WO2016113946A1 - クロム含有水の処理方法 - Google Patents
クロム含有水の処理方法 Download PDFInfo
- Publication number
- WO2016113946A1 WO2016113946A1 PCT/JP2015/076199 JP2015076199W WO2016113946A1 WO 2016113946 A1 WO2016113946 A1 WO 2016113946A1 JP 2015076199 W JP2015076199 W JP 2015076199W WO 2016113946 A1 WO2016113946 A1 WO 2016113946A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- chromium
- water
- hydrogen sulfide
- containing water
- solution
- Prior art date
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Classifications
-
- 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
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Definitions
- the present invention relates to a method for treating water containing chromium.
- Methods for removing metal elements from water include coagulation precipitation methods, ion exchange methods, adsorption methods that adsorb to adsorbents such as activated carbon, electrical adsorption methods, and magnetic adsorption methods. Coagulation precipitation methods using agents are often used.
- the coagulation precipitation method includes adding a neutralizer to the water to be treated and increasing the pH to solidify the metal as a hydroxide, and then filtering the solid and liquid by an operation such as filtration. The liquid is separated, the liquid is discharged outside the factory, and the solid is processed at a disposal site or the like.
- a neutralizing agent used in the coagulation precipitation method an inexpensive calcium-based neutralizing agent such as limestone or slaked lime is generally used.
- Patent Document 1 discloses a reduction process in which ferrous ions are added to water containing hexavalent chromium to reduce hexavalent chromium to trivalent chromium, and alkali is added to the effluent water in the reduction process.
- the insolubilization process which makes trivalent chromium produced
- the sludge separation process which isolate
- a chromium-containing wastewater treatment method is disclosed in which part of the sludge separated in the sludge separation step is introduced into the reduction step.
- the present invention has been proposed in view of the above circumstances, and an object of the present invention is to provide a method for treating chromium-containing water that can treat water containing chromium (chromium-containing water) at low cost.
- the present inventors have made extensive studies to solve the above-described problems. As a result, the present invention finds that it is possible to effectively treat at low cost by reducing chromium contained in water to be treated using thin hydrogen sulfide discharged from processes such as various factories and plants. It came to complete. That is, the present invention provides the following.
- water containing chromium and a liquid containing 5 ppm to 50 ppm of hydrogen sulfide are mixed, and an acid is added to adjust the pH to 3.5 or less and ORP 200 mV to 400 mV.
- a reduction step of reducing chromium contained in the water, and a neutralizer is added to the solution obtained through the reduction step to adjust the pH to 8 to 9, thereby reducing the reduced chromium contained in the solution to water.
- a precipitation separation step of separating the precipitate of the hydroxide by precipitation as an oxide.
- the second invention of the present invention is the method for treating chromium-containing water according to the first invention, wherein the acid is sulfuric acid.
- the neutralizing agent is any one or more of calcium oxide, calcium carbonate, and calcium hydroxide. It is a processing method of contained water.
- a trivalent solution is added to the mixed solution of the water containing chromium and the liquid containing hydrogen sulfide. It is a method for treating chromium-containing water, characterized by coexisting an iron compound.
- a fifth invention of the present invention is the method for treating chromium-containing water according to the fourth invention, wherein the trivalent iron compound is iron hydroxide.
- water containing chromium can be effectively treated at low cost.
- the method for treating water containing chromium includes a reduction step of reducing chromium contained in water and a solution obtained through the reduction step.
- chromium contained in the water to be treated is reduced. More specifically, in this reduction step, chromium-containing water and a liquid containing 5 to 50 ppm of hydrogen sulfide are mixed, acid is added to adjust the pH to 3.5 or less, and the oxidation-reduction potential (ORP) ) To 200 mV to 400 mV to reduce chromium in water.
- ORP oxidation-reduction potential
- FIG. 1 is a schematic diagram showing an example of a reaction tank for performing a method for treating chromium-containing water.
- a chromium-containing water 11 to be treated and a liquid 12 containing 5 to 50 ppm of hydrogen sulfide are charged into a reaction tank 1A having a desired capacity.
- the hexavalent chromium contained in the chromium-containing water 11 is reduced to trivalent chromium.
- the reduction process in a reduction
- the liquid 12 containing hydrogen sulfide having a concentration of 5 ppm to 50 ppm is used to reduce chromium contained in the chromium-containing water 11. It is characterized by that.
- chromium is reduced using the liquid 12 containing hydrogen sulfide having a predetermined concentration discharged from a process such as a factory or a plant, that is, process water.
- the reduction treatment can be performed at a low cost without preparing a new reducing agent.
- the liquid (process water) 12 containing hydrogen sulfide having a concentration of 5 ppm to 50 ppm cannot be used as a use application of a sulfurizing agent or the like because of its low hydrogen sulfide concentration. Therefore, conventionally, the process water discharged from factories or the like has to be detoxified by fixing the hydrogen sulfide as sulfur. However, costs also arise in the detoxification process. On the other hand, in this Embodiment, since the said process water 12 is used in order to reduce
- the concentration of hydrogen sulfide if the concentration is less than 5 ppm, the concentration is too low to allow the reduction reaction to proceed sufficiently. On the other hand, if the concentration of hydrogen sulfide exceeds 50 ppm, there is a possibility that it will be used as a main use application such as a sulfurizing agent.
- liquid 12 containing 5 ppm to 50 ppm of hydrogen sulfide is used to mix with chromium-containing water 12.
- a liquid containing hydrogen sulfide may be used, and a liquid adjusted to a hydrogen sulfide concentration of 5 ppm to 50 ppm by blowing it into the liquid may be used.
- the pH of the mixed solution of the chromium-containing water 11 and the liquid 12 containing hydrogen sulfide is adjusted to 3.5 or lower, and the ORP is adjusted to 200 mV to 400 mV to cause a reduction reaction.
- the pH of the mixed solution is adjusted by adding acid 13 as shown in FIG.
- the acid is not particularly limited, and for example, sulfuric acid, hydrochloric acid, nitric acid or the like can be used, and sulfuric acid is particularly preferably used.
- Sulfuric acid is generally used in various factories and plants, and can be easily used without making new investments in storage facilities and the like.
- the pH of the mixed solution if the pH exceeds 3.5, the reduction reaction cannot proceed efficiently. Therefore, by adding an acid to the mixed solution, the pH is adjusted to 3.5 or less and subjected to a reduction treatment, and more preferably to 3.0 or less.
- the upper limit value of the pH is not particularly limited, but is preferably 1.0 or more from the viewpoint of making the amount of acid used in an appropriate range.
- the ORP of the mixed solution is adjusted by increasing or decreasing the amount of chromium-containing water 11 and the amount of hydrogen sulfide (the amount of liquid 12 containing hydrogen sulfide) that are added and mixed in the reaction vessel.
- the ORP of the mixed solution if the ORP is less than 200 mV, a large amount of hydrogen sulfide is required and it is difficult to perform efficient treatment. On the other hand, when the ORP exceeds 400 mV, the reduced chromium is oxidized. For this reason, the ORP is adjusted to 200 mV to 400 mV for reduction treatment, and more preferably 250 mV to 350 mV.
- the reduction step when mixing the chromium-containing water 11 and the liquid 12 containing 5 ppm to 50 ppm of hydrogen sulfide, it is preferable to add a trivalent iron compound 14 to coexist.
- the amount of hydrogen sulfide contained in the liquid 12 containing hydrogen sulfide is reduced by chromium. May be greater than the amount of hydrogen sulfide required.
- the liquid 12 containing 5 ppm to 50 ppm of hydrogen sulfide which is the process water discharged from the factory or plant, for the reduction treatment of chromium
- the amount of hydrogen sulfide contained in the process water 12 is substantially greater than the amount of hydrogen sulfide required for chromium reduction.
- surplus hydrogen sulfide in the mixed solution in the reaction tank 1A can be effectively rendered harmless.
- iron hydroxide Fe (OH) 3
- iron hydroxide Fe (OH) 3
- Chromium-containing water 11 can be treated.
- the addition amount of the trivalent iron compound 14 is not particularly limited, and an excess amount can be added. Also, the timing of addition is not particularly limited, and for example, it can be added after adding a chromium-containing water 11 or a liquid 12 containing hydrogen sulfide to cause a reduction reaction.
- the solution (chromium-containing solution) 11 ′ obtained by the reduction treatment is collected by the dispensing pump 4 and transferred to the reaction tank 1 ⁇ / b> B that performs the treatment in the next precipitation separation step. Further, the gas (cycle gas) 15 generated in the reduction reaction is collected through the cycle line 5 connected to the scrubber.
- ⁇ Precipitation separation step> In the precipitation separation step, a neutralizing agent is added to the solution obtained through the reduction step to produce and separate chromium hydroxide precipitates. More specifically, in this precipitation separation step, the reduced chromium is agglomerated and separated as a hydroxide and separated by adding a neutralizing agent to the solution after the reduction treatment and adjusting the pH to 8-9. .
- FIG. 1 (B) is a schematic diagram showing an example of a reaction tank that performs the treatment in the precipitation separation step.
- the chromium-containing solution 11 ′ transferred from the reaction tank 1A used for the treatment in the reduction process is charged into the reaction tank 1B having a desired capacity.
- the pH of the solution is adjusted to 8-9 by adding a neutralizing agent 16 to the chromium-containing solution 11 ′.
- a post-treatment liquid 20 in which the reduced chromium in the solution is aggregated as a hydroxide to form a precipitate, and chromium is removed.
- the neutralizing agent 16 is not particularly limited, but is preferably one or more of calcium oxide, calcium carbonate, and calcium hydroxide. These neutralizing agents 16 are particularly preferable because they are inexpensive and easily available.
- the pH of the solution if the pH is less than 8, chromium hydroxide may not be generated effectively. On the other hand, when the pH exceeds 9, the amount of the neutralizing agent 16 to be added is not preferable.
- the chromium hydroxide precipitate is separated from the chromium-removed solution (treated solution) 20 by solid-liquid separation operation, and only the treated solution 20 is recovered.
- the post-treatment liquid 20 can be recovered by, for example, the dispensing pump 4.
- Example 1 First, as a reduction step, water 250 m 3 / hr containing chromium at a concentration of 0.39 mg / L and liquid 10 m 3 / hr containing hydrogen sulfide at a concentration of 5 ppm are charged into the reaction vessel and mixed.
- the ORP was adjusted to 200 mV to 400 mV, and sulfuric acid was added to adjust the pH of the mixed solution to 2.71 for reduction treatment.
- iron hydroxide was simultaneously added to the mixed solution as a trivalent iron compound.
- the chromium concentration in the water was changed from 0.39 mg / L to 0.02 mg / L, and it was possible to effectively reduce chromium.
- Example 2 The chromium-containing water was treated in the same manner as in Example 1 except that a liquid containing hydrogen sulfide at a concentration of 50 ppm was mixed.
- the chromium concentration in the water was changed from 0.39 mg / L to 0.01 mg / L, and the chromium could be effectively reduced.
- the chromium concentration in the water obtained by such a treatment method that is, the treatment only with the addition of the neutralizing agent was 0.38 mg / L, which was only slightly decreased.
Abstract
Description
還元工程では、処理対象の水に含まれるクロムを還元する。より具体的に、この還元工程では、クロム含有水と、5ppm~50ppmの硫化水素を含む液体とを混合し、酸を添加してpHを3.5以下に調整し、また酸化還元電位(ORP)を200mV~400mVに調整して、水中のクロムを還元する。
沈殿分離工程では、還元工程を経て得られた溶液に中和剤を添加してクロムの水酸化物沈殿を生成させて分離する。より具体的に、この沈殿分離工程では、還元処理後の溶液に中和剤を添加してpHを8~9に調整することによって、還元されたクロムを水酸化物として凝集沈殿させて分離する。
先ず、還元工程として、クロムを0.39mg/Lの濃度で含有する水250m3/hrと、硫化水素を5ppmの濃度で含む液体10m3/hrとを反応槽内に装入して混合し、ORPを200mV~400mVに調整するとともに、硫酸を添加して混合溶液のpHを2.71に調整して還元処理を施した。なお、混合溶液には、3価の鉄化合物として水酸化鉄を同時に添加した。
硫化水素が50ppmの濃度で含む液体を混合させたこと以外は、実施例1と同様にしてクロム含有水を処理した。
クロム濃度が0.39mg/Lの水250m3/hrに、中和剤として炭酸カルシウムと水酸化カルシウムとを添加してpHを8.5とし、水中のクロムを水酸化物として沈殿分離した。
2 攪拌装置
11 クロム含有水
11’ クロム含有溶液
12 硫化水素を含む液体(プロセス水)
13 酸
14 3価の鉄化合物
15 環集ガス
16 中和剤
20 処理後液
Claims (5)
- クロムを含む水と、5ppm~50ppmの硫化水素を含む液体とを混合し、酸を添加することによってpH3.5以下、及びORP200mV~400mVに調整し、該水に含まれるクロムを還元する還元工程と、
前記還元工程を経て得られる溶液に中和剤を添加してpH8~9に調整することによって、該溶液に含まれる還元されたクロムを水酸化物として沈殿させ、該水酸化物の沈殿を分離する沈殿分離工程と
を有することを特徴とするクロム含有水の処理方法。 - 前記酸は、硫酸であることを特徴とする請求項1に記載のクロム含有水の処理方法。
- 前記中和剤は、酸化カルシウム、炭酸カルシウム、水酸化カルシウムのいずれか1つ以上であることを特徴とする請求項1に記載のクロム含有水の処理方法。
- 前記還元工程において、前記クロムを含む水と前記硫化水素を含む液体との混合溶液に、3価の鉄化合物を共存させることを特徴とする請求項1に記載のクロム含有水の処理方法。
- 前記3価の鉄化合物は、水酸化鉄であることを特徴とする請求項4に記載のクロム含有水の処理方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2015377617A AU2015377617B2 (en) | 2015-01-13 | 2015-09-15 | Chromium-containing water treatment method |
CA2973460A CA2973460C (en) | 2015-01-13 | 2015-09-15 | Chromium-containing water treatment method |
CN201580066052.1A CN107001083A (zh) | 2015-01-13 | 2015-09-15 | 含铬水的处理方法 |
US15/542,485 US10442715B2 (en) | 2015-01-13 | 2015-09-15 | Chromium-containing water treatment method |
EP15877898.5A EP3246290B1 (en) | 2015-01-13 | 2015-09-15 | Chromium-containing water treatment method |
PH12017501260A PH12017501260B1 (en) | 2015-01-13 | 2017-07-10 | Chromium-containing water treatment method |
Applications Claiming Priority (2)
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JP2015-004374 | 2015-01-13 | ||
JP2015004374A JP6413772B2 (ja) | 2015-01-13 | 2015-01-13 | クロム含有水の処理方法 |
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WO2016113946A1 true WO2016113946A1 (ja) | 2016-07-21 |
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PCT/JP2015/076199 WO2016113946A1 (ja) | 2015-01-13 | 2015-09-15 | クロム含有水の処理方法 |
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US (1) | US10442715B2 (ja) |
EP (1) | EP3246290B1 (ja) |
JP (1) | JP6413772B2 (ja) |
CN (1) | CN107001083A (ja) |
AU (1) | AU2015377617B2 (ja) |
CA (1) | CA2973460C (ja) |
PH (1) | PH12017501260B1 (ja) |
WO (1) | WO2016113946A1 (ja) |
Families Citing this family (1)
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JP2019122885A (ja) * | 2018-01-12 | 2019-07-25 | 学校法人智香寺学園埼玉工業大学 | 廃水処理方法、及び廃水処理システム |
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2015
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- 2015-09-15 US US15/542,485 patent/US10442715B2/en not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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JP6413772B2 (ja) | 2018-10-31 |
EP3246290A4 (en) | 2018-06-27 |
CA2973460C (en) | 2019-07-23 |
EP3246290A1 (en) | 2017-11-22 |
JP2016129867A (ja) | 2016-07-21 |
CN107001083A (zh) | 2017-08-01 |
AU2015377617B2 (en) | 2019-01-24 |
PH12017501260A1 (en) | 2018-01-15 |
US10442715B2 (en) | 2019-10-15 |
AU2015377617A1 (en) | 2017-07-20 |
CA2973460A1 (en) | 2016-07-21 |
EP3246290B1 (en) | 2019-08-21 |
PH12017501260B1 (en) | 2018-01-15 |
US20180273411A1 (en) | 2018-09-27 |
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