CN116924507A - Multifunctional mixed medicament - Google Patents
Multifunctional mixed medicament Download PDFInfo
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- CN116924507A CN116924507A CN202311181459.1A CN202311181459A CN116924507A CN 116924507 A CN116924507 A CN 116924507A CN 202311181459 A CN202311181459 A CN 202311181459A CN 116924507 A CN116924507 A CN 116924507A
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- China
- Prior art keywords
- mixed medicament
- chitosan
- multifunctional
- multifunctional mixed
- membered heterocyclic
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- 239000003814 drug Substances 0.000 title claims abstract description 64
- 229920001661 Chitosan Polymers 0.000 claims abstract description 68
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 37
- 239000002699 waste material Substances 0.000 claims abstract description 31
- 238000010276 construction Methods 0.000 claims abstract description 30
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 21
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004927 clay Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims description 29
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- 239000011737 fluorine Substances 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- UJBXVTJYSIDCIE-UHFFFAOYSA-N 2-[(2-sulfanylidene-3h-1,3,4-thiadiazol-5-yl)sulfanyl]acetic acid Chemical compound OC(=O)CSC1=NNC(=S)S1 UJBXVTJYSIDCIE-UHFFFAOYSA-N 0.000 claims description 14
- -1 thiadiazole compound Chemical class 0.000 claims description 14
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 229940080258 tetrasodium iminodisuccinate Drugs 0.000 claims description 10
- GYBINGQBXROMRS-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)butanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)NC(C([O-])=O)CC([O-])=O GYBINGQBXROMRS-UHFFFAOYSA-J 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000006196 deacetylation Effects 0.000 claims description 3
- 238000003381 deacetylation reaction Methods 0.000 claims description 3
- 238000007112 amidation reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 44
- 150000002500 ions Chemical class 0.000 abstract description 16
- 238000006115 defluorination reaction Methods 0.000 abstract description 8
- 239000013049 sediment Substances 0.000 abstract description 5
- 238000004062 sedimentation Methods 0.000 abstract description 5
- 238000004061 bleaching Methods 0.000 abstract description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000292 calcium oxide Substances 0.000 abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 22
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 19
- 239000002351 wastewater Substances 0.000 description 17
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- FCHXJFJNDJXENQ-UHFFFAOYSA-N pyridoxal hydrochloride Chemical compound Cl.CC1=NC=C(CO)C(C=O)=C1O FCHXJFJNDJXENQ-UHFFFAOYSA-N 0.000 description 10
- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- 229940079593 drug Drugs 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008177 pharmaceutical agent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940059260 amidate Drugs 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a multifunctional mixed medicament, and relates to the field of water treatment. The multifunctional mixed medicament adopts the construction waste as the raw material, thereby realizing the recycling of resources, and the construction waste contains silicate and calcium oxide; the size of calcium fluoride sediment can be increased, so that the sedimentation speed is high, and mud bleaching is not easy to occur; in addition, the construction waste, the five-membered heterocyclic compound modified chitosan and silicate clay are stirred and mixed to prepare the multifunctional mixed medicament, so that the multifunctional mixed medicament has good defluorination effect, heavy metal ion removal effect, COD removal effect and turbidity reduction effect.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a multifunctional mixed medicament.
Background
In the production process of semiconductor, glass industry, coking, coal chemical industry, metallurgy, thermal power plant, phosphorus chemical industry and other industries, sewage containing fluoride ions is often generated. At present, the treatment method of the fluorine-containing wastewater at home and abroad mainly comprises treatment processes such as chemical precipitation, flocculation precipitation, adsorption and the like, wherein a lime precipitation rule is the most commonly applied traditional process, and the process usually treats the fluorine-containing wastewater by a multistage precipitation method, but has the defects of reduced utilization efficiency of lime, large slag quantity, higher calcium concentration and pH value in effluent, and incomplete removal of fluorine ions. However, caO or Ca (OH) is singly used 2 To treat fluorine-containing wastewater to produce CaF 2 The sediment is very fine and is difficult to settle, and fine sediment particles are adsorbed on Ca (OH) 2 The utilization efficiency of calcium salt on the particle surface is lower, the solubility is increased because of very slow precipitation process, and the concentration of residual fluoride in water is high, so that the concentration of fluoride ions can be reduced to about 15mg/L, and the concentration of fluoride ions can not reach the national emission standard within 10 mg/L. The most commonly used fluorine removing agents in the market are polyaluminium chloride and activated alumina, which respectively have the defects of low adsorption capacity, secondary pollution caused by aluminum loss in the using process, and the like. And for many fluorine-containing wastewater, such as wastewater in the color field, besides fluorine ions, a large amount of heavy metal ions are contained, and the current technology cannot remove the fluorine ions and the heavy metal ions at the same time.
A large amount of construction waste is generated in construction of buildings or structures, decoration, removal and other building activities.
The multifunctional mixed medicament mainly utilizes silicate and calcium salt to carry out adsorption precipitation, changes the structure of the flocs, improves the self density of the flocs, increases the pH range of the flocs sedimentation, and obtains better sedimentation efficiency, which is equivalent to treating waste with waste.
Disclosure of Invention
The invention aims to provide a multifunctional mixed medicament which has good defluorination effect, heavy metal ion removal effect, COD removal effect and turbidity reduction effect.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a multifunctional mixed medicament comprising silicate clay mixed with pentaheterocycle compound modified chitosan and construction waste; the five-membered heterocyclic compound comprises a thiadiazole compound; the deacetylation degree of the chitosan is more than or equal to 95 percent.
According to an embodiment of the present invention, the thiadiazole-based compound comprises (5-mercapto-1, 3, 4-thiadiazol-2-ylthio) acetic acid.
The invention also discloses a preparation method of the five-membered heterocyclic compound modified chitosan, which comprises the following steps: the five-membered heterocyclic compound modified chitosan is prepared by amidation reaction of (5-mercapto-1, 3, 4-thiadiazole-2-yl thio) acetic acid and chitosan.
The invention provides a preparation method of five-membered heterocyclic compound modified chitosan, which adopts (5-mercapto-1, 3, 4-thiadiazole-2-yl thio) acetic acid to amidate the modified chitosan, and uses the prepared five-membered heterocyclic compound modified chitosan for preparing a multifunctional mixed medicament, so that the multifunctional mixed medicament has good defluorination effect, heavy metal ion removal effect, COD removal effect and turbidity reduction effect.
Specifically, the preparation method of the five-membered heterocyclic compound modified chitosan comprises the following steps:
adding chitosan into a mixed solution of methanol and ultrapure water (the volume ratio of the methanol to the ultrapure water is 1:0.7-1.3), stirring and mixing for 25-40min, then sequentially adding 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and (5-mercapto-1, 3, 4-thiadiazol-2-ylthio) acetic acid, carrying out light shielding reaction for 10-18h, washing with the ultrapure water for 3-5 times, washing with ethanol for 3-5 times, and freeze-drying to obtain the five-membered heterocyclic compound modified chitosan.
According to the embodiment of the invention, the mass volume ratio of the chitosan to the mixed solution is as follows: 1g, 25-40mL; the mass ratio of the chitosan to the 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide is as follows: 1:0.8-1.3.
According to an embodiment of the invention, the mass ratio of the chitosan to the (5-mercapto-1, 3, 4-thiadiazol-2-ylthio) acetic acid is as follows: 1:1.5-2.
The invention also discloses application of the five-membered heterocyclic compound modified chitosan prepared by the preparation method in preparation of a multifunctional mixed medicament.
The invention also discloses application of the five-membered heterocyclic compound modified chitosan prepared by the preparation method in water treatment.
The invention also discloses the application of the five-membered heterocyclic compound modified chitosan prepared by the preparation method in heavy metal and fluorine removal in water treatment.
The invention also discloses a preparation method of the multifunctional mixed medicament, which comprises the following steps: crushing construction waste, adding sulfamic acid aqueous solution, stirring and mixing uniformly, adding tetrasodium iminodisuccinate, stirring and mixing, suction filtering and drying to obtain treated construction waste; adding glacial acetic acid and pentaheterocycle compound modified chitosan into silicate clay, stirring and mixing, suction filtering, drying, adding into the treated construction waste, stirring and mixing to obtain the multifunctional mixed medicament.
The invention adopts the construction waste as the raw material, thereby realizing the reutilization of resources; because the construction waste contains silicate and calcium oxide; the size of calcium fluoride sediment can be increased, so that the sedimentation speed is high, and mud bleaching is not easy to occur; the deep defluorination and the effective removal of heavy metals can be realized, and the defluorination effect is ensured to meet the treatment requirement; realizes the synchronous removal of heavy metal and fluoride ions, and is not affected by the treatment process.
Specifically, the preparation method of the multifunctional mixed medicament comprises the following steps:
crushing construction waste, sieving with a 1000-1500 mesh molecular sieve, adding 5-8wt% sulfamic acid aqueous solution, stirring and mixing for 1-4h, adding tetrasodium iminodisuccinate, stirring and mixing for 4-7h, sieving with a 1000-1500 mesh molecular sieve, standing and settling, suction filtering, drying and grinding to obtain treated construction waste; adding glacial acetic acid and pentaheterocycle compound modified chitosan into silicate clay, stirring and mixing for 0.8-1.5h, standing and settling, suction filtering, drying, grinding, adding into the treated construction waste, stirring and mixing for 1-3h to obtain the multifunctional mixed medicament.
According to the embodiment of the invention, in the multifunctional mixed medicament, the usage amount of construction waste is 15-30 parts by weight, the usage amount of five-membered heterocyclic compound modified chitosan is 3-5 parts by weight, the usage amount of sulfamic acid is 1-3 parts by weight, the usage amount of glacial acetic acid is 3-5 parts by weight, the usage amount of silicate clay is 35-50 parts by weight, and the usage amount of tetrasodium iminodisuccinate is 5-10 parts by weight.
The invention also discloses application of the multifunctional mixed medicament in water treatment.
The invention also discloses application of the multifunctional mixed medicament in removing heavy metals and fluorine in water treatment.
The beneficial effects of the invention include:
the invention obtains the multifunctional mixed medicament, which adopts the construction waste as the raw material, realizes the reutilization of resources, and contains silicate and calcium oxide; the size of calcium fluoride sediment can be increased, so that the sedimentation speed is high, and mud bleaching is not easy to occur; according to the invention, the construction waste, the five-membered heterocyclic compound modified chitosan and silicate clay are stirred and mixed, and the prepared multifunctional mixed medicament has good defluorination effect, heavy metal ion removal effect, COD removal effect and turbidity reduction effect.
Therefore, the invention provides the multifunctional mixed medicament which has good defluorination effect, heavy metal ion removal effect, COD removal effect and turbidity reduction effect.
Drawings
FIG. 1 is an infrared spectrogram test result of five-membered heterocyclic compound modified chitosan and chitosan prepared in example 1;
FIG. 2 shows the fluorine removal effect test results of the multifunctional mixed pharmaceutical agent samples prepared in examples 1 to 7;
FIG. 3 is a graph showing the results of the test for the effect of removing heavy metal ions from the multifunctional mixed pharmaceutical agent samples prepared in examples 1 to 7;
FIG. 4 shows the COD removing effect test results of the multifunctional mixed pharmaceutical agent samples prepared in examples 1 to 7;
FIG. 5 shows the results of the turbidity-reducing effect test of the multifunctional mixed-drug samples prepared in examples 1 to 7.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear and clear, the technical solutions of the present invention are described in further detail below with reference to the specific embodiments:
example 1:
a preparation method of a multifunctional mixed medicament comprises the following steps:
crushing construction waste (the construction waste mainly comprises concrete, stone and dregs, wherein the mass ratio of the concrete to the stone to the dregs is 1:0.2:0.22), sieving with a 1200-mesh molecular sieve, adding sulfamic acid water solution with the concentration of 5wt%, stirring and mixing for 1h, adding tetrasodium iminodisuccinate, stirring and mixing for 5h, sieving with the 1200-mesh molecular sieve, standing and settling, suction filtering, drying and grinding to obtain the treated construction waste; adding glacial acetic acid and pentaheterocycle compound modified chitosan into silicate clay, stirring and mixing for 1h, standing and settling, suction filtering, drying and grinding, adding into the treated construction waste, stirring and mixing for 2h to obtain a multifunctional mixed medicament; in the multifunctional mixed medicament, the amount of construction waste is 15 parts by weight, the amount of chitosan modified by five-membered heterocyclic compounds is 3 parts by weight, the amount of sulfamic acid is 1 part by weight, the amount of glacial acetic acid is 3 parts by weight, the amount of silicate clay is 35 parts by weight, and the amount of tetrasodium iminodisuccinate is 5 parts by weight.
The preparation method of the five-membered heterocyclic compound modified chitosan comprises the following steps:
adding chitosan (the deacetylation degree is more than or equal to 95%, the viscosity is 150 mpa.s) into a mixed solution of methanol and ultrapure water (the volume ratio of the methanol to the ultrapure water is 1:0.7), stirring and mixing for 25min, then sequentially adding 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and (5-mercapto-1, 3, 4-thiadiazol-2-ylthio) acetic acid, carrying out light-shielding reaction for 18h, washing with the ultrapure water for 3 times, washing with ethanol for 3 times, and freeze-drying to obtain the five-membered heterocyclic compound modified chitosan. Wherein the mass volume ratio of the chitosan to the mixed solution is as follows: 1g:25mL; the mass ratio of the chitosan to the 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide is as follows: 1:0.8; the mass ratio of the chitosan to the (5-mercapto-1, 3, 4-thiadiazole-2-yl thio) acetic acid is as follows: 1:1.5.
Example 2:
the preparation method of the multifunctional mixed medicament is different from that of the embodiment 1: in the multifunctional mixed medicament, the amount of construction waste is 30 parts by weight, the amount of chitosan modified by five-membered heterocyclic compounds is 5 parts by weight, the amount of sulfamic acid is 3 parts by weight, the amount of glacial acetic acid is 5 parts by weight, the amount of silicate clay is 50 parts by weight, and the amount of tetrasodium iminodisuccinate is 10 parts by weight.
The preparation method of five-membered heterocyclic compound modified chitosan is different from that of example 1: the mass volume ratio of the chitosan to the mixed solution is as follows: 1g:40ml; the mass ratio of the chitosan to the 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide is as follows: 1:1.3; the mass ratio of the chitosan to the (5-mercapto-1, 3, 4-thiadiazole-2-yl thio) acetic acid is as follows: 1:2.
Example 3:
the preparation method of the multifunctional mixed medicament is different from that of the embodiment 1: in the multifunctional mixed medicament, the amount of construction waste is 20 parts by weight, the amount of chitosan modified by five-membered heterocyclic compounds is 4 parts by weight, the amount of sulfamic acid is 2 parts by weight, the amount of glacial acetic acid is 4 parts by weight, the amount of silicate clay is 40 parts by weight, and the amount of tetrasodium iminodisuccinate is 8 parts by weight.
The preparation method of five-membered heterocyclic compound modified chitosan is different from that of example 1: the mass volume ratio of the chitosan to the mixed solution is as follows: 1g:30ml; the mass ratio of the chitosan to the 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide is as follows: 1:1; the mass ratio of the chitosan to the (5-mercapto-1, 3, 4-thiadiazole-2-yl thio) acetic acid is as follows: 1:1.7.
Example 4:
the preparation method of the multifunctional mixed medicament is different from that of the embodiment 1: in the multifunctional mixed medicament, the amount of construction waste is 25 parts by weight, the amount of chitosan modified by five-membered heterocyclic compounds is 3.5 parts by weight, the amount of sulfamic acid is 1.5 parts by weight, the amount of glacial acetic acid is 3.5 parts by weight, the amount of silicate clay is 45 parts by weight, and the amount of tetrasodium iminodisuccinate is 6 parts by weight.
The preparation method of five-membered heterocyclic compound modified chitosan is different from that of example 1: the mass volume ratio of the chitosan to the mixed solution is as follows: 1g:35mL; the mass ratio of the chitosan to the 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide is as follows: 1:1.1; the mass ratio of the chitosan to the (5-mercapto-1, 3, 4-thiadiazole-2-yl thio) acetic acid is as follows: 1:1.8.
Example 5:
the preparation method of the multifunctional mixed medicament is different from that of the embodiment 1: and chitosan is adopted to replace the five-membered heterocyclic compound modified chitosan.
Example 6:
the preparation method of the multifunctional mixed medicament is different from that of the embodiment 1: sulfamic acid derivatives are used instead of sulfamic acid.
A process for the preparation of sulfamic acid derivatives comprising: the pyridoxal hydrochloride and sulfamic acid are adopted to generate Schiff base reaction to prepare the sulfamic acid derivative.
The invention provides a preparation method of sulfamic acid derivatives, which adopts pyridoxal hydrochloride to modify sulfamic acid, and uses the prepared sulfamic acid derivatives for preparing multifunctional mixed medicaments, so that the multifunctional mixed medicaments have better defluorination effect, heavy metal ion removal effect, COD removal effect and turbidity reduction effect.
Specifically, the preparation method of the sulfamic acid derivative comprises the following steps:
adding sulfamic acid into a phosphoric acid buffer solution, then adding pyridoxal hydrochloride, stirring at room temperature for 3-4.5h, adding sodium borohydride, continuously reacting at constant temperature for 20-30h, precipitating with absolute ethanol, adding ultrapure water, and spin-evaporating and drying to obtain sulfamic acid derivatives.
According to an embodiment of the present invention, the phosphate buffer solution is neutral.
According to the embodiment of the invention, the mass volume ratio of the sulfamic acid to the phosphoric acid buffer solution is as follows: 1g, 40-60mL; the mass ratio of sulfamic acid to pyridoxal hydrochloride is as follows: 1:2-4; the mass ratio of sulfamic acid to sodium borohydride is as follows: 1:0.8-1.3; the mass volume ratio of sulfamic acid to ultrapure water is as follows: 1g, 20-40mL.
The invention also discloses application of the sulfamic acid derivative in preparing a multifunctional mixed medicament.
The invention also discloses application of the sulfamic acid derivative in water treatment.
The invention also discloses application of the sulfamic acid derivative in heavy metal removal and fluorine removal in water treatment.
Further, the method comprises the steps of,
a process for the preparation of sulfamic acid derivatives comprising the steps of:
adding sulfamic acid into a phosphoric acid buffer solution (the phosphoric acid buffer solution is neutral), then adding pyridoxal hydrochloride, stirring for 3 hours at room temperature, adding sodium borohydride, continuing to react at constant temperature for 20 hours, precipitating with absolute ethanol, adding ultrapure water, and spin-evaporating and drying to obtain the sulfamic acid derivative. Wherein, the mass volume ratio of sulfamic acid to phosphoric acid buffer solution is: 1g:40ml; the mass ratio of sulfamic acid to pyridoxal hydrochloride is as follows: 1:2; the mass ratio of sulfamic acid to sodium borohydride is as follows: 1:0.8; the mass volume ratio of sulfamic acid to ultrapure water is as follows: 1 g/20 mL.
The hydrogen spectrum of sulfamic acid derivatives is:
1 H NMR（400MHz，CDCl 3 ）：8.28（1H，Py-H），9.56（1H，Py-OH），2.53（3H，s，Py-CH 3 ），4.59（2H，s，Py-CH 2 -OH），4.53（2H，s，Py-CH 2 -NH），5.25（1H，Py-CH 2 -OH），7.36（1H，Py-CH 2 -NH），4.18（1H，SO 2 -OH），HRMS(ESI)：C 8 H 12 N 2 O 5 S，m/z [M+H] + ，284.05。
example 7:
the preparation method of the multifunctional mixed medicament is different from that of example 5: sulfamic acid derivatives are used instead of sulfamic acid.
The sulfamic acid derivative was prepared in the same manner as in example 6.
Test example:
1. infrared spectroscopy testing
And testing the sample by adopting a Fourier infrared spectrometer and a potassium bromide tabletting method.
The five-membered heterocyclic compound modified chitosan and chitosan prepared in example 1 were subjected to the above test, and the results are shown in fig. 1. As can be seen from FIG. 1, compared with the infrared spectrum of chitosan, the infrared spectrum of the five-membered heterocyclic compound modified chitosan is 1132cm -1 The infrared characteristic absorption peak of the C-S bond exists, which shows that (5-mercapto-1, 3, 4-thiadiazole-2-yl thio) acetic acid participates in the five-membered heterocyclic compound modified chitosan.
2. Fluorine removal test
Adding a multifunctional mixed reagent sample into fluorine-containing wastewater, wherein the concentration of fluorine ions in the wastewater is 30mg/L, the dosage of the multifunctional mixed reagent sample is 20mg/L, stirring for 10min at 30 ℃, standing for 30min, taking supernatant, testing the concentration of fluorine ions by using an Ion700 Siemens-Feeier Ion meter, and the fluorine removal rate is calculated according to the following formula:
R/%=[(G0-G1)/G0]×100%
wherein R is the fluorine removal rate; g0 is the concentration of fluoride ions in the wastewater before treatment; g1 is the concentration of fluoride ions in the treated wastewater.
The above-described test was performed on the multifunctional mixed-drug samples prepared in examples 1 to 7, and the results are shown in fig. 2. As can be seen from fig. 2, compared with examples 5 and 6 and 7, the fluorine removal rate of example 1 is significantly improved, which indicates that the five-membered heterocyclic compound modified chitosan has an improved fluorine removal effect on the multifunctional mixed medicament sample when used for preparing the multifunctional mixed medicament sample; example 6 also showed an increase in fluorine removal rate as compared with example 1 and example 7, and demonstrated that the sulfamic acid derivative prepared from pyridoxal hydrochloride was used to prepare a multifunctional mixed reagent sample, which resulted in a good fluorine removal effect.
3. Heavy metal ion removal effect
Adding a multifunctional mixed reagent sample into the wastewater, wherein the concentration of cadmium ions in the wastewater is 20mg/L, the dosage of the multifunctional mixed reagent sample is 50mg/L, stirring for 10min at 30 ℃, standing for 30min, taking supernatant, and measuring the concentration of cadmium ions by an atomic absorption spectrometry; the calculation formula of the heavy metal ion removal rate is the same as that of test example 2.
The above-described test was performed on the multifunctional mixed-drug samples prepared in examples 1 to 7, and the results are shown in fig. 3. As can be seen from fig. 3, compared with examples 5 and 6 and 7, the removal rate of heavy metal ions is significantly improved, which indicates that the five-membered heterocyclic compound modified chitosan has an effect of improving the removal effect of heavy metal ions in the multifunctional mixed medicament sample when being used for preparing the multifunctional mixed medicament sample; example 6 also showed an increase in the removal rate of heavy metal ions compared with example 1 and example 7 compared with example 5, indicating that the sulfamic acid derivative prepared from pyridoxal hydrochloride provides a good removal effect of heavy metal ions when used in the preparation of a multifunctional mixed reagent sample.
COD removal Effect test
Adding a multifunctional mixed reagent sample into the wastewater, wherein the COD content in the wastewater is 1250mg/L, the dosage of the multifunctional mixed reagent sample is 80mg/L, stirring for 10min at 30 ℃, standing for 30min, taking supernatant, and testing the COD content in the wastewater by adopting a standard potassium dichromate method; the COD removal rate calculation formula is the same as that of test example 2.
The above-described test was performed on the multifunctional mixed-drug samples prepared in examples 1 to 7, and the results are shown in fig. 4. As can be seen from fig. 4, compared with examples 5 and 6 and 7, the removal rate of COD is significantly improved, which indicates that the five-membered heterocyclic compound modified chitosan has an improvement effect on the removal effect of COD in the multifunctional mixed medicament sample when used for preparing the multifunctional mixed medicament sample; example 6 also showed an increase in COD removal rate as compared with example 1 and example 7 as compared with example 5, indicating that the sulfamic acid derivative prepared from pyridoxal hydrochloride provides a good COD removal effect in the multifunctional mixed drug sample when used in the preparation of the multifunctional mixed drug sample.
5. Turbidity reduction Effect test
Adding a multifunctional mixed reagent sample into the wastewater, wherein the turbidity of the wastewater is 63NTU, the dosage of the multifunctional mixed reagent sample is 80mg/L, stirring for 10min at 30 ℃, standing for 30min, taking supernatant, and testing the turbidity of the wastewater by adopting a turbidity meter; the turbidity drop rate calculation formula was the same as in test example 2.
The above-described test was performed on the multifunctional mixed-drug samples prepared in examples 1 to 7, and the results are shown in fig. 5. As can be seen from fig. 5, the turbidity reduction rate of example 1 is significantly improved compared with that of example 5 and example 6 compared with that of example 7, which indicates that the five-membered heterocyclic compound modified chitosan has an improvement effect on the turbidity reduction effect of the multifunctional mixed medicament sample when used for preparing the multifunctional mixed medicament sample; the increase in turbidity decrease rate of example 6 compared with example 1 and example 7 compared with example 5 indicates that the sulfamic acid derivative prepared from pyridoxal hydrochloride provides a good turbidity decrease effect in the multifunctional mixed-drug sample when used in the preparation of the multifunctional mixed-drug sample.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A multifunctional mixed medicament, characterized in that: the multifunctional mixed medicament comprises silicate clay mixed with pentaheterocycle compound modified chitosan and construction waste; the five-membered heterocyclic compound comprises a thiadiazole compound; the deacetylation degree of the chitosan is more than or equal to 95 percent.
2. A multi-functional mixed medicament as claimed in claim 1, wherein: the thiadiazole compound comprises (5-mercapto-1, 3, 4-thiadiazole-2-ylthio) acetic acid.
3. The method for preparing the multifunctional mixed medicament of claim 1, comprising: crushing construction waste, adding sulfamic acid aqueous solution, stirring and mixing uniformly, adding tetrasodium iminodisuccinate, stirring and mixing, suction filtering and drying to obtain treated construction waste; adding glacial acetic acid and pentaheterocycle compound modified chitosan into silicate clay, stirring and mixing, suction filtering, drying, adding into the treated construction waste, stirring and mixing to obtain the multifunctional mixed medicament.
4. A method of preparing a multifunctional mixed medicament according to claim 3, wherein: in the multifunctional mixed medicament, the amount of construction waste is 15-30 parts by weight, the amount of chitosan modified by five-membered heterocyclic compounds is 3-5 parts by weight, the amount of sulfamic acid is 1-3 parts by weight, the amount of glacial acetic acid is 3-5 parts by weight, the amount of silicate clay is 35-50 parts by weight, and the amount of tetrasodium iminodisuccinate is 5-10 parts by weight.
5. The method for preparing the five-membered heterocyclic compound modified chitosan in claim 1, comprising the following steps: the five-membered heterocyclic compound modified chitosan is prepared by amidation reaction of (5-mercapto-1, 3, 4-thiadiazole-2-yl thio) acetic acid and chitosan.
6. The method for preparing the five-membered heterocyclic compound modified chitosan according to claim 5, wherein the method is characterized in that: the mass ratio of the chitosan to the (5-mercapto-1, 3, 4-thiadiazole-2-ylthio) acetic acid is as follows: 1:1.5-2.
7. Use of the five-membered heterocyclic compound modified chitosan prepared by the preparation method of any one of claims 5-6 in the preparation of multifunctional mixed medicament.
8. Use of the multifunctional mixed medicament of any one of claims 1-2 for heavy metal and fluorine removal in water treatment.
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