WO2022252354A1 - Modified biochar algae inhibitor, use thereof, and preparation method therefor - Google Patents
Modified biochar algae inhibitor, use thereof, and preparation method therefor Download PDFInfo
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- WO2022252354A1 WO2022252354A1 PCT/CN2021/106374 CN2021106374W WO2022252354A1 WO 2022252354 A1 WO2022252354 A1 WO 2022252354A1 CN 2021106374 W CN2021106374 W CN 2021106374W WO 2022252354 A1 WO2022252354 A1 WO 2022252354A1
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- algae
- biochar
- modified biochar
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- 241000195493 Cryptophyta Species 0.000 title claims abstract description 80
- 239000003112 inhibitor Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 17
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003763 carbonization Methods 0.000 claims description 18
- 239000002028 Biomass Substances 0.000 claims description 17
- 230000002401 inhibitory effect Effects 0.000 claims description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000003619 algicide Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000007164 Oryza sativa Nutrition 0.000 claims description 7
- 235000009566 rice Nutrition 0.000 claims description 7
- 239000010902 straw Substances 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 108010049746 Microcystins Proteins 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 23
- 230000008569 process Effects 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003053 toxin Substances 0.000 abstract description 2
- 231100000765 toxin Toxicity 0.000 abstract description 2
- 230000005389 magnetism Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 241000192710 Microcystis aeruginosa Species 0.000 description 10
- 241000192700 Cyanobacteria Species 0.000 description 6
- 241000209094 Oryza Species 0.000 description 6
- 229930002868 chlorophyll a Natural products 0.000 description 6
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- SRUWWOSWHXIIIA-UKPGNTDSSA-N Cyanoginosin Chemical compound N1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](C)[C@H](C(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@H](C(O)=O)N(C)C(=O)[C@@H](C)[C@@H]1\C=C\C(\C)=C\[C@H](C)[C@@H](O)CC1=CC=CC=C1 SRUWWOSWHXIIIA-UKPGNTDSSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 108010067094 microcystin Proteins 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
Definitions
- the invention relates to a preparation method of modified biochar based on rice straw and its application in the process of inhibiting algae and adsorbing microcystin, belonging to the technical field of water pollution treatment.
- modified biochar As a common adsorption material, modified biochar is widely used in the field of soil remediation, and it is rich in surface functional groups, such as carboxyl, hydroxyl and lactone functional groups. At the same time, the modified biochar has a variety of pore structures, which can provide a large number of attachment sites for groups and increase the loading capacity. But at present, biochar and modified biochar are rarely used in the field of algae inhibition. Therefore, using the good adsorption performance of modified biochar to prepare a kind of adsorption material with abundant raw materials, strong adsorption capacity and rapid removal of algae in actual water bodies is worthy of further research.
- the present invention provides modified biochar based on rice straw, using self-synthesized colloidal precipitation of ferric oxide to modify magnesium oxide-based biochar, through the synergistic effect of the two to inhibit algae, and at the same time Microcystins are adsorbed during the process, thereby controlling the outbreak of cyanobacteria blooms.
- the present invention provides a modified biochar algicide, which is obtained by modifying magnesium oxide-based biochar with ferric iron tetroxide.
- the magnesium oxide-based biochar is obtained by carbonizing biomass and magnesium chloride as precursors under anoxic conditions.
- the carbonization temperature is 400-700°C.
- the carbonization temperature is 500°C.
- the present invention provides a method for the aforementioned modified biochar algae inhibitor to inhibit algae, specifically: adding the modified biochar algae inhibitor to the treated algae liquid; the modified biochar The dosage of the algicide is 0.5-4.0 g/L relative to the treated algae liquid.
- the present invention provides the application of the aforementioned modified biochar algicide to adsorb microcystins in water bodies.
- the specific application process is to add the modified biochar algicide to the water body containing microcystin.
- the present invention provides a method for preparing the aforementioned modified biochar algicide, the specific steps of which are as follows:
- Step 1 adding biomass to anhydrous magnesium chloride solution, stirring, evaporating and crystallizing to obtain biomass crystals.
- the biomass crystals are carbonized to obtain magnesium oxide-based biochar.
- Step 2 mixing ferric oxide colloid and magnesium oxide-based biochar, stirring, and standing for drying to obtain a modified biochar algastatic agent.
- the biomass described in step 1 is obtained by grinding the dried rice straw through a crusher and passing it through a 200-mesh sieve.
- the biomass crystals are placed in a crucible and wrapped with tinfoil. Then put it in a box-type atmosphere furnace with nitrogen, and carbonize at high temperature under the condition of anoxic.
- the preparation process of the ferric oxide colloid is as follows: adding ferrous chloride tetrahydrate, anhydrous ferric chloride, dilute hydrochloric acid solution and ammonia water to the ultrapure water after passing nitrogen gas for a preset period of time.
- the ratio of the amount of ferrous ions in the ferrous chloride tetrahydrate to the ferric ions in the anhydrous ferric chloride is 2:1.
- the colloidal precipitate produced in the mixed solution is ferric oxide colloid.
- the mass ratio of anhydrous magnesium chloride and biomass is 5:2.
- the high-temperature carbonization conditions in step 1 are as follows: firstly heat to the target temperature at a heating rate of 5° C./min, continue carbonization at the target temperature for 2 hours, and cool naturally to room temperature.
- the target temperature of the carbonization treatment is 400-700°C.
- the stirring described in step 2 adopts magnetic stirring, and the stirring time is 30 min.
- the modified biochar algae inhibitor provided by the present invention is obtained by modifying magnesium oxide-based biochar with ferric oxide, which has a significant algae inhibitory effect on cyanobacteria bloom outbreak water bodies, and can be used in the process of algae inhibition
- the algae liquid is quickly clarified and transparent, and can form magnetic and easy-settling flocs, which is convenient for the recovery and reuse of modified biochar.
- the modified biochar used in the present invention does not need to pre-treat the algae liquid during the algae inhibition process (that is, the process of removing the medium, including centrifugation and washing) to achieve effective algae inhibition, and the cost of algae inhibition is less time. While saving the time for algae inhibition, it can achieve the same or higher algae inhibition efficiency as the existing algae inhibition process.
- the present invention uses rice straw as a raw material, and obtains magnesium oxide-based modified biochar after modification.
- the modified biochar has rich sources of raw materials and is easy to obtain and cheap. It can react with algae in a short time to achieve the desired effect of algae removal.
- the modified biochar prepared by the present invention can also rapidly absorb microcystins while inhibiting algae.
- Figure 1 is a comparison chart of the removal rate of algae cells by modified biochar algicides prepared at different carbonization temperatures.
- Figure 2 is a graph showing the relationship between the removal rate of algae cells over time under different dosages of BMC600 modified biochar algae inhibitor.
- Figure 3 is a comparison chart of the algae inhibitors of BMC600, BM600 and BC600 modified biochar algae inhibitors under the same conditions.
- a preparation method of modified biochar algae inhibitor the specific steps are as follows:
- the dried rice straw was crushed and passed through a 200-mesh sieve, and then 1.0 g of biomass raw material under the sieve was added to 100 ml of 2.5 g/L magnesium chloride, stirred for 24 hours, evaporated and crystallized. Four parts of biomass after appropriate crystallization were taken and placed in four crucibles respectively.
- Nitrogen was passed through the four-necked flask containing 120mL of ultrapure water for 1 hour, and 2.0g FeCl 2 4H 2 O and 0.8g FeCl 3 , 20mL 0.4mol/L HCl and 15mL 0.7mol/L ammonia water were added respectively after removing the interfering gas, namely A colloidal precipitate of ferric oxide is generated.
- Take four colloidal precipitates of ferroferric oxide add 2.4g of BC400, BC500, BC600 and BC700 magnesium oxide-based biochars prepared above, stir for 30min, let stand and dry, and obtain four kinds of modified charcoal prepared at different carbonization temperatures.
- Biochar algicides respectively marked as BMC400, BMC500, BMC600 and BMC700.
- the modified biochar algae inhibitors prepared at different carbonization temperatures carry out the algae inhibition method, and the specific process is as follows:
- Step 1 Take the microcystis aeruginosa algae liquid grown to the logarithmic phase cultured by BG11 without any pretreatment.
- Step 2 Add four parts of 0.4 g of modified biochar algicides prepared at different calcination temperatures (i.e. BMC400, BMC500, BMC600 and BMC700) to four parts of 100 mL of algae suspension, and the magnetic stirring speed is set to 100 rpm. After reacting for 5 minutes, place a strong magnet at the bottom of the reactor and let it stand for 10 minutes.
- modified biochar algicides prepared at different calcination temperatures i.e. BMC400, BMC500, BMC600 and BMC700
- Step 3 Take four samples of the supernatant of the algal suspension, measure the concentration of chlorophyll a, and determine the removal rate T of the microcystis aeruginosa cells by the modified biochar algicides prepared at four different carbonization temperatures.
- the cell removal rate T of Microcystis aeruginosa was calculated by measuring the chlorophyll a content of the algae liquid before and after the test, and the specific calculation formula was as follows:
- C 0 is the initial concentration of chlorophyll a in the algae suspension
- C 1 is the concentration of chlorophyll a in the algae suspension after being treated with algicide. Since chlorophyll a can represent the density of algal cells and the photosynthetic ability of algal cells, this expression can accurately obtain the removal rate T of Microcystis aeruginosa cells.
- the obtained algae cell removal rate results are shown in Figure 1.
- the results show that the four modified activated carbon algae inhibitors all have obvious algae inhibitory effects; especially after the BMC600 modified biochar algae inhibitor reacted for 5 minutes, the algae cells were removed.
- the rate can reach 97.5%, the anti-algae effect is the best, and it is the best carbonization temperature, which has obvious advantages compared with other ratios.
- Step 1 Take the microcystis aeruginosa algae liquid grown to the logarithmic phase cultured by BG11 without any pretreatment.
- Step 2 Using BMC600 modified biochar to conduct four sets of algae inhibition tests on the suspension of Microcystis aeruginosa.
- the amount of algae suspension was 100ml, and the magnetic stirring speed was set at 100rpm.
- the dosages of BMC600 modified biochar in the four groups of algae inhibition tests were 0.5, 1.0, 2.0, 3.0, 4.0 g/L respectively.
- samples were taken at 0, 1, 2, 3, 4, and 5 minutes after the catalyst was added, and the chlorophyll a concentration of the samples was measured, and the removal rate T of Microcystis aeruginosa cells was calculated respectively.
- FIG. 3 is a comparison chart of the algae inhibition efficiency of BMC600 modified biochar, BM600 modified biochar and BC600 modified biochar under the same conditions.
- the results showed that under the same treatment conditions, the removal rate of BC600 modified biochar to algae cells was 6.4% within 5 minutes, and the removal rate of BM600 modified biochar to algae cells was 23.2% in the same time, both of which were far lower. 97.5% of BMC600 modified biochar.
- BC600 and BM600 modified biochars have almost no removal effect on Microcystis aeruginosa cells in a short period of time, while the algae-inhibiting effect of magnesium oxide-based biochars modified by Fe3O4 has been obtained.
- the great improvement shows that the algae inhibitory effect of the modified biochar algae inhibitor provided by the present invention is not obtained by the simple superposition of biochar, magnesium oxide and ferric oxide, which shows that magnesium oxide and ferric oxide Iron played a crucial role in the modification of biochar.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Water Treatment By Sorption (AREA)
Abstract
A modified biochar algae inhibitor, a use thereof, and a preparation method therefor. The modified biochar is obtained by modifying magnesium oxide-based biochar by means of ferroferric oxide. The modified biochar is used to perform algae inhibition and algal toxin adsorption, and raw materials are rich in source and cheap and easy to obtain. During algae inhibition, a solution can be quickly clarified and transparent, and a floc which has magnetism and is easy to sink is formed, such that recycling and reuse of the modified biochar are facilitated. In addition, the modified biochar can achieve effective algae inhibition without pretreatment of an algae solution during algae inhibition, such that time is less consumed, and the algae inhibition efficiency which is the same as or higher than that of an existing algae inhibition process is achieved.
Description
本发明涉及一种基于水稻秸秆的改性生物炭的制备方法及在抑藻及吸附微囊藻毒素过程中的应用，属于水污染处理技术领域。The invention relates to a preparation method of modified biochar based on rice straw and its application in the process of inhibiting algae and adsorbing microcystin, belonging to the technical field of water pollution treatment.
全球气候变暖、温室效应、水体富营养化等全球问题加剧及工农业大量含氮、磷污染物输入湖库导致的蓝藻水华现象，已成为国内外学者关注和研究的热点。根据生态环境部报告数据，截至2020年8月4日，全国97个重点湖(库)中，仍有33个湖库呈富营养状态，富营养化湖库中的蓝藻水华现状依旧严峻。同时，蓝藻分泌的藻毒素会抑制水体中其他生物的生长与繁殖，最终导致一系列较为严重的公共卫生事件，对于蓝藻水华的控制迫在眉睫。Global warming, greenhouse effect, water eutrophication and other global problems have intensified, and cyanobacteria blooms caused by a large amount of nitrogen and phosphorus pollutants from industry and agriculture into lakes and reservoirs have become the focus of attention and research by scholars at home and abroad. According to the data reported by the Ministry of Ecology and Environment, as of August 4, 2020, 33 of the 97 key lakes (reservoirs) in the country are still in a state of eutrophication, and the status of cyanobacteria blooms in eutrophic lakes is still severe. At the same time, algae toxins secreted by cyanobacteria can inhibit the growth and reproduction of other organisms in the water, eventually leading to a series of serious public health incidents, and the control of cyanobacteria blooms is imminent.
改性生物炭作为一种常见吸附材料，广泛应用于土壤修复领域，其富含表面官能团，例如羧基、羟基和内酯官能团等。同时，改性生物炭具有多样的孔隙结构，能为基团提供大量的附着位点，增加负载量。但目前，生物炭及改性生物炭极少应用于抑藻领域。因此，运用改性生物炭良好的吸附性能，制备一种原材料来源丰富、吸附性强且能够快速去除实际水体中藻类的吸附材料，值得继续深入研究。As a common adsorption material, modified biochar is widely used in the field of soil remediation, and it is rich in surface functional groups, such as carboxyl, hydroxyl and lactone functional groups. At the same time, the modified biochar has a variety of pore structures, which can provide a large number of attachment sites for groups and increase the loading capacity. But at present, biochar and modified biochar are rarely used in the field of algae inhibition. Therefore, using the good adsorption performance of modified biochar to prepare a kind of adsorption material with abundant raw materials, strong adsorption capacity and rapid removal of algae in actual water bodies is worthy of further research.
现阶段，各种抑藻材料及工艺在实际抑藻应用中均存在处理用时较长、原材料短缺和造成二次污染等缺点。目前未见将基于水稻秸秆的生物炭经改性后作为抑藻材料及吸附微囊藻毒素的相关报道。在实际水体中，该种改性生物炭可否达到良好的抑藻效能也尚未可知。At present, various algae-inhibiting materials and processes have shortcomings such as long processing time, shortage of raw materials, and secondary pollution in actual algae-inhibiting applications. So far, there is no report on the use of modified rice straw-based biochar as an algae-inhibiting material and adsorption of microcystins. In actual water bodies, it is not yet known whether this modified biochar can achieve good algae inhibition.
发明内容Contents of the invention
针对上述的技术问题，本发明提供了基于水稻秸秆的改性生物炭，利用自主合成的四氧化三铁胶状沉淀改性氧化镁基生物炭，通过二者的协同作用进行抑藻，同时在过程中吸附微囊藻毒素，从而控制蓝藻水华的爆发。Aiming at the above-mentioned technical problems, the present invention provides modified biochar based on rice straw, using self-synthesized colloidal precipitation of ferric oxide to modify magnesium oxide-based biochar, through the synergistic effect of the two to inhibit algae, and at the same time Microcystins are adsorbed during the process, thereby controlling the outbreak of cyanobacteria blooms.
第一方面，本发明提供一种改性生物炭抑藻剂，其通过四氧化三铁对氧化镁基生物炭进行改性得到。In the first aspect, the present invention provides a modified biochar algicide, which is obtained by modifying magnesium oxide-based biochar with ferric iron tetroxide.
作为优选，所述的氧化镁基生物炭通过生物质和氯化镁作为前驱体在缺氧条件下炭化 后得到。所述的炭化温度为400～700℃。Preferably, the magnesium oxide-based biochar is obtained by carbonizing biomass and magnesium chloride as precursors under anoxic conditions. The carbonization temperature is 400-700°C.
作为优选，所述的炭化温度为500℃。Preferably, the carbonization temperature is 500°C.
第二方面，本发明提供了前述的改性生物炭抑藻剂进行抑藻的方法，具体为：向被处理藻液中投加该改性生物炭抑藻剂；所述的改性生物炭抑藻剂相对于被处理藻液的用量为0.5～4.0g/L。In a second aspect, the present invention provides a method for the aforementioned modified biochar algae inhibitor to inhibit algae, specifically: adding the modified biochar algae inhibitor to the treated algae liquid; the modified biochar The dosage of the algicide is 0.5-4.0 g/L relative to the treated algae liquid.
第三方面，本发明提供了前述的改性生物炭抑藻剂在水体中吸附微囊藻毒素的应用。具体应用过程为向含有微囊藻毒素的水体中投加该改性生物炭抑藻剂。In a third aspect, the present invention provides the application of the aforementioned modified biochar algicide to adsorb microcystins in water bodies. The specific application process is to add the modified biochar algicide to the water body containing microcystin.
第四方面，本发明提供了前述的改性生物炭抑藻剂的制备方法，其具体步骤如下：In a fourth aspect, the present invention provides a method for preparing the aforementioned modified biochar algicide, the specific steps of which are as follows:
步骤一、将生物质加入无水氯化镁溶液，搅拌后蒸发结晶，得到生物质结晶体。将生物质结晶体进行碳化处理，得到氧化镁基生物炭。Step 1: adding biomass to anhydrous magnesium chloride solution, stirring, evaporating and crystallizing to obtain biomass crystals. The biomass crystals are carbonized to obtain magnesium oxide-based biochar.
步骤二、将四氧化三铁胶体与氧化镁基生物炭混合后搅拌，并静置烘干，得到改性生物炭抑藻剂。 Step 2, mixing ferric oxide colloid and magnesium oxide-based biochar, stirring, and standing for drying to obtain a modified biochar algastatic agent.
作为优选，步骤一中所述的生物质通过将干燥的水稻秸秆经破碎机磨碎后过200目筛得到。Preferably, the biomass described in step 1 is obtained by grinding the dried rice straw through a crusher and passing it through a 200-mesh sieve.
作为优选，步骤一中所述的碳化处理是将生物质结晶体置于坩埚中，并用锡箔纸包裹。后置于通有氮气的箱式气氛炉中，在缺氧条件下高温炭化。Preferably, in the carbonization treatment described in step 1, the biomass crystals are placed in a crucible and wrapped with tinfoil. Then put it in a box-type atmosphere furnace with nitrogen, and carbonize at high temperature under the condition of anoxic.
作为优选，所述的四氧化三铁胶体的制备过程为：在通氮气预设时长后的超纯水中加入四水合氯化亚铁、无水氯化铁、稀盐酸溶液和氨水。四水合氯化亚铁中二价亚铁离子与无水氯化铁中三价铁离子的物质的量之比为2:1。混合液中产生的胶质沉淀即为四氧化三铁胶体。Preferably, the preparation process of the ferric oxide colloid is as follows: adding ferrous chloride tetrahydrate, anhydrous ferric chloride, dilute hydrochloric acid solution and ammonia water to the ultrapure water after passing nitrogen gas for a preset period of time. The ratio of the amount of ferrous ions in the ferrous chloride tetrahydrate to the ferric ions in the anhydrous ferric chloride is 2:1. The colloidal precipitate produced in the mixed solution is ferric oxide colloid.
作为优选，步骤一中，无水氯化镁与生物质的质量比为5:2。As preferably, in step one, the mass ratio of anhydrous magnesium chloride and biomass is 5:2.
作为优选，步骤一所述的高温炭化条件为：先以5℃/min的加热速率加热至目标温度，在目标温度下继续炭化2h，自然冷却到室温。Preferably, the high-temperature carbonization conditions in step 1 are as follows: firstly heat to the target temperature at a heating rate of 5° C./min, continue carbonization at the target temperature for 2 hours, and cool naturally to room temperature.
作为优选，步骤一，碳化处理的目标温度为400～700℃。Preferably, in step 1, the target temperature of the carbonization treatment is 400-700°C.
作为优选，步骤二中所述的搅拌采用磁力搅拌，搅拌时长为30min。Preferably, the stirring described in step 2 adopts magnetic stirring, and the stirring time is 30 min.
本发明具有的有益效果是：The beneficial effects that the present invention has are:
1、本发明提供的改性生物炭抑藻剂通过对氧化镁基生物炭进行四氧化三铁改性得到，其对蓝藻水华爆发水体具有显著的抑藻效果，在抑藻过程中可使藻液快速澄清透明，并能够形成具有磁性且易沉降的絮凝物，便于改性生物炭回收与再利用。1. The modified biochar algae inhibitor provided by the present invention is obtained by modifying magnesium oxide-based biochar with ferric oxide, which has a significant algae inhibitory effect on cyanobacteria bloom outbreak water bodies, and can be used in the process of algae inhibition The algae liquid is quickly clarified and transparent, and can form magnetic and easy-settling flocs, which is convenient for the recovery and reuse of modified biochar.
2、本发明使用的改性生物炭在抑藻过程中不需要对藻液进行前处理(即去除培养基的过程，包括离心和洗涤)就能够实现有效抑藻，且抑藻所需耗费的时间更少。在节约抑藻时长的同时，达到与现有抑藻工艺相同或更高的抑藻效能。2. The modified biochar used in the present invention does not need to pre-treat the algae liquid during the algae inhibition process (that is, the process of removing the medium, including centrifugation and washing) to achieve effective algae inhibition, and the cost of algae inhibition is less time. While saving the time for algae inhibition, it can achieve the same or higher algae inhibition efficiency as the existing algae inhibition process.
3、本发明以水稻秸秆为原材料，通过改性后制得氧化镁基改性生物炭，所述改性生物炭相比于已有的抑藻材料，其原材料来源丰富且易得廉价，同时可在短时间内与藻类反应，达到理想的除藻效果。3. The present invention uses rice straw as a raw material, and obtains magnesium oxide-based modified biochar after modification. Compared with the existing algae-inhibiting materials, the modified biochar has rich sources of raw materials and is easy to obtain and cheap. It can react with algae in a short time to achieve the desired effect of algae removal.
4、本发明制备的改性生物炭在抑藻的同时，还能够快速吸附微囊藻毒素。4. The modified biochar prepared by the present invention can also rapidly absorb microcystins while inhibiting algae.
图1为不同炭化温度下制得的改性生物炭抑藻剂对藻细胞去除率的比较图。Figure 1 is a comparison chart of the removal rate of algae cells by modified biochar algicides prepared at different carbonization temperatures.
图2为BMC600改性生物炭抑藻剂不同投加量下藻细胞去除率随时间的变化关系图。Figure 2 is a graph showing the relationship between the removal rate of algae cells over time under different dosages of BMC600 modified biochar algae inhibitor.
图3为BMC600、BM600和BC600改性生物炭抑藻剂在相同条件下的抑藻效能对比图。Figure 3 is a comparison chart of the algae inhibitors of BMC600, BM600 and BC600 modified biochar algae inhibitors under the same conditions.
以下结合具体实施例，对本发明作进一步描述。The present invention will be further described below in conjunction with specific embodiments.
实施例1Example 1
一种改性生物炭抑藻剂的制备方法，具体步骤如下：A preparation method of modified biochar algae inhibitor, the specific steps are as follows:
将干燥的水稻秸秆破碎后过200目筛，然后取1.0g筛下生物质原料加入100ml的2.5g/L氯化镁，搅拌24h，蒸发结晶。取四份适量结晶后的生物质分别置于四个坩埚中。用锡箔纸包裹装有生物质的坩埚，置于通氮气的箱式气氛炉中缺氧炭化；四个坩埚分别设置目标温度为400℃、500℃、600℃和700℃，并以5℃/min的加热速率加热至目标温度，在目标温度下继续炭化2h，自然冷却到室温，得到四种不同的氧化镁基生物炭，密封保存备用，分别标记为BC400，BC500，BC600和BC700。The dried rice straw was crushed and passed through a 200-mesh sieve, and then 1.0 g of biomass raw material under the sieve was added to 100 ml of 2.5 g/L magnesium chloride, stirred for 24 hours, evaporated and crystallized. Four parts of biomass after appropriate crystallization were taken and placed in four crucibles respectively. Wrap the crucible containing the biomass with tin foil, and place it in a nitrogen-filled box-type atmosphere furnace for anaerobic carbonization; set the target temperatures of the four crucibles at 400°C, 500°C, 600°C, and 700°C, respectively, and set the temperature at 5°C/ Heating at a heating rate of min to the target temperature, continued carbonization at the target temperature for 2 h, and naturally cooled to room temperature to obtain four different magnesia-based biochars, which were sealed and stored for future use, respectively labeled as BC400, BC500, BC600 and BC700.
对盛有120mL超纯水的四口烧瓶通氮气1h，排除干扰气后分别加入2.0g FeCl
2·4H
2O和0.8g FeCl
3、20mL 0.4mol/L HCl和15mL 0.7mol/L氨水，即生成四氧化三铁胶状沉淀。取四份四氧化三铁胶状沉淀，分别加入2.4g前述制备的BC400，BC500，BC600和BC700氧化镁基生物炭，搅拌30min，静置烘干，得到四种不同碳化温度制得的改性生物炭抑藻剂，分别标记为BMC400，BMC500，BMC600和BMC700。
Nitrogen was passed through the four-necked flask containing 120mL of ultrapure water for 1 hour, and 2.0g FeCl 2 4H 2 O and 0.8g FeCl 3 , 20mL 0.4mol/L HCl and 15mL 0.7mol/L ammonia water were added respectively after removing the interfering gas, namely A colloidal precipitate of ferric oxide is generated. Take four colloidal precipitates of ferroferric oxide, add 2.4g of BC400, BC500, BC600 and BC700 magnesium oxide-based biochars prepared above, stir for 30min, let stand and dry, and obtain four kinds of modified charcoal prepared at different carbonization temperatures. Biochar algicides, respectively marked as BMC400, BMC500, BMC600 and BMC700.
在上述合成过程中，取消加入氯化镁改性的过程，以相同的过程制备四种不同的四氧化三铁改性的生物炭BM400，BM500，BM600和BM700。In the above synthesis process, the modification process of adding magnesium chloride was canceled, and four different ferric oxide modified biochars BM400, BM500, BM600 and BM700 were prepared by the same process.
实施例2Example 2
不同炭化温度制得的改性生物炭抑藻剂进行抑藻方法，具体过程如下：The modified biochar algae inhibitors prepared at different carbonization temperatures carry out the algae inhibition method, and the specific process is as follows:
步骤一、取由BG11培养的生长至对数期的铜绿微囊藻藻液，不经任何前处理。Step 1: Take the microcystis aeruginosa algae liquid grown to the logarithmic phase cultured by BG11 without any pretreatment.
步骤二、将四份0.4g的不同煅烧温度下制备的改性生物炭抑藻剂(即BMC400，BMC500，BMC600和BMC700)分别加入到四份100mL藻悬液中，磁力搅拌转速设置为100rpm，反应5min后，在反应器底部放置强磁铁，静置10min。 Step 2. Add four parts of 0.4 g of modified biochar algicides prepared at different calcination temperatures (i.e. BMC400, BMC500, BMC600 and BMC700) to four parts of 100 mL of algae suspension, and the magnetic stirring speed is set to 100 rpm. After reacting for 5 minutes, place a strong magnet at the bottom of the reactor and let it stand for 10 minutes.
步骤三、分别取四份藻悬液的上清液样品，进行叶绿素a浓度进行测定，确定四种不同炭化温度制得的改性生物炭抑藻剂对铜绿微囊藻细胞的去除率T。Step 3: Take four samples of the supernatant of the algal suspension, measure the concentration of chlorophyll a, and determine the removal rate T of the microcystis aeruginosa cells by the modified biochar algicides prepared at four different carbonization temperatures.
铜绿微囊藻细胞去除率T通过测量试验前后藻液的叶绿素a含量计算得到，具体计算公式如下：The cell removal rate T of Microcystis aeruginosa was calculated by measuring the chlorophyll a content of the algae liquid before and after the test, and the specific calculation formula was as follows:
其中，C
0为藻悬液中的初始叶绿素a浓度；C
1为藻悬液在经过抑藻剂处理后的叶绿素a浓度。由于叶绿素a可表示藻细胞密度，同时也可表示藻细胞的光合作用能力，故该表达式能够准确的获取铜绿微囊藻细胞的去除率T。
Among them, C 0 is the initial concentration of chlorophyll a in the algae suspension; C 1 is the concentration of chlorophyll a in the algae suspension after being treated with algicide. Since chlorophyll a can represent the density of algal cells and the photosynthetic ability of algal cells, this expression can accurately obtain the removal rate T of Microcystis aeruginosa cells.
所得的藻细胞去除率结果如图1所示，结果表明，四种改性活性炭抑藻剂均有明显的抑藻效果；特别是BMC600改性生物炭抑藻剂在反应5min后，藻细胞去除率可达97.5％，抑藻效果最佳，为最佳炭化温度，相对于其他比例具有显著的优益性。The obtained algae cell removal rate results are shown in Figure 1. The results show that the four modified activated carbon algae inhibitors all have obvious algae inhibitory effects; especially after the BMC600 modified biochar algae inhibitor reacted for 5 minutes, the algae cells were removed. The rate can reach 97.5%, the anti-algae effect is the best, and it is the best carbonization temperature, which has obvious advantages compared with other ratios.
实施例3Example 3
BMC600改性生物炭抑藻剂在不同投加量、不同处理时间情况下的抑藻效能对比，具体如下：The comparison of algae inhibitory effect of BMC600 modified biochar algae inhibitor under different dosage and different treatment time is as follows:
步骤一、取由BG11培养的生长至对数期的铜绿微囊藻藻液，不经任何前处理。Step 1: Take the microcystis aeruginosa algae liquid grown to the logarithmic phase cultured by BG11 without any pretreatment.
步骤二、以BMC600改性生物炭，对铜绿微囊藻藻液藻悬液进行四组抑藻试验。每组抑藻试验中，藻悬液的用量均为100ml，磁力搅拌转速设置为100rpm。四组抑藻试验中BMC600改性生物炭的投加量分别为0.5、1.0、2.0、3.0、4.0g/L。每组抑藻试验均在投加催化剂后的0、1、2、3、4、5min时取样，并测定样品的叶绿素a浓度，并分别计算铜绿微囊藻细胞的去除率T。Step 2: Using BMC600 modified biochar to conduct four sets of algae inhibition tests on the suspension of Microcystis aeruginosa. In each group of algae inhibition tests, the amount of algae suspension was 100ml, and the magnetic stirring speed was set at 100rpm. The dosages of BMC600 modified biochar in the four groups of algae inhibition tests were 0.5, 1.0, 2.0, 3.0, 4.0 g/L respectively. For each group of algae inhibition tests, samples were taken at 0, 1, 2, 3, 4, and 5 minutes after the catalyst was added, and the chlorophyll a concentration of the samples was measured, and the removal rate T of Microcystis aeruginosa cells was calculated respectively.
各投加量下BMC600改性生物炭对应的藻细胞去除率随时间的变化关系如图2所示。结果表明，复合催化剂投加量为4.0g/L时，反应进行5min后，藻细胞去除率可达97.5％ 以上，而投加量为5.0g/L时，抑藻效果显著下降，说明4.0g/L的投加量对于抑藻效果具有显著优益性。The relationship between the removal rate of algae cells corresponding to BMC600 modified biochar with time at various dosages is shown in Figure 2. The results show that when the dosage of the composite catalyst is 4.0g/L, the removal rate of algae cells can reach more than 97.5% after the reaction is carried out for 5 minutes; The dosing amount of /L has a significant advantage in inhibiting algae.
对比例1Comparative example 1
将4.0g/L未经改性的氧化镁基生物炭(具体为BC600)加入至铜绿微囊藻藻液中，经磁力搅拌5min并静置10min。抑制条件与实施例2相同。Add 4.0 g/L unmodified magnesium oxide-based biochar (specifically, BC600) into the algae liquid of Microcystis aeruginosa, stir it by magnetic force for 5 min and let it stand for 10 min. Inhibition conditions were the same as in Example 2.
对比例2Comparative example 2
将4.0g/L负载四氧化三铁的生物炭(具体为BM600)加入至铜绿微囊藻藻液中，经磁力搅拌5min并静置10min。抑制条件与实施例2相同。4.0 g/L of biochar (specifically BM600) loaded with ferric oxide was added to the liquid of Microcystis aeruginosa, stirred by magnetic force for 5 min and allowed to stand for 10 min. Inhibition conditions were the same as in Example 2.
图3为BMC600改性生物炭、BM600改性生物炭和BC600改性生物炭在相同条件下的抑藻效能对比图。结果表明，相同的处理条件下，BC600改性生物炭在5min内对藻细胞的去除率为6.4％，BM600改性生物炭在相同时间内对藻细胞的去除率为23.2％，二者远低于BMC600改性生物炭的97.5％。表明在相同投加量下，BC600和BM600改性生物炭在短时间内对铜绿微囊藻细胞基本无去除效果，而经四氧化三铁改性后氧化镁基生物炭的抑藻效能得到了极大的提升，说明本发明提供的改性生物炭抑藻剂的抑藻效果并非生物炭、氧化镁和四氧化三铁的简单叠加能够得到，表明在抑藻过程中氧化镁及四氧化三铁对生物炭的改性起到了至关重要的作用。Figure 3 is a comparison chart of the algae inhibition efficiency of BMC600 modified biochar, BM600 modified biochar and BC600 modified biochar under the same conditions. The results showed that under the same treatment conditions, the removal rate of BC600 modified biochar to algae cells was 6.4% within 5 minutes, and the removal rate of BM600 modified biochar to algae cells was 23.2% in the same time, both of which were far lower. 97.5% of BMC600 modified biochar. It shows that under the same dosage, BC600 and BM600 modified biochars have almost no removal effect on Microcystis aeruginosa cells in a short period of time, while the algae-inhibiting effect of magnesium oxide-based biochars modified by Fe3O4 has been obtained. The great improvement shows that the algae inhibitory effect of the modified biochar algae inhibitor provided by the present invention is not obtained by the simple superposition of biochar, magnesium oxide and ferric oxide, which shows that magnesium oxide and ferric oxide Iron played a crucial role in the modification of biochar.
Claims (10)
- 一种改性生物炭抑藻剂，其特征在于：通过四氧化三铁对氧化镁基生物炭进行改性得到。A modified biochar algae inhibitor is characterized in that it is obtained by modifying magnesium oxide-based biochar with ferric iron tetroxide.
- 根据权利要求1所述的一种改性生物炭抑藻剂，其特征在于：所述的氧化镁基生物炭通过生物质和氯化镁作为前驱体在缺氧条件下炭化后得到；所述的炭化温度为400～700℃。A kind of modified biochar algastatic agent according to claim 1, is characterized in that: described magnesium oxide-based biochar is obtained after carbonization under anoxic condition by biomass and magnesium chloride as precursor; Described carbonization The temperature is 400-700°C.
- 根据权利要求2所述的一种改性生物炭抑藻剂，其特征在于：所述的炭化温度为500℃。A modified biochar algicide according to claim 2, characterized in that: the carbonization temperature is 500°C.
- 使用如权利要求1所述的一种改性生物炭抑藻剂进行抑藻的方法，其特征在于：投加的改性生物炭抑藻剂相对于被处理藻液的用量为0.5～4.0g/L。The method for inhibiting algae using a modified biochar algae inhibitor as claimed in claim 1 is characterized in that: the amount of the modified biochar algae inhibitor added relative to the treated algae liquid is 0.5 ~ 4.0g /L.
- 如权利要求1所述的一种改性生物炭抑藻剂吸附水体中微囊藻毒素的应用。The application of a modified biochar algastatic agent for absorbing microcystins in water bodies as claimed in claim 1.
- 一种改性生物炭抑藻剂的制备方法，其特征在于：步骤一、将生物质加入无水氯化镁溶液，搅拌后蒸发结晶，得到生物质结晶体；将生物质结晶体进行碳化处理，得到氧化镁基生物炭；A preparation method of a modified biochar algae inhibitor, characterized in that: step 1, adding biomass to anhydrous magnesium chloride solution, stirring and then evaporating and crystallizing to obtain biomass crystals; carbonizing the biomass crystals to obtain magnesium oxide Biochar-based;步骤二、将四氧化三铁胶体与氧化镁基生物炭混合后搅拌，并静置烘干，得到改性生物炭抑藻剂。Step 2, mixing ferric oxide colloid and magnesium oxide-based biochar, stirring, and standing for drying to obtain a modified biochar algastatic agent.
- 根据权利要求6所述的制备方法，其特征在于：步骤一中所述的生物质通过将干燥的水稻秸秆经破碎机磨碎后过200目筛得到。The preparation method according to claim 6, characterized in that: the biomass described in step 1 is obtained by grinding the dried rice straw through a crusher and passing it through a 200-mesh sieve.
- 根据权利要求6所述的制备方法，其特征在于：步骤一中所述的碳化处理是将生物质结晶体置于坩埚中，并用锡箔纸包裹；后置于通有氮气的箱式气氛炉中，在缺氧条件下高温炭化。The preparation method according to claim 6, characterized in that: the carbonization treatment described in step 1 is to place the biomass crystals in a crucible and wrap them with tinfoil paper; then place them in a box-type atmosphere furnace with nitrogen, Carbonization at high temperature under anoxic conditions.
- 根据权利要求6所述的制备方法，其特征在于：所述的四氧化三铁胶体的制备过程为：在通氮气预设时长后的超纯水中加入四水合氯化亚铁、无水氯化铁、稀盐酸溶液和氨水；四水合氯化亚铁中二价亚铁离子与无水氯化铁中三价铁离子的物质的量之比为2:1；混合液中产生的胶质沉淀即为四氧化三铁胶体。The preparation method according to claim 6, characterized in that: the preparation process of the colloidal ferric oxide is: add ferrous chloride tetrahydrate, anhydrous chlorine, Ferrous chloride, dilute hydrochloric acid solution and ammoniacal liquor; The ratio of the amount of ferrous ferrous ions in ferrous chloride tetrahydrate to the amount of ferric ions in anhydrous ferric chloride is 2:1; the colloid produced in the mixed solution Precipitation is ferric oxide colloid.
- 根据权利要求6所述的制备方法，其特征在于：步骤一中，无水氯化镁与生物质的质量比为5:2。The preparation method according to claim 6, characterized in that: in step 1, the mass ratio of anhydrous magnesium chloride to biomass is 5:2.
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| CN110252242A (en) * | 2019-05-17 | 2019-09-20 | 兰州大学 | A kind of preparation method and modification biological charcoal of modification biological charcoal |
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| CN110252242A (en) * | 2019-05-17 | 2019-09-20 | 兰州大学 | A kind of preparation method and modification biological charcoal of modification biological charcoal |
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