CN116178590B - Microbial nutrition synergist suitable for wastewater treatment - Google Patents
Microbial nutrition synergist suitable for wastewater treatment Download PDFInfo
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- CN116178590B CN116178590B CN202211576549.6A CN202211576549A CN116178590B CN 116178590 B CN116178590 B CN 116178590B CN 202211576549 A CN202211576549 A CN 202211576549A CN 116178590 B CN116178590 B CN 116178590B
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- cyclodextrin
- starch
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- 235000016709 nutrition Nutrition 0.000 title claims abstract description 53
- 230000000813 microbial effect Effects 0.000 title claims abstract description 50
- 230000035764 nutrition Effects 0.000 title claims abstract description 43
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 31
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical class OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 47
- 229920002472 Starch Polymers 0.000 claims abstract description 38
- 239000008107 starch Substances 0.000 claims abstract description 38
- 235000019698 starch Nutrition 0.000 claims abstract description 38
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims abstract description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 10
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims abstract description 10
- 229930182821 L-proline Natural products 0.000 claims abstract description 10
- 229940095100 fulvic acid Drugs 0.000 claims abstract description 10
- 239000002509 fulvic acid Substances 0.000 claims abstract description 10
- 229960002429 proline Drugs 0.000 claims abstract description 10
- 229920000858 Cyclodextrin Polymers 0.000 claims description 26
- 239000001116 FEMA 4028 Substances 0.000 claims description 19
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 19
- 229960004853 betadex Drugs 0.000 claims description 19
- RBHIUNHSNSQJNG-UHFFFAOYSA-N 6-methyl-3-(2-methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2(C)OC2CC1C1(C)CO1 RBHIUNHSNSQJNG-UHFFFAOYSA-N 0.000 claims description 17
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 16
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000003623 enhancer Substances 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 2
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 2
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 2
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 2
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 2
- 229960001031 glucose Drugs 0.000 claims description 2
- 229940032147 starch Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 34
- 229920000881 Modified starch Polymers 0.000 abstract description 23
- 239000004368 Modified starch Substances 0.000 abstract description 23
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 23
- 235000019426 modified starch Nutrition 0.000 abstract description 23
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 19
- VUVPNTYTOUGMDG-UHFFFAOYSA-N 1-(2-hydroxyethyl)-3-prop-2-enylthiourea Chemical compound OCCNC(=S)NCC=C VUVPNTYTOUGMDG-UHFFFAOYSA-N 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000012360 testing method Methods 0.000 description 19
- 244000005700 microbiome Species 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 230000004060 metabolic process Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002068 microbial inoculum Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere 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
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 235000000621 Bidens tripartita Nutrition 0.000 description 1
- 240000004082 Bidens tripartita Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241000192710 Microcystis aeruginosa Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 208000006637 fused teeth Diseases 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic 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
- C02F3/00—Biological treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/06—Nutrients for stimulating the growth of microorganisms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a microbial nutrition synergist suitable for wastewater treatment, and relates to the technical field of wastewater treatment. The microbial nutrition synergist is prepared from starch, beta-cyclodextrin derivatives, L-proline, fulvic acid and EDTA; the method has good ammonia nitrogen removal rate, COD removal effect and heavy metal removal effect; the invention also adopts N- (2-hydroxyethyl) -N' -2-propenyl thiourea to modify the starch, and uses the modified starch for preparing the microbial nutrition synergist, so that the microbial nutrition synergist has better ammonia nitrogen removal rate, COD removal effect and heavy metal removal effect.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a microbial nutrition synergist suitable for wastewater treatment.
Background
With the world economic development and the improvement of the scientific and technical level, the development of various industrial processes accelerates the demand and use of water, and causes the discharge of wastewater, especially industrial wastewater, to increase, and pollutants generated in industrial production flow into the environment in large quantities. At present, the problem to be solved in the ecological water environment protection of China is that the discharge amount of ammonia nitrogen is far more than the acceptable environmental capacity of the water body, the discharge of industrial ammonia nitrogen wastewater becomes a main cause of exceeding the ammonia nitrogen content of the surface water body, and the current ammonia nitrogen exceeds COD (chemical oxygen demand) to become a primary standard for influencing the quality of the surface water environment. A large amount of nitrogen-containing substances, ions and the like enter the water body environment, so that the normal operation of nitrogen circulation among water, solid and gas is influenced, a series of serious water body environment problems such as red tide, water bloom and the like are brought, and serious threats are generated to the life safety of aquatic organisms such as fish scales, algae, zooplankton and the like and even human beings.
At present, three modes of physical treatment, chemical treatment and biological treatment are mainly adopted for wastewater treatment. The biological treatment method has the characteristics of small pollution, high efficiency, no secondary pollution and the like, and is widely applied to wastewater treatment. The biological treatment technology is that the microorganism takes organic pollutants in the sewage as self nutrition sources, and utilizes self metabolic process to decompose and convert the pollutants in the sewage, so as to convert the organic pollutants into inorganic matters with stable structure, no toxicity or low toxicity.
During wastewater treatment, contaminants are removed by adsorption and degradation by microorganisms. The microorganism has the characteristics of high growth and reproduction speed and vigorous metabolism. During sewage treatment, a great amount of nutrient substances are consumed in the normal growth and propagation of microorganisms and in the stable metabolic process. In order to achieve the expected effect of wastewater treatment, the advantages of the microorganism treatment method are fully exerted, the capability of removing organic pollutants and other toxic and harmful substances is improved, and a technology of adding a biological synergist can be adopted, so that a sewage treatment plant can better maintain the normal functions of a microorganism community under the water quality condition of high pollutant load, and the capability of improving the water quality of the microorganism community is enhanced.
Disclosure of Invention
The invention aims to provide a microbial nutrition synergist suitable for wastewater treatment, which has good ammonia nitrogen removal rate, COD removal effect and heavy metal removal effect.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a cyclodextrin derivative comprising dipentene dioxide and cyclodextrin; the cyclodextrin comprises one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin; the substitution degree of the cyclodextrin derivative is 3.5-4.
The invention also discloses a preparation method of the beta-cyclodextrin derivative, which comprises the following steps: is prepared by substitution reaction of dipentene dioxide and beta-cyclodextrin.
Specifically, the preparation method of the beta-cyclodextrin derivative comprises the following steps:
adding 1.5-2wt% sodium hydroxide solution into beta-cyclodextrin, slowly adding 20-25wt% ethyl acetate solution of dipentene dioxide, stirring at 0-3 deg.c for reaction for 12-15 hr, reacting at room temperature for 70-75 hr, neutralizing with 1-1.5mol/L hydrochloric acid solution, steaming, drying, and purifying with silica gel chromatographic column to obtain beta-cyclodextrin derivative.
According to an embodiment of the invention, the mass-to-volume ratio of the beta-cyclodextrin to the sodium hydroxide solution is 1g:4.5-5.5mL; the molar ratio of the beta-cyclodextrin to the dipentene dioxide is 1:4-6.
The invention also discloses a microbial nutrition synergist suitable for wastewater treatment, which comprises the cyclodextrin derivative, and more preferably comprises the beta-cyclodextrin derivative.
The invention provides a preparation method of a beta-cyclodextrin derivative, which takes dipentene dioxide as a modifier, and makes nucleophilic substitution reaction with beta-cyclodextrin to prepare the beta-cyclodextrin derivative which is used for preparing a microbial nutrition synergist, and the prepared microbial nutrition synergist is used for wastewater treatment, so that the beta-cyclodextrin derivative has good ammonia nitrogen removal rate, COD removal effect and heavy metal removal effect; the reason is probably because the beta-cyclodextrin derivative prepared from the dipentene dioxide is favorable for generating a reticular structure and enhancing the flocculation effect, and the beta-cyclodextrin derivative provides a carbon source required by the growth of microorganisms, promotes the growth and propagation of the microorganisms and has good effects on ammonia nitrogen removal rate, COD removal effect and heavy metal removal effect in wastewater treatment.
According to the embodiment of the invention, in the microbial nutrition synergist, the cyclodextrin derivative is used in an amount of 10-15 parts by weight.
According to an embodiment of the invention, the microbial nutrition enhancer further comprises glucose, starch, L-proline, fulvic acid, EDTA.
According to the embodiment of the invention, in the microbial nutrition synergist, the dosage of glucose is 7-10 parts by weight; the starch dosage is 2-4 parts.
According to the embodiment of the invention, in the microbial nutrition synergist, the L-proline is used in an amount of 2-5 parts by weight; the dosage of fulvic acid is 10-15 parts; the EDTA is used in an amount of 0.5-1 part.
According to the embodiment of the invention, the microbial nutrition enhancer further comprises deionized water, and the deionized water is used in an amount of 30-45 parts by weight.
The invention also discloses application of the beta-cyclodextrin derivative prepared by the preparation method in wastewater treatment.
In order to further enhance the effect of the microbial nutrition synergist on wastewater treatment, the invention also adopts modified starch to replace starch.
The invention also discloses a preparation method of the modified starch, which comprises the following steps: the modified starch is prepared by adopting N- (2-hydroxyethyl) -N' -2-propenyl thiourea to carry out grafting reaction with starch.
The invention provides a preparation method of modified starch, which takes epichlorohydrin as a cross-linking agent, potassium persulfate as an initiator, and N- (2-hydroxyethyl) -N' -2-propenyl thiourea as a monomer to carry out grafting reaction with starch, wherein the prepared modified starch is used for preparing a microbial nutrition synergist, so that the microbial nutrition synergist has better ammonia nitrogen removal rate, COD removal effect and heavy metal removal effect in wastewater treatment; the reason is probably because the sulfur element can participate in the synthesis of enzymes in the microorganism, so that the metabolic activity of the microorganism is further promoted, and in addition, S, N atoms in N- (2-hydroxyethyl) -N' -2-propenyl thiourea can be coordinated with metal ions, and the ligand is introduced into the sulfur element to serve as a double-tooth chelating site, so that the modified starch has good effects on ammonia nitrogen removal rate, COD removal effect and heavy metal removal effect in wastewater treatment.
Specifically, the preparation method of the modified starch comprises the following steps:
adding sodium hydroxide solution with the concentration of 0.2-0.25mol/L (the mass volume ratio of the starch to the sodium hydroxide solution is 1g:2-2.5 mL) into the starch, then slowly adding epoxy chloropropane at the temperature of 45-55 ℃ for reaction for 3-3.5h; adjusting pH to 6.5-7 with 1-1.5mol/L hydrochloric acid solution, standing for precipitation, washing with deionized water for 4-7 times, suction filtering, drying to obtain crosslinked starch, adding deionized water (the mass volume ratio of crosslinked starch to deionized water is 1g:5-8 mL), gelatinizing at 85-90 ℃ for 1-1.5h, cooling to 79-83 ℃, adding OP-10 and potassium persulfate (the dosage is 5-5.5 mmol/L) under nitrogen atmosphere, adding N- (2-hydroxyethyl) -N' -2-propenyl thiourea after 5-8min, sealing for 3.5-4.5h, adjusting pH to 6.5-7 with 0.2-0.25mol/L sodium hydroxide solution, adding ethanol for precipitation, filtering, drying, purifying with acetone as solvent, and drying with Soxhlet extractor to obtain modified starch.
According to an embodiment of the present invention, the cross-linking degree of the above cross-linked starch is 0.55 to 0.6% by dry weight of the starch.
According to the embodiment of the invention, the mass ratio of the starch to the OP-10 is 1:0.008-0.015; the mass ratio of the starch to the N- (2-hydroxyethyl) -N' -2-propenyl thiourea is 1:1.1-1.35.
The invention also discloses application of the modified starch prepared by the preparation method in wastewater treatment.
The beneficial effects of the invention include:
the invention obtains a microorganism nutrition synergist which is applicable to wastewater treatment, and the microorganism nutrition synergist is prepared from beta-cyclodextrin derivatives obtained by modification of starch and dipentene dioxide, L-proline, fulvic acid and EDTA; the method has good ammonia nitrogen removal rate, COD removal effect and heavy metal removal effect; the invention also adopts N- (2-hydroxyethyl) -N' -2-propenyl thiourea as a modifier to modify starch, and uses the modified starch for preparing the microbial nutrition synergist, so that the microbial nutrition synergist has better ammonia nitrogen removal rate, COD removal effect and heavy metal removal effect.
Therefore, the invention provides the microbial nutrition synergist which is suitable for wastewater treatment, and has good ammonia nitrogen removal rate, COD removal effect and heavy metal removal effect.
Drawings
FIG. 1 is an infrared spectrum test result of the beta-cyclodextrin derivative and beta-cyclodextrin prepared in example 1;
FIG. 2 shows the infrared spectrum of modified starch prepared in example 5 and the results of the infrared spectrum test of the starch.
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 microorganism nutrition synergist suitable for wastewater treatment is prepared by mixing glucose, starch, beta-cyclodextrin derivative, L-proline, fulvic acid, EDTA and deionized water; wherein, the dosage of glucose is 7 parts by weight; the starch dosage is 2 parts; the dosage of the beta-cyclodextrin derivative is 10 parts; the dosage of the L-proline is 2 parts; the dosage of fulvic acid is 10 parts; EDTA is used in an amount of 0.5 part; the deionized water was used in an amount of 30 parts.
A process for the preparation of a beta-cyclodextrin derivative comprising the steps of:
adding a sodium hydroxide solution with the concentration of 1.5 weight percent into beta-cyclodextrin, slowly adding an ethyl acetate solution with the concentration of 20 weight percent of dipentene dioxide, stirring and reacting for 12 hours at the temperature of 0 ℃, then reacting for 70 hours at the room temperature, neutralizing by adopting a hydrochloric acid solution with the concentration of 1mol/L, performing rotary evaporation drying, and purifying by a silica gel chromatographic column to obtain the beta-cyclodextrin derivative; wherein the mass volume ratio of the beta-cyclodextrin to the sodium hydroxide solution is 1g to 4.5mL; the molar ratio of beta-cyclodextrin to dipentene dioxide is 1:4.
Example 2:
the microbial nutritional potentiator suitable for wastewater treatment differs from example 1: the dosage of glucose is 10 parts by weight; the starch dosage is 4 parts; the dosage of the beta-cyclodextrin derivative is 15 parts; the dosage of the L-proline is 5 parts; the dosage of fulvic acid is 15 parts; EDTA was used in an amount of 1 part; the deionized water was used in an amount of 45 parts.
The process for the preparation of the beta-cyclodextrin derivatives differs from that of example 1: the mass volume ratio of the beta-cyclodextrin to the sodium hydroxide solution is 1g to 5.5mL; the molar ratio of beta-cyclodextrin to dipentene dioxide is 1:6.
Example 3:
the microbial nutritional potentiator suitable for wastewater treatment differs from example 1: the dosage of glucose is 8 parts by weight; the starch dosage is 3 parts; the dosage of the beta-cyclodextrin derivative is 12 parts; the dosage of the L-proline is 3 parts; the dosage of fulvic acid is 12 parts; EDTA is used in an amount of 0.6 part; the deionized water was used in an amount of 35 parts.
The process for the preparation of the beta-cyclodextrin derivatives differs from that of example 1: the mass volume ratio of the beta-cyclodextrin to the sodium hydroxide solution is 1g to 5mL; the molar ratio of beta-cyclodextrin to dipentene dioxide is 1:5.
Example 4:
the microbial nutritional potentiator suitable for wastewater treatment differs from example 1: beta-cyclodextrin is used instead of beta-cyclodextrin derivatives.
Example 5:
the microbial nutritional potentiator suitable for wastewater treatment differs from example 1: modified starch is used to replace starch.
The preparation method of the modified starch comprises the following steps:
adding sodium hydroxide solution with the concentration of 0.2mol/L (the mass volume ratio of the starch to the sodium hydroxide solution is 1g:2 mL) into the starch, then slowly adding epichlorohydrin at 45 ℃ for reaction for 3h; adjusting pH to 6.5 by using 1mol/L hydrochloric acid solution, standing for precipitation, washing with deionized water for 4 times, filtering and drying to obtain crosslinked starch, adding deionized water (the mass volume ratio of the crosslinked starch to the deionized water is 1g:5 mL), stirring and gelatinizing for 1h at 88 ℃, cooling to 80 ℃, adding OP-10 and potassium persulfate (the dosage is 5 mmol/L) under nitrogen atmosphere, adding N- (2-hydroxyethyl) -N' -2-propenyl thiourea after 5min, performing airtight reaction for 3.5h, adjusting pH to 6.5 by using 0.2mol/L sodium hydroxide solution, adding ethanol for precipitation, filtering and drying, purifying and drying by using acetone as a solvent by using a Soxhlet extractor, and obtaining modified starch; wherein, the crosslinking degree of the crosslinked starch is 0.55% of the dry weight mass of the starch; the mass ratio of the starch to the OP-10 is 1:0.015; the mass ratio of the starch to the N- (2-hydroxyethyl) -N' -2-propenyl thiourea is 1:1.1.
Example 6:
the microbial nutritional potentiator suitable for wastewater treatment differs from example 4: modified starch is used to replace starch.
The modified starch was prepared in the same manner as in example 5.
Test example 1:
infrared spectroscopy testing
Measuring an infrared spectrogram of the sample by using an infrared spectrometer manufactured by Perkin Elmer company in the United states to characterize the structure of the sample; the determination was carried out by potassium bromide tabletting.
The above test was performed on the beta-cyclodextrin derivative prepared in example 1 and beta-cyclodextrin, and the results are shown in fig. 1. As can be seen from FIG. 1, the infrared spectrum of the beta-cyclodextrin derivative is as high as 912cm -1 The presence of an infrared characteristic absorption peak of the epoxy group indicates that the dipentene dioxide participates in the formation reaction of the beta-cyclodextrin derivative.
The modified starch prepared in example 5 and the starch were subjected to the above test, and the results are shown in fig. 2. As can be seen from FIG. 2, the infrared spectrum of the modified starch is at 1482cm -1 、1372cm -1 、1088cm -1 The presence of an infrared characteristic absorption peak of thiourea groups suggests that N- (2-hydroxyethyl) -N' -2-propenyl thiourea participates in the modified starch formation reaction.
Test example 2:
COD removal Effect test
The experimental wastewater is industrial wastewater of a certain company, the COD content is 390.52mg/L, the microbial inoculum (model GANDEW-MIX, purchased from Shanghai Gao environmental engineering Co., ltd.) is added in an amount of 10mg/L, and after 4d, the COD in the wastewater is measured by adopting a potassium dichromate method.
COD removal rate/% = [ (U0-U1)/U0 ]. Times.100%
Wherein U0 is the COD content in the wastewater before the experiment, and mg/L; u1 is the COD content in the wastewater after the experiment, and mg/L.
TABLE 1 COD removal Effect test results
| Experimental grouping | COD removal rate/% |
| Example 1 | 32.2 |
| Example 2 | 35.8 |
| Example 3 | 33.5 |
| Example 4 | 26.3 |
| Example 5 | 49.6 |
| Example 6 | 42.1 |
The above-described tests were performed on the microbial nutritional potentiators prepared in examples 1-6, and the results are shown in Table 1. As can be seen from table 1, compared with example 4 and example 5 and example 6, the removal rate of COD is significantly improved, which indicates that the beta-cyclodextrin derivative prepared from dipentene dioxide is used for preparing the microbial nutrition enhancer, so that the microbial nutrition enhancer has good removal effect of COD; compared with the embodiment 1 and the embodiment 6 and the embodiment 4, the embodiment 5 also obviously improves the COD removal rate, which shows that the modified starch is used for preparing the microbial nutrition synergist by adopting the N- (2-hydroxyethyl) -N' -2-propenyl thiourea to modify the starch, so that the microbial nutrition synergist has good COD removal effect.
Test example 3:
ammonia nitrogen removal rate test
The experimental wastewater is production wastewater of a certain company, the ammonia nitrogen content is 30.62mg/L, the microbial inoculum (model GANDEW-MIX, purchased from Shanghai Gangdu environmental engineering Co., ltd.) is added at 10mg/L, the microbial nutrition synergist is added at 0.5mg/L, and after 4d, the Nahner reagent spectrophotometry is adopted to test the ammonia nitrogen removal rate.
TABLE 2 Ammonia nitrogen removal test results
| Experimental grouping | Ammonia nitrogen removal rate/% |
| Example 1 | 38.5 |
| Example 2 | 40.1 |
| Example 3 | 39.4 |
| Example 4 | 29.2 |
| Example 5 | 46.8 |
| Example 6 | 37.3 |
The above-described tests were performed on the microbial nutritional potentiators prepared in examples 1-6, and the results are shown in Table 2. As can be seen from table 2, compared with example 4 and example 5 and example 6, the ammonia nitrogen removal rate is significantly improved, which illustrates that the beta-cyclodextrin derivative prepared from dipentene dioxide is used for preparing the microbial nutrition synergist, so that the microbial nutrition synergist has good ammonia nitrogen removal effect; compared with the embodiment 1 and the embodiment 6 and the embodiment 4, the ammonia nitrogen removal rate is also obviously improved, which shows that the modified starch is used for preparing the microbial nutrition synergist by adopting the N- (2-hydroxyethyl) -N' -2-propenyl thiourea to modify the starch, so that the microbial nutrition synergist has good ammonia nitrogen removal effect.
Test example 4:
heavy metal removal effect test
The experimental wastewater is industrial wastewater of a certain company, the concentration of heavy metal ions is 129.87 mug/L, the microbial bacterial dosage (model GANDEW-MIX, purchased from Shanghai Gao environmental engineering Co., ltd.) is 10mg/L, the microbial nutrition synergist dosage is 0.5mg/L, and after 3d, the content of heavy metal in the wastewater is tested by adopting ICP-MS. ICP-MS parameters: high-frequency emission power 1550W, sampling depth 6.4mm, cooling gas flow 15L/min, carrier gas flow 1L/min, fog room temperature 2 ℃, scanning mode: peak jump, observation point/peak: 3, cycle times: 3 times, 60s each for sample analysis.
TABLE 3 test results of heavy metal removal effect
| Experimental grouping | Heavy metal removal rate/% |
| Example 1 | 52.6 |
| Example 2 | 54.2 |
| Example 3 | 53.5 |
| Example 4 | 41.1 |
| Example 5 | 60.5 |
| Example 6 | 49.3 |
The above-described tests were conducted on the microbial nutritional potentiators prepared in examples 1 to 6, and the results are shown in Table 3. As can be seen from table 3, compared with example 4 and example 5 and example 6, the heavy metal removal rate is significantly improved, which indicates that the beta-cyclodextrin derivative prepared from dipentene dioxide is used for preparing the microbial nutrition enhancer, so that the microbial nutrition enhancer has good heavy metal removal effect; compared with the embodiment 1 and the embodiment 6 and the embodiment 4, the heavy metal removal rate of the embodiment 5 is also obviously improved, which shows that the modified starch is used for preparing the microbial nutrition synergist by adopting the N- (2-hydroxyethyl) -N' -2-propenyl thiourea to modify the starch, so that the microbial nutrition synergist has good heavy metal removal effect.
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 (7)
1. A cyclodextrin derivative characterized by: the derivative is prepared by substitution reaction of dipentene dioxide and cyclodextrin substances; the cyclodextrin comprises one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin; the substitution degree of the cyclodextrin derivative is 3.5-4.
2. A cyclodextrin derivative according to claim 1, wherein: the cyclodextrin is beta-cyclodextrin.
3. A cyclodextrin derivative according to claim 1, wherein: the mol ratio of the beta-cyclodextrin to the dipentene dioxide is 1:4-6.
4. A microbial nutrition synergist suitable for wastewater treatment is characterized in that: comprising the cyclodextrin derivative of claim 1.
5. A microbial nutritional enhancer suitable for use in wastewater treatment according to claim 4, wherein: the microbial nutrition synergist also comprises glucose, starch, L-proline, fulvic acid and EDTA.
6. A microbial nutritional enhancer suitable for use in wastewater treatment according to claim 5, wherein: in the microbial nutrition synergist, the dosage of the cyclodextrin derivative is 10-15 parts by weight; the dosage of glucose is 7-10 parts; the starch dosage is 2-4 parts; the dosage of the L-proline is 2-5 parts; the dosage of fulvic acid is 10-15 parts; the EDTA is used in an amount of 0.5-1 part.
7. Use of a cyclodextrin derivative as defined in claim 2 or 3 in wastewater treatment.
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