CN105384263B - Sulfamic acid modification of chitosan water antisludging agent and preparation method thereof - Google Patents
Sulfamic acid modification of chitosan water antisludging agent and preparation method thereof Download PDFInfo
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- CN105384263B CN105384263B CN201510900190.7A CN201510900190A CN105384263B CN 105384263 B CN105384263 B CN 105384263B CN 201510900190 A CN201510900190 A CN 201510900190A CN 105384263 B CN105384263 B CN 105384263B
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Abstract
The invention discloses a kind of sulfamic acid modification of chitosan water antisludging agent and preparation method thereof.The antisludging agent includes sulfamic acid modification of chitosan, and its substitution value is 50~90%.Its preparation method, comprise the following steps：1) chitosan solid and deionized water are weighed, is configured to chitosan aqueous solution；2) by told chitosan aqueous solution heating water bath and stir process；3) sulfamic acid is added into chitosan aqueous solution, after reacting 4~8h, is cooled to room temperature；4) reactant is recrystallized in ethanol, then isolated crystal product；5) resulting crystal product vacuum drying treatment is obtained into antisludging agent.It facts have proved, the sulfamic acid modification of chitosan water antisludging agent of the present invention, with high hydrolytic resistance, the scale problems that especially there are high scale-inhibiting properties can effectively prevent hard water (hardness >=150mg/L) to acid underground heat hard water, especially effectively prevent the scale problems of acid (PH ＜ 7) underground heat hard water.
Description
Technical field
The invention belongs to GEOTHERMAL WATER antisludging agent technical field, in particular to a kind of sulfamic acid modification of chitosan water antisludging agent
And preparation method thereof.
Background technology
Currently, the use of conventional energy resource such as coal, oil and natural gas is faced with resource exhaustion, pollutes the predicament of environment.
Geothermal energy belongs to China《Renewable Energy Law》The renewable new energy type that (2006) are included in, typically by pumping underground hot water
And utilize, it is one of energy-conservation, the effective way of emission reduction.But the fouling of GEOTHERMAL WATER must face in geothermal energy application
One problem.It is still currently employed Main Means that GEOTHERMAL WATER is handled using antisludging agent.
Natural polymer antisludging agent has the characteristics of environmentally friendly, can avoid the secondary pollution to water body.Wherein, chitin is only
Inferior to the second largest natural organic polymer compounds of cellulose, it be shell-fish (shrimp crab) animal, insect ectoskeleton master
Want composition.Chitin molecule is transformed, deacetylate, obtains chitosan.The activity of chitosan has been known as compared with crust to be carried
It is high.Chitosan sheet contains reactive group hydroxyl and amino as linear molecule in strand, and the ortho position of amino is hydroxyl,
The cage molecule that similar network structure is formed in chitosan molecule can be made, therefore, chitosan can have certain absorption, complexing,
Chelating ability, therefore have certain anti-tartar effect.But chitosan is only used as wadding in water process at present because its hydrolytic resistance is poor
Solidifying agent application, chitosan is applied to still need for antisludging agent and improves its hydrolytic resistance, the technology is also in the initial period of research, state
Inside and outside pertinent literature is also fewer.
The content of the invention
The problem of existing for prior art, it is an object of the invention to provide a kind of sulfamic acid modification of chitosan water resistance dirt
Agent and preparation method thereof, the sulfamic acid modification of chitosan water antisludging agent has high hydrolytic resistance, especially to acid underground heat
Hard water has high scale-inhibiting properties.
To achieve the above object, the invention provides a kind of sulfamic acid modification of chitosan water antisludging agent, including：Amino sulphur
Sour modification of chitosan, its substitution value are 50~90%, and preferably its substitution value is 60~80%.
The preparation method of the sulfamic acid modification of chitosan water antisludging agent, comprises the following steps successively：
1) chitosan solid and deionized water are weighed in 80~120ml of 1g ︰ ratio, is configured to chitosan aqueous solution；
2) by told chitosan aqueous solution heating water bath and 0.2~0.8h of stir process, bath temperature is 55 ± 5 DEG C；
3) sulfamic acid, reaction 4 are added into chitosan aqueous solution for 1 ︰ 1~4 by the mass ratio of Ke Ju Tang ︰ sulfamic acids
After~8h, room temperature is cooled to；
4) reactant is recrystallized in ethanol, then isolated crystal product；
5) resulting crystal product vacuum drying treatment is obtained into antisludging agent.
Preferably,：In step 3), the mass ratio of the Ke Ju Tang ︰ sulfamic acids is 1 ︰ 2~3.
Further, in step 4), centrifugation rotating speed is 2500~3500r/min.
Yet further, in step 4), the ethanol is the ethanol of volume fraction 90~99%.
The sulfamic acid modification of chitosan water antisludging agent and its preparation technology control principle of the present invention is analyzed as follows：
Because chitosan has certain absorption, complexing, chelating ability, there is certain anti-tartar effect, be a kind of wadding in itself
Solidifying agent, when the dosage of chitosan in water exceedes a certain amount of, it just shows flocculating property, makes the Ca in water2+Plasma flocculation is heavy
Form sediment, show scale inhibition performance and decline state.But because its hydrolytic Resistance is poor, scale effect is restricted and only made in water process
For flocculant application.It is of the invention then by sulfamic acid modification of chitosan, because contained sulfonic acid group belongs to hydrophilic class group, and
It is acid stronger, molecule chain rigidity is enhanced, improves the heat endurance of product, while inhibits hydrolysis to make to a certain extent
With improving the stability of modification of chitosan.The present invention preparation method by strictly control reaction bath temperature, chitosan with
The factor such as sulfamic acid reactant amount ratio and reaction time, obtain the substitution value of sulfamic acid modification of chitosan for 50~
90%.And the antisludging agent that substitution value is 50~90% has excellent scale-inhibiting properties, to hard water, in especially acid underground heat hard water
The antisludging agent of the present invention is added, scale problems can effectively be prevented by the effect adsorbed, be complexed, chelated.
It was verified that the sulfamic acid modification of chitosan water antisludging agent of the present invention, has high hydrolytic resistance, especially to acid
Property underground heat hard water has the scale problems that high scale-inhibiting properties can effectively prevent hard water (hardness >=150mg/L), especially effectively
Prevent the scale problems of acid (PH≤7) underground heat hard water.
Embodiment
Sulfamic acid modification of chitosan water antisludging agent of the present invention and preparation method thereof is made with reference to specific embodiment
It is further described.
The sulfamic acid modification of chitosan water antisludging agent of embodiment 1~6, including sulfamic acid modification of chitosan, it substitutes
Degree is as shown in table 1 respectively.The preparation method of the sulfamic acid modification of chitosan water antisludging agent, successively including step：
1) it is that 1g ︰ 100ml weigh chitosan solid and deionized water by Ke glycan Gu Ti ︰ deionized waters, in the ratio of table 1
Match into chitosan aqueous solution；
2) above-mentioned chitosan aqueous solution is placed in heating water bath and simultaneously 0.2~0.8h of stir process, bath temperature 55
±5℃；
3) chitosan of table 1 is pressed：The ratio of sulfamic acid adds sulfamic acid, after reacting 4~8h, is cooled to room temperature；
4) above-mentioned reaction product is recrystallized in volume ratio is 95% ethanol, thereafter with 2500~3500r/min rotating speeds
It is centrifugally separating to obtain product；
5) isolated product is dried in vacuo to 24h at 40 DEG C and can obtain antisludging agent.
Shown in specific preparation technology parameter and table 1, the substitution value measure of products obtained therefrom is carried out using photometric titration, scale inhibition
Rate is determined using static scale inhibition method, and detection GEOTHERMAL WATER sample is chosen to be：Hardness >=150mg/L, the acid underground heat hard water of PH ＜ 7.
Detected value is as shown in table 1.
In table 1, mChitosan︰ mSulfamic acidMass ratio by taking chitosan and sulfamic acid in the step 3) of preparation method.No
Substitution value DS different values are have impact on from sulfamic acid reaction with the chitosan matched.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| mChitosan︰ mSulfamic acid | 1 ︰ 1 | 1 ︰ 2 | 1 ︰ 2.5 | 1 ︰ 3 | 1 ︰ 3.5 | 1 ︰ 4 |
| Step 3) reaction time, h | 4.5 | 6 | 5 | 7 | 8 | 7.5 |
| Bath temperature is reacted, 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 example can be seen that the sulfamic acid modification of chitosan water antisludging agent of the present invention by selecting suitable shell
Glycan can realize the substitution value of 50~90% proportions with sulfamic acid reaction ratio, and high rigidity acidity GEOTHERMAL WATER scale inhibition is made
With obvious, scale inhibition performance reaches more than 80%, has excellent scale-inhibiting properties.
Claims (5)
- A kind of 1. sulfamic acid modification of chitosan water antisludging agent, it is characterised in that：It includes sulfamic acid modification of chitosan, and it takes Dai Du is 50~90%, its preparation method, is comprised the following steps successively：1) chitosan solid and deionized water are weighed in 80~120ml of 1g ︰ ratio, is configured to chitosan aqueous solution；2) by the chitosan solution heating water bath, simultaneously 0.2~0.8h of stir process, bath temperature are 55 ± 5 DEG C simultaneously；3) sulfamic acid is added for 1 ︰ 1~4 by the mass ratio of Ke Ju Tang ︰ sulfamic acids, after reacting 4~8h, is cooled to room temperature；4) reaction product is recrystallized in ethanol, is then centrifuged for isolated crystal product；5) by resulting crystal product vacuum drying treatment.
- 2. sulfamic acid modification of chitosan water antisludging agent according to claim 1, it is characterised in that：Its substitution value be 60~ 80%.
- 3. sulfamic acid modification of chitosan water antisludging agent according to claim 1, it is characterised in that：In step 4), centrifugation Separation rotating speed is 2500~3500r/min.
- 4. sulfamic acid modification of chitosan water antisludging agent according to claim 1 or 2, it is characterised in that：In step 4), institute It is the ethanol that volume fraction is 90~99% to state ethanol.
- 5. sulfamic acid modification of chitosan water antisludging agent according to claim 1 or 2, it is characterised in that：In step 3), institute The mass ratio for stating Ke Ju Tang ︰ sulfamic acids is 1 ︰ 2~3.
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| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
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| CN101767853B (en) * | 2009-03-20 | 2011-10-26 | 上海立昌环境工程有限公司 | Preparation and application of environment-friendly biodegradable paint mist polycoagulant |
| CN103012619B (en) * | 2013-01-11 | 2015-04-08 | 河北工业大学 | Water-soluble sulfonated/quaternized chitosan and preparation method thereof |
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