CN117509860B - Flocculant and preparation method thereof - Google Patents
Flocculant and preparation method thereof Download PDFInfo
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- CN117509860B CN117509860B CN202410016828.XA CN202410016828A CN117509860B CN 117509860 B CN117509860 B CN 117509860B CN 202410016828 A CN202410016828 A CN 202410016828A CN 117509860 B CN117509860 B CN 117509860B
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002608 ionic liquid Substances 0.000 claims abstract description 41
- 229920002472 Starch Polymers 0.000 claims abstract description 37
- 239000008107 starch Substances 0.000 claims abstract description 37
- 235000019698 starch Nutrition 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000005576 amination reaction Methods 0.000 claims description 27
- 229920000881 Modified starch Polymers 0.000 claims description 25
- 239000004368 Modified starch Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 235000019426 modified starch Nutrition 0.000 claims description 25
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- NNUNDQZDGVWLPX-UHFFFAOYSA-N (2-hydroxy-4-propoxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCC)=CC=C1C(=O)C1=CC=CC=C1 NNUNDQZDGVWLPX-UHFFFAOYSA-N 0.000 claims description 14
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 11
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 11
- WJAXXWSZNSFVNG-UHFFFAOYSA-N 2-bromoethanamine;hydron;bromide Chemical compound [Br-].[NH3+]CCBr WJAXXWSZNSFVNG-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 12
- 239000002351 wastewater Substances 0.000 abstract description 12
- 239000008394 flocculating agent Substances 0.000 abstract description 9
- 238000005189 flocculation Methods 0.000 abstract description 9
- 230000016615 flocculation Effects 0.000 abstract description 9
- 229940037003 alum Drugs 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 4
- 150000002891 organic anions Chemical class 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 230000003311 flocculating effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000005553 drilling Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a flocculant and a preparation method thereof, belonging to the technical field of sewage treatment, wherein the flocculant is formed by mixing polyaluminium chloride and an organic flocculant according to the weight ratio of 1:1; on one hand, the advantages of inorganic flocculant polyaluminium chloride can be exerted, on the other hand, ionic liquid is introduced into an organic flocculant structure, the ionic liquid can be matched with the inorganic flocculant, and then is added into the wastewater by compounding with organic anions, so that a compressed double electric layer can be generated, suspended particles in the wastewater lose stability, colloidal particles are mutually aggregated to enlarge particles, and floccules and alum flowers are formed, thereby achieving the effect of water treatment and further improving the flocculation effect; the organic flocculant takes starch as a matrix, so that the degradability can be improved, and the technical problem that most of the organic flocculants are difficult to degrade and pollute the environment at present is solved.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a flocculant and a preparation method thereof.
Background
The flocculation precipitation method of important components in water treatment engineering greatly depends on the performance of flocculant. The flocculant used at present is mainly divided into two major categories of inorganic and organic, wherein the organic polymeric flocculant has the advantages of less amount, wide application range, less influence by salt and environmental conditions, less sludge amount, good treatment effect and the like compared with the inorganic flocculant, and is attracting more and more attention.
Therefore, development of green flocculant is urgently needed. Starch is widely used in various industrial fields as a natural resource, and with the development of industrial production technology and the continuous appearance of new products, the requirements on the properties of starch are more and more severe, and the properties of raw starch are not suitable for many application fields. In addition, although natural polymer flocculants such as starch have the characteristic of easy degradation, the flocculants have low charge density and small molecular weight, cannot exert excellent flocculation performance, and are also urgently required to be further modified.
Disclosure of Invention
In order to solve the technical problems, the invention provides a flocculant and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
a flocculant is prepared by mixing polyaluminium chloride and an organic flocculant according to the weight ratio of 1:1;
the organic flocculant is prepared by the following steps:
step S1: adding starch into deionized water, magnetically stirring for 15min, heating to 80 ℃, introducing nitrogen, continuously stirring and gelatinizing for 1h, cooling to 55-70 ℃, adding ceric ammonium nitrate, stirring for 1min, adding 4-propoxy-2-hydroxybenzophenone and dimethyl diallyl ammonium chloride, stirring at a constant speed, and reacting for 2h to obtain modified starch;
in the step S1, ceric ammonium nitrate is used as an initiator, starch is gelatinized, and then 4-propoxy-2-hydroxybenzophenone, dimethyl diallyl ammonium chloride and starch are polymerized under the action of the initiator to prepare modified starch, and cations are introduced to synthesize a starch-based cationic flocculant, so that the advantages of the cationic flocculant can be exerted;
step S2: adding modified starch and amination ionic liquid into deionized water, heating in a water bath at 55-60 ℃, stirring at a constant speed, reacting for 12 hours, and removing solvent by rotary evaporation after the reaction is finished to obtain the organic flocculant.
In the step S2, the aminated ionic liquid reacts with a structural unit of diphenyl ketone on modified starch through a characteristic structure of Schiff base, and is grafted on a starch side chain, the ionic liquid can be matched with an inorganic flocculant, and is added into waste water through compounding with organic anions, so that a compressed double electric layer is generated, suspended particles in the waste water lose stability, colloidal particle substances are mutually aggregated to enlarge the particles, and flocculating bodies and alum flowers are formed, thereby achieving the effect of water treatment, further improving the flocculation effect, and solving the technical problems that the ionic liquid is easy to run off and poor in compatibility after being used as an independent flocculation component to be blended with a matrix.
Further: in the step S1, the dosage ratio of the starch, the 4-propoxy-2-hydroxy diphenyl ketone, the dimethyl diallyl ammonium chloride and the deionized water is controlled to be 1-2 g:3-5 g:2-3 g:150 mL, and the dosage of the ceric ammonium nitrate is 2-2.5% of the weight of the starch.
Further: in the step S2, the weight ratio of the modified starch, the amination ionic liquid and the deionized water is controlled to be 5-8:1-2:50-70.
Further: the amination ionic liquid in the step S2 is prepared by the following steps:
adding bromoethylamine hydrobromide and N-methylimidazole into a three-necked flask, heating in an oil bath, refluxing with absolute ethyl alcohol for 20-24h, evaporating (removing ethanol) after the refluxing is finished, and then drying in vacuum at 75 ℃ for 6h to obtain an intermediate 1; mixing the intermediate 1 with potassium hydroxide, adding into a vacuum drying oven, drying for 12-24h, adding ethanol, (removing impurity potassium bromide), and obtaining an intermediate 2; adding the intermediate 2 and potassium hexafluorophosphate into absolute ethyl alcohol, heating to 65 ℃, continuously reacting for 18 hours, and then carrying out vacuum suction filtration and rotary evaporation to obtain the amination ionic liquid.
In the step S2, N-methylimidazole reacts with bromoethylamine hydrobromide to obtain an intermediate 1, potassium hydroxide is added to react to obtain an intermediate 2, and finally, the intermediate 2 and potassium hexafluorophosphate are subjected to ion exchange reaction to obtain an amination ionic liquid, and amino is introduced into an ionic liquid structure;
further: the weight ratio of bromoethylamine hydrobromide, N-methylimidazole and absolute ethyl alcohol is controlled to be 1:1-1.2:100, the mol ratio of the intermediate 1 to potassium hydroxide is controlled to be 1:1, and the mol ratio of the intermediate 2 to potassium hexafluorophosphate is controlled to be 1:1.
A method for preparing a flocculant, comprising the steps of:
uniformly mixing polyaluminium chloride and an organic flocculant according to the weight ratio of 1:1 to prepare the high-efficiency flocculant.
The invention has the beneficial effects that:
according to the invention, the flocculant is prepared, the polyaluminium chloride and the organic flocculant are uniformly mixed according to the weight ratio of 1:1, on one hand, the advantage of inorganic flocculant polyaluminium chloride can be exerted, on the other hand, the ionic liquid is introduced into the organic flocculant structure, can be matched with the inorganic flocculant, and is then added into the wastewater by compounding with organic anions, so that a compressed double electric layer can be generated, suspended particles in the wastewater lose stability, colloidal particles are mutually aggregated to enlarge particles, and flocculating bodies and alum flowers are formed, thereby achieving the effect of water treatment and further improving the flocculating effect.
The organic flocculant synthesized by the invention takes starch as a matrix, so that the degradability can be improved, the technical problem that most of the organic flocculants are difficult to degrade and pollute the environment at present is solved, secondly, the 4-propoxy-2-hydroxybenzophenone, the dimethyl diallyl ammonium chloride and the starch are polymerized under the action of an initiator in the preparation process to prepare the modified starch, on one hand, cations can be introduced to synthesize a starch-based cationic flocculant, the advantages of the cationic flocculant can be brought into play, on the other hand, the subsequent reaction with the aminated ionic liquid can be facilitated, the ionic liquid is introduced to facilitate the synergistic inorganic flocculant to bring into play of flocculation effect, and in addition, the organic flocculant further prolongs the branched chain through the ionic liquid, so that the space structure of the organic flocculant is expanded, and the space network structure with larger specific surface area has better adsorption bridging performance than that of the branched chain structure, and further improves the flocculation effect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A flocculant is prepared by mixing polyaluminium chloride and an organic flocculant according to the weight ratio of 1:1;
the organic flocculant is prepared by the following steps:
step S1: adding starch into deionized water, magnetically stirring for 15min, heating to 80 ℃, introducing nitrogen, continuously stirring and gelatinizing for 1h, then cooling to 55 ℃, adding ceric ammonium nitrate, stirring for 1min, adding 4-propoxy-2-hydroxybenzophenone and dimethyl diallyl ammonium chloride, uniformly stirring and reacting for 2h to obtain modified starch, controlling the dosage ratio of starch, 4-propoxy-2-hydroxybenzophenone, dimethyl diallyl ammonium chloride and deionized water to be 1 g:3 g:2 g:150 mL, wherein the dosage of ceric ammonium nitrate is 2% of the weight of the starch;
step S2: adding modified starch and amination ionic liquid into deionized water, heating in a water bath at 55 ℃, stirring at a constant speed, reacting for 12 hours, and removing solvent by rotary evaporation after the reaction is finished to prepare the organic flocculant, wherein the weight ratio of the modified starch to the amination ionic liquid to the deionized water is controlled to be 5:1:50.
The amination ionic liquid is prepared by the following steps:
adding bromoethylamine hydrobromide and N-methylimidazole into a three-neck flask, heating in an oil bath, refluxing with absolute ethyl alcohol for 20h, evaporating to remove the alcohol after the refluxing is finished, and then drying in vacuum at 75 ℃ for 6h to obtain an intermediate 1; mixing the intermediate 1 with potassium hydroxide, adding the mixture into a vacuum drying oven, drying for 12 hours, adding ethanol, and removing impurity potassium bromide to obtain an intermediate 2; adding the intermediate 2 and potassium hexafluorophosphate into absolute ethyl alcohol, heating to 65 ℃, continuously reacting for 18 hours, vacuum-filtering, and rotary-steaming to obtain the amination ionic liquid, wherein the weight ratio of bromoethylamine hydrobromide to N-methylimidazole to the absolute ethyl alcohol is controlled to be 1:1:100, the mol ratio of the intermediate 1 to potassium hydroxide is 1:1, and the mol ratio of the intermediate 2 to potassium hexafluorophosphate is 1:1.
Example 2
A flocculant is prepared by mixing polyaluminium chloride and an organic flocculant according to the weight ratio of 1:1;
the organic flocculant is prepared by the following steps:
step S1: adding starch into deionized water, magnetically stirring for 15min, heating to 80 ℃, introducing nitrogen, continuously stirring and gelatinizing for 1h, then cooling to 55-70 ℃, adding ceric ammonium nitrate, stirring for 1min, adding 4-propoxy-2-hydroxybenzophenone and dimethyldiallyl ammonium chloride, uniformly stirring and reacting for 2h to obtain modified starch, controlling the dosage ratio of starch, 4-propoxy-2-hydroxybenzophenone, dimethyldiallyl ammonium chloride and deionized water to be 1.5 g:4 g:2.5 g:150 mL, wherein the dosage of ceric ammonium nitrate is 2.2% of the weight of the starch;
step S2: adding modified starch and amination ionic liquid into deionized water, heating in a 58 ℃ water bath, stirring at a constant speed, reacting for 12 hours, and removing solvent by rotary evaporation after the reaction is finished to prepare the organic flocculant, wherein the weight ratio of the modified starch to the amination ionic liquid to the deionized water is controlled to be 6:1:60.
The amination ionic liquid is prepared by the following steps:
adding bromoethylamine hydrobromide and N-methylimidazole into a three-neck flask, heating in an oil bath, refluxing with absolute ethyl alcohol for 24 hours, evaporating to remove the alcohol after the refluxing is finished, and then drying in vacuum at 75 ℃ for 6 hours to obtain an intermediate 1; mixing the intermediate 1 with potassium hydroxide, adding the mixture into a vacuum drying oven, drying for 24 hours, adding ethanol, and removing impurity potassium bromide to obtain an intermediate 2; adding the intermediate 2 and potassium hexafluorophosphate into absolute ethyl alcohol, heating to 65 ℃, continuously reacting for 18 hours, vacuum-filtering, and rotary-steaming to obtain the amination ionic liquid, wherein the weight ratio of bromoethylamine hydrobromide to N-methylimidazole to the absolute ethyl alcohol is controlled to be 1:1.1:100, the mol ratio of the intermediate 1 to potassium hydroxide is 1:1, and the mol ratio of the intermediate 2 to potassium hexafluorophosphate is 1:1.
Example 3
A flocculant is prepared by mixing polyaluminium chloride and an organic flocculant according to the weight ratio of 1:1;
the organic flocculant is prepared by the following steps:
step S1: adding starch into deionized water, magnetically stirring for 15min, heating to 80 ℃, introducing nitrogen, continuously stirring and gelatinizing for 1h, then cooling to 70 ℃, adding ceric ammonium nitrate, stirring for 1min, adding 4-propoxy-2-hydroxybenzophenone and dimethyl diallyl ammonium chloride, uniformly stirring and reacting for 2h to obtain modified starch, controlling the dosage ratio of starch, 4-propoxy-2-hydroxybenzophenone, dimethyl diallyl ammonium chloride and deionized water to be 2 g:5 g:3 g:150 mL, and the dosage of ceric ammonium nitrate to be 2.5% of the weight of the starch;
step S2: adding modified starch and amination ionic liquid into deionized water, heating in a water bath at 60 ℃, stirring at a constant speed, reacting for 12 hours, and removing solvent by rotary evaporation after the reaction is finished to prepare the organic flocculant, wherein the weight ratio of the modified starch to the amination ionic liquid to the deionized water is controlled to be 8:2:70.
The amination ionic liquid is prepared by the following steps:
adding bromoethylamine hydrobromide and N-methylimidazole into a three-neck flask, heating in an oil bath, refluxing with absolute ethyl alcohol for 24 hours, evaporating to remove the alcohol after the refluxing is finished, and then drying in vacuum at 75 ℃ for 6 hours to obtain an intermediate 1; mixing the intermediate 1 with potassium hydroxide, adding the mixture into a vacuum drying oven, drying for 24 hours, adding ethanol, and removing impurity potassium bromide to obtain an intermediate 2; adding the intermediate 2 and potassium hexafluorophosphate into absolute ethyl alcohol, heating to 65 ℃, continuously reacting for 18 hours, vacuum-filtering, and rotary-steaming to obtain the amination ionic liquid, wherein the weight ratio of bromoethylamine hydrobromide to N-methylimidazole to the absolute ethyl alcohol is controlled to be 1:1.2:100, the mol ratio of the intermediate 1 to potassium hydroxide is 1:1, and the mol ratio of the intermediate 2 to potassium hexafluorophosphate is 1:1.
Comparative example 1
In this comparative example, compared with example 1, dimethyl diallyl ammonium chloride was not added, and the preparation method is as follows:
a flocculant is prepared by mixing polyaluminium chloride and an organic flocculant according to the weight ratio of 1:1;
the organic flocculant is prepared by the following steps:
step S1: adding starch into deionized water, magnetically stirring for 15min, heating to 80 ℃, introducing nitrogen, continuously stirring and gelatinizing for 1h, then cooling to 55-70 ℃, adding ceric ammonium nitrate, stirring for 1min, adding 4-propoxy-2-hydroxybenzophenone, uniformly stirring and reacting for 2h to obtain modified starch, controlling the dosage ratio of the starch, the 4-propoxy-2-hydroxybenzophenone and the deionized water to be 1 g:3 g:150 mL, wherein the dosage of the ceric ammonium nitrate is 2% of the weight of the starch;
step S2: adding modified starch and amination ionic liquid into deionized water, heating in a water bath at 55 ℃, stirring at a constant speed, reacting for 12 hours, and removing solvent by rotary evaporation after the reaction is finished to prepare the organic flocculant, wherein the weight ratio of the modified starch to the amination ionic liquid to the deionized water is controlled to be 5:1:50.
The preparation method of the amination ionic liquid is the same as that of the example 1.
Comparative example 2
In this comparative example, compared with example 1, no ionic liquid was added, and the preparation method is as follows:
a flocculant is prepared by mixing polyaluminium chloride and an organic flocculant according to the weight ratio of 1:1;
the organic flocculant is prepared by the following steps:
adding starch into deionized water, magnetically stirring for 15min, heating to 80 ℃, introducing nitrogen, continuously stirring and gelatinizing for 1h, then cooling to 55 ℃, adding ceric ammonium nitrate, stirring for 1min, adding 4-propoxy-2-hydroxybenzophenone and dimethyl diallyl ammonium chloride, uniformly stirring and reacting for 2h to obtain modified starch, controlling the dosage ratio of starch, 4-propoxy-2-hydroxybenzophenone, dimethyl diallyl ammonium chloride and deionized water to be 1 g:3 g:2 g:150 mL, and the dosage of ceric ammonium nitrate to be 2% of the weight of the starch.
Comparative example 3
In this comparative example, compared to example 1, the ionic liquid was not incorporated into the starch, and the preparation method is as follows:
a flocculant is prepared by mixing polyaluminium chloride and an organic flocculant according to the weight ratio of 1:1;
the organic flocculant is prepared by the following steps:
step S1: adding starch into deionized water, magnetically stirring for 15min, heating to 80 ℃, introducing nitrogen, continuously stirring and gelatinizing for 1h, then cooling to 55 ℃, adding ceric ammonium nitrate, stirring for 1min, adding dimethyl diallyl ammonium chloride, uniformly stirring and reacting for 2h to obtain modified starch, controlling the dosage ratio of the starch to the dimethyl diallyl ammonium chloride to the deionized water to be 1 g:2 g:150 mL, wherein the dosage of the ceric ammonium nitrate is 2% of the weight of the starch;
step S2: adding modified starch and amination ionic liquid into deionized water, heating in a water bath at 55 ℃, stirring at a constant speed, reacting for 12 hours, and removing solvent by rotary evaporation after the reaction is finished to prepare the organic flocculant, wherein the weight ratio of the modified starch to the amination ionic liquid to the deionized water is controlled to be 5:1:50.
The preparation method of the amination ionic liquid is the same as that of the example 1.
Performance test:
the waste water-based drilling fluid for flocculation experiments is waste drilling fluid of oil field drilling sites, a certain amount of waste drilling fluid is taken and stirred in a beaker, flocculant is added, the addition amount of the flocculant is 5g/L, the mixture is stirred for 5min at a rotating speed of 200r/min, then the mixture is stirred for 10min at a rotating speed of 50r/min, and the supernatant is measured after standing for 30 min.
Adding flocculant (the mass concentration of the flocculant is 10 g/L) into the wastewater by a pipette, shaking the wastewater upside down for 10 times, standing the wastewater for 20min, and measuring the CODcr, chromaticity, turbidity and oil content of supernatant.
COD (chemical oxygen demand) was measured using the HJ828-2017 standard;
the chromaticity is measured by using GB11903-89 standard;
turbidity was measured using GB13200-91 standard;
the oil content was determined using the SL93.2-1994 standard.
The properties of the flocculants prepared in examples 1 to 3 and comparative examples 1 to 3 were examined, and the results are shown in Table 1 below:
as can be seen from the above Table 1, the flocculants prepared in examples 1 to 3 of the present invention have better effect than comparative example 1, because the flocculants prepared in the present invention are formed by mixing polyaluminum chloride and organic flocculants in a weight ratio of 1:1, the advantages of inorganic flocculants polyaluminum chloride can be exerted;
compared with the flocculant prepared in the comparative example 2, the flocculant prepared in the embodiment 1-3 has better effect, because the introduced ionic liquid can be matched with an inorganic flocculant and then added into the wastewater by compounding with organic anions, a compressed double electric layer can be generated, so that suspended particles in the wastewater lose stability, colloidal particles mutually agglomerate to enlarge particles, and flocculating bodies and alum flowers are formed, thereby achieving the effect of water treatment and further improving the flocculating effect.
Compared with the flocculant prepared in the comparative example 3, the flocculant prepared in the embodiment 1-3 has better effect, because the organic flocculant is connected with the ionic liquid, the branched chain is further prolonged, the space structure of the flocculant is expanded, the space structure of a multi-adsorption layer is formed, the space network structure with larger specific surface area has better adsorption bridging performance than the branched chain structure, and the flocculation effect is further improved.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (5)
1. A flocculant, characterized in that: is formed by mixing polyaluminium chloride and an organic flocculant according to the weight ratio of 1:1;
the organic flocculant is prepared by the following steps:
step S1: adding starch into deionized water, magnetically stirring for 15min, heating to 80 ℃, introducing nitrogen, continuously stirring and gelatinizing for 1h, cooling to 55-70 ℃, adding ceric ammonium nitrate, stirring for 1min, adding 4-propoxy-2-hydroxybenzophenone and dimethyl diallyl ammonium chloride, stirring at a constant speed, and reacting for 2h to obtain modified starch;
step S2: adding modified starch and amination ionic liquid into deionized water, heating in a water bath at 55-60 ℃, stirring at a constant speed, reacting for 12 hours, and removing solvent by rotary evaporation after the reaction is finished to prepare an organic flocculant;
the amination ionic liquid is prepared by the following steps:
adding bromoethylamine hydrobromide and N-methylimidazole into a three-neck flask, heating in an oil bath, refluxing with absolute ethyl alcohol for 20-24h, evaporating after the refluxing is finished, and then vacuum drying at 75 ℃ for 6h to obtain an intermediate 1; mixing the intermediate 1 with potassium hydroxide, adding into a vacuum drying oven, drying for 12-24h, and adding ethanol to obtain an intermediate 2; adding the intermediate 2 and potassium hexafluorophosphate into absolute ethyl alcohol, heating to 65 ℃, continuously reacting for 18 hours, and then carrying out vacuum suction filtration and rotary evaporation to obtain the amination ionic liquid.
2. A flocculant according to claim 1, characterized in that: in the step S1, the dosage ratio of the starch, the 4-propoxy-2-hydroxy diphenyl ketone, the dimethyl diallyl ammonium chloride and the deionized water is controlled to be 1-2 g:3-5 g:2-3 g:150 mL, and the dosage of the ceric ammonium nitrate is 2-2.5% of the weight of the starch.
3. A flocculant according to claim 1, characterized in that: in the step S2, the weight ratio of the modified starch, the amination ionic liquid and the deionized water is controlled to be 5-8:1-2:50-70.
4. A flocculant according to claim 1, characterized in that: the weight ratio of bromoethylamine hydrobromide, N-methylimidazole and absolute ethyl alcohol is controlled to be 1:1:100 to 1:1.2:100, the mol ratio of the intermediate 1 to potassium hydroxide is controlled to be 1:1, and the mol ratio of the intermediate 2 to potassium hexafluorophosphate is controlled to be 1:1.
5. A method of preparing a flocculant according to claim 1, wherein: the method comprises the following steps:
uniformly mixing polyaluminium chloride and an organic flocculant according to the weight ratio of 1:1 to prepare the high-efficiency flocculant.
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| CN1816592A (en) * | 2003-07-08 | 2006-08-09 | 罗盖特公司 | Cationic liquid starchy composition and uses thereof |
| CN105218688A (en) * | 2015-10-29 | 2016-01-06 | 黄河水利职业技术学院 | Starch flocculant of a kind of polyamine cationic polymer modification and preparation method thereof |
| CN107573440A (en) * | 2017-08-30 | 2018-01-12 | 武汉理工大学 | A kind of cationic large biological molecule flocculant and preparation method thereof |
| CN111018067A (en) * | 2019-12-30 | 2020-04-17 | 陆建生 | Preparation method of environment-friendly safe high-efficiency sewage flocculant |
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| WO2013142352A1 (en) * | 2012-03-20 | 2013-09-26 | The Research Foundation Of State University Of New York | Flocculation of lignocellulosic hydrolyzates |
| CA3041594A1 (en) * | 2016-12-08 | 2018-06-14 | Kemira Oyj | Method and composition for treating tailings |
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| CN1816592A (en) * | 2003-07-08 | 2006-08-09 | 罗盖特公司 | Cationic liquid starchy composition and uses thereof |
| CN105218688A (en) * | 2015-10-29 | 2016-01-06 | 黄河水利职业技术学院 | Starch flocculant of a kind of polyamine cationic polymer modification and preparation method thereof |
| CN107573440A (en) * | 2017-08-30 | 2018-01-12 | 武汉理工大学 | A kind of cationic large biological molecule flocculant and preparation method thereof |
| CN111018067A (en) * | 2019-12-30 | 2020-04-17 | 陆建生 | Preparation method of environment-friendly safe high-efficiency sewage flocculant |
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