CN111138683A - Sodium lignosulfonate water reducing agent and preparation method thereof - Google Patents
Sodium lignosulfonate water reducing agent and preparation method thereof Download PDFInfo
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- CN111138683A CN111138683A CN202010060427.6A CN202010060427A CN111138683A CN 111138683 A CN111138683 A CN 111138683A CN 202010060427 A CN202010060427 A CN 202010060427A CN 111138683 A CN111138683 A CN 111138683A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The invention provides a sodium lignosulfonate water reducing agent which is prepared by the following steps: s1, drying chestnut shells, grinding, ball-milling and sieving to obtain chestnut shell powder, and extracting to obtain degreased chestnut shell powder; s2, adding degreased chestnut shell powder into 1-hexyl-3-methyl-imidazolium bisulfate to obtain a mixed solution, and adding the mixed solution into a micro-jet extractor to extract lignin; s3, reacting lignin, sodium sulfite, formaldehyde and distilled water to obtain sodium lignosulphonate; and S4, grafting sodium lignosulfonate and tartaric acid to obtain the sodium lignosulfonate water reducing agent. The invention also provides a preparation method of the sodium lignosulfonate water reducing agent. The sodium lignosulfonate water reducing agent provided by the invention has high sulfonation rate and water reducing rate, and also has good dispersibility and an effect of improving the compressive strength of concrete.
Description
Technical Field
The invention relates to a water reducing agent, in particular to a sodium lignosulfonate water reducing agent and a preparation method thereof.
Background
The water reducing agent can reduce the water consumption for mixing and improve the strength of concrete under the condition of unchanged concrete workability and cement consumption; or the admixture can save the cement consumption under the condition of unchanged workability and strength, and the appearance form of the admixture is divided into water aqua and powder. The water reducing agent can be divided into the following components: lignosulphonates; polycyclic aromatic salts; water-soluble resin sulfonates, and the like. Wherein, the main raw material of the lignosulfonate water reducing agent is lignosulfonate. Lignin is a natural aromatic high polymer with the content second to that of cellulose and chitin in the nature, and lignosulfonate (water reducing agent) is a lignin product with the widest application. The lignosulfonate water reducing agent mainly comprises calcium lignosulfonate, sodium lignosulfonate, magnesium lignosulfonate and the like.
Chinese patent application CN201710285311.0 discloses a natural sodium lignosulfonate water reducing agent for buildings, which comprises the following raw materials in parts by weight: 20-30 parts of naturally extracted lignin, 1-5 parts of sulfur, 15% sodium hydroxide solution 15-25 parts, 98% concentrated sulfuric acid 1-5 parts, 5-10 parts of formaldehyde, 1-5 parts of casein and 1-5 parts of tricyclic aromatic hydrocarbon. The invention has the problems of low sulfonation rate and water reducing rate, poor dispersibility and poor effect of improving the compressive strength of concrete.
Disclosure of Invention
The invention aims to solve the technical problem of providing the sodium lignosulfonate water reducing agent which has higher sulfonation rate and water reducing rate, better dispersibility and an effect of improving the compressive strength of concrete.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a sodium lignosulfonate water reducing agent is prepared by the following steps:
s1, drying chestnut shells at 80 ℃ for 24 hours, grinding and then ball-milling, sieving with a 100-mesh sieve to obtain chestnut shell powder, adding the chestnut shell powder into a toluene petroleum ether mixed solution, and placing the mixture in a Soxhlet extractor for extraction at 90 ℃ for 3 hours to obtain degreased chestnut shell powder;
s2, adding the degreased Chinese chestnut shell powder obtained in the step S1 into 1-hexyl-3-methyl-imidazolium bisulfate, uniformly stirring to obtain a mixed solution, adding the mixed solution into a micro-jet extractor to extract to obtain an extracting solution, centrifuging the extracting solution for 15 minutes to obtain a supernatant, concentrating the supernatant under reduced pressure, adding the concentrated supernatant into an ethanol solution, uniformly stirring, placing the mixture in a refrigerator, standing for 24 hours at 4 ℃, taking out the mixture, centrifuging the mixture for 15 minutes to obtain a precipitate, repeatedly washing the precipitate with deionized water, and freeze-drying the precipitate to obtain lignin;
s3, adding the lignin, sodium sulfite, formaldehyde and distilled water obtained in the step S2 into a reaction vessel, adjusting the pH value to 11, heating to 130 ℃, reacting for 3 hours to obtain a reaction liquid, carrying out suction filtration on the reaction liquid to obtain a filtrate, concentrating the filtrate under reduced pressure, and carrying out freeze drying to obtain sodium lignosulfonate;
s4, adding the sodium lignosulfonate and ammonium persulfate solution obtained in the step S3 into a reaction container, starting stirring under the protection of nitrogen, adding tartaric acid into the reaction container when the temperature rises to 70 ℃, continuously stirring for reaction for 3 hours to obtain a crude product, adding the crude product into acetone to separate out a precipitate, placing the precipitate into a Soxhlet extractor for extraction with ethanol for 5 hours, taking out the precipitate, and drying at 80 ℃ for 5 hours to obtain the sodium lignosulfonate water reducer.
Further, in the step S1, the volume ratio of toluene to petroleum ether in the toluene petroleum ether solution is 1:1, and the ratio of chestnut shell powder to toluene petroleum ether solution is 1g:40 mL.
Further, in the step S2, the weight ratio of the defatted chestnut shell powder to the 1-hexyl-3-methyl-imidazolium bisulfate is 1 (25-30), the extraction temperature of the micro-jet extractor is 70 ℃, the pressure of the micro-jet extractor is 120MPa, the centrifugation speed is 5000-6000rpm, the volume fraction of the ethanol solution is 80%, and the volume ratio of the supernatant to the ethanol solution is 1: 5.
Further, in the step S3, the mass ratio of the lignin, the sodium sulfite, the formaldehyde and the distilled water is (12.5-15) to 1:0.25: 30.
Further, in the step S4, the mass concentration of the ammonium persulfate solution is 5%, the mass ratio of the sodium lignosulfonate, the ammonium persulfate solution and the tartaric acid is 1:0.2 (0.2-0.3), and the mass ratio of the crude product to the acetone is 1: 10.
The invention also provides a preparation method of the sodium lignosulfonate water reducing agent.
In order to solve the technical problems, the technical scheme is as follows:
a preparation method of a sodium lignosulfonate water reducing agent comprises the following steps:
s1, drying chestnut shells at 80 ℃ for 24 hours, grinding and then ball-milling, sieving with a 100-mesh sieve to obtain chestnut shell powder, adding the chestnut shell powder into a toluene petroleum ether mixed solution, and placing the mixture in a Soxhlet extractor for extraction at 90 ℃ for 3 hours to obtain degreased chestnut shell powder;
s2, adding the degreased Chinese chestnut shell powder obtained in the step S1 into 1-hexyl-3-methyl-imidazolium bisulfate, uniformly stirring to obtain a mixed solution, adding the mixed solution into a micro-jet extractor to extract to obtain an extracting solution, centrifuging the extracting solution for 15 minutes to obtain a supernatant, concentrating the supernatant under reduced pressure, adding the concentrated supernatant into an ethanol solution, uniformly stirring, placing the mixture in a refrigerator, standing for 24 hours at 4 ℃, taking out the mixture, centrifuging the mixture for 15 minutes to obtain a precipitate, repeatedly washing the precipitate with deionized water, and freeze-drying the precipitate to obtain lignin;
s3, adding the lignin, sodium sulfite, formaldehyde and distilled water obtained in the step S2 into a reaction vessel, adjusting the pH value to 11, heating to 130 ℃, reacting for 3 hours to obtain a reaction liquid, carrying out suction filtration on the reaction liquid to obtain a filtrate, concentrating the filtrate under reduced pressure, and carrying out freeze drying to obtain sodium lignosulfonate;
s4, adding the sodium lignosulfonate and ammonium persulfate solution obtained in the step S3 into a reaction container, starting stirring under the protection of nitrogen, adding tartaric acid into the reaction container when the temperature rises to 70 ℃, continuously stirring for reaction for 3 hours to obtain a crude product, adding the crude product into acetone to separate out a precipitate, placing the precipitate into a Soxhlet extractor for extraction with ethanol for 5 hours, taking out the precipitate, and drying at 80 ℃ for 5 hours to obtain the sodium lignosulfonate water reducer.
Further, in the step S1, the volume ratio of toluene to petroleum ether in the toluene petroleum ether solution is 1:1, and the ratio of chestnut shell powder to toluene petroleum ether solution is 1g:40 mL.
Further, in the step S2, the weight ratio of the defatted chestnut shell powder to the 1-hexyl-3-methyl-imidazolium bisulfate is 1 (25-30), the extraction temperature of the micro-jet extractor is 70 ℃, the pressure of the micro-jet extractor is 120MPa, and the centrifugation speed is 5000-6000 rpm.
Further, in the step S3, the mass ratio of the lignin, the sodium sulfite, the formaldehyde and the distilled water is (12.5-15) to 1:0.25: 30.
Further, in the step S4, the mass concentration of the ammonium persulfate solution is 5%, the mass ratio of the sodium lignosulfonate, the ammonium persulfate solution and the tartaric acid is 1:0.2 (0.2-0.3), and the mass ratio of the crude product to the acetone is 1: 10.
Compared with the prior art, the invention has the following beneficial effects:
1) the preparation method comprises the steps of degreasing chestnut shells to prepare degreased chestnut shell powder, mixing the degreased chestnut shell powder with 1-hexyl-3-methyl-imidazolium bisulfate, extracting lignin through micro-jet, reacting the lignin with sodium sulfite and the like to prepare sodium lignosulfonate, and grafting the sodium lignosulfonate with tartaric acid to obtain the sodium lignosulfonate water reducing agent. In the process of extracting lignin, the 1-hexyl-3-methyl-imidazolium bisulfate can effectively dissolve and separate cellulose and hemicellulose in the degreased chestnut shell powder, so that the extraction rate of the lignin is improved, a synergistic effect is generated on the surface of the lignin under the action of microjet, the reaction degree of the lignin and sodium sulfite is improved, and the sulfonation rate of the lignin is further improved. Compared with other lignin extraction methods, the extraction rate is higher when the chestnut shells are subjected to micro-jet extraction, and the micro-jet extraction can also increase the activity of lignin, improve the grafting rate of sodium lignosulfonate and tartaric acid, and further improve the water reducing rate of the sodium lignosulfonate water reducing agent. On the other hand, the grafting with tartaric acid can effectively improve the water reducing rate and the dispersibility of the sodium lignosulfonate water reducing agent, and can also greatly improve the effect of the sodium lignosulfonate water reducing agent on improving the compressive strength of concrete.
2) The chestnut shells used as the main raw material belong to food waste, are usually discarded as food waste for treatment, cause resource waste, have adverse effects on the environment, are effectively recycled, and have better economic and environmental protection values.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, and the exemplary embodiments and descriptions thereof herein are provided to explain the present invention but not to limit the present invention.
Example 1
Preparing a sodium lignosulfonate water reducing agent according to the following steps:
s1, drying chestnut shells at 80 ℃ for 24 hours, grinding and then ball-milling, sieving with a 100-mesh sieve to obtain chestnut shell powder, adding the chestnut shell powder into a toluene petroleum ether mixed solution (the volume ratio of toluene to petroleum ether is 1:1), wherein the ratio of the chestnut shell powder to the toluene petroleum ether solution is 1g:40mL, and placing the chestnut shell powder into a Soxhlet extractor to extract for 3 hours at 90 ℃ to obtain degreased chestnut shell powder;
s2, adding the degreased Chinese chestnut shell powder obtained in the step S1 into 1-hexyl-3-methyl-imidazolium bisulfate, uniformly stirring to obtain a mixed solution, wherein the weight ratio of the degreased Chinese chestnut shell powder to the 1-hexyl-3-methyl-imidazolium bisulfate is 1:25, adding the mixed solution into a micro-jet extractor, extracting to obtain an extracting solution, the extracting temperature of the micro-jet extractor is 70 ℃, the pressure of the extracting solution is 120MPa, centrifuging the extracting solution at 5000rpm for 15 minutes to obtain a supernatant, concentrating the supernatant under reduced pressure, adding the concentrated supernatant into 80 volume percent ethanol solution with the volume 5 times of that of the extracting solution, uniformly stirring, placing the mixture into a refrigerator, standing the mixture for 24 hours at 4 ℃, taking out the mixture, centrifuging the mixture at 5000rpm for 15 minutes to obtain precipitates, repeatedly washing the precipitates with deionized water, and freeze-drying to obtain lignin;
s3, adding the lignin, sodium sulfite, formaldehyde and distilled water which are obtained in the step S2 and have the mass ratio of 12.5:1:0.25:30 into a reaction container, adjusting the pH value to 11, heating to 130 ℃, reacting for 3 hours to obtain reaction liquid, carrying out suction filtration on the reaction liquid to obtain filtrate, carrying out reduced pressure concentration on the filtrate, and carrying out freeze drying to obtain sodium lignosulfonate;
s4, adding the sodium lignosulfonate obtained in the step S3 and an ammonium persulfate solution with the mass concentration of 5% into a reaction container, starting stirring under the protection of nitrogen, adding tartaric acid into the reaction container when the temperature rises to 70 ℃, continuously stirring for reacting for 3 hours to obtain a crude product, wherein the mass ratio of the sodium lignosulfonate to the ammonium persulfate solution to the tartaric acid is 1:0.2:0.2, adding the crude product into acetone to separate out a precipitate, the mass ratio of the crude product to the acetone is 1:10, placing the precipitate into a Soxhlet extractor to be extracted for 5 hours by using ethanol, taking out, and drying at 80 ℃ for 5 hours to obtain the sodium lignosulfonate water reducer.
Example 2
Preparing a sodium lignosulfonate water reducing agent according to the following steps:
s1, drying chestnut shells at 80 ℃ for 24 hours, grinding and then ball-milling, sieving with a 100-mesh sieve to obtain chestnut shell powder, adding the chestnut shell powder into a toluene petroleum ether mixed solution (the volume ratio of toluene to petroleum ether is 1:1), wherein the ratio of the chestnut shell powder to the toluene petroleum ether solution is 1g:40mL, and placing the chestnut shell powder into a Soxhlet extractor to extract for 3 hours at 90 ℃ to obtain degreased chestnut shell powder;
s2, adding the degreased chestnut shell powder obtained in the step S1 into 1-hexyl-3-methyl-imidazolium bisulfate, uniformly stirring to obtain a mixed solution, wherein the weight ratio of the degreased chestnut shell powder to the 1-hexyl-3-methyl-imidazolium bisulfate is 1:30, adding the mixed solution into a micro-jet extractor, extracting to obtain an extracting solution, the extracting temperature of the micro-jet extractor is 70 ℃, the pressure is 120MPa, centrifuging the extracting solution at 6000rpm for 15 minutes to obtain a supernatant, concentrating the supernatant under reduced pressure, adding the concentrated supernatant into 80% volume fraction ethanol solution with 5 times of volume, uniformly stirring, placing the mixture into a refrigerator, standing at 4 ℃ for 24 hours, taking out the mixture, centrifuging the mixture at 6000rpm for 15 minutes to obtain a precipitate, repeatedly washing the precipitate with deionized water, and freeze-drying to obtain lignin;
s3, adding the lignin, sodium sulfite, formaldehyde and distilled water which are obtained in the step S2 and have the mass ratio of 15:1:0.25:30 into a reaction container, adjusting the pH value to 11, heating to 130 ℃, reacting for 3 hours to obtain reaction liquid, performing suction filtration on the reaction liquid to obtain filtrate, concentrating the filtrate under reduced pressure, and performing freeze drying to obtain sodium lignosulfonate;
s4, adding the sodium lignosulfonate obtained in the step S3 and an ammonium persulfate solution with the mass concentration of 5% into a reaction container, starting stirring under the protection of nitrogen, adding tartaric acid into the reaction container when the temperature rises to 70 ℃, continuously stirring for reacting for 3 hours to obtain a crude product, adding the sodium lignosulfonate, the ammonium persulfate solution and the tartaric acid into acetone to separate out a precipitate, wherein the mass ratio of the crude product to the acetone is 1:10, placing the precipitate into a Soxhlet extractor, extracting with ethanol for 5 hours, taking out, and drying at 80 ℃ for 5 hours to obtain the sodium lignosulfonate water reducer.
Example 3
Preparing a sodium lignosulfonate water reducing agent according to the following steps:
s1, drying chestnut shells at 80 ℃ for 24 hours, grinding and then ball-milling, sieving with a 100-mesh sieve to obtain chestnut shell powder, adding the chestnut shell powder into a toluene petroleum ether mixed solution (the volume ratio of toluene to petroleum ether is 1:1), wherein the ratio of the chestnut shell powder to the toluene petroleum ether solution is 1g:40mL, and placing the chestnut shell powder into a Soxhlet extractor to extract for 3 hours at 90 ℃ to obtain degreased chestnut shell powder;
s2, adding the defatted chestnut shell powder obtained in the step S1 into 1-hexyl-3-methyl-imidazolium bisulfate, uniformly stirring to obtain a mixed solution, wherein the weight ratio of the defatted chestnut shell powder to the 1-hexyl-3-methyl-imidazolium bisulfate is 1:27, adding the mixed solution into a micro-jet extractor, extracting to obtain an extracting solution, the extracting temperature of the micro-jet extractor is 70 ℃, the pressure is 120MPa, centrifuging the extracting solution at the speed of 5500rpm for 15 minutes to obtain a supernatant, concentrating the supernatant under reduced pressure, adding the concentrated supernatant into 80 volume percent ethanol solution with the volume of 5 times of the volume, uniformly stirring, placing the mixture into a refrigerator, standing the mixture at the temperature of 4 ℃ for 24 hours, taking out the mixture, centrifuging the mixture at the speed of 5500rpm for 15 minutes to obtain precipitates, repeatedly washing the precipitates with deionized water, and freeze-drying to obtain;
s3, adding the lignin, sodium sulfite, formaldehyde and distilled water which are obtained in the step S2 and have the mass ratio of 14:1:0.25:30 into a reaction container, adjusting the pH value to 11, heating to 130 ℃, reacting for 3 hours to obtain reaction liquid, performing suction filtration on the reaction liquid to obtain filtrate, concentrating the filtrate under reduced pressure, and performing freeze drying to obtain sodium lignosulfonate;
s4, adding the sodium lignosulfonate obtained in the step S3 and an ammonium persulfate solution with the mass concentration of 5% into a reaction container, starting stirring under the protection of nitrogen, adding tartaric acid into the reaction container when the temperature rises to 70 ℃, continuously stirring for reacting for 3 hours to obtain a crude product, adding the sodium lignosulfonate, the ammonium persulfate solution and the tartaric acid into acetone to separate out a precipitate, wherein the mass ratio of the crude product to the acetone is 1:10, placing the precipitate into a Soxhlet extractor, extracting with ethanol for 5 hours, taking out, and drying at 80 ℃ for 5 hours to obtain the sodium lignosulfonate water reducer.
Example 4
Preparing a sodium lignosulfonate water reducing agent according to the following steps:
s1, drying chestnut shells at 80 ℃ for 24 hours, grinding and then ball-milling, sieving with a 100-mesh sieve to obtain chestnut shell powder, adding the chestnut shell powder into a toluene petroleum ether mixed solution (the volume ratio of toluene to petroleum ether is 1:1), wherein the ratio of the chestnut shell powder to the toluene petroleum ether solution is 1g:40mL, and placing the chestnut shell powder into a Soxhlet extractor to extract for 3 hours at 90 ℃ to obtain degreased chestnut shell powder;
s2, adding the degreased Chinese chestnut shell powder obtained in the step S1 into 1-hexyl-3-methyl-imidazolium bisulfate, uniformly stirring to obtain a mixed solution, wherein the weight ratio of the degreased Chinese chestnut shell powder to the 1-hexyl-3-methyl-imidazolium bisulfate is 1:28, adding the mixed solution into a micro-jet extractor, extracting to obtain an extracting solution, the extracting temperature of the micro-jet extractor is 70 ℃, the pressure of the extracting solution is 120MPa, centrifuging the extracting solution at 5000rpm for 15 minutes to obtain a supernatant, concentrating the supernatant under reduced pressure, adding the concentrated supernatant into 80 volume percent ethanol solution with the volume 5 times of that of the extracting solution, uniformly stirring, placing the mixture into a refrigerator, standing the mixture for 24 hours at 4 ℃, taking out the mixture, centrifuging the mixture at 5000rpm for 15 minutes to obtain precipitates, repeatedly washing the precipitates with deionized water, and freeze-drying to obtain lignin;
s3, adding the lignin, sodium sulfite, formaldehyde and distilled water which are obtained in the step S2 and have the mass ratio of 13:1:0.25:30 into a reaction container, adjusting the pH value to 11, heating to 130 ℃, reacting for 3 hours to obtain reaction liquid, performing suction filtration on the reaction liquid to obtain filtrate, concentrating the filtrate under reduced pressure, and performing freeze drying to obtain sodium lignosulfonate;
s4, adding the sodium lignosulfonate obtained in the step S3 and an ammonium persulfate solution with the mass concentration of 5% into a reaction container, starting stirring under the protection of nitrogen, adding tartaric acid into the reaction container when the temperature rises to 70 ℃, continuously stirring for reacting for 3 hours to obtain a crude product, adding the sodium lignosulfonate, the ammonium persulfate solution and the tartaric acid into acetone to separate out a precipitate, wherein the mass ratio of the crude product to the acetone is 1:10, placing the precipitate into a Soxhlet extractor, extracting with ethanol for 5 hours, taking out, and drying at 80 ℃ for 5 hours to obtain the sodium lignosulfonate water reducer.
Reference example 1
In contrast to example 3, in step S2, 1-hexyl-3-methyl-imidazolium hydrogensulfate was replaced by distilled water.
Reference example 2
The difference from example 3 is that in step S2, water bath heating extraction at 70 ℃ was used instead of the microfluid extraction.
Reference example 3
Unlike embodiment 3, step S4 is not included.
Comparative example: example 1 of patent application No. CN 201710285311.0.
The first test example: sulfonation Rate test
The sulfonation rates of examples 1 to 4, reference examples 1 to 3 and comparative example were measured, respectively, and the test results are shown in table 1:
| sulfonation Rate (%) | |
| Example 1 | 61.0 |
| Example 2 | 60.6 |
| Example 3 | 61.4 |
| Example 4 | 60.2 |
| Reference example 1 | 51.1 |
| Reference example 2 | 50.5 |
| Reference example 3 | 61.4 |
| Comparative example | 32.7 |
TABLE 1
As can be seen from Table 1, the sulfonation rates of inventive examples 1-4 are all significantly higher than the comparative example, with example 3 having the highest sulfonation rate. The procedure of reference examples 1-3 is different from that of example 1 in that the sulfonation ratio of reference examples 1 and 2 is reduced by a little, which shows that the sulfonation ratio of sodium lignosulfonate water reducer can be effectively increased by both 1-hexyl-3-methyl-imidazolium bisulfate used in the micro-jet extraction and the micro-jet extraction operation.
Test example two: water reduction test
The water reducing rates of examples 1 to 4, reference examples 1 to 3 and comparative example were measured with reference to GB/T50080-:
| water loss (%) | |
| Example 1 | 20.4 |
| Example 2 | 20.3 |
| Example 3 | 20.6 |
| Example 4 | 20.2 |
| Reference example 1 | 20.6 |
| Reference example 2 | 16.7 |
| Reference example 3 | 15.5 |
| Comparative example | 8.9 |
TABLE 2
As can be seen from Table 2, the water reduction rates of inventive examples 1-4 are all significantly higher than the comparative example, with example 3 having the highest water reduction rate. The steps of reference examples 1-3 are different from example 1 in that the water reducing rate of reference examples 2 and 3 is reduced slightly, which shows that the micro-jet extraction operation and the grafting with tartaric acid can effectively improve the water reducing rate of the sodium lignosulfonate water reducer.
Test example three: test of effect of improving compressive strength of concrete
The compressive strength ratios of examples 1-4, reference examples 1-3 and comparative example 28d were measured with reference to GB/T50080-:
| 28d compressive Strength ratio (%) | |
| Example 1 | 132 |
| Example 2 | 130 |
| Example 3 | 133 |
| Example 4 | 131 |
| Reference example 1 | 133 |
| Reference nutExample 2 | 133 |
| Reference example 3 | 110 |
| Comparative example | 105 |
TABLE 3
As can be seen from Table 3, the 28d compressive strength ratios of the examples 1 to 4 of the invention are all significantly higher than those of the comparative examples, which shows that the water reducing agent prepared by the invention has a good effect of improving the compressive strength of concrete, wherein the compressive strength ratio of the example 3 is the highest. The steps of reference examples 1-3 are different from those of example 1, wherein the 28d compressive strength ratio of reference example 3 is reduced a lot, which shows that the effect of improving the compressive strength of the concrete by the sodium lignosulfonate water reducing agent can be greatly improved by grafting with tartaric acid.
Test example four: dispersibility test
The test method comprises the following steps: weighing 8 groups of 0.2g coal water slurry coal, respectively adding the coal water slurry coal into 8 conical flasks, respectively preparing water reducing agent solutions with the concentration of 1g/L from examples 1-4, reference examples 1-3 and comparative examples, respectively adding the water reducing agent solutions into 8 conical flasks, carrying out water bath constant temperature oscillation for 2 hours, standing, taking supernate, centrifuging, injecting the supernate into an electrophoresis cell, and measuring the Zeta potential on the surface of the coal, wherein the larger the absolute value of the Zeta potential is, the better the dispersibility is. The test results are shown in table 4:
| zeta potential (mV) | |
| Example 1 | -29.3 |
| Example 2 | -29.5 |
| Example 3 | -29.8 |
| Example 4 | -29.6 |
| Reference example 1 | -29.8 |
| Reference example 2 | -29.8 |
| Reference example 3 | -16.4 |
| Comparative example | -12.1 |
TABLE 4
As can be seen from Table 4, the Zeta potential absolute value ratios of the examples 1 to 4 of the invention are all significantly higher than those of the comparative examples, which shows that the water reducing agent prepared by the invention has better dispersibility, wherein the Zeta potential absolute value of the example 3 is the highest. The steps of referential examples 1 to 3 are different from those of the referential example 1 in that the Zeta potential absolute value of referential example 3 is not reduced so much, and the fact that the grafting with tartaric acid is effective in improving the dispersibility of the sodium lignin sulfonate water reducing agent.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A sodium lignosulfonate water reducing agent is characterized in that: the method comprises the following steps:
s1, drying chestnut shells at 80 ℃ for 24 hours, grinding and then ball-milling, sieving with a 100-mesh sieve to obtain chestnut shell powder, adding the chestnut shell powder into a toluene petroleum ether mixed solution, and placing the mixture in a Soxhlet extractor for extraction at 90 ℃ for 3 hours to obtain degreased chestnut shell powder;
s2, adding the degreased Chinese chestnut shell powder obtained in the step S1 into 1-hexyl-3-methyl-imidazolium bisulfate, uniformly stirring to obtain a mixed solution, adding the mixed solution into a micro-jet extractor to extract to obtain an extracting solution, centrifuging the extracting solution for 15 minutes to obtain a supernatant, concentrating the supernatant under reduced pressure, adding the concentrated supernatant into an ethanol solution, uniformly stirring, placing the mixture in a refrigerator, standing for 24 hours at 4 ℃, taking out the mixture, centrifuging the mixture for 15 minutes to obtain a precipitate, repeatedly washing the precipitate with deionized water, and freeze-drying the precipitate to obtain lignin;
s3, adding the lignin, sodium sulfite, formaldehyde and distilled water obtained in the step S2 into a reaction vessel, adjusting the pH value to 11, heating to 130 ℃, reacting for 3 hours to obtain a reaction liquid, carrying out suction filtration on the reaction liquid to obtain a filtrate, concentrating the filtrate under reduced pressure, and carrying out freeze drying to obtain sodium lignosulfonate;
s4, adding the sodium lignosulfonate and ammonium persulfate solution obtained in the step S3 into a reaction container, starting stirring under the protection of nitrogen, adding tartaric acid into the reaction container when the temperature rises to 70 ℃, continuously stirring for reaction for 3 hours to obtain a crude product, adding the crude product into acetone to separate out a precipitate, placing the precipitate into a Soxhlet extractor for extraction with ethanol for 5 hours, taking out the precipitate, and drying at 80 ℃ for 5 hours to obtain the sodium lignosulfonate water reducer.
2. The sodium lignosulfonate water reducing agent of claim 1, which is characterized in that: in the step S1, the volume ratio of toluene to petroleum ether in the toluene petroleum ether solution is 1:1, and the ratio of chestnut shell powder to toluene petroleum ether solution is 1g:40 mL.
3. The sodium lignosulfonate water reducing agent of claim 1, which is characterized in that: in the step S2, the weight ratio of the defatted chestnut shell powder to the 1-hexyl-3-methyl-imidazolium bisulfate is 1 (25-30), the extraction temperature of the micro-jet extractor is 70 ℃, the pressure of the micro-jet extractor is 120MPa, the centrifugation speed is 5000-6000rpm, the volume fraction of the ethanol solution is 80%, and the volume ratio of the supernatant to the ethanol solution is 1: 5.
4. The sodium lignosulfonate water reducing agent of claim 1, which is characterized in that: in the step S3, the mass ratio of the lignin, the sodium sulfite, the formaldehyde and the distilled water is (12.5-15) to 1:0.25: 30.
5. The sodium lignosulfonate water reducing agent of claim 1, which is characterized in that: in the step S4, the mass concentration of the ammonium persulfate solution is 5%, the mass ratio of the sodium lignosulfonate to the ammonium persulfate solution to the tartaric acid is 1:0.2 (0.2-0.3), and the mass ratio of the crude product to the acetone is 1: 10.
6. The preparation method of the sodium lignin sulfonate water reducing agent according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
s1, drying chestnut shells at 80 ℃ for 24 hours, grinding and then ball-milling, sieving with a 100-mesh sieve to obtain chestnut shell powder, adding the chestnut shell powder into a toluene petroleum ether mixed solution, and placing the mixture in a Soxhlet extractor for extraction at 90 ℃ for 3 hours to obtain degreased chestnut shell powder;
s2, adding the degreased Chinese chestnut shell powder obtained in the step S1 into 1-hexyl-3-methyl-imidazolium bisulfate, uniformly stirring to obtain a mixed solution, adding the mixed solution into a micro-jet extractor to extract to obtain an extracting solution, centrifuging the extracting solution for 15 minutes to obtain a supernatant, concentrating the supernatant under reduced pressure, adding the concentrated supernatant into an ethanol solution, uniformly stirring, placing the mixture in a refrigerator, standing for 24 hours at 4 ℃, taking out the mixture, centrifuging the mixture for 15 minutes to obtain a precipitate, repeatedly washing the precipitate with deionized water, and freeze-drying the precipitate to obtain lignin;
s3, adding the lignin, sodium sulfite, formaldehyde and distilled water obtained in the step S2 into a reaction vessel, adjusting the pH value to 11, heating to 130 ℃, reacting for 3 hours to obtain a reaction liquid, carrying out suction filtration on the reaction liquid to obtain a filtrate, concentrating the filtrate under reduced pressure, and carrying out freeze drying to obtain sodium lignosulfonate;
s4, adding the sodium lignosulfonate and ammonium persulfate solution obtained in the step S3 into a reaction container, starting stirring under the protection of nitrogen, adding tartaric acid into the reaction container when the temperature rises to 70 ℃, continuously stirring for reaction for 3 hours to obtain a crude product, adding the crude product into acetone to separate out a precipitate, placing the precipitate into a Soxhlet extractor for extraction with ethanol for 5 hours, taking out the precipitate, and drying at 80 ℃ for 5 hours to obtain the sodium lignosulfonate water reducer.
7. The preparation method of the sodium lignosulfonate water reducing agent according to claim 6, which is characterized by comprising the following steps: in the step S1, the volume ratio of toluene to petroleum ether in the toluene petroleum ether solution is 1:1, and the ratio of chestnut shell powder to toluene petroleum ether solution is 1g:40 mL.
8. The preparation method of the sodium lignosulfonate water reducing agent according to claim 6, which is characterized by comprising the following steps: in the step S2, the weight ratio of the defatted chestnut shell powder to the 1-hexyl-3-methyl-imidazolium bisulfate is 1 (25-30), the extraction temperature of the micro-jet extractor is 70 ℃, the pressure of the micro-jet extractor is 120MPa, and the centrifugation speed is 5000-6000 rpm.
9. The preparation method of the sodium lignosulfonate water reducing agent according to claim 6, which is characterized by comprising the following steps: in the step S3, the mass ratio of the lignin, the sodium sulfite, the formaldehyde and the distilled water is (12.5-15) to 1:0.25: 30.
10. The preparation method of the sodium lignosulfonate water reducing agent according to claim 6, which is characterized by comprising the following steps: in the step S4, the mass concentration of the ammonium persulfate solution is 5%, the mass ratio of the sodium lignosulfonate to the ammonium persulfate solution to the tartaric acid is 1:0.2 (0.2-0.3), and the mass ratio of the crude product to the acetone is 1: 10.
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