CN112266422A - Cationic starch and preparation method thereof - Google Patents
Cationic starch and preparation method thereof Download PDFInfo
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- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
- C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
Abstract
The invention discloses cationic starch and a preparation method thereof, wherein the preparation method of the cation comprises the following steps: obtaining starch slurry; adding a cationic etherifying agent into the starch slurry, and adding an alkaline catalyst for reaction after a first preset time interval to obtain cationic starch; wherein the addition amount of the cationic etherifying agent is larger than that of the basic catalyst so that the reaction of the cationic etherifying agent is finished later than that of the basic catalyst. Through the mode, the method can improve the substitution degree of the starch and ensure the quality of the cationic starch, so that the preparation efficiency of the cationic starch is improved.
Description
Technical Field
The invention relates to the technical field of starch preparation, in particular to cationic starch and a preparation method thereof.
Background
A wide variety of starch derivatives can be obtained from natural starch after chemical modification, and the starch derivatives have wide application range in industry. Among them, cationic starch is a branch of modified starch which is being studied and industrially applied. Cationic starch is widely used in the paper industry as a derivative of starch. The positive charge of cationic starch enables it to bind to negatively charged substrates and adsorb other negatively charged additives to be retained on the substrate. Therefore, the cationic starch can realize the functions of increasing the retention rate of pulp fine fibers and fillers, improving the drainage performance and the like in papermaking, and improve the ash content and the paper forming strength of cationic starch paper.
The general method for preparing the cationic starch mainly comprises wet preparation and dry preparation, wherein the dry preparation has simple and quick reaction and low requirement on equipment, but the stability is slightly poor. The method for preparing the cationic starch by the paper mill is carried out by adopting a wet process. However, when the wet process is adopted, due to the influence of the reaction temperature, the reaction concentration and the alkali addition amount, starch is easy to gelatinize, the reaction efficiency is influenced, and starch is gelatinized and stuck in a reaction barrel tank and cannot be cleaned in severe cases, so that the conversion efficiency of the starch is reduced.
In the general case of the method, the gelatinization is usually inhibited by adding a larger amount of a swelling inhibitor (sodium chloride), thereby increasing the degree of substitution of the starch. However, since the paper mill does not have a washing process for preparing the cationic starch, the residue of the excessive salt substances adversely affects the quality of the cationic starch.
Disclosure of Invention
The invention provides cationic starch and a preparation method thereof, which aim to solve the problem that the quality and the substitution degree of the cationic starch are difficult to guarantee simultaneously in the prior art.
In order to solve the technical problems, the invention provides a preparation method of cationic starch, which comprises the following steps: obtaining starch slurry; adding a cationic etherifying agent into the starch slurry, and adding an alkaline catalyst for reaction after a first preset time interval to obtain cationic starch; wherein the addition amount of the cationic etherifying agent is larger than that of the basic catalyst so that the reaction of the cationic etherifying agent is finished later than that of the basic catalyst.
Adding a cationic etherifying agent into the starch slurry, and adding an alkaline catalyst for reaction after a first preset time interval, wherein the step of obtaining the cationic starch comprises the following steps: uniformly mixing the starch slurry, the alkaline catalyst and the cationic etherifying agent to obtain a mixed solution; heating the mixed solution to 42-53 ℃, and reacting for 8-24 hours; and adding a pH regulator into the mixed solution to enable the pH value of the mixed solution to be in a preset range, so as to obtain the cationic starch.
Wherein the adding of the pH regulator to the mixed solution to make the pH value of the mixed solution in a preset range to obtain the cationic starch comprises: diluting the mixed solution with the pH value within the preset range to the concentration of 3-5%, and heating to 90-98 ℃ for cooking for 5-15 minutes.
Wherein the preset range of the pH value is 6.5-7.5.
Adding a cationic etherifying agent into the starch slurry, and adding an alkaline catalyst for reaction after a first preset time interval, wherein the step of obtaining the cationic starch comprises the following steps: and adding a cationic etherifying agent with the starch slurry absolute amount of 5.0-10.0% into the starch slurry, and adding an alkaline catalyst with the starch slurry absolute amount of 2.0-3.0% after the first preset time interval for reaction to obtain the cationic starch.
Wherein the step of adding the alkaline catalyst with the starch slurry oven dry weight of 2.0-3.0% for reaction after the first preset time interval comprises the following steps: preparing an alkaline catalyst with the absolute dry weight of 2.0-3.0% of the starch slurry into an alkaline solution with the concentration of 8% -12%; and adding the 8% -12% alkaline solution into the starch slurry for reaction after a first preset time interval.
Wherein the alkaline catalyst comprises one or more of sodium hydroxide and sodium bicarbonate; the cationic etherifying agent includes 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 4-chloro-2-butenyl trimethyl ammonium chloride, and epoxypropyl trimethyl ammonium chloride.
Wherein the step of obtaining a starch slurry comprises: obtaining raw starch, wherein the raw starch comprises one or more of cassava starch, corn starch, potato starch and wheat starch; mixing the raw starch with water to obtain the starch slurry with the mass fraction of 37-46%.
Wherein, the range of the first preset time is as follows: (0, 4] sec.
In order to solve the technical problems, the invention also provides cationic starch prepared by any one of the preparation methods of the cationic starch.
The invention has the beneficial effects that: different from the situation of the prior art, the method adds the cationic etherifying agent and the alkaline catalyst into the starch slurry, and reduces the hydrolysis phenomenon of the cationic etherifying agent in the starch slurry by the reaction between the cationic etherifying agent and the alkaline catalyst, thereby ensuring the effective rate of the cationic etherifying agent and improving the substitution degree of the starch. In addition, in the embodiment, the cationic etherifying agent is added into the starch slurry at first preset time intervals, the alkaline catalyst is added for reaction, and the reaction finishing time of the cationic etherifying agent is later than that of the alkaline catalyst, so that the cationic etherifying agent can exist in the whole reaction process of the alkaline catalyst, the alkaline catalyst is prevented from directly reacting with the starch, the starch gelatinization phenomenon is caused, and the quality of the cationic starch is improved. Therefore, the embodiment further improves the substitution degree of the starch, enhances the conversion efficiency of the starch and improves the generation efficiency of the cationic starch.
Drawings
FIG. 1 is a schematic flow chart of an embodiment of a method for preparing cationic starch according to the present invention;
FIG. 2 is a schematic flow chart of another embodiment of the method for preparing cationic starch provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, fig. 1 is a schematic flow chart of an embodiment of a method for preparing cationic starch according to the present invention, wherein the method for preparing cationic starch of the present embodiment comprises the following steps:
step S11: obtaining starch slurry.
Weighing a certain amount of raw starch, adding water, mixing, and uniformly stirring to obtain starch slurry. Wherein the native starch may be a solid starch, or a liquid starch that has been mixed with water.
Mixing raw starch with water to obtain starch slurry with preset concentration for preparing cationic starch. The specific value of the predetermined concentration may depend on the actual production of the cationic starch, for example: starch slurry with mass fraction of 38%, 40%, 42% or 45% is obtained, which is not limited herein.
Step S12: adding a cationic etherifying agent into the starch slurry, and adding an alkaline catalyst for reaction after a first preset time interval to obtain cationic starch; wherein the addition amount of the cationic etherifying agent is larger than that of the basic catalyst so that the reaction of the cationic etherifying agent is finished later than that of the basic catalyst.
And adding a cationic etherifying agent into the starch slurry, and adding an alkaline catalyst to react after a first preset time interval to obtain the cationic starch.
In general, cationic starch is prepared by reacting starch with a cationic etherifying agent. However, the cationic etherifying agent is easily hydrolyzed in the starch slurry, so that the cationic etherifying agent is lost, resulting in a decrease in the degree of substitution of the starch, thereby decreasing the conversion efficiency between the starch and the cationic starch.
In this embodiment, the cationic etherifying agent and the alkaline catalyst are added to the starch slurry, and then the cationic etherifying agent and the alkaline catalyst are reacted with each other to activate the cationic etherifying agent, so that the cationic etherifying agent generates an active group, and the active group of the cationic etherifying agent is reacted with the starch to generate the cationic starch. In the embodiment, the alkaline catalyst is added, so that the alkaline catalyst and the cationic etherifying agent can be reacted in one step, and the hydrolysis phenomenon of the cationic etherifying agent in the starch slurry is reduced. Thereby ensuring the effective rate of the cationic etherifying agent to a certain extent and improving the substitution degree of the starch. Meanwhile, the embodiment avoids the addition of the swelling inhibitor, thereby avoiding the residue of the swelling inhibitor in the cationic starch and improving the purity and quality of the cationic starch.
Starch is easy to be gelatinized with alkaline substances in an environment with a high pH value, so that the reaction efficiency is influenced, the starch is stuck in a reaction barrel groove and cannot be cleaned, and the reaction environment is polluted. Therefore, in this embodiment, the cationic etherifying agent is added to the starch slurry, and the alkaline catalyst is added after a first predetermined time interval to perform the reaction. And the addition amount of the cationic etherifying agent is made larger than that of the alkaline catalyst, so that the reaction finishing time of the cationic etherifying agent is later than that of the alkaline catalyst. In the whole reaction process, the cationic etherifying agent exists through the whole reaction process of the alkaline catalyst, so that the alkaline catalyst firstly reacts with the cationic etherifying agent, and the direct reaction of the alkaline catalyst and starch is avoided, thereby avoiding the gelatinization phenomenon. To further increase the degree of substitution of the starch.
Through the manner, in the preparation method of the cation, the cation etherifying agent and the alkaline catalyst are added into the starch slurry to reduce the hydrolysis phenomenon of the cation etherifying agent in the starch slurry, so that the efficiency of the cation etherifying agent is ensured, and the substitution degree of the starch is improved. In addition, in the embodiment, the cationic etherifying agent is added into the starch slurry at first preset time intervals, the alkaline catalyst is added for reaction, and the reaction finishing time of the cationic etherifying agent is later than that of the alkaline catalyst, so that the cationic etherifying agent can exist in the whole reaction process of the alkaline catalyst, and the alkaline catalyst is prevented from directly reacting with the starch, and the starch gelatinization phenomenon is avoided. Therefore, the embodiment further improves the substitution degree of the starch, enhances the conversion efficiency of the starch and improves the generation efficiency of the cationic starch. Meanwhile, the embodiment avoids the addition of the swelling inhibitor, thereby avoiding the residue of the swelling inhibitor in the cationic starch and improving the purity and quality of the cationic starch.
Referring to fig. 2, fig. 2 is a schematic flow chart of another embodiment of the method for preparing cationic starch of the present invention, wherein the method for preparing cationic starch of the present embodiment comprises the following steps:
step S21: obtaining raw starch, wherein the raw starch comprises one or more of cassava starch, corn starch, potato starch and wheat starch, and mixing the raw starch with water to obtain starch slurry with the mass fraction of 37-46%.
Obtaining raw starch, wherein the raw starch comprises one or more of cassava starch, corn starch, potato starch and wheat starch. In a specific application scenario, raw starch consisting of a single tapioca starch may be obtained. In a specific application scenario, raw starch consisting of a mixture of corn starch and potato starch may be obtained. In a specific application scene, raw starch mixed with starch in cassava starch, corn starch, potato starch and wheat starch can also be obtained. The native starch of this embodiment only needs to be one or more of tapioca starch, corn starch, potato starch and wheat starch, and the specific mixture ratio is not limited.
After weighing a certain amount of raw starch, mixing the raw starch with water to obtain a starch slurry with a mass fraction of 37-46%, wherein the specific concentration can be determined according to practical application, for example: the mass fraction of the starch slurry may be 37.5%, 38%, 39.5%, 41.3%, 42%, 43.7%, 44.4%, 45%, 45.5%, 46%, etc., and is not limited herein. In a specific application scenario, 200g of cassava native starch can be weighed, 263g of water is added, and the starch slurry is prepared after uniform mixing and stirring. In a specific application scenario, 200g of cassava native starch can be weighed, 190g of water is added, and the starch slurry is prepared after uniform mixing and stirring. In a specific application scenario, 200g of corn native starch can also be weighed and added into 240g of water, and the starch slurry is prepared after uniform mixing and stirring.
Step S22: adding a cationic etherifying agent with 5.0-10.0% of starch slurry absolute dry weight into the starch slurry, and adding an alkaline catalyst with 2.0-3.0% of starch slurry absolute dry weight after a first preset time interval for reaction.
Adding a cationic etherifying agent with the absolute dry weight of 5.0-10.0% of starch slurry into the starch slurry. Wherein the cationic etherifying agent is one of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 4-chloro-2-butenyl trimethyl ammonium chloride and epoxypropyl trimethyl ammonium chloride. In a specific application scenario, the cationic etherifying agent may be 3-chloro-2-hydroxypropyl trimethyl ammonium chloride. In one particular application scenario, the cationic etherifying agent may be 4-chloro-2-butenyl trimethyl ammonium chloride. In a specific application scenario, the cationic etherifying agent may also be epoxypropyltrimethylammonium chloride. The amount of the cationic etherifying agent may be 5.0%, 5.5%, 6.1%, 6.8%, 7.0%, 7.6%, 8.0%, 8.2%, 8.7%, 9.4%, 9.8%, 10.0% of the starch slurry in terms of the oven dry weight.
After the cationic etherifying agent is added to the starch slurry and after a first preset time interval, adding an alkaline catalyst with the starch slurry absolute dry weight of 2.0-3.0% to the starch slurry. Wherein, the alkaline catalyst can be one or more of sodium hydroxide and sodium bicarbonate. Wherein, the addition amount of the alkaline catalyst can be 2.0%, 2.1%, 2.4%, 2.5%, 2.6%, 2.8% and 3.0% of the absolute dry amount of the starch slurry.
After the basic catalyst is obtained, it is prepared into a basic solution with a concentration of 8% -12%. The reaction is carried out by adding alkaline solution with the concentration of 8% -12% to the starch slurry after a first preset time interval. The concentration of the alkaline solution may be 8%, 8.5%, 9.3%, 10%, 11%, 11.3%, 12%, or the like.
The addition amount of the cationic etherifying agent is larger than that of the alkaline catalyst, so that the alkaline catalyst is ensured to react with the cationic etherifying agent before the starch reaction, and the direct reaction of the alkaline catalyst and the starch is avoided, and the gelatinization reaction is avoided.
Wherein, the range of the first preset time is as follows: (0, 4) seconds, specifically, 0.5 seconds, 1 second, 2 seconds, 3 seconds, 4 seconds, etc., or 1.3 seconds, 2.7 seconds, 3.5 seconds, etc. in the present embodiment, the first predetermined time is set to control the alkaline catalyst to be added later than the cationic etherifying agent to the starch slurry, so as to prevent the alkaline catalyst from directly reacting with the starch to generate gelatinization before the starch conversion reaction begins, but since the cationic etherifying agent itself generates hydrolysis reaction in the starch slurry, the specific time interval of the first predetermined time cannot be too long to reduce the hydrolysis of the cationic etherifying agent, and in the present embodiment, the reaction end time of the alkaline catalyst is earlier than the cationic etherifying agent by controlling the addition amount of the cationic etherifying agent to be greater than the addition amount of the alkaline catalyst, that is, the cationic etherifying agent passes through the entire reaction process of the alkaline catalyst, thereby avoiding the direct reaction of the alkaline catalyst and the starch and the occurrence of gelatinization. This example can increase the efficiency of the cationic etherifying agent, and the degree of substitution of the starch, thereby increasing the yield of cationic starch.
In a specific application scenario, the cationic etherifying agent and the basic catalyst can be added into a metering pump, so that the adding time and the adding amount of the cationic etherifying agent and the basic catalyst can be controlled by the metering pump.
Step S23: uniformly mixing the starch slurry, the alkaline catalyst and the cationic etherifying agent to obtain a mixed solution, heating the mixed solution to 42-53 ℃, reacting for 8-24 hours, adding the pH regulator into the mixed solution, and enabling the pH value of the mixed solution to be in a preset range to obtain the cationic starch.
After the cationic etherifying agent and the alkaline catalyst are added to the starch slurry, the alkaline catalyst and the cationic etherifying agent are uniformly mixed to obtain a mixed solution. And heating the mixed solution to 42-53 ℃, reacting for 8-24 hours, adding a pH regulator into the mixed solution to enable the pH value of the mixed solution to be in a preset range, and terminating the etherification reaction to obtain the cationic starch. Wherein the preset range of the pH value is 6.5-7.5. The pH regulator may be citric acid or other acidity regulator. The temperature of the mixed solution can be raised to 42 ℃, 44.5 ℃, 45 ℃, 48.7 ℃, 50 ℃ and 52.1 ℃, which are not limited herein. The reaction time may also be 8 hours, 10.3 hours, 15 hours, 20.5 hours, 24 hours, etc., wherein the reaction time may be set based on actual requirements, and is not limited herein.
In a specific application scenario, the mixed solution may be heated to 50 ℃ for 24 hours. And adding citric acid to adjust the pH value of the mixed solution to be between 6.5 and 7.5, thereby finishing the reaction and obtaining the cationic starch.
In this embodiment, after the cationic etherifying agent and the alkaline catalyst are added to the starch slurry, the cationic etherifying agent and the alkaline catalyst are first reacted with each other to activate the cationic etherifying agent, so that the cationic etherifying agent generates an epoxy active group, and then the epoxy active group of the cationic etherifying agent reacts with the starch to generate the cationic starch. In the embodiment, the alkaline catalyst is added, so that the alkaline catalyst and the cationic etherifying agent can be reacted in one step, and the hydrolysis phenomenon of the cationic etherifying agent in the starch slurry is reduced. Therefore, the effective rate of the cationic etherifying agent is ensured to a certain extent, the substitution degree of the starch is improved, and the reaction finishing time of the alkaline catalyst is earlier than that of the cationic etherifying agent by controlling the adding amounts of the cationic etherifying agent and the alkaline catalyst, so that the gelatinization phenomenon caused by the direct reaction of the alkaline catalyst and the starch is avoided, and the substitution degree and the quality of the cationic starch are improved.
In addition, in the embodiment, by adding the cationic etherifying agent with a lower concentration and the alkaline catalyst with a higher concentration, the high substitution degree of the starch can be realized, so that the conversion efficiency of the starch to the cationic starch is improved. In addition, in the preparation method of the cation, a swelling inhibitor (salt substance) is not required to be added, so that the purity of the cation starch is improved, and the quality of the cation starch is ensured to a certain extent.
The above-described embodiment of the present invention will be specifically described below by way of specific examples and comparative examples.
Control group one: weighing 200g of cassava native starch, adding 263g of water to prepare starch slurry, adding 10.6g of cationic etherifying agent under a stirring state, uniformly stirring, then adding 44g of sodium hydroxide (the concentration is 8%), adding 17.6g of sodium chloride, heating to 40 ℃, reacting for 8 hours, diluting to 4% concentration slurry, heating to 95 ℃, and cooking for 10 minutes to prepare a control group sample I.
Control group two: weighing 200g of cassava native starch, adding 190g of water to prepare starch slurry, adding 17.6g of cationic etherifying agent under a stirring state, uniformly stirring, then adding 44g of sodium hydroxide (the concentration is 8%), adding 17.6g of sodium chloride, heating to 50 ℃, reacting for 8 hours, diluting to 4% of slurry, heating to 95 ℃, and cooking for 10 minutes to prepare a control group sample II.
The first embodiment is as follows: weighing 200g of cassava native starch, adding 263g of water to prepare starch slurry, adding 10.6g of 4-chloro-2-butenyl trimethyl ammonium chloride as a cationic etherifying agent through a metering pump, adding 44g of sodium hydroxide (the concentration is 8%) after 2 seconds, ending the alkali in advance for 2 seconds, stirring and mixing uniformly, heating to 40 ℃ for reaction for 8 hours, diluting to 4% concentration slurry, heating to 95 ℃, and cooking for 10 minutes to prepare a sample I.
Example two: weighing 200g of cassava native starch, adding 190g of water to prepare starch slurry, adding 17.6g of cationic etherifying agent 3-chloro-2-hydroxypropyl trimethyl ammonium chloride through a metering pump, adding 44g of sodium hydroxide (the concentration is 12%) at intervals of 2S, ending the alkali in advance for 2S, stirring and mixing uniformly, heating to 50 ℃ for reaction for 24 hours, diluting to 4% concentration slurry, heating to 95 ℃, and cooking for 10 minutes to prepare a sample II.
Example three: weighing 200g of corn native starch, adding 240g of water to prepare starch slurry, adding 14.0g of cationic etherifying agent epoxypropyl trimethyl ammonium chloride through a metering pump, adding 44g of sodium hydroxide (the concentration is 10%) after 1 second, ending the alkali in advance by 1s, uniformly stirring and mixing, heating to 45 ℃, reacting for 12 hours, diluting to 4% concentration slurry, heating to 95 ℃, and cooking for 10 minutes to prepare a sample III.
Physical property tests were conducted on the cationic starches prepared in the above examples and comparative examples.
(1) And (3) comparing the physical properties of the starch:
TABLE 1 cationic starch Property test results
Compared with the process of the comparative example, the reaction efficiency of the sample I is higher under the condition of the same chemical addition amount, and the sample II and the sample III can react under the conditions of higher temperature, higher concentration and higher alkali addition amount without obvious gelation. The cationic starches of examples 1-3 had higher degree of substitution and viscosity than the cationic starch of the control group. The first control sample has low substitution degree and low viscosity; the control sample two even showed severe gelation.
In a specific application scenario, the mixed solution with the pH value within a preset range can be diluted to 3-5% concentration, and the temperature is raised to 90-98 ℃ for cooking for 5-15 minutes to obtain the cationic starch. To apply cationic starch. In a specific application scenario, the mixed solution with the pH value within a preset range can be diluted to 4% concentration, and heated to 95 ℃ for cooking for 10 minutes to obtain the cationic starch product. Wherein, the products of the cationic starch comprise paper products such as cartons, paper boxes, paper bags and the like.
The following will compare the properties of paper products prepared from the above examples with those of the cationic starch prepared in the comparative example.
(2) Wet end application effect:
test preparation:
taking pulped pulp with the mass percentage concentration of 4.0 percent, namely each sample (NBKP: LBKP: BC is 15:75:10, wherein the LBKP is short fiber, the NBKP is long fiber, and the BC is BCTMP chemical mechanical pulp), adding water for dilution, and uniformly mixing and stirring to obtain the pulp with the mass percentage concentration of 0.3 percent; 20 percent of filler (solid content is 18 percent) relative to the absolute dry weight of the slurry, 0.5 to 1.5 percent of homemade modified product (solid content is 1 percent), 200ppm of RA (solid content is 0.2 percent, cationic polyacrylamide aqueous solution) and silicalite stock solution (solid content is 1 percent, anionic silicon dioxide aqueous solution is used by diluting 100 times) are added into the slurry in turn under stirring, and the mixture is uniformly mixed and stirred to be made into sheets, and the physical properties of the paper are measured.
Table 2 paper physical property test results
Since the cationic starch of the second control sample is severely gelatinized and cannot be used for making paper, the comparison does not relate to the second control sample. As can be seen from the test results in table 2, under the method of making cationic starch of this example, drainage, retention and sheet strength were superior for sample one at the same chemical addition. The pulp made by the cationic starch prepared in the examples 1 to 3 has certain improved strength, such as cohesion, tensile index, bursting index and folding endurance, and simultaneously, the ash content of the paper is improved, the drainage is increased, and therefore, good retention and drainage effects can be achieved. In addition, since corn starch was used in example 3 and tapioca starch was used in the first control group, the drainage performance of the paper of sample three was slightly inferior to that of the first control group due to the difference in starch type, which is caused by the difference in starch type itself, and when the starch used in example 1 and example 2 was tapioca starch, the drainage performance was significantly superior to that of the first control group.
Therefore, the preparation method of the cation of the embodiment can improve the substitution degree of the starch, can normally react under the condition of high-concentration alkali without adding an expansion inhibitor, improves the reaction efficiency, has no salt impurity residue, ensures the quality of the cation starch, further improves the strength of the cation starch paper, and improves the cohesion, the tensile index, the bursting index and the folding resistance to a certain extent, simultaneously improves the ash content retention of the paper, increases the drainage and can play a good role in retention and drainage.
Through the manner, the cationic etherifying agent and the alkaline catalyst are added into the starch slurry, so that the cationic etherifying agent and the alkaline catalyst react with each other, the hydrolysis phenomenon of the cationic etherifying agent in the starch slurry is reduced, the effective rate of the cationic etherifying agent is ensured, and the substitution degree of the starch is improved. In addition, in the embodiment, the cationic etherifying agent is added into the starch slurry at first preset time intervals, the alkaline catalyst is added at first preset time intervals for reaction, and the reaction finishing time of the cationic etherifying agent is later than that of the alkaline catalyst by controlling the addition amounts of the cationic etherifying agent and the alkaline catalyst, so that the cationic etherifying agent can exist in the whole reaction process of the alkaline catalyst, and the alkaline catalyst is prevented from directly reacting with starch, and the starch gelatinization phenomenon is caused. Therefore, the embodiment further improves the substitution degree of the starch, enhances the conversion efficiency of the starch and improves the generation efficiency of the cationic starch. Simultaneously, this embodiment can also not add under the condition of inflation inhibitor can be under the normal reaction of high concentration alkali condition, has promoted reaction efficiency, and no salt impurity remains simultaneously, has guaranteed cationic starch's quality to improve performances such as drainage, reservation and the paper intensity of cationic starch paper.
Based on the same inventive concept, the present invention also provides a cationic starch which can be prepared by the preparation method of the cationic starch described in all the above examples. Wherein the cationic starch is obtained by obtaining starch slurry; adding a cationic etherifying agent into the starch slurry, and adding an alkaline catalyst after a first preset time interval to perform reaction. Wherein the addition amount of the cationic etherifying agent is larger than that of the basic catalyst so that the reaction of the cationic etherifying agent is finished later than that of the basic catalyst. The cationic starch of the embodiment has high substitution degree and conversion efficiency, does not contain salt substances, has high quality, and has high performance of draining, retaining and paper strength of cationic starch paper.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A method for preparing cationic starch, which is characterized by comprising the following steps:
obtaining starch slurry;
adding a cationic etherifying agent into the starch slurry, and adding an alkaline catalyst for reaction after a first preset time interval to obtain cationic starch; wherein the addition amount of the cationic etherifying agent is larger than that of the basic catalyst so that the reaction of the cationic etherifying agent is finished later than that of the basic catalyst.
2. The method for preparing cationic starch according to claim 1, wherein the step of adding a cationic etherifying agent to the starch slurry and adding an alkaline catalyst to react after a first predetermined time interval to obtain the cationic starch comprises:
uniformly mixing the starch slurry, the alkaline catalyst and the cationic etherifying agent to obtain a mixed solution;
heating the mixed solution to 42-53 ℃, and reacting for 8-24 hours;
and adding a pH regulator into the mixed solution to enable the pH value of the mixed solution to be in a preset range, so as to obtain the cationic starch.
3. The method for preparing cationic starch according to claim 2, wherein the adding a pH regulator to the mixed solution to make the pH value of the mixed solution in a preset range to obtain the cationic starch comprises:
diluting the concentration of the mixed solution with the pH value within the preset range to 3-5%, and heating to 90-98 ℃ for cooking for 5-15 minutes.
4. A method for preparing cationic starch according to claim 2 or 3, wherein said predetermined range of pH values is 6.5-7.5.
5. The method for preparing cationic starch according to claim 1, wherein the step of adding a cationic etherifying agent to the starch slurry and adding an alkaline catalyst to react after a first predetermined time interval to obtain the cationic starch comprises:
and adding a cationic etherifying agent with the starch slurry absolute amount of 5.0-10.0% into the starch slurry, and adding an alkaline catalyst with the starch slurry absolute amount of 2.0-3.0% after the first preset time interval for reaction to obtain the cationic starch.
6. The method for preparing cationic starch according to claim 5, wherein the step of adding an alkaline catalyst in an amount of 2.0-3.0% of the absolute dry weight of the starch slurry to react after a first predetermined time interval comprises:
preparing an alkaline catalyst with the absolute dry weight of 2.0-3.0% of the starch slurry into an alkaline solution with the concentration of 8% -12%;
and adding the 8% -12% alkaline solution into the starch slurry for reaction after a first preset time interval.
7. The method for producing cationic starch according to claim 1,
the alkaline catalyst comprises one or more of sodium hydroxide and sodium bicarbonate;
the cationic etherifying agent includes 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 4-chloro-2-butenyl trimethyl ammonium chloride, and epoxypropyl trimethyl ammonium chloride.
8. The method for preparing cationic starch according to claim 1, wherein the step of obtaining a starch slurry comprises:
obtaining raw starch, wherein the raw starch comprises one or more of cassava starch, corn starch, potato starch and wheat starch;
mixing the raw starch with water to obtain the starch slurry with the mass fraction of 37-46%.
9. The method for preparing cationic starch according to claim 1, wherein the first predetermined time is in the range of: (0, 4] sec.
10. A cationic starch produced by the method of claim 1 to 9.
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| CN104119455A (en) * | 2014-07-14 | 2014-10-29 | 金东纸业（江苏）股份有限公司 | Cation modified starch, preparation method and applications thereof |
| EA201600004A1 (en) * | 2015-11-24 | 2017-05-31 | Учреждение Белорусского государственного университета "Научно-исследовательский институт физико-химических проблем" (НИИ ФХП БГУ) | The method of producing cationic starches dispersed in cold water and used as flocculant |
| CN108409873A (en) * | 2018-03-01 | 2018-08-17 | 金东纸业（江苏）股份有限公司 | cationic starch and preparation method thereof |
| CN110092844A (en) * | 2018-01-30 | 2019-08-06 | 金东纸业（江苏）股份有限公司 | Cationic starch and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119455A (en) * | 2014-07-14 | 2014-10-29 | 金东纸业（江苏）股份有限公司 | Cation modified starch, preparation method and applications thereof |
| EA201600004A1 (en) * | 2015-11-24 | 2017-05-31 | Учреждение Белорусского государственного университета "Научно-исследовательский институт физико-химических проблем" (НИИ ФХП БГУ) | The method of producing cationic starches dispersed in cold water and used as flocculant |
| CN110092844A (en) * | 2018-01-30 | 2019-08-06 | 金东纸业（江苏）股份有限公司 | Cationic starch and preparation method thereof |
| CN108409873A (en) * | 2018-03-01 | 2018-08-17 | 金东纸业（江苏）股份有限公司 | cationic starch and preparation method thereof |
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