CN115873135A - Polyanionic cellulose and preparation method and application thereof - Google Patents
Polyanionic cellulose and preparation method and application thereof Download PDFInfo
- Publication number
- CN115873135A CN115873135A CN202111144985.1A CN202111144985A CN115873135A CN 115873135 A CN115873135 A CN 115873135A CN 202111144985 A CN202111144985 A CN 202111144985A CN 115873135 A CN115873135 A CN 115873135A
- Authority
- CN
- China
- Prior art keywords
- etherifying agent
- product
- cellulose
- polyanionic cellulose
- sodium sulfonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 75
- 239000001913 cellulose Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- 239000000047 product Substances 0.000 claims abstract description 57
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 238000006266 etherification reaction Methods 0.000 claims abstract description 28
- 238000005553 drilling Methods 0.000 claims abstract description 17
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012530 fluid Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 9
- UMJJNXFVAMHNIE-UHFFFAOYSA-N ClCC[Na] Chemical compound ClCC[Na] UMJJNXFVAMHNIE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- TWFHAEGZFQHISA-UHFFFAOYSA-N chlorobenzene;sodium Chemical compound [Na].ClC1=CC=CC=C1 TWFHAEGZFQHISA-UHFFFAOYSA-N 0.000 claims abstract description 4
- AHCDZZIXAMDCBJ-UHFFFAOYSA-N CCC[Na] Chemical compound CCC[Na] AHCDZZIXAMDCBJ-UHFFFAOYSA-N 0.000 claims abstract 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 229920000742 Cotton Polymers 0.000 claims description 14
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical group OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 13
- 229940106681 chloroacetic acid Drugs 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 2
- YPKOTWSAVCIFAM-UHFFFAOYSA-N [Na].CCC Chemical compound [Na].CCC YPKOTWSAVCIFAM-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003113 alkalizing effect Effects 0.000 abstract description 11
- 238000001914 filtration Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 63
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 238000002156 mixing Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000002002 slurry Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 238000005098 hot rolling Methods 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 229940080314 sodium bentonite Drugs 0.000 description 3
- 229910000280 sodium bentonite Inorganic materials 0.000 description 3
- AKTHLFYZKHPYBY-UHFFFAOYSA-M sodium;1-chloroethanesulfonate Chemical compound [Na+].CC(Cl)S([O-])(=O)=O AKTHLFYZKHPYBY-UHFFFAOYSA-M 0.000 description 3
- TZLNJNUWVOGZJU-UHFFFAOYSA-M sodium;3-chloro-2-hydroxypropane-1-sulfonate Chemical compound [Na+].ClCC(O)CS([O-])(=O)=O TZLNJNUWVOGZJU-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- XLKHCFJHGIAKFX-UHFFFAOYSA-M sodium;4-chlorobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(Cl)C=C1 XLKHCFJHGIAKFX-UHFFFAOYSA-M 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to the field of oilfield chemistry, and discloses polyanionic cellulose and a preparation method and application thereof. The preparation method comprises the following steps: (1) Alkalizing a cellulose raw material to obtain an alkalized product; (2) In the presence of a solvent, carrying out etherification reaction on the alkalization product and a composite etherifying agent, and carrying out post-treatment on the reaction product to obtain polyanionic cellulose; wherein the auxiliary etherifying agent is selected from at least one of 4-chlorobenzene sulfonic acid, 4-chlorobenzene sodium sulfonate, 3-chlorine-2-hydroxyl propyl sodium sulfonate and chloroethyl sodium sulfonate. The prepared polyanionic cellulose has excellent temperature resistance and filtration loss reduction performance when being used as a water-based drilling fluid additive.
Description
Technical Field
The invention relates to the field of oilfield chemistry, and particularly relates to a temperature-resistant polyanionic cellulose and a preparation method and application thereof.
Background
Polyanionic cellulose is water-soluble ionic cellulose ether, can form viscous solution when dissolved in water, and has the effects of thickening, dispersing, film forming, binding, colloid protection and the like. Based on the characteristics, polyanionic cellulose is used as a drilling auxiliary agent in a large amount, can play roles of increasing viscosity, improving mud cake quality, reducing filtration loss and the like in drilling fluid, and is an important chemical treatment agent for maintaining stable performance of the drilling fluid, improving rheological property of the drilling fluid, reducing filtration loss of harmful liquid to stratum, stabilizing well wall, ensuring well diameter regulation and protecting oil-gas reservoir. The polyanionic cellulose is prepared from natural fibers, belongs to an environment-friendly drilling aid, and is expected to be used more and more in the future along with the improvement of the requirement on the environmental protection property of the drilling fluid.
At present, with the reduction of shallow easy-to-open oil and gas resources, china gradually enters a deep oil and gas resource exploitation stage, the formation temperature rises along with the increase of the drilling depth, the upper limit of the use temperature of common polyanionic cellulose is about 100 ℃, and the polyanionic cellulose is degraded and loses efficacy due to continuous temperature rise, so the application range of the polyanionic cellulose is greatly limited.
CN105566500A discloses a preparation method of a particle type polyanionic cellulose, which comprises the following steps: (1) Alkalizing cellulose, etherifying, mixing with ethanol water solution, adjusting pH to 6.5-8.5, washing, and centrifuging to obtain intermediate material; (2) The intermediate material enters a stirrer, the temperature is controlled to be 20-60 ℃, deionized water is sprayed onto the intermediate material while stirring, and the stirring is carried out for 40-100min, so as to obtain a primary cellulose product; (3) Drying, drying and crushing the stirred primary cellulose product to obtain the granular polyanionic cellulose. The method aims at solving the problems that polyanionic cellulose is easy to agglomerate and is difficult to dissolve, and the conventional chloroacetic acid etherifying agent is used.
CN104448010A discloses a preparation method of instant polyanionic cellulose, which comprises: (1) Alkalizing cellulose, etherifying, mixing with ethanol water solution, adjusting pH to 6.5-8.5, washing, and centrifuging to obtain intermediate material; (2) Mixing the intermediate material with ethanol water solution I, adding the mixed solution A, and performing crosslinking reaction at normal temperature for 30-80min under stirring; the mixed solution A is formed by mixing glyoxal, an acidic aqueous solution and an ethanol aqueous solution II, wherein the dosage of the glyoxal in the mixed solution A is 3-8% of the weight of the cellulose, the acidic aqueous solution in the mixed solution A is an acetic acid aqueous solution and/or a citric acid aqueous solution, and the dosage of the acidic aqueous solution is 0.1-1.5% of the weight of the cellulose; (3) And (3) centrifugally separating, drying, crushing and sieving the material after the crosslinking reaction to obtain the instant polyanionic cellulose. The method overcomes the problem that the common polyanionic cellulose is easy to form fish eyes in the dissolving process, greatly shortens the dispersion and dissolution time of the polyanionic cellulose in water, reduces the slurry preparation time of the drilling fluid on site, and uses the conventional chloroacetic acid etherifying agent in the preparation process.
In conclusion, the improvement direction of the prior polyanionic cellulose mainly aims at material consumption, product appearance and dissolution performance in the production process, the molecular structure of the product is not changed, and the temperature resistance of the product is not greatly improved. Therefore, the polyanionic cellulose with higher temperature resistance is developed, the application range of the polyanionic cellulose is further expanded, and the polyanionic cellulose has important significance for exploiting deep oil and gas resources.
Disclosure of Invention
The invention aims to overcome the problems of insufficient temperature resistance and unsatisfactory fluid loss effect under high temperature conditions of polyanionic cellulose prepared by the prior art, and provides polyanionic cellulose and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a polyanionic cellulose, comprising:
(1) Carrying out alkalization treatment on a cellulose raw material to obtain an alkalized product;
(2) In the presence of a solvent, carrying out etherification reaction on the alkalization product and a composite etherifying agent, and carrying out post-treatment on the reaction product to obtain polyanionic cellulose; wherein,
the composite etherifying agent contains a main etherifying agent and an auxiliary etherifying agent, wherein the auxiliary etherifying agent is selected from at least one of 4-chlorobenzene sulfonic acid, 4-chlorobenzene sodium sulfonate, 3-chlorine-2-hydroxy propane sodium sulfonate and chloroethyl sodium sulfonate.
In a second aspect, the present invention provides a polyanionic cellulose prepared by the process of the first aspect.
In a third aspect the present invention provides the use of a polyanionic cellulose according to the second aspect described above in an aqueous based drilling fluid.
Through the technical scheme, the invention has the following beneficial effects:
(1) The specific composite etherifying agent is used in the etherification reaction, and under the combined action of the main etherifying agent and the auxiliary etherifying agent, the prepared polyanionic cellulose has excellent temperature resistance, viscosity increasing effect and filtration loss reducing performance. Adding 1% w/v of the polyanionic cellulose to 4% w/v of the sodium-bentonite-based slurry, after hot rolling the resulting slurry for 16h at 150%
The value is kept well, the viscosity retention rate is higher than 50%, and the medium-pressure filtration loss is not higher than 16mL;
(2) Multiple alkalization or etherification is not needed in the preparation process, and the process is simple and easy to control.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a preparation method of polyanionic cellulose in a first aspect, which comprises the following steps:
(1) Carrying out alkalization treatment on a cellulose raw material to obtain an alkalized product;
(2) In the presence of a solvent, carrying out etherification reaction on the alkalization product and a composite etherifying agent, and carrying out post-treatment on the reaction product to obtain polyanionic cellulose; wherein,
the composite etherifying agent contains a main etherifying agent and an auxiliary etherifying agent, wherein the auxiliary etherifying agent is selected from at least one of 4-chlorobenzene sulfonic acid, 4-chlorobenzene sodium sulfonate, 3-chlorine-2-hydroxy propane sodium sulfonate and chloroethyl sodium sulfonate.
According to the present invention, preferably, the cellulose raw material is selected from at least one of refined cotton, absorbent cotton, cotton linter, and lignocellulose. Wherein the main components of the cellulose raw material comprise 44.44wt% of carbon, 6.17wt% of hydrogen and 49.39wt% of oxygen.
According to the present invention, in order to prepare polyanionic cellulose having better temperature resistance, viscosity increasing property and fluid loss reducing property, preferably, the polymerization degree of the cellulose raw material may be 400 to 3000.
According to the present invention, the composite etherifying agent is a mixture containing both a main etherifying agent and an auxiliary etherifying agent. Wherein, preferably, the main etherifying agent may be selected from chloroacetic acid and/or sodium chloroacetate; preferably, the auxiliary etherifying agent may be selected from at least one of 4-chlorobenzenesulfonic acid, 4-chlorobenzenesulfonic acid sodium salt, 3-chloro-2-hydroxypropanesulfonic acid sodium salt, and chloroethanesulfonic acid sodium salt, and more preferably, may be selected from at least one of 4-chlorobenzenesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid sodium salt, and chloroethanesulfonic acid sodium salt.
According to the present invention, among the composite etherifying agents, it is preferable to use a main etherifying agent: the weight ratio of the auxiliary etherifying agent is 4:1-8, more preferably 3:1-2, so that the prepared polyanionic cellulose has better temperature resistance and filtration loss reduction performance.
According to the present invention, in the step (1), the alkalization treatment may be performed by methods and processes which are conventional in the art, and the present invention is not particularly limited thereto, and for example, the cellulose raw material may be soaked in an excess alkali solution at a temperature of 10 to 30 ℃ for 0.5 to 4 hours. The alkali solution used in the alkalization treatment can be an aqueous solution of sodium hydroxide and/or potassium hydroxide, and the concentration of the alkali solution can be 10-50wt%, and more preferably 20-40wt%. And obtaining the alkalization product which is the alkali cellulose.
According to the statement, in the step (2), the alkalization product obtained in the step (1) is mixed with a solvent and heated, the temperature is raised to the temperature required by the etherification reaction, and then the composite etherifying agent is added for the etherification reaction. Wherein the solvent may be at least one selected from the group consisting of ethanol, ethylene glycol, n-butanol, isopropanol, isobutanol, benzene and toluene; the composite etherifying agent comprises: the weight ratio of the cellulose raw material is 4-10, preferably 6-10:10; the solvent is as follows: the weight ratio of the cellulose raw material is 10-20.
In the present invention, preferably, the conditions of the etherification reaction may include: the temperature is 50-150 ℃ and the time is 1-3h.
According to the statement, in step (2), the post-treatment, comprising neutralization, washing and drying, carried out in sequence, can be carried out in the manner and parameters conventional in the art. For example, after the etherification reaction is completed, acetic acid diluted by an organic solvent may be added to neutralize the product of the etherification reaction to a pH of 6 to 8, and then the product may be repeatedly washed with an aqueous alcohol solution and dried to obtain the final product polyanionic cellulose.
In a second aspect, the present invention provides a polyanionic cellulose obtainable by the process of the first aspect hereinbefore described.
In a third aspect the present invention provides the use of a polyanionic cellulose according to the first aspect described above in an aqueous based drilling fluid.
The present invention will be described in detail below by way of examples. In the following examples and comparative examples,
in the case where no specific description is made, the materials used are those which are generally commercially available.
Example 1
(1) Mixing 5.0g of refined cotton with the polymerization degree of about 800 with 10g of NaOH aqueous solution with the concentration of 40wt%, and soaking and alkalizing for 1h at 20 ℃ to obtain an alkalized product;
(2) Adding the alkalized product and 100g of methylbenzene into a four-neck flask together for mixing, stirring and heating in a water bath, and setting the etherification reaction temperature to be 75 ℃; the method comprises the following steps of (1) preparing chloroacetic acid: 4-chlorobenzenesulfonic acid =3:1 (mass ratio) preparing 5.0g of composite etherifying agent, dripping the composite etherifying agent into the mixture after the reaction temperature is reached, and carrying out etherification reaction for 3 hours at a set temperature;
(3) After the reaction is finished, dropwise adding acetic acid diluted by isopropanol to neutralize until the pH value is 6-8, then adopting an isopropanol aqueous solution with the concentration of 95wt% to wash the product, and drying for 24 hours at 75 ℃ to obtain the product polyanionic cellulose (marked as S1).
Example 2
(1) Mixing 5.0g of refined cotton with the polymerization degree of about 800 with 10g of NaOH aqueous solution with the concentration of 40wt%, and soaking and alkalizing for 1h at 20 ℃ to obtain an alkalized product;
(2) Adding the alkalized product and 100g of isopropanol into a four-neck flask together for mixing, stirring and heating in a water bath, and setting the etherification reaction temperature to 80 ℃; mixing the following raw materials in parts by weight: 4-chlorobenzenesulfonic acid =3:2 (mass ratio) preparing 5.0g of composite etherifying agent, dripping the composite etherifying agent into the mixture after the reaction temperature is reached, and carrying out etherification reaction for 1 hour at a set temperature;
(3) After the reaction is finished, dropwise adding acetic acid diluted by isopropanol to neutralize until the pH value is 6-8, then washing the product by adopting an isopropanol aqueous solution with the concentration of 95wt%, and drying for 24 hours at 75 ℃ to obtain the product polyanionic cellulose (marked as S2).
Example 3
(1) Mixing 5.0g of refined cotton with the polymerization degree of about 600 with 20g of NaOH aqueous solution with the concentration of 20wt%, and soaking and alkalizing for 1h at the temperature of 20 ℃ to obtain an alkalized product;
(2) Adding the alkalized product and 50g of isopropanol into a four-neck flask together for mixing, stirring and heating in a water bath, and setting the etherification reaction temperature to be 75 ℃; the method comprises the following steps of (1) preparing chloroacetic acid: sodium 3-chloro-2-hydroxypropanesulfonate =2:1 (mass ratio) preparing 3.0g of composite etherifying agent, dripping the composite etherifying agent into the mixture after the reaction temperature is reached, and carrying out etherification reaction for 1 hour at a set temperature;
(3) After the reaction is finished, dropwise adding acetic acid diluted by isopropanol to neutralize until the pH value is 6-8, then washing the product by adopting an isopropanol aqueous solution with the concentration of 95wt%, and drying for 24 hours at 75 ℃ to obtain the product polyanionic cellulose (marked as S3).
Example 4
(1) Mixing 5.0g of refined cotton with the polymerization degree of about 800 with 10g of NaOH aqueous solution with the concentration of 40wt%, and soaking and alkalizing for 1h at the temperature of 20 ℃ to obtain an alkalized product;
(2) Adding the alkalized product and 50g of isopropanol into a four-neck flask together for mixing, stirring and heating in a water bath, and setting the etherification reaction temperature to be 75 ℃; mixing the following raw materials in parts by weight: sodium chloroethanesulfonate =2:1 (mass ratio) preparing 3.0g of composite etherifying agent, dripping the composite etherifying agent into the mixture after the reaction temperature is reached, and carrying out etherification reaction for 3 hours at a set temperature;
(3) After the reaction is finished, adding acetic acid diluted by isopropanol dropwise to neutralize until the pH value is 6-8, then washing the product by adopting an isopropanol aqueous solution with the concentration of 95wt%, and drying for 24 hours at 75 ℃ to obtain the product polyanionic cellulose (marked as S4).
Example 5
(1) Mixing 5.0g of refined cotton with the polymerization degree of about 600 with 20g of NaOH aqueous solution with the concentration of 20wt%, and soaking and alkalizing for 1h at the temperature of 20 ℃ to obtain an alkalized product;
(2) Adding the alkalized product and 50g of isopropanol into a four-neck flask together for mixing, stirring and heating in a water bath, and setting the etherification reaction temperature to 80 ℃; the method comprises the following steps of (1) preparing chloroacetic acid: 4-chlorobenzenesulfonic acid =2:1 (mass ratio) preparing 3.0g of composite etherifying agent, dripping the composite etherifying agent into the mixture after the reaction temperature is reached, and carrying out etherification reaction for 1 hour at a set temperature;
(3) After the reaction is finished, adding acetic acid diluted by isopropanol dropwise to neutralize until the pH value is 6-8, then washing the product by adopting an isopropanol aqueous solution with the concentration of 95wt%, and drying for 24 hours at 75 ℃ to obtain the product polyanionic cellulose (marked as S5).
Example 6
(1) Mixing 5.0g of refined cotton with the polymerization degree of about 600 with 20g of NaOH aqueous solution with the concentration of 20wt%, and soaking and alkalizing for 1h at the temperature of 20 ℃ to obtain an alkalized product;
(2) Adding the alkalized product and 50g of isopropanol into a four-neck flask together for mixing, stirring and heating in a water bath, and setting the etherification reaction temperature to 80 ℃; the method comprises the following steps of (1) preparing chloroacetic acid: 4-chlorobenzenesulfonic acid =1:2 (mass ratio), preparing 5.0g of composite etherifying agent, dripping the composite etherifying agent after the reaction temperature is reached, and carrying out etherification reaction for 1 hour at a set temperature;
(3) After the reaction is finished, dropwise adding acetic acid diluted by isopropanol to neutralize until the pH value is 6-8, then washing the product by adopting an isopropanol aqueous solution with the concentration of 95wt%, and drying for 24 hours at 75 ℃ to obtain the product polyanionic cellulose (marked as S6).
Example 7
(1) Mixing 5.0g of refined cotton with the polymerization degree of about 800 with 10g of NaOH aqueous solution with the concentration of 40wt%, and soaking and alkalizing for 1h at 20 ℃ to obtain an alkalized product;
(2) Adding the alkalized product and 100g of benzene into a four-neck flask together for mixing, stirring and heating in a water bath, and setting the etherification reaction temperature to be 75 ℃; the method comprises the following steps of (1) preparing chloroacetic acid: sodium 4-chlorobenzenesulfonate =3:1 (mass ratio) preparing 5.0g of composite etherifying agent, dripping the composite etherifying agent into the mixture after the reaction temperature is reached, and carrying out etherification reaction for 1 hour at a set temperature;
(3) After the reaction is finished, dropwise adding acetic acid diluted by isopropanol to neutralize until the pH value is 6-8, then washing the product by adopting an isopropanol aqueous solution with the concentration of 95wt%, and drying for 24 hours at 75 ℃ to obtain the product polyanionic cellulose (marked as S7).
Example 8
(1) Mixing 5.0g of refined cotton with the polymerization degree of 2600 or so with 20g of NaOH aqueous solution with the concentration of 20wt%, and soaking and alkalizing for 1h at 20 ℃ to obtain an alkalized product;
(2) Adding the alkalized product and 50g of isopropanol into a four-neck flask together for mixing, stirring and heating in a water bath, and setting the etherification reaction temperature to be 75 ℃; the method comprises the following steps of (1) preparing chloroacetic acid: 4-chlorobenzenesulfonic acid =4:1 (mass ratio) preparing 5.0g of composite etherifying agent, dripping the composite etherifying agent into the mixture after the reaction temperature is reached, and carrying out etherification reaction for 1 hour at a set temperature;
(3) After the reaction is finished, dropwise adding acetic acid diluted by isopropanol to neutralize until the pH value is 6-8, then washing the product by adopting an isopropanol aqueous solution with the concentration of 95wt%, and drying for 24 hours at 75 ℃ to obtain the product polyanionic cellulose (marked as S8).
Comparative example 1
The process of example 1 is followed except that in step (2), the composite etherifying agent is replaced with chloroacetic acid of the same weight as that, i.e., chloroacetic acid alone is used as etherifying agent. Otherwise, the product (denoted as D1) was obtained in the same manner as in example 1.
Comparative example 2
The procedure was followed as in example 1, except that in step (2), the composite etherifying agent was replaced with 4-chlorobenzenesulfonic acid of the same weight as that of the composite etherifying agent, i.e., 4-chlorobenzenesulfonic acid alone was used as the etherifying agent. Otherwise, the product (designated as D2) was obtained in the same manner as in example 1.
Comparative example 3
The procedure of example 1 was followed except that in step (2), 4-chlorobenzenesulfonic acid in the composite etherifying agent was replaced with epichlorohydrin. The other conditions were the same as in example 1 to obtain the product (designated as D3).
Comparative example 4
The process of example 1 is followed except that, in step (2), chloroacetic acid: 4-chlorobenzenesulfonic acid =1:3 (mass ratio). Otherwise, the product (designated as D4) was obtained in the same manner as in example 1.
Test example
The products prepared in examples 1 to 8 and comparative examples 1 to 4 and a commercially available polyanionic cellulose were added as an auxiliary agent to a water-based drilling fluid base slurry to evaluate the properties of the different polyanionic celluloses described above. In the following test examples, the following test examples were carried out,
the rheological parameters of the drilling fluid are measured by a six-speed viscometer according to the method specified in GB/T16783.2-2012;
medium pressure fluid loss (API, mL) was measured using a medium pressure fluid loss gauge and according to the method specified in GB/T29170-2012;
the manufacturer of the six-speed rotary viscometer is Beijing research institute for mineral exploration, model WT-AUTO-900;
the manufacturer of the medium-pressure fluid loss instrument is Qingdao electronics ltd, model ZNS.
Preparing base slurry of the water-based drilling fluid: 16g of sodium bentonite for drilling fluid (purchased from Poyobo mud technology Co., ltd.) was added to 400mL of tap water, stirred at 10000r/min for 30min, and allowed to stand in a closed state for 24h to obtain 4% w/v sodium bentonite-based slurry (designated as base slurry A).
To 400mL of the base slurry A prepared as described above were added 4g (i.e., 1% w/v) of each of the products S1 to S8 obtained in examples 1 to 8, the products D1 to D4 obtained in comparative examples 1 to 4, and a commercially available polyanionic cellulose (trade name: LV-PAC, available from Hebei Swallow chemical Co., ltd.) and the slurry was stirred at 3000r/min for 20 minutes, and then the slurry was transferred to an aging tank, the aging tank was placed in a high temperature roller heating furnace, hot-rolled at 150 ℃ for 16 hours, cooled to room temperature, and then stirred at 3000r/min for 10 minutes to test the rheological properties, medium pressure filtration loss and viscosity retention of the slurry before and after hot-rolling, and the results are shown in Table 1.
Wherein, the viscosity retention rate is calculated according to the formula (1),
TABLE 1
As can be seen from Table 1, the addition of 1% w/v polyanionic cellulose S1-S8 to the base slurry A of the water-based drilling fluid significantly increased the viscosity of the base slurry, and the slurry was hot rolled at 150 ℃ for 16 hours
The value is kept better, the viscosity retention rate is more than 50%, and the medium-pressure filtration loss is not higher than 16mL, which shows that the polyanionic cellulose provided by the application has better viscosity increasing and temperature resistanceAnd fluid loss additive effect.
Compared with the prior art, the composite etherifying agent in the method is not used in the preparation process of the products D1-D4, so that the viscosity retention rate of the slurry is remarkably reduced after the slurry is hot rolled for 16 hours at 150 ℃, the filtration loss is higher than 20mL, and the slurry cannot resist the high temperature of 150 ℃. And the viscosity retention rate of the slurry is only 11.8% after hot rolling for 16h at 150 ℃ by using the commercially available polyanionic cellulose LV-PAC, and the temperature resistance has obvious difference from S1-S8.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for producing a polyanionic cellulose, comprising:
(1) Carrying out alkalization treatment on a cellulose raw material to obtain an alkalized product;
(2) In the presence of a solvent, carrying out etherification reaction on the alkalization product and a composite etherifying agent, and carrying out post-treatment on the reaction product to obtain polyanionic cellulose; wherein,
the composite etherifying agent contains a main etherifying agent and an auxiliary etherifying agent, wherein the auxiliary etherifying agent is selected from at least one of 4-chlorobenzene sulfonic acid, 4-chlorobenzene sodium sulfonate, 3-chlorine-2-hydroxyl propane sodium sulfonate and chloroethyl sodium sulfonate.
2. The method of claim 1, wherein the cellulosic feedstock is selected from at least one of refined cotton, cotton wool, cotton linters, and lignocellulose;
preferably, the degree of polymerization of the cellulosic feedstock is from 400 to 3000.
3. The process according to claim 1 or 2, wherein the primary etherifying agent is selected from chloroacetic acid and/or sodium chloroacetate; the auxiliary etherifying agent is selected from at least one of 4-chlorobenzene sulfonic acid, 3-chlorine-2-hydroxyl propyl sodium sulfonate and chloroethyl sodium sulfonate.
4. The process of any one of claims 1-3, wherein the primary etherifying agent: the weight ratio of the auxiliary etherifying agent is 4:1 to 8, preferably 3:1-2.
5. The method according to any one of claims 1 to 4, wherein, in the step (1), the alkali solution used for the alkalization treatment is an aqueous solution of sodium hydroxide and/or potassium hydroxide.
6. A process according to claim 5, wherein the concentration of the lye is 10 to 50wt%, preferably 20 to 40wt%.
7. The process according to any one of claims 1 to 6, wherein, in step (2), the conditions of the etherification reaction include: the temperature is 50-80 ℃, and the time is 1-3h;
preferably, the complex etherifying agent: the weight ratio of the cellulose raw material is 4-10, preferably 6-10:10;
preferably, the solvent: the weight ratio of the cellulose raw material is 10-20;
preferably, the solvent is selected from at least one of ethanol, ethylene glycol, n-butanol, isopropanol, isobutanol, benzene, and toluene.
8. The method according to any one of claims 1 to 7, wherein in step (2), the post-treatment comprises neutralization, washing and drying, which are carried out sequentially.
9. A polyanionic cellulose obtainable by the process of any one of claims 1 to 8.
10. Use of a polyanionic cellulose according to claim 9 in an aqueous drilling fluid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111144985.1A CN115873135B (en) | 2021-09-28 | 2021-09-28 | Polyanionic cellulose, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111144985.1A CN115873135B (en) | 2021-09-28 | 2021-09-28 | Polyanionic cellulose, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115873135A true CN115873135A (en) | 2023-03-31 |
| CN115873135B CN115873135B (en) | 2024-06-28 |
Family
ID=85763598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111144985.1A Active CN115873135B (en) | 2021-09-28 | 2021-09-28 | Polyanionic cellulose, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115873135B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB833173A (en) * | 1957-06-25 | 1960-04-21 | Henkel & Cie Gmbh | Continuous mixing of alkali cellulose with etherification agents |
| DE3246676A1 (en) * | 1982-12-16 | 1984-06-20 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of water-soluble sodium carboxymethylcellulose |
| US4650863A (en) * | 1984-05-15 | 1987-03-17 | Hoechst Aktiengesellschaft | Preparation of water-soluble mixed cellulose ethers |
| US5455341A (en) * | 1992-12-08 | 1995-10-03 | Wolff Walsrode Aktiengesellschaft | Highly substituted carboxymethyl sulfoethyl cellulose ethers (CMSEC), a process for their production and their use in textile printing |
| EP2196224A1 (en) * | 2008-12-11 | 2010-06-16 | Speciality Fibres and Materials Limited | Absorbent material |
| CN105646950A (en) * | 2016-01-15 | 2016-06-08 | 上海惠广精细化工有限公司 | Preparation method for modified hydroxypropyl methyl cellulose special for industrial thermal mortar series |
-
2021
- 2021-09-28 CN CN202111144985.1A patent/CN115873135B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB833173A (en) * | 1957-06-25 | 1960-04-21 | Henkel & Cie Gmbh | Continuous mixing of alkali cellulose with etherification agents |
| DE3246676A1 (en) * | 1982-12-16 | 1984-06-20 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of water-soluble sodium carboxymethylcellulose |
| US4650863A (en) * | 1984-05-15 | 1987-03-17 | Hoechst Aktiengesellschaft | Preparation of water-soluble mixed cellulose ethers |
| US5455341A (en) * | 1992-12-08 | 1995-10-03 | Wolff Walsrode Aktiengesellschaft | Highly substituted carboxymethyl sulfoethyl cellulose ethers (CMSEC), a process for their production and their use in textile printing |
| EP2196224A1 (en) * | 2008-12-11 | 2010-06-16 | Speciality Fibres and Materials Limited | Absorbent material |
| CN105646950A (en) * | 2016-01-15 | 2016-06-08 | 上海惠广精细化工有限公司 | Preparation method for modified hydroxypropyl methyl cellulose special for industrial thermal mortar series |
Non-Patent Citations (4)
| Title |
|---|
| 吴鑫磊;闫丽丽;王立辉;王发云;: "环保型钻井液用降滤失剂研究进展", 钻井液与完井液, no. 03, pages 12 - 20 * |
| 王中华;杨小华;: "水溶性纤维素类钻井液处理剂制备与应用进展", 精细与专用化学品, no. 09, pages 15 - 18 * |
| 王康 等: ""海洋浮式钻井天车升沉补偿实验教学平台研制"", 《实验技术与管理》, vol. 36, no. 04, pages 20 - 24 * |
| 王爱荣 等: ""复合醚化淀粉降滤失剂的合成与性能测试"", 《化工技术与开发》, vol. 47, no. 03, 31 March 2018 (2018-03-31), pages 8 - 12 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115873135B (en) | 2024-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4031307A (en) | Cationic polygalactomannan compositions | |
| CN102226080B (en) | Breakdown fluid and preparation method thereof | |
| CN102286108B (en) | Method for preparing potassium carboxymethylcellulose | |
| CN101514233B (en) | Amphoteric guar gum, preparation method and application thereof | |
| CN113087817B (en) | Guar gum derivative and preparation method and application thereof | |
| CN102898589A (en) | Novel environment-friendly high-molecular polymerized emulsion and preparation method thereof | |
| CN110724503B (en) | High-temperature salt-resistant filtrate reducer modified gum resin for drilling fluid | |
| CN111234789B (en) | Filtrate reducer acrylamide/acrylic acid copolymer for drilling fluid | |
| CN104497154A (en) | Preparation method of hydroxy butyl starch ether or hydroxy butyl modified starch ether | |
| CN108623747B (en) | A kind of modified starch resistant to high temperatures and its preparation method and application | |
| CN117088993B (en) | Guar gum for oilfield fracturing and preparation method thereof | |
| CN115873135A (en) | Polyanionic cellulose and preparation method and application thereof | |
| CN102093481A (en) | Method for preparing instant carboxymethylcellulose | |
| CN110257041B (en) | Guar gum-nano cellulose fiber crosslinking thickener for fracturing fluid and preparation method thereof | |
| ITVA20120030A1 (en) | FORMULATIONS FOR PAINTS | |
| CN110922956B (en) | Unsaturated long-chain-table active agent fracturing fluid and preparation and gel breaking methods thereof | |
| CN101323647A (en) | Preparation of anion guar gum | |
| CN101838334A (en) | Preparation method of high viscosity polyanion cellulose | |
| CN116554853A (en) | Modified fracturing fluid thickener and preparation method thereof | |
| CN107298720A (en) | The preparation method of the polyanion cellulose of the viscous heatproof low filtration loss of height | |
| CA2771279A1 (en) | Modification of solid polysaccharide with transesterification agent | |
| CN110922957B (en) | Twin-tail viscoelastic surfactant gel fracturing fluid, preparation method thereof and colloid relieving method | |
| CN107522791B (en) | Vegetable gum containing sulfonic group and preparation method and application thereof | |
| CN110845372A (en) | Multiolefin hook type surfactant gel fracturing fluid and preparation and gel breaking methods thereof | |
| CN116063585B (en) | Modified temperature-resistant guanidine gum and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |