CN1049876C - Water purification methed using rice hulls - Google Patents
Water purification methed using rice hulls Download PDFInfo
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- CN1049876C CN1049876C CN92113095A CN92113095A CN1049876C CN 1049876 C CN1049876 C CN 1049876C CN 92113095 A CN92113095 A CN 92113095A CN 92113095 A CN92113095 A CN 92113095A CN 1049876 C CN1049876 C CN 1049876C
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- 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
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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Abstract
To prepare an active chaff having increased surface area and adsorption ability from chaff and to utilize the active chaff for water cleaning treatment by adding an inorg. acid and/or an alkali to carbonized chaff or silver white color chaff, heating it, thereafter filtering and drying. An aq. soln. of an inorg. acid (such as hydrochloric acid) and/or an alkali (such as sodium hydroxide) are (or) are added to carbonized chaff or silver white color chaff, and the added substance is heated, thereafter filtered and dried. For example, a 10% aq. soln. of hydrochloric acid is added to the carbonized chaff, which is heated under reflux, and thereafter cooled to the normal temp. The surface area of the active carbonized chaff is 114 m<2> /g, which is prepared by washing the content with water, neutralizing with an aq. NaOH soln., thereafter further washing with water, filtering and drying. As a result, the active chaff having increased surface area and adsorption ability can be prepared from chaff. Various toxic contaminating substances dissolved in water can be removed by using the active chaff.
Description
The present invention relates to water purification commonly, particularly preparation has the method for active rice husk of good surface adsorptive power, utilizes their good adsorptive poweies to purify waste water can to reach the hazardous substance of removing various polluted water or from the purpose of the pollutent of polluted water.
Along with the excessive increase and the industrial expansion of population, increasing for the quantity discharged of sanitary sewage, agricultural and livestock industry waste water, trade effluent; The water quality of water, particularly earth surface is subjected to more and more faster pollution and deterioration.Therefore, in order simply and economically to remove pollutent from polluted water, especially various toxic organic compounds comprise haloform, heavy metal cation, sterilant, washing composition etc., and people have worked out various types of method for purifying water and equipment and have been generalized to the whole world.
For example, according to reports, generally organic reaction produces a kind of toxic organic compound haloform (hereinafter referred is " THMs ") in the water by being dissolved on halogen atom.Now proposed to produce for restriction various types of methods of purifying waste water of THMs, they are 1) in the water purification process, organism in the removal polluted water or the precursor of THMs, this has reduced organic concentration in the water; 2) replace chlorine and use special sterilizing agent such as hypochlorous anhydride and ozone, they do not produce THMs after purifying waste water finishing.If use dioxide peroxide or the such strong oxidizer of ozone in the water purification process, the organism that is dissolved in so in the water will be oxidized, this respect, and the concentration of THMs precursor is reduced basically.In addition,, also proposed another kind of method, promptly utilized the absorption of vegetable active carbon, concentrate and filtered out the organism in the water in order to reduce the concentration of THMs precursor.But above-mentioned these known methods are that what type all exists some problems, because oxygenant and vegetable active carbon are quite expensive, particularly can produce deleterious ozone residue inevitably with ozonize sewage the time; Like this, just must remove ozone residue in the water by additional process, the current of promptly finished water or preliminary cleaning through activated carbon layer with the residue ozone in the removal water.
Disclose a kind of method of production lightweight silicate aggregate in the U.S. Pat 4 488 908, carbon content is pulverized after the heat treated in water less than 4% rice hull ash and alkali metal hydroxide, boric acid etc. obtained.This aggregate can be used as insulation and fire-retardant material etc., as the adsorptive power of this product shortage of silicate aggregate to all contaminations.
Therefore, an object of the present invention is to provide the method that preparation has the active rice husk of good surface adsorptive power; In the process of purifying waste water, use to have the active rice husk that high surface is a high absorption capacity, can effectively and economically remove pollutent in the above-mentioned polluted water such as various toxic organic compound, heavy metal cation, sterilant, washing composition.
One aspect of the present invention provides the method for the active rice husk of preparation high surface area and high surface adsorption ability, this method comprises the following steps: in the rice husk of carbonating or argenteous rice husk to add inorganic acid aqueous solution or alkali aqueous solution and obtains product, product is handled in thermal backflow, be cooled to room temperature, washing is filtered and drying.
In one embodiment of the invention, inorganic acid aqueous solution is hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or fluorspar acid solution, sodium hydroxide or potassium hydroxide solution in the alkali aqueous solution.
Recently, it is reported existing annual about 5,470, the 000 ton rice yield of Korea, like this, from the mill processes of paddy, certainly lead to about 1,300,000 ton rice by product---rice husk.Generally, most of rice husk is become the rice husk of carbonating by carbonating, and it can make metal keep liquid state under the ironmaking temperature.The intrinsic composition of general rice husk is the 20-30% of silicate, the about 30-50% of carbon and very a spot of potassium, calcium, magnesium, aluminium, iron, manganese etc.Except the rice husk of above-mentioned carbonating, also can by complete oxidation wherein carbon and prepare silvery white rice husk by former rice husk, they almost are made up of silicate entirely for this reason.
According to method of the present invention, two kinds of above-mentioned rice husks are carbonating rice husk and silvery white rice husk, in various aqueous acids (inorganic acid solution example hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and fluorspar acid solution) or alkali aqueous solution such as hydrogen sodium hydride and potassium hydroxide solution, heat, filter then, clean, dry to improve their total surface area, come down to have strengthened adsorptive power.For the convenience of description of the invention, the high surface rice husk with the Chemical Pretreatment preparation is called activated carbon acidifying rice husk below, it is made by the rice husk of carbonating at this; If make from silvery white rice husk, being called so is active silvery white rice husk.Prepare various types of active rice husks and analyze, in table 1, provide its result to measure their composition.Utilize chemical treatment, promptly bronsted lowry acids and bases bronsted lowry is handled, and makes the product rice husk have required surfactivity, and the average surface area that it is reported every kind of carbonating rice husk is in fact from handling preceding about 103m
2/ g brings up to the about 114m after the acid treatment
2/ g, the about 400-450m after the alkaline purification
2/ g.On the other hand, the average surface area that it is reported every kind of silvery white rice husk has the about 4.6m of raising before handle slightly
2/ g arrives the about 6-8m after acid or the alkaline purification
2/ g (seeing Table 2).
The acid or the alkaline purification result that it is believed that two kinds of rice husks show, have removed the metallic cation of water-soluble silicate and minute quantity from rice husk, and on the rice husk outside surface, newly formed a large amount of micropores, like this, no matter be the rice husk of what type, their total surface area all obtains increasing.In addition, show according to the surface analysis result to the product rice husk shown in the table 2 that activated carbon acidifying rice husk not only has micropore but also also has macropore, especially, the surface-area of this class rice husk is 180-190m
2/ g, the micro-pore diameter that accounts for these rice husk total surface areas 40-50% is not less than 20 respectively.When the diameter in hole is not less than 20 , show that the adsorptive power of these rice husks is better less than the adsorptive power of 20 rice husks than the aperture; Therefore, for the final adsorptive power of determining active rice husk, diameter is not less than the surface-area in 20 holes and the ratio of rice husk total surface area is an important parameters.As a comparison, according to the final activated carbon of raw material, one, the surface-area of common vegetable active carbon is 58-210m
2/ g, the diameter that accounts for activated carbon total surface area 6-30% micropore is at least 20 .
Table 1 (proximate analysiss of various active rice husks)
| Sample | Component (wt%) | |
| C H N Si | ||
| The carbonating rice husk | Orthocarbonic acid rice husk activated carbon acidifying rice husk (A) aActivated carbon acidifying rice husk (AB) bActivated carbon acidifying rice husk (BA) cActivated carbon acidifying rice husk (HF) cActivated carbon acidifying rice husk (B, 1h) eActivated carbon acidifying rice husk (B, 2h) eActivated carbon acidifying rice husk (B, 3h) eActivated carbon acidifying rice husk (B, 4h) eActivated carbon acidifying rice husk (B, 5h) e | 43.8 1.31 0.43 20.2 24.2 0.70 0.48 29.6 71.5 1.76 0.74 1.47 76.1 1.84 0.84 1.0 74.9 - - 0.14 69.8 2.13 0.81 1.44 79.8 2.18 0.76 0.86 78.2 2.35 0.75 0.86 68.3 2.57 0.79 0.86 78.9 2.11 0.73 1.14 |
A: prepare these rice husks and be by the thermal backflow 2 hours in the 10%HCl aqueous solution of carbonating rice husk, filter, clean and dry.
B: prepare these rice husks and be by the thermal backflow 2 hours in the 10%HCl aqueous solution earlier of carbonating rice husk, filter, clean; And then the thermal backflow in the 10%NaOH aqueous solution of this product, filtration, cleaning and dry.
C: prepare these rice husks and be earlier the thermal backflow 2 hours in the 10%NaOH aqueous solution of carbonating rice husk, filter, clean; And then the thermal backflow 2 hours in 10% aqueous solution of this product, filter, clean and dry.
D: preparing these rice husks is the thermal backflow in the HF aqueous solution of carbonating rice husk, filters, and cleans and drying.
E: prepare these rice husks and be the thermal backflow 1,2,3,4 or 5 hours in the 10%NaOH aqueous solution of carbonating rice husk, filter, clean and dry.
Table 2 (surface analyses of various adsorptives)
| Adsorptive | Bore dia (A) | The mean diameter in hole (A) | Pore volume (cc/g) | Total pore volume (cc/g) | Hole area (m 2/g） | Total hole area (m 2/g) | BET surface-area (m 2/g) | Largest hole volume (cc/g) |
| A grain carbon is lived | 563.6-476.7 476.7-387.8 387.8-322.4 322.4-262.3 262.3-209.6 209.6-167.8 167.8-137.8 137.8-108.7 108.7-88.5 88.5-72.0 72.0-59.1 59.1-47.5 47.5-38.2 38.2-32.3 32.3-24.7 24.7-21.0 | 511.7 421.9 347.8 234.9 228.8 182.8 148.3 118.7 95.5 77.7 63.5 51.2 41.0 34.1 26.7 21.9 | 0.0069 0.0073 0.0071 0.0071 0.0089 0.097 0.0084 0.0093 0.0083 0.0080 0.0093 0.0141 0.0186 0.0161 0.0460 0.0244 | 0.0069 0.0142 0.0212 0.0284 0.0373 0.0470 0.0334 0.0647 0.0730 0.0310 0.0903 0.1045 0.1231 0.1395 0.1855 0.2099 | 0.537 0.693 0.811 1.003 1.559 2.127 2.258 3.138 3.464 4.126 5.872 11.074 18.160 19.216 68.795 44.601 | 0.537 1.230 2.011 3.044 4.603 6.230 8.988 12.126 15.590 19.716 25.587 36.661 54.821 74.038 142.833 187.434 | 1028.3 | 0.5983 |
| ) tree coconut palm (carbon bioplasm height | 572.9-471.0 471.0-388.2 388.2-328.7 328.7-252.8 252.8-208.0 208.0-171.6 171.6-138.6 138.6-113.3 113.3-89.5 89.5-72.3 72.3-60.5 60.5-48.1 48.1-39.7 39.7-32.1 32.1-24.5 24.5-20.4 | 510.2 420.3 352.4 279.5 224.7 185.2 150.3 122.3 97.6 78.1 64.6 52.1 42.3 34.4 26.4 21.4 | 0.0004 0.003 0.0003 0.0003 0.0009 0.0008 0.0014 0.0013 0.0023 0.0023 0.0020 0.0030 0.0031 0.0054 0.0128 0.0122 | 0.0004 0.0008 0.0011 0.0019 0.0023 0.0036 0.0050 0.0067 0.0090 0.0114 0.0133 0.0164 0.0194 0.0248 0.0376 0.0198 | 0.036 0.033 0.036 0.108 0.157 0.182 0.367 0.575 0.944 1.193 1.215 2.333 2.894 6.295 19.318 22.812 | 0.036 0.069 0.105 0.213 0.371 0.552 0.919 1.495 2.438 3.621 4.836 7.169 10.063 16.358 35.676 58.488 | 884.3 | 0.4149 |
| ) brown (the carbon bioplasm height of coal | 585.7-467.4 467.4-398.2 398.2-313.1 313.1-263.7 263.7-219.1 219.1-173.5 173.5-142.5 142.5-113.2 113.2-92.0 92.0-76.6 76.6-59.8 59.8-49.7 49.7-39.3 39.3-33.3 33.3-24.3 24.3-20.2 | 511.8 425.9 344.2 282.8 236.2 189.8 153.9 123.4 99.4 82.0 65.2 53.0 42.5 35.1 26.5 21.1 | 0.0090 0.0078 0.0146 0.071 0.0166 0.0203 0.0182 0.0256 0.0285 0.0295 0.0383 0.0233 0.0230 0.0153 0.0380 0.0131 | 0.0090 0.0167 0.0313 0.0385 0.0551 0.0751 0.0936 0.1191 0.1476 0.1771 0.2154 0.2392 0.2672 0.2325 0.3205 0.3337 | 0.701 0.732 1.696 1.005 2.819 4.273 4.730 8.283 11.455 14.390 23.533 17.953 26.363 17.445 57.424 24.841 | 0.701 1.432 3.129 4.133 6.952 11.225 13.954 24.237 35.693 50.082 73.618 91.568 117.931 135.376 192.799 217.640 | 631.3 | 0.5406 |
| Adsorptive | Bore dia (A) | The mean diameter in hole (A) | Pore volume (cc/g) | Total pore volume (cc/g) | Hole area (m 2/g) | The total area (the m in hole 2/g) | BET surface-area (m 2/g) | Largest hole volume (cc/g) |
| The sour carbon of shell riceization is former | 557.5-491.4 491.4-377.9 377.9-314.3 314.3-255.3 255.3-206.0 206.0-167.0 167.0-138.6 138.6-110.1 110.1-88.9 88.9-72.3 72.3-58.2 47.1-38.2 38.2-31.1 31.1-23.8 23.8-20.1 | 513.7 118.5 338.7 277.4 224.1 181.3 149.2 120.1 96.2 78.0 62.9 41.0 33.2 25.7 21.0 | 0.0010 0.0014 0.0013 0.0014 0.0018 0.0019 0.0018 0.0024 0.0027 0.0027 0.0028 0.0027 0.0027 0.0057 0.0036 | 0.0010 0.0024 0.0042 0.0056 0.0074 0.0092 0.0110 0.0134 0.0161 0.0189 0.0217 0.0277 0.0303 0.0360 0.0397 | 0.079 0.130 0.209 0.207 0.319 0.410 0.479 0.796 1.135 1.404 1.797 2.641 3.236 8.869 6.899 | 0.079 0.209 0.418 0.625 0.941 1.354 1.823 2.629 3.761 5.168 6.964 12.205 15.441 24.302 31.209 | 147.4 | 0.0999 |
| ) B A (live by the sour carbon of shell riceization | 690.3-461.5 461.5-309.6 309.6-277.8 277.8-211.7 211.7-177.5 177.5-133.8 133.8-112.5 112.5-89.6 89.6-72.2 72.2-58.3 58.3-47.7 47.7-39.1 39.1-31.4 31.4-23.9 23.9-20.0 | 529.3 353.4 290.0 234.0 190.3 152.3 121.7 97.4 78.1 62.9 51.2 41.8 33.7 25.7 20.9 | 0.0072 0.0044 0.0033 0.0068 0.0086 0.0106 0.0144 0.0215 0.0184 0.0181 0.0160 0.0159 0.0163 0.0192 0.0080 | 0.0072 0.0116 0.0148 0.0216 0.0302 0.0403 0.0553 0.0767 0.0952 0.1133 0.1292 0.1452 0.1614 0.1807 0.1387 | 0.543 0.495 0.452 1.161 1.799 2.791 4.741 8.821 9.434 11.499 12.512 15.240 19.315 29.859 15.262 | 0.543 1.037 1.490 2.651 4.450 7.241 11.982 20.803 30.238 41.737 54.249 69.490 88.304 118.663 133.925 | 216.1 | 0.2286 |
| ) A B (live by the sour carbon of shell riceization | 594.3-517.2 517.2-398.4 398.4-314.0 314.0-281.1 281.1-205.9 205.9-171.7 171.7-138.5 138.5-110.6 110.6-89.0 89.0-72.0 72.0-58.3 58.3-48.0 48.0-39.7 39.7-31.7 31.7-23.9 23.9-20.1 | 549.2 441.0 344.5 294.5 230.5 184.3 150.6 120.4 96.4 77.8 62.9 51.3 42.3 34.0 25.8 21.0 | 0.0025 0.0046 0.0076 0.0033 0.0082 0.0077 0.0088 0.0125 0.0127 0.0134 0.0140 0.0140 0.0160 0.0201 0.0286 0.0123 | 0.0025 0.0071 0.0147 0.0180 0.0262 0.0339 0.0427 0.0552 0.0679 0.0813 0.0953 0.1094 0.1253 0.1455 0.1741 0.1864 | 0.185 0.417 0.879 0.445 1.430 1.668 2.347 4.159 5.267 6.886 8.903 10.928 15.096 23.675 44.342 23.468 | 0.185 0.602 1.481 1.926 3.356 5.024 7.371 11.530 16.796 23.682 32.585 43.513 53.609 82.283 126.625 150.094 | 294.3 | 0.2590 |
| 620.9-479.5 479.5-400.3 400.3-325.1 325.1-260.0 | 530.4 431.2 353.6 283.9 | 0.0044 0.0039 0.0036 0.0056 | 0.0044 0.0080 0.0120 0.0176 | 0.333 0.337 0.445 0.786 | 0.333 0.670 1.115 1.901 |
| Adsorptive | Bore dia (A) | The mean diameter in hole (A) | Pore volume (cc/g) | The cubic capacity in hole (cc/g) | Hole area (m 2/g) | The total area (the m in hole 2/g) | BET surface-area (m 2/g) | The largest hole volume |
| ) h 2, B (live by the sour carbon of shell riceization | 260.0-212.8 212.8-168.3 168.3-138.4 138.4-110.5 110.5-89.1 89.1-72.3 72.3-58.2 58.2-48.0 48.0-39.5 39.5-31.7 31.7-23.9 23.9-20.0 | 230.4 184.2 149.3 120.3 96.5 78.1 62.9 51.3 42.1 34.0 25.8 20.9 | 0.0063 0.0037 0.0093 0.0114 0.0118 0.0135 0.0161 0.0176 0.0210 0.0287 0.0399 0.0170 | 0.0238 0.0325 0.0413 0.0532 0.0650 0.0785 0.0949 0.1125 0.1335 0.1623 0.2021 0.2191 | 1.083 1.893 2.492 3.734 4.383 6.901 10.463 13.721 19.907 33.762 61.718 32.445 | 2.989 4.383 7.375 11.158 16.011 22.942 33.405 47.126 67.033 100.794 162.513 194.958 | 445.5 | 0.3385 |
| ) h 5, B (live by the sour carbon of shell riceization | 666.1-485.2 485.2-395.2 395.2-338.7 338.7-259.5 259.5-208.2 208.2-171.3 171.3-141.3 141.3-111.7 111.7-90.0 90.0-74.1 74.1-58.9 58.9-48.0 48.0-39.4 39.4-31.6 31.6-23.9 23.9-20.0 | 545.7 429.1 361.4 287.2 226.8 185.0 152.4 121.9 97.5 79.6 63.9 51.5 42.1 33.9 25.8 20.9 | 0.0043 0.0046 0.0028 0.0055 0.0077 0.0064 0.0071 0.0119 0.0123 0.0101 0.0163 0.0183 0.0199 0.0270 0.0374 0.0164 | 0.0043 0.0039 0.0117 0.0172 0.0249 0.0313 0.0384 0.0503 0.0626 0.0727 0.0890 0.1073 0.1273 0.1543 0.1917 0.2081 | 0.314 0.426 0.311 0.769 1.356 1.381 1.871 3.904 5.016 5.098 10.212 14.194 18.931 31.881 58.058 31.284 | 0.314 0.740 1.051 1.820 3.176 4.557 6.428 10.332 15.379 20.476 30.689 44.882 63.813 95.695 153.752 185.036 | 491.2 | 0.3148 |
A: use N
2Under liquid nitrogen temperature, measure.
Finish carbonating rice husk and/or active silvery white rice husk that primary and foremost purpose of the present invention is to use surfactivity to improve, it is by 1) in the preliminary cleaning process, the rice husk of finely powdered is added in the sewage or 2) in the water treatment procedure of practice, water purifies vegetable active carbon conventional in the storehouse and replaces with rice husk.The result has removed water pollutant such as various toxic organic compound, heavy metal cation, sterilant, washing composition etc. effectively from sewage.
The following examples and comparing embodiment have only also further elaborated the good characteristic of they all contaminations in removing sewage in order to the method for explanation preparation activated carbon acidifying rice husk of the present invention and active silvery white rice husk, must not think the qualification to invention scope.
Embodiment 1-1 is to 1-3 (preparation activated carbon acidifying rice husk)
Embodiment 1-1 (preparation activated carbon acidifying rice husk [A])
The rice husk of the 60g carbonating of packing in flask adds the 700ml 10%HCl aqueous solution, mixes.The mixture thermal backflow was handled 2 hours, cool to room temperature; The product water cleans two or three times, with the neutralization of the NaOH aqueous solution; Then, the rice husk water that neutralized cleans two or three times, filters and drying.The surface-area of product activated carbon acidifying rice husk [A] is 114m
2/ g.
Embodiment 1-2 (preparation activated carbon acidifying rice husk [B])
The rice husk of the 60g carbonating of packing in flask adds the 700ml 10%HCl aqueous solution, is mixed together.Subsequently, thermal backflow was handled this mixture 2 hours and cool to room temperature.Water wash products two or three times, with the HCl aqueous solution neutralization of dilution, water cleans this rice husk that neutralize two or three times then, filters also drying.The surface-area of product activated carbon acidifying rice husk [B] is 380-450m
2/ g.
Embodiment 1-3 (preparation of activated carbon acidifying rice husk [AB] and activated carbon acidifying rice husk [BA])
The 60g carbonating of packing in flask rice husk adds the 700ml 10%HCl aqueous solution, is mixed together.Thermal backflow treating mixture 2 hours and cool to room temperature; Wash product two or three times then, filter, reinstall flask.Subsequently, the 700ml 10%NaOH aqueous solution is joined in the flask, its pre-treatment rice husk with the inside is mixed; This mixture 2 hours and cool to room temperature are handled in thermal backflow: washing product two or three times: with the HCl aqueous solution neutralization of dilution; The rice husk that neutralized is washed two or three times again; Filter and drying.The surface-area of final activated carbon acidifying rice husk [AB] is 216m
2/ g.In addition, the order of exchanged acid and alkaline purification repeats same step and prepares activated carbon acidifying rice husk [BA]; The surface-area of these rice husks [BA] is 294m
2/ g.
Embodiment 2-1 is to 2-3 (preparing active silvery white rice husk)
Silvery white rice husk replaces the carbonating rice husk, repeats the same steps as of embodiment 1-1 to 1-3.The scope of the surface-area of final active silvery white rice husk is respectively from 6m
2/ g is to 8m
2/ g.
Embodiment 3 (, measuring water purifying PH, turbidity, BOD. and COD. so) if in water treatment procedure, use active rice husk of the present invention
Activated carbon acidifying rice husk [B] by embodiment 1-2 preparation becomes smalls with active silvery white rice husk [AB] separated pulverizing that is prepared by embodiment 2-3, adds sewage to be clean in the 1l reservoir; Then, this mixture stirred 30 minutes under rotating speed 150rpm.Then, sneak into the 12mg poly aluminium chloride, under same rotational speed, stirred 6 minutes; This mixture restir 20 minutes under the rotating speed 70rpm that reduces places room temperature.After treating that all floating matters are deposited in the bottom of the reservior, measure PH, turbidity, the BOD.COD of upper water.In order relatively to use the measurement result of active rice husk of the present invention,, the results are shown in table 3 to purifying the mensuration that the water that obtains carries out same quality with vegetable active carbon ordinary method.In the present embodiment, turbidity is measured with HACH ratio/XR turbidometer, according to open source literature " standard method of check water and waste water " measure BODs (Washington D.17ed, 1989), the spectrophotometer measurement that CODs is made by Dr.Lange Co..
As shown in table 3, use purifying waste water of activated carbon acidifying rice husk of the present invention [B], active silvery white rice husk [AB], to compare with purifying waste water of obtaining with common vegetable active carbon method, they demonstrate similar result respectively on PH and turbidity.But, activated carbon acidifying rice husk [B] and active silvery white rice husk [AB] and conventional plant activated carbon comparison sheet, it has better effect on BOD that purifies waste water and COD.
Table 3
Embodiment 4-1 is to 4-3 (measuring water purifying haloform concentration) under the situation of process use activated carbon acidifying rice husk of the present invention of purifying waste water
Embodiment 4-1
Poly aluminium chloride 12mg/L and Cl
20.5ppm join (from the Dduk-Sum of Korea Hangang) in the sewage.This mixture stirred 6 minutes under the about 150rpm of rotating speed, stirred 20 minutes under the rotating speed 70rpm that reduces again, and product subsequently places under the room temperature.After treating that all floating matters all are deposited in the bottom of the reservior, detect upper water, the results are shown in table 4 to determine the concentration of haloform.
Embodiment 4-2
The product water filtration that obtains from embodiment 4-1 flow through vegetable active carbon-coating (diameter 6cm, high 20cm, heavy 280g) or activated carbon acidifying rice husk [B] layer (diameter 6cm, high 20cm, heavy 50g).With vapor-phase chromatography (Purge ﹠amp; Trap ECD) detects every kind of filtrate to determine the concentration of haloform in the water, the results are shown in table 4.Table 4 (THM
sMensuration) (unit: ppb)
| Sample (streamflow, L) | Chloroform | BDCM a | DBCM b | Bromofom |
| Raw water | 31.4 | n.d. | n.d. | n.d. |
| Do not purify waste water+PAC c+ chlorine (0.5ppm) | 4.4 | n.d. | n.d. | n.d. |
| Do not purify waste water+PAC+ chlorine (5) (0.5ppm) handles back stream (10) through the vegetable active carbon-coating d (15) (18) | n.d. ＜1 1 1 | n.d. n.d. n.d. n.d. | n.d. n.d. n.d. n.d. | n.d. n.d. n.d. n.d. |
| Do not purify waste water+PAC+ chlorine (5) (0.5ppm) handles back stream (10) through activated carbon acidifying rice husk (15) [B] layer (18) | n.d. ＜1 1.9 1 | n.d. n.d. n.d. n.d. | n.d. n.d. n.d. n.d. | n.d. n.d. n.d. n.d. |
A:BDCM is two bromodichloromethanes;
B:DBCM is two bromochloromethanes;
C:PAC is a poly aluminium chloride;
D: vegetable active carbon is selected from the activated carbon granule of Kanto Chemical Co.Inc..
Embodiment 5 (measuring residual pesticide dosage under with activated carbon acidifying rice husk of the present invention [B] situation) in the process of purifying waste water
For making activated carbon acidifying rice husk of the present invention and conventional plant activated carbon relatively absorb and remove the characteristic of sterilant, strong toxicity sterilant diazinon, Sumithion and thiophos are dissolved in respectively in the water so that three kinds of aqueous solution, the i.e. thiophos of the Sumithion of the diazinon of 6ppm, 12ppm and 18ppm to be provided.The concentration of above-mentioned every kind of sterilant is 300 times of Korea's tap water maximum acceptable concentration.These solution filter vegetable active carbon-coating of flowing through (diameter 6cm, high 20cm, heavy 280g) or activated carbon acidifying rice husk [B] layer (diameter 6cm, high 20cm, heavy 50g) subsequently.To determine the concentration of residual pesticide, the results are shown in table 5 with every kind of filtrate of gas chromatographic detection.As shown in table 5, detected result is as using conventional vegetable active carbon-coating, after every kind of insecticide solution of 15 liters is flowed through the vegetable active carbon-coating, diazinon 1.2ppm, Sumithion 1.4ppm and thiophos 3.2ppm are arranged respectively in the filtrate, if but use activated carbon acidifying rice husk [B] layer, when every kind of insecticide solutions of 30 liters pass through this activated carbon acidifying rice husk [B] layer, there is not residual sterilant in the filtrate.
Table 5 (mensuration of the residual pesticide adsorptive power of conventional plant activated carbon and activated carbon acidifying rice husk of the present invention [B])
| Sample (streamflow rises) | Insecticide concentration (mg/L) | ||
| Diazinon | Sumithion | Thiophos | |
| Filtering solution not | 6 | 12 | 18 |
| Filter (15) with the vegetable active carbon-coating | 1.2 | 1.4 | 3.2 |
| Filter (20) (25) (30) with activated carbon acidifying (15) rice husk [B] layer | ＜0.005 ＜0.005 ＜0.005 ＜0.005 | ＜0.005 ＜0.005 ＜0.005 ＜0.005 | ＜0.005 ＜0.005 ＜0.005 ＜0.005 |
A: vegetable active carbon is selected from the activated carbon granule of Kanto Chemical Co.Inc..
Embodiment 6 (measuring residual phenol under with activated carbon acidifying rice husk of the present invention [B] situation) at water treatment procedure
For the absorption of activated carbon acidifying rice husk more of the present invention [B] and conventional plant activated carbon with remove a kind of characteristic of toxic organics phenol, phenol is dissolved in the water to obtain containing the aqueous solution of 4.47ppm phenol.The concentration of above-mentioned phenol is 900 times that Korea drinks underwater maximum allowable concentration.Subsequently, the phenol aqueous solution filters vegetable active carbon-coating of flowing through (diameter 6cm, high 20cm, heavy 280g) or activated carbon acidifying rice husk [B] layer (diameter 6cm, high 20cm, heavy 50g).Detect every kind of filtrate to determine the concentration of residual phenol with vapor-phase chromatography, the results are shown in table 6.As shown in table 6, measurement result after every kind of phenol solution of 15 liters is flowed through this carbon-coating, has phenol 1.2ppm as using the vegetable active carbon-coating in the filtrate; But, if use activated carbon acidifying rice husk [B] layer, when 15 liters phenol solution is flowed through this rice husk [B] layer, the also phenol of noresidue in the filtrate.Be measured to subsequently, after 30 liters of phenol solutions flow through activated carbon acidifying rice husk [B], just detect the residual phenol that 12ppm is arranged in the filtrate.
Table 6 (measuring the residual phenol adsorption capacity of conventional plant activated carbon and activated carbon acidifying rice husk of the present invention [B])
| Sample (the phenol solution flow, L) | Phenol concentration (mg/L) |
| Unfiltered solution | 4.47 |
| Filter (20) (30) by vegetable active carbon-coating (15) | 0.042 0.084 0.140 |
| Filter (20) (25) (30) by activated carbon acidifying (15) rice husk [B] layer | n.d. 0.004 0.007 0.012 |
A: vegetable active carbon is selected from the activated carbon granule of Kanto Chemical Co.Inc..
Embodiment 7 (use at water treatment procedure and measure residual interfacial agent negatively charged ion under the situation of activated carbon acidifying rice husk of the present invention [B])
Absorption and the anionic characteristic of removal interfacial agent for activated carbon acidifying rice husk more of the present invention [B] and conventional plant activated carbon, a kind of synthetic detergent Sodium dodecylbenzene sulfonate is dissolved in the water and obtains containing the aqueous solution of 4.47ppm Sodium dodecylbenzene sulfonate, this concentration is 10 times of Korea's tap water maximum acceptable concentration.Subsequently, the aqueous solution filters vegetable active carbon-coating of flowing through (diameter 6cm, high 20cm, heavy 280g) or activated carbon acidifying rice husk [B] layer (diameter 6cm, high 20cm, heavy 50g).Detect every kind of filtrate to determine the anionic concentration of residual interfacial agent with absorption photometer (methylenum coeruleum method), the results are shown in table 7.As shown in table 7, use the vegetable active carbon-coating if determine, go up and state solution when 5 by behind this carbon-coating, the residual interfacial agent negatively charged ion of 0.47ppm is arranged in the filtrate; But,, go up when stating solution also almost noresidue interfacial agent negatively charged ion by this rice husk layer up to 30 if use activated carbon acidifying rice husk [B] layer.
Table 7 (mensuration of the residual interfacial agent negatively charged ion adsorptive power of conventional plant activated carbon and activated carbon acidifying rice husk of the present invention [B])
| Sample (solution flow rises) | The concentration of Sodium dodecylbenzene sulfonate (mg/L) |
| Unfiltered solution | 4.47 |
| By the filtering solution of vegetable active carbon-coating (5) (15) (25) (30) | 0.47 1.0 0.6 0.8 |
| By activated carbon acidifying rice (15) shell [B] layer filtering (30) solution | ＜0.02 ＜0.02 |
A: vegetable active carbon is selected from the activated carbon granule of Kanto Chemical Co.Inc..
Embodiment 8 (under the situation of process use activated carbon acidifying rice husk [A], [B], [AB], [BA] of purifying waste water, measuring heavy metal cation)
5.1gFeCl
36H
2O, 7.41gCuCl
2, 3.8gMnCl
24H
2O, 15.93gZn (NO
3)
26H
2O, 1.35gCr (NO
3)
29H
2O, 0.8gPb (NO
3)
2, 0.1gCd (NO
3) 4H
2O and distilled water add together in the flask and obtain 1 liter of aqueous solution that contains heavy metal.Subsequently, the Hg of the above-mentioned aqueous solution of 100ml, 10ml 100ppm
2+The water of solution and predetermined amount mixes and obtains 35 liters of dilute aqueous.This be equipped with the aqueous solution filter the conventional plant activated carbon layer of flowing through (diameter 6cm, high 20cm, heavy 280g) or four kinds of activated carbon acidifying rice husks [A], [B], [AB], [BA] layer (each diameter 6cm, high 20cm, heavy 50g).With atomic absorption spectroscope (AA), inductively coupled plasma spectroscope (ICP) or inductivity coupled plasma mass spectrometry spectroscope (ICP-mass) detect every kind of filtrate and remain in the filtrate to have determined whether heavy metal cation, the results are shown in table 8.As shown in table 8, use conventional vegetable active carbon-coating if determine, to go up when stating solution when 1 by this carbon-coating, most of heavy metal cation is stayed in the filtrate; But, if use activated carbon acidifying rice husk [B], [AB], [BA] layer, go up when stating solution up to 30 by these rice husk layers, in every kind of filtrate except Mn
2+, Zn
2+Almost there is not other heavy metal cation.Especially, go up when stating solution up to 45, also do not detect Cr fully by activated carbon acidifying rice husk [B], [AB] or [BA] layer
3+, Pb
2+And Hg
2+
Table 8 (measuring the heavy metal cation adsorptive power of conventional plant activated carbon and activated carbon acidifying rice husk [A], [B], [AB], [BA])
| Sample (discharge, L) | Metallic cation concentration (mg/L) | |||||||
| Fe 1+ | Cu 2+ | Mn 2+ | Zn 2+ | Cr 3+ | Pb 2+ | Cd 2+ | Hg 2+ | |
| Unfiltered solution | 2.71 | 9.4 | 3.03 | 9.9 | 0.47 | 0.8 | 0.1 | 0.03 |
| Filter (1) by the vegetable active carbon-coating | 1.93 | 5.53 | 3.02 | 0.33 | 0.11 | |||
| Filter (4) (5) (6) (8) (10) by activated carbon acidifying rice husk (A) (1) (2) layer | 0.69 1.73 2.09 | 0.82 4.44 7.09 9.37 9.40 | 1.1 2.90 3.38 3.52 3.38 3.21 3.14 | 6.6 6.6 11.5 11.7 11.1 10.4 | 0.047 0.l2 0.25 0.31 | ＜0.01 | 0.06 0.09 0.11 0.12 0.11 | ＜0.005 |
| (B) filter (16) (18) (20) (22) (24) (26) (28) (30) (32) (34) (36) (38) (40) (42) (44) by activated carbon acidifying rice husk layer (15) | 0.12 0.25 0.27 0.35 0.39 1.06 1.52 0.62 1.36 2.07 2.39 | 0.20 1.58 4.35 5.08 8.81 11.03 12.17 | 0.43 0.85 4.18 6.52 6.81 6.24 6.15 5.74 5.28 4.81 4.34 4.41 3.87 3.56 3.44 | 0.05 1.07 4.4 9.4 13.2 10.8 15.2 17.4 17.6 16.2 19.2 15.8 13.6 12.2 | 0.07 0.11 0.23 0.31 0.30 0.30 0.27 0.24 | |||
| (BA) filter (13) (15) (20) (23) (25) (30) (35) (37) (40) (45) by activated carbon acidifying rice husk layer (11) (12) | 0.74 0.41 0.25 | 0.1 0.89 1.98 8.60 8.26 10.86 13.52 | 0.59 1.49 3.64 5.38 5.79 5.55 5.64 4.07 4.19 3.57 3.25 | 0.14 0.81 6.2 11.0 12.4 11.4 11.4 15.2 14.6 12.8 | 0.07 0.09 0.19 0.21 0.27 0.20 0.22 | |||
| Sample (discharge, L) | Metallic cation concentration＜mg/L 〉 | |||||||
| Fe 4+ | Cu 3+ | Mn 2+ | Zn 2+ | Cr 3+ | Pb 3+ | Cd 2+ | Hg 2+ | |
| (48) (50) (55) (57) (60) (62) | 0.42 0.32 0.28 0.33 0.22 0.23 | 14.07 13.34 13.19 12.36 11.77 11.50 | 3.13 3.07 3.02 3.02 3.02 3.02 | 11.4 10.8 11.2 11.0 10.6 10.6 | 0.07 0.15 0.20 0.25 0.27 | 0.11 0.15 0.53 0.50 0.45 0.51 | 0.15 0.15 0.13 0.13 0.13 0.13 | |
| (B) filter (12) (15) (19) (20) (25) (30) (31) (32) (35) (38) (40) (45) (50) (51) (52) (53) by activated carbon acidifying rice husk layer (11) | 0.15 0.25 0.64 0.99 1.20 1.31 1.29 | 0.1 0.42 0.36 1.26 4.63 9.20 12.0 13.07 13.36 14.32 | 0.09 0.74 2.11 3.06 6.07 6.28 6.06 5.79 5.85 5.48 4.75 3.84 3.57 3.49 3.49 3.49 | 0.16 0.64 5.2 11.8 13.2 14.4 12.0 14.0 13.8 12.4 14.4 13.8 13.2 13.2 | 0.06 0.10 0.16 0.22 0.23 0.23 0.23 0.23 0.23 | |||
A: vegetable active carbon is selected from the activated carbon granule of Kanto Chemical Co.Inc..
Example 9-1 is to 9-2 (using under the situation of activated carbon acidifying rice husk of the present invention [B] mensuration [2] to heavy metal cation) at water treatment procedure
Embodiment 9-1 (preparing the heavy metal aqueous solution respectively)
1.44gCd (NO
3) 4H
2O, 1.45gHg (NO
3)
2, 1.96gPb (NO
3)
2, 0.38gMnCl
24H
2O, 0.769gZnSO
4.6H
2O, 0.054gCr (NO
3)
29H
2O, 0.254gFeCl
36H
2O, 1.11gCuCl
2Or 0.062gCl
2(CH
3CO
2)
2Add together in the flask with 35 premium on currency and obtain the heavy metal aqueous solution.
Embodiment 9-2
Every heavy metal species aqueous solution by embodiment 9-1 preparation filters vegetable active carbon-coating of flowing through (diameter 6cm, high 20cm, heavy 280g) or activated carbon acidifying rice husk of the present invention [B] layer (diameter 6cm, high 20cm, heavy 50g).With atomic absorption spectroscope (AA), inductively coupled plasma spectroscope (ICP) or inductivity coupled plasma mass spectrometry spectroscope (ICP-mass) detect every kind of filtrate and stay in the filtrate to have determined whether heavy metal cation.The results are shown in table 9.As shown in table 9, determine activated carbon acidifying rice husk of the present invention [B] and have the adsorptive power good most of heavy metal cations.
Table 9 (measuring the heavy metal cation adsorptive power of conventional plant activated carbon and activated carbon acidifying rice husk of the present invention [B])
| Metallic cation | Do not filter concentration (mg/L) | Filter back concentration (solution flow) |
| Cd 2+ Hg 2+ Mn 2+ Mn 2+ Zn 2+ U 4+ Mg 2+ Cu 2+ Fe 3+ Cu 2+ Cr 3+ | 20 20 20 3 5 1 50 100 1.5 15 0.2 | n.d. (25L) 0.8 (27L) n.d. (33L) n.d. (45L) n.d. (50L) n.d. (75L) 0.00063 (15L) 0.00104 (2L) 0.050 (28L) 0.018 (1.5L) 0.23 (1.5L) 25.8 (2L) n.d. (13.5L) 0.02 (43L) n.d. (30L) |
As mentioned above, the invention provides the method for preparing the active rice husk of novelty from former rice husk with good surface activated adsorption ability and ion transfer capability, use these active rice husks to purify waste water, by cohesion, absorption and filtration, can effectively and economically from sewage, remove the objectionable impurities or the pollutent of various polluted water.
Detailed description of the present invention is special referring to embodiment preferred, still belongs in the spirit and scope of the present invention but should understand some change and adjust.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR18329/91 | 1991-10-17 | ||
| KR910018329 | 1991-10-17 |
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| Publication Number | Publication Date |
|---|---|
| CN1073153A CN1073153A (en) | 1993-06-16 |
| CN1049876C true CN1049876C (en) | 2000-03-01 |
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ID=19321427
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92113095A Expired - Fee Related CN1049876C (en) | 1991-10-17 | 1992-10-17 | Water purification methed using rice hulls |
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| Country | Link |
|---|---|
| JP (1) | JPH0639277A (en) |
| KR (1) | KR950011929B1 (en) |
| CN (1) | CN1049876C (en) |
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|---|---|---|---|---|
| CN100457640C (en) * | 2006-06-28 | 2009-02-04 | 尹军 | Combined treatment method for polluted underground water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4840846B2 (en) * | 2005-09-13 | 2011-12-21 | 秋田県 | Phosphorus recovery material, production method thereof, and fertilizer using phosphorus recovery material |
| CN100455347C (en) * | 2007-04-19 | 2009-01-28 | 浙江大学 | Preparation and use method of multi-stage adsorbent for high-concentration refractory organic wastewater |
| CN102500330A (en) * | 2011-10-13 | 2012-06-20 | 西南科技大学 | Preparation and use methods of helianthus stem and leaf adsorbing material for heavy metals |
| CN103100371B (en) * | 2011-11-10 | 2015-07-22 | 西南科技大学 | Distillers' grains acid modified adsorption material and preparation process thereof |
| JP2013170967A (en) * | 2012-02-22 | 2013-09-02 | Syoken Gijutsu Kk | Radioactive substance decontamination method, radioactive substance adsorbent and radioactive substance decontamination apparatus |
| CN102671617B (en) * | 2012-05-02 | 2014-03-05 | 上海绿帝环保科技有限公司 | A preparation method of a material for adsorbing refractory organic pollutants |
| CN104162410B (en) * | 2014-05-15 | 2016-02-03 | 浙江海洋学院 | A kind of preparation method of natural material adsorbent and the sewage water treatment method of employing natural material adsorbent |
| CN104211045B (en) * | 2014-09-04 | 2016-05-18 | 江南大学 | A kind of simple and quick method of preparing rice husk base porous charcoal/silicon dioxide composite material |
| CN105170108B (en) * | 2015-10-19 | 2017-10-13 | 辽宁大学 | A kind of rice husk cellulose adsorbent and its preparation method and application |
| CN106277089A (en) * | 2016-08-17 | 2017-01-04 | 安徽省怀远县鑫泰粮油有限公司 | A kind of shell of Oryza glutinosa is the method that sewage purification filter plate prepared by raw material |
| CN106966501A (en) * | 2017-04-18 | 2017-07-21 | 中国水产科学研究院南海水产研究所 | A kind of modified rice husk filling biofilter and denitrification process |
| CN112877093B (en) * | 2021-01-14 | 2023-12-05 | 长江大学 | Demulsifier, demulsifier composition and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5781880A (en) * | 1980-11-10 | 1982-05-22 | Toho Aen Kk | Method and device for treatment of shaft waste water |
-
1992
- 1992-09-22 KR KR1019920017280A patent/KR950011929B1/en not_active Expired - Fee Related
- 1992-10-13 JP JP4299110A patent/JPH0639277A/en active Pending
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457640C (en) * | 2006-06-28 | 2009-02-04 | 尹军 | Combined treatment method for polluted underground water |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0639277A (en) | 1994-02-15 |
| KR930007814A (en) | 1993-05-20 |
| KR950011929B1 (en) | 1995-10-12 |
| CN1073153A (en) | 1993-06-16 |
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