CN115873140A - Preparation method of modified starch fluid loss additive for drilling fluid - Google Patents
Preparation method of modified starch fluid loss additive for drilling fluid Download PDFInfo
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- CN115873140A CN115873140A CN202111168216.5A CN202111168216A CN115873140A CN 115873140 A CN115873140 A CN 115873140A CN 202111168216 A CN202111168216 A CN 202111168216A CN 115873140 A CN115873140 A CN 115873140A
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- 229920000881 Modified starch Polymers 0.000 title claims abstract description 26
- 238000005553 drilling Methods 0.000 title claims abstract description 22
- 239000004368 Modified starch Substances 0.000 title claims abstract description 21
- 239000012530 fluid Substances 0.000 title claims abstract description 21
- 235000019426 modified starch Nutrition 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000654 additive Substances 0.000 title claims description 15
- 230000000996 additive effect Effects 0.000 title claims description 15
- 229920002472 Starch Polymers 0.000 claims abstract description 32
- 235000019698 starch Nutrition 0.000 claims abstract description 32
- 239000008107 starch Substances 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 23
- 238000006266 etherification reaction Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000003607 modifier Substances 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000000839 emulsion Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000007873 sieving Methods 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 229920002261 Corn starch Polymers 0.000 claims abstract 2
- 239000008120 corn starch Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 5
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- IWEQUOTXTVDJTH-UHFFFAOYSA-M 3,3-dihydroxypropyl-dimethyl-(trichloromethyl)azanium chloride Chemical compound [Cl-].ClC([N+](C)(C)CCC(O)O)(Cl)Cl IWEQUOTXTVDJTH-UHFFFAOYSA-M 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 3
- 229940106681 chloroacetic acid Drugs 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- AZSFNUJOCKMOGB-UHFFFAOYSA-K cyclotriphosphate(3-) Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-K 0.000 claims description 2
- 229940005740 hexametaphosphate Drugs 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 8
- 239000002002 slurry Substances 0.000 abstract description 5
- 238000005189 flocculation Methods 0.000 abstract description 4
- 230000016615 flocculation Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 239000000725 suspension Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 2
- 230000000903 blocking effect Effects 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a preparation method of a modified starch filtrate reducer for drilling fluid, which comprises the following steps: 1) And (3) crosslinking: preparing corn starch with low sulfur content into starch emulsion with the concentration of 30-50%, heating to 40-60 ℃, adding a first modifier with the mass of 0.05-1% of the dry basis weight of the starch, keeping the temperature, stirring for 1-2 hours in a closed manner, centrifuging and drying; 2) Alkalization: adding a pH regulator, and reacting for 1-2 hours at 50-55 ℃; 3) Etherification: adding a second modifier for etherification treatment for 1-2 h, and then drying and sieving to obtain a finished product. According to the invention, the starch is subjected to compound modification according to the steps of crosslinking, alkalization and etherification, so that the temperature resistance of the compound modified starch can reach 127-149 ℃, the gelatinization temperature of the product is increased, the good suspension capacity is still maintained at high temperature, the blocking capacity is improved by uniformly dispersing solid particles in slurry, the solubility and flocculation of the starch are improved by etherification treatment, and the starch has proper viscosity after high-temperature gelatinization and can effectively control the filtration loss of the water-based drilling fluid with good compatibility.
Description
Technical Field
The invention relates to the field of petroleum drilling, in particular to a preparation method of a modified starch fluid loss additive for drilling fluid.
Background
Starch has been widely used as a fluid loss additive for drilling fluid, but the application of natural starch in industry is greatly limited due to the defects of difficult cold water dissolution, easy decay and easy gelatinization and the like. Aiming at the problems, people successfully develop various starch modified products through modification methods such as physics, chemistry and the like, such as pregelatinized starch, carboxymethyl starch and graft modified starch which are widely used in the fluid loss additive for drilling fluid. But the temperature resistance of the pregelatinized starch is only 100 ℃, and the pregelatinized starch is only physically modified, so that the pregelatinized starch is easy to ferment in the field use process, the viscosity of the drilling fluid is increased, and the filtration loss is increased; the carboxymethyl modified starch has slightly poor temperature resistance and can only resist 120 ℃, and although the polymer graft modified starch can effectively improve the temperature resistance, the conventional graft copolymerization monomer can cause serious viscosity effect; preparation and property research of high-crosslinking modified starch, in the process of food and fermentation science volume 45 (fifth stage), mixed solution of inorganic salt such as sodium sulfate or sodium chloride and sodium hydroxide is used for preparing starch milk for crosslinking reaction, and addition of the inorganic salt cannot prevent gelatinization of the starch milk in alkaline environment, so that the crosslinked starch cannot be successfully prepared. Yang Feng, etc. provides a process for preparing crosslinked starch by using epichlorohydrin, and the crosslinked starch prepared by the process has small viscosity after high-temperature gelatinization and cannot play a good role in reducing the filtration loss in drilling fluid.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of the modified starch fluid loss additive for the drilling fluid, the preparation method is simple, and the obtained modified starch has good temperature resistance and good fluid loss property at high temperature.
Based on the problems, the technical scheme provided by the invention is a preparation method of a modified starch fluid loss additive for drilling fluid, which comprises the following steps:
1) And (3) crosslinking: preparing starch with low sulfur content into starch emulsion with concentration of 30-50%, heating to 40-60 deg.C, adding first modifier with mass of 0.05-1% of dry weight of starch, keeping temperature, stirring for 1-2 hr, centrifuging, and oven drying;
2) Alkalization: adding a pH regulator, and reacting for 1-2 hours at 50-55 ℃;
3) Etherification: adding a second modifier for etherification, drying and sieving to obtain a finished product.
In the step 1), the drying temperature is kept at 60-85 ℃, and the drying is required until the water content is lower than 6%, and because the crosslinked semi-finished product contains water, the semi-finished product is gelatinized in the alkalization process, and the gelatinized semi-finished product is treated as a failure in the production process.
In the step 2), the alkalization reaction does not need to be heated, but a small amount of moisture is generated in the alkalization reaction, the heating is used for evaporating the moisture generated in the alkalization reaction, the temperature is selected, if the temperature is lower than 50 ℃, the moisture is evaporated too slowly, the cost is increased, the economic benefit and the product application and popularization are influenced, and if the temperature exceeds 55 ℃, the gelatinization is generated under the condition that the alkali and the moisture exist at the same time.
The second modifier needs to be dissolved by ethanol, and the dosage of the ethanol does not exceed 15 percent of the weight of the starch. In the etherification process, the temperature is kept between 50 and 55 ℃ for reaction for 1 to 2 hours, the product after the etherification process needs to be dried until the water content is below 10 percent, the product is crushed and screened by a 60-mesh vibrating screen, and the undersize product is the finished product.
The first modifier is one or a combination of more of epichlorohydrin, phosphorus oxychloride, adipic acid, hexametaphosphate and trimetaphosphate, the use of the cross-linking agent enables the molecules of the starch to generate proper cross-linking, improves the gelatinization temperature, the aging temperature and the oxidation resistance of the starch, achieves the aim of resisting temperature, keeps good suspension capacity at a high temperature of more than 120 ℃, suspends and uniformly disperses solid particles in slurry, improves the plugging capacity and effectively reduces the filtration loss.
The pH regulator is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. The swelling property and the physical viscosity of the starch can be improved by alkalization treatment, the improvement of the physical viscosity is beneficial to the suspension and the uniform dispersion of solid particles, and the filtration loss is reduced.
The second modifier is one or a combination of more of chloromethane, chloroacetic acid and trichlorodihydroxypropyltrimethylammonium chloride. The semi-finished products generated in the first two steps are etherified, the solubility and the flocculation of the starch are improved, the improvement of the flocculation can improve the viscosity of the water-based slurry, and finally the filtration loss is reduced.
The invention has the advantages and beneficial effects that:
according to the invention, the salt-resistant, shear-resistant and high-temperature-resistant composite modified starch for the drilling fluid is obtained by carrying out composite modification on common starch according to crosslinking, alkalization and etherification, the temperature resistance can reach 127-149 ℃, the gelatinization temperature of the product is improved, the temperature resistance of the product is improved, good suspension capacity is kept at a high temperature of more than 120 ℃, the plugging capacity is improved by suspending and uniformly dispersing solid particles in slurry, and the filtration loss is effectively reduced; and the etherification treatment improves the solubility and flocculation of the starch, correspondingly improves the viscosity of the water-based mud, and has proper viscosity after high-temperature gelatinization, so that the filtration loss of the water-based drilling fluid with good compatibility can be effectively controlled.
The etherification requires a weak alkaline condition, if salt etherification such as sodium chloroacetate is directly performed by salt, the sodium chloroacetate is a strong alkaline weak acid salt, the product is weak alkaline, however, sodium chloroacetate is high in price, economic benefit is not practical application, and high-cost products lack competitiveness, so that the production cost can be greatly reduced by adopting a method of etherification by acid after alkalization. The preparation method of the modified starch fluid loss additive for drilling fluid prepared by the steps is simple, easy to operate, low in cost, free of pre-gelatinization and suitable for large-scale production.
Detailed Description
The following describes in detail embodiments of the present invention.
Embodiment 1 a method for preparing a modified starch fluid loss additive for drilling fluid, comprising the following steps:
1) Preparing 200g of starch into starch emulsion with the concentration of 30%, heating to 55 ℃, adding 1ml of epoxy chloropropane, keeping the temperature, stirring for 2 hours in a closed manner, centrifuging, and drying until the water content is 5%;
2) Adding 50mL of saturated sodium hydroxide solution, and keeping the temperature at 50 ℃ for reaction for 1.5 hours;
3) Dissolving 10 g of chloroacetic acid with 40ml of ethanol, then dropwise adding the solution into the mixed solution obtained in the step 2) for etherification, then drying the solution until the water content is below 10%, crushing the solution, and screening the crushed solution through a 60-mesh vibrating screen to obtain undersize products, namely the finished product.
Example 2
1) Preparing starch 200g into starch emulsion with the concentration of 50%, heating to 60 ℃, adding 0.5ml of epoxy chloropropane and 1 g of adipic acid, keeping the temperature, stirring for 2 hours in a closed manner, centrifuging, and drying until the water content is 5%;
2) Adding 100ml of 50% sodium carbonate solution, and keeping the temperature at 55 ℃ for reacting for 2 hours;
3) Dissolving 5 g of trichlorodihydroxypropyl trimethyl ammonium chloride by 40 g of ethanol, then dropwise adding the solution into the mixed solution obtained in the step 2) for etherification, then drying until the water content is below 10%, crushing and screening by a 60-mesh vibrating screen, and taking undersize products to obtain finished products.
The product obtained by the embodiment is respectively prepared into a water-based slurry system with the existing pregelatinized starch obtained by the pregelatinized treatment and the hydroxymethyl starch obtained by the hydroxymethyl treatment, and the comparative data of the water loss condition under high temperature and high pressure is obtained by tests, and is shown in the following table:
table 1 mud formulation and high temperature high pressure water loss:
as can be seen from the comparative data in Table 1, the product has the temperature resistance of 127-149 ℃ and has better fluid loss rate reduction.
Although the embodiments of the present invention have been described in detail, the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (6)
1. A preparation method of a modified starch fluid loss additive for drilling fluid is characterized by comprising the following steps: the method comprises the following steps:
1) And (3) crosslinking: preparing corn starch with low sulfur content into starch emulsion with the concentration of 30-50%, heating to 40-60 ℃, adding a first modifier with the mass of 0.05-1% of the dry basis weight of the starch, keeping the temperature, stirring for 1-2 hours in a closed manner, centrifuging and drying;
2) Alkalization: adding a pH regulator, and reacting for 1-2 hours at 50-55 ℃;
3) Etherification: adding a second modifier for etherification treatment for 1-2 h, and then drying and sieving to obtain a finished product.
Wherein the first modifier is one or a combination of more of epichlorohydrin, phosphorus oxychloride, adipic acid, hexametaphosphate or trimetaphosphate, and the pH regulator is one or a combination of more of sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate; the second modifier is one or a combination of more of methyl chloride, chloroacetic acid or trichlorodihydroxypropyltrimethylammonium chloride.
2. The preparation method of the modified starch fluid loss additive for drilling fluid according to claim 1, which is characterized by comprising the following steps: the drying temperature in the step 1) is kept between 60 and 85 ℃.
3. The preparation method of the modified starch fluid loss additive for drilling fluid according to claim 2, characterized by comprising the following steps: in the step 1), the semi-finished product needs to be dried until the water content is lower than 6%.
4. The preparation method of the modified starch fluid loss additive for drilling fluid according to claim 1, which is characterized by comprising the following steps: the second modifier needs to be dissolved by ethanol, and the dosage of the ethanol does not exceed 15 percent of the weight of the starch.
5. The preparation method of the modified starch fluid loss additive for drilling fluid according to claim 1, which is characterized by comprising the following steps: in the etherification treatment process in the step 3), the temperature is kept between 50 and 55 ℃ for reaction for 1 to 2 hours.
6. The preparation method of the modified starch fluid loss additive for drilling fluid according to claim 1, which is characterized by comprising the following steps: in the step 3), the etherified product needs to be dried to the water content of below 10 percent, crushed and screened by a 60-mesh vibrating screen, and the screened product is taken as a finished product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111168216.5A CN115873140A (en) | 2021-09-29 | 2021-09-29 | Preparation method of modified starch fluid loss additive for drilling fluid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111168216.5A CN115873140A (en) | 2021-09-29 | 2021-09-29 | Preparation method of modified starch fluid loss additive for drilling fluid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1690083A (en) * | 2004-04-23 | 2005-11-02 | 郝庆阳 | Composite modified starch and its preparing method |
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| CN105452300A (en) * | 2013-08-08 | 2016-03-30 | 生物聚合物网络有限公司 | Modified starch |
| CN105859895A (en) * | 2016-06-23 | 2016-08-17 | 吴也平 | Preparation method of sodium carboxymethyl starch with superhigh viscosity |
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2021
- 2021-09-29 CN CN202111168216.5A patent/CN115873140A/en active Pending
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