0 |
| 68 | 0.3056 | 0.10 | 61.0 |
| 69 | 0.3056 | 0.15 | 55.0 |
| 70 | 0.3056 | 0.20 | 53.0 |
| 71 | 0.3056 | 0.30 | 43.0 |
| 72 | 0.3056 | 0.50 | 33.0 |
| 73 | 0.5285 | 0.00 | 65.0 |
| 74 | 0.5285 | 0.05 | 62.0 |
| 75 | 0.5285 | 0.10 | 56.0 |
| 76 | 0.5285 | 0.15 | 52.0 |
| 77 | 0.5285 | 0.20 | 46.0 |
| 78 | 0.5285 | 0.30 | 38.0 |
| 79 | 0.5285 | 0.50 | 30.0 |
Table 5 modified starch dosage is to the influence of drilling fluid apparent viscosity and filter loss
| Comparative example | Substitution value | Starch dosage/% | Apparent viscosity/mp.s | Filter loss/ml |
| 80 | 0.1071 | 0.0 | 22.0 | 14.8 |
| 81 | 0.1071 | 0.5 | 435.0 | 8.0 |
| 82 | 0.1071 | 1.5 | 73.0 | 6.4 |
| 83 | 0.1071 | 2.5 | 122.0 | 6.0 |
| 84 | 0.1071 | 3.5 | 56.0 | 5.4 |
| 85 | 0.1594 | 0.0 | 22.0 | 14.8 |
| 86 | 0.1594 | 0.5 | 43.0 | 8.4 |
| 87 | 0.1594 | 1.5 | 94.0 | 6.1 |
| 88 | 0.1594 | 2.5 | 137.0 | 4.5 |
| 89 | 0.1594 | 3.5 | 190.0 | 4.0 |
| 90 | 0.3056 | 0.0 | 22.0 | 14.8 |
| 91 | 0.3056 | 0.5 | 40.0 | 8.6 |
| 92 | 0.3056 | 1.5 | 76.0 | 6.8 |
| 93 | 0.3056 | 2.5 | 115.0 | 6.4 |
| 94 | 0.3056 | 3.5 | 155.0 | 5.5. |
Table 6 NaCl content is to the influence of drilling fluid apparent viscosity and filter loss
| ? | Substitution value | NaCl/wt% | Apparent viscosity/mp.s | Filter loss/ml |
| Embodiment 95 | 0.1071 | 0.0 | 92.0 | 6.1 |
| Embodiment 96 | 0.1071 | 1.0 | 66.0 | 5.6 |
| Embodiment 97 | 0.1071 | 2.0 | 63.0 | 5.2 |
| Embodiment 98 | 0.1071 | 3.0 | 60.0 | 6.4 |
| Embodiment 99 | 0.1071 | 5.0 | 55.0 | 8.0 |
| Embodiment 100 | 0.1071 | 7.0 | 52.0 | 8.8 |
| Embodiment 101 | 0.1594 | 0.0 | 115.0 | 4.8 |
| Embodiment 102 | 0.1594 | 1.0 | 91.0 | 4.6 |
| Embodiment 103 | 0.1594 | 2.0 | 79.0 | 5.6 |
| Embodiment 104 | 0.1594 | 3.0 | 66.0 | 5.8 |
| Embodiment 105 | 0.1594 | 5.0 | 61.0 | 6.0 |
| Embodiment 106 | 0.1594 | 7.0 | 59.0 | 6.5 |
| Embodiment 107 | 0.3056 | 0.0 | 89.0 | 5.0 |
| Embodiment 108 | 0.3056 | 1.0 | 66.0 | 4.7 |
| Embodiment 109 | 0.3056 | 2.0 | 62.0 | 4.9 |
| Embodiment 110 | 0.3056 | 3.0 | 57.0 | 5.9 |
| Embodiment 111 | 0.3056 | 5.0 | 52.0 | 6.1 |
| Embodiment 112 | 0.3056 | 7.0 | 51.0 | 6.4 |
| Comparative example 3 | -- | 0.0 | 25.0 | 22.4 |
| Comparative example 4 | -- | 1.0 | 33.0 | 23.2 |
| Comparative example 5 | -- | 2.0 | 24.0 | 25.0 |
| Comparative example 6 | -- | 3.0 | 22.0 | 28.0 |
| Comparative example 7 | -- | 5.0 | 16.0 | 32.4 |
| Comparative example 8 | -- | 7.0 | 10.0 | 38.6 |
Table 7 CaCl
2Content is to the influence of drilling fluid apparent viscosity and filter loss
| ? | Substitution value | CaCl 2/wt% | Apparent viscosity/mp.s | Filter loss/ml |
| Embodiment 113 | 0.1071 | 0.0 | 92.0 | 6.1 |
| Embodiment 114 | 0.1071 | 0.1 | 96.0 | 5.0 |
| Embodiment 115 | 0.1071 | 0.2 | 84.0 | 5.4 |
| Embodiment 116 | 0.1071 | 0.3 | 79.0 | 5.9 |
| Embodiment 117 | 0.1071 | 0.5 | 68.0 | 6.2 |
| Embodiment 118 | 0.1071 | 0.7 | 57.0 | 6.5 |
| Embodiment 119 | 0.1594 | 0.0 | 115.0 | 4.8 |
| Embodiment 120 | 0.1594 | 0.1 | 110.0 | 4.6 |
| Embodiment 121 | 0.1594 | 0.2 | 113.0 | 4.7 |
| Embodiment 122 | 0.1594 | 0.3 | 116.0 | 4.8 |
| Embodiment 123 | 0.1594 | 0.5 | 95.0 | 5.2 |
| Embodiment 124 | 0.1594 | 0.7 | 65.0 | 6.0 |
| Embodiment 125 | 0.3056 | 0.0 | 89.0 | 5.0 |
| Embodiment 126 | 0.3056 | 0.1 | 96.0 | 4.5 |
| Embodiment 127 | 0.3056 | 0.2 | 86.0 | 4.6 |
| Embodiment 128 | 0.3056 | 0.3 | 81.0 | 4.9 |
| Embodiment 129 | 0.3056 | 0.5 | 63.0 | 5.1 |
| Embodiment 130 | 0.3056 | 0.7 | 48.0 | 5.4 |
| Comparative example 9 | -- | 0.0 | 25.0 | 22.4 |
| Comparative example 10 | -- | 0.1 | 29.0 | 20.5 |
| Comparative example 11 | -- | 0.3 | 35.0 | 21.6 |
| Comparative example 12 | -- | 0.5 | 32.0 | 23.7 |
| Comparative example 13 | -- | 0.7 | 20.0 | 31.2 |
Table 8 temperature is to the influence of drilling fluid apparent viscosity and filter loss
| ? | Substitution value | Apparent viscosity/mp.s | Filter loss/ml | Temperature/℃ |
| Embodiment 131 | 0.1071 | 92.0 | 6.1 | Room temperature |
| Embodiment 132 | 0.1071 | 71.0 | 4.8 | 120.0 |
| Embodiment 133 | 0.1071 | 71.0 | 4.7 | 140.0 |
| Embodiment 134 | 0.1071 | 48.0 | 4.5 | 160.0 |
| Embodiment 135 | 0.1594 | 115.0 | 4.8 | Room temperature |
| Embodiment 136 | 0.1594 | 80.0 | 5.6 | 120.0 |
| Embodiment 137 | 0.1594 | 66.0 | 5.3 | 140.0 |
| Embodiment 138 | 0.1594 | 68.0 | 3.5 | 160.0 |
| Embodiment 139 | 0.3056 | 89.0 | 5.0 | Room temperature |
| Embodiment 140 | 0.3056 | 70.0 | 4.7 | 120.0 |
| Embodiment 141 | 0.3056 | 91.0 | 4.3 | 140.0 |
| Embodiment 142 | 0.3056 | 55.0 | 7.2 | 160.0 |
| Comparative example 14 | -- | 25.0 | 22.4 | 25.0 |
| Comparative example 15 | -- | 29.0 | 20.6 | 90.0 |
| Comparative example 16 | -- | 33.0 | 20.3 | 110.0 |
| Comparative example 17 | -- | 46.0 | 18.6 | 130.0 |
Claims (11)
1. the present invention relates to a kind of amphipathic starch and preparation method thereof, it is characterized in that introducing hydrophilic radical and hydrophobic grouping respectively on the dehydrated glucose unit ring of starch molecule chain backbone, the starch derivative of gained is possess hydrophilic property and oil loving amphiphilic simultaneously.
Described a kind of amphipathic starch, adopt following two reactions steps to obtain hydrophilic and lipophilicity respectively:
(1) at first, water-alcohol is reaction medium, and alkali is catalyzer, is hydrophilization reagent and starch reaction with halohydrocarbon or epoxide, obtains wetting ability starch;
(2) secondly, be raw material with hydrophilic starch, water-alcohol is reaction medium, and alkali is catalyzer, is hydrophobization reagent and this hydrophilic starch reaction with aliphatics acyl chlorides or acid anhydrides, obtains hydrophobicity starch, i.e. amphipathic starch.
According to a kind of parents' starch of above-mentioned two reactions steps preparation, its concrete experimental technique is as follows:
At first, in introducing the hydrophilic radical reaction, be that 20 ~ 80% alcoholic solution is a reaction medium with volume fraction, it is that 5 ~ 35% starch forms starch emulsion with accounting for total system massfraction.In starch emulsion, add a certain amount of alkali quaternization 30min in 20 ~ 30 ℃ of water-baths earlier, be warming up to 35 ~ 75 ℃ then and add hydrophilic reagent and remaining alkali continuation reaction 100 ~ 300min, reaction finishes to drip a certain amount of protonic acid solution is neutralized to neutrality, through filtering, washing and 60 ℃ of vacuum-drying 24h, crushing screening gets hydrophilic starch powder.
Secondly, be raw material with the hydrophilic starch of gained, hydrophilic starch accounts for total system massfraction 5 ~ 25% in water-pure reaction medium, form starch emulsion.Then, in starch emulsion, add a certain amount of alkali quaternization 20min in 20 ~ 30 ℃ of water-baths, be warming up to 25 ~ 55 ℃ again and add hydrophobic agents and residue alkali continuation reaction 60 ~ 180min.Reaction drips a certain amount of protonic acid solution is neutralized to neutrality after finishing, and product precipitates in ethanol to be separated out, filter, washs and 60 ℃ of vacuum-drying 24h, and crushing screening gets parents' starch powder.
2. according to right 1 described a kind of amphipathic starch, it is characterized in that described starch material is a kind of or any two kinds mixture in conventional corn, potato, cassava, wheat, the sweet potato.
3. according to right 1 described a kind of amphipathic starch, it is characterized in that adopting hydrophilic reagent such as chloric ethane, chloracetic acid, oxyethane, propylene oxide or the chloro ethanol of band hydrophilic radical, with the hydroxyl generation substitution reaction of starch polymer.
4. according to right 1 described a kind of amphipathic starch, it is characterized in that hydrophilic radical or hydrophobic grouping, all in the alcoholic solution medium, react that pure reagent is a kind of in methyl alcohol, ethanol, the Virahol or they mixture arbitrarily.
5. according to right 1 described a kind of amphipathic starch, it is characterized in that starch, alkali, hydrophilic reagent are 1.0: 0.1 ~ 5.0: 1.0 ~ 10.0(preferred 1.0: 0.5 ~ 1.5: 1.0 ~ 3.0 according to mol ratio).Wherein, the molar weight of starch is pressed dehydrated glucose unit calculating.
6. according to right 1 described a kind of amphipathic starch, it is characterized in that hydrophobic grouping is formyl chloride, Acetyl Chloride 98Min., propionyl chloride, different propionyl chloride, butyryl chloride, Benzoyl chloride, diacetyl oxide, propionic anhydride, maleic anhydride or any two kinds of mixing, with the hydroxyl generation substitution reaction of starch polymer.
7. according to right 1 described a kind of amphipathic starch, it is characterized in that hydrophilic starch, alkali, hydrophobic agents are preferred 1.0: 0.2 ~ 2.5:0.2 of 1.0: 0.1 ~ 25:0.1 ~ 25(~ 2.5 according to mol ratio).Wherein, hydrophilic starch calculates according to the dehydrated glucose unit that is connected to hydrophilic radical.
8. according to right 1 described a kind of amphipathic starch, it is characterized in that prepared parents' starch has 100 ~ 200 ℃ high-temperature stability.
9. according to right 1 described a kind of amphipathic starch, it is water-soluble to it is characterized in that prepared parents' starch has, and the water filter loss of its drilling fluid was less than 10ml/30 minute.
10. according to right 1 described a kind of amphipathic starch, it is characterized in that NaCl, the CaCl of prepared parents' starch at 1000 ~ 100000mg/L
2Perhaps has very high stability in their blended salt solution.
11. according to right 1 described a kind of amphipathic starch, it is characterized in that the hydrocarbon flow duct of the protection of shutoff when prepared parents' starch is used to bore out hydrocarbon zone reservoir, stop water intrusion and damage hydrocarbon zone.And when hydrocarbon zone is produced, do not need de-plugging just can make hydrocarbon flow enter recovery well smoothly, improve the rate of oil and gas recovery.
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| CN103509125A (en) * | 2012-06-21 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method for hydrophobically modified carboxymethyl starch used for drilling fluid |
| CN104558216A (en) * | 2013-10-27 | 2015-04-29 | 中国石油化工集团公司 | Kneading preparation method and application method of high-hydrophobicity modified starch |
| CN104559948A (en) * | 2013-10-27 | 2015-04-29 | 中国石油化工集团公司 | Degradable fluid loss additive for oil-base drilling fluids and preparation method thereof |
| CN104710967A (en) * | 2013-12-17 | 2015-06-17 | 中国石油化工集团公司 | Self-plugging releasing temperature resistant temporary plugging agent used for water-based drilling fluid and preparation method thereof |
| CN106674362A (en) * | 2016-11-21 | 2017-05-17 | 华南理工大学 | Method for preparing paraphthaloyl chloride crosslinked starch by using ethanol solvent |
| CN107459581A (en) * | 2017-08-30 | 2017-12-12 | 广州市高士实业有限公司 | A kind of amphiphilic composite modified starch derivative and preparation method thereof |
| CN108404887A (en) * | 2018-04-24 | 2018-08-17 | 浙江虹达特种橡胶制品有限公司 | A method of sorbing material is made by high molecular material |
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| CN103509125B (en) * | 2012-06-21 | 2016-04-20 | 中国石油化工股份有限公司 | The drilling fluid preparation method of hydrophobically modified carboxy methyl starch |
| CN104558216A (en) * | 2013-10-27 | 2015-04-29 | 中国石油化工集团公司 | Kneading preparation method and application method of high-hydrophobicity modified starch |
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| CN106674362A (en) * | 2016-11-21 | 2017-05-17 | 华南理工大学 | Method for preparing paraphthaloyl chloride crosslinked starch by using ethanol solvent |
| CN107459581A (en) * | 2017-08-30 | 2017-12-12 | 广州市高士实业有限公司 | A kind of amphiphilic composite modified starch derivative and preparation method thereof |
| CN109971439A (en) * | 2017-12-28 | 2019-07-05 | 中国石油化工股份有限公司 | A kind of drilling fluid graft modified starch anti-sloughing agent and preparation method thereof |
| CN109971439B (en) * | 2017-12-28 | 2021-08-31 | 中国石油化工股份有限公司 | Graft modified starch anti-sloughing agent for drilling fluid and preparation method thereof |
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