CN115819629B - High-temperature-resistant and salt-resistant cellulose ether and preparation method and application thereof - Google Patents
High-temperature-resistant and salt-resistant cellulose ether and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of cellulose ether, and provides high-temperature-resistant and salt-resistant cellulose ether, and a preparation method and application thereof. The invention adopts low boiling point ether solvent to alkalize cellulose under higher temperature and pressure, gasifies the low boiling point ether solvent under the alkalization condition, and quickly permeates into a cellulose crystallization area under the pressure condition to effectively dissociate the crystallization area, and opens a permeation channel, so that alkali can quickly enter the crystallization area to thoroughly activate the cellulose, thereby leading nonionic groups and ionic groups introduced in later stage to enter the crystallization area to react, improving the efficiency and uniformity of subsequent etherification reaction, and finally, the obtained cellulose ether has high content of ionic groups and nonionic groups and is uniformly distributed on cellulose molecular chains. The cellulose ether disclosed by the invention can play an excellent role in tackifying and compatibilizing by being added into high brine drilling and completion fluid, has good high temperature resistance, and also has the advantages of environmental friendliness and small addition amount.
Description
Technical Field
The invention relates to the technical field of cellulose ether, in particular to high-temperature-resistant and salt-resistant cellulose ether, and a preparation method and application thereof.
Background
Cellulose ether is a high molecular compound with an ether structure and is prepared by cellulose ether, and cellulose ether varieties are various, and the cellulose ether is widely applied to various industries, for example, in chemical building materials, the cellulose ether can be used as a water-retaining agent, a thickening agent, leveling property, a binder and the like; in the polyvinyl chloride industry, cellulose ether is used as an emulsifier and a dispersant; in emulsion paint, the cellulose ether can play a thickening role, prevent pigment gelation and improve construction leveling property.
In addition, the cellulose ether can be used in petroleum drilling and added into drilling and completion fluids for increasing the viscosity of the drilling and completion fluids and reducing the water loss. The traditional drilling and completion fluid is oil-based drilling and completion fluid, and the main components of the drilling and completion fluid comprise diesel oil, asphalt, water, an emulsifying agent, a weighting agent and the like, and the oil-based drilling and completion fluid has the defects of heavy pollution and high price. With the strong development of unconventional oil gas and the continuous improvement of environmental protection demands in recent years, solid-free high brine environmental protection type water-based drilling and completion fluids begin to replace heavy pollution and high-price oil-based drilling and completion fluids, and are gradually popularized.
The solid-free high-brine environment-friendly water-based drilling and completion fluid is a high-brine environment and contains high-concentration divalent metal ions (such as Ca 2+ Etc.), divalent metal ions can produce bonding action with polymer molecular chains, and rapidly compress macromolecular coils to force the macromolecular coils to be separated from the solution. The cellulose ether products in the market mainly achieve tackifying by entanglement of long molecular chains in aqueous solution, the products are easily affected by metal ions in a high brine environment, the tackifying effect is poor, the cellulose ether products can be separated out of the solution until the viscosity is completely lost when the cellulose ether products are severe, and the cellulose ether products are poor in performance at high temperature (above 100 ℃).
Disclosure of Invention
In view of the above, the invention provides a high-temperature-resistant and salt-resistant cellulose ether, and a preparation method and application thereof. The cellulose ether provided by the invention has good high temperature resistance and salt tolerance, and is suitable for drilling and completion fluids in high brine environments.
In order to achieve the above object, the present invention provides the following technical solutions:
the preparation method of the high-temperature-resistant and salt-resistant cellulose ether comprises the following steps:
alkalizing a cellulose raw material, an alkali metal hydroxide aqueous solution and an ether solvent by first mixing to obtain alkalized cellulose; the alkalization temperature is 30-70 ℃, the pressure is 0.5-6 MPa, and the ether solvent is gasified under the alkalization temperature and pressure conditions;
and respectively carrying out etherification reaction on the alkalized cellulose by using a nonionic etherifying agent and an ionic etherifying agent to obtain the high-temperature-resistant and salt-resistant cellulose ether.
Preferably, the concentration of the alkali metal hydroxide aqueous solution is 30-52 wt%, and the mass ratio of the cellulose raw material to the alkali metal hydroxide aqueous solution is 1 (0.5-1.7); the mass ratio of the cellulose raw material to the ether solvent is 1 (0.3-1.1); the carbon number of the ether solvent is less than or equal to 6.
Preferably, the alkalizing comprises: heating and pressurizing the mixture obtained by the first mixing, keeping the temperature and the pressure after reaching the alkalization temperature and the alkalization pressure, and then reducing the temperature and the pressure; the temperature and pressure rise time is less than or equal to 10min, the heat preservation and pressure maintaining time is 20-80 min, and the temperature and pressure relief time is 10-30 min;
the temperature and pressure reduction is carried out to 20-40 ℃ and the pressure is reduced to normal pressure.
Preferably, the etherification reaction comprises the steps of:
carrying out a first etherification reaction after the alkalized cellulose and the nonionic etherifying agent are mixed for the second time to obtain a first etherification product feed liquid;
and thirdly mixing the first etherification product feed liquid, the alcohol solvent and the ionic etherifying agent, and then carrying out a second etherification reaction.
Preferably, the nonionic etherifying agent comprises one or more of a monohaloalkane and an alkylene oxide; the mass ratio of the nonionic etherifying agent to the cellulose raw material is (0.8-2.5): 1; the ionic etherifying agent comprises one or more of halogenated alkyl sulfonate, alkenyl sulfonate and halogenated carboxylic acid; the mass ratio of the ionic etherifying agent to the cellulose is (0.1-0.5): 1;
the temperature of the first etherification reaction is 85-95 ℃, the pressure is more than 1.5MPa, and the time is 20-80 min; the temperature of the second etherification reaction is 60-100 ℃, the time is 60-120 min, and the pressure is more than 0.02 MPa.
Preferably, the second mixing comprises: stirring and dispersing the alkalized cellulose and the nonionic etherifying agent under the airtight and pressurized conditions; the stirring and dispersing time is 30-90 min, the pressure of the closed pressurization is 0.5-3 MPa, and the stirring and dispersing temperature is 30-60 ℃.
Preferably, after the second etherification reaction is finished, refining the obtained product feed liquid;
the refining treatment comprises the following steps: and washing, neutralizing, centrifuging, stripping, drying and crushing the product feed liquid obtained by the second etherification reaction in sequence to obtain the cellulose ether refined product.
The invention also provides the high-temperature-resistant and salt-resistant cellulose ether prepared by the preparation method, wherein the content of nonionic groups of the high-temperature-resistant and high-calcium-resistant cellulose ether is more than or equal to 2 weight percent, and the content of ionic groups is more than or equal to 2.5 weight percent.
The invention also provides application of the high-temperature-resistant and salt-resistant cellulose ether in drilling and completion fluid containing metal ions.
The invention also provides drilling and completion fluid, which comprises the high-temperature-resistant and salt-resistant cellulose ether.
The invention provides a preparation method of high-temperature-resistant and salt-resistant cellulose ether, which comprises the following steps: alkalizing a cellulose raw material, an alkali metal hydroxide aqueous solution and an ether solvent by first mixing to obtain alkalized cellulose; the alkalization temperature is 30-70 ℃, the pressure is 0.5-6 MPa, and the ether solvent is gasified under the alkalization temperature and pressure conditions; and respectively carrying out etherification reaction on the alkalized cellulose by using a nonionic etherifying agent and an ionic etherifying agent to obtain the high-temperature-resistant and salt-resistant cellulose ether. The invention adopts low boiling point ether solvent to alkalize cellulose under higher temperature and pressure conditions, the higher temperature and pressure are favorable for destroying the stability of cellulose crystal area at the initial stage of alkalization, the low boiling point ether solvent is gasified under the alkalization condition and quickly permeates into the cellulose crystal area under the pressure effect, the crystal area is effectively dissociated, a permeation channel is opened, the alkali can quickly enter the crystal area to partially and thoroughly activate the cellulose, thus nonionic groups and ionic groups introduced at the later stage can enter the crystal area to react, the efficiency and uniformity of the subsequent etherification reaction are improved, the content of ionic groups and nonionic groups in the finally obtained cellulose ether is high, and the cellulose ether is uniformly distributed on a cellulose molecular chain, and the high temperature resistance and salt resistance of the obtained modified cellulose ether are further improved. At present, when cellulose alkalization is carried out in the field, the alkalization is carried out under the action of alkali liquor by taking alcohol or isopropanol as a solvent at low temperature and constant pressure, the alkalization can only realize the activation effect on a non-crystalline region of cellulose, is almost ineffective on a crystalline region of cellulose, has low reaction uniformity and efficiency, and finally, the molecular chain of the obtained cellulose ether only contains substituent groups in the non-crystalline region, has uneven distribution, low content and poor salt tolerance, and cannot be applied to a high-halogen environment.
The invention is compatible with the characteristics of ionic cellulose ether and nonionic cellulose ether, and introduces nonionic groups and ionic groups on a cellulose main chain through two-step etherification reaction, wherein the nonionic groups are not ionized in an aqueous medium and are not precipitated because of multivalent salt in a system, so that the invention has the characteristic of multivalent metal salt resistance, the ionic groups can form stronger ionic bonds with the multivalent metal salt, the intermolecular crosslinking effect can be achieved, and further the tackifying effect is realized in a high halogen environment, and the higher the multivalent ion concentration is, the larger the tackifying amplitude is.
Furthermore, the alkalization swelling and the introduction of the ionic groups need to consume more alkali, and the introduction of the nonionic groups hardly consumes alkali, so the nonionic groups are preferably introduced first, the one-time alkalization swelling is realized, the two types of substitution are completed, the alkalization swelling effect is improved, and the consumption of the medicament is saved.
The invention also provides the high-temperature-resistant salt-resistant cellulose ether prepared by the preparation method, and the cellulose ether provided by the application has good high-temperature resistance and good salt-resistant effect, especially good effect of resisting multivalent (more than divalent) metal salt.
The invention also provides application of the high-temperature-resistant and salt-resistant cellulose ether in high brine drilling and completion fluid. The cellulose ether provided by the invention has good high temperature resistance and salt resistance, can play an excellent role in tackifying and compatibilizing when being added into a high brine drilling and completion fluid, has good high temperature resistance, and has the advantages of environmental protection and small addition. The tackifying, compatibilizing and high temperature resisting mechanisms of the cellulose of the invention are described below:
when the cellulose ether is adopted to tackify drilling and completion fluid, the viscosity can be improved by adopting a conventional method, namely a method for increasing the concentration of the cellulose ether; it is also possible to keep the concentration of the cellulose ether unchanged, increase the viscosity by the concentration of the polyvalent (divalent or more) metal salt, and when the polyvalent metal salt reaches a saturated state, the viscosity of the solution reaches a maximum. The second tackifying method is based on the principle that polyvalent metal ions are used as fillers of cellulose ether frameworks, form ionic bonds with ionic groups of cellulose ether, and further realize tackifying effect due to strong intermolecular interaction force, but the bonding is different from crosslinking, and the crosslinked aqueous solution is gel-like, and is uniform viscous liquid.
The cellulose ether provided by the invention contains more ionic groups, and the ionic groups and the multivalent metal ions form stable ionic bonds, so that the movement of the multivalent metal ions is effectively hindered, and the salt crystallization is slowed down, thereby realizing the effect of capacity increase (namely increasing the solubility of the multivalent metal ions).
Finally, in the solution of the high-concentration multivalent metal ions, strong ionic bonds formed by ionic groups in the cellulose ether and the multivalent metal ions are more, and the interaction force between the cellulose ether is enhanced, so that the high temperature resistance of the product is improved.
Detailed Description
The invention provides a preparation method of high-temperature-resistant and salt-resistant cellulose ether, which comprises the following steps:
alkalizing a cellulose raw material, an alkali metal hydroxide aqueous solution and an ether solvent by first mixing to obtain alkalized cellulose; the alkalization temperature is 30-70 ℃, the pressure is 0.5-6 MPa, and the ether solvent is gasified under the alkalization temperature and pressure conditions;
and respectively carrying out etherification reaction on the alkalized cellulose by using a nonionic etherifying agent and an ionic etherifying agent to obtain the high-temperature-resistant and salt-resistant cellulose ether.
The invention firstly mixes cellulose raw material, alkali metal hydroxide aqueous solution and ether solvent for alkalization to obtain alkalized cellulose. In the present invention, the cellulose raw material is preferably wood pulp or purified cotton; the cellulose is preferably crushed into flocculus or filiform and then used, and the diameter of the crushed material is preferably less than or equal to 1cm. In the present invention, the alkali metal hydroxide is preferably sodium hydroxide, potassium hydroxide or lithium hydroxide; the concentration of the alkali metal hydroxide aqueous solution is preferably 30 to 52wt%, and in the embodiment of the present invention, the concentration of the alkali metal hydroxide aqueous solution may be specifically 30wt%, 35wt%, 45wt%, or 52wt%. In the present invention, the mass ratio of the cellulose to the alkali metal hydroxide aqueous solution is preferably 1 (0.5 to 1.7), more preferably 1 (1.0 to 1.5); the mass ratio of the cellulose to the ether solvent is preferably 1 (0.3 to 1.1), more preferably 1 (0.5 to 0.8). In the present invention, the number of carbon atoms of the ether-based solvent is preferably not more than 6, more preferably 2 to 6, and specifically, the ether-based solvent preferably includes one or more of dimethyl ether, diethyl ether and dipropyl ether; when a plurality of ether solvents are used, a mixed solvent of dimethyl ether and diethyl ether is preferably used, and the volume ratio of dimethyl ether to diethyl ether in the mixed solvent is preferably (0.5-2): 1, more preferably 1:1; in the specific embodiment of the present invention, the purity of the ether solvent is preferably 30 to 95%; in the present invention, the volume of the ether solvent is calculated as the actual content of the ether, and for example, when 1L of dimethyl ether having a purity of 50% is added, the actual volume of dimethyl ether is 0.5L.
In the present invention, the alkalizing temperature is 30 to 70 ℃, preferably 40 to 60 ℃; the pressure of the alkalization is 0.5-6 MPa, preferably 1-3 MPa; the ether solvent is gasified under the alkalizing temperature and pressure conditions. In the present invention, the alkalizing preferably includes: heating and pressurizing a mixture of cellulose, an alkali metal hydroxide aqueous solution and an ether solvent to reach alkalization temperature and pressure, preserving heat and pressure, and then cooling and releasing pressure; the temperature and pressure rise time is preferably less than or equal to 10min, more preferably 5-10 min; the time of heat preservation and pressure maintaining is preferably 20-80 min; the total time of heating, boosting, heat preservation and pressure maintaining is preferably 30-90 min; the time for cooling and pressure relief is preferably 10-30 min, more preferably 15-20 min, the temperature and pressure relief is that the temperature is reduced to 20-40 ℃ and the pressure is relieved to normal pressure.
After alkalization, the feed liquid of the alkalized cellulose is obtained, other treatments are not needed, and the obtained feed liquid is directly subjected to subsequent reactions.
After alkalization is finished, the invention respectively carries out etherification reaction on the alkalized cellulose by using a nonionic etherifying agent and an ionic etherifying agent to obtain the high-temperature-resistant and salt-resistant cellulose ether. In the present invention, the nonionic etherifying agent preferably includes one or more of monohaloalkane and alkylene oxide; the number of carbon atoms of the monohalogenated alkane is preferably 1 to 5, more preferably 1 to 3, and the monohalogenated alkane is preferably chlorinated alkane; in particular, the monohaloalkane preferably comprises one or more of chloromethane, chloroethane and chloropropane; the number of carbon atoms of the alkylene oxide is preferably 2 to 5, more preferably 2 to 3, and the alkylene oxide is preferably one or more of ethylene oxide and propylene oxide; in the embodiment of the present invention, when a mixture of a plurality of nonionic etherifying agents is used, a mixture of monochloroethane and propylene oxide is preferably used, and the mass ratio of monochloroethane to propylene oxide is preferably 1 (1 to 4), more preferably 1:1.
In the present invention, the mass ratio of the nonionic etherifying agent to the cellulose is preferably (0.8 to 2.5): 1, more preferably (1 to 2): 1.
In the present invention, the ionic etherifying agent preferably includes one or more of haloalkylsulfonate, alkenylsulfonate and halogenated carboxylic acid; the haloalkylsulfonate preferably comprises one or more of sodium 2-chloroethanesulfonate, sodium 3-chloro-2-hydroxypropyl sulfonate and sodium 3-chloropropanesulfonate; the alkenyl sulfonate preferably comprises one or more of sodium ethylene sulfonate, sodium methacrylate sulfonate and sodium allylsulfonate; the halogenated carboxylic acid preferably comprises one or more of chloroacetic acid, dichloroacetic acid, trichloroacetic acid, 2-chloropropionic acid and 3-chloropropionic acid; when a mixture of a plurality of ionic etherifying agents is used, a mixture of sodium ethylene sulfonate and chloroacetic acid is preferred, and the mass ratio of sodium ethylene sulfonate to chloroacetic acid in the mixture is preferably 1 (1-5), more preferably 1:1.
In the present invention, the mass ratio of the ionic etherifying agent to the cellulose is preferably (0.1 to 0.5): 1, more preferably (0.2 to 0.4): 1.
In the present invention, the etherification reaction preferably includes the steps of: carrying out a first etherification reaction after the alkalized cellulose and the nonionic etherifying agent are mixed for the second time to obtain a first etherification product feed liquid;
and thirdly mixing the first etherification product feed liquid, the alcohol solvent and the ionic etherifying agent, and then carrying out a second etherification reaction to obtain the high-temperature-resistant and salt-resistant cellulose ether.
The method comprises the steps of carrying out a first etherification reaction after the alkalized cellulose and the nonionic etherifying agent are mixed for the second time, so as to obtain a first etherification product feed liquid. In the present invention, the second mixture is preferably: stirring and dispersing the alkalized cellulose and the nonionic etherifying agent for 30-90 min, preferably 50-60 min under the airtight and pressurized conditions; the pressure of the closed pressurization is preferably 0.5-3 MPa, more preferably 1.5-2.5 MPa, the temperature of the closed pressurization is preferably 30-60 ℃, more preferably 40-50 ℃, and in the specific embodiment of the invention, the nonionic etherifying agent is preferably directly added into the obtained alkalized cellulose feed liquid for secondary mixing after alkalization is completed and the temperature and the pressure are reduced. The invention is stirred and dispersed under the airtight and pressurized condition, which is favorable for the nonionic etherifying agent to penetrate more into the crystallization area of the cellulose, thereby etherifying the crystallization area.
In the present invention, the temperature of the first etherification reaction is preferably 85 to 95 ℃, more preferably 88 to 92 ℃; the pressure of the first etherification reaction is preferably 1.5MPa or more, more preferably 1.5 to 5MPa; the time of the first etherification reaction is preferably 20 to 80 minutes, more preferably 40 to 60 minutes.
After the first etherification reaction is finished, the invention preferably performs cooling and pressure relief, wherein the cooling is preferably reduced to below 60 ℃, and particularly 15-60 ℃; the pressure relief is preferably carried out to normal pressure, and the time for reducing the temperature and relieving the pressure is preferably 10-50 min. The invention has no requirement on the cooling and pressure relief rates.
After the first etherification reaction is cooled and depressurized, other treatments are not needed, and the subsequent reaction is directly carried out.
After the first etherification reaction is finished, the obtained first etherification product feed liquid, an alcohol solvent and an ionic etherifying agent are mixed for the third time and then subjected to the second etherification reaction, so that the high-temperature-resistant and salt-resistant cellulose ether is obtained. In the present invention, the alcohol solvent is preferably one or both of ethanol and isopropanol, the weight ratio of the alcohol solvent to the cellulose is preferably (1.5 to 5): 1, more preferably (2 to 4): 1, and the alcohol solvent is a solvent for the second etherification reaction. In a specific embodiment of the present invention, the volume fraction of the ethanol is preferably 70 to 95%, and the volume fraction of the isopropanol is preferably 70 to 90%.
In the present invention, in a specific embodiment of the present invention, the third mixing is preferably:
after the temperature of the first etherification product feed liquid is reduced below 60 ℃, adding an alcohol solvent into the feed liquid, and after the temperature of the mixed material is continuously reduced to 20-50 ℃, adding an ion etherifying agent into the feed liquid to obtain a third mixed material;
stirring and dispersing the third mixed material under normal pressure, wherein the temperature of the material liquid is 20-50 ℃ during stirring and dispersing, and the stirring and dispersing time is 20-60 min.
In the invention, the first etherification product feed liquid is more preferably cooled to 50-60 ℃; the temperature of the alcohol solvent to be added is more preferably 5 to 10 ℃. In the invention, the temperature for continuing to cool is more preferably cooled to 30-40 ℃; the second stirring and dispersing time is more preferably 30 to 50min, and in embodiments may be specifically 30min, 40min, 50min or 60min. According to the invention, after the ionic etherifying agent is added, the ionic etherifying agent is stirred and dispersed for a period of time, so that the etherifying agent can fully permeate, the reaction uniformity is improved, the better the etherifying agent permeation effect is when the time is longer, and the improvement of the reaction uniformity is facilitated.
In the present invention, the temperature of the second etherification reaction is preferably 60 to 100 ℃, more preferably 70 to 90 ℃, the time of the second etherification reaction is preferably 60 to 120min, more preferably 80 to 100min, and the pressure of the second etherification reaction is preferably 0.02MPa or more, more preferably 0.02 to 0.5MPa. The invention preferably carries out the second etherification reaction by heating to the temperature of the second etherification reaction after the stirring and dispersing are completed.
And after the second etherification reaction is finished, obtaining a cellulose ether crude product, wherein the cellulose ether crude product can be directly used after being dried and crushed, and can be further refined to obtain a refined product for reuse. In the invention, the temperature of the drying is preferably 100-160 ℃; the pulverization is preferably carried out by pulverizing the dried cellulose ether to 40 mesh or less.
In the present invention, the refining treatment method is preferably as follows:
and washing, neutralizing, centrifuging, stripping, drying and crushing the product feed liquid obtained by the second etherification reaction in sequence to obtain the cellulose ether refined product.
In the present invention, the washing detergent is preferably isopropyl alcohol; the neutralizing agent for neutralization is preferably an organic acid or an inorganic acid, and particularly preferably acetic acid; the invention preferably adds the neutralizing agent into the detergent, then washes the product feed liquid, and the pH value of the washing end point is preferably 6-9; the steam stripping is preferably carried out by a steam stripping machine, and the alcohol solvent in the materials is recovered through steam stripping; the present invention is not particularly limited to the drying and pulverizing, and conditions well known to those skilled in the art may be employed.
The invention also provides the high-temperature-resistant and salt-resistant cellulose ether prepared by the preparation method. In the invention, the nonionic group content of the high temperature resistant and high calcium resistant cellulose ether is more than or equal to 2wt%, preferably 2 to 30wt%, more preferably 5 to 25wt%; the ionic group content is more than or equal to 2.5wt%, preferably 2.5-25 wt%, more preferably 5-20 wt%; the nonionic groups preferably include one or more of methyl, ethyl, propyl, hydroxyethyl, and hydroxypropyl; the ionic group preferably includes one or more of a sulfonic acid group and a carboxymethyl group. In the high temperature resistant and salt resistant cellulose ether of the present invention, the ionic groups and the nonionic groups are uniformly distributed in the crystalline region and the amorphous region of the cellulose ether.
The invention also provides application of the high-temperature-resistant and salt-resistant cellulose ether in drilling and completion fluid containing metal ions. In the invention, the metal ions in the drilling and completion fluid containing the metal ions can be monovalent and/or multivalent metal ions, the concentration of the multivalent metal ions is not required, and the concentration can be any concentration until saturation; the polyvalent metal ion is a metal ion having a valence of +2 or more, preferably including Ca 2+ 、Mg 2+ 、Sr 2+ 、Ba 2+ 、Al 3+ 、Zn 2+ And Cu 2+ One or more of the following; the addition amount of the high-temperature-resistant and salt-resistant cellulose ether in the high-brine drilling and completion fluid is preferably 0.2-5 wt%, more preferably 0.5-4 wt%; the high-temperature-resistant salt-resistant cellulose ether disclosed by the invention can play roles in tackifying, solubilizing and resisting high temperature when being added into a high-brine drilling and completion fluid.
In the present invention, when the high temperature resistant salt resistant cellulose ether is used to adjust the viscosity of drilling and completion fluids, the adjustment preferably comprises increasing the amount of the high temperature resistant salt resistant cellulose ether in the drilling and completion fluids (noted as method one); or the consumption of the high-temperature-resistant and salt-resistant cellulose ether is kept unchanged, and the content of polyvalent metal ions in drilling and completion fluids is increased (recorded as a second method); in the first method, the dosage of the cellulose ether specifically refers to the weight of the cellulose ether in drilling and completion fluids, and the viscosity of the drilling and completion fluids increases along with the increase of the weight of the cellulose ether in the drilling and completion fluids; in the second method, when the weight of cellulose ether in the drilling and completion fluid is kept constant, the viscosity of the drilling and completion fluid is increased along with the increase of the content of polyvalent metal ions, and the viscosity of the drilling and completion fluid is maximized when the polyvalent metal ions reach saturation.
In a specific embodiment of the present invention, the concentration of cellulose ether in the drilling and completion fluid is preferably 0.2 to 5wt% when the method is used, the concentration of metal ions is preferably 10 to 30wt%, and the concentration of cellulose ether in the drilling and completion fluid is preferably 0.2 to 5wt% when the method is used, and the concentration of metal ions is preferably 60 to saturated.
The conventional ionic cellulose ether in the field has a certain salt resistance effect, but has better effect in monovalent metal salt (sodium chloride and the like) environment, the monovalent metal ions can lead the polymer to be curled to lower the viscosity, and the high-concentration divalent metal ions can generate bonding effect with polymer molecular chains besides the effect of aggravating the monovalent metal ions, so that macromolecular coils are rapidly compressed to force the ionic cellulose ether to be separated out of the solution, the conventional ionic cellulose ether has low ionic group content and uneven distribution, and after the ionic cellulose ether is combined with polyvalent metal ions, the molecular chains are seriously curled, the water-solubility is seriously reduced, the viscosity is obviously reduced along with the increase of the polyvalent metal ions, and the ionic cellulose ether can be separated out of the solution until the viscosity is completely lost, so that the ionic cellulose ether is more awkward at high temperature.
Because the conventional natural modified cellulose ether cannot be applied to drilling and completion fluids of high brine, petrochemical derivative polymers are generally adopted at present to improve the rheological property and the temperature resistance of the drilling and completion fluids of the high brine, but the products have strict use conditions, can be generally only applied to the brine with lower concentration (less than or equal to 30 percent of calcium chloride and mass/volume), and have poor environmental protection, high price and larger dosage (5 to 10 percent). The high-temperature-resistant salt-resistant cellulose ether disclosed by the invention has the advantages of wide use conditions, capacity of adjusting the rheological properties of drilling and completion fluids by adjusting the concentration of polyvalent metal ions, capacity increase, environmental friendliness, small addition and the like.
The invention also provides drilling and completion fluid (particularly drilling fluid or completion fluid), which comprises the high-temperature-resistant and salt-resistant cellulose ether according to the scheme; the content of the high temperature resistant and salt resistant cellulose ether in the drilling and completion fluid is preferably 0.5 to 5wt%, more preferably 0.5 to 3wt%, and even more preferably 1 to 2wt%.
The invention has no special requirements on other components in the drilling and completion fluids, and can be adopted by those skilled in the art, such as the components commonly used in high brine environment-friendly water-based drilling and completion fluids.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the cellulose material used was wood pulp, which was crushed to a particle size of 1cm or less; the concentration of the aqueous sodium hydroxide solution used was 50wt%, the purity of dimethyl ether was 40%, the purity of diethyl ether was 50%, the purity of ethanol was 95%, the purity of isopropyl alcohol used in the reaction process was 80%, and the purity of isopropyl alcohol used in the post-treatment process was 70%.
Example 1
Adding 1kg of broken cellulose and 1.1 times (the multiple in the embodiment is the weight multiple of cellulose) of sodium hydroxide aqueous solution and 0.7 times of dimethyl ether into a reaction kettle, pressurizing to 1-2 MPa, heating to 40-70 ℃, cooling to 20-40 ℃ after 60min (including the time of heating up, pressurizing and maintaining the temperature), depressurizing to normal pressure, cooling and depressurizing for 20min, adding 1.67 times of chloromethane after cooling and depressurizing, stirring and dispersing for 60min under the conditions of 30-60 ℃ and 1.5-2.5 MPa, heating to 92 ℃, keeping the pressure above 1.5MPa, reacting for 50min, cooling (not more than 60 ℃) for 30min, adding 3 times of ethanol at not more than 10 ℃ into the materials, continuously cooling to 20-40 ℃, adding 0.3 times of sodium 2-chloroethanesulfonate, stirring and dispersing for 40min under the normal pressure, gradually reaching 80 ℃ and keeping the pressure above 0.02MPa, reacting for 90min, and obtaining a crude product, drying, grinding, and further obtaining a crude product, drying, and carrying out centrifugal grinding, and drying.
Example 2
Adding 1kg of crushed cellulose, 1.1 times of sodium hydroxide aqueous solution and 0.6 times of diethyl ether into a reaction kettle, pressurizing to 1.5-2.5 MPa, heating to 30-60 ℃, cooling to 20-40 ℃ after 60min (including the time of heating up, pressurizing and maintaining the temperature) and releasing the pressure, releasing the pressure to normal pressure, wherein the time of cooling and releasing the pressure is 20min, adding 1.6 times of monochloroethane after the cooling and releasing are finished, stirring and dispersing for 80min under the condition that the temperature is 50-70 ℃ and the pressure is 3.0-4.5 MPa, heating to 95 ℃ and maintaining the pressure above 2MPa, reacting for 70min, then cooling (not more than 60 ℃) and releasing the pressure (to normal pressure) for 35min, adding 3.5 times of isopropanol with the temperature not more than 10 ℃ to materials, continuing to cool to 30-50 ℃, adding 0.2 times of sodium ethylene sulfonate, stirring and dispersing for 70min under the normal pressure and gradually heating to 85 ℃, and maintaining the pressure above 0.3MPa, reacting for 100min, obtaining a crude product, and drying and crushing the crude product, and further obtaining the crude product through washing, neutralizing, refining, steam stripping and crushing.
Example 3
Adding 1kg of crushed cellulose, 1.2 times of sodium hydroxide aqueous solution and 0.72 times of dimethyl ether and diethyl ether (the volume ratio is 1:1) into a reaction kettle, pressurizing to 2-3 MPa, heating to 30-60 ℃ for 50min (comprising the time of heating, pressurizing and maintaining the temperature), cooling to 20-40 ℃, releasing pressure to normal pressure, cooling and releasing pressure for 20min, adding 1.7 times of nonionic etherifying agent (a mixture of 1:1 by mass ratio of monochloroethane and propylene oxide) after cooling and releasing, stirring and dispersing for 90min at 40-70 ℃ and 3.0-5.0 MPa, heating to 95 ℃ and keeping the pressure above 3MPa, reacting for 70min, cooling (not more than 60 ℃) and releasing pressure (to normal pressure), adding isopropanol with 3.0 times of temperature not more than 10 ℃ to the material, continuously cooling to 30-50 ℃, adding 0.35 times of ionic etherifying agent (a mixture of 1:1 by mass ratio of sodium ethylene sulfonate and chloroacetic acid), stirring and dispersing for 70min at 20-50 ℃, gradually heating to 3.85 ℃ and keeping the pressure, drying, and grinding to obtain a crude product, and drying, or drying, and further obtaining a crude product after the crude product, drying and grinding and drying.
Example 4
Adding 1kg of crushed cellulose, 1.1 times of sodium hydroxide aqueous solution and 0.7 times of dipropyl ether into a reaction kettle, pressurizing to 1-2 MPa, heating to 40-70 ℃, cooling to 20-40 ℃ after 60min (including the time of heating up, pressurizing, heat preservation and pressure maintaining), depressurizing to normal pressure, cooling and depressurizing for 20min, adding 1.67 times of chloromethane after cooling and depressurizing are finished, stirring and dispersing for 60min under the conditions of 30-60 ℃ and 1.5-2.5 MPa, heating to 92 ℃ and maintaining the pressure above 1.5MPa, reacting for 50min, cooling (not more than 60 ℃) and depressurizing (to normal pressure) for 30min, adding 3 times of ethanol with the temperature not more than 10 ℃ into the material, continuously cooling to 20-40 ℃, adding 0.3 times of 2-chloroethane sodium sulfonate, stirring and dispersing for 40min under the normal pressure, gradually heating to 80 ℃, maintaining the pressure above 0.02MPa, reacting for 90min, obtaining a crude product, and drying and crushing, washing, neutralizing, drying, refining, stripping and obtaining the crude product.
Example 5
Adding 1kg of crushed cellulose, 1.1 times of sodium hydroxide aqueous solution and 0.7 times of dimethyl ether into a reaction kettle, pressurizing to 1-2 MPa, heating to 40-70 ℃, cooling to 20-40 ℃ after 60min (comprising the time of heating up, pressurizing, heat preservation and pressure maintaining), depressurizing to normal pressure, wherein the time of cooling down and depressurizing is 20min, adding 1.67 times of propylene oxide after cooling down and depressurizing are finished, stirring and dispersing for 60min under the conditions of temperature of 30-60 ℃ and pressure of 1.5-2.5 MPa, heating to 92 ℃ and keeping the pressure above 1.5MPa, reacting for 50min, then cooling down (not more than 60 ℃) and depressurizing (to normal pressure), adding 3 times of ethanol to the material, continuously cooling down to 20-40 ℃, adding 0.3 times of chloroacetic acid, stirring and dispersing for 40min under normal pressure, gradually heating to 80 ℃, keeping the pressure above 0.02MPa, reacting for 90min, obtaining a crude product, and further obtaining the crude product after crushing, washing, neutralizing, centrifuging, drying, refining, stripping and obtaining the crude product.
Comparative example 1
Other conditions were the same as in example 2, except that the pressure in the alkalizing step was changed to normal pressure, specifically: 1kg of crushed cellulose, 1.1 times of sodium hydroxide aqueous solution and 0.6 times of diethyl ether are added into a reaction kettle, the temperature is raised to 30-60 ℃, the reaction is carried out for 60min under normal pressure, then the temperature is reduced to 20-40 ℃, then 1.6 times of monochloroethane is added, and the subsequent operation steps are the same as in example 2.
Comparative example 2
Other conditions were the same as in example 2, and only the alkalizing solvent was changed from diethyl ether to isopropyl alcohol.
Comparative example 3
The ionic group-nonionic group modified cellulose ether is prepared by adopting a conventional method, and the steps are as follows:
adding crushed cellulose, 1.1 times of sodium hydroxide aqueous solution and 0.6 times of ethanol into a reaction kettle, stirring for 80min at 20-30 ℃ and normal pressure, adding 1.6 times of monochloroethane after the completion, stirring for 80min at normal pressure, heating to 80 ℃, keeping the pressure less than or equal to 0.2MPa, reacting for 70min, cooling (less than or equal to 60 ℃), adding 3.5 times of isopropanol with the temperature less than or equal to 10 ℃ until the temperature of the material is continuously reduced to 30-50 ℃, adding 0.2 times of sodium ethylene sulfonate, stirring and dispersing for 70min at 20-40 ℃, gradually heating to 85 ℃, keeping the pressure less than or equal to 0.2MPa, reacting for 100min to obtain a crude product, and drying and crushing the crude product, wherein the crude product can be directly used, or can be washed, neutralized, centrifuged, stripped, dried and crushed to obtain a refined product.
Test example 1
The cellulose ether purified products obtained in examples 1 to 5 and comparative examples 1 to 3 were tested for the content of ionic groups and nonionic groups, and the results are shown in Table 1.
Table 1 ionic group and nonionic group contents (mass fraction) of the cellulose ether purified products obtained in examples 1 to 3 and comparative examples 1 to 3
| Project | Nonionic group content | Ionic group content |
| Example 1 | 21％ | 11％ |
| Example 2 | 19％ | 13％ |
| Example 3 | 28％ | 17％ |
| Example 4 | 19％ | 11％ |
| Example 5 | 8％ | 16％ |
| Comparative example 1 | 19％ | 4％ |
| Comparative example 2 | 1％ | 2％ |
| Comparative example 3 | 0.5％ | 1％ |
The crystal area ratio of wood pulp and refined cotton is more than 50%, and the crystal area of fiber is compact and can not be penetrated by medicine, so that when the cellulose ether is prepared by conventional method, the cellulose is usually reacted in non-crystal area, the content of ionic groups and non-ionic groups of cellulose is low, and the distribution is uneven. As can be seen from the data in table 1, the cellulose ether prepared in comparative examples 1 to 3 has a smaller content of ionic groups and nonionic groups, while the cellulose ether prepared in examples 1 to 5 has a greatly improved content of both ionic groups and nonionic groups, indicating that the method of the present invention can open the crystalline region of cellulose so that the ionic groups and nonionic groups enter the crystalline region to react.
Test example 2
The cellulose ether refined products prepared in examples 1 to 5 and comparative examples 1 to 3 (purity about 90%) were tested while using commercially available sodium carboxymethyl cellulose as a control by the following test method:
400mL of fresh water is weighed, 8 g (2%, w/v) of cellulose ether is added, calcium chloride is added into the solution, 60% (w/v) of calcium chloride solution is prepared respectively, after complete dissolution, the density and rheological property of the solution at normal temperature are tested, then the solution is subjected to 150 ℃ heat rolling aging for 16 hours, and after the completion, the solution is cooled to normal temperature, and the density and rheological property are tested.
Other conditions were the same as the above test procedure, and only the amount of calcium chloride added was changed to prepare a saturated calcium chloride solution, which was tested according to the above test method.
The test results are shown in Table 2.
TABLE 2 Effect of cellulose ethers on rheological Properties of calcium chloride solutions
As can be seen from the contents in table 2, after the cellulose ethers prepared in examples 1 to 5 were added, the viscosity of the calcium chloride solution at normal temperature was significantly increased, and the viscosity decrease after high temperature treatment was small; the viscosity increase was greater for the saturated calcium chloride solution than for the 60% calcium chloride solution, indicating that the viscosity of the solution increased with increasing calcium ion concentration after the addition of the cellulose ether of the present invention. In contrast, in comparative example 1, when the cellulose ether is prepared, the high temperature and high pressure condition is not adopted in the alkalization process, in comparative example 2, isopropanol is adopted as the solvent in the alkalization process, although the high temperature and high pressure condition is adopted, the boiling point of the isopropanol is higher, gasification cannot occur, in comparative example 3, the isopropanol is adopted as the solvent, the alkalization is carried out at normal temperature and normal pressure, the crystallization area of the cellulose cannot be opened by the methods in comparative examples 1 to 3, the number of substituent groups in the finally obtained cellulose ether is less and uneven, as can be seen from the data in table 2, the viscosity of the calcium chloride solution is obviously reduced after the cellulose ether in comparative example 1 is added, and the viscosity of the saturated calcium chloride solution is increased compared with the viscosity of the 60% calcium chloride solution, but the amplitude is small; while comparative examples 2 to 3 and commercially available sodium carboxymethylcellulose have substantially no thickening effect.
Test example 3
Other test conditions were the same as in test example 1, and only the calcium chloride was replaced with a polyvalent complex salt, which was a commercial product, a novel complex salt of model HD-160, and an inorganic salt having a divalent metal ion as a main component was a mixture. Preparing a 60% multivalent composite salt solution and a saturated multivalent composite salt solution by adopting multivalent metal salt; the test was conducted in accordance with the method of test example 2, and the results are shown in Table 3.
TABLE 3 Effect of cellulose ethers on rheological Properties of multivalent Metal salt solutions
As can be seen from the data in table 3, the cellulose ether of the present invention can exert an obvious thickening effect when added to a polyvalent metal complex salt solution, and has good high temperature resistance, and the solution viscosity increases as the concentration of the polyvalent metal complex salt increases. The cellulose ether of comparative example 1 has poor tackifying effect and is not resistant to high temperatures; comparative examples 2 to 3 and commercially available sodium carboxymethylcellulose have substantially no thickening effect.
Test example 4
The cellulose ethers prepared in examples 1 to 5 and comparative examples 1 to 3 were tested for compatibilizing effect by the following test methods:
350mL of fresh water was taken, 1.75 g (0.5%, w/v) of cellulose ether was added, and a multivalent complex salt (model number consistent with test example 3) was added to the solution to saturation, and the density was measured; the density of the saturated complex salt solution without the cellulose ether added was also tested as a blank. The test results are shown in Table 4.
Table 4 cellulose ether compatibilization test results
As can be seen from the data in table 4, the solubility of calcium chloride increases after the cellulose ethers prepared in examples 1 to 5 of the present invention are added, indicating that the cellulose ethers of the present invention have a compatibilizing effect, whereas the cellulose ethers prepared in comparative examples 1 to 3 have no compatibilizing effect.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The preparation method of the high-temperature-resistant and salt-resistant cellulose ether comprises the following steps:
alkalizing a cellulose raw material, an alkali metal hydroxide aqueous solution and an ether solvent by first mixing to obtain alkalized cellulose; the alkalizing temperature is 30-70 ℃, the pressure is 0.5-6 MPa, and the ether solvent is gasified under the alkalizing temperature and pressure conditions; the ether solvent comprises one or more of dimethyl ether, diethyl ether and dipropyl ether;
respectively carrying out etherification reaction on the alkalized cellulose by using a nonionic etherifying agent and an ionic etherifying agent to obtain the high-temperature-resistant and salt-resistant cellulose ether;
the etherification reaction comprises the following steps: carrying out a first etherification reaction after the alkalized cellulose and the nonionic etherifying agent are mixed for the second time to obtain a first etherification product feed liquid; thirdly mixing the first etherification product feed liquid, an alcohol solvent and an ionic etherifying agent, and then carrying out a second etherification reaction;
the second mixing includes: stirring and dispersing the alkalized cellulose and the nonionic etherifying agent under the airtight and pressurized conditions; the stirring and dispersing time is 30-90 min, the pressure of the closed pressurization is 0.5-3 MPa, and the stirring and dispersing temperature is 30-60 ℃;
the third mixing is as follows: after the temperature of the first etherification product feed liquid is reduced to below 60 ℃, adding an alcohol solvent into the feed liquid, and after the temperature of the mixed material is continuously reduced to 20-50 ℃, adding an ion etherifying agent into the feed liquid to obtain a third mixed material; stirring and dispersing the third mixed material under normal pressure, wherein the temperature of the material liquid is 20-50 ℃ during stirring and dispersing, and the stirring and dispersing time is 20-60 min;
the nonionic etherifying agent comprises one or more of a monohalogenated alkane and an alkylene oxide; the mass ratio of the nonionic etherifying agent to the cellulose raw material is (0.8-2.5): 1; the ionic etherifying agent comprises one or more of halogenated alkyl sulfonate, alkenyl sulfonate and halogenated carboxylic acid; the mass ratio of the ionic etherifying agent to the cellulose is (0.1-0.5): 1.
2. The preparation method according to claim 1, wherein the concentration of the alkali metal hydroxide aqueous solution is 30-52 wt%, and the mass ratio of the cellulose raw material to the alkali metal hydroxide aqueous solution is 1 (0.5-1.7); the mass ratio of the cellulose raw material to the ether solvent is 1 (0.3-1.1); the carbon number of the ether solvent is less than or equal to 6.
3. The preparation method according to claim 1 or 2, wherein the alkalization comprises: heating and pressurizing the mixture obtained by the first mixing, keeping the temperature and the pressure after reaching the alkalization temperature and the alkalization pressure, and then reducing the temperature and the pressure; the temperature and pressure rise time is less than or equal to 10min, the heat preservation and pressure maintaining time is 20-80 min, and the temperature and pressure relief time is 10-30 min;
and the temperature and pressure reduction is carried out until the temperature is reduced to 20-40 ℃ and the pressure is reduced to normal pressure.
4. The preparation method according to claim 1, wherein the temperature of the first etherification reaction is 85-95 ℃, the pressure is more than 1.5MPa, and the time is 20-80 min; the temperature of the second etherification reaction is 60-100 ℃, the time is 60-120 min, and the pressure is more than 0.02 MPa.
5. The method according to claim 1, wherein after the second etherification reaction is completed, further comprising subjecting the obtained product feed liquid to a refining treatment;
the refining treatment comprises the following steps: and washing, neutralizing, centrifuging, stripping, drying and crushing the product feed liquid obtained by the second etherification reaction in sequence to obtain the cellulose ether refined product.
6. The high temperature resistant and salt resistant cellulose ether prepared by the preparation method of any one of claims 1 to 5, wherein the content of nonionic groups of the high temperature resistant and high calcium resistant cellulose ether is more than or equal to 2wt%, and the content of ionic groups is more than or equal to 2.5wt%.
7. Use of the high temperature resistant, salt-tolerant cellulose ether of claim 6 in a drilling and completion fluid containing metal ions.
8. Drilling and completion fluids comprising the high temperature and salt resistant cellulose ether of claim 6.
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