CN111186892A - Ammonia nitrogen remover containing natural mineral substances and used for surface water treatment and preparation method thereof - Google Patents
Ammonia nitrogen remover containing natural mineral substances and used for surface water treatment and preparation method thereof Download PDFInfo
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- CN111186892A CN111186892A CN201911287995.3A CN201911287995A CN111186892A CN 111186892 A CN111186892 A CN 111186892A CN 201911287995 A CN201911287995 A CN 201911287995A CN 111186892 A CN111186892 A CN 111186892A
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 16
- 239000011707 mineral Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002352 surface water Substances 0.000 title abstract description 12
- 239000000126 substance Substances 0.000 title description 4
- 239000011435 rock Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 48
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002734 clay mineral Substances 0.000 claims abstract description 35
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001603 clinoptilolite Inorganic materials 0.000 claims abstract description 30
- 239000004575 stone Substances 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 24
- 229960000892 attapulgite Drugs 0.000 claims abstract description 24
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 24
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 24
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 24
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- 238000002156 mixing Methods 0.000 claims abstract description 10
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- 239000000843 powder Substances 0.000 claims description 47
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052900 illite Inorganic materials 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
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- 238000006243 chemical reaction Methods 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 28
- 229910021529 ammonia Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000006378 damage Effects 0.000 description 7
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 6
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- 238000012360 testing method Methods 0.000 description 5
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 4
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
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- 239000010457 zeolite Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010010904 Convulsion Diseases 0.000 description 1
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- 108010054147 Hemoglobins Proteins 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000000711 cancerogenic effect Effects 0.000 description 1
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- 150000002823 nitrates Chemical class 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- 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
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides an ammonia nitrogen remover for surface water treatment and a preparation method thereof. The ammonia nitrogen remover is formed by mixing natural minerals such as clinoptilolite, medical stone, clay mineral, kaolinite, calcium sulfate, aluminum sulfate, magnesium oxide, diatomite, modified bentonite, modified volcanic rock, attapulgite and the like, can convert, decompose, flocculate and settle ammonia nitrogen in surface water, and has little influence on the pH value of the water in the reaction process.
Description
Technical Field
The invention relates to the field of surface water treatment, in particular to an ammonia nitrogen remover for surface water treatment and a preparation method thereof.
Background
Nowadays, the living standard of people is continuously improved, economy is rapidly developed, the problem of environmental pollution gradually becomes a main problem which puzzles the physical and mental health of people, water pollution is just the most important aspect, and the important pollution source examination results and surface water monitoring results in recent years show that the phenomenon of exceeding the standard of ammonia nitrogen in water indexes is still serious. The source of ammonia nitrogen is identified, the harm of the ammonia nitrogen is known, and effective treatment measures are taken to become a necessary link for protecting the water environment from being polluted by the ammonia nitrogen.
Ammonia nitrogen (NH 3-N for short) refers to free ammonia (NH3) and ammonium salt (NH) in water4+) The composition ratio of the nitrogen and the nitrogen in the form is determined by the pH value and the temperature of water, when the pH value is higher, the proportion of free ammonia is higher, and vice versa, the proportion of ammonia salt is higher, and the water temperature is opposite. The ring ruin ammonia nitrogen remover is a reagent developed by ring ruin aiming at sewage of various industries for removing ammonia nitrogen in water. The ammonia nitrogen in the water is mainly derived from the decomposition products of nitrogenous organic matters in domestic sewage under the action of microorganisms, coking, synthetic ammonia and other industrial wastewater. The average nitrogen content in domestic sewage can reach 2.5kg-4.5kg per person per year, and the runoff of rainwater and the loss of agricultural chemical fertilizers are also important sources of nitrogen. In addition, ammonia nitrogen is discharged into the environment from factories such as steel, petrifaction, coking, ammonia synthesis, power generation, cement and the like, and industrial wastewater, gas dust containing ammonia and smoke are discharged into the environment; with the continuous improvement of the living standard of people, more and more private cars are provided, and a large number of transportation means such as cars, trucks of various types and the like also discharge a certain amount of ammonia-containing automobile tail gas to the ambient air. Ammonia in these gases dissolves in water, forming ammonia nitrogen.
Aiming at the pollution factors, the harm brought by ammonia nitrogen does not vary in a small amount:
1. influence on human health ammonia can carry out the nitrification process of ammonia in natural environment, namely the biological decomposition and transformation link of organic matters, and the ammoniation converts complex organic matters into ammonia nitrogen. The speed is high, and the nitrification is to oxidize ammonia nitrogen into nitrate and nitrite under the action of nitrosobacteria and nitrifying bacteria and under the aerobic condition; denitrification is the reduction of nitrate and nitrite to nitrogen by denitrifying bacteria under the condition of external supply of organic carbon source. The products of nitrate and nitrite generated by the nitrification of ammonia nitrogen in water body are harmful to drinking water. Drinking water with high concentrations of nitrates and nitrites may cause two health hazards to the human body, and long-term drinking is extremely harmful to the body, namely, the induction of methemoglobinemia and the production of carcinogenic nitrosamines. Nitrate is reduced to nitrite under the action of gastrointestinal bacteria, and the nitrite can be combined with hemoglobin to form methemoglobin, so as to cause oxygen deficiency.
2. Influence on the ecological environment
The main harm of ammonia nitrogen to aquatic organisms is free ammonia. Its toxicity is several tens of times greater than that of the ammonium salt and increases with increasing alkalinity. The toxicity of ammonia nitrogen has a close relationship with the pH value and the water temperature of the pool water, and under the general condition, the higher the pH value and the water temperature is, the stronger the toxicity is, and the harm to fish is similar to that of nitrite. Fish are sensitive to ammonia nitrogen in water and have acute and chronic degrees. The harm of chronic ammonia nitrogen poisoning is as follows: reduced feeding and slower growth; tissue damage, reducing oxygen transport between tissues; both the fish and the shrimp need to carry out ion exchange (sodium, calcium and the like) with water, and the excessive ammonia nitrogen can increase the permeability of the gills and damage the ion exchange function of the gills; the aquatic organisms are in a stress state for a long time, the susceptibility of the animals to diseases is increased, and the growth speed is reduced; reducing reproductive capacity, reducing fecundity, reducing survival rate of eggs, and delaying spawning reproduction. The acute ammonia nitrogen poisoning hazard is as follows: the aquatic organisms appear as a hyper, loss of balance in the water, convulsion, and even death in severe cases.
In view of the above, the present inventors have developed a natural mineral-containing ammonia nitrogen remover and a preparation method thereof.
Disclosure of Invention
The invention provides a powdery ammonia nitrogen remover formed by mixing natural minerals, which comprises the following components in parts by weight: 50-60 parts of clinoptilolite, 5-10 parts of medical stone, 5-10 parts of high CEC clay mineral, 20-30 parts of aluminum sulfate, 10-20 parts of calcium sulfate, 1-10 parts of magnesium oxide, 15-20 parts of diatomite, 20-25 parts of modified bentonite, 10-15 parts of modified volcanic rock and 5-10 parts of attapulgite.
As an embodiment of the invention, the raw materials are prepared from the following components in parts by weight: 55 parts of clinoptilolite, 10 parts of medical stone, 8 parts of high CEC clay mineral, 25 parts of aluminum sulfate, 20 parts of calcium sulfate, 5 parts of magnesium oxide, 15 parts of diatomite, 25 parts of modified bentonite, 10 parts of modified volcanic rock and 10 parts of attapulgite.
As an embodiment of the invention, the raw materials are prepared from the following components in parts by weight: 60 parts of clinoptilolite, 5 parts of medical stone, 10 parts of high CEC clay mineral, 30 parts of aluminum sulfate, 15 parts of calcium sulfate, 10 parts of magnesium oxide, 15 parts of diatomite, 20 parts of modified bentonite, 15 parts of modified volcanic rock and 8 parts of attapulgite.
As an embodiment of the invention, the raw materials are prepared from the following components in parts by weight: 50 parts of clinoptilolite, 8 parts of medical stone, 8 parts of high CEC clay mineral, 25 parts of aluminum sulfate, 10 parts of calcium sulfate, 6 parts of magnesium oxide, 12 parts of diatomite, 23 parts of modified bentonite, 12 parts of modified volcanic rock and 5 parts of attapulgite.
In one embodiment of the present invention, the high CEC clay mineral is at least one of montmorillonite, illite, and sepiolite.
In one embodiment of the present invention, the modified bentonite is prepared by the following steps:
(1) putting bentonite into a beaker, adding a dilute sulfuric acid (with the mass concentration of 60%) solution, and stirring while adding until the solution is uniformly stirred;
(2) stirring the solution obtained in the step (1) for 30min and then standing for 2 h;
(3) placing the solution after standing in a low-speed centrifuge for centrifugal separation under the condition of 5000r/min, and taking out the residual solid;
(4) washing the solid obtained in the step (3) to be neutral by using distilled water;
(5) putting the product obtained in the step (4) into an oven, drying the product at 105 ℃ and keeping the weight constant to obtain a modified bentonite solid;
(6) and grinding the solid modified bentonite into powder, and sieving the powder by a 100-mesh sieve to obtain the modified bentonite.
As an embodiment of the present invention, the preparation method of the modified volcanic rock is as follows:
s01, grinding the volcanic rock particles to 100-200 meshes;
s02, washing the volcanic rock powder with deionized water for multiple times and then airing;
s03 selecting 100g of air-dried volcanic rock powder, placing the powder in a 1000mL beaker, and adding MnCl with the concentration of 0.8moL/L2·4H2Soaking in O solution for 30min, wherein the solid-liquid ratio is 1: 8, taking out and airing for later use after soaking;
s03 placing the dried volcanic rock powder as in S03 in a 1000mL beaker, adding 1.25% (g/L) KMnO4Soaking the solution for 30min, wherein the solid-liquid ratio is 1: 8, taking out and airing for later use after soaking;
s05, washing the air-dried volcanic rock powder in the S04 by deionized water, and repeating the modification operations of S03 and S04 for 6 times;
and S06, obtaining the modified volcanic rock after the operation is finished.
The second aspect of the invention provides a preparation method of the ammonia nitrogen remover, which comprises the following steps:
step 1: preparing raw materials according to the following components: clinoptilolite, medical stone, clay mineral, kaolinite, calcium sulfate, aluminum sulfate, magnesium oxide, diatomite, modified bentonite, modified volcanic rock and attapulgite;
step 2: respectively crushing the raw materials of clinoptilolite, medical stone and high CEC clay mineral obtained in the step 1, and sieving the crushed raw materials by a 300-400-mesh sieve to obtain corresponding powder for later use;
and step 3: mixing clinoptilolite powder, medical stone powder and high CEC clay mineral powder obtained in the step (2), heating and secondarily crushing the mixed powder at 150 ℃, continuing for 20-30min, and cooling for later use;
and 4, step 4: putting the material uniformly stirred and cooled in the step 3, aluminum sulfate, calcium sulfate, magnesium oxide, diatomite, modified bentonite, modified volcanic rock and attapulgite into a stirrer, and uniformly stirring;
and 5: and (4) continuously crushing the material prepared in the step (4), and sieving the crushed material by a 300-400-mesh sieve to obtain the ammonia nitrogen remover.
Has the advantages that:
1. the invention relates to an ammonia nitrogen remover for treating surface water and a preparation method thereof. The ammonia nitrogen remover is formed by mixing natural minerals such as clinoptilolite, medical stone, clay mineral, kaolinite, calcium sulfate, aluminum sulfate, magnesium oxide, diatomite, modified bentonite, modified volcanic rock, attapulgite and the like, can convert, decompose, flocculate and settle ammonia nitrogen in surface water, and has little influence on the pH value of the water in the reaction process.
2. The method takes the natural mineral substances as main components, does not need large-scale construction equipment, and can remove the ammonia nitrogen in the surface water body only by simply spraying and stirring to promote the ammonia nitrogen remover to be fully mixed with the water body.
3. The invention has the beneficial effects that: the invention has no toxicity and harm, high reaction speed and good purification effect, and the product is stable and does not dissolve back into the water body in the process of removing ammonia nitrogen
Drawings
FIG. 1: test results for example 1.
FIG. 2: and (5) photo before river regulation.
FIG. 3: photographs of the river after 2 weeks of treatment.
FIG. 4: and (5) photo of the river course after 1 month of treatment.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
The invention provides a powdery ammonia nitrogen remover formed by mixing natural minerals, which comprises the following components in parts by weight: 50-60 parts of clinoptilolite, 5-10 parts of medical stone, 5-10 parts of high CEC clay mineral, 20-30 parts of aluminum sulfate, 10-20 parts of calcium sulfate, 1-10 parts of magnesium oxide, 15-20 parts of diatomite, 20-25 parts of modified bentonite, 10-15 parts of modified volcanic rock and 5-10 parts of attapulgite.
As an embodiment of the invention, the raw materials are prepared from the following components in parts by weight: 55 parts of clinoptilolite, 10 parts of medical stone, 8 parts of high CEC clay mineral, 25 parts of aluminum sulfate, 20 parts of calcium sulfate, 5 parts of magnesium oxide, 15 parts of diatomite, 25 parts of modified bentonite, 10 parts of modified volcanic rock and 10 parts of attapulgite.
As an embodiment of the invention, the raw materials are prepared from the following components in parts by weight: 60 parts of clinoptilolite, 5 parts of medical stone, 10 parts of high CEC clay mineral, 30 parts of aluminum sulfate, 15 parts of calcium sulfate, 10 parts of magnesium oxide, 15 parts of diatomite, 20 parts of modified bentonite, 15 parts of modified volcanic rock and 8 parts of attapulgite.
As an embodiment of the invention, the raw materials are prepared from the following components in parts by weight: 50 parts of clinoptilolite, 8 parts of medical stone, 8 parts of high CEC clay mineral, 25 parts of aluminum sulfate, 10 parts of calcium sulfate, 6 parts of magnesium oxide, 12 parts of diatomite, 23 parts of modified bentonite, 12 parts of modified volcanic rock and 5 parts of attapulgite.
In one embodiment of the present invention, the high CEC clay mineral is at least one of montmorillonite, illite, and sepiolite.
In one embodiment of the present invention, the modified bentonite is prepared by the following steps:
(1) putting bentonite into a beaker, adding a dilute sulfuric acid solution, and stirring while adding until the mixture is uniformly stirred;
(2) stirring the solution obtained in the step (1) for 30min and then standing for 2 h;
(3) placing the solution after standing in a low-speed centrifuge for centrifugal separation under the condition of 5000r/min, and taking out the residual solid;
(4) washing the solid obtained in the step (3) to be neutral by using distilled water;
(5) putting the product obtained in the step (4) into an oven, drying the product at 105 ℃ and keeping the weight constant to obtain a modified bentonite solid;
(6) and grinding the solid modified bentonite into powder, and sieving the powder by a 100-mesh sieve to obtain the modified bentonite.
As an embodiment of the present invention, the preparation method of the modified volcanic rock is as follows:
s01, grinding the volcanic rock particles to 100-200 meshes;
s02, washing the volcanic rock powder with deionized water for multiple times and then airing;
s03 selecting 100g to dryThe subsequent volcanic rock powder was placed in a 1000mL beaker and added with MnCl at a concentration of 0.8moL/L2·4H2Soaking in O solution for 30min, wherein the solid-liquid ratio is 1: 8, taking out and airing for later use after soaking;
s03 placing the dried volcanic rock powder as in S03 in a 1000mL beaker, adding 1.25% (g/L) KMnO4Soaking the solution for 30min, wherein the solid-liquid ratio is 1: 8, taking out and airing for later use after soaking;
s05, washing the air-dried volcanic rock powder in the S04 by deionized water, and repeating the modification operations of S03 and S04 for 6 times;
and S06, obtaining the modified volcanic rock after the operation is finished.
The second aspect of the invention provides a preparation method of the ammonia nitrogen remover, which comprises the following steps:
step 1: preparing raw materials according to the following components: clinoptilolite, medical stone, clay mineral, kaolinite, calcium sulfate, aluminum sulfate, magnesium oxide, diatomite, modified bentonite, modified volcanic rock and attapulgite;
step 2: respectively crushing the raw materials of clinoptilolite, medical stone and high CEC clay mineral obtained in the step 1, and sieving the crushed raw materials by a 300-400-mesh sieve to obtain corresponding powder for later use;
and step 3: mixing clinoptilolite powder, medical stone powder and high CEC clay mineral powder obtained in the step (2), heating and secondarily crushing the mixed powder at 150 ℃, continuing for 20-30min, and cooling for later use;
and 4, step 4: putting the material uniformly stirred and cooled in the step 3, aluminum sulfate, calcium sulfate, magnesium oxide, diatomite, modified bentonite, modified volcanic rock and attapulgite into a stirrer, and uniformly stirring;
and 5: and (4) continuously crushing the material prepared in the step (4), and sieving the crushed material by a 300-400-mesh sieve to obtain the ammonia nitrogen remover.
The frequent ammonia nitrogen pollution phenomena in reservoirs, rivers, natural lakes and the like are mainly caused by free ammonia (NH3) and ammonium salt (NH4 +). Ammonia nitrogen mainly affects the enzymatic hydrolysis reaction and membrane stability of aquatic organisms, and can cause massive death of the aquatic organisms. Clinoptilolite and high CEC clay mineral that this ammonia nitrogen remover contains can adsorb a large amount of ammonia nitrogen, combines together with the ammonia nitrogen and carries out ion exchange. The water quality improver coagulates the dirt particles in a form of wrapping the dirt particles, and produces a purifying effect.
The clinoptilolite adopted by the invention is natural zeolite with abundant domestic reserves. The zeolite has a developed pore and an ion exchange capacity of 200meq/100g or more. These clinoptilolites are in (Si, Al) O4In the tetrahedron, Si4+Partially with Al3+Instead, the balance between the negative (-) and positive (+) charges is lost, causing it to structurally become negative (-) state. This replaces the negatively charged switching states with positive ions and the surface is exchanged with positive (+) states. The "positive ions" of the surface can be easily exchanged with other ions.
The rock-making minerals adopted by the invention are important minerals which are not harmful to water ecology, such as quartz, muscovite, feldspar and the like. Increasing the specific gravity of the aggregate and inducing precipitation, particularly of muscovite, is more sterile and acts to prevent the propagation of algae in the precipitated sediment. The quartz, muscovite and feldspar may be used individually or in combination of two or more. The best combination is that quartz, muscovite and feldspar are mixed and used in a weight ratio of 5-8:3-7:1-5, and the effect is better because the formation and precipitation speed of aggregates can be effectively adjusted.
The high CEC clay mineral adopted by the invention is a mineral with high temperature recovery capability (CEC) in clay minerals, and more than 1 of vermiculite (vermiculite), montmorillonite (montmorillonite) and illite (illite) are preferably selected. These clay minerals also have a net bacterial action, preventing the algae from multiplying repeatedly in the settled sediment.
The invention adopts medical stone, has adsorptivity, dissolubility, regulation property, bioactivity and mineralization property, is a compound mineral or medicinal rock which is nontoxic and harmless to organisms and has certain bioactivity, can effectively adsorb heavy metals and reduce the biotoxicity of water.
The environment-friendly active natural mineral ammonia nitrogen remover containing the elements is processed into powder. Specifically, the preparation method comprises sieving various components, pulverizing powder with a particle size of less than 300 meshes, mixing the pulverized powder, heating the mixed powder to 150 deg.C with a heating device similar to a Raymond mill, and heating for 20-30 min.
Therefore, the invention is processed into powder, the ammonia nitrogen remover is directly sprayed in polluted water areas to condense and enrich pollutants, the water quality is improved through precipitation and decomposition, and the invention has the characteristics of taking natural minerals as main materials and not damaging the living environment of aquatic organisms.
The ammonia nitrogen remover is suitable for water bloom and red tide in reservoirs, rivers, natural lakes and underground water and water sources polluted by various pollutants.
To aid in understanding this invention, the following examples illustrate the importance of the invention to the industry. It is therefore to be understood that such changes and modifications are encompassed within the appended claims.
Experimental example 1: bench test for polluted water
The raw materials are selected to be composed of the following components in parts by weight: 55 parts of clinoptilolite, 10 parts of medical stone, 8 parts of high CEC clay mineral, 25 parts of aluminum sulfate, 20 parts of calcium sulfate, 5 parts of magnesium oxide, 15 parts of diatomite, 25 parts of modified bentonite, 10 parts of modified volcanic rock and 10 parts of attapulgite.
The preparation method of the modified bentonite comprises the following steps:
(1) putting bentonite into a beaker, adding a dilute sulfuric acid solution, and stirring while adding until the mixture is uniformly stirred;
(2) stirring the solution obtained in the step (1) for 30min and then standing for 2 h;
(3) placing the solution after standing in a low-speed centrifuge for centrifugal separation under the condition of 5000r/min, and taking out the residual solid;
(4) washing the solid obtained in the step (3) to be neutral by using distilled water;
(5) putting the product obtained in the step (4) into an oven, drying the product at 105 ℃ and keeping the weight constant to obtain a modified bentonite solid;
(6) and grinding the solid modified bentonite into powder, and sieving the powder by a 100-mesh sieve to obtain the modified bentonite.
The preparation method of the modified volcanic rock comprises the following steps:
s01, grinding the volcanic rock particles to 100-200 meshes;
s02, washing the volcanic rock powder with deionized water for multiple times and then airing;
s03 selecting 100g of air-dried volcanic rock powder, placing the powder in a 1000mL beaker, and adding MnCl with the concentration of 0.8moL/L2·4H2Soaking in O solution for 30min, wherein the solid-liquid ratio is 1: 8, taking out and airing for later use after soaking;
s03 placing the dried volcanic rock powder as in S03 in a 1000mL beaker, adding 1.25% (g/L) KMnO4Soaking the solution for 30min, wherein the solid-liquid ratio is 1: 8, taking out and airing for later use after soaking;
s05, washing the air-dried volcanic rock powder in the S04 by deionized water, and repeating the modification operations of S03 and S04 for 6 times;
and S06, obtaining the modified volcanic rock after the operation is finished.
The second aspect of this embodiment provides a preparation method of the ammonia nitrogen remover, including the following steps:
step 1: preparing raw materials according to the following components: clinoptilolite, medical stone, clay mineral, kaolinite, calcium sulfate, aluminum sulfate, magnesium oxide, diatomite, modified bentonite, modified volcanic rock and attapulgite;
step 2: respectively crushing the raw materials of clinoptilolite, medical stone and high CEC clay mineral obtained in the step 1, and sieving the crushed raw materials by a 300-400-mesh sieve to obtain corresponding powder for later use;
and step 3: mixing clinoptilolite powder, medical stone powder and high CEC clay mineral powder obtained in the step (2), heating and secondarily crushing the mixed powder at 150 ℃, continuing for 20-30min, and cooling for later use;
and 4, step 4: putting the material uniformly stirred and cooled in the step 3, aluminum sulfate, calcium sulfate, magnesium oxide, diatomite, modified bentonite, modified volcanic rock and attapulgite into a stirrer, and uniformly stirring;
and 5: and (4) continuously crushing the material prepared in the step (4), and sieving the crushed material by a 300-400-mesh sieve to obtain the ammonia nitrogen remover.
Taking out the water sample in the beaker 2, adding no ammonia nitrogen remover on the left side, and adding an ammonia nitrogen remover on the right side, wherein the test result is shown in figure 1; and water quality data was measured after the reaction.
As can be seen from FIG. 1, the water body to which the ammonia nitrogen remover is added on the right side is transparent and has reduced turbidity.
| Detecting an object | pH | NH3-H(mg/L) |
| Left side of | 7.3 | 5.2 |
| Right side | 7.5 | 1.3 |
As shown above, the color can be reduced by adding the ammonia nitrogen remover, so that the transparency is improved obviously. Meanwhile, the pH value is not changed greatly, and the ammonia nitrogen pollutants are effectively removed.
Experimental example 2: surface water treatment
The raw materials are selected to be composed of the following components in parts by weight: 60 parts of clinoptilolite, 5 parts of medical stone, 10 parts of high CEC clay mineral, 30 parts of aluminum sulfate, 15 parts of calcium sulfate, 10 parts of magnesium oxide, 15 parts of diatomite, 20 parts of modified bentonite, 15 parts of modified volcanic rock and 8 parts of attapulgite.
The experimental subject is located in New zone I of XiancanAnd (6) treating the river channel. The river course receives domestic sewage for a long time, the stock pollution is serious, and the problem of ammonia nitrogen pollution is prominent. The effective water storage capacity of the experimental object is about 1000m3Adding 800ppm of ammonia nitrogen remover accounting for 8 tons; the test results are shown in FIGS. 2 to 4.
Fig. 3 and 4 are graphs showing the change of the river channel after the ammonia nitrogen agent is added. As shown in fig. 2, before the ammonia nitrogen remover is added, the visibility of water is 0, and the water body is dark green. After the water quality is improved, the water body is transparent, and the color of the water is gradually lightened along with the time. After 2 weeks the water became clear and bottomed. In the river regulation experiment, after the ammonia nitrogen remover is added for 1 month (figure 4) and compared with the ammonia nitrogen remover added for 1 week (figure 3), the water body is still bright without dyeing phenomenon, the bottom mud can be clearly seen, and the visibility of the water body is very high. In consideration of natural factors, the ammonia nitrogen remover containing natural active mineral substances can play a good long-term effect.
Industrial applicability of the invention
The method can be used for treating ammonia nitrogen pollution of various surface water, does not influence natural ecology, and is beneficial to the development of environmental protection industry.
Claims (8)
1. The powdery ammonia nitrogen remover formed by mixing natural minerals is characterized by comprising the following components in parts by weight: 50-60 parts of clinoptilolite, 5-10 parts of medical stone, 5-10 parts of high CEC clay mineral, 20-30 parts of aluminum sulfate, 10-20 parts of calcium sulfate, 1-10 parts of magnesium oxide, 15-20 parts of diatomite, 20-25 parts of modified bentonite, 10-15 parts of modified volcanic rock and 5-10 parts of attapulgite.
2. The powdery ammonia nitrogen remover according to claim 1, characterized in that: the raw materials comprise the following components in parts by weight: 55 parts of clinoptilolite, 10 parts of medical stone, 8 parts of high CEC clay mineral, 25 parts of aluminum sulfate, 20 parts of calcium sulfate, 5 parts of magnesium oxide, 15 parts of diatomite, 25 parts of modified bentonite, 10 parts of modified volcanic rock and 10 parts of attapulgite.
3. The powdery ammonia nitrogen remover according to claim 1, characterized in that: the raw materials comprise the following components in parts by weight: 60 parts of clinoptilolite, 5 parts of medical stone, 10 parts of high CEC clay mineral, 30 parts of aluminum sulfate, 15 parts of calcium sulfate, 10 parts of magnesium oxide, 15 parts of diatomite, 20 parts of modified bentonite, 15 parts of modified volcanic rock and 8 parts of attapulgite.
4. The ammonia nitrogen remover according to claim 1, characterized in that: the raw materials comprise the following components in parts by weight: 50 parts of clinoptilolite, 8 parts of medical stone, 8 parts of high CEC clay mineral, 25 parts of aluminum sulfate, 10 parts of calcium sulfate, 6 parts of magnesium oxide, 12 parts of diatomite, 23 parts of modified bentonite, 12 parts of modified volcanic rock and 5 parts of attapulgite.
5. The powdery ammonia nitrogen remover according to claim 1, characterized in that: the high CEC clay mineral is at least one of montmorillonite, illite and sepiolite.
6. The powdery ammonia nitrogen remover according to claim 1, characterized in that: the preparation method of the modified bentonite comprises the following steps:
(1) putting bentonite into a beaker, adding a dilute sulfuric acid solution, and stirring while adding until the mixture is uniformly stirred;
(2) stirring the solution obtained in the step (1) for 30min and then standing for 2 h;
(3) placing the solution after standing in a low-speed centrifuge for centrifugal separation under the condition of 5000r/min, and taking out the residual solid;
(4) washing the solid obtained in the step (3) to be neutral by using distilled water;
(5) putting the product obtained in the step (4) into an oven, drying the product at 105 ℃ and keeping the weight constant to obtain a modified bentonite solid;
(6) and grinding the solid modified bentonite into powder, and sieving the powder by a 100-mesh sieve to obtain the modified bentonite.
7. The powdery ammonia nitrogen remover according to claim 1, wherein the modified volcanic rock is prepared by the following steps:
s01, grinding the volcanic rock particles to 100-200 meshes;
s02, washing the volcanic rock powder with deionized water for multiple times and then airing;
s03 selecting 100g of air-dried volcanic rock powder, placing the powder in a 1000mL beaker, and adding MnCl with the concentration of 0.8moL/L2·4H2Soaking in O solution for 30min, wherein the solid-liquid ratio is 1: 8, taking out and airing for later use after soaking;
s03 the volcanic rock powder dried in the S03 was placed in a 1000mL beaker and treated with 1.25% KMnO4Soaking the solution for 30min, wherein the solid-liquid ratio is 1: 8, taking out and airing for later use after soaking;
s05, washing the air-dried volcanic rock powder in the S04 by deionized water, and repeating the modification operations of S03 and S04 for 6 times;
and S06, obtaining the modified volcanic rock after the operation is finished.
8. The method for preparing the powdery ammonia nitrogen remover according to claim 1, characterized in that: the method comprises the following steps:
step 1: preparing raw materials according to the following components: clinoptilolite, medical stone, clay mineral, kaolinite, calcium sulfate, aluminum sulfate, magnesium oxide, diatomite, modified bentonite, modified volcanic rock and attapulgite;
step 2: respectively crushing the raw materials of clinoptilolite, medical stone and high CEC clay mineral obtained in the step 1, and sieving the crushed raw materials by a 300-400-mesh sieve to obtain corresponding powder for later use;
and step 3: mixing clinoptilolite powder, medical stone powder and high CEC clay mineral powder obtained in the step (2), heating and secondarily crushing the mixed powder at 150 ℃, continuing for 20-30min, and cooling for later use;
and 4, step 4: putting the material uniformly stirred and cooled in the step 3, aluminum sulfate, calcium sulfate, magnesium oxide, diatomite, modified bentonite, modified volcanic rock and attapulgite into a stirrer, and uniformly stirring;
and 5: and (4) continuously crushing the material prepared in the step (4), and sieving the crushed material by a 300-400-mesh sieve to obtain the ammonia nitrogen remover.
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| CN111701578A (en) * | 2020-06-30 | 2020-09-25 | 广西夏阳环保科技有限公司 | Adsorbent for sewage treatment and preparation method thereof |
| CN112723432A (en) * | 2020-11-17 | 2021-04-30 | 杭州筑净环境科技有限公司 | Preparation method of ammonia removal material |
| CN115057506A (en) * | 2021-07-05 | 2022-09-16 | 浙江尚源环境科技有限公司 | Ammonia nitrogen remover based on natural minerals and preparation method thereof |
| CN115259527A (en) * | 2022-06-25 | 2022-11-01 | 广西七彩环境科技有限公司 | Water quality improving degradation agent and method for improving water quality by degradation agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111701578A (en) * | 2020-06-30 | 2020-09-25 | 广西夏阳环保科技有限公司 | Adsorbent for sewage treatment and preparation method thereof |
| CN112723432A (en) * | 2020-11-17 | 2021-04-30 | 杭州筑净环境科技有限公司 | Preparation method of ammonia removal material |
| CN115057506A (en) * | 2021-07-05 | 2022-09-16 | 浙江尚源环境科技有限公司 | Ammonia nitrogen remover based on natural minerals and preparation method thereof |
| CN115259527A (en) * | 2022-06-25 | 2022-11-01 | 广西七彩环境科技有限公司 | Water quality improving degradation agent and method for improving water quality by degradation agent |
| CN116273185A (en) * | 2023-03-01 | 2023-06-23 | 大连理工大学 | A kind of immobilized bifunctional catalyst and its method for preparing cyclic carbonate in outer loop reaction process |
| CN116273185B (en) * | 2023-03-01 | 2024-04-19 | 大连理工大学 | A kind of immobilized bifunctional catalyst and method for preparing cyclic carbonate in outer loop reaction process |
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