CN114212895B - Composition and device for treating acidic iron ore waste liquid and preparation method thereof - Google Patents
Composition and device for treating acidic iron ore waste liquid and preparation method thereof Download PDFInfo
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- CN114212895B CN114212895B CN202111520384.6A CN202111520384A CN114212895B CN 114212895 B CN114212895 B CN 114212895B CN 202111520384 A CN202111520384 A CN 202111520384A CN 114212895 B CN114212895 B CN 114212895B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000007788 liquid Substances 0.000 title claims abstract description 64
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 54
- 239000002699 waste material Substances 0.000 title claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 title abstract description 15
- 230000000813 microbial effect Effects 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 20
- 239000004568 cement Substances 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004927 clay Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000004088 foaming agent Substances 0.000 claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims description 38
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 25
- 235000010413 sodium alginate Nutrition 0.000 claims description 25
- 239000000661 sodium alginate Substances 0.000 claims description 25
- 229940005550 sodium alginate Drugs 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- 241000196324 Embryophyta Species 0.000 claims description 18
- 235000010410 calcium alginate Nutrition 0.000 claims description 13
- 239000000648 calcium alginate Substances 0.000 claims description 13
- 229960002681 calcium alginate Drugs 0.000 claims description 13
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims description 13
- 239000004005 microsphere Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 10
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005187 foaming Methods 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 241000737241 Cocos Species 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000006260 foam Substances 0.000 claims description 5
- 239000001963 growth medium Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 241000589516 Pseudomonas Species 0.000 claims description 4
- 241000588986 Alcaligenes Species 0.000 claims description 3
- 241000193830 Bacillus <bacterium> Species 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 239000002068 microbial inoculum Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract 2
- 244000005700 microbiome Species 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 241000282414 Homo sapiens Species 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 230000002411 adverse Effects 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
- 239000002585 base Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003568 thioethers Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000010878 waste rock Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
-
- 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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/04—Enzymes or microbial cells immobilised on or in an organic carrier entrapped within the carrier, e.g. gel or hollow fibres
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
- C02F2003/003—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/32—Biological treatment of water, waste water, or sewage characterised by the animals or plants used, e.g. algae
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Abstract
The invention discloses a composition for treating acidic iron ore waste liquid, a device and a preparation method thereof, wherein the composition comprises the following components in percentage by mass: 40-50% of low-alkaline cement, 5-15% of polyethylenimine, 5-10% of immobilized microbial agent, 0.1-0.5% of foaming agent, 0.1-1% of clay, 1-2% of active carbon, 0.5-2% of plant fiber and the balance of water; the device is a plate-shaped filter material and is prepared from the composition; the substrate material in the invention is low-alkaline cement, and the substrate material is foamed to form a device with a large number of pores and proper hardness for treating acidic iron ore waste liquid, has a certain water impact resistance, can efficiently and rapidly adsorb metal ions in the acidic iron ore waste liquid and improve the pH value in the waste liquid through the synergistic effect of the components in the device, and the treated plate material collects a large number of metal elements such as iron and the like, and can be used for cultivating and planting aquatic plants in water ecological restoration after professional treatment.
Description
Technical Field
The invention belongs to the technical field of mine wastewater treatment, and particularly relates to a composition and device for treating acidic iron ore waste liquid and a preparation method thereof.
Background
With the rapid development of socioeconomic performance, the demand of human beings for mineral resources is increasing, and the discharge of industrial wastewater generated during the exploitation and processing of mineral resources is also increasing. The acid mine wastewater which has the largest pollution range and the largest hazard degree is acid wastewater discharged by mines, and the acid mine wastewater contains heavy metals with higher concentration and lower pH value, so that serious negative effects are caused on mining production and ecological environment. In the production process of mine enterprises, the main reason for the generation of the acid waste water is that the ore and surrounding rock contain sulphide minerals, and the sulphide minerals are oxidized and decomposed in the production processes of ore exploitation, transportation, ore dressing, waste rock discharge, tailing storage and the like, and are hydrated to form the acid mine waste water. Particularly in the exploitation roadway, under the condition of massive infiltration of underground water and good ventilation, a very favorable condition is provided for oxidation and decomposition of sulphide minerals.
The acidic ore wastewater is low in pH value and high in acidity, contains a large amount of heavy metals, cannot be directly recycled, is usually discharged into water bodies such as rivers and lakes near mines, changes the pH value of the water bodies, inhibits or prevents the growth of bacteria and microorganisms, and prevents the self-purification of the water bodies. The interaction of the acidic water and mineral substances in the water body can generate certain salts, which can have adverse effects on the growth of fresh water organisms and plants, so that the water body around a mining area is seriously polluted, most aquatic organisms such as fish, algae, plankton and the like die, the aggregate structure of soil is destroyed, the soil is hardened, and crops are withered and yellow; under the anoxic state, a large amount of SO4 2- in the acid mine wastewater is acted by the desulphurizing bacteria, and the generated H 2 S gas has serious toxic action on organisms; the acidic wastewater has strong corrosion damage to water pump accessories, pipes and tunnel equipment, so that equipment is frequently maintained, the safety of miners can be directly endangered, and if natural water is polluted by acid for a long time, the water quality is gradually acidified, and serious damage is caused to the ecological environment.
At present, the conventional methods for treating the acidic wastewater are as follows: 1) The neutralization method is characterized in that a certain alkaline substance is added into acid mine wastewater to perform acid-base neutralization treatment, so that neutralization reaction is performed on the acid mine wastewater, the pH value of the mine wastewater is improved, the wastewater becomes neutral, and some specially removed heavy metal ions are not easy to remove; 2) According to the vulcanizing method, vulcanizing agents are added into mine waste liquid to fully react, a large amount of metal ions in the mine waste liquid are removed through precipitation and filtration, so that clean mine waste water is obtained, but hydrogen sulfide harmful to human bodies is often generated when the vulcanizing agents are used, and therefore, the method is rarely used; 3) The method can effectively remove heavy metal substances in the mine wastewater, has relatively high efficiency, but has certain selectivity, and only has very high extraction efficiency for substances with relatively low heavy metal content; 4) The microorganism method can effectively treat heavy metal substances or other pollutants in mine wastewater, but the microorganism is not easy to survive, and can not continuously treat the pollutants for a long time.
Since the above-mentioned different treatment methods have drawbacks, it is necessary to develop a composition and an apparatus for treating the waste acidic iron ore liquid, thereby realizing an efficient treatment of the waste acidic iron ore liquid.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a composition and a device for treating acidic iron ore waste liquid and a preparation method thereof. The device can be produced in batches and used in scale, the used formula materials have no adverse effect on water environment, the device can be used for acid removal treatment of mine wastewater, the treated tail water is further purified by the artificial wetland, the aim of harmless to human beings is achieved, a large amount of metal elements such as iron are collected by the treated plates, and the treated plates can be used for cultivation and field planting of aquatic plants in water ecological restoration after professional treatment.
It is an object of the present invention to provide a composition for treating acidic iron ore waste liquid.
The composition for treating the acidic iron ore waste liquid comprises the following components in percentage by mass: 40 to 50 percent of low-alkaline cement, 5 to 15 percent of polyethyleneimine, 5 to 10 percent of immobilized microorganism bacterial agent, 0.1 to 0.5 percent of foaming agent, 0.1 to 1 percent of clay, 1 to 2 percent of active carbon, 0.5 to 2 percent of plant fiber and the balance of water.
It is another object of the present invention to provide an apparatus for treating acidic iron ore waste liquid.
An apparatus for treating acidic iron ore waste liquid, which is a plate-shaped filter material and which is prepared from the above composition.
Further, the bottom of the device for treating the acidic iron ore waste liquid is also provided with a layer of coconut palm cushion, and the thickness of the coconut palm cushion is 2-5 cm.
Further, the immobilized microbial agent is prepared by embedding microbial agents into calcium alginate microspheres and is used for adsorbing metal ions in acidic wastewater.
Still further, the microbial agent is selected from one or more of bacillus, pseudomonas and alcaligenes.
Further, the clay is selected from one or more of perlite, vermiculite, pumice, bentonite and medical stone.
A final object of the present invention is to provide a method for manufacturing a device for treating acidic iron ore waste liquid.
A method for preparing a device for treating acidic iron ore waste liquid, wherein the device is a plate-shaped filter material and specifically comprises the following steps:
S1, preparing an immobilized microbial agent;
S2, according to mass percentage, adding 40-50% of low-alkali cement, 5-15% of polyethyleneimine, 0.1-1% of clay, 1-2% of activated carbon and 0.5-2% of plant fiber, and then adding a part of water, and rapidly and uniformly stirring to obtain slurry;
S3, adding residual water into 0.1-0.5% of foaming agent, injecting the prepared foam into the slurry obtained in the step S2 after passing through a foaming machine, uniformly mixing, then adding 5-10% of immobilized microbial agent prepared in the step S1, and continuously mixing to obtain a mixed solution;
s4, pouring the mixed solution obtained in the step S3 into a mold, and taking down the mold after the mixed solution is fixed, thereby obtaining the device for treating the acidic iron ore waste liquid.
Further, in step S1, the preparation of the immobilized microbial agent specifically includes the following steps:
S11, activating a microbial agent: inoculating microbial inoculum into LB culture medium, shake flask for expansion culture;
S12, mixing microbial bacteria liquid with sodium alginate solution: dissolving a certain amount of sodium alginate in water, and mixing the sodium alginate solution with the microbial liquid obtained in the step S1, wherein the final concentration of the sodium alginate solution is 2-3% (W/V);
s13, preparing an immobilized microbial agent: slowly dripping the mixed solution of the microbial liquid and the sodium alginate solution obtained in the step S12 into a calcium chloride solution with the concentration of 5-10% (W/V), standing for 2-4h, filtering, and washing to obtain the immobilized microbial agent.
Further, in step S12, the concentration of the microbial liquid is 10 9～1010 cfu/ml.
Further, a layer of coconut palm fiber cushion is paved at the bottom of the die, and the thickness of the coconut fiber cushion is 2-5 cm.
Compared with the prior art, the invention has the following advantages:
The matrix material is low-alkaline cement, and the low-alkaline cement is subjected to foaming treatment to form a device with a large number of pores and proper hardness for treating acidic iron ore waste liquid, and has a certain resistance to hydraulic impact. The low-alkali cement belongs to an alkaline mixture, and when the iron ore waste liquid passes through, the low-alkali cement can contact the platy filter material in a large area and perform neutralization reaction with alkaline components in the low-alkali cement, so that the acidity of the waste liquid is effectively reduced. The polyethyleneimine is a high molecular polymer, and contains strong primary amine groups and secondary amine groups, when the device is placed in acidic waste water, the waste water enters the device through pores of low-alkaline cement, at the moment, a part of polyethyleneimine is hydrolyzed, and the hydrolyzed product reacts with acidic substances in the waste water, so that the pH value of acidic iron ore waste liquid is improved; meanwhile, because the polyethyleneimine is a high molecular polymer, the self reticular structure of the polyethyleneimine is filled in the pores of the low-alkali cement, and plays a certain role in fixing the immobilized microbial agent in the pores;
The immobilized microbial agent adopts calcium alginate microspheres for embedding, after the microorganisms are immobilized, the activity can be kept for a long time, micropores on the surfaces of the calcium alginate microspheres can allow wastewater to enter freely, so that metal ions in the wastewater are adsorbed by the microbial agent well and continuously, and the calcium alginate microspheres are exchanged with the external metal-containing wastewater continuously, so that the quality of the wastewater is improved;
The addition of clay and active carbon enables the device to have more pores, and a plurality of pores in the device can enable oxygen to quickly enter calcium alginate microspheres in the device, so that microbial agents in the device can be better propagated, and metabolic wastes generated by microorganisms can be quickly discharged through the pores; meanwhile, clay and active carbon are porous substances, so that metals in the wastewater can be well adsorbed;
the plant fiber is also a macromolecular substance, on one hand, metal ions in the wastewater can be adsorbed, and meanwhile, under the acidic condition, the plant fiber can be hydrolyzed into micromolecular saccharides and other substances, and the substances enter the inner layer of the calcium alginate microsphere through micropores on the surface of the calcium alginate microsphere for the growth, propagation and utilization of microorganisms;
The coconut palm pad is also a macromolecular substance, is arranged at the bottom of the device, is convenient to fix the device when placed in deeper wastewater, and can be hydrolyzed into micromolecular saccharide substances for microorganism growth, propagation and utilization when absorbing metal ions;
Through the synergistic effect among the components in the device, the device can efficiently and rapidly adsorb metal ions in the acidic iron ore waste liquid and improve the pH value in the waste liquid, the treated tail water is further purified by the artificial wetland, the purpose of harmless to human is achieved, a large amount of metal elements such as iron are collected by the treated plates, and the treated plates can be used for cultivation and field planting of aquatic plants in water ecological restoration after professional treatment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flow chart showing the production of the apparatus for treating acidic iron ore waste liquid according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments, and that all other embodiments obtained by persons of ordinary skill in the art without making creative efforts based on the embodiments in the present invention are within the protection scope of the present invention.
Other reagents and equipment used in the present invention are commercially available unless otherwise specified.
Example 1
An apparatus for treating acidic iron ore waste liquid, which is a plate-shaped filter material and is prepared from the following compositions in percentage by mass: 40% of low-alkali cement, 5% of polyethyleneimine, 5% of immobilized microorganism microbial agent, 0.1% of foaming agent, 0.1% of clay, 1% of activated carbon, 0.5% of plant fiber and the balance of water.
The preparation method of the device for treating the acidic iron ore waste liquid comprises the following steps of:
S1, preparing an immobilized microbial agent;
s11, activating a microbial agent: inoculating bacillus into LB culture medium, shake flask enlarging culture;
S12, mixing microbial bacteria liquid with sodium alginate solution: dissolving a certain amount of sodium alginate in water, and mixing the sodium alginate solution with the microbial liquid obtained in the step S1, wherein the final concentration of the sodium alginate solution is 2% (W/V);
S13, preparing an immobilized microbial agent: slowly dripping the mixed solution of the microbial liquid and the sodium alginate solution obtained in the step S12 into a calcium chloride solution with the concentration of 5% (W/V), standing for 2 hours, filtering, and washing to obtain the immobilized microbial agent;
S2, according to mass percentage, 40% of low-alkali cement, 5% of polyethyleneimine, 0.1% of clay, 1% of active carbon and 0.5% of plant fiber are added, and then a part of water is added, and rapid stirring is carried out, so that slurry is obtained;
S3, adding residual water into 0.1% of the foaming agent, injecting the prepared foam into the slurry obtained in the step S2 after passing through a foaming machine, uniformly mixing, then adding 5% of the immobilized microbial agent prepared in the step S1, and continuously mixing to obtain a mixed solution;
s4, pouring the mixed solution obtained in the step S3 into a mold, and taking down the mold after the mixed solution is fixed, thereby obtaining the device for treating the acidic iron ore waste liquid.
Example 2
An apparatus for treating acidic iron ore waste liquid, which is a plate-shaped filter material and is prepared from the following compositions in percentage by mass: 45% of low-alkaline cement, 10% of polyethyleneimine, 7% of immobilized microorganism microbial agent, 0.3% of foaming agent, 0.5% of clay, 1.5% of activated carbon, 1.2% of plant fiber and the balance of water.
The preparation method of the device for treating the acidic iron ore waste liquid comprises the following steps of:
S1, preparing an immobilized microbial agent;
S11, activating a microbial agent: inoculating pseudomonas into LB culture medium, shake flask for expansion culture for later use;
s12, mixing microbial bacteria liquid with sodium alginate solution: dissolving a certain amount of sodium alginate in water, and mixing the sodium alginate solution with the microbial liquid obtained in the step S1, wherein the final concentration of the sodium alginate solution is 2.5% (W/V);
S13, preparing an immobilized microbial agent: slowly dripping the mixed solution of the microbial liquid and the sodium alginate solution obtained in the step S12 into a calcium chloride solution with the concentration of 7% (W/V), standing for 3 hours, filtering, and washing to obtain the immobilized microbial agent;
S2, according to mass percentage, 45% of low-alkali cement, 10% of polyethyleneimine, 0.5% of clay, 1.5% of active carbon and 1.2% of plant fiber are added, and then a part of water is added, and quick stirring is carried out, so as to obtain slurry;
s3, adding residual water into 0.3% of the foaming agent, injecting the prepared foam into the slurry obtained in the step S2 after passing through a foaming machine, uniformly mixing, then adding 7% of the immobilized microbial agent prepared in the step S1, and continuously mixing to obtain a mixed solution;
s4, pouring the mixed solution obtained in the step S3 into a mold, and taking down the mold after the mixed solution is fixed, thereby obtaining the device for treating the acidic iron ore waste liquid.
Example 3
An apparatus for treating acidic iron ore waste liquid, which is a plate-shaped filter material and is prepared from the following compositions in percentage by mass: 50% of low-alkali cement, 15% of polyethyleneimine, 10% of immobilized microorganism microbial agent, 0.5% of foaming agent, 1% of clay, 2% of activated carbon, 2% of plant fiber and the balance of water.
The preparation method of the device for treating the acidic iron ore waste liquid comprises the following steps of:
S1, preparing an immobilized microbial agent;
S11, activating a microbial agent: inoculating pseudomonas and alcaligenes into LB culture medium, shake flask expansion culture for standby;
s12, mixing microbial bacteria liquid with sodium alginate solution: dissolving a certain amount of sodium alginate in water, and mixing the sodium alginate solution with the microbial liquid obtained in the step S1, wherein the final concentration of the sodium alginate solution is 3% (W/V);
S13, preparing an immobilized microbial agent: slowly dripping the mixed solution of the microbial liquid and the sodium alginate solution obtained in the step S12 into a calcium chloride solution with the concentration of 10% (W/V), standing for 4 hours, filtering, and washing to obtain the immobilized microbial agent;
S2, according to mass percentage, 50% of low-alkali cement, 15% of polyethyleneimine, 1% of clay, 2% of active carbon and 2% of plant fiber are added, and then a part of water is added, and quick stirring is carried out, so that slurry is obtained;
S3, adding residual water into 0.5% of the foaming agent, injecting the prepared foam into the slurry obtained in the step S2 after passing through a foaming machine, uniformly mixing, then adding 10% of the immobilized microbial agent prepared in the step S1, and continuously mixing to obtain a mixed solution;
s4, pouring the mixed solution obtained in the step S3 into a mold, and taking down the mold after the mixed solution is fixed, thereby obtaining the device for treating the acidic iron ore waste liquid.
Comparative example 1
The preparation method of the apparatus for treating acidic iron ore waste liquid is basically the same as in example 2, except that polyethyleneimine is not added in step S2.
Comparative example 2
The preparation method of the device for treating acidic iron ore waste liquid is basically the same as in example 2, except that the immobilized microbial agent is not added in step S3.
Comparative example 3
The preparation method of the device for treating acidic iron ore waste liquid is basically the same as in example 2, except that no plant fiber is added in step S2.
Example 4 application experiment of apparatus for treating acidic iron ore waste liquid
The devices of examples 1 to 3 and comparative examples 1 to 3, which were uniform in size and shape, were placed in parallel containers containing waste liquid having the same initial pH and metal ion concentration, and after a certain period of time (7 days, 15 days and 30 days), the pH value of the waste liquid in the vicinity of the device and the adsorption amount of metal ions by the device were measured, and the results are shown in table 1 below:
TABLE 1 results of application experiments of apparatus for treating acidic iron ore waste liquid
As can be seen from the results in the table, the device for treating acidic iron ore waste liquid prepared in examples 1-3 can well adsorb metal ions in waste water, and the adsorption capacity of the metal ions reaches 60mg/L after 30 days; after 30 days of treatment, the pH value of the acidic iron ore waste liquid is increased from 2.5 to about 6.5, and basically reaches the discharge standard;
Comparative example 1 differs from example 2 in that no polyethyleneimine was added. As a result, it was found that after 30 days of treatment, the pH value of the waste acidic iron ore liquid was increased from 2.5 to about 3.5 only, and the metal ion adsorption amount was slightly lowered, because polyethyleneimine is a high molecular polymer containing strong primary amine groups and secondary amine groups, when the device was put into acidic waste water, the waste water entered the interior of the device through the pores of low alkaline cement, at this time, a part of polyethyleneimine was hydrolyzed, and the hydrolyzed product reacted with acidic substances in the waste water, thereby improving the pH value of the waste acidic iron ore liquid; meanwhile, because the polyethyleneimine is a high molecular polymer, the self reticular structure of the polyethyleneimine is filled in the pores of the low-alkali cement, and plays a certain role in fixing the immobilized microbial agent in the pores;
Comparative example 2 differs from example 2 in that no immobilized microbial agent was added. As a result, after 30 days of treatment, the adsorption capacity of metal ions is greatly reduced, because the immobilized microbial agent adopts calcium alginate microspheres for embedding, the activity of the immobilized microorganisms can be kept for a long time, micropores on the surfaces of the calcium alginate microspheres can allow wastewater to enter freely, so that the metal ions in the wastewater are better and continuously adsorbed by the microbial agent, and the calcium alginate microspheres are continuously exchanged with the wastewater containing the outside metal, thereby improving the quality of the wastewater;
Comparative example 3 differs from example 2 in that no plant fiber was added. As a result, it was found that the adsorption amount of metal ions was reduced to some extent after 30 days of treatment, because the plant fiber is also a macromolecular substance, on the one hand, metal ions in wastewater could be adsorbed, and at the same time, under acidic conditions, the plant fiber could be hydrolyzed into substances such as small molecular saccharides, which enter into the inner layer of calcium alginate microspheres through micropores on the surface of the calcium alginate microspheres for microbial growth and propagation.
In conclusion, through the synergistic effect among the components in the device, the device can efficiently and rapidly adsorb metal ions in the acidic iron ore waste liquid and improve the pH value in the waste liquid.
The above examples are only specific embodiments of the present invention for illustrating the technical solution of the present invention, but not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the foregoing examples, it will be understood by those skilled in the art that the present invention is not limited thereto: any person skilled in the art may modify or easily conceive of the technical solution described in the foregoing embodiments, or perform equivalent substitution of some of the technical features, while remaining within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention, and are intended to be included in the scope of the present invention.
Claims (5)
1. A method for preparing a device for treating acidic iron ore waste liquid, which is characterized in that the device is a plate-shaped filter material and specifically comprises the following steps:
S1, preparing an immobilized microbial agent;
S2, mixing 40-50% of low-alkali cement, 5-15% of polyethyleneimine, 0.1-1% of clay, 1-2% of activated carbon and 0.5-2% of plant fiber by mass percent, and then adding a part of water, and rapidly and uniformly stirring to obtain slurry;
S3, adding residual water into 0.1-0.5% of foaming agent by mass percent, injecting the prepared foam into the slurry obtained in the step S2 after passing through a foaming machine, uniformly mixing, and then adding 5-10% of immobilized microbial agent prepared in the step S1, and continuously mixing to obtain a mixed solution;
S4, pouring the mixed solution obtained in the step S3 into a mold, and taking down the mold after the mixed solution is fixed to obtain the device for treating the acidic iron ore waste liquid;
The immobilized microbial agent is prepared by embedding a microbial agent into calcium alginate microspheres and is used for adsorbing metal ions in acidic wastewater.
2. The preparation method according to claim 1, wherein in the step S1, the preparation of the immobilized microbial agent specifically comprises the following steps:
S11, activating a microbial agent: inoculating microbial inoculum into LB culture medium, shake flask for expansion culture;
s12, mixing a microbial agent and a sodium alginate solution: dissolving a certain amount of sodium alginate in water, and mixing the sodium alginate solution with the microbial agent obtained in the step S11, wherein the final concentration of the sodium alginate solution is 2-3% W/V;
S13, preparing an immobilized microbial agent: slowly dripping the mixed solution of the microbial agent and the sodium alginate solution obtained in the step S12 into a calcium chloride solution with the concentration of 5-10% W/V, standing for 2-4 h, filtering, and washing to obtain the immobilized microbial agent.
3. The method according to claim 2, wherein the concentration of the microbial agent in step S12 is 10 9～1010 cfu/ml.
4. The method of claim 1, wherein a layer of coconut palm fiber mat is laid on the bottom of the mold, and the thickness of the coconut fiber mat is 2-5 cm.
5. The method of claim 1, wherein the microbial agent is selected from one or more of bacillus, pseudomonas and alcaligenes.
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| CN101607809A (en) * | 2009-07-22 | 2009-12-23 | 尤为 | Microorganism concrete brick and preparation method thereof |
| CN109097591A (en) * | 2018-08-02 | 2018-12-28 | 中南大学 | Calcium-alginate-immobilized microbial adsorbent and preparation method thereof and the application in recycling platinum group metal secondary resource |
| CN109880629A (en) * | 2019-02-20 | 2019-06-14 | 雷小鹏 | A kind of preparation method of soil remediation material |
| CN109896563A (en) * | 2019-04-04 | 2019-06-18 | 四川大学 | A kind of high efficiency method for administering the iron-containing acidic waste water that discarded coal mine generates |
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| DE10047709A1 (en) * | 2000-09-25 | 2002-05-02 | Thomas Willuweit | Process for the treatment of water using microorganisms |
| KR101184691B1 (en) * | 2012-04-03 | 2012-09-20 | 석성기업주식회사 | Body containing nature mineral for water purification and its manufacturing method |
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| CN101607809A (en) * | 2009-07-22 | 2009-12-23 | 尤为 | Microorganism concrete brick and preparation method thereof |
| CN109097591A (en) * | 2018-08-02 | 2018-12-28 | 中南大学 | Calcium-alginate-immobilized microbial adsorbent and preparation method thereof and the application in recycling platinum group metal secondary resource |
| CN109880629A (en) * | 2019-02-20 | 2019-06-14 | 雷小鹏 | A kind of preparation method of soil remediation material |
| CN109896563A (en) * | 2019-04-04 | 2019-06-18 | 四川大学 | A kind of high efficiency method for administering the iron-containing acidic waste water that discarded coal mine generates |
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