CN105384263A - Sulfamic acid modified chitosan water scale inhibitor and preparation method thereof - Google Patents
Sulfamic acid modified chitosan water scale inhibitor and preparation method thereof Download PDFInfo
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- CN105384263A CN105384263A CN201510900190.7A CN201510900190A CN105384263A CN 105384263 A CN105384263 A CN 105384263A CN 201510900190 A CN201510900190 A CN 201510900190A CN 105384263 A CN105384263 A CN 105384263A
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Abstract
The invention discloses a sulfamic acid modified chitosan water scale inhibitor and a preparation method thereof. The scale inhibitor comprises sulfamic acid modified chitosan with a degree of substitution of 50 to 90%. The preparation method comprises the following steps: (1) weighing chitosan solid and deionized water and preparing a chitosan water solution; (2) heating the chitosan water solution in a water bath, and stirring the chitosan water solution; (3) adding sulfamic acid into the chitosan water solution, carrying out reactions for 4 to 8 hours, and cooling to the room temperature; (4) re-crystallizing the reaction products in ethanol, and separating the recrystallization product to obtain a crystal product; (5) drying the obtained crystal product in vacuum to obtain the inhibitor. The practice has proved that the sulfamic acid modified chitosan water scale inhibitor has a high performance on resisting hydrolysis and a high scale inhibiting performance for acidic geothermal hard water, can effectively prevent scaling of hard water with a hardness not less than 150 mg/L, and has an especially good effect on inhibiting the scaling of acidic geothermal hard water with a pH value less than 7.
Description
Technical field
The invention belongs to GEOTHERMAL WATER Scale inhibitors technical field, specifically refer to a kind of thionamic acid modified chitosan water Scale inhibitors and preparation method thereof.
Background technology
Current, the use of conventional energy resources as coal, oil and natural gas is faced with the predicament of resource exhaustion, contaminate environment.Geothermal energy belongs to the renewable new forms of energy type that China " Renewable Energy Law " (2006) are listed in, is generally utilized by pumping underground hot water, is one of effective way that is energy-conservation, that reduce discharging.But, in Geothermal energy application the fouling of GEOTHERMAL WATER be must faced by a difficult problem.Scale inhibitors process is adopted to remain the Main Means of current employing to GEOTHERMAL WATER.
Natural polymer Scale inhibitors has the feature of environmental protection, can avoid the secondary pollution to water body.Wherein, chitin is only second to cellulosic second largest natural organic high-molecular compound, and it is the ectoskeletal main component of crustaceans (shrimp crab) animal, insect.Chitin molecule is transformed, deacetylate, obtain chitosan.The activity of chitosan comparatively crust has have raising.Chitosan is originally as thread-like molecule, containing reactive group hydroxyl and amino in molecular chain, and the ortho position of amino is hydroxyl, can make in chitosan molecule, to form similar cancellated cage molecule, therefore, chitosan can have certain absorption, complexing, chelating ability, therefore has certain anti-tartar effect.But, chitosan because of its resistance to hydrolysis poor, at present only in water treatment as flocculation agent application, chitosan is applied as Scale inhibitors and still needs and improve its resistance to hydrolysis, this technology is also in the initial period of research, and domestic and international pertinent literature is also fewer.
Summary of the invention
For prior art Problems existing, the object of this invention is to provide a kind of thionamic acid modified chitosan water Scale inhibitors and preparation method thereof, described thionamic acid modified chitosan water Scale inhibitors has high resistance to hydrolysis, especially has high scale-inhibiting properties to acid underground heat hard water.
For achieving the above object, the invention provides a kind of thionamic acid modified chitosan water Scale inhibitors, comprising: thionamic acid modified chitosan, its substitution value is 50 ~ 90%, and preferably its substitution value is 60 ~ 80%.
The preparation method of described thionamic acid modified chitosan water Scale inhibitors, comprises the following steps successively:
1) weigh chitosan solid and deionized water in the ratio of 1g ︰ 80 ~ 120ml, be mixed with chitosan aqueous solution;
2) by told chitosan aqueous solution heating in water bath and stir process 0.2 ~ 0.8h, bath temperature is 55 ± 5 DEG C;
3) be that 1 ︰ 1 ~ 4 adds thionamic acid in chitosan aqueous solution by the mass ratio of Ke Ju Tang ︰ thionamic acid, after reaction 4 ~ 8h, be cooled to room temperature;
4) by described reactant recrystallization in ethanol, be then separated and obtain crystal product;
5) namely obtained crystal product vacuum drying treatment is obtained Scale inhibitors.
Preferably: step 3) in, the mass ratio of described Ke Ju Tang ︰ thionamic acid is 1 ︰ 2 ~ 3.
Further, step 4) in, centrifugation rotating speed is 2500 ~ 3500r/min.
Again further, step 4) in, described ethanol is the ethanol of volume fraction 90 ~ 99%.
Thionamic acid modified chitosan water Scale inhibitors of the present invention and preparation technology's control principle thereof are analyzed as follows:
Because chitosan has certain absorption, complexing, chelating ability, have certain anti-tartar effect, itself be a kind of flocculation agent, when in water, the dosage of chitosan exceedes a certain amount of, it just shows flocculating property, makes the Ca in water
2+plasma flocculation sediment, shows scale inhibition performance decline state.But due to its resistant to hydrolysis poor performance, scale effect is restricted and only applies as flocculation agent in water treatment.The present invention is then by thionamic acid modified chitosan, and because contained sulfonic acid group belongs to hydrophilic class group, and acidity is stronger, enhance molecule chain rigidity, improve the thermostability of product, inhibit hydrolytic action to a certain extent simultaneously, improve the stability of modified chitosan.Preparation method of the present invention controls reaction water bath temperature, chitosan and the factor such as thionamic acid reactant amount ratio and reaction times by strict, and the substitution value obtaining thionamic acid modified chitosan is 50 ~ 90%.And the Scale inhibitors that substitution value is 50 ~ 90% has excellent scale-inhibiting properties, add Scale inhibitors of the present invention in hard water, especially acid underground heat hard water, effectively can prevent scale problems by the effect of absorption, complexing, chelating.
Facts have proved, thionamic acid modified chitosan water Scale inhibitors of the present invention, there is high resistance to hydrolysis, especially to acid underground heat hard water, there is the scale problems that high scale-inhibiting properties effectively can prevent hard water (hardness >=150mg/L), especially effectively prevent the scale problems of acidity (PH≤7) underground heat hard water.
Embodiment
Below in conjunction with specific embodiment, thionamic acid modified chitosan water Scale inhibitors of the present invention and preparation method thereof is described in further detail.
The thionamic acid modified chitosan water Scale inhibitors of embodiment 1 ~ 6, comprises thionamic acid modified chitosan, and its substitution value is as shown in table 1 respectively.The preparation method of described thionamic acid modified chitosan water Scale inhibitors, comprises step successively:
1) be that 1g ︰ 100ml weighs chitosan solid and deionized water by chitosan Gu Ti ︰ deionized water, become chitosan aqueous solution by the proportions of table 1;
2) above-mentioned chitosan aqueous solution is placed in heating in water bath and simultaneously stir process 0.2 ~ 0.8h, bath temperature is 55 ± 5 DEG C;
3) in table 1 chitosan: the ratio of thionamic acid adds thionamic acid, after reaction 4 ~ 8h, room temperature is cooled to;
4) be recrystallization in 95% ethanol by above-mentioned reaction product in volume ratio, obtain product with the centrifugation of 2500 ~ 3500r/min rotating speed thereafter;
5) Scale inhibitors can be obtained by being separated the product vacuum-drying 24h at 40 DEG C obtained.
Shown in concrete preparation technology parameter and table 1, the substitution value of products obtained therefrom measures and adopts photometric titration to carry out, and scale inhibition performance adopts static scale inhibition method to measure, and detects GEOTHERMAL WATER sample and is chosen to be: hardness >=150mg/L, acid PH < 7 underground heat hard water.
Detected value is as shown in table 1.
In Table 1, m
chitosan︰ m
thionamic acidstep 3 for preparation method) in get the mass ratio of chitosan and thionamic acid.Chitosan and the thionamic acid of different ratio react the different values that have impact on substitution value DS.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| m Chitosan︰m Thionamic acid | 1︰1 | 1︰2 | 1︰2.5 | 1︰3 | 1︰3.5 | 1︰4 |
| Step 3) reaction times, h | 4.5 | 6 | 5 | 7 | 8 | 7.5 |
| Reaction water bath temperature, DEG C | 60 | 55 | 58 | 60 | 60 | 52 |
| GEOTHERMAL WATER pH value | 6.5 | 6.4 | 6.8 | 6.2 | 6.6 | 6.5 |
| Substitution value, % | 53 | 62 | 70 | 76 | 84 | 89 |
| Scale inhibition performance, % | 82 | 83 | 85 | 87 | 71 | 68 |
Above embodiment can be found out, the substitution value of thionamic acid modified chitosan water Scale inhibitors of the present invention by selecting suitable chitosan and thionamic acid reaction ratio can realize 50 ~ 90% proportional ranges, obvious to the acid GEOTHERMAL WATER scale effect of high rigidity, scale inhibition performance reaches more than 80%, has excellent scale-inhibiting properties.
Claims (6)
1. a thionamic acid modified chitosan water Scale inhibitors, is characterized in that: it comprises thionamic acid modified chitosan, its substitution value is 50 ~ 90%.
2. thionamic acid modified chitosan water Scale inhibitors according to claim 1, is characterized in that: its substitution value is 60 ~ 80%.
3. the preparation method of thionamic acid modified chitosan water Scale inhibitors according to claim 1, comprises the following steps successively:
1) weigh chitosan solid and deionized water in the ratio of 1g ︰ 80 ~ 120ml, be mixed with chitosan aqueous solution;
2) by told chitosan solution heating in water bath and simultaneously stir process 0.2 ~ 0.8h, bath temperature is 55 ± 5 DEG C;
3) be that 1 ︰ 1 ~ 4 adds thionamic acid by the mass ratio of Ke Ju Tang ︰ thionamic acid, after reaction 4 ~ 8h, be cooled to room temperature;
4) by described reaction product recrystallization in ethanol, then centrifugation obtains crystal product;
5) by obtained crystal product vacuum drying treatment.
4. the preparation method of thionamic acid modified chitosan water Scale inhibitors according to claim 3, is characterized in that: step 4) in, centrifugation rotating speed is 2500 ~ 3500r/min.
5. the preparation method of the thionamic acid modified chitosan water Scale inhibitors according to claim 3 or 4, is characterized in that: step 4) in, described ethanol to be volume fraction be 90 ~ 99% ethanol.
6. the preparation method of the thionamic acid modified chitosan water Scale inhibitors according to claim 3 or 4, is characterized in that: step 3) in, the mass ratio that described shell gathers sugared ︰ thionamic acid is 1 ︰ 2 ~ 3.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793443A (en) * | 2018-06-28 | 2018-11-13 | 芜湖市棠华建材科技有限公司 | Environmentally friendly antisludging agent |
| CN108821454A (en) * | 2018-06-28 | 2018-11-16 | 芜湖市棠华建材科技有限公司 | Recirculated cooling water antisludging agent |
| CN108840453A (en) * | 2018-06-28 | 2018-11-20 | 芜湖市棠华建材科技有限公司 | Modification of chitosan water antisludging agent |
| CN108862639A (en) * | 2018-06-28 | 2018-11-23 | 芜湖市棠华建材科技有限公司 | Composite slow release antisludging agent |
| CN108862641A (en) * | 2018-06-28 | 2018-11-23 | 芜湖市棠华建材科技有限公司 | Recirculated cooling water slow-release scale inhibitor |
| CN113121025A (en) * | 2021-03-29 | 2021-07-16 | 安阳工学院 | Tracer type bio-based scale inhibitor and preparation method and application thereof |
| CN115228442A (en) * | 2021-04-22 | 2022-10-25 | 湖南大学 | Preparation and application of 4-sodium vinylbenzene sulfonate modified chitosan adsorbent |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793443A (en) * | 2018-06-28 | 2018-11-13 | 芜湖市棠华建材科技有限公司 | Environmentally friendly antisludging agent |
| CN108821454A (en) * | 2018-06-28 | 2018-11-16 | 芜湖市棠华建材科技有限公司 | Recirculated cooling water antisludging agent |
| CN108840453A (en) * | 2018-06-28 | 2018-11-20 | 芜湖市棠华建材科技有限公司 | Modification of chitosan water antisludging agent |
| CN108862639A (en) * | 2018-06-28 | 2018-11-23 | 芜湖市棠华建材科技有限公司 | Composite slow release antisludging agent |
| CN108862641A (en) * | 2018-06-28 | 2018-11-23 | 芜湖市棠华建材科技有限公司 | Recirculated cooling water slow-release scale inhibitor |
| CN113121025A (en) * | 2021-03-29 | 2021-07-16 | 安阳工学院 | Tracer type bio-based scale inhibitor and preparation method and application thereof |
| CN113121025B (en) * | 2021-03-29 | 2023-10-27 | 安阳工学院 | Trace type bio-based scale inhibitor and preparation method and application thereof |
| CN115228442A (en) * | 2021-04-22 | 2022-10-25 | 湖南大学 | Preparation and application of 4-sodium vinylbenzene sulfonate modified chitosan adsorbent |
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